CN1158624A - 聚二烯烃的气相生产 - Google Patents
聚二烯烃的气相生产 Download PDFInfo
- Publication number
- CN1158624A CN1158624A CN95195203A CN95195203A CN1158624A CN 1158624 A CN1158624 A CN 1158624A CN 95195203 A CN95195203 A CN 95195203A CN 95195203 A CN95195203 A CN 95195203A CN 1158624 A CN1158624 A CN 1158624A
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- CN
- China
- Prior art keywords
- polymeric segment
- reactor
- bed
- promotor
- polyhutadiene
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 82
- 230000008569 process Effects 0.000 title claims description 39
- 238000012685 gas phase polymerization Methods 0.000 title description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 108
- 239000000178 monomer Substances 0.000 claims abstract description 70
- 239000003054 catalyst Substances 0.000 claims abstract description 51
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229920001195 polyisoprene Polymers 0.000 claims abstract description 32
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 claims abstract description 24
- 239000007789 gas Substances 0.000 claims description 78
- 229920000642 polymer Polymers 0.000 claims description 51
- 239000007788 liquid Substances 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 42
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 36
- 239000002245 particle Substances 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 27
- -1 ether compound Chemical class 0.000 claims description 25
- 239000006229 carbon black Substances 0.000 claims description 23
- 229910017052 cobalt Inorganic materials 0.000 claims description 21
- 239000010941 cobalt Substances 0.000 claims description 21
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 21
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- 239000000377 silicon dioxide Substances 0.000 claims description 18
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- 229960001866 silicon dioxide Drugs 0.000 claims description 18
- 238000009833 condensation Methods 0.000 claims description 16
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
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- 239000004411 aluminium Substances 0.000 claims description 7
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 6
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- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical group CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 6
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 6
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- 239000004927 clay Substances 0.000 claims description 5
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 5
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- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical group F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
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- 229920001155 polypropylene Polymers 0.000 claims description 2
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 claims 2
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- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims 1
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 8
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- 238000005054 agglomeration Methods 0.000 description 7
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 7
