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Numéro de publicationCN101048458 B
Type de publicationOctroi
Numéro de demandeCN 200580037324
Numéro PCTPCT/US2005/034946
Date de publication7 juil. 2010
Date de dépôt28 sept. 2005
Date de priorité13 oct. 2004
Autre référence de publicationCN101048458A
Numéro de publication200580037324.1, CN 101048458 B, CN 101048458B, CN 200580037324, CN-B-101048458, CN101048458 B, CN101048458B, CN200580037324, CN200580037324.1, PCT/2005/34946, PCT/US/2005/034946, PCT/US/2005/34946, PCT/US/5/034946, PCT/US/5/34946, PCT/US2005/034946, PCT/US2005/34946, PCT/US2005034946, PCT/US200534946, PCT/US5/034946, PCT/US5/34946, PCT/US5034946, PCT/US534946
InventeursP·S·拉维尚卡尔
Déposant埃克森美孚化学专利公司
Exporter la citationBiBTeX, EndNote, RefMan
Liens externes:  SIPO, Espacenet
Elastomeric reactor blend compositions
CN 101048458 B
Résumé
Disclosed herein are various processes, including but not limited to a continuous process for making an elastomer composition having a Mooney Viscosity (ML (1+4) @ 125 DEG C) of from 16 to 180, the composition including a first polymer and a second polymer, the process comprising: polymerizing a first monomer system that includes propylene and one or both of ethylene and propylene in a solvent using a first catalyst system in a first polymerization zone to provide a first polymer, having 60 wt% or more units derived from propylene, including isotactically-arranged propylene-derived sequencesand further having a heat of fusion less than 45 J/g or a melting point less than 105 DEG C or both and a Mooney Viscosity (ML (1+4) @ 125 DEG C) of from I to 45; polymerizing a second monomer system that includes ethylene or an alpha-olefin, or both, in a solvent using a second catalyst system in a second polymerization zone to provide a second polymer which is an elastomeric polymer that is either non-crystalline or has ethylene-derived crystallinity; combining the first polymer and the second polymer in a mixture that includes solvent and unreacted monomer; and removing solvent from the mixture to provide an elastomer composition that having a Mooney Viscosity (ML (1+4) @ 125 DEG C) of from 16 to 180.
Revendications(12)  Langue du texte original : Chinois
1.制备含有第一聚合物和第二聚合物的弾性体组合物的连续方法,该方法包括: 在第一聚合区中,使用第一催化剂体系在溶剂中聚合包括丙烯和こ烯的第一単体体系,以提供第一聚合物,该第一聚合物具有60wt%或更多的由丙烯衍生的単元,包括全同立构排列的丙烯衍生的序列和进ー步具有低于45J/g的熔化热或低于105°C的熔点或同时具备这两种属性以及1-45的门尼粘度;其中熔化热或熔点通过差示扫描量热法使用ASTME-794-95程序測定,门尼粘度在ML(1+4) @125°C下测定; 在第二聚合区中,使用第二催化剂体系在溶剂中聚合包括こ烯的第二单体体系,以提供第二聚合物,该第二聚合物是弾性体和非结晶的或具有源于こ烯的结晶度; 将该第一聚合物和第二聚合物在包括溶剂和未反应单体的混合物中合井; 从该混合物中除去溶剂和丙烯以及こ烯单体,以提供弾性体组合物;以及将丙烯和こ烯单体以及溶剂再循环用于聚合;其中: 该第一聚合进行至将丙烯単体消耗到低于用于制备该第二聚合物所需水平的水平; 该第二聚合和再循环进行至将こ烯単体減少到低于用于制备该第一聚合物所需水平的水平,并且对于第一聚合添加附加补充丙烯単体,和对于第二聚合添加附加补充こ烯单体。 Continuous process 弾 of body composition 1. Preparation containing a first polymer and the second polymer, the method comprising: in a first polymerization zone, using a first polymerization catalyst system comprising a first propylene and ko-ene in a solvent radiolabeling body system, to provide a first polymer, the first polymer having 60wt% or more derived from propylene radiolabeling element, including isotactic arrangement of propylene derived sequences and further having a feed ー less than 45J / g of hot melt or below the melting point of 105 ° C, or both have these two properties and Mooney viscosity 1-45; where the heat of fusion or melting point by differential scanning calorimetry using ASTME-794-95 program, Mooney viscosity Determination of the ML (1 + 4) @ 125 ° C under; in the second polymerization zone, polymerization using the second catalyst system comprises a second monomer system ko ethylenically in a solvent, to provide a second polymer, the second body and the polymer is 弾 of crystallinity or non-crystalline alkylene having from ko; the first and second polymers Hapjeong comprising solvent and unreacted monomer mixture; the solvent was removed from the mixture and propylene and a diene monomer ko, to provide a Tan of composition; ko and propylene and diene monomer and solvent is recycled for the polymerization; wherein: the first polymerization is carried out to consume the body to below the propylene radiolabeling for preparing the The second level of polymer desired level; the second polymerization and recycle will be to reduce the ko-ene radiolabeling for preparing the body to a level lower than the first desired level of the polymer, and adding an additional supplementary first polymerization of propylene radiolabeling body, and add an additional supplement for the second polymerization ko diene monomer.
2.根据权利要求I所述的方法,其中所述弾性体组合物具有16-180的门尼粘度;其中熔化热或熔点通过差示扫描量热法使用ASTME-794-95程序測定,门尼粘度在ML(1+4)@125°C 下測定。 2. The method of claim I, wherein said 弾 composition having 16-180 of Mooney viscosity; wherein the heat of fusion or melting point by differential scanning calorimetry using ASTME-794-95 procedure, Mooney viscosity measured ML (1 + 4) @ 125 ° C under.
3.根据权利要求I所述的方法,其中所述第二聚合物是こ烯和丙烯以及ニ烯的无规共聚物。 3. The method according to claim I, wherein said second polymer is a ko-ene and propylene, and random copolymers ni ene.
4.根据权利要求I所述的方法,其中在串联方式操作中,将所述第一聚合区的流出物的至少一部分连续引入到第二聚合区,和/或在并联方式操作中,将所述第一聚合区的流出物的至少一部分与第二聚合区的流出物合并。 4. The method claimed in claim I wherein, wherein in tandem operation, continuously introducing at least a portion of the effluent of the first polymerization zone to a second polymerization zone, and / or in parallel operation, the said effluent from the first polymerization zone is combined with at least a portion of the effluent of the second polymerization zone.
5.根据权利要求I所述的方法,其中所述第一聚合区中生产的聚合物相对第一和第二聚合区中生产的总聚合物的聚合分割比是5-95。 5. The method according to claim I, wherein said polymerization division ratio in the first polymerization zone the polymer produced relative to the first and second polymerization zone of the total polymer produced is 5-95.
6.根据权利要求I所述的方法,其中包括第一聚合物和第二聚合物的混合物通过脱挥发分来后加工,以形成粒料或包装物。 6. The method according to claim I, wherein the mixture comprising a first polymer and the second polymer by devolatilization be processed to form pellets or packaging.
7.根据权利要求I所述的方法,其中所生产的第一聚合物的分数和第二聚合物的分数独立地通过分割来自再循环的供给到第一和第二聚合的溶剂的量和通过提供附加新鲜进料以改变流量和每ー聚合的除热能力来控制,该第一聚合在低于第一聚合物的熔点的温度下进行,以及该第二聚合在比用于第一聚合的温度高20-200°C的温度下进行。 7. A method according to claim I, fraction and a second fraction of the polymer wherein the first polymer produced independently by dividing the amount of supply from recycled to the polymerization solvent and by first and second providing additional fresh feed to vary the flow rate and heat removal capability to control each ー polymerization, the first polymerization at a temperature below the melting point of the first polymer proceeds, and the second for the polymerization in the first polymerization ratio at a temperature of 20-200 ° C high temperature.
8.根据权利要求I所述的方法,其中使用转移剂来限制第一或第二聚合区中的分子量。 8. The method according to claim I, wherein the transfer agent is used to restrict the first or second polymerization zone of molecular weight.
9.根据权利要求I所述的方法,其中将所述再循环料流分割为第一再循环料流和第二再循环料流,将该第一再循环料流引入到第一聚合区以及将该第二再循环料流引入到第二聚合区o 9. The method of claim I, wherein said recycle stream into a first recycle stream and second recycle stream, the first recycle stream is introduced into the first polymerization zone, and The introduction of a second recycle stream to the second polymerization zone o
10.根据权利要求9所述的方法,其中选择足以获得⑴所需第二聚合温度;或(ii)所需聚合分割比的在第二再循环料流中的溶剂的量。 10. The method according to claim 9, wherein selecting ⑴ sufficient to obtain a desired second polymerization temperature; or (ii) the amount of solvent in the second division ratio of the recycle stream in the desired polymerization.
11.根据权利要求I所述的方法,其中,从所述混合物中除去溶剂和未反应单体包括(i)让该混合物进行第一溶剂分离步骤,用于浓缩剰余溶剂中的聚合物;(ii)让该浓缩溶液进行第二步骤,用于进一歩除去溶剂并形成造粒用的熔融聚合物;和(iii)将从第一和第二步骤中提取的溶剂合井,以提供合并的再循环料流;(iv)将该合并的再循环料流引入到第一聚合区或第二聚合区或第一聚合区和第二聚合区二者中。 11. The method of claim I, wherein the solvent is removed from the mixture and unreacted monomers include (i) so that the mixture was subjected to a first solvent separation step for concentrating 剰 remainder solvent polymer; ( ii) allow the concentrated solution was subjected to a second step, for feeding a Bu solvent was removed and the formation of granulation of molten polymer; and (iii) from the first and the second step extraction solvent Hapjeong to provide consolidated recycle stream; (iv) the combined recycle stream introduced into the first polymerization zone or the second polymerization zone, or the first polymerization zone and the second polymerization zone both.
12.根据权利要求11所述的方法,其中第一歩包括让所述混合物的至少一部分进行液-液相分离,从而提供富含溶剂的部分和贫溶剂部分。 12. The method according to claim 11, wherein the first 歩 comprising allow at least a portion of said liquid mixture - liquid phase separation, thereby providing a solvent-rich portion and a solvent-lean portion.
Description  Langue du texte original : Chinois
弹性体反应器共混物组合物[0001] 相关串请的交叉引用[0002] 本申请要求2004年10月13日提出的序号60/618,301和2005年I月20日提出的60/645,138的权益,这两篇申请的公开内容引入供参考。 Elastomeric reactor blend compositions [0001] Cross-Reference to Related string please [0002] This application claims the No. 13 October, 2004 made the 60 / 618,301 and 20 January 2005, I submitted 60/645 138 interest, disclosure of these two applications are incorporated herein by reference. [0003] 背景发明领域[0004] 本申请涉及弹性体反应器共混物组合物以及用于制备包括具有不同结晶水平和/ 或类型的第一聚合物和第二聚合物的弹性体组合物的连续方法。 [0003] BACKGROUND Field of the Invention [0004] The present application relates to elastomeric reactor blend compositions and for preparing include different levels of crystallinity and / or the type of elastomer composition of the first polymer and the second polymer having a continuous process. [0005] 相关技术的描述[0006] 本发明的实施方案涉及弹性体反应器共混物组合物。 Description [0005] Related art [0006] Embodiments of the invention relate to elastomeric reactor blend compositions. 人们正在不断努力来制备具有理想性能和属性平衡的聚合物组合物,以获得可用于许多应用的增强的组合物。 People are constantly trying to prepare a polymer composition having the desired balance of properties and attributes, to obtain a composition useful for the enhancement of many applications. 取决于预期的具体应用和具体共混物,这种组合物增强本身可以按许多方式表现。 Depending on the intended specific application and the specific blend, such compositions can exhibit enhanced itself in many ways. 这种增强包括、 但不限于(I)在诸如研磨、挤出、压延和注塑之类的工艺中在熔态下的加工性能;(2)在固态下的初始物理性能,例如韧性、粘性、粘合力、抗撕裂性、拉伸和伸长;(3)如果要固化或硫化,固化速率和状态的改进;和(4)如由这种物理性能在高温下保持所确定的长期物理性能例如热老化。 Such enhancements include, but are not limited to (I), such as milling, extrusion, calendering and injection molding processes like processability in the molten state; and (2) initial physical properties in the solid state, such as toughness, tack, adhesion, tear resistance, tensile and elongation; (3) If a curing or vulcanization, improve the cure rate and state; and (4) as indicated by such physical properties as determined to maintain the long-term physical properties at high temperatures such as thermal aging. 已经提出了各种方法来获得具有所需性能和属性的聚合物组合物,但这些方法具有许多缺点。 Various methods have been proposed to obtain a polymer composition having the desired properties and attributes, but these methods have a number of disadvantages. [0007] US专利No. 6,635,715公开了含有不同量的高结晶丙烯型聚合物的具有低水平的全同立构结晶度的乙烯-丙烯弹性体。 [0007] US Patent No. 6,635,715 discloses a high crystalline propylene polymer containing different amounts of a low level of isotactic crystallinity ethylene - propylene elastomers. 这些共混物通过物理共混各种组分来制备。 These blends were prepared by physically blending the various components. [0008] US专利No. 6,329,477公开了在使用双环戊二烯基类金属茂催化剂的聚合物组合物的生产中使用串联反应器,但所述组合物不含具有显著不同丙烯含量的两种聚合物。 [0008] US Patent No. 6,329,477 discloses the use in the production of dual-cyclopentadienyl-type metallocene catalyst polymer composition reactors in series, but the composition does not contain a propylene content have significantly different The two polymers. 涉及生产聚合物组合物的其它专利是US专利Nos. 6,319,998和6,207, 756。 Other patents relate to the production of polymer compositions are US Patent Nos. 6,319,998 and 6,207, 756. [0009] W098/02471和US专利No. 6,545,088公开了在使用单环戊二烯基类金属茂催化剂生产EP橡胶中使用串联反应器。 [0009] W098 / 02471 and US Patent No. 6,545,088 discloses the use of series reactors in a single cyclopentadienyl-type metallocene catalyst in the production of EP rubber. [0010] WO 03/040201公开了使用非金属茂类催化剂的串联反应器操作,以生产具有不同结晶度的聚合物组合物。 [0010] WO 03/040201 discloses the use of non-metallocene catalysts in series reactor operation, in order to produce a polymer composition having a different crystallinity. 没有暗示使用使分子量等适于工业弹性体应用的再循环或加工条件的连续操作方法。 Does not imply the use of molecular weight, such as continuous operation method is suitable for industrial applications elastomer recycling or processing conditions. [0011] 其它 [0011] Other

背景技术 BACKGROUND

参考文献包括US专利No. 6,747,114,US专利申请公开2004/198913, WO 1997/36942 和WO 2002/34795。 References include US Patent No. 6,747,114, US Patent Application Publication No. 2004/198913, WO 1997/36942 and WO 2002/34795.

[0012] 本发明的目的是开发新型聚合物组合物,其中利用串联和/或并联反应器操作的益处来提供具有16-180的总门尼粘度的有用弹性体,以及使用串联反应器再循环,同时还在该组合物中提供具有不同结晶度的聚合物(全同立构丙烯型,乙烯型或完全无定形的)。 [0012] The object of the present invention is to develop novel polymer composition, wherein the use of the benefits of series and / or parallel reactor operation to provide useful elastomers having an overall Mooney viscosity of 16-180, and the use of series reactor recycle , while still in the composition provides a polymer having a different crystallinity (isotactic propylene type, ethylene type, or fully amorphous). 还有,本发明的目的是提供能够使这种聚合物组合物以工业规模有效制备的连续多反应器工艺条件。 Still another object of the present invention is to provide enable the continuous multi-reactor process conditions such polymer compositions prepared in an industrial scale effectively.

[0013] 概述 [0013] Overview

[0014] 本发明公开了多种方法,包括、但不限于制备具有16-180的门尼粘度(ML (1+4) @125°C )的弹性体组合物的连续方法,该组合物包括第一聚合物和第二聚合物, 该方法包括:在第一聚合区中,使用第一催化剂体系在溶剂中聚合包括丙烯与乙烯和丙烯中的一种或两种的第一单体体系,以提供第一聚合物,该第一聚合物具有60wt%*更多的由丙烯衍生的单元,包括全同立构排列的丙烯衍生的序列和进一步具有低于45J/g的熔化热或低于105°C的熔点或同时具备这两种属性以及1-45的门尼粘度(ML(1+4)@125°C );在第二聚合区中,使用第二催化剂体系在溶剂中聚合包括乙烯或α -烯烃或二者的第二单体体系,以提供第二聚合物,该第二聚合物是非结晶的或具有源于乙烯的结晶度的弹性体聚合物;将该第一聚合物和第二聚合物在包括溶剂和未反应单体的混合物中合并;以及从该混合物中除去溶剂,以提供具有16-180的门尼粘度(ML(1+4)@125°C )的弹性体组合物。 [0014] The present invention discloses a variety of methods, including, but a continuous process the elastomer composition is not limited to preparing a 16-180 of Mooney viscosity (ML (1 + 4) @ 125 ° C), which composition comprises The first polymer and the second polymer, the method comprising: in a first polymerization zone, using a first polymerization catalyst system comprising a first monomer in a solvent system of propylene with ethylene and propylene in one or both, to provide a first polymer, the first polymer having 60wt% * more units derived from propylene, including isotactic propylene derived sequences and arranged further having less than 45J / g or below the heat of fusion 105 ° C melting point or simultaneously these two attributes, and 1-45 have a Mooney viscosity (ML (1 + 4) @ 125 ° C); in a second polymerization zone, polymerization using a second catalyst system in a solvent comprising ethylene or α - olefin second monomer system, or both, to provide a second polymer, the second polymer is non-crystalline or elastomeric polymer having a crystallinity derived from ethylene; the first polymer and the second polymer is incorporated includes solvent and unreacted monomer mixture; and removing the solvent from the mixture to provide elastomeric having 16-180 of Mooney viscosity (ML (1 + 4) @ 125 ° C) of composition.

[0015] 本发明公开了多种方法,包括、但不限于制备含有第一聚合物和第二聚合物的弹性体组合物的连续方法,该方法包括:在第一聚合区中,使用第一催化剂体系在溶剂中聚合包括丙烯和乙烯与丙烯中的一种或两种的第一单体体系,以提供第一聚合物,该第一聚合物具有60wt%或更多由丙烯衍生的单元,包括全同立构排列的丙烯衍生的序列;在第二聚合区中,使用第二催化剂体系在溶剂中聚合包括乙烯或α-烯烃或二者的第二单体体系, 以提供第二聚合物,该第二聚合物是弹性体和非结晶的或具有源于乙烯的结晶度;将该第一聚合物和第二聚合物在包括溶剂和未反应单体的混合物中合并;从该混合物中除去溶齐U,以提供弹性体组合物;并且将丙烯和乙烯单体以及溶剂再循环;其中该第一聚合进行至将丙烯单体消耗到低于制备该第二聚合物所需的水平;该第二聚合和再循环进行至将乙烯单体减少到低于制备该第一聚合物所需的水平,并且对于第一聚合添加其它补充丙烯单体,而对于第二聚合添加其它补充乙烯单体。 [0015] The present invention discloses a variety of methods, including, but a continuous process comprising a first polymer and the second polymer of the elastomer composition is not limited to preparation, the method comprising: in a first polymerization zone, using the first a polymerization catalyst system comprising a first monomer in a solvent system of propylene and ethylene and propylene in one or both, to provide a first polymer, the first polymer having 60wt% or more units derived from propylene, include propylene derived sequences isotactic arrangement; in the second polymerization zone, including the use of the second ethylene polymerization catalyst system or the second system α- olefin monomer in a solvent, or both, to provide a second polymer , the second polymer is elastomeric and amorphous or having a degree of crystallinity from ethylene; the first polymer and the second polymer is incorporated includes solvent and unreacted monomer mixture; from the mixture The solvent was removed Qi U, to provide the elastomer composition; and propylene and ethylene monomers and solvent is recycled; wherein the first monomer is propylene polymerization was carried out to consume the second polymer to a desired level below the preparation; the second polymerization and recycle will be to reduce the ethylene monomers to prepare the first polymer is lower than the desired level, and the other complementary to the first addition polymerizable acrylic monomer, and for adding the second polymerizable vinyl monomer other supplementary body. 该方法可以作为串联反应器或并联反应器设计。 This method can be used as reactors in series or parallel reactor design.

[0016] 本发明还公开了多级反应器系统,包括用于制备含有第一聚合物和第二聚合物的弹性体组合物的多级反应器系统,该系统包括:(a)形成第一聚合物的第一聚合区,该第一结构具有至少一个用于接收第一单体混合物和溶剂的进口和至少一个用于分配含有第一聚合物的第一流出物的出口;(b)形成第二聚合物的第二聚合区,其具有至少一个用于接收第二单体混合物和溶剂的进口和至少一个用于分配含有第二聚合物的第二流出物的出口;(c)用于接收含有溶剂、未反应单体、第一聚合物和第二聚合物的流出物的容器或其它区;(d)用于将流出物从该第一结构引入到该第二结构中的第一流出物主管线,使得该反应器系统能够使用该流出物主管线以串联方式操作;(e)用于使该第一流出物绕过该第二反应器的第一流出物旁通管线,使得该反应器系统能够使用该流出物旁通管线以并联方式操作;和(f)用于将流出物从该第二结构引入到该第三结构中的第二流出物管线。 [0016] The present invention also discloses a multi-stage reactor system comprising a multi-stage reactor system for preparing an elastomer composition comprising a first polymer and the second polymer, the system comprising: (a) forming a first polymer of the first polymerization zone, the first structure having at least one inlet of the first monomer mixture for receiving and solvent and at least one outlet for dispensing a first effluent containing a first polymer; (b) forming a The second polymerization zone of the second polymer, having at least one inlet of the second monomer mixture for receiving and solvent and at least one outlet for dispensing a second effluent comprising a second polymer; (c) for first (d) means for introducing the effluent from the first structure to the second structure; receiving contain solvents, unreacted monomers effluent, the first polymer and the second polymer or other container zone owner outflow line, such that the reactor system can use the effluent line owner operate in tandem; (e) for causing the first effluent to bypass the second reactor effluent from the first bypass line, so that The reactor system can be used in the effluent by-pass line parallel operation; and (f) means for introducing the effluent from the second structure to the third structure of the second effluent line.

[0017] 还公开了用于制备含有第一聚合物和第二聚合物的弹性体组合物的多级反应器系统,该系统包括:(a)形成第一聚合物的第一聚合区,该第一结构具有至少一个用于接收第一单体混合物和溶剂的进口和至少一个用于分配含有第一聚合物的第一流出物的出口; (b)形成第二聚合物的第二聚合区,该第二结构具有至少一个用于接收第二单体混合物和溶剂的进口和至少一个用于分配含有第二聚合物的第二流出物的出口;(c)用于接收含有溶剂、未反应单体、第一聚合物和第二聚合物的流出物的容器或其它区;和(d)设计成将含有溶剂和未反应单体的流出物引入到该第一聚合区、或第二聚合区、或串联或并联的第一聚合区和第二聚合区中的再循环管线。 [0017] Also disclosed is a multi-stage reactor system for preparing an elastomer composition comprising a first polymer and the second polymer, the system comprising: (a) forming a first polymer of the first polymerization zone, the a first structure having at least one for receiving the inlet of the first monomer mixture and solvent and at least one outlet for dispensing a first effluent containing a first polymer; the second polymerization zone (b) forming a second polymer , the second structure having at least one inlet of the second monomer mixture for receiving and solvent and at least one outlet for dispensing a second effluent comprising a second polymer; (c) means for receiving comprising a solvent, unreacted monomers, first polymer and the second polymer or other container effluent zone; and (d) designed to contain a solvent and unreacted monomer stream is introduced into the first polymerization zone, or the second polymerisation area, or in series or in parallel the first polymerization zone and the second polymerization zone of recirculation line.

[0018] 附图简要说明 [0018] BRIEF DESCRIPTION

[0019] 图I说明了能够以串联反应器或并联反应器方式运行的反应器设计的一个实例。 [0019] Figure I illustrates an example capable of reactors in series or parallel reactors run reactor design.

[0020] 详细描述 [0020] Detailed Description

[0021] 现在进行详细说明,首先是各种定义和性能,随后概述具体实施方案,它们的一些在权利要求中被反映,然后单独论述所要求的方法的某些方面。 [0021] now be described in detail, beginning with various definitions and properties, followed by an overview of the specific embodiments, some of them are reflected in the claims, and then separate discusses some aspects of the claimed method.

[0022] A.定义、性能和试验程序 [0022] A. definitions, performance and test procedures

[0023] 以下定义了本文所使用的各种术语。 [0023] The following defines the various terms used herein. 即使以下没有定义在权利要求中使用的术语,但它应该被给予所属领域技术人员对于该术语所给出的最宽的定义,如在至少一种印刷出版物(例如字典或文章)、授权专利或公开申请中所反映的。 Even if there is no following term definitions used in the claims, but it should be given to the person skilled in the broadest definition of the term given, as in at least one printed publication (e.g., a dictionary or article), issued patent or public, as reflected in the application.