- 239000012808 vapor phase Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 150000001721 carbon Chemical group 0.000 description 6
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 150000001869 cobalt compounds Chemical class 0.000 description 4
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 4
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 4
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- 229910052761 rare earth metal Inorganic materials 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
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- 230000001105 regulatory effect Effects 0.000 description 1
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- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 1
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
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- VPULIQHINAVFKO-UHFFFAOYSA-N triethylalumane Chemical compound CC[Al](CC)CC.CC[Al](CC)CC.CC[Al](CC)CC VPULIQHINAVFKO-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
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- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
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- B01J8/1827—Feeding of the fluidising gas the fluidising gas being a reactant
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- B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
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- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
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- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
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Abstract
在气相反应器中生产聚丁二烯或聚异戊二烯的方法,该法是将丁二烯或异戊二烯单体和任选的惰性气体连续地或间断地通入聚合段,同时将聚合段的温度保持在低于聚合段存在的单体露点并在过渡金属催化剂及惰性颗粒材料存在下进行生产的。
Description
本申请是1994年8月2日美国优先申请的申请号为284797的部分继续申请。
发明领域
本发明涉及一种在气相反应器中生产聚二烯烃的方法。更具体而言,本发明涉及一种在气相流化床反应器中制造聚丁二烯和聚异戊二烯的方法。
发明背景
聚二烯烃,例如聚丁二烯和聚异戊二烯,用溶液聚合方法已经生产很多年了,最近则用块状或本体聚合方法生产。用于聚合丁二烯,特别是1,3-丁二烯的各种催化剂溶液和块状或本体聚合方法,适于生产具有高含量1,4-顺式丁二烯的聚丁二烯,是在现有技术中公知的技术。聚丁二烯特别适于制造轮胎、传动带,和其它注射或挤出橡胶制品或弹性体制品。
在溶液聚合中,丁二烯是在一种惰性溶剂或稀释剂中聚合,其惰性溶剂或稀释剂不进入制得的聚合物的结构或对制得的聚合物没有不利影响。这种溶剂通常是脂肪族烃、芳香族烃和环状脂肪烃如戊烷、己烷、庚烷、苯、甲苯、环己烷等。溶剂/单体体积比可变化范围宽,在块状聚合中,反应介质基本上无溶剂,和用单体作为稀释剂。
用于生产聚合物,特别是聚烯烃聚合物的气相流化床和搅拌反应器方法的发现,使有可能生产非常理想并改进性能的各种各样的新聚合物。用于生产此类聚合物的这些气相方法,特别是气相流化床方法,与其它常规方法相比,提供一种基本投资费用大幅度降低,并且显著节约能量消耗的生产聚合物的方法。
在常规的气相流化床方法中,将含有一种或多种单体的气态流通入含有在聚合段正在生长的聚合物颗粒床的流化床反应器中,同时将聚合催化剂连续或间歇加入聚合段。所需的聚合物产品全用周知的技术自聚合段卸出、脱气、稳定和包装以便装运。由于聚合反应是放热的,在聚合段产生的大量热必须移走,以防止聚合物颗粒过热和熔融在一起。这是通过将未反应的热气体从聚合段中连续移走,并用较冷的气体代替而实现的。将从聚合段移出的热气体压缩,并在热交换器中冷却、另外补充一定量的单体以取代已聚合的和从反应段中移走的单体,然后循环入反应器底部。循环气体的冷却可在一个或多个热交换器中完成。压缩和冷却顺序根据设计进行选择,但通常优选在冷却之前使热气体压缩。气体注入和流出反应器的流速保持到使聚合物颗粒床维持流化状态的水平。在搅拌床反应器中生产聚合物很相似,主要区别在于所使用的有助于保持聚合物床处于流化状态或其它较好的混合状态的机械搅拌装置。
常规的气相流化床树脂生产在现有技术中是众所周知的,例如,在美国专利4379758、4383095和4876320中公开的,这里作为参考被引入。
在气相搅拌反应器中生产聚合物物质在现有技术中也是众所周知的,通过在美国专利3256263中描述的方法和设备来举例说明。
最近,在美国专利4994534和5304588中,谈到了粘性聚合物,包括聚丁二烯橡胶,可以在惰性颗粒材料存在下,在有催化剂存在下,高于粘性聚合物的软化温度的聚合反应条件下,在流化床反应器中生产。优选的催化剂是过渡金属催化剂。实例中使用的这种催化剂是钛和钒基的催化剂体系,其中也包括助催化剂和任选的促进剂。在气相法中生产的粘性聚合物是含有橡胶和惰性材料混合物的颗粒,这种颗粒的芯主要是橡胶而壳主要是惰性材料。另外,美国专利5317036公开了一种气相聚合方法,采用无载体可溶性催化剂,比如过渡金属配位催化剂。这种催化剂以溶液通入反应器,例如流化床中。用这种方法生产的聚烯烃可以含有二烯烃。EP0647657A1,公开了用于共轭二烯气相聚合的载体稀土催化剂。
多年来,人们误认为使任何种类的液体进入气相反应器的聚合段将不可避免导致树脂颗粒的附聚、形成大块状聚合物并最终使反应器完全停止运转。基于此,使得气相聚合物生产者小心翼翼避免将进入反应器的循环气流冷却至温度低于聚合反应中使用的任何单体的冷凝温度。
共聚单体如己烯-1、4-甲基戊烯和辛烯-1用于生产乙烯共聚物-聚合物特别有价值。这些较高级α-烯烃具有相当高的冷凝温度。由于人们认为在聚合段的液态单体将导致附聚、结块甚至最终使反应器停止运转,与从聚合段移走热的速度有关的生产速率受到认为需要保持进入反应器的循环气流的温度总高于存在于循环气流中的沸点最高的单体的冷凝温度严格限制。
甚至对于在搅拌反应器中进行聚合反应的情况,也要仔细操作以保持树脂床温高于循环气体流组分的冷凝温度。
为了最大限度地移走热,通常将液体喷雾入或注入聚合物床中或聚合床上,于此液体通过暴露于较热的循环气体流中立即闪蒸为气体状态。用此技术因Joules-Thompson效应实现了有限量的辅助冷却,但并未将循环气体流冷却到可能发生冷凝的程度。此方法通常包含先分别将循环气流部分冷却为液态单体贮存,然后再分别加入聚合床中或床上的繁琐并且耗能的步骤。这种方法的例子可在美国专利3254070、3300457、3652527和4012573中找到。
后来发现,与人们长期坚持认为的在循环气体流中存在液体会导致附聚和反应器停止运转相反,完全有可能将整个循环气体流冷却至出现大量单体冷凝的温度,当这些液体在与循环气体流平衡的温度下加入反应器中时不会出现想象的可怕结果。冷却整个循环气体使其在相互平衡温度下生成气-液两相混合物,以便在气体流中含有的液体不会立即闪蒸为蒸汽。取而代之的是由于气体和液体总物料都在比以前认为的可能温度显著低的温度下进入聚合段,会产生大量的冷却。此方法对于气相法,特别是使用冷凝温度相当低的共聚单体所生产的聚合物的产率有显著改进。这种方法,通常称为“冷凝模式”操作,在美国专利4543399和4588790中进行了详细描述,这里作为参考被引入。在冷凝模式操作中,将进入聚合段的气液两相混合物十分迅速加热并在进入聚合段后在很短距离内完全汽化。甚至在最大的工业反应器中,所有液体进入聚合段后不久即被完全汽化;接着所有气态循环气流的温度受聚合反应的放热性显著升高。以冷凝模式操作气相反应器的能力被认为有可能由于进入伴有有效恒定返混流化床的反应器中的气液两相流体比两相汽液体循环流进入处之上较短距离内的更迅速加热,在聚合物床中没有液体存在。
我们现在已发现液态单体可以存在于遍及整个聚合物床中,条件是存在于床中的液态单体被吸附在存在于床中的固体颗粒物料上或吸收入固体颗粒物料中,例如这些颗粒物料为存在于床中的生产出来的聚合物或流化助剂,只要进入聚合段处之上短距离内(与冷凝模式操作一样)没有相当大量的游离液态单体存在。此发现使得有可能在气相反应器中,用冷凝温度比在气相反应器中生产常规聚烯烃的温度高得多的单体生产聚合物。评论此发现的另一方面是现在使得有可能在气相反应器中,用容易冷凝的单体(即1,3-丁二烯,标准沸点为-4.5℃),期望单体处于液态存在的条件下生产聚合物。此外,以前认为气相法用低于中等冷凝温度一些单体或全部单体生产聚合物是不能实现的,因为在冷凝温度低于聚合段温度的全部浓单体条件中,每个催化剂颗粒生产的聚合物太少。本发明的此发现,现在可经济实施的用冷凝温度高于聚合段温度的浓单体生产聚合物,即液态单体遍及整个聚合物床中,条件是存在于床中的液态单体被吸附在存在于聚合物床中的固体颗粒物料上或吸收入固体颗粒物料中,和/或生成的聚合物产品存在于反应器的聚合段中。本发明有可能用气相法生产各种以前认为不能用连续气相法生产的聚合物。
本发明的另一好处是操作用作为液态溶解于聚合物中存在的单体比用不溶解于聚合物中,即只存在于气相中的单体,在活性催化剂中心上得到的单体浓度更大。这一点将使用于生产聚合物的催化剂生产率最大。本发明的再一个好处是在聚合物颗粒中的热传递是通过单体蒸发移走热量而得到改善。与单体不溶解,即只存在于气相中的操作相比,这将使聚合物颗粒温度更均匀,更均匀的聚合物性能,聚合物结垢少,并可改进聚合物的形态。
发明概述
本发明提供一种在有聚合段的搅拌床或气相流化床聚合反应器中,在聚合反应条件下生产聚丁二烯或聚异戊二烯的方法,该方法包括:
(i)在一种惰性颗粒材料,和任选至少一种惰性气体存在下,将丁二烯或异戊二烯单体加入到含有一种正在生长的聚合物颗粒床的所述聚合段中,
(ii)将含有一种镍、钴、钛、金属组分或它们的混合物的聚合催化剂,一种助催化剂,和任选的一种促进剂,连续地或间断地加入所述聚合段中;
(iii)连续地或间段地从所述聚合段卸出聚丁二烯或聚异戊二烯;
(iv)从该聚合段卸出未反应的丁二烯或异戊二烯,压缩和冷却该丁二烯或异戊二烯和有惰性气体存在时的该惰性气体,同时保持该聚合段的温度低于存在所述聚合段中单体的露点。
也提供了用这样的颗粒生产的粒状颗粒和制品。
附图阐述
特别适于生产聚丁二烯或聚异戊二烯的流化床反应系统在附图中加以说明。
发明详述
虽然本发明不限于任何特定类型或种类聚合反应,但本发明特别适于烯烃聚合反应,包括沸点相当高的单体或容易冷凝的单体的均聚反应和共聚反应,如聚丁二烯或聚异戊二烯。
能够进行烯烃聚合反应的沸点较高的单体或容易冷凝的单体的例子如下:
A.分子量较高的α烯烃如癸烯-1、十二碳烯-1等和苯乙烯。
B.二烯烃如己二烯、乙烯基环己烯、双环戊二烯、丁二烯、异丁烯、异戊二烯、亚乙基降冰片烯等等。
C.极性乙烯基单体如丙烯腈、马来酸酯、醋酸乙烯酯、丙烯酸酯、甲基丙烯酸酯、乙烯基三烷基硅烷等等。
这些沸点较高的单体或容易冷凝的单体可根据本发明,使用惰性气体作为循环于反应器中气液两相混合物的气态组分进行均聚。用于此目的合适的惰性物质包括氮气和在温度低于选取的在聚合段保持的温度下维持气态的饱和烃。
沸点较高的单体或容易冷凝的单体还可与一种或多种沸点较低的单体如乙烯、丙烯和丁烯及上面提到的那些沸点较高的其它单体共聚,唯一要求是沸点较高的单体与至少一种沸点较低的单体或惰性物质的冷凝温度之间有明显差别,这样可使循环气体流中存在足够的气体以使进行切实可行的、状态稳定的连续操作。因此,根据本发明方法,苯乙烯和丁二烯可共聚生产苯乙烯-丁二烯橡胶(SBR)。
根据我们的发明,沸点较高的单体或容易冷凝的单体可直接加入聚合反应段或与循环气流一起载入聚合反应段。或两者结合。在优选实施方案中,该聚合段的温度保持低于存在聚合段中的单体(如1,3-丁二烯或异戊二烯)的冷凝温度。在另一实施方案中,聚合段的条件(如温度、压力、单体浓度)是该聚合段中基本上不存在不被吸附在固体颗粒物上或不被吸附在固体颗粒物中的液体。换言之,所述的聚合段中的条件是保持该聚合段中的部分单体是不被吸附到固体颗粒物中的液体。
本发明的实施不限于任何特定类型或种类的催化剂。任何用于进行气相聚合反应的催化剂都适用在本发明的实施中。以前在较高沸点或容易冷凝的单体(如丁二烯和异戊二烯)的浆液聚合、溶液聚合或块状聚合中用的催化剂也可用在本发明中。
常规的Ziegler-Natta催化剂,意即那些由烷基金属或金属氢化物与过渡金属化合物反应而形成的,优选用于实施本发明。其中由烷基铝与周期表中第I族至III族金属的盐反应形成的催化剂特别有用。
可用于实施本发明的催化剂举例说明如下:
A.钛基催化剂,如在美国专利4376062、4379758中所叙述的。
B.铬基催化剂,如在美国专利3709853、3709954和4077904中所叙述的。
C.钒基催化剂,如氯氧化钒、乙酰丙酮钒。
D.金属茂催化剂,如在美国专利4530914、4665047、4752597、5218071、5272236和5278272中所叙述的。
E.阳离子型金属卤化物,如三卤化铝。
F.钴催化剂和其混合物,如在美国专利4472559和4182814中所叙述的。
G.镍催化剂和其混合物,如在美国专利4155880和4102817中所叙述的。
本发明方法中使用的过渡金属催化剂可以含有金属组分,助催化剂和任选的促进剂。金属组分可以是过渡金属化合物或两种或多种过渡金属化合物的混合物。一般,催化剂的过渡金属组分是可溶性的或不可溶性的、载体型的或非载体型的,或者有或没有填料的喷雾干燥的。换言之,该聚合催化剂可以用本领域技术人员熟知的技术生产的预聚物形式加到聚合段。