[0024]为了方便起见,标明许多特殊测试程序来测定诸如分子量、门尼粘度、多分散性(MWD)等性能。 [0024] For convenience, many special test procedure indicated the molecular weight was determined, the Mooney viscosity, polydispersity (MWD) and other properties such as. 然而,当普通技术人员阅读本专利和希望确定组合物或聚合物是否具有在权利要求中标明的特定性能时,那么可以按照任何公开或公认的方法或测试程序来测定该性能,但特意标明的程序是优选的。 However, when one of ordinary skill reading this patent and wishes to determine whether a composition or polymer indicated in the claims when a particular performance, it can be disclosed or recognized in accordance with any method or test procedure to determine the performance, but specially marked procedures are preferred. 每一权利要求应该被认为覆盖了任何这种程序的结果,即使不同程序可能获得不同的结果或测量值。 Each claim should be considered to cover the results of any of such procedures, even though different programs may obtain different results or measurements. 因此,本领域普通技术人员可以预期在权利要求书中所反映的测量性能的实验变化。 Accordingly, those of ordinary skill can expect experimental variations in the claims reflects the measured performance. 就大体上的测试方法的性质而言,所有数值可以被认为是“大约”或“近似”规定值, Substantially on the nature of the test method, all values may be considered as "about" or "approximately" the predetermined value,

[0025] 连续。 [0025] in a row. 当用于描述方法或方法的一个方面例如工艺步骤时,术语“连续”及其派生词包括“连续地”应该覆盖连续供给和排出试剂和反应产物,使得可以达到稳态、稳定反应条件的任何方法或步骤。 When used to describe an aspect of a method or process step during the process, the term "continuous" and its derivatives include, for example, "continuous" should cover continuously supplying and discharging the reagents and reaction products, making it possible to reach a steady state, stable reaction conditions, any methods, or steps.

[0026] 非结晶。 [0026] The non-crystalline. 术语“非结晶”应该是指无规立构或无定形的,应该排除全同立构或间同立构(如本文其它地方所定义),还应该排除在没有退火的情况下具有可测定熔点(使用DSC程序)、或者在退火一周(168小时)后产生了可测定熔点的任何材料。 The term "amorphous" should refer to the atactic or amorphous, should be excluded from among isotactic or (as defined elsewhere herein) isotactic, should also be excluded in the absence of annealing can be measured with a melting point (using a DSC procedure), or annealing week (168 hours) after generation of the melting point of any material can be determined.

[0027] 聚合物。 [0027] polymers. 除了特定上下文所要求的以外,本文使用的术语“聚合物”是在特定聚合区或反应器内通过特定连续聚合生产的产物。 In addition to the requirements of the particular context, the term "polymer" used herein is a product in a particular polymerization zone or a continuous polymerization reactor through a particular production.

[0028] 聚合。 [0028] polymerization. 本文所使用的术语“聚合”应该被给予本领域技术人员在表示将单体转化为聚合物时所使用的最宽的含义。 As used herein, the term "polymerization" is to be accorded to those skilled in the broadest meaning indicated conversion of monomer to polymer when used. 聚合区是指发生聚合的区域,一般由用于形成基本上无规聚合物的返混型反应器所形成。 The polymerization zone is an area where polymerization occurs, is generally formed from a substantially random polymers for the formation of back-mixed reactor.

[0029] 聚合分割比(polysplit)。 [0029] polymerization split ratio (polysplit). 本文所使用的术语“聚合分割比”应该是指由第一聚合区生产的第一聚合物(丙烯聚合物)的重量除以第一聚合物和第二聚合物(乙烯聚合物) 的总重量的计算结果。 As used herein, the term "polymerization division ratio" shall mean the weight of the first polymer produced by the first polymerization zone (propylene polymer) divided by the first polymer and the second polymer (ethylene polymer) of the total weight of calculations. 该同一定义同样适合于串联和并联反应器配置。 The same definition is also suitable for series and parallel reactor configurations. 也就是说,丙烯聚合物总被认为是分子。 That is, the propylene polymer is always regarded as molecules.

[0030] 熔点、熔化热和结晶。 [0030] Melting point, heat of fusion and crystallization. 本文所述的聚合物和组合物可以用它们的熔点(Tm)和熔化热来表征,所述性能可以受共聚单体或通过聚合物链阻碍微晶形成的位阻杂质的存在的影响。 Polymers and compositions described herein can be used to their melting point (Tm) and heat of fusion is characterized, the performance can be affected by the presence of a comonomer or hindered by the polymer chains formed crystallites steric hindrance of impurities. 这些性能可以通过差示扫描量热法(DSC)使用ASTM E-794-95(E-794-01的变型)程序或在US专利No. 6,747,114、第8栏、第14-31行中所公开的程序来测定,该专利由此全文引入供参考。 These properties can be used ASTM E-794-95 (E-794-01 variant) program or 6,747,114, column 8, in US Patent No. by Differential scanning calorimetry (DSC), of 14-31 procedure disclosed row determined, whereby this patent is incorporated by reference.

[0031] 共聚单体含量。 [0031] The comonomer content. 聚合物的共聚单体含量和序列分布可以使用13C核磁共振谱法(NMR)通过本领域技术人员公知的方法来测定。 Comonomer content and sequence distribution of the polymer by those skilled in the known method can be measured by using 13C nuclear magnetic resonance spectroscopy (NMR). 离散分子量范围的共聚单体含量可以使用本领域技术人员公知的方法来测定,包括傅里叶变换红外光谱法(FTIR)与GPC的结合,如在Wheeler 和Willis, Applied Spectroscopy, 1993,第47 卷,第1128-1130 页中所述的。 Comonomer content of discrete molecular weight ranges can be used a method known to a person skilled in the art be determined, including Fourier Transform Infrared Spectroscopy (FTIR) in conjunction with GPC, as in Wheeler and Willis, Applied Spectroscopy, 1993, vol. 47 , pp. 1128-1130 described. 对于含有高于75wt%丙烯的丙烯-乙烯共聚物,这种聚合物的共聚单体含量(乙烯含量) 可以如下测定:在大约150°C或更高的温度下压制薄而均匀的薄膜,并将其安装在Perkin Elmer PE1760红外分光光度计上。 Containing greater than 75wt% propylene for propylene - ethylene copolymer, the comonomer content of such a polymer (ethylene content) can be determined as follows: at about 150 ° C or higher temperatures pressed thin and uniform film, and be mounted on the Perkin Elmer PE1760 infrared spectrophotometer. 记录样品的从600CHT1到4000CHT1的全部光谱,根据以下方程式可以计算乙烯的单体重量百分率:乙烯wt%= 82. 585-111. 987X+30. 045X2,其中X是在1155CHT1处的峰高与在722CHT1或732CHT1处(随便哪一个更高)的峰高的比率。 Samples from all recorded spectra 600CHT1 to 4000CHT1, the following equation can be calculated according to the monomer weight percent of ethylene: Ethylene wt% = 82. 585-111 987X + 30 045X2, wherein X is at the peak and at high 1155CHT1. 722CHT1 or 732CHT1 place (just which one higher) peak height ratios. 对于具有75wt%或更低丙烯含量的丙烯-乙烯共聚物,该共聚单体(乙烯)含量可以使用在Wheeler和Willis中所述的程序来测定。 For having 75wt% or less propylene content of the propylene - ethylene copolymer, the comonomer (ethylene) content can use the program described in Wheeler and Willis are determined.

[0032] 立构规整度。 [0032] stereoregularity. 术语“立构规整度”是指聚合物中来自丙烯的甲基残基的取向的立构规整性。 The term "tacticity" refers to a polymer of methyl residues derived from propylene of the orientation of stereoregularity. 本文所述的聚合物的“三单元组立构规整度”可以如在US专利No. 5,504, 172以及US专利No. 6,642,316、第6栏第38行到第9栏第18行中所述由该聚合物的13C核磁共振(NMR)谱测定;这些专利由此全文引入供参考。 Polymer herein "triad tacticity" may be as in US Patent No. 5,504, 172 and US Patent No. 6,642,316, column to column 9, line 6, No. 38 line 18 the spectrum of the polymer was measured by 13C nuclear magnetic resonance (NMR); whereby these patents incorporated by reference.

[0033] 多烯烃含量。 [0033] Multi-olefin content. 存在于聚合物组分中的多烯烃的量可以通过定量测量存在于聚合后的聚合物中的侧挂游离烯烃的量来推断。 Component present in the polymer in an amount of polyenes can be measured by quantifying the presence of the polymer after polymerization in the amount of free pendant olefin inferred. 已经确立了几种程序例如碘值和用1H或13C NMR 测定烯烃含量。 Several programs have been established such as iodine value and olefin content was measured by 1H or 13C NMR. 在多烯烃是ENB的特定情况下,存在于聚合物中的多烯烃的量可以使用ASTM D 3900测定。 In the particular case multiolefin is ENB, and present in the polymer in an amount of polyenes can be determined using ASTM D 3900. 多烯烃的存在量以(例如)乙烯和丙烯衍生的单元的总重量为基准表/Jn ο Multi-olefin in the presence of an amount (e.g.) of the total weight of ethylene and propylene derived units as a reference table / Jn ο

[0034] 立构规整度指数。 [0034] tacticity index. 这里表示为“m/r”的立构规整度指数可以通过13C核磁共振(NMR)测定。 Denoted herein as "m / r" stereoregularity index can be determined by 13C nuclear magnetic resonance (NMR). 立构规整度指数m/r 可以如在HN Cheng,Macromolecules, 17,1950 (1984)中所定义的那样测定。 The tacticity index m / r may be as in HN Cheng, Macromolecules, 17, 1950, as measured (1984) defined.

[0035] 全同立构、间同立构和无规立构。 [0035] isotactic, syndiotactic and atactic. 本文所使用的术语“无规立构”被定义为是指立构规整度指数2. 0- 4. O的任何聚合物。 As used herein, the term "atactic" is defined to mean any tacticity index of polymer 2. 0- 4. O. 本文所使用的术语“间同立构”被定义为是指立构规整度指数为1.0到(但不包括)2. O的任何聚合物。 As used herein, the term "syndiotactic" is defined to mean a tacticity index of 1.0 to (but not including) 2. O of any polymer. 本文所使用的术语“全同立构”被定义为是指立构规整度指数大于4. O的任何聚合物。 As used herein, the term "isotactic" is defined to mean any polymer tacticity index greater than 4. O's.

[0036] 分子量特性。 [0036] molecular characteristics. 本文所述的聚合物组分(或聚合物)的各种分子量特性(例如Mw 和Mn)和分子量分布Mw/Mn (MWD)可以根据在US专利No. 6,525,157的第5栏第1_44行中公开的程序测定,该专利由此全文引入供参考。 Polymer components described herein (or polymer) of various molecular weights characteristics (e.g., Mw and Mn) and molecular weight distribution Mw / Mn (MWD) according to the first described in US Patent No. 6,525,157 in column 5, 1_44 line measurement procedures disclosed, whereby this patent is incorporated by reference.

[0037] 门尼粘度。 [0037] The Mooney viscosity. 术语“门尼粘度”是这里用于表征某些聚合物、聚合物组分和聚合物组合物的术语。 The term "Mooney viscosity" herein, the term certain polymers, polymer components, and polymer compositions for characterization. 本文所使用的术语门尼粘度(ML(1+4)@125°C)或简写“门尼粘度”按照在US 专利No. 6,686,415中所述的定义和测量程序来定义和测定;该专利由此全文引入供参考, 尤其是在第6栏第59行到第7栏第59行中的文本。 As used herein, the term Mooney viscosity (ML (1 + 4) @ 125 ° C) or abbreviated "Mooney viscosity" is defined and measured in accordance with US Patent No. described in the definition and measurement procedures 6,686,415 ; thus the patent is incorporated by reference, especially in column 6, line 59, column 7, line 59 of the text to. 可供选择地,这里提到的任何“门尼粘度”值(包括在权利要求中的那些)被视为包括根据用于测定门尼粘度的任何公认的、公开的程序测定的任何门尼粘度。 Alternatively, any "Mooney viscosity" values mentioned here (including those in the claims) is regarded as including any Mooney viscosity according to the determination of any recognized, the procedures disclosed in the Mooney viscosity measurement .

[0038] 本文所使用的术语“MFR”表示“熔体流动速率”,并且用来表征聚合物、组分和组合物。 [0038] The term used herein "MFR" means "melt flow rate", and is used to characterize polymers, components and compositions. “MFR”的单位是克/10分钟,这里用于测定MFR的试验以在ASTM-1238中所述的任何变型和条件(在230°C下,使用2. 16kg)进行。 "MFR" units of g / 10 minutes, measured for MFR in any test where variations and conditions as described in ASTM-1238 (at 230 ° C, the use of 2. 16kg) performed.

[0039] 分子间溶解度和组成分布。 [0039] Intermolecular solubility and composition distribution. 在某些权利要求中可能提到的其它特性是“分子间溶解度分布”和“分子间组成分布”。 Other features in some claims may be mentioned that "the distribution of intermolecular solubility" "intermolecular composition distribution" and. 还有,尤其对于所述第一聚合物的某些实施方案,本文所使用的“均匀分布”被定义为共聚物组成和聚合丙烯的立构规整度的两种分布的分子间统计学上无显著差别。 Also, especially for certain embodiments of the first polymer, as used herein "uniformly distributed" intermolecular two distributions is defined as a copolymer composition and the polymerization of propylene tacticity no statistically significant difference. 这些术语的定义和计算它们的方式公开在US专利No. 6,525,157的第9栏第30-41行和第10栏第16-53行中;所述专利由此全文引入供参考。 Definitions of these terms and calculate their way disclosed in US Patent No. 6,525,157, column 9 of the first 30-41 rows and column 10, lines 16-53; thus the patent is incorporated by reference.

[0040] B.方法和组合物的具体实施方案 Specific embodiments [0040] B. Methods and compositions

[0041] 以下阐述具体实施方案,它们的一些也被包括在权利要求中。 [0041] The following specific embodiments set forth, some of them are also included in the claims. 每一项所附权利要求定义了一项单独的发明,在侵权判定时,它被认为包括在所述权利要求中规定的各种要素或限定的等同物。 Defines a separate invention, each of the appended claims, when the infringement, it is considered to include the provision of the various elements of the claims or equivalents defined. 取决于上下文,以下所有提到的“发明”在某些情况下可以仅仅是指某些具体实施方案。 Depending on the context, all of the following mentioned "invention" in some cases may simply refer to certain specific embodiments. 在其它情况下,应该认识到,所提到的“发明”是指一项或多项,但未必是全部权利要求中所述的主题。 In other cases, it should be recognized that the reference to "the invention" refers to one or more, but not necessarily all the claims in the subject matter. 以下更详细地说明每一项发明,包括具体实施方案、变型和实施例,但本发明不限于这些实施方案、变型或实施例,它们的目的是使本领域普通技术人员能够结合本专利中的信息与可获得的信息和技术来实现和利用本发明。 The following description of each of the invention in more detail, including specific embodiments, versions and examples, but the present invention is not limited to these embodiments, versions or examples, they are intended to enable those skilled in the art are capable of binding in this patent Information and available information and technology to make and use the invention.

[0042] 在以上或其它地方所述的任何方法中,从所述混合物中除去的溶剂和未反应单体可以再循环到第一聚合区或第二聚合区,或第一聚合区和第二聚合区二者中。 [0042] In any of the methods above or elsewhere herein, the solvent was removed from the mixture and unreacted monomers may be recycled to the first polymerization zone or the second polymerization zone, or the first polymerization zone and the second both in the polymerization zone.

[0043] 在以上或其它地方所述的任何方法中,在再循环的过程中,在引入到第一或第二聚合区之前,可以至少部分分离所述溶剂和未反应单体。 [0043] In any of the methods above or elsewhere herein, the recirculation process, prior to introduction into the first or second polymerization zone can be at least partially separated from the solvent and unreacted monomers.

[0044] 在以上或其它地方所述的任何方法中,所述第一聚合物例如可以具有16-180的门尼粘度(ML(1+4)@125°C )以及低于45J/g的熔化热或低于105°C的熔点或同时具备这两种属性,而所述第二聚合物具有1-45的门尼粘度(ML(1+4)@125°C )。 [0044] In any method described above or elsewhere herein, the first polymer may have a 16-180 e.g. a Mooney viscosity (ML (1 + 4) @ 125 ° C) and less than 45J / g of heat of fusion of 105 ° C or lower than the melting point or have these two properties simultaneously, while the second polymer has 1-45 Mooney viscosity (ML (1 + 4) @ 125 ° C).

[0045] 在以上或本文其它地方所述的任何方法中,所述第二聚合物例如可以是乙烯和丙烯的无规共聚物。 [0045] In any of the methods described above or elsewhere herein in, for example, the second polymer may be a random copolymer of ethylene and propylene.

[0046] 在以上或本文其它地方所述的任何方法中,所述第一聚合区的流出物的至少一部分可以连续引入到第二聚合区中。 [0046] In any of the methods above or elsewhere herein described, the effluent from the first polymerization zone at least a portion may be continuously introduced into the second polymerization zone.

[0047] 在以上或本文其它地方所述的任何方法中,所述第一聚合区的流出物的至少一部分可以与第二聚合区的流出物合并。 [0047] In any of the methods described above or elsewhere herein, the at least a portion of the effluent of the first polymerization zone can be combined with the effluent of the second polymerization zone.

[0048] 在以上或本文其它地方所述的任何方法中,所述第一和第二聚合区可以从串联操作方式改变为并联操作方式, 或者由并联操作方式改变为串联操作方式,或者以这两种操作方式操作。 [0048] In any of the methods described above or elsewhere herein, the first and the second polymerization zone can be changed from operation in series mode to parallel mode of operation, or by a parallel operation mode is changed to tandem operation mode, or in which two operation manner.

[0049] 在以上或本文其它地方所述的任何方法中,所述聚合分割比可以例如是5-95。 In any of the methods described above or elsewhere herein, the polymerization of the [0049] division ratio may be, for example, 5-95.

[0050] 在以上或本文其它地方所述的任何方法中,所述组合物可以是具有5-35的聚合分割比、16-100的门尼粘度(ML(1+4)@125°C )和30_80wt%乙烯含量的改性EP橡胶。 [0050] In any of the methods described above or elsewhere herein, the said composition may be a division ratio of polymerization 5-35, 16-100 of Mooney viscosity (ML (1 + 4) @ 125 ° C) and 30_80wt% ethylene content of the modified EP rubber.

[0051] 在以上或本文其它地方所述的任何方法中,所述组合物可以是具有65-95的聚合分割比、16-45的门尼粘度(ML(1+4)@125°C )和25_50wt%的乙烯含量的改性丙烯弹性体。 [0051] In any of the methods described above or elsewhere herein, the said composition may be a division ratio of polymerization 65-95, 16-45 Mooney viscosity (ML (1 + 4) @ 125 ° C) and 25_50wt% ethylene content of the modified propylene elastomer.

[0052] 在以上或本文其它地方所述的任何方法中,所述含有第一聚合物和第二聚合物的混合物可以通过脱挥发分来后加工以形成粒料或包装物(bale),回收未反应单体和溶剂, 并将它们再循环到第一和第二聚合区,或者这两个聚合区。 [0052] In any of the methods described above or elsewhere herein, the mixture of the first polymer and the second polymer-containing devolatilization can be processed to form pellets or packaging (bale), the recovery The unreacted monomers and solvent, and they are recycled to the first and the second polymerization zone, or both polymerization zones.

[0053] 以上或本文其它地方所述的任何方法例如可以进一步包括再循环丙烯和乙烯单体以及溶剂,其中进行所述第一聚合以便将丙烯单体消耗至低于制备第二聚合物所需水平的水平,其中进行第二聚合和再循环以便将乙烯单体减少至低于制备第一聚合物所需水平的水平,并且添加附加补充丙烯单体用于第一聚合,添加附加补充乙烯单体用于第二聚合。 [0053] any of the methods described above or elsewhere herein, for example, may further comprise recycling propylene and ethylene monomers and a solvent, wherein in order to carry out the first polymerization of propylene monomer is consumed to prepare a second polymer is less than the desired horizontal level, in which the second polymerization and recycle in order to reduce the ethylene monomers to a level below the desired level of the first polymer was prepared, and add an additional supplemental propylene monomer used in the first polymerization, adding additional supplemental ethylene single body for the second polymerization.

[0054] 以上或本文其它地方所述的任何方法例如可以进一步包括提供再循环料流,其中,所生产的第一聚合物的分数和第二聚合物的分数独立地通过分割来自再循环的供给到第一和第二聚合的溶剂的量和通过提供附加新鲜进料以改变流量和每一聚合的除热能力来控制,该第一聚合在低于第一聚合物的熔点的温度下进行,以及该第二聚合在比用于第一聚合的温度高20-200°C的温度下进行。 [0054] any of the methods described above or elsewhere herein, for example, may further include providing a recycle stream, wherein the produced fraction and a second fraction of the first polymer is a polymer obtained by dividing supplied independently from recycled to the first and second amount of solvent and the polymerization is controlled by providing additional fresh feed to vary the flow rate and heat removal capacity for each polymerization, the polymerization of the first polymer at lower than the melting point of the first temperature, and the second polymerization at higher temperatures than used in the first polymerization temperature of 20-200 ° C.

[0055] 在以上或本文其它地方所述的任何方法中,可以使用转移剂例如氢来限制分子量。 [0055] In any of the methods described above or elsewhere herein, the transfer agent such as hydrogen may be used to limit the molecular weight.

[0056] 在以上或本文其它地方所述的任何反应器系统中,采用并联方式可以对确定聚合分割比是否对应于预选择的聚合分割比是灵敏的。 [0056] The reactor system of any above or elsewhere herein described, using parallel polymerization can be determined whether the division ratio corresponding to the division ratio of the pre-selected polymerization is sensitive.

[0057] 在以上或本文其它地方所述的任何反应器系统中,采用并联方式可以对确定丙烯聚合物的丙烯含量是灵敏的。 [0057] The reactor system of any above or elsewhere herein, the parallel mode can be determined using the propylene polymer is a propylene content sensitive.

[0058] 在以上或本文其它地方所述的任何方法中,从串联方式改变为并联方式例如可以灵敏确定反应器共混物组合物的乙烯含量。 [0058] In any of the methods described above or elsewhere herein, the change from in series to parallel for example, sensitive determine the ethylene content of the reactor blend composition.

[0059] 在以上或本文其它地方所述的任何方法中,当聚合分割比大于或等于构成FPP(第一聚合物丙烯含量)和BPE(共混物聚合物乙烯含量)的计算总和(calculated combination)的C3C2系数时,优选使用并联方式。 [0059] In any of the methods described above or elsewhere herein, when the division ratio is greater than or equal to the polymerization constituting FPP (first polymer propylene content) and BPE (blend polymer ethylene content) of the sum of the calculated (calculated combination ) when C3C2 coefficient, is preferably used in parallel.

[0060] 在以上或本文其它地方所述的任何方法中,当聚合分割比大于575*(100-FPP)°_14 *(BPE)_°_81时,优选使用并联方式,其中FPP是丙烯含量(丙烯聚合物的wt%), BPE是串联反应器共混物组合物或并联反应器共混物组合物的乙烯含量。 [0060] In any of the methods described above or elsewhere herein, the division ratio when the polymerization is greater than 575 * (100-FPP) ° _14 * (BPE) _ ° _81 is preferably used in parallel, wherein FPP is the propylene content ( propylene polymers wt%), BPE is the ethylene content of the series reactor blend composition or the parallel reactor blend composition.

[0061] 以上或本文其它地方所述的任何方法可以另外包括将该再循环料流分割为第一再循环料流和第二再循环料流,将该第一再循环料流引入到第一聚合区以及将该第二再循环料流引入到第二聚合区。 [0061] The method of any of the above or elsewhere herein may additionally comprise the recycle stream into a first recycle stream and second recycle stream, the first recycle stream is introduced into a first the polymerization zone and the second recycle stream is introduced into the second polymerization zone.

[0062] 以上或本文其它地方所述的任何方法可以另外包括将大部分的再循环料流引入到第二聚合区。 [0062] The method of any of the above or elsewhere herein may additionally comprise the majority of the recycle stream is introduced into the second polymerization zone.

[0063] 以上或本文其它地方所述的任何方法可以另外包括选择足以获得(i)所需第二聚合温度;或(ii)所需聚合分割比的在第二再循环料流中的溶剂的量。 [0063] The method of any of the above or elsewhere herein may additionally comprise selecting sufficient to obtain (i) a desired second polymerization temperature; or (ii) the desired division ratio of the polymerization solvent in the second recycle stream of the amount.

[0064] 在以上或本文其它地方所述的任何方法中,从所述混合物中除去溶剂和未反应单体可以包括(i)让该混合物进行第一分离步骤,以提供从该混合物中提取的第一富含溶剂的料流(它还可以被定义为第一聚合物贫乏的料流,优选不含或含有很少的聚合物)和第一富含聚合物的料流;(ϋ)让该第一富含聚合物的料流进行第二分离步骤,以便提供更浓缩的第二富含聚合物的料流;和(iii)将该富含溶剂的料流合并,以提供合并的再循环料流,用于进给到第一聚合区或第二聚合区或第一聚合区和第二聚合区二者中。 [0064] In any of the methods described above or elsewhere herein, the mixture is removed from the solvent and unreacted monomer may include (i) so that the mixture was subjected to a first separation step, in order to provide extracted from the mixture of The first solvent-rich stream (it can be defined as the first polymer-poor stream, preferably no or little polymer) and a first polymer-rich stream of; (ϋ) Let The first polymer-rich stream subjected to a second separation step, in order to provide a more concentrated stream of a second polymer-rich; and (iii) the solvent-rich stream combined to provide further merged recycle stream for feeding into the first polymerization zone or the second polymerization zone, or the first polymerization zone and the second polymerization zone both. 该富含溶剂的料流可以同样含有挥发性未反应单体。 The solvent-rich stream can also contain volatile unreacted monomer. 该第一步骤可以包括液体分离或蒸发,不论是否加热。 The first step may include liquid separation or evaporation, whether heat. 可以对该浓缩的富含聚合物的料流施加真空,以提取最后的痕量溶剂和单体。 Vacuum may be applied to the polymer-rich stream concentrate to extract the last traces of solvent and monomer. 这可以通过从搅拌的聚合物物质中真空提取来完成。 This can be extracted from the polymer by vacuum with stirring to complete the material. 该搅拌可以用如其它地方所述的薄膜或链状(strand)蒸发器、双螺杆挤出机或脱挥发分LIST装置来提供。 The stirring may be used, such as a film or a chain (strand) other parts of the evaporator, a twin-screw extruder or a devolatilizing LIST means provided.