当金属组分被载在载体上时,典型载体包括:例如二氧化硅,炭黑,多孔交联聚苯乙烯,多孔交联聚丙烯,氧化铝,氧化钍、氧化锆或者卤化镁(例如氯化镁)载体材料。二氧化硅,炭黑和氧化铝是优选的载体材料。典型的二氧化硅和炭黑载体是固体,颗粒,多孔材料对聚合基本是惰性的。它以干粉状应用,其平均粒径约为10~250μm,优选的约为30~100μm;表面积至少为200m2/g,优选的至少约为250m2/g;孔径至少为100,优选的至少为200,一般,载体用量约为0.1~1.0毫摩尔过渡金属/g载体。优选实施方案中,两种类型炭黑作为载体。DARCO G-60(水萃取pH=5)以干粉状应用,其表面积为505m2/g,平均粒径为100μm,孔隙度为1.0~1.5cm3/g。NORIT A(水萃取的pH=9-11)以干粉应用,其表面积为720m2/g,平均粒径为45~80μm。
金属组分可用众所周知的方法被浸渍在载体上,例如,在载体材料存在下,将金属组分溶解于溶剂中或稀释剂中,例如烃或四氢呋喃中,然后在减压下蒸发除去溶剂或稀释剂。换言之,过渡金属组分可以溶解于溶剂或者稀释剂例如氢或四氢呋喃中,喷雾干燥,生成所希望的包括几乎没有二氧化硅或其它无机固体含量的良好形状的催化剂产物前体上。
用于制造聚丁二烯和聚异戊二烯的优选的过渡金属化合物是含有镍、钛、钴的化合物,其中钴和镍化合物是最优选的化合物。催化剂的金属组分的镍化合物是镍与单或双配位基的含有20个以上碳原子有机配位体有机镍化合物。“配位体”被定义为与金属原子或离子键合在一起的离子或分子和被认为键合到金属原子或离子上的离子或分子。单配位基意味有一个位置与金属可以生成共价键或配位键。双配位基意味有两个位置与金属生成共价键或配位键。有机镍化合物一般溶于惰性溶剂中。因此任何盐或含有1-20个碳原子的有机酸均可使用。有机镍化合物的代表化合物有:苯甲酸镍、乙酸镍、萘酸镍、辛酸镍、新癸酸镍、2-乙基己酸镍、二(π-烯丙基镍)、二(π-环辛基-1,5-二烯)镍,二(π-烯丙基镍三氟乙酸酯)、二(α-呋喃基二肟)镍、十六烷酸镍、硬脂酸镍、乙酰丙酮镍、硅含氧化铝的醛镍、二(水杨醛乙烯基二亚胺镍、二(环戊基二烯基)镍、环戊基二烯镍亚硝酰和四羰基镍。含有镍的优选化合物是羧酸镍盐或镍的有机络合化合物。
可以与含有镍组分一起使用的助催化剂包括:三乙基铝(TEAL)、三异丁基铝(TIBA)、一氯二乙基铝(DEAL)、部分水解二乙基氯化铝(DEAO)、甲基铝氧烷(MAO)或者改性甲基铝氧烷(MMAO)。
当MMAO或MMAO作为助催化剂时,它可以是下列物质的一种:(a)带支链的或环齐聚的聚烃基氧化物)S,其含有通式-(Al(R”’)O)-重复单元,式中R”’为氢、含有1~12个碳原子的烷基,或芳基,如被取代的或未被取代的苯基或萘基;(b)通式为〔A+〕〔BR* 4 -〕的离子盐,式中A+是能够从催化剂的过渡金属组分萃取出烷基、卤素或氢的阳离子路易氏酸或布朗斯台德酸(质子酸),B是硼,R*是被取代的芳香烃,优选的是过氟苯基;(C)通式为BR*3的硼烷基,式中R*如上规定的。
铝氧烷是本领域众所周知的,包括齐聚的线性烷基铝氧烷,结构式如下:和齐聚环烷基铝氧烷,其结构式如下:式中s为1-40,优选的为10-20;p是3-40,优选的为3-20;和R”’为含1-12碳原子的烷基,优选的为甲基或芳基,如被取代的或不被取代的苯基或萘基。改性甲基铝氧烷是用本领域的技术人员已知的技术,用C2-C12烷基,优选的是用异丁基取代20-80重量%的甲基生成的。
可与含镍组分一起用的促进剂包括氟化氢(HF)、或三氟化硼(BF3),或HF和/或BF3醚合物。
钛化合物(钛酸酯)可以是TiCl4、TiBr4、TiI4或Ti(OR)4,其中R是烷基。
可与含钛组分一起使用的助催化剂包括TEAL、TIBA、二烷基铝碘化物和MAO。
可与含钛组分一起使用的促进剂包括碘、有机醚合物。对于异戊二烯,使用TiCl4、TIBA和DPE(二苯基醚)的组合物。
钴化合物可以是任何有机化合物,例如有机酸的钴盐类、铝络合物等等。优选的钴化合物是从下列基团中选择:β-丙酮钴络合物,例如乙酰丙酮钴II和乙酰丙酮钴(III);β-酮酸钴络合物,例如乙酰丙酮酸乙基酯钴络合物;含有6个或多个碳原子的有机羧酸钴盐类,例如辛酸钴、环烷酸钴、苯甲酸钴;卤化钴铬合物,例如钴的氯化物-吡啶络合物;钴氯化物-乙醇络合物和与丁二烯配位的钴络合物,例如(1,3-丁二烯)〔1-(2-甲基-3-丁烯基)-π-烯丙基〕钴,它的制备,例如,将钴化合物与有机铝化合物、有机镍化合物或烷基镁化合物和1,3-丁二烯混合。其它典型钴化合物是山梨酸钴、乙二酸钴、乙基己酸钴、硬脂酸钴、和类似化合物,其中含有5-20碳原子的分子的有机部分,优选的是含8-18碳原子的分子的有机部分和一个或两个羧基官能团,以及乙酰丙酮酯。
与含有钴组分一起使用的助催化剂包括倍半氯化乙基铝(EASC)、二氯乙基铝(EADC)、DEACO、MAO和它们的混合物。
如果需要,可以使用少量水作为含钴金属组分的促进剂。
本发明中使用的流化助剂是对反应化学惰性的惰性颗粒材料。这类流化助剂包括炭黑、二氧化硅、粘土和其它类似材料如滑石。有机聚合材料也可以作为流化助剂使用。炭黑和二氧化硅为优选的流化助剂,最优选的是炭黑。被使用的炭黑材料初始粒径约为10-100nm,其聚集态(初始结构)的平均粒径约为0.1-10μm。炭黑的比表面积约为30-1500m2/gm和炭黑对邻苯二甲酸二丁酯(DBP)的吸附量约为80-350cc/100g。
被使用的二氧化硅是无定形态的,其初始粒径约为5-50nm,其聚集态的平均粒径约为0.1-10μm。二氧化硅的附聚物的平均粒径约为2-120μm。被使用的二氧化硅比表面积约为50-500m2/gm和它对邻苯二甲酸二丁酯(DBP)的吸附量约为100-400cc/100g。
本发明所使用的粘土平均粒径约为0.01-10μm和其比表面积约为3-30m2/gm。它对油的吸收率约为20-100g/100g。
可使用的有机聚合物包括乙烯、丙烯、丁烯和其它α-烯烃的聚合物和共聚物及聚苯乙烯,它们为粒状或粉末状。这些有机聚合材料的平均粒径约为0.01-100μm,优选的约为0.01-10μm。
一般情况下,流化助剂的使用量一般依赖于使用材料的类型和生产聚丁二烯和聚异戊二烯的类型。当使用炭黑和二氧化硅作为流化助剂时,它们的使用量约为0.3%-80%(重量计),优选的约为5%-60%,最优选的约为10%-45%〔均以生产最终产物(聚丁二烯和聚异戊二烯)的重量为基础计〕。典型的,当使用粘土和滑石作为流化助剂时,其用量以生产最终产物的重量为基础计约为0.3%-80%,优选的约为12%-75%。使用有机聚合材料的用量约为0.1%-50%(重量计),优选的约为0.1%-10%(重量计),均以生产最终产物的重量为基础计。
流化助剂在反应器顶部或在接近反应器顶部或在反应器的底部通入反应器,或者将流化助剂先通入循环管线直接通入反应器底部。优选的方案是将流化助剂从反应器的顶部或接近反应器的顶部通入反应器或者在流化床的上部通入反应器。优选的是将流化助剂通入反应器之前先进行净化处理以除去痕量的水份和氧。这一点可以用氮气吹扫和传统方法加热完成上述净化处理。流化助剂可以单独加入,或者与一种或多种单体一起加入,或者与可溶性非载体型催化剂一起加入。优选的是流化助剂单独加入。
本发明中特别适于生产聚合物物料的流化床反应体系在附图中进行说明。图标中,反应器10由反应段12和速度降低段14组成。
通常,反应段的高度与直径之比可在约2.7∶1至约4.6∶1范围内变化。当然此范围可以变到较大的或较小的比例,并且取决于所需的生产量。速度降低段14的截面积通常为约2.6至约2.8乘以反应段12的截面积的范围内。
反应段12包括一正在生长的聚合物颗粒、形成的聚合物颗粒和少量催化剂的床,该床被以补充进料形式的可聚合的和改性气体组分及通过反应段的循环流体连续流动而流化。为保持一个能生存的流化床,通过流化床的表面气体速度必须超过流化所需的最小流速,优选至少超过最小流速0.1ft/sec。通常表面气体速度不超过5.0ft/sec,并且一般不大于2.5ft/sec就足够了。
床始终含有颗粒以防止形成局部“热点”,并在整个反应段中截留和分配催化剂。开始时,反应器在气体流动之前通常充满一层特定的聚合物颗粒。这些颗粒可与要形成的聚合物种类相同或不同。当不同时,它们作为第一批产品与形成的所需聚合物颗粒一起卸出。最终,所需聚合物颗粒的流化床取代初始床。