[0065] 在以上或本文其它地方所述的任何方法中,从所述混合物中除去溶剂和未反应单体可以包括将至少一部分的该混合物进行液相分离(优选在高压下),以提供富含溶剂的部分(贫聚合物部分)和贫溶剂部分(富含聚合物的部分),其中将该富含溶剂的部分(例如作为再循环料流)引入到第一聚合区或第二聚合区或第一和第二聚合区二者中。 [0065] In any of the methods described above or elsewhere herein, the solvent was removed and the unreacted monomer from the mixture, the mixture may comprise at least a portion of the liquid phase separation (preferably at high pressure) to provide a rich solvent-containing portion (polymer-lean portion) and a portion of lean solvent (polymer-rich portion), wherein the solvent-rich portion (e.g., as a recycle stream) is introduced into the first polymerization zone or the second polymerization zone or the first and second polymerization zone both.

[0066] 在以上或本文其它地方所述的任何方法中,从所述混合物中除去溶剂和未反应单体可以包括将至少一部分的该混合物脱挥发分,以提供富含溶剂的部分和贫溶剂部分,其中将该富含溶剂的部分引入到第一聚合区或第二聚合区或第一和第二聚合区二者中,例如作为再循环的一部分。 [0066] In any of the methods described above or elsewhere herein, the solvent was removed from the mixture, and unreacted monomers may comprise at least a portion of the mixture was devolatilized to provide a solvent-rich portion and a lean solvent portion, wherein the solvent-rich portion is introduced into the first polymerization zone or the second polymerization zone or both the first and the second polymerization zone, for example as part of the recycling.

[0067] 在以上或本文其它地方所述的任何方法中,所述再循环料流可以引入到第一聚合区和第二聚合区,以提供一种再循环分割比(split),其中该再循环分割比至少部分根据预选择的聚合分割比或至少部分根据第一或第二聚合区的温度来调节。 [0067] In any of the methods described above or elsewhere herein, said recycle stream may be introduced into the first polymerization zone and the second polymerization zone to provide a recycle split ratio (split), wherein the re- circulating at least part of the division ratio according to a pre-selected polymerization division ratio or at least partially to adjust the temperature according to the first or second polymerization zone.

[0068] 以上或本文其它地方所述的任何方法可以按串联反应器方式运行,其中将再循环料流引入到第一聚合区和第二聚合区,以提供一种再循环分割比,其中供给反应器I的再循环料流百分率等于2. 8*(PS)°_67*(RT2/RTl)in,其中PS =聚合分割比;RT2 =第二反应器温度(V );和RTl =第一反应器温度(V )。 [0068] any of the methods described above or elsewhere herein may be run in series reactor mode wherein a recycle stream is introduced into the first polymerization zone and the second polymerization zone to provide a recycle split ratio, wherein the supply recycle stream reactor I is equal to the percentage of 2. 8 * (PS) ° _67 * (RT2 / RTl) in, where PS = polymerization split ratio; RT2 = second reactor temperature (V); and RTl = first reactor temperature (V).

[0069] 以上或本文其它地方所述的任何方法可以按并联反应器方式运行,其中将再循环料流引入到第一聚合区和第二聚合区,以提供一种再循环分割比,其中供给反应器I的再循环料流百分率等于4. 5*(PS)°_55*(RT2/RT1)°_67,其中PS =聚合分割比;RT2 =第二反应器温度(V );和RTl =第一反应器温度(V )。 [0069] any of the methods described above or elsewhere herein may be run in parallel reactor mode wherein a recycle stream is introduced into the first polymerization zone and the second polymerization zone to provide a recycle split ratio, wherein the supply recycle stream reactor I is equal to the percentage of 4. 5 * (PS) ° _55 * (RT2 / RT1) ° _67, where PS = polymerization split ratio; RT2 = second reactor temperature (V); and RTl = s a temperature of the reactor (V).

[0070] 本文公开的组合物是具有16-180的总门尼粘度(ML(1+4)@125°C )和低于50J/ g的熔化热的粒状或包装物形式的组合物,其包括第一聚合物和第二聚合物,其中该第一聚合物是具有至少60%的丙烯衍生的单元的含量并且包括全同立构排列的丙烯衍生的序列和低于45J/g的熔化热或低于105°C的熔点的弹性体无规聚合物,该第二聚合物是没有结晶性或具有乙烯型结晶性的乙烯和丙烯衍生的单元的共聚物。 [0070] The composition disclosed herein is an overall Mooney viscosity of 16-180 (ML (1 + 4) @ 125 ° C) and less than 50J / g heat of fusion or packaging in the form of a granular composition, which comprising a first polymer and the second polymer, wherein the first polymer is a content of at least 60% of propylene-derived units and includes isotactic propylene derived sequences and arranged lower than 45J / g heat of fusion elastomer or below 105 ° C of the melting point of a random polymer, the second polymer is not crystalline or crystalline ethylene-type copolymer having an ethylene and propylene derived units.

[0071] 在以上或本文其它地方所述的某些方法中,所述组合物的门尼粘度(ML(1+4)§1250C )是16-180 ;或从16或20或24的任何下限到180或140或120的任何上限。 [0071] In some methods described above or elsewhere herein, the said composition has a Mooney viscosity (ML (1 + 4) §1250C) is 16-180; any lower limit or from 16 or 20 or 24, to any upper limit of 180 or 140 or 120.

[0072] 在以上或本文其它地方所述的某些方法中,所述第一聚合物的MFR是O. 5-100g/10min ;或从O. 5 或O. 8 或I. 0g/10min 的任何下限到40 或30 或20g/10min 的任何上限。 [0072] In some methods described above or elsewhere herein, the MFR of the first polymer is O. 5-100g / 10min; or from O. 5 or O. 8 or I. 0g / 10min of any lower limit to any upper limit 40 or 30 or 20g / 10min in.

[0073] 在以上或本文其它地方所述的某些方法中,所述反应器共混物的MFR是O. 05-1. 3g/10min ;或从O. 05 或O. 06 或O. 07g/10min 的任何下限到I. 3 或I. O 或O. 8g/10min的任何上限。 [0073] In some methods described above or elsewhere herein, the MFR of said reactor blend is is O. 05-1 3g / 10min;. Or from or O. 06 O. 05 O. 07g or Any 3 or I. O or O. any upper 8g / 10min lower limit to I. / 10min of.

[0074] 在以上或本文其它地方所述的某些方法中,所述第一聚合物的分子量(Mw)是80000-400,000 ;或从100,000 或120,000 或140,000 的任何下限到400,000 或350,000 或300, 000的任何上限。 Or from any of 100,000 or 120,000 or 140,000; [0074] In some methods described above or elsewhere herein, the molecular weight of the first polymer (Mw) is 80000-400,000 The lower limit to 400,000 or 350,000 or 300, any upper 000.

[0075] 在以上或本文其它地方所述的某些方法中,所述第一聚合物的分子量(Mn)是40,000-200,000 ;或从50,000 或60,000 或70,000 的任何下限到200,000 或175,000 或150,000的任何上限。 [0075] In some methods described above or elsewhere herein, the molecular weight of the first polymer (Mn) is 40,000 to 200,000; or 50,000 or 60,000 or 70,000 from any lower limit to any upper limit of 200,000 or 175,000 or 150,000.

[0076] 在以上或本文其它地方所述的某些方法中,所述组合物的分子量(Mw)是60,000-800,000 ;或从60,000 或90,000 或120,000 的任何下限到800,000 或700,000 或600,000的任何上限。 [0076] In some methods described above or elsewhere herein, the molecular weight of the composition (Mw) is 60,000-800,000; from any or 60,000 or 90,000 or 120,000 lower limit to any upper limit of 800,000 or 700,000 or 600,000.

[0077] 在以上或本文其它地方所述的某些方法中,所述组合物的分子量(Mn)是30,000-160,000 ;或从30,000 或45,000 或60,000 的任何下限到160,00 或140,000 或120,000的任何上限。 [0077] In some methods described above or elsewhere herein, the molecular weight of the composition (Mn) is 30,000-160,000; or any from 30,000 or 45,000 or 60,000 lower limit to any upper limit of 160,00 or 140,000 or 120,000.

[0078] 在以上或本文其它地方所述的某些方法中,所述第一聚合物的多分散性(Mw/Mn) 是I. 8-2. 3 ;或从I. 8或I. 9或2. O的任何下限到2. 3或2. 2或2. I的任何上限。 [0078] In some methods described above or elsewhere herein, the polydispersity of the first polymer (Mw / Mn) is I. 8-2 3;. Or from I. 8 or I. 9 or any lower limit to 2.3 or 2.2 or any upper limit of 2. O 2. I of.

[0079] 在以上或本文其它地方所述的某些方法中,所述组合物的多分散性(Mw/Mn)是I. 8-10 ;或从2. 2或2. O或I. 8的任何下限到10或6或3. 5的任何上限。 [0079] In some methods described above or elsewhere herein, the composition of the polydispersity (Mw / Mn) is I. 8-10; or from 2.2 or 2. O or I. 8 any lower limit to any upper limit 10 or 6 or 3.5 in.

[0080] 在以上或本文其它地方所述的某些方法中,所述聚合分割比(作为总组合物的百分率的第一聚合中制备的第一聚合物的量)是5-95 ;或从5或15或25的下限到95或80 或60的上限。 [0080] In some methods described above or elsewhere herein, the division ratio of the polymerization (as a percentage of the total composition amount of the first polymer is prepared in a first polymerisation) is 5-95; or from The lower limit to an upper limit of 95 or 80 or 60 or 15 or 25 5.

[0081] 在以上或本文其它地方所述的某些方法中,所述第一聚合物占总组合物的5-95wt% ο [0081] In some methods described above or elsewhere herein, the first polymer is 5-95wt% of the total composition ο

[0082] 第一和第二催化剂可以是相同的;或者它们可以是不同的,但在某些实施方案中, 可以具有相同的活化剂,如在本文其它地方更详细说明的。 [0082] The first and second catalyst may be the same; or they may be different, but in certain embodiments, may have the same activator, as described elsewhere in more detail below. 在以上或本文其它地方所述的某些方法中,第一催化剂和/或第二催化剂可以是金属茂。 In certain methods described above or elsewhere herein, the first catalyst and / or the second catalyst may be a metallocene. 在一个更具体的方面,第一和/ 或第二催化剂是单环戊二烯基化合物。 In a more specific aspect, the first and / or second catalyst is a monocyclopentadienyl compound. 第一和/或第二催化剂可以是双环戊二烯基化合物。 Bis-cyclopentadienyl compounds of the first and / or second catalyst may be. 第一和/或第二催化剂的环戊二烯基配体可以是茚基配体。 The first and / or second catalyst cyclopentadienyl ligand may be the indenyl ligands. 第一和/或第二催化剂还可以是齐格勒-纳塔催化剂。 The first and / or second catalyst may also be a Ziegler - Natta catalyst. 第一和/或第二催化剂还可以是吡啶胺催化剂。 The first and / or second catalyst may also be pyridyl amine catalyst. 在一个具体的方面,第一催化剂可以是在PCT公开WO 03/040201中提到的任何催化剂,尤其是提到的在双反应器方案中被供给第一反应器的那些。 In a specific aspect, the first catalyst may be any catalyst described in PCT Publication WO 03/040201 mentioned, especially mentioned are those supplied to the first reactor in a dual reactor scheme. 类似地,虽然第二催化剂还可以是在PCT公开TO 03/040201中提到的任何催化剂,更具体的第二催化剂是提到的在串联反应器配置中被供给第二反应器的那些。 Similarly, although the second catalyst may also be any catalyst disclosed TO 03/040201 mentioned in PCT, a more specific second catalyst is referred to in a series reactor configuration is supplied to the second reactor of those.

[0083] 从最广义的方面来说,所述组合物可以使用任何SSC(单中心催化剂)来制备。 [0083] In its broadest terms, the composition can be prepared using any SSC (single site catalyst). 这种催化剂可以是通常含有周期表第3-10族过渡金属;和至少一个在聚合过程中保持键合于该过渡金属的辅助配体的过渡金属配合物。 Such catalysts may be generally contain Periodic Table Group 3-10 transition metal; and at least one transition metal in the polymerization process to maintain the transition metal is bonded to the auxiliary ligand complexes. 优选地,该过渡金属以还原阳离子状态使用, 并且用助催化剂或活化剂稳定。 Preferably, the transition metal cation to restore the state of use, and with a cocatalyst or activator stability.

[0084] 在以上或本文其它地方所述的任何方法中,所述第一和第二催化剂可以是非担载催化剂。 [0084] In any of the methods described above or elsewhere herein, the first and the second catalyst may be a non-supported catalyst.

[0085] 在以上或本文其它地方所述的任何方法中,可以对所述第二催化剂进行选择和使用以引入基本上没有立构规整性的高级α-烯烃。 [0085] In any of the methods described above or elsewhere herein, the second catalyst may be selected and used to introduce substantially no stereoregularity advanced α- olefins.

[0086] 在以上或本文其它地方所述的某些方法中,所述第一催化剂是手性双环戊二烯基衍生物,而所述第二催化剂是非手性桥连芴基环戊二烯基衍生物。 [0086] In some methods described above or elsewhere herein, the first catalyst is a chiral biscyclopentadienyl derivative and the second catalyst is a non-chiral bridged fluorenyl cyclopentadienyl derivatives.

[0087] 在以上或本文其它地方所述的某些方法中,所述第一和第二催化剂与非配位阴离子活化剂结合使用,第一和第二反应器使用相同的活化剂,并且任选附带有清除剂例如清除用的含铝衍生物。 [0087] In some methods described above or elsewhere herein, the combination of the first and second catalyst and non-coordinating anion activators, the first and second reactors using the same activator, and either election comes with scavengers such as clearing with aluminum-containing derivatives.

[0088] 在以上或本文其它地方所述的某些方法中,所述非配位阴离子是具有至少两个带有稠环体系、优选全氟环和最优选四芳基复合物的配体的硼配合物。 [0088] In certain methods above or elsewhere herein described, the non-coordinating anion having a fused ring system having at least two, preferably perfluoro cyclic ligand and most preferably four of the aryl compound boron complexes.

[0089] 本文所述的某些组合物不含或含有低于5wt%的填料和不含或含有低于IOwt % 的熔点为> 110°c的全同立构聚丙烯级分。 [0089] Certain compositions described herein contain no or less than 5wt% of filler and contain no or less than IOwt% of a melting point of> 110 ° c of an isotactic polypropylene fraction.

[0090] 在本文所述的某些组合物中,所述组合物具有l_45J/g的总熔化热。 [0090] In certain compositions described herein, the composition has l_45J / g of the total heat of fusion.

[0091] 在本文所述的某些组合物中,第一聚合物的门尼粘度低于25门尼ML(l+4, 125。。),比总组合物的门尼ML(1+4,125。。)低至少10个单位。 [0091] In certain compositions described herein, the Mooney viscosity of the first polymer is less than 25 Mooney ML (l + 4, 125 ..), the total composition ratio of Mooney ML (1 + 4 , 125 ..) lower by at least 10 units.

[0092] 以乙烯和丙烯衍生的单元的组合含量为基准计,本文所述的某些组合物具有低于95wt %的乙烯衍生的单元的总含量。 [0092] In a combination of the content of ethylene and propylene derived units as a reference count, certain compositions described herein having an ethylene derived units less than 95wt% of the total content.

[0093] 本文所述的某些组合物含有40_60wt 优选45wt %或55wt %的乙烯衍生的单J Li ο [0093] Certain compositions described herein contain 40_60wt preferably 45wt% or 55wt% of ethylene-derived single-J Li ο

[0094] 本文所述的某些组合物具有低于30wt%的乙烯衍生的单元。 [0094] Certain compositions described herein having an ethylene derived units less than 30wt% of the.

[0095] C.多级聚合 [0095] C. multistage polymerization

[0096] 本文所述的反应器共混物在连续“多级聚合”中形成,是指进行两种(或多种)不同聚合(或聚合阶段)。 [0096] The reactor blends described herein are formed in a continuous "multi-stage polymerization", and refers to the two (or more) different polymerization (or polymerization stages). 更具体地说,多级聚合可以包括两个或多个顺序聚合(还称为“串联方法”),或两个或多个平行聚合(还称为“并联方法”)。 More specifically, a multistage polymerization may include two or more sequential polymerization (also referred to as "tandem method"), or two or more parallel polymerization (also referred to as "parallel method").

[0097] 将在所述连续多反应器溶液装置的各个反应器中制备的聚合物以溶液形式共混, 不预先从溶剂中分离出来。 [0097] The form of a solution of the polymer blend in each of the continuous reactor of the multiple reactor apparatus for preparing a solution, without prior separation from the solvent. 该共混物可以是串联反应器操作的产物,其中第一反应器的流出物进入第二反应器,而第二反应器的流出物可以输送到包括脱挥发分的后处理步骤。 The blend may be the product of reactors in series operation, wherein the effluent from the first reactor into the second reactor, and the effluent from the second reactor may be fed to the devolatilization include post-processing step. 该共混物还可以是并联反应器操作的产物,其中两个反应器的流出物被合并,并输送到后处理步骤。 The blend may also be the product of the parallel reactor operation, in which the effluent of the two reactors are combined and delivered to the post-processing step. 任何一个选择方案提供了脱挥发分共混物中的聚合物的均匀混合。 Any options provided devolatilization uniformly mixed blend of polymer. 任何一种情况均可制成各种聚合分割比,从而在各个反应器中生产的聚合物的量的比例可以在宽范围内改变。 In any case can be made of various polymeric division ratio, so the proportion of the amount in each reactor the polymer produced may be varied over a wide range.

[0098] 以下论述组成反应器共混物组合物的第一聚合物和第二聚合物,随后是串联方法部分,再后是并联方法部分。 [0098] The following discussion of the first polymer and the second polymer reactor blend composition, followed by the series Methods section, and then after the parallel methods section. 在适当的场合下,在串联和并联方法之间的相应区别将被标明,否则串联方法的论述应该被视为同样适合于并联方法。 In appropriate situations, the corresponding difference between the series and parallel method will be marked, otherwise the series process discussion should be regarded as equally applicable to parallel method.

[0099] D.第一聚合物(丙烯聚合物) [0099] D. the first polymer (propylene polymer)

[0100] 如上所述,这里的反应器共混物优选至少包括第一聚合物,它优选是通过第一聚合反应(在本文其它地方所述的条件下)和优选在作为串联方法或并联方法的一部分的“第一反应器”内形成的聚合物。 [0100] As described above, the reactor blends herein preferably include at least a first polymer, it is preferably through a first polymerization reaction (under conditions described elsewhere herein) and preferably in series or in parallel as a method method the polymer portion of the "first reactor" formed therein.

[0101] 如下所述,第一聚合物(在这里还称为“丙烯聚合物”)应该具有(最少)50wt%丙烯单元,优选更多。 [0101] As described below, the first polymer (herein also referred to as "propylene polymer") should have (at least) 50wt% propylene units, preferably more. 第一聚合物应该是具有>60wt%的由丙烯衍生的单元,具有全同立构排列的丙烯衍生的序列和具有低于45J/g的熔化热的丙烯聚合物(优选聚丙烯共聚物)。 The first polymer should have> 60wt% of units derived from propylene, having a propylene polymer (preferably a polypropylene copolymer) isotactic propylene derived sequences and arranged with less than 45J / g of heat of fusion. 第一聚合物优选具有至少5wt%非丙烯共聚单体单元,例如乙烯单元,更优选至少IOwt %或更多乙烯单元。 The first polymer preferably has at least 5wt% non-propylene comonomer units, e.g., ethylene units, more preferably at least IOwt% or more ethylene units. 第一聚合物的结晶度由全同立构聚丙烯序列产生。 Crystallinity of the first polymer is generated by the sequence of isotactic polypropylene. 第一聚合物的全同立构规整度可以用占优势的丙烯残基以mm三单元组存在于聚合物中来例证。 Isotactic tacticity of the first polymer may be a propylene dominant residues exist mm triads in the polymer is exemplified.

[0102] 第一聚合物的结晶度可以用熔化热来表示。 Crystallinity [0102] The first polymer may be represented by the heat of fusion. 本发明的第一聚合物可以具有I. OJ/g 或I. 5J/g 或3. OJ/g 或4. OJ/g 或6. OJ/g 或7. OJ/g 的任何下限到30J/g 或40J/g 或50J/ g或60J/g或75J/g的任何上限的通过DSC测定的熔化热。 A first polymer of the present invention may have I. OJ / g or I. 5J / g or 3. OJ / g or 4. OJ / g or 6. OJ / g or 7. OJ / g of any lower limit to 30J / g or 40J / g or 50J / g or 60J / g or 75J / g of any upper limit of the heat of fusion measured by DSC. 优选地,第一聚合物的熔化热低于45J/g。 Preferably, the heat of fusion of the first polymer is less than 45J / g. 不希望受理论的制约,据信第一聚合物一般具有全同立构可结晶的丙烯序列,以上熔化热被认为是归因于这些结晶链段的熔融。 Without wishing to be constrained by theory, it is believed that the first polymer typically has an isotactic crystallizable propylene sequences, the above heat of fusion is considered to be attributed to the melting of these crystalline segments.

[0103] 第一聚合物的结晶度大小还可以反映在其熔点上。 Crystallinity Size [0103] The first polymer may also be reflected in its melting point. 优选地,第一聚合物具有单一熔点。 Preferably, the first polymer has a single melting point. 然而,丙烯共聚物样品常常显示了与该主峰相邻的次级熔融峰。 However, the propylene copolymer and the samples often show secondary melting peaks adjacent to the main peak. 最高峰被认为是熔点。 Highest peak is considered the melting point. 本文所述的第一聚合物可以具有115°C或110°C或105°C或90°C或80°C或70°C的任何上限到(TC或20°C或25 V或30°C或35 V或40°C或45 V的任何下限的通过DSC测定的熔点。优选地,第一聚合物具有低于105°C,更优选低于100°C,甚至更优选低于90°C的熔点。 还有,优选的是,第一聚合物具有高于约25°C或40°C的熔点。 Any upper limit described herein may have a first polymer 115 ° C or 110 ° C or 105 ° C or 90 ° C or 80 ° C or 70 ° C to (TC or 20 ° C or 25 V or 30 ° C or 35 V or 40 ° C or any lower limit of the melting point measured by DSC. preferably 45 V, the first polymer having less than 105 ° C, more preferably below 100 ° C, even more preferably below 90 ° C melting point. It is preferable that the first polymer has greater than about 25 ° C or 40 ° C melting point.

[0104] 对于第一聚合物,至少75wt%、或至少80wt%、或至少85wt%、或至少90wt%、或至少95wt%、或至少97wt%、或至少99wt%的该聚合物可溶于单一温度级分中,或可溶于两个相邻温度级分中,剩余部分的该聚合物可溶于紧跟着的前一个或后一个温度级分中。 [0104] For the first polymer, at least 75wt%, or at least 80wt%, or at least 85wt%, or at least 90wt%, or at least 95wt%, or at least 97wt%, or at least 99wt% of the polymer is soluble in a single temperature fractions, or two adjacent soluble fractions temperature, the polymer can be dissolved in the remaining part followed the previous or a temperature fractions. 这些百分率是在23°C下开始的例如在己烷中的级分,后续级分是在23°C以上以大约8°C的增量增加的温度下的级分。 These percentages are e.g. in hexane at 23 ° C fractions at the beginning of the subsequent fraction is at least 23 ° C to about 8 ° C level incremental increase of temperature points. 满足这种分级要求意味着聚合物的聚合丙烯的立构规整度具有统计学上无显著的分子间差别。 Tacticity meet this requirement means that the polymer grade propylene polymer having no significant inter-molecular statistical difference.

[0105] 在某些实施方案中,如用测定三单元组立构规整度的方法所确定的,第一聚合物中的mm三单元组的百分率具有98 %或95 %或90 %或85 %或82 %或80 %或75 %的任何上限和50 %或60 %的任何下限。 [0105] In certain embodiments, such as the measuring group tacticity of three units determined by the method, the percentage of the first polymer in mm triads of 98% or 95% or 90% or 85% or 82% or 80% or 75% or 50% of any upper limit and any lower limit of 60%.

[0106] 某些第一聚合物具有大于0%,或在50%或25%的任何上限到3%或10%的任何下限范围内的全同立构规整度指数。 [0106] Some of the first polymer has greater than 0%, or 50% or 25% of any upper limit to isotactic tacticity index of 3% or 10% of any lower limit range.

[0107] 某些第一聚合物的立构规整度(m/r)可以具有800或1000或1200的任何上限, 并且这些聚合物可以具有40或60的任何下限。 [0107] Certain tacticity of the first polymer (m / r) may have any upper limit of 800 or 1000 or 1200, and those polymers may have any lower limit of 40 or 60.

[0108] 如下所述,第一聚合(以及第二聚合)在某些情况下可以在α-烯烃的存在下进行;这样,当存在这种α-烯烃时所形成的聚合物包括由这种α-烯烃“衍生的单元”。 [0108] As described below, the first polymerization (and the second polymerization) can be carried out in the presence of α- olefins, in some cases; Thus, when the presence of such a polymer formed including α- olefins by such α- olefin "derived units." 可以将相同的α-烯烃或不同的α-烯烃引入到第一和第二聚合中。 Α- olefin same or different α- olefins may be introduced into the first and second polymerization. 通常,这种α-烯烃优选具有3-10个碳原子。 Typically, such α- olefins preferably having 3-10 carbon atoms. 这些α-烯烃的特定实例是C3-C2tlCi-烯烃,包括、但不限于丙烯;丁烯-I ;戍烯-I ;2~甲基戍烯-I ;3_甲基丁烯-I ;己烯-I ;3_甲基戍烯-I ;4_甲基戍烯-I ; 3,3_ 二甲基丁烯-I ;庚烯-I ;己烯-I ;甲基己烯-I ;二甲基戊烯-I ;三甲基丁烯-I ;乙基戍烯-I ;辛烯-I ;甲基戍烯-I;二甲基丁烯-I;二甲基戍烯-I ;乙基己烯-I ;甲基乙基戍烯-I ;二乙基己烯-I ;丙基戍烯-I;癸烯_1,甲基壬烯-I;壬烯-I;二甲基辛烯-I;二甲基庚烯-I ;乙基辛烯-I ;甲基乙基丁烯-I ;二乙基己烯-I ;十二碳烯-I和十六碳烯-I。 These specific examples of α- olefins are C3-C2tlCi- olefins, including, but not limited to propylene; butene -I; pentene -I; 2 ~ methyl pentene -I; 3_ methylbutene -I; hexyl ene -I; 3_ methyl pentene -I; 4_ methyl pentene -I; 3,3_ dimethyl butene -I; heptene -I; hexene -I; methyl hexene -I; dimethyl pentene -I; trimethyl-butene -I; ethyl pentene -I; octene -I; methyl pentene -I; dimethyl butene -I; dimethyl pentene -I ; ethylhexenal -I; methyl ethyl pentene -I; diethyl-hexene -I; propyl pentene -I; decene _1, methyl nonenes -I; nonenyl -I; two A Kissin ene -I; dimethyl-heptene -I; B Kissin ene -I; methyl ethyl butene -I; diethyl-hexene -I; dodecene -I and hexadecenyl -I.

[0109] 第一聚合物可以任选包括多烯烃。 [0109] The first polymer may optionally include a polyene. 该任选的多烯烃可以是具有至少两个不饱和键的任何烃结构,其中至少一个不饱和键容易被引入到聚合物中。 The multiolefin may be optionally having at least two unsaturated bonds any hydrocarbon structure, wherein the at least one unsaturated bond is easily incorporated into the polymer. 第二个键可以部分参与聚合,形成长链分支,但优选提供了适于在后聚合方法中的后续固化或硫化的至少一些不饱和键。 The second key may be partially participate in the polymerization, the formation of long chain branching, but is preferably adapted to provide a post-polymerization process subsequent curing or vulcanization of at least some of the unsaturated bond. 任选的多烯烃的实例包括、但不限于丁二烯,戊二烯,己二烯(例如1,4_己二烯),庚二烯(例如I,6-庚二烯),辛二烯(例如I,7-辛二烯),壬二烯(例如I,8-壬二烯),癸二烯(例如I,9-癸二烯),i^一碳二烯(例如I,10- i^一碳二烯),十二碳二烯(例如I,11-十二碳二烯),十三碳二烯(例如1,12-十三碳二烯),十四碳二烯(例如1,13-十四碳二烯), 十五碳二烯,十六碳二烯,十七碳二烯,十八碳二烯,十九碳二烯,二十碳二烯,二i^一碳二烯,二十二碳二烯,二十三碳二烯,二十四碳二烯,二十五碳二烯,二十六碳二烯,二十七碳二烯,二十八碳二烯,二十九碳二烯,三十碳二烯和分子量(Mw)低于1000g/mol的聚丁二烯类。 Examples of the optional polyene include, but are not limited to butadiene, pentadiene, hexadiene (e.g., 1,4_-hexadiene), heptadiene (e.g. I, 6- heptadiene), suberic alkenyl (e.g. I, 7- octadiene), nonadiene (e.g. I, 8- nonadiene), decadiene (e.g. I, 9- decadiene), i ^ a carbon-diene (e.g., I, 10- i ^ a carbon-diene), dodecadiene (eg I, 11- dodecadiene), tridecadiene (eg 1,12 tridecadiene), tetradecenoic two alkenyl (e.g., 1,13-tetradecadiene), pentadecadiene, sixteen carbon dienes, seventeen carbon dienes, octadecadienoic, nineteen carbon dienes, twenty carbon dienes, two i ^ a carbon-diene, two dodecadiene Twenty-three-carbon-diene, tetracosahexaenoic diene, two pentadecadiene, twenty-sixth carbon diene, xxvii carbon diene octacos-diene, 29-diene-carbon, carbon-diene and thirty (Mw) of less than 1000g / mol of polybutadiene. 直链无环二烯的实例包括、但不限于1,4_己二烯和1,6_辛二烯。 Straight chain acyclic dienes include, but are not limited to 1,4_ 1,6_-hexadiene and octadiene. 支链无环二烯的实例包括、但不限于5-甲基-1,4-己二烯,3,7- 二甲基-1,6-辛二烯和3,7- 二甲基-1,7-辛二烯。 Branched chain acyclic dienes include, but are not limited to, 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene and 3,7-dimethyl - 1,7-octadiene. 单环脂环族二烯的实例包括、但不限于1,4_环己二烯,1,5_环辛二烯和1,7_环十二碳二烯。 Examples of single ring alicyclic dienes include, but are not limited to 1,4_ cyclohexadiene, cyclooctadiene and 1,7_ 1,5_ ring dodecadiene. 多环脂环族稠环和桥连环状二烯的实例包括、但不限于四氢茚;降冰片二烯;甲基四氢茚;二环戊二烯;双环-(2. 2. I)-庚-2,5-二烯;和烯基_、烷叉基_、环烯基-和环烷叉基降冰片烯[包括例如5-亚甲基-2-降冰片烯,5-乙叉基-2-降冰片烯,5-丙烯基-2-降冰片烯,5-异丙叉基-2-降冰片烯,5- (4-环戊烯基)-2-降冰片烯,5-环己叉基-2-降冰片烯和5-乙烯基-2-降冰片烯]。 Multi-ring alicyclic fused and bridged ring cyclic dienes examples include, but are not limited to tetrahydroindene; norbornadiene; methyl-tetrahydroindene; dicyclopentadiene; bicyclic - (. 2 2. I) - hepta-2,5-diene; and alkenyl _, _ alkylidene, cycloalkenyl - and cycloalkylidene norbornene [including, for example 5-methylene-2-norbornene, 5-acetate Fork-2-norbornene, 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5- (4-cyclopentenyl) -2-norbornene, 5- cyclohexylidene-2-norbornene and 5-vinyl-2-norbornene]. 环烯基取代的烯烃的实例包括、但不限于乙烯基环己烯, 烯丙基环己烯,乙烯基环辛烯,4-乙烯基环己烯,烯丙基环癸烯,乙烯基环十二碳烯和四环(A-11,12) -5,8-十二碳稀。 Examples of cycloalkenyl-substituted olefins include, but are not limited to vinyl cyclohexene, allyl cyclohexene, vinyl cyclooctene, 4-vinyl cyclohexene, allyl cyclodecene, vinyl ring dodecene and tetracyclo (A-11,12) -5,8- twelve carbon thin.

[0110] 含有乙烯的任何第一聚合物优选具有统计学上无显著分子内组成差别,该组成是沿着同一链的链段(分子内)的丙烯与乙烯的比率。 [0110] Any of the first polymer preferably contains ethylene composition having no significant difference in the molecular statistically, this composition is the same along the segment chain (intramolecular) the ratio of propylene to ethylene. 该组成分析由用于合成这些聚合物的方法推断出来,还可以通过13CNMR测定,其定位了相对于相邻丙烯残基的共聚单体残基和丙烯插入错误。 The composition analysis by the method used for the synthesis of these polymers inferred, also determined by 13CNMR, its positioning with respect to the neighboring propylene residues of comonomer residues and propylene insertion errors.

[0111] 第一聚合物还优选具有统计学上无显著分子内立构规整度差别,这归因于丙烯单元沿着同一链的链段(分子内)全同立构取向。 [0111] The first polymer also preferably has no tacticity differences within statistically significant molecule, which is attributed to the propylene units along the segments of the same chain (intramolecular) isotactic orientation. 该组成分析由以下详细分析的结果推断出来,所述分析包括差示扫描量热法、电子显微镜和驰豫测定。 The composition analysis of the results deduced from the analysis of the following detailed out, the analysis includes Differential scanning calorimetry, electron microscopy and relaxation measurement. 在立构规整度有显著分子内差异的情况下,形成了如下所述的“立构嵌段”结构,其中彼此相邻的全同立构丙烯残基的数目比统计的大得多。 Under the significant difference in molecular tacticity case, formed as described below, "stereo-block" structure, adjacent to each other in which the number of isotactic propylene residues is much greater than statistical. 此外,这些聚合物的熔点取决于结晶度,因为更明显嵌段状的聚合物应该具有更高的熔点以及在室温溶剂中的溶解度降低。 In addition, the melting point depends on the degree of crystallinity of these polymers, since the polymer is more obvious block form should have a higher melting point and lower solubility in room temperature solvents.

[0112] E.第二聚合物(乙烯聚合物) [0112] E. The second polymer (ethylene polymer)

[0113] 本文所述的反应器共混物包括第二聚合物组分(第二聚合物),它优选是(或包括)具有超过3(^丨%或4(^丨%或5(^丨%的由乙烯单体衍生的单元的弹性体。第二聚合物的结晶度和因此其它性能优选不同于第一聚合物的那些。 [0113] The reactor blends described herein include a second polymer component (second polymer), which preferably is (or includes) having more than three (^ Shu% or 4 (or 5% ^ Shu (^ Crystallinity of the second polymer and thus other properties different from the first polymer is preferably those Shu% derived from ethylene monomer units of the elastomer.

[0114] 优选地,第二聚合物(还称为“乙烯聚合物”)是非结晶的,例如无规立构或无定形的, 但在某些实施方案中,第二聚合物是结晶的(包括“半结晶”)。 [0114] Preferably, the second polymer (also referred to as "vinyl polymer") is non-crystalline, e.g., atactic or amorphous, but in certain embodiments, the second polymer is crystalline ( including "semi-crystalline"). 但第二聚合物的任何结晶度优选来源于乙烯,许多公开的方法、程序和技术可用来评价特定材料的结晶度是否来源于乙烯。 But any crystallinity of the second polymer is preferably derived from ethylene, many of the disclosed methods, procedures and techniques available to evaluate the degree of crystallinity of a particular material is derived from ethylene. 通过从组合物中除去第一聚合物和然后测定残留第二聚合物的结晶度,可以将第二聚合物的结晶度与第一聚合物的结晶度区分开来。 By removing the first polymer from the composition and then measuring the residual crystallinity of the second polymer, the crystallinity region can crystallinity of the second polymer to the first polymer separately. 所测定的这种结晶度通常使用均聚乙烯的结晶度来校准并且与共聚单体含量相关联。 Such crystallinity measured crystallinity of polyethylene are generally used to calibrate and is associated with the comonomer content. 这些情况下的结晶度百分率作为均聚乙烯结晶度的百分率测定,并由此确定结晶度来源于乙烯。 Under these conditions the degree of crystallinity as the average percentage of the percentage of polyethylene crystallinity measured, and thereby determine the degree of crystallinity derived from ethylene.

[0115] 优选地,除了由乙烯衍生的单元以外,第二聚合物还包括由α -烯烃单体衍生的单元,在某些实施方案中,它与用于形成第一聚合物的α-烯烃单体相同,在其它实施方案中,至少部分不同于用于形成第一聚合物的α -烯烃单体,在该情况下,它被称为“第二α-烯烃”。 [0115] Preferably, in addition to units derived from ethylene, the second polymer further comprises α - olefin monomer derived units, in some embodiments, it used to form a first olefin polymer of α- the same monomers, in other embodiments, at least a portion for forming the first polymer is different from the α - olefin monomer, in this case, it is called "second α- olefins." 可以使用以上在第一聚合物中列举的任何α-烯烃单体,尤其丁烯-I、戊烯-I、 己烯-I、庚烯-I或辛烯-I。 Can use any α- olefin monomers cited above in the first polymer, especially butene -I, pentene -I, hexene -I, heptene or octene -I -I. 有利地,第二聚合物可以使用选自以上对于第一聚合物所列举的单体中的不同α-烯烃单体和/或不同量的单体,例如乙烯和α-烯烃单体来配制,以制备不同类型的第二聚合物,例如具有所需性能的乙烯弹性体。 Advantageously, the second polymer may be selected from the above monomers for the first polymer enumerated different α- olefin monomer and / or different amounts of monomers, such as ethylene and α- olefin monomers formulated, to prepare different types of second polymers, e.g., having the desired properties of the ethylene elastomer. 因此,可以制备共混物组合物,其中该组合物包括具有一组性能的第一聚合物和具有一组不同性能的第二聚合物,这样,该组合物具有所需性能的期望混合或平衡。 Thus, blend compositions may be prepared, wherein the composition comprises a first polymer and a second polymer having a group having a different set of performance properties, so that the composition has the desired mix or balance of desired properties . 有利地,可以使用连续多级方法(串联或并联)来形成该组合物,不需要应用任何分离步骤,例如除去溶剂、例如通过脱挥发分、或在分离之后不需要物理合并聚合物。 Advantageously, it is possible to use a continuous multistage process (series or parallel) to form the composition, does not need to apply any separation step, e.g., the solvent is removed, for example by devolatilization, or after separation of the polymer without physically combined.

[0116] 优选地,第二聚合物在(或通过)第二聚合过程中形成,在串联反应器的情况下,这优选在位于进行第一聚合并且形成大多数的第一聚合物的反应器的下游的反应器中进行。 [0116] Preferably, the second polymer in (or through) the second polymerization process is formed, in the case of series reactors, which is preferably located in a first polymerization reactor and the formation of the majority of the first polymer downstream of the reactor is carried out. 在包括并联聚合和/或并联反应器的并联方法的情况下,“第二聚合物”可以与“第一聚合物”同时形成,但将产物流(仍然包括溶剂)在充分形成第一和第二聚合物之后合并。 In the case comprises a parallel polymerization and / or parallel reactor parallel process, "second polymer" may be the "first polymer" formed simultaneously, but the product stream (still including solvent) are formed in the first and the full After merging two polymers.

[0117] 优选地,第二聚合物包括(或是)弹性体聚合物,它优选是具有高分子量(如由门尼粘度所测定的)和低结晶度的乙烯-α -烯烃弹性体(包括乙烯-环烯烃和乙烯-α -烯烃-二烯烃)。 [0117] Preferably, the second polymer includes (or is) an elastomeric polymer, it is preferably a high molecular weight (e.g., measured by Mooney viscosity), and low crystallinity ethylene -α - olefin elastomer (including ethylene - cyclic olefin and ethylene -α - - olefin-diene). 第二聚合物可以用任何适当的催化剂、但优选用下述催化剂制备。 The second polymer may be any suitable catalyst, but is preferably prepared by the following catalyst. 在至少一个具体实施方案中,第二聚合物在不同于用于聚合第一聚合物的催化剂(例如“第一催化齐U”)的催化剂(例如“第二催化剂”)的存在下形成。 In at least one embodiment, the second polymer is formed in a catalyst different from the catalyst for polymerizing the first polymer (e.g., "first catalytic Qi U") (e.g., "second catalyst") under the presence of. 可以形成具有选择组成(例如单体类型和含量)和性能的许多第二聚合物。 Many of the second polymer can be formed with a choice composition (such as a monomer type and content) and performance.

[0118] 第一聚合物的一个目的是提高第二聚合物的特性。 An object of the [0118] first polymer is to improve the properties of the second polymer. 取决于预期的特定应用和特定共混物,这种提高可以本身以许多方式体现。 Depending on the intended specific application and the specific blend, this increase may reflect itself in many ways. 这种提高包括、但不限于以下方面的改进:固化速率和状态;如由诸如研磨、挤出、压延和注塑之类的方法所定义的加工性能;物理性能例如韧性、粘性、粘合力、抗撕裂性、拉伸和伸长率以及如由这种物理性能在高温下的保持所定义的热老化。 This increase including, but not limited to the following improvements: the cure rate and state; such as by milling, extrusion, calendering and injection molding methods or the like as defined processability; physical properties such as toughness, tack, adhesion, tear resistance, tensile and elongation and heat from such physical properties as maintained at a high temperature as defined aging.

[0119] 例如,在US专利No. 6,376,610中所述的乙烯、α -烯烃、乙烯基降冰片烯弹性体的任何一种,或引入作为多烯烃的ENB的任何这种弹性体(主要打算用于电力电缆涂料), 可以作为第二聚合物形成。 [0119] For example, in an ethylene, α US Patent No. 6,376,610 described - olefin, vinyl norbornene drop any elastomer, or incorporated polyene ENB any such elastomer (primarily intend to use in power cables paint), may be formed as a second polymer. 该专利描述所述弹性体、它们的性能和制备它们的方法的部分由此为了US专利实施的目的引入供参考。 This patent describes the elastomers, their properties and methods of making them whereby the part for the purpose of US patent incorporated by reference.

[0120] 还有,在US专利No. 6,271,311中所述的乙烯、α -烯烃弹性体聚合物组合物的任何一种,或引入作为多烯烃的ENB的任何这种弹性体(其主要打算用于形成挤出制品),可以作为第二聚合物形成。 [0120] Further, in US Patent No. ethylene, α described in 6,271,311 - olefin elastomeric polymer composition of any one, or more olefins ENB incorporated by any such elastomers ( which is primarily intended for forming the extruded article), may be formed as a second polymer. 该专利描述所述弹性体、它们的性能和制备它们的方法的部分由此为了US专利实施的目的引入供参考。 This patent describes the elastomers, their properties and methods of making them whereby the part for the purpose of US patent incorporated by reference.

[0121] 此外,第二聚合物可以是在US专利No. 5,807,946中所述的乙烯、α-烯烃、乙烯基降冰片烯弹性体的任何一种,或者引入作为多烯烃的ENB的任何这种弹性体,主要打算用于车辆部件。 [0121] Further, the second polymer may be a vinyl US Patent No. 5,807,946 described, α- olefins, vinyl norbornene drop any elastomer, or the introduction of any such as a multi-olefin of ENB elastomers, primarily intended for vehicle components. 该专利描述所述弹性体、它们的性能和制备它们的方法的部分由此为了US 专利实施的目的引入供参考。 This patent describes the elastomers, their properties and methods of making them whereby the part for the purpose of US patent incorporated by reference.

[0122] 另外,在US专利No. 5,766,713中所述的乙烯、α -烯烃、乙烯基降冰片烯弹性体的任何一种,或引入作为多烯烃的ENB的任何这种弹性体(主要打算用于车辆软管),可以作为第二聚合物形成。 [0122] Further, in the ethylene, α US Patent No. 5,766,713 described - olefin, vinyl norbornene drop any elastomer, or incorporated polyene ENB any such elastomers (mainly intended for vehicles hose) can be formed as a second polymer. 该专利描述所述弹性体、它们的性能和制备它们的方法的部分由此为了US专利实施的目的引入供参考。 This patent describes the elastomers, their properties and methods of making them whereby the part for the purpose of US patent incorporated by reference.

[0123] 还有,在US专利No. 5,698,650中所述的乙烯、α -烯烃、乙烯基降冰片烯弹性体的任何一种,或引入作为多烯烃的ENB的任何这种弹性体(主要打算用于车辆刹车部件和动力传输皮带),可以作为第二聚合物形成。 [0123] Further, in US Patent No. 5,698,650 described ethylene, α - olefin, vinyl norbornene drop any elastomer, or incorporated polyene ENB any such elastic body (mainly intended for vehicle brake parts and power transmission belts), can be formed as a second polymer. 该专利描述所述弹性体、它们的性能和制备它们的方法的部分由此为了US专利实施的目的引入供参考。 This patent describes the elastomers, their properties and methods of making them whereby the part for the purpose of US patent incorporated by reference.

[0124] 此外,在US专利No. 5,656,693中所述的乙烯、α -烯烃、乙烯基降冰片烯弹性体的任何一种,或引入作为多烯烃的ENB的任何这种弹性体(具有改进固化性能),可以作为第二聚合物形成。 [0124] Further, in the ethylene, α US Patent No. 5,656,693 described - olefin, vinyl norbornene drop any elastomer, or incorporated polyene ENB any such elastomers (with improved curability), may be formed as a second polymer. 该专利描述所述弹性体、它们的性能和制备它们的方法的部分由此为了US专利实施的目的引入供参考。 This patent describes the elastomers, their properties and methods of making them whereby the part for the purpose of US patent incorporated by reference.

[0125] 还有,在US专利No. 5,654,370中所述的乙烯、α -烯烃、非共轭双环二烯弹性体聚合物的任何一种,或引入作为多烯烃的ENB的任何这种弹性体(其然后可以配混和压延为片材),可以作为第二聚合物形成。 [0125] Further, in the ethylene, α described in 5,654,370 US Patent No. - olefin, non-conjugated bicyclic diene elastomeric any polymer, or introduced as any polyene ENB Such elastomers (which may then be compounded and calendered into a sheet), may be formed as a second polymer. 该专利描述所述弹性体、它们的性能和制备它们的方法的部分由此为了US专利实施的目的引入供参考。 This patent describes the elastomers, their properties and methods of making them whereby the part for the purpose of US patent incorporated by reference.

[0126] 最后,在US专利No. 5,571,883中所述的乙烯、α -烯烃、乙烯基降冰片烯弹性体的任何一种,或引入作为多烯烃的ENB的任何这种弹性体(其可以用于形成机动车辆振动阻尼部件),可以作为第二聚合物形成。 [0126] Finally, in the ethylene, α US Patent No. 5,571,883 described - olefin, vinyl norbornene drop any elastomer, or incorporated polyene ENB any such elastomers (which may be used to form motor vehicle vibration damping member), may be formed as a second polymer. 该专利描述所述弹性体、它们的性能和制备它们的方法的部分由此为了US专利实施的目的引入供参考。 This patent describes the elastomers, their properties and methods of making them whereby the part for the purpose of US patent incorporated by reference.