在流化床中使用的部分或完全活化的前体组成和/或催化剂优选贮存于储罐16中并用对贮存材料惰性的气体,如氮气或氩气覆盖备用。
流化通过流体高速循环流入并流过床实现,通常其流速为补充流体进料速度的50-150倍。流化床具有各个移动颗粒的紧密物料的一般外观,这是由通过床的气体的渗透造成的。通过床的压力降等于或稍大于床的重量除以截面积。所以它取决于反应器的几何形状。
补充流体在18处加入床中。补充流体的组成由气体分析仪21测定。用气体分析仪21测定循环流的组成,并调节补充流的组成以便反应段中保持基本稳定状态的气体组成。
气体分析仪为常规气体分析仪,可按常规方法操作测定循环流的组成以容易保持进料流组分的比例,此仪器可通过很多途径买到。气体分析仪21通常从位于速度降低段14和热交换器24之间的取样点接收气体。
沸点较高的单体可以各种方式加入反应段,包括通过喷嘴(图中没有表示出)直接注入床中或由位于床上部的喷嘴(未表示出)喷在床的顶部,这样通过循环气流可有助于消除一些夹带的粉尘。如消耗速度相当小,较重的单体可简单地通过悬浮于进入反应器底部的循环气流加入反应段。
为确保完全流态化,循环流和(需要时)部分补充流通过循环管线22在床的底部26处回到反应器中。优选在回料处之上设一气体分配器板28,以有助于使床流化。循环流通过床时吸收聚合反应产生的反应热。
在床中未反应的部分流化流从聚合段移去,优选使它通过床上面的速度降低段14,在此处将夹带的颗粒可落回床中。
循环流在压缩机30中被压缩后,在回到床中之前通过热交换段移走热量。热交换段通常为一热交换器24,它可以是卧式或立式类型。如果需要,可使用几个热交换器分步降低循环气流的温度。还有可能将压缩机设在热交换器的下游或几个热交换器之间的中间处。循环流经冷却后从反应器底26回到反应器中并通过气体分配器板28进入流化床。气体折流板32优选安装在反应器入口处以阻止所含的聚合物颗粒沉降出并附聚成固体块料,同时防止液体累积在反应器底部,还有助于循环气流中含液体过程与不含液体过程之间及不含液体过程与含液体过程之间易于转化。适于此目的的气体折流板的例子是在美国专利4933 149中所述的设备。
选择的床温通过不断移走反应热在稳定状态条件下保持基本恒温。没有出现明显的温度梯度存在于床的上部分。温度梯度会存在于床底部约6至12英寸厚的层中,此即入口流体温度与床的剩余物的温度之间的梯度。
良好的气体分配对于反应器操作起重要作用。流化床中含有正在生长的和已形成的散式聚合物颗粒及催化剂颗粒。由于聚合物颗粒是热的并且可能有活性,必须防止其沉降,因为如果允许静止物料存在,含在其中的任何活性催化剂都可使反应继续并造成熔化。所以,以足以保持整个床处于流化状态的速度使循环流体扩散通过床是重要的。
气体分配板28是一种实现良好气体分配的优选装置,可以是筛子、长眼筛板、孔板、泡罩型板等等。板的元件都可以是固定的,或可用美国专利3298792中所述的活动型板。无论其如何设计,它必须使循环流体扩散通过床底的颗粒以保持床处于流化状态,同时当反应器停止运转时还应起到支撑树脂颗粒静止床的作用。
优选的气体分配器板28的类型为金属的并具有穿过其表面分布的孔。这些孔直径一般为大约1/2英寸。这些孔延伸过板。在每个孔上设一如36标记的三角形角铁,它安装在板28上面。这些角铁起到分配流体沿板表面流动的作用以避免固体滞流段。此外当床沉降时它们可防止聚合物流过孔。
任何对催化剂和反应物惰性的流体也可存在于循环流中。若要使用活化剂化合物,优选将其加入自热交换器24的反应系统下游,在此情况下,活化剂可从给料器38经管线40加入循环系统中。
在本发明实施中,操作温度可为约-100℃至约150℃范围内,其中温度为约40℃至约120℃是优选的。
对于生产聚烯烃树脂,流化床反应器可在压力高达大约1000psi,优选压力为大约100psi至大约600psi条件下操作。在较高压力下操作有利于热交换,原因在于随着压力的增加,气体单位体积热容量也增加。
部分或所有活化的前体组成和/或催化剂(以下统称为催化剂)以与消耗相同的速度从分配器板28上面的42处注入床中。催化剂优选从床中发生聚合物颗粒混合良好之处注入。在分配板上面某处注入催化剂对于令人满意的地操作流化床聚合反应器是一重要特征。将催化剂注入分配器板下的区域,可能那里引起开始聚合并最终造成分配器板堵塞。将催化剂直接注入床中有助于催化剂在整个床中均匀分配并趋于避免形成催化剂浓度高的局部点,这种点会引起“热点”的形成。将催化剂在床上面注入反应器中会导致过量的催化剂夹带进循环管线中,并在此管线中发生聚合可能最终导致管线和热交换器堵塞。
可用各种技术将载体催化剂注入反应器。然而,优选用如在美国专利3779712中公开的催化剂加料器将催化剂连续加入反应器中。对于溶液、液体或淤浆状态的催化剂的加料方法,优选地是按照Brady等的美国专利5,317,036和1995年3月31日提交的美国申请的申请号414,522题名为“在粘性聚合物生产过程中控制颗粒生长的方法”的公开方法进行加料。催化剂优选在与反应器壁相距为反应器直径的20%至40%,高度为床高的约5%至约30%处加入反应器中。
对催化剂惰性气体,如氮气或氩气,优选用于将催化剂载入床中。
床中聚合物生产速率取决催化剂注入速度和循环流中单体的浓度。可方便地通过简单调节催化剂注入速率控制生产速率。
由于催化剂注入速率的任何变化将改变反应速率,因而床中产生热的速率也会改变。将进入反应器中的循环流的温度调高或调低以适当产生热的速率的变化。这就确保了床中的温度基本维持恒定。当然,要用流化床和循环流冷凝系统两者的完备仪器检测床中温度的任何变化,以便能使操作器或常规自控系统可适当调节循环流的温度。
在给定的操作条件下,流化床通过按颗粒聚合物产品的形成速率,卸出作为产品部分床以保持其高度基本恒定。由于产生热的速率直接涉及到产品形成速率,如果无可汽化的液体存在于入口流体中,则测量的穿过反应器的流体的温度升高(入口流体温度与出口流体温度之差)表示在恒定流体流速下颗粒聚合物的形成速率。
对于从反应器10中卸出的颗粒聚合物产品,需要并且优选从产品中分离出流体并使流体回到循环管线22中。现有技术中有很多方法完成此过程。一个优选系统如附图所示。所以,流体和产品在44处离开反应器10并经阀门48进入产品卸料罐46中,阀门48设计为球形阀,以便打开时将其对流动的限制减至最小。位于产品卸料罐46上面和下面的阀门为常规阀门50、52,后者适合提供一路线使产品进入产品缓冲罐54中。产品缓冲罐54有一放空装置,如管线56所示,及一进气体装置,如管线58所示。在产品缓冲罐54的底部还设一卸料阀60,当其处于开启的位置时,卸出产品为了输送去贮存。当阀门50处于开启位置时,将流体释放进缓冲罐62。从缓冲罐62出来的流体直接通过过滤吸收器64,然后经过压缩机66后经管线68进入循环管线22。
在典型操作模式中,阀门48开启而阀门50、52处于关闭位置。产品和流体进入产品卸料罐46。将阀门48关闭并使产品沉降于产品卸料罐46中。然后打开阀门50使流体从产品卸料罐46中流入缓冲罐62中,从此将其连续压回循环管线22中。然后阀门50关闭时,打开阀门52使产品卸料罐46中的所有产品流入产品缓冲罐54中。然后关闭阀门52。将产品用惰性气体,优选氮气清洗,惰性气体通过管线58进入产品缓中罐54并经管线56放空。然后产品从产品缓冲罐54经阀门60卸出并经管线20输送去贮存。
阀门开关的特定时间顺序通过使用现有技术中公知的常规程序控制器实现。此外,阀门通过周期性地将气流直接通过阀门并返回到反应器而基本保持无附聚颗粒。
可替代使用的另一优选产品卸料系统是在Robert G.Aronson于1981年7月28日申请的申请号为287815、名称为“流化床卸料系统”的现在已批准的美国专利US4621952中公开并要求保护的系统。此系统使用包括沉降罐和输送罐的至少一(平行)对罐串联排列,并将从沉降罐顶分离出的气相送回反应器中靠近流化床顶的某处。所述替代的优选产品卸料系统免去了需要如附图体系中所示的再压缩管线64、66、68。
流化床反应器中装有适当的放空(未表示出)系统使床在起动和关闭时放空。反应器不需要使用搅拌和/或刮壁。循环管线22和其中的设备(压缩机30、热交换器24)表面应光滑,并且避免不必要的障碍以便不阻碍循环流体流动或不夹带颗粒。
可按照本发明生产的聚合物例子如下:
聚异戊二烯
聚苯乙烯
聚丁二烯
SBR(丁二烯与苯乙烯的共聚合聚合物)
ABS(丙烯腈、丁二烯和苯乙烯的聚合物)
Nitrile(丁二烯与丙烯腈的共聚物)
Butyl(异丁烯与异戊二烯的共聚物)
EPR(乙烯与丙烯的共聚物)
EPDM(乙烯与丙烯和二烯如己二烯、双环戊二烯或亚乙基降冰片烯的共聚物)
Neoprene(氯丁橡胶)
Silicone(聚二甲基硅氧烷)
乙烯与乙烯基三甲氧基硅烷的共聚物
乙烯与一种或多种丙烯腈、马来酸酯、醋酸乙烯酯、丙烯酸和甲基丙烯酸酯等等的共聚物。
当需要使用一种或多种沸点都相当高并且在优选用于按照本发明的气相流化床生产的温度和压力条件下为液体的单体生产聚合物或共聚物时,必须使用在选取的流化床中聚合的条件下保持气态的惰性物质。适合此目的的惰性气体如氮气、氩气、氖气、氪气等等。饱和烃如乙烷、丙烷、丁烷等及卤代烷如氟利昂也可使用。在所述条件下保持气态的其它材料如二氧化碳、只要基本上是惰性的并且不影响催化剂的性能,也可使用。
氮气,因其物理性质和价格相对低廉,优选用作由高沸点单体如苯乙烯、乙烯基醋酸、丙烯腈、丙烯酸甲酯、甲基丙烯酸甲酯等等生产聚合物的介质。在相当低的温度下保持气态的烷烃如乙烷、丙烷也是优选的。
防止反应器结垢和聚合物附聚的常规技术可用于实施本发明。这些技术的例子有加入微小分离的颗粒物料以防止附聚,如在美国专利4994534和5200477中所述的;加入产生负电荷的化学物质以平衡正电压或加入产生正电荷的化学物质以中和负电势,如美国专利4803251中描述的。还可以连续或间歇加入抗静电剂以防止或中和产生的静电荷。
本发明的颗粒状聚丁二烯和/或聚异戊二烯弹性体可以采用本领域技术人员众所周知的设备和方法,与下列其它物质混合:比如其它弹性体,如天然橡胶、丁苯橡胶、(卤代)丁基橡胶、乙烯-丙烯-二烯橡胶;增强填料,如炭黑、二氧化硅;加工助剂、抗降解剂和硫化剂。在这些混合物中,初级颗粒形状的聚丁二烯或聚异戊二烯与其它弹性体混合比用固体球形传统聚丁二烯或聚异戊二烯混合的更均匀。一般地希望将弹性混合体混合均匀以使硫化物的机械性能最佳化、此外,如果将本发明的惰性颗粒材料作为聚合过程中或聚合后仍保持颗粒度的助剂,也偶然成为该聚合物的增强填料(如炭黑),而另一好处可能是将该填料分散于该混合物中所需要的混合时间可在较短时间内完成。这是因为填料在一般情况下,在将它分散之前必须在混合过程中首先解附聚,在这种情况下,填料在参与混合过程中已经基本上解附聚和被分散了。
由上一节描述的颗粒状自由流动的聚丁二烯和/或聚异戊二烯制备的弹性混合物,与由球状聚丁二烯和/或聚异戊二烯制备的弹性混合物相比,特别适宜制做充气轮胎的组分。比如生产汽车子午线轮胎,其专用配方弹性混合物可以通过挤出机模头挤出生产子午线轮胎用的外胎面、胎侧壁、外护圈包布组件用的胶条或生产空气支撑轮胎衬里层用的片状胶料。其它专门配方的弹性混合物可以压延成帘布织物或钢丝帘布织物,以生产帘布层用的帘布加强层片状胶料和轮胎的环形带组件。这种“生”轮胎或未硫化轮胎的制造方法是将各种组件(环形带和外胎面除外)组装在圆形鼓表面上,再径向扩张,轴向压缩这些组合件,以便生产腰鼓外形,然后将前述环形带和外胎面组件放置在腰鼓形周围的位置上。最后生轮胎的硫化是对着闭式加热铝模具内表面吹高压蒸汽进行硫化的。在流化过程的初期,当各种弹性混合物直到软化易流动时,对着模具内表面的轮胎压力生产出最精确外型、胎面花纹、侧壁文字和装饰标志。在硫化过程的后期,在各种弹性混合物中间发生了热-活化交联反应,以致于当模具最后打开时,每种混合物都进行了交联,其交联程度对预期的应用基本上是优化的。
当本发明的颗粒状聚丁二烯用作轮胎混合物的组件时,它特别赋于其耐磨性、耐疲劳断裂、生热低、低滚动阻力。本发明的颗粒状聚异戊二烯,特别赋于轮胎装配粘性和生坯强度,这一点可使生胎的装配和装卸简便,同时赋于其耐撕裂和耐切割性。本领域技术人员用已知的技术也可以将由本发明的气相法生产的颗粒状自由流动聚丁二烯和聚异戊二烯用于其它模塑制品和挤出制品。本领域技术人员用已知的技术也可以将由本发明的气相法生产的颗粒状相对自由流动丁苯橡胶(SBR)用于模塑制品和挤出制品。
下面的实施例是用于说明本发明的。
实施例1
在本发明方法实施例中,前述流化床反应系统按下面的描述进行操作以生产乙烯-丙烯二烯三元共聚物。在下列反应条件生产聚合物:反应器温度为40℃,压力为290psia。反应器内单体和共聚单体的分压(露点)对乙烯为90psia,对丙烯为198psia。氢气的分压为2.0psia。将亚乙基-降冰片烯(ENB)以0.53lb/h的速度注入反应器的聚合物。反应器体积为55ft3;反应器内树脂的重量为112lbs。本实施例中使用的催化剂体系为乙酰丙酮钒,并用氯化二乙基铝作为助催化剂,并用三氯乙酸乙酯作为促进剂。生产速率为20lb/h。产品的门尼值为55。
注入的ENB有75%通过聚合结合于聚合物中。溶于聚合物中的未反应的ENB为聚合物重量的0.66%。对于反应器内的112lb树脂,未反应的ENB总量为0.74lb。若未反应的ENB在反应器内完全气化,其分压应为0.6764psia。
在40℃时,乙烯的饱和压力为2187.7psia,丙烯为337.1psia,ENB为0.262psia。由于反应器内乙烯和丙烯的分压比其饱和压力要小得多,不存在冷凝的乙烯或丙烯。然而,计算出反应器内未反应的ENB的分压比其饱和压力大得多。所以ENB必然保持液体状态并被聚合物吸收。
实施例2
按照下列反应条件在上述流化床反应体系中制备乙烯-丙烯二烯三元共聚物:反应器温度40℃,压力363.4psia。反应器内单体和共聚单体的分压对于乙烯为90psia,丙烯为198.2psia。氢气的分压为2.2psia,氮气的分压为72.6。将单体亚乙基降冰片烯(ENB)以0.53lb/h的速率注入反应器的聚合段。反应器的体积为55ft3。反应器内树脂的重量为112lbs。本实施例中使用的催化剂体系为乙酰丙酮钒,用氯化二乙基铝作为助催化剂,三氯醋酸乙酯为促进剂。生产速率为20lb/h。产品的门尼值为55。
注入的ENB有75%通过聚合被结合进聚合物中。溶解于聚合物中的未反应的剩余ENB为聚合物重量的0.66%。反应器内树脂量为112lb,未反应的ENB总量为0.74lb。若未反应的ENB在反应器内完全气化,其分压应为0.6764psia。
在40℃时,乙烯的饱和压力为2187.7psia,丙烯为337.1psia,ENB为0.262psia。由于反应器内乙烯和丙烯的分压比其饱和压力小得多,因此没有乙烯或丙烯冷凝。然而,计算出的反应器内未反应的ENB的分压比其饱和压力大得多。因此,ENB必然保持液体状态并被聚合物吸收。
实施例3-10
下列实施例3-10以表的形式列出,根据本发明按照表中的操作条件生产各种不同的聚合物。这些实施例使用不同的催化剂体系和不同循环气体组成说明本发明的实施。实施例标号 3 4 5 6
产品: 聚丁二烯 SBR ABS 聚苯乙烯反应条件温度(℃) 40 40 40 40压力(psi) 100 110 200 100表面速率 1.75 2.0 1.5 1.5(ft/s)生产速率 30 25 20 40(lb/h)反应器总体积 55 55 55 55
(ft3)反应段体积 7.5 7.5 7.5 7.5
(ft3)
床高(ft) 7.0 7.0 7.0 7.0
床直径(ft) 1.17 1.17 1.17 1.17
床重(lbs) 112 112 112 112循环气体组成:
N2 20 27.3 58.0 99.7