[0127] 因此,如在以上专利中所举例的,第二聚合物可以包括一种或多种任选的多烯烃, 尤其包括二烯烃;因此,第二聚合物可以是乙烯-丙烯-二烯共聚物(通常称为“EPDM”)。 [0127] Accordingly, as exemplified in the above patents, the second polymer may comprise one or more optional polyenes, including particularly a diene; therefore, the second polymer may be an ethylene - propylene - diene copolymer (commonly referred to as "EPDM"). 该任选的多烯烃被认为是具有至少两个不饱和键的任何烃结构,其中至少一个不饱和键容易被引入到聚合物中。 The optional polyene is considered to have at least two unsaturated bonds any hydrocarbon structure, wherein the at least one unsaturated bond easily be incorporated into the polymer. 第二个键可以部分参与聚合,以形成长链分支,但优选提供了适合于在后聚合方法中的后续固化或硫化的至少一些不饱和键。 The second key may be partially participate in the polymerization to form long chain branches but preferably provides at least some unsaturated bonds suitable for subsequent post-polymerization process of curing or vulcanization. 任选的多烯烃的实例包括、但不限于丁二烯,戊二烯,己二烯(例如1,4_己二烯),庚二烯(例如I,6-庚二烯),辛二烯(例如I,7-辛二烯),壬二烯(例如I,8-壬二烯),癸二烯(例如I,9-癸二烯),i^一碳二烯(例如1,10- i^一碳二烯),十二碳二烯(例如1,11-十二碳二烯),十三碳二烯(例如I,12-十三碳二烯),十四碳二烯(例如1,13-十四碳二烯),十五碳二烯,十六碳二烯,十七碳二烯,十八碳二烯,十九碳二烯,二十碳二烯,二i^一碳二烯,二十二碳二烯,二十三碳二烯,二十四碳二烯,二十五碳二烯,二十六碳二烯,二十七碳二烯,二十八碳二烯,二十九碳二烯,三十碳二烯和分子量(Mw)低于lOOOg/mol的聚丁二烯类。 Examples of the optional polyene include, but are not limited to butadiene, pentadiene, hexadiene (e.g., 1,4_-hexadiene), heptadiene (e.g. I, 6- heptadiene), suberic alkenyl (e.g. I, 7- octadiene), nonadiene (e.g. I, 8- nonadiene), decadiene (e.g. I, 9- decadiene), i ^ a carbon dienes (e.g. 1, 10- i ^ a carbon-diene), dodecadiene (eg 1,11 dodecadiene), tridecadiene (eg I, 12- tridecadiene), tetradecenoic two alkenyl (e.g., 1,13-tetradecadiene), pentadecadiene, sixteen carbon dienes, seventeen carbon dienes, octadecadienoic, nineteen carbon dienes, twenty carbon dienes, two i ^ a carbon-diene, two dodecadiene Twenty-three-carbon-diene, tetracosahexaenoic diene, two pentadecadiene, twenty-sixth carbon diene, xxvii carbon diene octacos-diene, 29 carbon dienes, thirty carbon diene and a molecular weight (Mw) less than lOOOg / mol of polybutadiene. 直链无环二烯的实例包括、但不限于1,4_己二烯和1,6_辛二烯。 Straight chain acyclic dienes include, but are not limited to 1,4_ 1,6_-hexadiene and octadiene. 支链无环二烯的实例包括、但不限于5-甲基-1,4-己二稀,3, 7_ 二甲基-1,6_羊二稀和3, 7_ 二甲基-I, 7_羊二稀。 Branched chain acyclic dienes include, but are not limited to, 5-methyl-1,4-thin two, three, 7_ dimethyl -1,6_ sheep two thin and 3, 7_ dimethyl -I, 7_ sheep two thin. 单环脂环族二稀的实例包括、但不限于1,4_环己二烯,1,5_环辛二烯和1,7-环十二碳二烯。 Examples of single ring alicyclic di dilute include, but are not limited to, cyclohexadiene 1,4_, 1,5_-cyclooctadiene and 1,7-cyclododecadiene-diene. 多环脂环族稠环和桥连环状二烯的实例包括、但不限于四氢茚;降冰片二烯;甲基四氢茚;二环戊二烯, 双环-(2. 2. I)-庚-2, 5- 二烯;和烯基-、烧叉基-、环烯基_和环烧叉基降冰片烯[包括例如5-亚甲基-2-降冰片烯,5-乙叉基-2-降冰片烯,5-丙烯基-2-降冰片烯,5-异丙叉基_2_降冰片稀,5_(4_环戍稀基)-2_降冰片稀,5_环己叉基-2-降冰片稀和5_乙稀基-2-降冰片烯]。 Multi-ring alicyclic fused and bridged ring cyclic dienes examples include, but are not limited to tetrahydroindene; norbornadiene; methyl-tetrahydroindene; dicyclopentadiene, bicyclo - (. 2 2. I) - hept-2,5-diene; and alkenyl -, firing fork group -, cycloalkenyl and cycloalkyl _ burn fork norbornene [including, for example 5-methylene-2-norbornene, 5-acetate Fork-2-norbornene, 5-propenyl-2-norbornene, 5-isopropylidene norbornene _2_ dilute, 5_ (4_ ring Shu dilute yl) -2_ norbornyl dilute, 5 _ cyclohexylidene-2-norbornene diluted and 5_ ethylene-2-norbornene]. 环烯基取代的烯烃的实例包括、但不限于乙烯基环己烯,烯丙基环己烯, 乙烯基环辛烯,4-乙烯基环己烯,烯丙基环癸烯,乙烯基环十二碳烯和四环(A-ll,12)-5, 8-十二碳烯。 Examples of cycloalkenyl-substituted olefins include, but are not limited to vinyl cyclohexene, allyl cyclohexene, vinyl cyclooctene, 4-vinyl cyclohexene, allyl cyclodecene, vinyl ring dodecene and tetracyclo (A-ll, 12) -5, 8- dodecene.

[0128] F.串联方法 [0128] F. tandem method

[0129] 如上所述,多级聚合的一种形式是串联方法(例如,串联反应器方法)。 [0129] As described above, one form of multistage polymerization is a series process (e.g., series reactor process). 优选地,在包括顺序聚合的串联方法中,两个(或多个)反应器通过导管(例如管道)彼此“串联”连接,使得从一个反应器排出的材料(例如流出物)进给到另一个反应器,虽然在该两个反应器之间可以安装阀门或其它组件。 Preferably, the method comprises the series of sequential polymerization in two (or more) of the reactor via conduit (e.g. pipe) with each other "series" connection, such that one reactor is discharged from a material (e.g., effluent) is fed to another a reactor, although the valve can be installed between the two reactors or other components. 有时,该两个(或多个)串联反应器被称为单一“串联反应器”。 Sometimes, the two (or more) series reactors are referred to as a single "reactors in series."

[0130] 优选地,所述串联方法是包括将物料连续引入通过反应器的顺序设备组(串联反应器)的连续溶液聚合方法。 [0130] Preferably, the tandem method is continuously introduced into the material comprising a continuous solution polymerization process (reactors in series) is passed through the reactor sequential device group. 该反应器设备组包括至少两个串联(顺序)连接的聚合反应器,其中第一聚合物和第二聚合物各自在单独的反应器内制备。 The reactor device group comprising at least two polymerization reactors in series (sequentially) connection, wherein the first and second polymers are each prepared in a separate reactor. (第一和第二聚合物还可以称之为第一和第二聚合物“组分”。)第一反应器可以设计成在溶液中聚合第一聚合物。 (First and second polymers can also call the first and second polymer "component.") The first polymerization reactor can be designed in the first polymer solution. 将来自第一反应器的反应器流出物然后全部或部分引入到第二反应器,该第二反应器被设计成聚合第二聚合物。 The reactor effluent from the first reactor is then introduced into all or part of the second reactor, the second reactor is designed to polymerization of the second polymer. 这种配置确保了在第二反应器中制备的第二聚合物在第一聚合物的存在下制备,该第一聚合物在第一反应器内制备。 This arrangement ensures that the second polymer is prepared in the second reactor in the presence of the first polymer was prepared, the first polymer prepared in the first reactor. 当然,应该认识到,因为在第二反应器内聚合的反应剂包括单体和完全形成的第一聚合物,所以来自第二反应器(或在第二反应器中)的聚合产物(它是或包括“反应器共混物组合物”)可以不仅包括第二聚合物,而且包括一种或多种聚合物物质,该一种或多种聚合物物质包含或引入了“第一聚合物”或“第二聚合物”,但不纯粹落入根据本文的任何定义的“第一聚合物”或“第二聚合物”类别。 Of course, it should be appreciated that in the second reactor as the polymerization of monomer reactants comprising a first polymer and a fully formed, so from the second reactor (or in a second reactor) of the polymerization product (which is the or include "reactor blend composition") may include not only the second polymer, and comprises one or more polymeric species, the substance comprises one or more polymers or the introduction of the "first polymer" or the "second polymer", but does not fall under any solely defined herein "first polymer" or "second polymer" category. 然而, 要指出的是,该“第二聚合物”不过可以使用许多公认的分析方法和技术中的任何一种来独立地鉴定,不论是直接测量还是计算。 However, it is to be noted that the "second polymer", but can use many recognized analytical methods and techniques to identify any one of independently, either direct measurement or calculation.

[0131] 一般,除非另有规定,在每一反应器中的聚合可以通过本领域已知的任何聚合程序来进行,包括视需要或所希望根据情况和所使用的设备进行调节。 [0131] In general, unless otherwise specified, the polymerization in each reactor may be any known in the art to carry out the polymerization procedure, including, where necessary or desired to adjust according to the situation and the equipment used. 然而,优选的是,聚合在反应剂和产物完全溶于溶液中的条件下进行。 However, it is preferred that the polymerization reactants and products completely in solution under conditions. 这些聚合条件可以通过在适合的反应条件(包括温度和压力)下使用足量的两种聚合物组分所共有的溶剂作为聚合介质,使得聚合物混合物的所有组分保持在溶液中。 These polymerization conditions by using a sufficient amount of two polymer components common solvent under suitable reaction conditions (including temperature and pressure) as the polymerization medium, so that all the components of the polymer mixture is maintained in solution.

[0132] CFSTR。 [0132] CFSTR. 一种特别优选的配置是串联连接的至少两个连续流搅拌釜反应器(CFSTR) 设备组。 A particularly preferred configuration is a series of at least two continuous flow stirred tank reactors connected (CFSTR) device group. 这种配置的物理结构和构造本身可以是常规的。 This configuration of the physical structure and the structure itself may be conventional. 然而,每一反应器应该能够独立进给单体、溶剂、催化剂等。 However, each reactor should be capable of independently feeding monomer, solvent, catalyst and the like. 另外,为了合格用作CFSTR而提供的搅拌应足够强烈,以避免在反应器内出现未混合区。 Further, in order to provide qualified used CFSTR stirring should be sufficiently strong to prevent the mixing zone does not occur in the reactor. CSFTR的这种设计考虑是本领域技术人员所公知的。 Such design considerations CSFTR the skilled artisan known. 理想的是,除去起催化剂毒物作用的极性化合物。 Ideally, removal of catalyst poisons from the effect of polar compounds. 所有溶剂和单体进料可以用分子筛、氧化铝床或本领域已知的其它吸收剂纯化。 All solvent and monomer feeds can be molecular sieves, alumina beds, or other absorbents known in the art and purified. 在优选的实施方案中,在聚合过程中从每一反应器中除热。 In a preferred embodiment, during the polymerization heat removal from each reactor. 除热可以通过本领域公知的方法来完成,例如自动制冷、进料预冷却(绝热反应器)、冷却盘管或这些技术的各种组合。 Heat removal may be by methods known in the art to accomplish such automatic refrigeration, feed various combinations of pre-cooled (adiabatic reactors), cooling coils or these technologies. 用预冷却进料的绝热反应器是优选的。 The pre-cooled feed using an adiabatic reactor is preferable.

[0133] 聚合温度。 [0133] The polymerization temperature. 这里形成反应器共混物的方法的一个优选特征是进行不同反应(聚合)的不同温度。 A preferred feature of the process reactor blends formed here is different in different reaction temperature (polymerization) of. 温度可以采用本领域技术人员已知的设备和程序,用一个或几个温度探头在反应器内的一个或几个部位测定。 Temperature may be employed are known to those skilled in the equipment and procedures, one or more temperature measuring probe in one or more parts of the reactor. 在本文所述的某些实施方案中,第二聚合温度(例如第二反应器内的温度)高于第一聚合温度(例如第一反应器内的温度)。 In certain embodiments described herein, the second polymerization temperature (e.g., temperature of the second reactor) is higher than the first polymerization temperature (e.g., temperature within the first reactor). 这些温度在上文中规定,作为具体实施方案的一部分。 These temperatures are specified in the above, as part of a specific embodiment.

[0134] 反应压力。 [0134] The reaction pressure. 每一反应器内的压力应该足以在选择的反应器温度下将反应器内容物保持在溶液中。 The pressure in each reactor should be sufficient under the selected reaction temperature the reactor contents were maintained in solution. 优选地,将第一聚合(例如在第一反应器内进行的聚合)和第二聚合(例如在第二反应器内进行的聚合)“保持”在特定水平或范围内,意味着聚合压力在至少一种特定第一聚合物和/或反应器共混物的生产过程中保持充分恒定,但应该理解的是,在连续聚合周期中,可以定期调节,例如在起动、等级变化或维修期间。 Preferably, the first polymerization (e.g., polymerization in the first reactor) and the second polymerization (e.g., within the second polymerization reactor) "maintained" in a particular level or range, meaning that the polymerization pressure at least one specific first polymer and / or reactor blends of the production process to maintain substantially constant, it is to be understood that in the continuous polymerization cycles may be periodic adjustments, e.g., in the starting, the level variation or during maintenance. 虽然在某些情况下可以采用其它压力或压力范围,优选的是,第一聚合在2100kPa或1750kPa或HOOkPa或1050kPa 或700kPa 的任何下限到14,700kPa 或13,300kPa 或12,600kPa 或11,900kPa 或11,200kPa 的任何上限的压力下进行。 Although in some cases possible to use other pressure or pressure range, preferably, the first polymerization or 1750kPa at 2100kPa or HOOkPa or 1050kPa or 700kPa of any lower limit to 14,700kPa or 13,300kPa or 12,600kPa or 11,900kPa conducted under the pressure of any upper or 11,200kPa of. 优选的是,第二聚合(在某些实施方案中,设定在与第一聚合相同的水平下,或在相同的规定范围内)在2100kPa或1750kPa或HOOkPa或1050kPa或700kPa 的任何下限到14,700kPa 或13,300kPa 或12,600kPa 或11,900kPa 或11,200kPa 的任何上限的压力下进行。 Preferably, the second polymerization (in some embodiments, set at the same level under the first polymerization, or within the same specified range) or at any lower limit 2100kPa or HOOkPa or 1750kPa to 1050kPa or 700kPa 14 , under the pressure of 700kPa or 13,300kPa any upper or 12,600kPa or 11,900kPa or 11,200kPa be.

[0135] 停留时间。 [0135] The residence time. 本文所使用的术语“停留时间”是指特定聚合用的反应剂与催化剂一起在特定反应器内存在的平均时间。 As used herein, the term "residence time" refers to the specific reactants used in the polymerization catalyst together with the average time in the memory in a specific reactor. 这通过将反应器体积除以总体积流量来计算。 This is calculated by dividing the total volume of the reactor volume flow. 每一反应器内的停留时间取决于许多因素,包括反应器的尺寸。 The residence time in each reactor depends on many factors, including the size of the reactor. 每一反应器的停留时间的实例是1-180分钟;或更窄,5-30分钟。 Examples of each reactor the residence time is 1-180 minutes; or narrower, 5-30 minutes. 虽然在某些情况下可以采用其它停留时间或停留时间范围,但优选的是,第一停留时间为下限4分钟或5分钟或6分钟或7分钟或8分钟或9分钟到上限100分钟或90分钟或80分钟或70分钟或60分钟或50分钟。 Although in some cases may take other dwell time or residence time range, it is preferred that the first residence time is the lower limit for 5 minutes or 4 minutes or 6 minutes, or 7 minutes, or 8 minutes, or 9 minutes or 90 to an upper limit 100 minutes minutes or 80 minutes or 70 minutes or 60 minutes or 50 minutes. 优选的是,第二停留时间为下限4分钟或5分钟或6分钟或7分钟或8分钟或9分钟到上限30分钟或25分钟或20分钟或15分钟或12分钟或10分钟。 Preferably, the residence time of the second lower limit 4 minutes or 5 minutes, or 6 minutes, or 7 minutes, or 8 minutes, or 9 minutes to an upper limit 30 minutes or 25 minutes or 20 minutes or 15 minutes or 12 minutes or 10 minutes.

[0136] 单体。 [0136] monomer. 在两种聚合中使用的单体在本文的其它地方阐述,并且根据要形成的特定聚合物的所需组成来确定。 The monomers used in the polymerization of two elsewhere set forth herein, and in accordance with the desired composition of the particular polymer to be formed is determined. 单体例如可以包括乙烯(C2)和α-烯烃,包括高级α-烯烃(C4-C20)以及多烯烃,例如非共轭二烯类。 May include monomers such as ethylene (C2) and α- olefins, including advanced α- olefins (C4-C20), and polyenes, e.g., non-conjugated dienes. 一种特别有效的α-烯烃是丙烯,但如本文其它地方所述可以使用其它高级α-烯烃。 A particularly effective α- olefin is propylene, but as described elsewhere herein may be used other higher α- olefins.

[0137] 溶剂。 [0137] solvent. 如上所述,优选的方法包括溶液聚合,这需要溶剂。 As described above, preferred methods include solution polymerization, which requires a solvent. 可以在本文所述的第一和第二聚合中使用(例如引入到第一和第二反应器中)的溶剂的实例是烃类,例如脂族、月旨环族和芳族烃类。 Examples can be used in the first and second polymerization described herein (e.g., introduced into the first and second reactors) solvents are hydrocarbons, such as aliphatic, cycloaliphatic and month purpose aromatic hydrocarbons. 优选的溶剂是C12或更低级直链或支链饱和烃类,以及C5-C9饱和脂环族或芳族烃类。 Preferred solvents are C12 or lower straight-chain or branched-chain saturated hydrocarbons, and C5-C9 saturated alicyclic or aromatic hydrocarbons. 这种溶剂的实例是己烷,丁烷,戊烷,庚烷,环戊烷,环己烷,环庚烷,甲基环戊烧,甲基环己烧,异辛烧,苯,甲苯和二甲苯。 Examples of such solvents are hexane, butane, pentane, heptane, cyclopentane, cyclohexane, cycloheptane, methyl cyclopentyl burning, burn-methyl-cyclohexyl, isooctyl burning, benzene, toluene and xylene. 己烷是优选的。 Hexane is preferred. 优选地,在两种聚合中,例如在两个反应器中使用相同的溶剂,并且如下所述对溶剂进行再循环。 Preferably, in both the polymerization, for example using the same solvent in the two reactors, and the solvent was recycled as described below.

[0138] 流出料流。 [0138] effluent streams. 如本文其它地方所述的,在连续方法的操作过程中,每一反应器进行聚合,产生了流出料流。 As described elsewhere herein, during operation of a continuous process, each reactor polymerization was carried out to produce the effluent stream. 该流出料流可以由聚合产生的聚合物以及催化剂和任何未反应单体组成。 The effluent stream may be a polymer and a catalyst and any unreacted monomer is produced by polymerization of the composition. 每一流出料流的特征可以在于具有特定聚合物浓度。 Each effluent stream may be characterized by having a particular polymer concentration. 例如,每一反应器流出物中的聚合物浓度可以保持在1_30被%或3-20被%的范围内,以特定流出物的总重量为基准计。 For example, each reactor effluent polymer concentration can be maintained at 1_30% or 3-20% of the range is based on the total weight of the particular effluent as a reference count. 如在包括串联反应器配置的以下实施例中所举例的,第一流出物的聚合物浓度优选仅表示第一聚合物(这例如可以通过将所形成的聚合物与非聚合物材料分离来测定)。 As comprises a series, a first reactor effluent configuration of an exemplified embodiment of the following first polymer is preferably a polymer concentration (which may be for example a polymer with non-polymeric material by separating the formed will be determined only that ). 相反,第二流出物的聚合物浓度表示在既定时间下,例如在特定停留时间后或一些其它设定时间点测定的存在于第二反应器中的所有聚合物材料。 In contrast, the polymer concentration of the second effluent represents at predetermined time, e.g., after a certain residence time or some other set time measurement points present in the second reactor, all of the polymeric material. 该聚合物材料至少包括所述反应器共混物, 该反应器共混物可以包括一定量的第一聚合物与至少一种其它聚合物,例如属于第一聚合物与在第二聚合过程中存在的其它反应剂的反应产物、或其它反应剂本身例如单体的反应产物、或这两种形式的反应产物的第二聚合物。 The polymeric material comprises a blend of at least the reactor, the reactor blend can comprise an amount of a first polymer with at least one other polymer, such as polymers belonging to the first and in the second polymerization process the presence of the reaction product of other reactants, reagents, or other reaction product per se, for example monomers, or both forms of the second polymer reaction product. 虽然在某些情况下可以使用其它聚合物浓度或浓度范围,但优选的是,第一流出物聚合物浓度范围是Iwt %或2wt %或3wt %或4wt % 或5wt%或6wt%中的任何下限到30wt%或25wt%或20wt%或16wt%或12wt%或8wt% 中的任何上限。 While other polymers may be used in concentrations or concentration ranges in some cases, it is preferred that the first effluent polymer concentration range is in any Iwt% or 2wt% or 3wt%, or 5wt% or 4wt% or 6wt% of The lower limit to the 30wt% or 25wt% or 20wt% or 16wt% or 12wt% or 8wt% of any upper limit. 优选的是,第二流出物聚合物浓度范围是3wt %或4wt %或5wt %或6wt % 或7wt%或8wt%中的任何下限到30wt%或25wt%或20wt%或18wt%或16wt%或14wt% 中的任何上限。 Preferably, the second effluent polymer concentration is in the range of 3wt% or 5wt% or 4wt% or 6wt%, or 7wt% or 8wt% of any lower limit to 30wt% or 25wt% or 20wt% or 18wt% or 16wt% or 14wt% of the upper limit of any.

[0139] 聚合物回收。 [0139] polymer recovery. 可以通过将聚合物与流出物的其它成分分离而从任何一种流出物(例如第一反应器的流出物或第二反应器的流出物)中回收聚合物。 Can be prepared by the polymer and other components of the effluent recovered polymer is separated from the effluent of any kind (e.g., effluent from the first reactor or second reactor effluent). 可以使用常规分离方式。 You can use conventional separation methods. 例如,可以通过用非溶剂例如异丙醇、丙酮或正丁醇凝结而从流出物中回收聚合物,或者可以通过用热或蒸汽汽提溶剂或其它介质来回收聚合物。 For example, by such as isopropyl alcohol, acetone or n-butanol is recovered by condensation from the effluent in a non-solvent polymer, or may be by heat or steam stripping the solvent or other medium to recover the polymer. 可以将一种或多种常规添加剂例如抗氧化剂在回收工序中引入到聚合物中。 One or more conventional additives such as antioxidants incorporated into the polymer in the recovery step. 可能的抗氧化剂包括苯基-β_萘胺;二叔丁基氢醌,磷酸三苯酯,庚基化二苯基胺,2,2' -亚甲基-双(4-甲基-6-叔丁基)苯酚和2,2,4-三甲基-6-苯基-1,2- ニ氢喹啉。 Possible antioxidants include phenyl -β_ naphthylamine; di-tert-butylhydroquinone, triphenyl phosphate, heptyl diphenylamine, 2,2 '- methylene - bis (4-methyl-6-t butyl) phenol and 2,2,4-trimethyl-6-phenyl-1,2-dihydroquinoline-ni. 还可考虑其它回收方法例如通过使用下临界溶解温度(LCST),随后脱挥发分。 May also consider other recovery methods, such as by using the lower critical solution temperature (LCST), followed by devolatilization. 在串联和并联配置中,当反应器流出物已经被合并时,催化剂可能被钝化。 In series and parallel configuration, when the reactor effluent has been merged, the catalyst may be passivated. 钝化应该用来降低或消除在聚合物回收方法下游的进一歩失控的聚合。 Passivation should be used to reduce or eliminate the polymer recovery process downstream into a Bu runaway polymerization. 钝化可以通过与适合的极性物质例如水混合来进行,在再循环后的其残留效应可以用适合的分子筛或清除体系来抵消。 Passivation may be carried out by, for example water are mixed with a suitable polar substance, after which the residual effect may be recycled with a suitable molecular sieves or scavenging system to offset.

[0140] 聚合速率。 [0140] The polymerization rate. 对于使用进料冷却作为除热方法的绝热反应器,总聚合速率通过第二反应器的温度和进料温度之间的差来決定。 For feed cooling heat removal process as an adiabatic reactor, the total polymerization rate by the temperature difference between the second reactor and between the feed temperature is determined. 因为制冷受能够将进料冷却到大约_40°C的市购制冷装置的可获得性的限制,所以用可以运行第二反应器并且还产生具有期望性能例如分子量和长链支化的聚合物的最高温度来提高经济效应。 Since cooling by the feed can be cooled to a limited availability of about _40 ° C commercially available refrigeration devices, so you can run with a second reactor and also generates such as molecular weight and long chain branching of the polymer having the desired properties The maximum temperature to improve economic effects. 因此,希望第二反应器在比第一反应器明显更高的温度下运行。 It is therefore desirable to run the second reactor at significantly higher than the first reactor temperature. 影响聚合速率(还称为生产速率)的其它因素是溶剂类型和比率、单体类型和聚合物组成,因为聚合热随单体的选择而改变。 Other factors affecting the polymerization rate (also called production rate) are solvent type and rate, monomer type and polymer composition since the heat of polymerization varies with the choice of monomer.

[0141] 分子量。 [0141] molecular weight. 根据反应器共混物的所需性能,在某些情况下可以调节反应器共混物以及単独的第一聚合物和第二聚合物(聚合物组分)的分子量特性(例如Mw、Mn等)。 According to the desired properties of the reactor blends, in some cases can be adjusted reactor blends and radiolabeling separate first polymer and the second polymer (polymer components) The molecular weight characteristics (e.g., Mw, Mn, etc. ). 本文其它地方描述了这些分子量特性。 Described elsewhere herein these molecular features. 例如,每ー种聚合物的分子量特性可以通过选择反应器温度、单体浓度和通过任选添加链转移剂例如氢来决定。 For example, the molecular weight characteristics of each ー polymers can be obtained by selecting the reaction temperature, monomer concentration, and is determined by e.g., hydrogen, optionally adding a chain transfer agent. 还有,分子量一般可以通过提高反应温度来降低,以及通过增加单体浓度来提高。 Further, the molecular weight can generally be reduced by increasing the reaction temperature, and by increasing the monomer concentration to increase.

[0142] G.并联方法 [0142] G. parallel method

[0143] 多级聚合的另ー种形式是并联方法(并联聚合)。 [0143] Another ー multistage polymerization forms a parallel method (parallel polymerization). 在并联方法的一个实例中,两个反应器以使得単体、催化剂和溶剂独立进给到每ー个反应器来配置。 In one example of a parallel process, two reactors so that the radiolabeling body, catalyst and solvent to independently feed each ー reactor configured. 注意,术语“第一”和“第二”不暗示任何特定次序或顺序,但该术语为了方便而使用,使得本文提到的词语“第一,,(聚合物、聚合、催化剂、反应器等)可以同样适用于串联和并联方法,除非另有規定。实际上,第一和第二聚合优选在并联方法中同时进行。第一聚合的输入物(进料)(优选在第一反应器中进行)可以与以上在串联方法的第一聚合中所述的进料相同,例如包括単体(丙烯与こ烯和α-烯烃单体中的ー种或两种)、催化剂混合物和溶剤。输出物或流出物(例如聚合产物)也类似于串联方法中的第一聚合的流出物,例如第一聚合物、催化剂、溶剂和未反应单体,例如丙烯单体。优选地,第一和第二聚合均使用丙烯和こ烯作为単体,但比例不同。 Note that the terms "first" and "second" do not imply any particular order or sequence, but the term is used for convenience, referred to herein so that the words "first ,, (polymer, polymerization, catalyst, reactor, etc. ) can be equally applicable to both series and parallel method, unless otherwise specified. In fact, the first and second polymerizations are preferably performed simultaneously in a parallel process. The first polymeric material input (feed) (preferably in the first reactor be) described above may be connected in series in a first polymerization process in the same feed, for example including radiolabeling body (ko-ene with propylene and α- olefin monomer ー species or both), catalyst mixture and solvent Ji output thereof or effluent (e.g., polymerization product) also resembles the effluent of the series in a first method of polymerization, e.g., first polymer, catalyst, solvent and unreacted monomers, e.g., propylene monomer. Preferably, the first and second use the polymerization of propylene and ko ene as radiolabeling body, but in different proportions.

[0144] 第二聚合的输入物(进料)(优选在第二反应器中进行)与以上在串联方法的第ニ聚合中所述的进料相同,但具有至少ー个显著差别,就是进料不包括任何第一聚合物。 [0144] The second polymeric material input (feed) (preferably carried out in the second reactor) in the first writing is the same as the above method of polymerization in series in the feed, but having at least ー a significant difference, that is, into material does not include any first polymer. 另ー个区别是,优选将ニ烯加入到第二聚合区,例如反应器中。 Another ー difference is preferably the Ni-ene was added to the second polymerization zone, e.g., reactor. 第二聚合的进料例如可以包括単体(こ烯和α-烯烃)、催化剂混合物和溶剤。 The second polymeric may include, for example, radiolabeling feed body (ko-ene and α- olefins), catalyst mixture and solvent Ji. 输出物或流出物(例如聚合产物)是第二聚合物、催化剂、溶剂和未反应单体,例如こ烯单体。 Output or effluent (e.g., polymerization product) is second polymer, catalyst, solvent and unreacted monomers, e.g. ko alkenyl monomers.

[0145] 对于特定装置设计,装置生产率可以受再循环系统所提供的瓶颈的限制。 [0145] For a particular plant design, the device productivity can limit recirculation system provided by the bottleneck. 例如,对于同等量的聚合物和同样的聚合分割比,并联反应器操作通常需要比串联反应器操作再循环更大量的溶剤。 For example, polymerization of the polymer and the same amount of the same division ratio, generally parallel reactors operating in series reactor operation requires more than a greater amount of recycle solvent Ji. 还有,并联反应器操作比串联反应器操作允许更宽的停留时间和反应器条件的变化。 Also, allowing a wider residence time and reactor conditions change than the parallel reactor operating in series reactor operation. 在串联反应器操作中,通过将附加溶剂加入到第二反应器中,达到溶剂再循环的容量限制,第二反应器中的停留时间可以低于第一反应器中的停留时间。 In series reactor operation, by the additional solvent is added to the second reactor, to achieve the capacity limit of the solvent is recycled, the second reactor residence time may be lower than in the first reactor residence time. 用并联反应器,可以独立选择每一反应器的停留时间,只要总溶剂流量不超过再循环容量。 Shunt reactors, each reactor can be selected independently of the residence time, as long as the total solvent flow does not exceed the recycle capacity.

[0146] 使用不同聚合温度也是并联方法的ー个重要特征,以上关于串联反应器的论述同样适合于并联系统。 [0146] using different polymerization temperatures is also ー important feature, the above discussion of reactors in series is also suitable for parallel system parallel method. 还有,以上关于在串联反应器方法中使用的反应压カ的论述以同样方式适用于并联方法。 Also, the above discussion of reaction pressure of grades used in the reactors in series methods apply in the same manner parallel methods. 此外,串联反应器的停留时间的所有论述还适用于并联反应器。 In addition, all discussed in a series reactor residence time also applies to the parallel reactor.

[0147] 流出料流。 [0147] effluent stream. 如本文其它地方所述的,在连续方法的操作过程中,每一反应器进行聚合,产生了流出料流。 As described elsewhere herein, during operation of a continuous process, each reactor polymerization was carried out to produce the effluent stream. 该流出料流可以由聚合产生的聚合物以及催化剂和任何未反应单体组成。 The effluent stream may be a polymer and a catalyst and any unreacted monomer is produced by polymerization of the composition. 每ー流出料流的特征可以在于具有特定聚合物浓度。 Each ー effluent stream may be characterized by having a particular polymer concentration. 例如,每一反应器流出物中的聚合物浓度可以保持在l_30wt%或3_20wt%的范围内,以特定流出物的总重量为基准计。 For example, each reactor effluent polymer concentration can be maintained in the range l_30wt% or 3_20wt% based on the total weight of the particular effluent as a reference count. 在并联反应器中,可以有三种流出料流,即,每一反应器有ー种,还有合并的流出料流。 In parallel reactors, there are three effluent streams, i.e., each reactor has ー species, as well as the combined effluent stream. 两个反应器的每ー个的流出物的聚合物浓度优选表示仅仅在该反应器中制备的聚合物(这例如可以通过将所形成的聚合物与非聚合物材料分离来測定)。 Each ー preferably a polymer concentration of the effluent of the two reactors, said polymer prepared in only the reactor (which for example may be a polymer with non-polymeric material by separating the formed determined). 合并的流出物的聚合物浓度表示在既定时间下,例如在特定停留时间后或ー些其它设定时间点測定的存在于该两个反应器中的所有聚合物材料。 The combined polymer concentration of the effluent at a given time represents, for example, after a particular residence time or some other set point ー time measurement in the presence of all the polymeric materials in the two reactors. 该聚合物材料至少包括所述反应器共混物,该反应器共混物可以包括一定量的第一聚合物与至少ー种其它聚合物,例如第二聚合物,或其它反应剂本身例如単体的反应产物,或两种形式的反应产物。 The polymeric material comprises a blend of at least the reactor, the reactor blend can comprise an amount of a first polymer with at least ー more other polymers, such as the second polymer, or other reactive agent itself e.g. radiolabeling body The reaction product, or the reaction product of two forms. 虽然在某些情况下可以使用其它聚合物浓度或浓度范围,但优选的是,第一流出物聚合物浓度范围是下限IWt%或2wt%或3wt% 或4wt%或5wt%或6wt%到上限30wt%或25wt%或20wt%或16wt%或12wt%或8wt%。 While other polymers may be used in concentrations or concentration ranges in some cases, it is preferred that the first effluent polymer concentration range is a lower limit IWt% or 2wt% or 3wt%, or 5wt% or 4wt% or 6wt% to an upper limit 30wt% or 25wt% or 20wt% or 16wt% or 12wt% or 8wt%. 优选的是,合并流出物聚合物浓度范围是下限3wt%或4wt%或5wt%或6wt%或7wt%或8wt%到上限30wt%或25wt%或20wt%或18wt%或16wt%或14wt%。 Preferably, the combined effluent polymer concentration range is a lower limit of 3wt% or 5wt% or 4wt% or 6wt%, or 7wt% or 8wt% to 30wt% or the upper limit of 20wt% or 25wt% or 18wt% or 16wt% or 14wt%.

[0148] 聚合物回收。 [0148] polymer recovery. 可以通过将聚合物与流出物的其它成分分离而从任何一个反应器的流出物或合并流出物中回收聚合物。 Can be prepared by the polymer and other components of the effluent recovered polymer separated from the effluent or effluent merge any reactor. 可以使用常规分离方式。 You can use conventional separation methods. 例如,可以通过用非溶剂例如异丙醇、丙酮或正丁醇凝结而从流出物中回收聚合物,或者可以通过用热或蒸汽汽提溶剂或其它介质来回收聚合物。 For example, by such as isopropyl alcohol, acetone or n-butanol is recovered by condensation from the effluent in a non-solvent polymer, or may be by heat or steam stripping the solvent or other medium to recover the polymer. 一种或多种常规添加剂例如抗氧化剂可以在回收エ序中引入到聚合物中。 One or more conventional additives such as antioxidants can be incorporated into the polymer in the recovery Eito Preface. 可能的抗氧化剂包括苯基萘胺;ニ叔丁基氢醌,磷酸三苯酯,庚基化ニ苯基胺,2,2'_亚甲基-双(4-甲基-6-叔丁基)苯酚和2,2,4_三甲基-6-苯基-1,2-ニ氢喹啉。 Possible antioxidants include phenyl-naphthylamine; ni t-butylhydroquinone, triphenyl phosphate, heptyl of Ni phenylamine, 2,2'_ methylene - bis (4-methyl-6-tert-butyl) phenol and 2,2,4_ trimethyl-6-phenyl-1,2-dihydroquinoline-ni. 还可考虑其它回收方法例如通过使用LCST,随后脱挥发分。 Other recovery methods can also be considered for example by using LCST, then devolatilization.

[0149] 聚合速率。 [0149] The polymerization rate. 对于使用进料冷却作为除热方法的绝热反应器,并联反应器的总聚合速率通过每一反应器的温度和进料温度之间的差来決定。 For feed cooling heat removal process as an adiabatic reactor, the total polymerization rate of parallel reactors each reactor by differential temperature between the temperature and the feed is determined. 因为制冷受能够将进料冷却到大约-40°C的市购制冷装置的可获得性的限制,所以用可以运行该两个反应器并且还产生具有期望性能例如分子量和长链支化的聚合物的最高温度来提高经济效应。 Since cooling by the feed can be cooled to a limited availability of approximately -40 ° C refrigeration apparatus commercially available, it can be run with the two reactors and also generates such as molecular weight and long chain branching polymerization having the desired properties The maximum temperature material to improve economic effects. 影响聚合速率(还称为生产速率的其它因素是溶剂类型和比率、单体类型和聚合物组成,因为聚合热随单体的选择而改变。 Other factors affecting the polymerization rate (also called production rate of the solvent type and rate, monomer type and polymer composition since the heat of polymerization varies with the choice of monomer.

[0150] 分子量。 [0150] molecular weight. 根据反应器共混物的所需性能,在某些情况下可以调节反应器共混物以及単独的第一聚合物和第二聚合物(聚合物组分)的分子量特性(例如Mw、Mn等)。 According to the desired properties of the reactor blends, in some cases can be adjusted reactor blends and radiolabeling separate first polymer and the second polymer (polymer components) The molecular weight characteristics (e.g., Mw, Mn, etc. ). 本文其它地方描述了这些分子量特性。 Described elsewhere herein these molecular features. 例如,每ー种聚合物的分子量特性可以通过选择反应器温度、单体浓度和通过任选添加链转移剂例如氢来决定。 For example, the molecular weight characteristics of each ー polymers can be obtained by selecting the reaction temperature, monomer concentration, and is determined by e.g., hydrogen, optionally adding a chain transfer agent. 还有,分子量一般可以通过提高反应温度来降低,以及通过增加单体浓度来提高。 Further, the molecular weight can generally be reduced by increasing the reaction temperature, and by increasing the monomer concentration to increase.

[0151] H.组合的串联/并联配置 Series [0151] H. combined / parallel configuration

[0152] 在一个特别有利的实施方案中,提供包括串联反应器配置和并联反应器配置,并且ー种配置或另ー种配置可以根据某些标准来选择的反应器系统配置。 [0152] In a particularly advantageous embodiment, there is provided a reactor configuration comprising a series and a parallel reactor configuration, and other ー ー configurations or configurations can be selected according to certain criteria reactor system configuration. 例如ー种方法涉及使用串联方法来制备具有第一组性能和/或具有相应的第一聚合物和第二聚合物比例(例如既定聚合分割比)的反应器共混物组合物,随后使用并联方法来制备具有第二组性能和/或具有相应的第一聚合物和第二聚合物比例(例如既定聚合分割比)的反应器共混物组合物。 E.g. ー method involves prepared using tandem method having a first set of properties and / or having respective proportions of the first polymer and the second polymer (e.g., a predetermined division ratio of polymerization) of the reactor blend composition, followed by the use of parallel be prepared having a second set of properties and / or reactor blend composition having a respective first and second polymers ratio (e.g., a predetermined division ratio of polymerization) of. 优选但不必要的是,例如具有第一组性能的前一反应器共混物组合物在进行并联方法以生产后一反应器共混物组合物之前从系统中排出。 Preferably, but not necessary, for example, the former reactor blend composition having a first method for carrying out a parallel set of performance after production prior to a reactor blend composition is discharged from the system.

[0153] 在某些实施方案中,反应器共混物组合物如上所述使用串联方法来形成,例如包括在第一聚合区中在溶剂中使第一单体体系和能够为丙烯衍生的单元的序列提供全同立构规整度的第一催化剂体系的进料聚合,以提供第一聚合物和未反应单体的混合物,所述第一聚合物是丙烯聚合物,具有>60wt%由丙烯衍生的単元,包括全同立构排列的丙烯衍生的序列和进ー步具有低于45J/g的熔化热或低于105°C的熔点或同时具备这两种属性以及1-45的门尼粘度(ML(1+4)@125°C );以及在第二聚合区中在溶剂中使第一聚合物混合物、第二単体体系和第二催化剂体系的合并进料聚合,以提供包括第一聚合物和第二聚合物的混合物,所述第二聚合物是こ烯和丙烯衍生的单元的无规共聚物,其中该第ニ聚合物是非结晶的或具有こ烯型结晶度;其中:该总组合物具有25-180的总门尼粘度(ML(l+4)il25°C )和低于50J/g的熔化热。 [0153] In certain embodiments, a reactor blend composition as described above to form a tandem method, for example, in a first polymerization zone in a solvent a first monomer system and capable of propylene derived units comprising feed sequence provides isotactic tacticity first polymerization catalyst system, to provide a mixture of a first polymer and unreacted monomers, said first polymer is a propylene polymer, having> 60wt% of propylene derived radiolabeling element, including isotactic propylene derived sequences and arranged into ー further having less than 45J / g heat of fusion of 105 ° C or lower than the melting point or simultaneously possess both properties and a Mooney 1-45 Viscosity (ML (1 + 4) @ 125 ° C); and in a second polymerization zone combining the first polymer mixture, a second system and the second body radiolabeling feed a polymerization catalyst system in a solvent, to provide the first comprising a mixture of a polymer and a second polymer, said second polymer is a ko-ene and propylene-derived units of the random copolymer, wherein the first polymer is non-crystalline Ni-type crystallinity or alkenyl having ko; wherein: The total composition has a Mooney viscosity 25-180 total (ML (l + 4) il25 ° C) and less than 50J / g heat of fusion.

[0154] 然后,根据预定标准,所述方法可以转变为并联方法(优选在从容器内除去串联法生产的反应器共混物组合物之后),并且该并联方法可以包括在第一聚合区中在溶剂中使第一单体体系和能够为丙烯衍生的单元的序列提供全同立构规整度的第一催化剂体系的进料聚合,以提供第一聚合物和未反应单体的混合物,所述第一聚合物是丙烯聚合物,具有>60wt%由丙烯衍生的単元,包括全同立构排列的丙烯衍生的序列和进ー步具有低于45J/g的熔化热或低于105°C的熔点或同时具备这两种属性以及1-45的门尼粘度(ML(l+4)il25°C );在第二聚合区中在溶剂中使第二单体体系和第二催化剂体系的合并进料聚合,以提供包括第二聚合物的混合物,所述第二聚合物是こ烯和丙烯衍生的単元的无规共聚物,其中该第二聚合物是非结晶的或具有こ烯型结晶度;以及在溶剂的存在下将第一聚合物和第二聚合物合并,其中第一聚合物和第二聚合物的结合物具有25-180的门尼粘度(ML(l+4)il25°C )和低于50J/g的熔化热。 [0154] Then, according to predetermined criteria, the method can be converted to a parallel process (preferably after the container is removed from the production of the series reactor blend composition), and the parallel connection method can include a first polymerization zone a first monomer in a solvent system capable of sequence units of propylene-derived and provided isotactic tacticity feed the first polymerization catalyst system, to provide a mixture of a first polymer and unreacted monomers, the said first polymer is a propylene polymer, having> 60wt% derived from propylene radiolabeling element, including isotactic arrangement of propylene derived sequences and further having a feed ー less than 45J / g heat of fusion of 105 ° C or below melting point or simultaneously possess both properties, and 1-45 Mooney viscosity (ML (l + 4) il25 ° C); in the second polymerization zone of the second monomer system and a second catalyst system in a solvent of The combined feed polymerization, to provide a mixture comprising a second polymer, said second polymer is a ko-ene and propylene derived radiolabeling element of a random copolymer, wherein the second polymer is non-crystalline or crystalline having ethylenically ko degrees; and in the presence of a solvent the first polymer and the second polymer combined, wherein the combination of the first and second polymers having 25-180 of Mooney viscosity (ML (l + 4) il25 ° C) and less than 50J / g heat of fusion.

[0155] 图I示出了多级反应器配置的流程图的ー个实例。 [0155] Figure I shows a flow diagram of a multistage reactor arrangement of ー instances. 该流程图是要说明本文所述的某些方法(尤其是当与上述方法结合来观察时),包括涉及在串联反应器流程和并联反应器流程之间交替以及可变再循环的方法。 The flowchart is to illustrate some of the methods described herein (particularly when viewed in conjunction with the above-described method when), including those involving processes in a series reactor flow and parallel reactor and a variable alternating recycling method. 在该流程图中的每ー个方框(以下标明)表示装置或设备,它们可以是常规的,不需要详细说明。 Each ー a block in the flowchart (hereinafter indicated) represents apparatus or device, which may be conventional, and do not need to be described in detail. 连接方框的每一条线(下述)表示料流或物料流向,应当理解,料流可以通过各种类型的导管例如管道,这些导管可以具有中间设备(未示出),例如、但不限于标准接头、阀门和泵。 Each of the lines connecting the blocks (described below) shows stream or flow of materials, it should be appreciated that various types of stream through a catheter such as pipes, these conduits may have an intermediate device (not shown), such as, but not limited to, standard fittings, valves and pumps. 涉及反应器和其它组件的W02002/34795的内容在此引入供參考,尤其与也存在于本文图I中的组件例如分离器和反应器有关的细节。 Concerning the reactor and the other components of W02002 / 34795 is hereby incorporated by reference, in particular, is also present in this article and in Figure I assembly, for example details of the separator and the reactor.

[0156] 对于本文其它地方所述的方法的至少ー些实施方案,示出了总系统10,它是或包括方框12,即可以进行第一聚合的结构,并且优选是本文其它地方所述的“第一反应器”。 [0156] For the methods described elsewhere herein least ー some embodiments, the overall system 10 is shown, which is or includes box 12, i.e. a first polymeric structure can be, and preferably is described elsewhere herein The "first reactor." 方框14是或包括可以进行第二聚合的结构,并且优选是“第二反应器”。 Box 14 is or includes a second polymeric structure may be, and preferably is "the second reactor." 方框16是可以包括用于接收结构12和14中的一个或两个的输出物(例如流出料流36和/或38)的容器并且还可以包括液-液相分离设备的结构。 16 is a block may include a receiving structure 12 and 14 in one or both output (e.g., effluent stream 36 and / or 38) of the container and may also include liquid - liquid phase separation structure of the device. 方框18包括能够发生脱挥发分的结构,例如“脱挥器”。 Block 18 comprises devolatilization can occur structure, e.g., "devolatilizer." 方框20是接收以及排放単体和溶剂的结构,任选包括用于一起或単独分离单体和溶剂的分馏器或一些其它装置。 Block 20 is received and discharge radiolabeling body structure and a solvent, optionally comprising means for radiolabeling alone or together separate monomer and solvent fractionation or some other means.

[0157] 图I中的聚合可以作为串联方法(即顺序聚合)或作为并联方法(例如平行聚合)来实施。 [0157] Figure I is connected in series can be used as the polymerization method (i.e., sequentially polymerized) or as a parallel process (e.g., parallel polymerization) to implement. 參见图1,第一催化剂可以经由料流23引入到第一聚合区12 (例如反应器),通常作为本文其它地方所述的催化剂混合物的一部分。 Referring to Figure 1, a first portion of the catalyst stream 23 can be introduced into the first polymerization zone 12 (e.g., reactor), as generally described elsewhere herein the catalyst mixture via the feed. 単体可以经由料流26引入到聚合区12。 Radiolabeling body via stream 26 can be introduced into the polymerization zone 12. 新鲜单体可以经由料流28引入。 Fresh monomer can be introduced via feed stream 28. 第一聚合物(例如丙烯聚合物)在聚合区12中生产。 First polymer (e.g., propylene polymer) 12 produced in the polymerization zone. 当采用串联配置时,丙烯流出物(包括丙烯聚合物)经由料流34引入到第二聚合区14,其中进行第二聚合以生产第二聚合物(例如こ烯聚合物)。 When in-line configuration, the propylene effluent (including the propylene polymer) via stream 34 is introduced into the second polymerization zone 14, wherein the second polymerized to produce a second polymer (e.g. ko olefin polymer). 将经由料流36离开第二聚合的流出物(包括丙烯聚合物和こ烯聚合物)引入到第一分离器16中,在其中进行分离处理,例如液-液相分离,从而将富含聚合物的组分与非聚合物组分(即,基本上没有聚合物)分离。 The feed stream 36 through the effluent leaving the second polymerization (including the propylene polymer and olefin polymer ko) introduced into the first separator 16, in which the separation treatment, such as a liquid - liquid phase separation, thereby enriched polymerization components and non-polymeric components thereof (i.e., substantially no polymer) separation. 该非聚合物组分包括溶剂、未反应单体和催化剂。 The non-polymer component includes solvent, unreacted monomers and catalyst. 富含聚合物的组分优选主要包括本文所述的聚合物组合物,该聚合物组合物可以被描述为含有丙烯聚合物和こ烯聚合物的反应器共混物。 The polymer-rich component preferably includes primarily the polymer composition described herein, the polymer composition can be described as a reactor blend comprising a propylene polymer and olefin polymer of ko. 然而,该富含聚合物的组分还包括没有成功地在液-液分离器中脱除的诸如未反应单体(例如丙烯,こ烯和ニ烯)之类的材料。 However, the polymer-rich component further comprises not succeeded in liquid - such as unreacted monomers (e.g., propylene, and ni ko alkenyl ene) or the like material in the removed liquid separator. 因此,该富含聚合物的组分经由料流40进给到第二分离器,例如脱挥器18,其排出蒸气料流48和液体料流46,该液体料流46比脱挥发分之前的料流40具有更高浓度的聚合物。 Thus, the polymer-rich component fed via stream 40 to a second separator, e.g., devolatilizer 18, which is discharged vapor stream 48 and liquid stream 46, the liquid stream 46 than before devolatilization The stream 40 having a higher concentration of polymer. 料流40可以进ー步适当加工,以回收无溶剂产物。 Stream 40 can enter the appropriate processing ー steps to recover the solvent-free product. 将包括未反应单体和溶剂的蒸气料流48引入到结构20,单体和溶剂可以经由料流52由此排放,或者经由料流50再引入到再循环料流44中。 Will include unreacted monomer and solvent vapor stream 48 is introduced into the structure 20, whereby the monomer and the solvent may be discharged via stream 52 or reintroduced via stream 50 to the recycle stream 44. 结构20可以包括一个或多个分馏器(未示出),借此可以単独或联合脱除挥发单体,例如こ烯、丙烯和/或ニ烯(如ENB)。 Structure 20 may include one or more fractionators (not shown), whereby the joint can be removed individually or radiolabeling volatile monomers, e.g. ko-ene, propylene, and / or Ni-ene (e.g. ENB). 结构20还可以包括将料流48的蒸气内容物转化为液体的冷凝器。 Structure 20 may also include the contents of the vapor stream 48 is converted to liquid in the condenser. 液体输出料流50可以包括単体和在某些情况下的溶剂,料流50可以引入到该液体再循环料流42中,液体再循环料流42的组成视需要可以根据再引入単体的多少或量来调节,以提供再循环料流44。 Liquid output stream 50 may include a body and radiolabeling solvent in some cases, the stream 50 can be introduced to the liquid recycle stream 42, the liquid composition of the recycle stream 42 can optionally be introduced into the body, or the number of radiolabeling amount adjusted to provide the recycle stream 44. 再循环料流44可以经由料流30重新进给到聚合区14,并且可以将附加単体例如こ烯或ニ烯加入到该输入料流30中。 Recycle stream 44 via stream 30 can be fed back to the polymerization zone 14, and can be attached e.g. ko radiolabeling body alkenyl or Ni added to the ethylenically input stream 30. 再循环料流46可以经由料流26重新进给到聚合区12,并且可以经由料流28将附加单体例如丙烯或こ烯加入到该输入料流26中。 Recycle stream 46 via feed stream 26 can be fed back to the polymerization zone 12, and stream 28 may be additional monomers such as propylene or ko-ene was added to the input 26 via feed stream.