丁二烯 80 72.5 39.9 -
苯乙烯 - 0.2 0.15 0.3
丙烯腈 - - 1.95 -催化剂 Co(acac)3 *Co(acac)3 *Co(acac)3 *Cp2ZrMe2 **助催化剂: 三乙基铝 三乙基铝 三乙基铝 MAO***重单体进料速率
(lb/h)
丁二烯 46.2 9.62 2.46 -
苯乙烯 - 20.83 15.33 44.4 丙烯腈 - 7.08 -聚合物组成:丁二烯 100 25 8 -苯乙烯 75 69 100丙烯腈 - 23 -* 三乙酰丙酮钴** 二甲基二茂锆*** 甲基铝氧烷
实施例7
在本发明方法实施例中,前述流化床反应系统按下面的描述进行操作以生产聚丁二烯。在下列反应条件下生产聚合物:反应器温度55℃,总反应器压力为100psia。反应器内的丁二烯单体分压为80psia,氮气的分压为20psia。本实施例中使用的催化剂体系是三(乙酰丙酮)钴。它可以载在二氧化硅上或者作为二氯甲烷溶液再进料。甲基铝氧烷作助催化剂。调节催化剂和助催化剂进料的摩尔比Al∶Co为400∶1。在稳态下,单体以47.8lb/h速度通入反应系统。Dried N-650炭黑以20/b/h速度通入反应器。丁二烯单体以15lb/h速度离开反应器进入放空气流中。调节炭黑的含量后,产率为30lb/h聚合物。产品的门尼粘度ML(1+4@100℃)55。其它条件见表中实施例7。
在稳态下,以47.8lb/h丁二烯总量连续通入反应器,作为放空系统气体或作为聚合物离开反应器计算的丁二烯总量为45lb/h。在离开反应器的聚合物中未反应液态丁二烯单体必须保持2.8lb/h的差额。由于出料的聚合物与流化床中的聚合物是等量的,所以流化床中的聚合物必须含有同样比例的液态丁二烯,即必须有10.4lb液态单体溶解于112lb聚合物床中。
反应器体积为55fg3。在分压为80psia时,反应器的气相中有37.61b丁二烯。因此反应器中未聚合的丁二烯为48.01b(=37.6+10.4)。如果一旦这个反应器的气相中全是这种丁二烯,其分压为104psia,其冷凝温度为61℃。因此,55℃下的反应器是在低于聚合段中存在的单体冷凝温度下操作。从而气相反应器中的这种液相单体的存在不能引起聚合物的附聚。实施例标号 7 8 9 10
产品: 聚丁二烯 SBR ABS 聚异戊二烯反应条件温度(℃) 55 55 55 65总压力(psia) 100 110 200 100表面速率 1.75 2.0 1.5 1.75(ft/s)生产速率 30 25 20 30(lb/h)反应器总体积 55 55 55 55(ft3)反应段体积 7.5 7.5 7.5 7.5(ft3)床高(ft) 7.0 7.0 7.0 7.0床直径(ft) 1.17 1.17 1.17 1.17床重(lbs) 112 112 112 112循环气体组成(mole%):N2 20 27.3 58.0 70丁二烯 80 72.5 39.9 -苯乙烯 - 0.2 0.15 -丙烯腈 - - 1.95 -异戊二烯 - - - 30催化剂: Co(acac)3 * CpTiCl3 CpTiCl3 TiCl4助催化剂: MAO*** MAO*** MAO*** TEAL**单体进料速率(lb/h)丁二烯 47.8 9.62 2.46 -苯乙烯 - 20.83 1 .33 - 丙烯腈 - - 7.08 -异戊二烯 - - - 35.4总单体放空速率 15 1 1 2(lb/h)聚合物组成(wt.%):丁二烯 100 25 8 -苯乙烯 75 69 -丙烯腈 - - 23 -异戊二烯 - - - 100* 三乙酰丙酮钴** 二苯基醚*** 甲基铝氧烷
实施例11
向保持22℃恒温的气相搅拌床反应器中加入4.2lb干炭黑粉末起流化助剂作用。并向该反应器加入0.039lb倍半氯化乙基铝(EASC)。然后加入0.61lbs1,3-丁二烯和足够的氮气,以使总反应器压力达到315psia。开始加入少量载体CoCl2(吡啶)4催化剂。同时开始加入少量10%(重量)的倍半氯化乙基铝助催化剂异戊烷溶液。调节进料使Al∶Co为15∶1(摩尔比)。在2.2h聚合反应期间,补加入的丁二烯总量为6.84lbs,以代替已聚合的或放空的丁二烯。聚合期间离开反应器的少量放空气带走的丁二烯总量为0.22lbs。在聚合反应终了时,催化剂和助催化剂停止进料。反应器泄压,用氮气吹除剩余的丁二烯。从反应器中排放出聚合物,该产品不含由于发生附聚生成的任何团块。正相反,该产品应该是自由流动的、细粉状颗粒粉末。打开反应器并净化,以确保回收全部产品。调节炭黑初始加料量,使其满足回收固体产品总量的要求。分批生产期间生成的丁二烯聚合物和停车期间反应器中存在的丁二烯聚合物的残品总量为5.73lbs。由于加入反应器的丁二烯总量为7.45lbs(=6.84+0.61)和生成聚合物离开反应器的丁二烯及连续放空气中的丁二烯总量为5.95lbs(=5.73+0.22),因此,当聚合反应终了时,反应器中必须存有1.50lbs丁二烯单体。当泄压和放空时,这些单体应该从反应器中除去。
反应器体积为61.71(或2.18ft3)。在22℃时,1,3-丁二烯蒸汽压为35psia。因此以饱和气存在于反应器中的大量丁二烯为0.73lb。停车时反应器中存在的未聚合丁二烯总量为1.50lb,气相中最多为0.73lb,其余的丁二烯(0.77lb)必须存在于冷凝相中,比如溶解于聚合物中。因此,反应器是在低于单体存在的冷凝温度下操作。与5.73lb聚合物结合的液态单体0.77lb,总量为13.4lb冷凝丁二烯单体/100lbs聚丁二烯。在气相反应器中这种液态单体的存在并不引起聚合物的附聚。本实施例详情见下表。
12-18实施例按实施例11推导出;但是其变化见下表。
实施例12用的载体催化剂的制备
将31.9g二氧化硅(600℃活化)和7.272g CoCl2(吡啶)4加入到500ml干燥的氮气吹扫过的闪蒸釜中。150ml CH2Cl2加入该釜中。浆液搅拌几分钟,然后真空下除去溶剂。
实施例18用的溶液催化剂的制备。
将1.648g三(乙酰丙酮)钴加入经干燥氮气吹扫的闪蒸釜中,再加入100ml干燥的CH2Cl2。搅拌该混合物几分钟,并将其加入到密封可增压的钢瓶中,并以溶液加入反应器。实施例标号 11 12 13 14
产品: 聚丁二烯 聚丁二烯 聚丁二烯 聚丁二烯催化剂详述催化剂 载于二氧 载于二氧 载于二氧 载于二氧
化硅上的 化硅上的 化硅上的 化硅上的
二氯吡啶钴 二氯吡啶钴 乙酰丙酮钴 二氯吡啶钴助催化剂 异戊烷中的 甲苯中的15% 异戊烷中的 甲苯中的
10%EASC DEACO 10%EASC 10%MAO方法条件反应温度(℃) 22 23 20 20 丁二烯 30 30 30 30分压(psia)生产的聚 5.7 6.3 5.4 5.8合物(lb)反应时间 2hr10min 3hr 2hr15min 1hr20min产品分析炭黑N-650 44 38 44 45(%)分子筛平均 0.016 0.019 0.015 0.034粒径(英寸)Al催化剂 15 28 11 607进料比*聚合物中的 55 81 94 19钴含量(ppm)减粘粘度 1.5 1.0 1.0 3.6(dl/g)门尼粘度 42
ML(1+4@100℃)
顺式-1,4 93 92 92 98.4
含量%*连续进料中的Al/过渡金属的摩尔比实施例标号 15 16 17 18产品: 聚丁二烯 聚丁二烯 聚丁二烯 聚丁二烯催化剂详述催化剂 载于二氧 载于二氧 载于二氧 二氧甲烷
化硅上的 化硅上的 化硅上的 中的乙酰
二氯吡啶钴 二氯吡啶- 辛酸钴 丙酮钴
IPPD二胺钴 助催化剂 甲苯中10% 甲苯中15% 甲苯中15% 异戊烷中