[0158] 如上所述,图I中的方法可以作为平行聚合实施。 [0158] As described above, FIG. I is a polymerization method can be used as a parallel implementation. 此外,图I中的配置可以允许在(上述)串联方法和下面将要论述的平行聚合之间改变或切換。 In addition, the configuration in Figure I may allow (above) and the following series method change or switch between the polymerization will be discussed in parallel. 用平行聚合方法,离开第一聚合区12的流出料流34优选经由旁通料流38绕过第二聚合区14。 Using a parallel polymerization process, the material leaving the first polymerization zone effluent stream 12 of stream 34 is preferably 38 bypasses the second polymerization zone 14 via bypass material. 同时,単体经由输入料流30进给到第二聚合区14,该输入料流30可以包括来自料流32的新鲜单体和/或作为再循环料流44的一部分添加的単体。 Meanwhile, radiolabeling body 30 via the input stream fed to the second polymerization zone 14, the input stream 30 may include fresh monomer feed stream 32 and / or as a portion of the recycle stream 44 is added to the body from the radiolabeling. 根据并联配置,不将第一聚合物(丙烯聚合物)引入到第二聚合区14,而是仅仅经由料流30和24添加単体、溶剂和催化剂。 According to the parallel configuration, no first polymer (propylene polymer) is introduced into the second polymerization zone 14, but only via stream 30 and 24 add radiolabeling body, solvent and catalyst. 第二(こ烯)聚合物在第二聚合区中形成,包括こ烯聚合物、未反应单体、溶剂和催化剂的流出物经由料流36离开第二聚合区,并且与来自第一聚合区的包括第一(丙烯)聚合物的流出物在进入该容器(如图I所示)之前或可供选择地在进入该容器之后(未示出)合井。 Second (ko en) polymer formed in the second polymerization zone, including the olefin polymer ko, effluent unreacted monomer, solvent and catalyst via stream 36 leaving the second polymerization zone, and from the first polymerization zone and comprises a first effluent (propylene) polymer prior to entering the vessel (as shown in I below) or alternatively, after entering the vessel (not shown) Hapjeong. 如上所述,合并的流出物包括含有丙烯聚合物(在第一聚合区中形成)和こ烯聚合物(在第二聚合区中形成)的聚合物组合物。 As described above, the combined effluent comprises containing propylene polymer (formed in the first polymerization zone) and ko olefin polymer (formed in the second polymerization zone) of the polymer composition. 某些实施方案涉及使用相同反应器制备不同弾性体组合物的方法,例如,其中丙烯聚合物与こ烯聚合物的比例是不同的,或其中丙烯聚合物和こ烯聚合物的各自组成是不同的。 Certain embodiments relate to the use of the same reactor to prepare different 弾 a method of composition, e.g., wherein the ratio of the propylene polymer and olefin polymer ko are different, or wherein the propylene polymer and ko is the olefin polymer composition of each different a. 在各个反应器中生产的聚合物的比例可以改变。 Ratio in each reactor of the polymer produced may be changed. 在本发明的ー个方面,提供一种用于将串联方法配置改变(转换)为并联方法配置和/或将并联方法配置转变(转换)为串联方法配置的装置配置,优选根据预定标准进行提供。 In ー aspect of the present invention, there is provided a method for tandem configuration change (conversion) configuration and / or parallel configuration transformation method (converting) device configuration method configured for series parallel method, preferably according to a predetermined criteria to provide . 优选地,至少部分根据以下测量值的ー个或多个(和优选全部)(它们可以在改变或转换之前測定(预先测定))来选择并联方法:(a)预选择的聚合分割比(按第一聚合物的重量除以第一聚合物加第二聚合物的总重量计算);(b)丙烯聚合物(例如第一聚合物)的丙烯含量;和(C)反应器共混物组合物(第一和第二聚合物合井)的こ烯含量。 Preferably, at least one or more of the following part ー measured values (and preferably all) of (which can be determined prior to changing or conversion (measured in advance)) to select the parallel method: Split polymerization (a) a pre-selected ratio (by weight of the first polymer divided by the total weight of the first polymer plus the second polymer calculated); (b) a propylene polymer (e.g., first polymer) propylene content; and (C) of the reactor blend composition object (the first and second polymer Hapjeong) of ko ene content. 尤其优选的实施方案包括用串联方法形成第一弾性体组合物,然后改变单体和溶剂的流向至并联方法以提供具有不同聚合分割比或不同单体(C3或C2)含量的第二弾性体组合物的方法。 Particularly preferred embodiment the method comprises forming a first series of body composition 弾, then change the flow of monomers and solvent to a parallel method to provide a second 弾 of having different division ratio or different polymerizable monomers (C3 or C2) contents The method of compositions. 优选地,在聚合分割比大于或等于预选择的“C3C2系数”的同时采用并联方法。 Preferably, the division ratio of polymerization greater than or equal to a pre-selected "C3C2 coefficient" method, while in parallel. 广义地说,C3C2系数被定义为例如取决于FPP (第一聚合物丙烯含量)或BPE (共混物聚合物こ烯含量)或二者的ー些计算总和的任何值。 Broadly speaking, C3C2 coefficient is defined, for example, depending on any value FPP (first polymer propylene content) or BPE (blend polymer ethylene content ko) or both ー calculate the sum of these. 优选的C3C2系数更准确地被定义为575*(IOO-FPP)°_14*(BPE)81 (方程式I)。 A preferred C3C2 coefficient is more accurately defined as 575 * (IOO-FPP) ° _14 * (BPE) 81 (Formula I). 优选地,该串联方法在当聚合分割比等于或大于C3C2系数时改变为并联方法。 Preferably, the tandem method when the polymerization ratio is equal to or greater than the C3C2 division factor is changed to a parallel method. 改变的准确定时可能不必是严格要求的,通常在聚合分割比改变或在建议改变的目标聚合分割比被确定时才发生。 The exact timing of change may not necessarily be strictly required, usually in the polymerization split ratio changes or changes in the proposed target polymerization ratio is determined when the split occurred. 以下表I示出了与不同FPP和BPE值关联的不同最大聚合分割比,使得在等于或大于所示最大聚合分割比(例如,建议的设定点)的任何聚合分割比时应该实施并联方法(而非串联方法)。 The following Table I shows a different maximum polymerized different FPP and BPE values associated division ratio, so that when the polymerization is equal to or greater than the maximum division ratio shown (e.g., the proposed set point) than any of the polymerization segmentation method should be implemented in parallel (rather than the tandem method).

[0159]表 I [0159] Table I

[0160] [0160]

设定点~I最大聚合分割比|FPP (wt% C3) Ibpe (wt% C2) Maximum set point ~ I polymerization split ratio | FPP (wt% C3) Ibpe (wt% C2)

1 46 95 24 ' 1469524 '

2 36 95 40 ' 2369540 '

3 22 95 64 ' 3229564 '

4 48 88 27 ' 4488827 '

5 38 88 42 ' 5388842 '

6 23 88 64 ' 6238864 '

7 50 80 30 ' 7508030 '

8 40 80 44 ' 8408044 '

9 25 80 65 ' 9258065 '

[0161] 根据本文所述的方法可以生产表2中的以下范围的共混物: [0161] The methods described herein can be produced in the following Table 2, the range of blend:

[0162]表 2 [0162] Table 2

[0163] [0163]

[0164] I.再循环 [0164] I. recirculation

[0165] 本文所述的某些方法的一个特别有利的特征是可变的再循环特征,该再循环特征设想了几个不同的变型(实施方案)。 [0165] A particularly advantageous feature of some of the methods described herein is the variable recycle feature, which contemplates several different recycle feature variations (embodiment). 在该方法的至少ー个变型中,将既定量的来自流出物(例如第一流出物、第二流出物或合并流出物)的非聚合物引入到第一和第二聚合区的任何ー个或两个中,该第一和第二聚合区在至少某些实施方案中用第一和第二反应器表示。 In at least ー a variation of this method, a predetermined amount from the effluent (e.g., a first effluent, second effluent or a combined effluent) is introduced into any non-polymeric ー of first and second polymerization zone or both, the first and the second polymerization zone with at least some embodiments the first and second reactors expressed. 优选地,引入到第一和第二聚合区中的非聚合物的量各自彼此不同。 Preferably, the amount of non-polymer is introduced into a first and a second polymerization zone each different from each other. 取决于第一和第二聚合物的性质,该再循环材料可以是单独或组合的溶剂、催化剂或单体。 Depending on the nature of the first and second polymers, the recycled material may be used alone or in combination of solvents, catalysts or monomer.

[0166] 因此,在一个优选实施方案中,用连续方法来制备包括(上述)第一聚合物和第二聚合物的弾性体组合物。 [0166] Thus, in a preferred embodiment, be prepared by a continuous process comprising (above) the first and second polymers of the composition of Tan. 该方法优选包括使用相同或不同的催化剂体系(以上更详细说明的)以及也使用用于每ー聚合区的优选包括丙烯和こ烯、但比例不同的単体体系,分别在优选为共同(相同)溶剂的溶剂的存在下在第一和第二聚合区(串联或并联)中形成第一聚合物和第二聚合物。 The method preferably includes the use of the same or different catalyst systems (described above in greater detail) and is also used for each ー polymerization zone preferably includes propylene and ko-ene, but the proportion of different radiolabeling body system, respectively, preferably in a common (same) The first polymer and the second polymer formed in the first and the second polymerization zone (series or parallel) in the presence of a solvent solvent. 如上所述,第二聚合温度优选大大高于第一聚合温度,例如高20°C或更多,引入到第二聚合区的第二単体体系优选包括ニ烯,然而,优选在第一聚合区中不添加ニ烯或添加少量的ニ烯(低于2wt%或低于5wt%)。 As described above, the second polymerization temperature is preferably significantly higher than the first polymerization temperature, e.g., high 20 ° C or more, introduced into the second polymerization zone of the second body radiolabeling system preferably comprises Ni-ene, however, preferably in the first polymerization zone no addition of a small amount of Ni or Ni-ene-ene (less than 2wt% or less than 5wt%). 该方法包括在不同聚合区中聚合第一和第二聚合物,以及提供包括第一聚合物、第二聚合物、溶剂和未反应单体的反应器共混物。 The method comprises polymerizing in a polymerization zone in different first and second polymers, and providing a first polymer, second polymer, solvent and unreacted monomer in the reactor blend. 然后,该方法包括从反应器共混物中除去溶剂和未反应单体;将含有溶剂和未反应单体的再循环料流引入到第一聚合区和第二聚合区;以及回收包括第一聚合物和第二聚合物并且具有16-180或本文其它地方所规定的其它水平(或范围)的门尼粘度(ML(1+4)@125°C)的弾性体组合物。 Then, the method comprising the blend from the reactor to remove the solvent and unreacted monomer; the solvent and unreacted monomers containing recycle stream introduced into the first polymerization zone and the second polymerization zone; and recovering comprises a first polymer and the second polymer and having a level of 16-180 or other specified elsewhere herein (or range) of the Mooney viscosity (ML (1 + 4) @ 125 ° C) of 弾 of composition.

[0167] 优选地,所述方法包括将再循环料流分割为第一再循环料流和第二再循环料流,将该第一再循环料流引入到第一聚合区和将该第二再循环料流引入到第二聚合区。 [0167] Preferably, the method comprises the recycle stream into a first recycle stream and second recycle stream, the first recycle stream is introduced into the first polymerization zone and the second recycle stream is introduced into the second polymerization zone. 优选地,选择第二再循环料流中的溶剂的量以足以(i)获得相对于第一聚合温度的所需第二聚合温度;或(ii)获得下文和本文其它地方所述的所需聚合分割比。 Preferably, select the amount of solvent in the second recycle stream sufficient to (i) the first polymerization to obtain a desired temperature with respect to a second polymerization temperature; or (ii) to obtain the desired and described elsewhere described hereinafter polymerization split ratio.

[0168] 如本文其它地方所述,从反应器共混物中除去溶剂和未反应单体可以包括(i)让反应器共混物进行第一分离步骤,以提供第一富含溶剂的部分和第二贫溶剂部分;(ii)让第一贫溶剂部分进行第二分离步骤,以提供第二富含溶剂的部分和第二贫溶剂部分;(iii)将第一富含溶剂的部分和第二富含溶剂的部分合井,以提供合并的再循环料流;(iv)将该合并的再循环料流弓I入到第一聚合区和第二聚合区。 [0168] As described elsewhere herein, the blend from the reactor to remove the solvent and unreacted monomers may include (i) make reactor blends were first separation step to provide a portion of the first solvent-rich and a second portion of the lean solvent; (ii) a poor solvent so that a first part of a second separation step to provide a lean portion and a second portion of the second solvent-rich solvent; (iii) the first solvent-rich portion and Part Hapjeong second rich solvent to provide a combined recycle stream; (iv) the bow combined recycle stream into the first polymerization zone I and a second polymerization zone.

[0169] 此外,从所述混合物中除去溶剂和未反应单体可以包括让该混合物的至少一部分进行液相分离,以提供富含溶剂的部分(通常是贫聚合物部分)和贫溶剂部分(通常是富含聚合物的部分),其中该富含溶剂的部分被引入到第一聚合区和第二聚合区。 [0169] In addition, the solvent was removed from the mixture, and at least a portion of the unreacted monomer may comprise make the mixture liquid separation was conducted to provide a solvent-rich portion (typically a polymer-lean portion) and a portion of lean solvent ( Typically the polymer-rich portion), wherein the solvent-rich portion is introduced into the first polymerization zone and the second polymerization zone.

[0170] 另外,从所述混合物中除去溶剂和未反应单体可以包括让该混合物的至少一部分进行脱挥发分,以提供富含溶剂的部分和贫溶剂部分,其中该富含溶剂的部分被引入到第一聚合区和第二聚合区。 [0170] In addition, the solvent was removed from the mixture, and at least a portion of the unreacted monomer may comprise make the mixture be devolatilized to provide a solvent-rich portion and a portion of the lean solvent, wherein the solvent-rich portion is introduced into the first polymerization zone and the second polymerization zone.

[0171] 某些实施方案涉及使用相同反应器、但反应器之间的再循环分割比不同的制备不同弾性体组合物的方法。 [0171] Certain embodiments relate to the use of the same reactor, but the reactor recycle split between different 弾 different preparation than that of the composition of the method. 这些方法因此可以包括调节至不同反应器的再循环流量。 These methods thus include adjusting to a different reactor recirculation flow. 广义地说,“再循环量”(适用于间歇和连续方法的术语)可以改变。 Broadly speaking, the "recirculation quantity" (for batch and continuous process in terms) can be changed. 在连续方法中,然而,它是根据某些标准提供或确立的“再循环速率”(単位时间引入到反应器内的量)。 In a continuous process, however, it is provided or established based on certain criteria "recirculation rate" (Unit introduced to the amount of time within the reactor). “再循环速率”是一通用术语,包括(a)単位时间进给到两个反应器的再循环物料的总量(“总再循环速率”)或(b)单位时间进给到第一反应器的再循环物料的量(“第一反应器再循环速率”)或(c)单位时间进给到第二反应器的再循环物料的量(“第二反应器再循环速率”)。 "Recirculation rate" is a generic term that includes (a) radiolabeling bit time fed to the two reactors of the total recycle material ("total recirculation rate") or (b) per unit time fed to the first reactor the amount of recycled material ("the first reactor recycle rate") or (c) an amount per unit time fed to the second reactor recycle material (the "second reactor recycle rate"). 在那些情况下,“再循环物料”至少根据溶剂来定义,但还可以是溶剂加未反应单体,或作为还可以包括再循环催化剂的总再循环料流。 In those cases, "recycle material" defined in terms of at least solvent, but may also be solvent plus unreacted monomers, or as total recycled may also include recycled catalyst stream. 在某些实施方案中,可以调节上述再循环速率的任何ー个(lbs或kg/h),用来将第一再循环速率改变为不同再循环速率(例如第二速率或第三速率等)(kg/h)。 In certain embodiments, the above-described recirculation rate can be adjusted to any one ー (lbs or kg / h), is used to change the first recycle rate to a different recycle rate (e.g., a second rate or third rate, etc.) (kg / h). “再循环分割比”被定义为第一反应器再循环速率除以总再循环速率,可以用(如下所述的)百分率来表示。 "Recycling division ratio" is defined as the first reactor recycle rate divided by the total recycling rate, can be used (as described below) expressed as a percentage.

[0172] 在至少ー个实施方案中,至少根据下列测量值(它们可以在改变或转换之前测定(预測定))的ー个或多个(和优选全部)来调节再循环分割比:(a)预选择的聚合分割比(按第一聚合物的重量除以第一聚合物加第二聚合物的总重量计算);(b)第二聚合区(例如第二反应器)的温度;和(c)第一聚合区(第一反应器)的温度。 [0172] In at least ー embodiment, at least according to the following measurements (which can be measured (prediction set) before changing or conversion) of ー or more (and preferably all) to adjust the division ratio of the recycle: (a ) dividing the pre-selected polymerization ratio (by weight of the first polymer divided by the total weight of the first polymer plus the second polymer calculated); (b) the second polymerization zone (e.g., second reactor) temperature; and (c) a first polymerization zone (first reactor) temperature.

[0173] 尤其优选的实施方案包括使用串联方法形成第一弾性体组合物,然后根据上述标准(即C3C2系数)改变进给到并联方法的単体和溶剂的流量,以提供具有不同聚合分割比或不同単体(C3或C2)含量的第二弾性体组合物;进一步改变再循环分割比,优选根据以下标准。 [0173] A particularly preferred embodiment comprises forming a first 弾 of composition tandem method, and then varying the flow rate fed to the parallel method of radiolabeling body and the solvent according to the above criteria (i.e., C3C2 coefficient), to provide a different polymerization division ratio or second 弾 radiolabeling of different body composition (C3 or C2) contents; further altered recirculation division ratio, preferably according to the following criteria. 优选使用常规流量控制阀来控制再循环分割比。 Preferably using a conventional recirculation flow control valve to control the division ratio.

[0174] 当使用任何上述串联方法来制备弾性体组合物吋,“再循环分割比”定义为引入到第一聚合区(例如第一反应器)的总再循环溶剂的百分率,其应该用方程式2表示。 [0174] When prepared 弾 of compositions inch tandem method using any of the above, "recycling division ratio" is defined as the introduction into the first polymerization zone (e.g., first reactor) percentage of total recycling of the solvent, which should be expressed by equation 2 shows. 用方程式2表示的等式应该在该方法的一些时间点存在,即,在弾性体组合物的形成过程中,更优选地,它在整个方法中保持(但在连续方法中允许通常的エ艺波动(高于或低于该量))。 Equation represented by equation 2 should be at some point in time of the process exists, i.e., during the formation of 弾 of body composition, and more preferably, it is maintained throughout the process (but allowing normal Eito art in a continuous process volatility (higher or lower than this amount)). 在方程式2中,PS =聚合分割比;RT2 =第二反应器温度(°C );以及RTl =第一反应器温度(°C )。 In Equation 2, PS = polymerization division ratio; RT2 = second reactor temperature (° C); and RTl = first reactor temperature (° C). 方程式2規定,反应器I的再循环料流百分率等于2. 8*(PS)°_67*(RT2/RTl)in。 Equation 2 provides that the recycle stream is equal to the percentage of reactor I 2. 8 * (PS) ° _67 * (RT2 / RTl) in.

[0175] 当用任何上述并联方法制备弾性体组合物吋,“再循环分割比”,定义为引入到第一聚合区(例如第一反应器)的总再循环溶剂的百分率,其应该用方程式3表示。 [0175] When using any of the above-described method for preparing 弾 of parallel composition inch, "recycle division ratio" is defined as the introduction into the first polymerization zone (e.g., first reactor) percentage of total recycling of the solvent, which should be expressed by equation 3 shows. 与方程式2 —祥,用方程式3表示的等式应该在该方法的一些时间点存在,并且优选在整个方法中保持(允许波动)。 And Equation 2 - Cheung, equations represented by equation 3 should be at some point in time of the process exists, and is preferably maintained throughout the process (allowing fluctuations). 在方程式3中,PS =聚合分割比;RT2 =第二反应器温度(°C );以及RTl =第一反应器温度(°C )。 In Equation 3, PS = polymerization division ratio; RT2 = second reactor temperature (° C); and RTl = first reactor temperature (° C). 方程式3規定,反应器I的再循环料流百分率等于 Equation 3 provides that the recycle stream is equal to the percentage of reactor I

4. 5* (PS)し55* (RT2/RT1)0.67。 4. 5 * (PS) shi 55 * (RT2 / RT1) 0.67.

[0176] 对于串联反应器配置,以下表3示出了与不同PS值(聚合分割比)和RT2/RT1值关联的不同再循环分割比。 [0176] For a series reactor configuration, the following Table 3 shows the different PS values (polymerization division ratio) and various recycle RT2 / RT1 values associated division ratio. 对于并联反应器配置,以下表4示出了与不同PS值和RT2/RT1值关联的不同再循环分割比。 For the parallel reactor configuration, the following Table 4 shows the different PS values and recycle different RT2 / RT1 values associated division ratio. 反映了至少某些实施方案,每ー个组合被确定为ー个设定值。 Reflecting at least some embodiments, each ー ー combinations is determined as a set value.

[0177]表 3 [0177] Table 3

[0178] [0178]

[0181] J.聚合催化剂 [0181] J. polymerization catalyst

[0182] 按最宽范围来说,所述组合物可以使用任何SSC(单中心催化剂)制备。 [0182] according to the widest scope, the said composition can use any SSC (single site catalyst) was prepared. 这种催化剂可以是通常含有周期表第3-10族过渡金属和至少ー种在聚合过程中保持键合于过渡金属的辅助配体的过渡金属配合物。 Such catalysts may be generally contain Periodic Table Group 3-10 transition metal and at least ー holding a transition metal species bonded to the transition metal ancillary ligands during polymerization complexes. 优选地,该过渡金属以还原阳离子态使用,并且用助催化剂或活化剂来稳定。 Preferably, the transition metal cationic state to restore the use of, and treated with a cocatalyst or activator to stabilize.

[0183] 所述辅助配体可以是能够形成π键的结构,例如环戊ニ烯基类环结构。 [0183] The auxiliary ligand may be a structure capable of forming a π bond, such as cyclopentene ni alkenyls ring structure. 该辅助配体还可以是吡啶或氨基配体。 The auxiliary ligand may also be a pyridine or an amino ligand. 该过渡金属优选是周期表的第4族元素,例如钛、铪或锆,它们在聚合中以d°单价阳离子态使用,并且具有一个或两个下文详细描述的辅助配体。 The transition metal is preferably a Group 4 element of the periodic table, such as titanium, hafnium or zirconium, polymerizing them to d ° monovalent cationic state in use, and having one or described in detail below, two ancillary ligands. 用于配位聚合的这种催化剂的重要特征是能够夺取的配体和可插入乙烯(烯属)基团的配体。 Important features of such catalysts for coordination polymerization are the ligand capable of seizing and insertable ethylene (olefinic) group of the ligand.

[0184] 所述过渡金属配合物可以以适当的手性对丙烯単体施加一定程度的空间顺序。 [0184] The transition metal complex may be an appropriate chiral propylene radiolabeling body exert a certain degree of sequence space. 在需要更高分子量的第一聚合物或更高聚合温度的情况下,优选非配位或弱配位阴离子(本文所使用的术语非配位阴离子包括弱配位阴离子)作为助催化剂。 In the first case a higher molecular weight polymers require a higher polymerization temperature or, preferably non-coordinating or weakly coordinating anion (as used herein the term non-coordinating anion comprising weakly coordinating anions) as cocatalyst. 可供选择地,可以使用引入了氧-铝结构部分的铝氧烷或配合物。 Alternatively, the introduction of oxygen may be used - alumoxane or an aluminum complex moiety.

[0185] 可以将非配位阴离子的前体与以还原价态供给的过渡金属配合物一起使用。 [0185] precursor may be used together with a non-coordinating anion with valence transition metal complex supplied. 该前体可以进行氧化还原反应。 The precursor may undergo a redox reaction. 该前体可以是中性的,例如硼烷配合物,并且可以通过从该前体夺取配体而形成过渡金属阳离子。 The precursor may be neutral, such as borane complexes, and may be captured by the ligand to form a precursor from which the transition metal cations. 该前体可以是前体阳离子例如硼酸根以某些方式被中和和/或消除的离子对。 The precursor may be a precursor of a cation such as borate is neutralized in some manner and / or elimination of ion pairs. 该前体阳离子可以是如在EP 277 003和EP277 004中所述的铵盐。 The precursor cation may be as described in EP 277 003 EP277 004 in and ammonium salts. 该前体阳离子可以是如在EP 426 637中所述的三苯基碳鎗衍生物。 The precursor cation may be as described in EP triphenylcarbenium gun 426,637 derivatives. 非配位阴离子可以是第10-14族配合物,其中硼或铝是可以被卤化、尤其氟化的配体屏蔽的带电荷的原子。 Non-coordinating anion can be Group 10-14 complex wherein boron or aluminum that may be halogenated, particularly fluorinated ligand shield charged atoms. 优选四芳基取代的第10-14族非碳元素型阴离子,尤其氟基取代芳基上的氢原子或这些芳基的烷基取代基上的氢原子的那些。 Preferably tetraaryl substituted Group 10-14 non-carbon element-type anion, particularly fluorine-substituted on the aryl group a hydrogen atom or an alkyl group substituted with an aryl group such that a hydrogen atom on.

[0186] 所述非配位阴离子可以相对于过渡金属配合物的大约等摩尔量,例如至少O. 25、优选O. 5、尤其O. 8和例如不超过4、优选2和尤其I. 5的量使用。 [0186] The non-coordinating anion with respect to an approximately equimolar amount of transition metal complexes, such as at least O. 25, preferably O. 5, especially O. 8 and example not more than 4, preferably 2 and especially I. 5 amounts.

[0187] 所述过渡金属配合物可以是用于烯烃聚合的吡啶胺配合物,例如WO 03/040201 中所述的那些。 [0187] The transition metal complexes may be used for the polymerization of olefins pyridin-amine complexes, such as those described in WO 03/040201. 该过渡金属配合物可以是进行周期性分子内重排,以便提供所需的立构规整度中断的循变配合物,例如在Waymouth,US专利No. 6,559,262中所述的那些。 The transition metal complexes may be rearranged within the cyclic molecule, to provide the desired tacticity interruption through becomes complex, for example, in Waymouth, US Patent No. 6,559,262 those described. 该过渡金属配合物可以是如在Rieger EPl 070 087中所述的对丙烯插入具有混合影响的立构刚性配合物。 The transition metal complexes can be as rigid in stereoregular propylene insertion complexes with mixed effects EPl 070 087 described Rieger.