MAO EASC DEACO 10%DEAC方法条件反应温度(℃) 20 20 20 20丁二烯 30 30 30 25分压(psia)生产的聚 4.2 6.5 6.8 5.7合物(lb)反应时间 1hr 4hr30min 3hr10min 4hr30min产品分析炭黑N-650 56 44 41 44(%)分子筛平均 0.036 0.016 0.013 无粒径(英寸)Al催化剂 385 62 10 45进料比*聚合物中的 45 84 195 45钴含量(ppm)减粘粘度 1.0 1.1 1.0 0.7(dl/g)门尼粘度 40ML(1+4@100℃)顺式-1,4 95.7 96 92.1 90含量%+N-异丙基-N’-苯基-p-亚苯基二胺在催化剂中含量为15摩尔/摩尔催化剂*连续进料中的Al/过渡金属的摩尔比实施例标号 19 20 21
产品: 聚丁二烯 聚丁二烯 聚异戊二烯催化剂详述催化剂 环戊二烯 辛酸镍 TiCl4/
三氯化钛 二苯醚助催化剂 甲苯中的10% 10%TEAL TIBA
MAO 10%BF3醚合物产品条件反应温度(℃) 50 50 50单体分压 60 60 25(psia)反应时间 2hr 4hr 4hr产品分析炭黑 40 40 40N-650(%)助催化剂/ 500 60 10催化剂进料比* *连续进料中的Al/过渡金属的摩尔比
Claims (35)
1. 一种在具有聚合段的搅拌床或气体流化床聚合反应器中,在聚合反应条件下生产聚丁二烯或聚异戊二烯的方法,该方法包括:
(i)在一种惰性颗粒材料和任选至少一种惰性气体存在下,将丁二烯或异戊二烯单体加入到含有一种正在生长的聚合物颗粒床的所述聚合段中;
(ii)将一种含有镍、钴、钛金属组分、或它们的混合物的聚合催化剂,一种助催化剂和任选的一种促进剂连续地或间断地加入所述聚合段中;
(iii)将聚丁二烯或聚异戊二烯产品从所述聚合段连续地或间断地卸出;
(iv)将未反应的丁二烯或异戊二烯从所述聚合段卸出,压缩和冷凝所述丁二烯或异戊二烯和当有惰性气体存在时的该惰性气体,同时保持所述聚合段的温度低于存在于所述聚合段中单体的露点。
2.根据权利要求1的方法,其中所述聚合段的温度保持低于存在于所述聚合段的单体的冷凝温度。
3.根据权利要求1的方法,其中所述聚合段的条件是在所述聚合段中基本上不存在不被吸附在固体颗粒物上或不被吸附到固体颗粒物中的液体。
4.根据权利要求1的方法,其中所述聚合段的条件是至少部分单体是不被吸入固体颗粒物中的液体。
5.根据权利要求1的方法,其中所述聚合过程是在选自炭黑,二氧化硅,粘土,滑石及其混合物的惰性颗粒物存在下进行的。
6.根据权利要求5的方法,其中所述惰性颗粒物为炭黑,二氧化硅或它们的混合物。
7.根据权利要求1的方法,其中所述聚合催化剂含有一种镍金属组分;助催化剂选自三乙基铝,三异丁基铝,一氯二乙基铝,部分水解了的一氯二乙基铝,甲基铝氧烷,改性的甲基铝氧烷及它们的混合物;促进剂选自氟化氢,三氟化硼,一种氟化氢的醚合物,一种三氟化硼的醚合物,及它们的混合物。
8.根据权利要求1的方法,其中所述聚合催化剂含有一种钛金属组分;助催化剂选自三乙基铝,三异丁基铝,三烷基铝碘化物,甲基铝氧烷及它们的混合物和任选的促进剂是碘,一种有机醚合物,或它们的混合物。
9.根据权利要求1的方法,其中所述聚合催化剂含有一种钴金属组分;助催化剂选自倍半氯乙基铝,二氯乙基铝,部分水解的一氯二乙基铝,一氯二异丁基铝,部分水解的一氯二异丁基铝,一氯二乙基铝,甲基铝氧烷及它们的混合物。
10.根据权利要求9的方法,其中所述聚合催化剂另外还含有水作为一种促进剂。
11.根据权利要求1的方法,其中所述聚合催化剂载在如下物质上:二氧化硅,炭黑,多孔的交联聚苯乙烯,多孔的交联聚丙烯,氧化铝,氧化钍,氧化锆,氯化镁或它们的混合物。
12.根据权利要求11的方法,其中所述催化剂载在二氧化硅或炭黑上。
13.根据权利要求1的方法,其中所述丁二烯或异戊二烯是连续地加入的。
14.根据权利要求1的方法,其中所述方法是在一种用于控制所述反应器中静电程度的试剂或设备存在的条件下进行。
15.根据权利要求1的方法,其中所述反应器中的静电压基本保持中性。
16.根据权利要求1的方法,其中所述惰性气体为氮气。
17.根据权利要求1的方法,其中所述聚合催化剂为喷雾干燥的。
18.根据权利要求1的方法,其中所述聚合催化剂作为一种预聚合物加入聚合段中。
19.根据权利要求1的方法,其中所述加入到聚合段的聚合催化剂是一种液体,溶液或淤浆。
20.根据权利要求1的方法生产的颗粒状聚丁二烯或聚异戊二烯。
21.颗粒状的聚丁二烯或聚异戊二烯。
22.用权利要求1的聚丁二烯或聚异戊二烯生产的轮胎。
23.用颗粒状聚丁二烯或聚异戊二烯生产的轮胎。
24.用权利要求1的聚丁二烯或聚异戊二烯生产的模塑制品。
25.用颗粒状聚丁二烯或聚异戊二烯生产的模塑制品。
26.用权利要求1的聚丁二烯或聚异戊二烯生产的挤出制品。
27.用颗粒状聚丁二烯或聚异戊二烯生产的挤出制品
28.在含有聚合段的搅拌床或气体流化聚合反应器中,在聚合反应条件下生产聚丁二烯或聚异戊二烯的方法,该方法包括:
(i)在有一种惰性颗粒材料和任选至少一种惰性气体存在条件下,将丁二烯或异戊二烯单体加入到含有一种正在生长的聚合物颗粒床的所述聚合段中;
(ii)将一种含有镍、钴、钛金属组分或它们的混合物的聚合催化剂,一种助催化剂和任选的一种促进剂连续地或间断地加入所述聚合段中;
(iii)将聚丁二烯或聚异戊二烯产品从所述聚合段连续地或间歇地卸出;
(iv)将未反应的丁二烯或异戊二烯从所述聚合段卸出,压缩和冷却所述丁二烯和异戊二烯和当有惰性气体存在时的惰性气体。
29.在含有聚合段的搅拌床或气体流化聚合反应器中,在聚合反应条件下生产苯乙烯-丁二烯橡胶的方法,该方法包括:
(i)在有一种惰性颗粒材料和任选至少一种惰性气体存在条件下,将苯乙烯和丁二烯单体加入到含有一种正在生长的聚合物颗粒床的所述聚合段中;
(ii)将一种金属茂聚合催化剂,一种助催化剂和任选的一种促进剂连续地或间歇地加入所述聚合段中;
(iii)将苯乙烯-丁二烯橡胶产品从所述聚合段连续地或间歇地卸出;
(iv)将未反应的丁二烯和苯乙烯从所述聚合段卸出,压缩和冷却所述丁二烯和苯乙烯和当有所述惰性气体存在时的惰性气体,同时保持所述聚合段的温度低于存在于所述聚合段的至少一种单体的露点。
30.根据权利要求29的方法,其中所述聚合段的温度保持低于存在于所述聚合段的至少一种单体的冷凝温度。
31.根据权利要求29的方法,其中所述聚合段中的条件是使所述聚合段中基本上不存在不被吸附在固体颗粒物上或不被吸附到固体颗粒物中的液体。
32.根据权利要求29的方法,其中所述聚合段的条件为至少部分单体是不被吸入固体颗粒物中的液体。
33.根据权利要求29的方法,其中所述聚合方法是在选自炭黑,二氧化硅,粘土,滑石及其混合物的惰性颗粒物存在的条件下进行的,其中助催化剂是甲基铝氧烷。
34.根据权利要求29的方法生产的苯乙烯和丁二烯的颗粒状聚合物。
35.苯乙烯和丁二烯的颗粒状聚合物。
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CN108380141A (zh) * | 2018-03-16 | 2018-08-10 | 安丽华 | 鼓泡床反应器、甲基丙烯酸甲酯生产设备 |
CN110559845A (zh) * | 2018-06-06 | 2019-12-13 | 中国石油化工股份有限公司 | 一种含有丁二烯组分有机废气的化学处理方法 |
CN110559844A (zh) * | 2018-06-06 | 2019-12-13 | 中国石油化工股份有限公司 | 一种含有苯乙烯组分有机废气的化学预处理方法 |
CN110559844B (zh) * | 2018-06-06 | 2022-06-28 | 中国石油化工股份有限公司 | 一种含有苯乙烯组分有机废气的化学预处理方法 |
CN110559845B (zh) * | 2018-06-06 | 2022-06-28 | 中国石油化工股份有限公司 | 一种含有丁二烯组分有机废气的化学处理方法 |
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