[0188] 优选地,所述过渡金属配合物是具有以下通式的手性桥连双环戊ニ烯基衍生物: [0188] Preferably, the transition metal complex having the general formula of chiral bridged dicyclopentadiene ni alkenyl derivative:

[0189] LaLbLc1MDE [0189] LaLbLc1MDE

[0190] 其中La和Lb是以键连接于M的取代或未取代的环戊ニ烯基或杂环戊ニ烯基辅助配体,其中La和Lb配体通过第14族元素连接基以共价键桥连在一起,Lci是具有以配价键连接于M的任选中性的、非氧化配体(i等于0-3) ”是第4或5族过渡金属;D和E独立地是单阴离子不稳定配体,各自以σ键连接于Μ,任选互相桥连或与La或Lb桥连。单阴离子配体是通过适合的活化剂可置換的,以允许可聚合单体或大分子单体插入,以便在过渡金属组分的空配位点上进行配位聚合。 [0190] wherein La and Lb is the bond to M is a substituted or unsubstituted alkenyl group or a heterocyclic cyclopentyl ni ni enyl pentyl ancillary ligand, wherein the ligand La and Lb via a linking group to a total of 14 elements valence bond bridging together, Lci is having dative bond to M, optionally, a neutral, non-oxidizing ligand (i equals 0-3) "is the first 4 or 5 transition metal; D and E are independently is a monoanionic labile ligands, each in σ bond to Μ, optionally bridged to each other or with La or Lb bridging. monoanionic ligand by suitable activators displaceable to permit a polymerizable monomer or macromonomer inserted to the transition metal component be empty coordination site coordination polymerization.

[0191]当使用催化剂时,总催化剂体系一般另外包括作为清除剂的ー种或多种有机金属化合物。 [0191] When a catalyst, the total catalyst system generally additionally comprise as a scavenger ー or more kinds of organometallic compounds. 如在本申请中使用的此类化合物意欲包括有效从反应环境中除去极性杂质和提高催化剂活性的那些化合物。 Such compounds as used in this application, is intended to include effectively remove polar impurities from the reaction environment and increase catalyst activity of those compounds.

[0192] 在至少ー个实施方案中,聚合方法由以下步骤组成或包括以下步骤:在包括双(环戊ニ烯基)金属化合物和(I)非配位相容性阴离子活化剂或(2)铝氧烷活化剂的催化剂的存在下聚合。 [0192] In at least ー embodiment, a polymerization process comprising the steps of or comprises the steps of: including bis (cyclopentyl ni enyl) metal compound and (I) a non-coordinating anion activator or capacitive phase (2 ) in the presence of an activator of alumoxane polymerization catalyst. 可以使用的催化剂体系的非限制性实例在US专利Nos. 5,198,401和5,391,629中有述,其公开内容由此引入本文供參考。 Non-limiting examples of catalyst system may be used. 5,198,401 and 5,391,629 there are described in US Patent Nos, the disclosures of which are hereby incorporated herein by reference. 在该实施方案的ー个特定方面,铝氧烷活化剂可以以提供I : I到20,000 : I的铝与金属茂摩尔比的量使用。 The embodiment ー particular aspect, the aluminoxane activator may be provided in I: I to 20,000: I is the amount of aluminum to metallocene molar ratio used. 在该实施方案的另ー个特定方面,非配位相容性阴离子活化剂可以以提供10 : I到I : I的双环戊ニ烯基金属化合物与非配位阴离子的摩尔比的量使用。 In this embodiment ー another particular aspect, the non-coordinating anion activator may be capacitive phase to provide a 10: I to I: I dicyclopentadiene Ni-based metal compound and an ethylenically noncoordinating anion molar ratio of the amount of use. 在该实施方案的又ー个特定方面,该聚合反应包括让单体在本文所述的催化剂体系的存在下在-(TC到200°C的温度下反应I秒到10小时的时间。 In this embodiment also ー particular aspect, the polymerization comprises the monomers in the presence of a catalyst system as described herein in the - reaction of I second to 10 hours (at a temperature of 200 ° C to TC.

[0193] 在某些实施方案中,本发明的第一聚合物可以在手性金属茂催化剂与活化剂和任选的清除剂的存在下制备。 [0193] In certain embodiments, a first polymer of the present invention can be prepared in the presence of a chiral metallocene catalyst with an activator and optional scavenger. 优选使用单中心金属茂催化剂来提高聚合物的均匀性。 Preferably to improve the uniformity of the polymer with a single site metallocene catalyst. 因为仅需要有限的立构规整度,所以可以使用许多不同形式的单中心催化剂。 Since only a limited tacticity, it is possible to use many different forms of single site catalyst. 可能的单中心催化剂是金属茂,例如在US专利No. 5,026,798中所述的那些,它们具有单ー环戊ニ烯基环,有利地被取代和/或形成了多环结构的一部分,并且杂原子(通常氮原子,但也可能是磷原子或苯氧基)连接于第4族过渡金属,优选钛,但可能是锆或铪。 Possible single site catalysts are metallocenes, such as those described in US Patent No. 5,026,798, which has a single alkenyl group ni ー cyclopentyl ring, advantageously substituted and / or forming a polycyclic structure part, and the heteroatom (typically a nitrogen atom, but may also be a phosphorus atom or phenoxy group) is connected to the Group 4 transition metal, preferably titanium, but may be zirconium or hafnium. 另ー个实例是用B(CF)3M化的Me5CpTiMe3,用于制备具有至多4百万的Mn的弾性体聚丙烯。 Another ー instance with B (CF) 3M of Me5CpTiMe3, for the preparation of Mn having up to 4 million of the body of Dan polypropylene. 參见Sassmannshausen,Bochmann, Rosch, Lilge, J. Organomer. Chem. (1997)548,23-28。 See Sassmannshausen, Bochmann, Rosch, Lilge, J. Organomer. Chem. (1997) 548,23-28.

[0194] 其它可能的单中心催化剂是属于具有过渡族金属、优选铪或锆的双环戊ニ烯基衍生物的金属茂。 [0194] Other possible single site catalysts having a transition metal belonging to, preferably hafnium or zirconium dicyclopentadiene ni alkenyl derivative metallocenes. 这种金属茂可以是非桥连的,如US专利No. 4,522,982或US专利No. 5,747, 621中所述。 Such metallocenes may be non-bridged, as described in US Patent No. 4,522,982 or US Patent No. 5,747, 621 described. 该金属茂可以适于制备主要包括丙烯衍生的単元的聚合物,如US专利No. 5,969,070,该专利使用非桥连ニ氯•双(2-苯基茚基)合锆来制备熔点高于79°C的均质聚合物。 The metallocene may be adapted for preparing a polymer mainly comprising propylene derived radiolabeling element, as described in US Patent No. 5,969,070, which patent the use of Ni-chloro • unbridged bis (2-phenyl indenyl) zirconium dichloride was prepared melting point higher than 79 ° C in a homogeneous polymer. 该环戊ニ烯基环可以是取代的和/或是多环体系的一部分,如在以上US专利中所述。 The cyclopentyl ni alkenyl substituted ring may be part of and / or polycyclic ring systems, as described in the above US patents.

[0195] 其它可能的金属茂包括其中两个环戊ニ烯基通过桥基、通常单原子桥基例如硅或碳原子连接和选择基团占据两个剩余化合价的那些。 [0195] Other possible metallocenes include those in which the alkenyl group through two cyclopentyl ni bridging group, such as a group generally occupy the two remaining valencies that silicon or carbon atom, and select a single atom bridging group. 这种金属茂在以下文献中有述:us专利No. 6,048,950(其公开了ニ氯·双(茚基)双(ニ甲基甲硅烷基)合锆)和ΜΑ0);W098/27154(其公开了ニ甲基· ニ甲基甲硅烷基桥连的双茚基合铪与非配位阴离子活化齐IJ) ;EP1 070 087(其公开了在两个环戊ニ烯基配体之间具有非対称元素的桥连双环戊ニ烯基催化剂,用于获得具有弹性的聚合物)。 Such metallocenes have described in the following document: us Patent No. 6,048,950 (which discloses a Ni-chloro-bis (indenyl) bis (trimethylsilyl ni) zirconium) and ΜΑ0); W098 / 27154 (which discloses ni ni methyl trimethylsilyl bridged bis indenyl hafnium and a non-coordinating anion activator Qi IJ); EP1 070 087 (which discloses a two-cyclopentyl ni alkenyl ligands Dui between said elements having a non-bridged dicyclopentadiene ni alkenyl catalyst, for obtaining a polymer having elasticity). US专利Nos. 6,448,358和6,265,212中也描述了所述金属茂。 US Patent Nos. 6,448,358 and 6,265,212 are also described in the metallocene.

[0196] 单中心催化剂的活化方式可以改变。 [0196] Single site catalyst activation mode can be changed. 可以使用铝氧烷和优选甲基铝氧烷。 You can use the aluminoxane and preferably methylaluminoxane. 使用以在公开专利文献例如EP277 004、EP426 637等中所述的任何方式衍生和产生的非配位或弱配位阴离子活化剂(NCA)来获得高分子量。 Used for example in any way EP277 004, EP426 637, etc. and the derivatives disclosed in Patent Document generated in a non-coordinating or weakly coordinating anion activators (NCA) to obtain a high molecular weight. 一般认为活化包括夺取阴离子基团例如甲基,以形成金属茂阳离子,但根据某些文献,可以产生两性离子。 Activation is generally believed that includes abstracts an anionic group such as methyl, to form a metallocene cation, but according to some literature zwitterions may be produced. NCA前体可以是硼酸根或铝酸根的离子对,其中前体阳离子在以某些方式活化时被消除,例如,四(五氟苯基)硼的三苯甲基或铵衍生物(參见EP277 004)。 NCA precursor may be a borate or aluminate ion pair, wherein the cation precursor is activated at the time is eliminated in some manner, e.g., tetrakis (pentafluorophenyl) boron trityl or ammonium derivatives (see EP277 004). 该NCA前体可以是中性化合物,例如硼烷,它通过夺取和引入从金属茂所夺取的阴离子基团而形成阳离子(參见EP426 638)。 The NCA precursor can be neutral compounds such as borane, which is introduced by capturing and wrest from metallocene anionic groups to form a cation (see EP426 638).

[0197] K.具体催化剂 [0197] K. specific catalyst

[0198] 如本文其它地方所述,在某些实施方案中,在不同反应器中的聚合可以在相同的催化剂混合物的存在下进行,而在其它实施方案中,可以在不同的催化剂混合物的存在下进行。 [0198] As described elsewhere herein, in some embodiments, the polymerization in the different reactors may be conducted in the presence of the same catalyst mixture, while in other embodiments, may be present in different catalyst mixture carried out. 本文所使用的术语“催化剂混合物”(催化剂体系)包括至少ー种催化剂和至少ー种活化剂,但取决于上下文,本文所提到的“催化剂”通常还暗指活化剂。 As used herein, the term "catalyst mixture" (catalyst system) comprising at least at least ー ー catalysts and activators, but depending on the context, herein referred to as "catalyst" is usually also implies an activator.

[0199] 适当的催化剂混合物可以各种方式输送到相应的反应器。 [0199] The appropriate catalyst mixture may be delivered in various ways to the corresponding reactor. 例如,它可以作为溶液或淤浆独立地输送到反应器,刚好在反应器之前的管道内活化,或者预活化并作为活化溶液或淤浆泵送到反应器。 For example, it can be transported as an independent solution or slurry to the reactor, activated in the reactor just prior to the conduit, or preactivated and as an activating solution or a slurry pump to the reactor. 聚合在每一反应器中进行,其中反应剂组分(例如所需的单体、共聚单体、催化剂/活化剂、清除剂和任选的改性剂)优选连续添加到适当的反应器中。 Polymerization is carried out in each reactor, wherein the reaction component (e.g., the desired monomers, comonomers, catalyst / activator, scavenger, and optional modifiers) are preferably added continuously to the appropriate reactor . 在某些实施方案中,将两种催化剂混合物加入到第一反应器中,而在其它实施方案中,将ー种催化剂混合物加入到第一反应器中,将不同催化剂混合物加入到第二反应器中(虽然在后续操作中,来自第一反应器的至少ー些第一催化剂混合物可以与来自第一反应器的产物混合物一起引入到第二反应器中。 In certain embodiments, the two catalyst mixture was added to the first reactor, while in other embodiments, the catalyst mixture ー species added to the first reactor, the different catalyst mixture is added to the second reactor (although in subsequent operations, from the first reactor of at least some of the first catalyst mixture may ー with the product mixture from the first reactor is introduced together into the second reactor.

[0200] 在优选实施方案中,两种不同催化剂作为不同反应剂进料的一部分添加,例如“第一催化剂”可以是“第一反应剂进料”的一部分,“第二催化剂”可以是“第二反应剂进料”的一部分,但在至少ー些实施方案中(例如串联反应器),第一和第二催化剂在第二反应器进料中同时以某种程度存在(例如,当将第一流出物供给第二反应器时)。 [0200] In a preferred embodiment, two different catalysts as a different part of the feed reactant addition, e.g., "first catalyst" may be part of the "first reactant feed", the "second catalyst" may be " portion of the second reactant feed ", but in ー least some embodiments (e.g., series reactors), the first and second catalyst in the second reactor feed while the presence of a certain degree (e.g., when the the first effluent supplied to the second reactor). 优选地,在至少ー些实施方案中,第一催化剂是手性催化剂,而第二催化剂是非手性催化剂。 Preferably, at least ー some embodiments, the first catalyst is a chiral catalyst while the second catalyst is a chiral catalyst.

[0201] 在所述方法和组合物的某些实施方案中,不论是串联还是并联的第一和第二聚合各自可以使用相同的催化剂混合物。 [0201] In certain embodiments of the methods and compositions, either in series or in parallel with the first and second polymerization each may use the same catalyst mixture. 例如,在某些方法中,在两种聚合中可以使用US专利No. 6,207,756中所述的某些催化剂混合物,该专利由此全文引入供參考,尤其描述催化剂混合物的部分,例如第8栏第20行到第14栏第21行。 For example, in some methods, the polymerization can be used in both US Patent No. certain catalyst mixture described in 6,207,756, whereby this patent is incorporated by reference, in particular, part of the catalyst mixture described, e.g. column 8, line 20 to column 14, line 21. 优选的催化剂是等规的(isospecific)那些。 The preferred catalyst is isotactic (isospecific) those. 形成有用催化剂体系的具体实例的エ序在该专利的实施例I中给出。 Specific examples of useful catalyst system is formed of the Eito procedure given in Example I of this patent the.

[0202] 第一催化剂。 [0202] The first catalyst. 第一催化剂优选是手性催化剂。 The first catalyst is preferably a chiral catalyst. 在至少ー个具体实施方案中,第一聚合在属于“单中心聚合催化剂”的第一催化剂的存在下进行,该催化剂优选仅允许按单ー统计方式添加两种不同単体序列,例如丙烯序列和こ烯序列。 In at least ー specific embodiments, the first part of the polymerization in the presence of a "single-site polymerization catalyst," the first of a catalyst, the catalyst is preferably only permitted by a single ー statistics Add the two different radiolabeling sequences, e.g., propylene sequences and ko ene sequences. 第一催化剂优选在连续流搅拌釜聚合反应器内充分混合,使得对于该聚合物的基本上所有的聚合物链仅提供单ー聚合环境。 The first catalyst is preferably in a continuous flow stirred tank polymerization reactor thoroughly mixed, such that substantially all of the polymer for the polymer chains to provide only a single polymerization environment ー. 优选将该第一催化剂活化,意味着它以某些方式与活化剂结合。 The first catalyst is preferably activated, meaning that it in some way combined with an activator.

[0203] 作为至少ー个实例,第一催化剂可以包括双(环戊ニ烯基)金属化合物,并且可以与(I)非配位相容性阴离子活化剂或(2)铝氧烷活化剂结合。 [0203] At least ー instance, a first catalyst may include bis (cyclopentyl Ni-enyl) metal compound, and can be combined with (I) a non-coordinating anion activator phase capacitive or (2) an alumoxane activator as . (这里提到的所有“催化剂”优选还包括活化剂,除非另有規定。)可以使用的催化剂体系(包括活化剂)的非限制性实例在US专利Nos. 5,198,401和5,391,629中有述,它们的公开内容由此引入本文供參考。 (All "catalyst" mentioned here is preferably further comprises an activator, unless otherwise specified.) The catalyst system may be used (including the activator) of non-limiting example, in US Patent Nos. 5,198,401 and 5,391 , 629 are described, the disclosures of which are hereby incorporated herein by reference. 在该实施方案的ー个特定方面,铝氧烷活化剂可以以提供I : I到20,000 : I的铝与金属茂摩尔比的量使用。 The embodiment ー particular aspect, the aluminoxane activator may be provided in I: I to 20,000: I is the amount of aluminum to metallocene molar ratio used. 在该实施方案的另ー个特定方面,非配位相容性阴离子活化剂可以以提供10 : I到I : I的双环戊ニ烯基金属化合物与非配位阴离子的摩尔比的量使用。 In this embodiment ー another particular aspect, the non-coordinating anion activator may be capacitive phase to provide a 10: I to I: I dicyclopentadiene Ni-based metal compound and an ethylenically noncoordinating anion molar ratio of the amount of use. 在该实施方案的又ー个特定方面,该聚合反应包括让单体在本文所述的催化剂体系的存在下在-0°C到200°C的温度下反应I秒到10小时的时间。 In this embodiment also ー particular aspect, the polymerization reaction in the presence of a monomer comprising allow catalyst system described herein reaction I second to 10 hours at a temperature of -0 ° C to 200 ° C time.

[0204] 第二催化剂。 [0204] The second catalyst. 第二催化剂(如果不同于第一催化剂)优选是非手性催化剂,还优选在连续流搅拌釜反应器内充分混合。 The second catalyst (if different than the first catalyst) is preferably a non-chiral catalyst, further preferably in a continuous flow stirred tank reactor and mixed thoroughly. 优选将该第二催化剂活化,意味着它以某些方式与活化剂结合。 The second catalyst is preferably activated, meaning that it in some way combined with an activator. 第二催化剂的实例在本文的其它地方有描述,并且在W000/24793中也有描述,该专利由此引入供參考。 Examples of the second catalyst is elsewhere described herein, and in W000 / 24793 also described in this patent are hereby incorporated by reference.

[0205] 实施例 [0205] EXAMPLE

[0206] 以下实施例描述了通过使用两个串联配置的连续流搅拌釜反应器进行的连续聚合形成由两种不同类型的聚合物组成的反应器共混物的方法,向该两个反应器连续进给不同単体混合物和催化剂混合物。 [0206] The following examples describe the method of forming the reactor blends of two different types of polymer composition by using a series arrangement of two continuous flow stirred tank continuous polymerization reactor, and to the two reactors continuous feed mixture and catalyst mixture radiolabeling different body. 将己烷溶剂进给到每ー个反应器中,以使每一反应器的内容物保持在溶液中。 The hexane solvent was fed to each ー reactors, so that each of the reactor contents were maintained in solution. 第二反应器的温度明显高于第一反应器。 Second reactor temperature is significantly higher than the first reactor. 每ー催化剂料流通过将催化剂和活化剂在900ml甲苯中预混合,然后使用计量泵进给到相应反应器来制备。 Each ー catalyst stream through the catalyst and activator pre-mixed in 900ml of toluene, and then prepared using a metering pump feeding into the respective reactor. 催化剂混合物A (进给到反应器I)是非担载ニ甲基· ニ甲基甲硅烷基双(茚基)合铪催化剂和四(五氟苯基)硼ニ甲基苯胺鎗活化剂的混合物。 (Fed to the reactor I) non-supported Ni methyl ni dimethylsilyl bis (indenyl) hafnium dichloride catalyst and tetra (pentafluorophenyl) boron ni methylaniline gun activators catalyst mixture A mixture of . 催化剂混合物B (进给到反应器2)是如在US专利No. 6,506,857 (催化剂A)实施例I和4中所公开的非担载ニ甲基•ニ-(対-三こ基甲娃烧基节基)_■价碳基(环戍_■稀基)(2_7 _■叔丁基荷基)合給与在催化剂混合物A中所使用的相同活化剂的混合物。 Catalyst mixture B (fed to Reactor 2) is as described in US Patent No. 6,506,857 (Catalyst A) Examples I and non-supported Ni-methyl-4 disclosed embodiments • ni - (Dui - three ko yl methyl baby burn yl section yl) _ ■ carbyl group (ring Shu _ ■ dilute yl) (2_7 _ ■ t Dingjiheji) was combined to give the same activators in the catalyst A used in the mixture. 催化剂添加速率在表5中给出。 The catalyst addition rate is given in Table 5. 在反应器I中使用三正辛基铝作为清除剂。 Using tri-n-octyl aluminum as a scavenger in the reactor I below.

[0207]表 5 [0207] Table 5

[0208] [0208]

[0209]表 6 [0209] Table 6

[0210] [0210]

[0211] 反应器I聚合生产了包括第一聚合物产物的流出物。 [0211] I the polymerization reactor produce a polymer product comprising a first effluent. 将包括未反应单体和催化剂混合物的该流出物进给到反应器2,在此于不同反应条件下进行聚合。 The catalyst mixture comprising unreacted monomer and the effluent is fed to the reactor 2, in this polymerization was carried out under different reaction conditions. 例如,在反应器2中,使用明显更高的反应器温度。 For example, in the reactor 2, a significantly higher reactor temperature. 还有,引入多烯烃(5-こ叉基-2-降冰片烯)。 Also, the introduction of multi-olefins (5- ko fork-2-norbornene). 每一反应器的生产速率通过定时收集流出物,随后蒸发溶剂和测定剩余固体浓度来确定。 Production rate of each reactor effluent was collected via a timing, followed by evaporation of the solvent and measuring the remaining solids concentration is determined. 反应器I的生产速率通过停止反应器2中的反应和然后使用该相同エ序定时收集反应器I的流出物来确定。 I production rate of the reactor by stopping the reaction in reactor 2 and then use the same timing sequence Eito collected reactor effluent I determined. 当两个反应器充分运行时,按照相同エ序使用反应器2的输出来測定总生产速率。 When two reactors are fully operational, the program uses the same output Eito reactor 2 to determine the total production rate. 使用该信息,计算反应器I生产速率与总生产速率的比率。 Using this information, calculate the production rate of the reactor I and the ratio of the total production rate. 该比率在表6中被称为“聚合分割比”。 The ratio in Table 6 is called "polymerization division ratio." 使用催化剂补充和进料速率以及生产速率,按催化剂效率计算催化剂生产率(g聚合物“催化剂)。 Supplement and catalyst feed rate and production rate, the catalyst efficiency is calculated by catalyst productivity (g polymer "catalyst).

[0212] 在姆一反应器中形成的聚合物产物的各种性能在表7和8中报告。 [0212] In various properties Farm formed in one reactor in the polymer product are reported in Tables 7 and 8. 如表7中所见到的,反应器I中形成的聚合物具有21wt%的こ烯含量。 As seen in Table 7, the polymer formed in reactor I having 21wt% of the ko-ene content. 相反,从反应器2排出的聚合物产物具有61wt%こ烯含量,该聚合物产物是包括反应器I中形成的聚合物加反应器2中形成的其它聚合物的反应器共混物。 In contrast, the polymer product is discharged from the reactor 2 having 61wt% ko-ene content of the polymer product is a reactor blend comprising other polymers added to the reactor polymer formed in reactor I 2 formed. 由第一聚合物和反应器共混物こ烯含量以及聚合分割比计算的第二聚合物的こ烯值为75%。 The first polymer and reactor blend ethylene content and polymerization ko ko-ene calculated division ratio of the second polymer is 75%. ENB的值为6.9%。 The ENB is 6.9%. 所报告的其它测定性能包括门尼粘度、熔体指数、分子量数据和支化測量(g'和BI),全部在表7和8中反映。 Other reported properties determined included Mooney viscosity, melt index, molecular weight data and branching measurements (g 'and BI), all reflected in Tables 7 and 8 in.

[0213]表 7 [0213] Table 7

[0214] [0214]

[0215]表 8 [0215] Table 8

[0216] [0216]

Citations de brevets
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*US2004/0198913 Titre non disponible
US6319998 *1 mars 199920 nov. 2001Exxon Mobil Chemical Patents Inc.Method for making polymer blends by using series reactors
US6329477 *2 mars 199911 déc. 2001Exxonmobil Chemical Patents Inc.Method for increasing diene conversion in EPDM type polymerizations
US6747114 *21 déc. 20008 juin 2004Exxonmobil Chemical Patents Inc.Polypropylene-based adhesive compositions
*WO2097/36942A1 Titre non disponible
*WO2098/02471A1 Titre non disponible
Classifications
Classification internationaleC08F2/06, C08L23/14, C08F2/00, C08L23/16
Classification coopérativeC08L23/142, C08L23/16, C08F210/06
Classification européenneC08L23/16, C08F210/06, C08L23/14A
Événements juridiques
DateCodeÉvénementDescription
3 oct. 2007C06Publication
28 nov. 2007C10Request of examination as to substance
7 juil. 2010C14Granted