CN1249733A - 用于制备烃树脂的金属氧化物固体酸催化剂 - Google Patents
用于制备烃树脂的金属氧化物固体酸催化剂 Download PDFInfo
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- CN1249733A CN1249733A CN98803007A CN98803007A CN1249733A CN 1249733 A CN1249733 A CN 1249733A CN 98803007 A CN98803007 A CN 98803007A CN 98803007 A CN98803007 A CN 98803007A CN 1249733 A CN1249733 A CN 1249733A
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- Prior art keywords
- monomer
- metal oxide
- oxide solid
- heteropolyacid
- catalyzer
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Classifications
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
- C08F4/12—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of boron, aluminium, gallium, indium, thallium or rare earths
- C08F4/14—Boron halides or aluminium halides; Complexes thereof with organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F240/00—Copolymers of hydrocarbons and mineral oils, e.g. petroleum resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
Abstract
金属氧化物固体酸用作催化剂,用于含有纯单体(例如苯乙烯基单体),C5单体,和C9单体中至少之一的原料聚合制备烃树脂。在使用前,可以从固体酸催化剂上除去自由缔合水。制备的树脂的软化点(环球法)为约5~170℃。这些催化剂比传统的Friedel-Crafts聚合催化剂好,因为酸性位点是固体的组成部分。固体酸催化剂是相对安全的、可重复使用的催化剂,它消除或至少减少了残余酸或副产物对得到的树脂产品的污染。
Description
相关申请
本申请按照35 U.S.C.§119(e)要求如下优选权:1997年1月8日申请的美国临时申请No.60/035,217;1997年1月9日申请的美国临时申请No.60/034,579;和1997年1月10日申请的美国临时申请No.60/035,797;这些申请所公开的全部内容作为参考,特意结合在本申请中。
发明背景1.发明领域
本发明涉及用作催化剂的金属氧化物固体酸,用于含有纯单体,C5单体,和C9单体中至少一种的原料聚合制备烃树脂,本发明还涉及用固体酸催化剂制备烃树脂的方法,和用这种方法生产的烃树脂。2.背景讨论
烃树脂是低分子量热塑性材料,通过热或催化聚合制备。该类树脂可以由数种不同来源的单体衍生得到。单体来源包括炼油过程的裂解石油馏出物,松节油馏分(例如由天然产物蒸馏得到的萜烯),造纸厂副产物,煤焦油,和各种纯的烯烃单体。
得到的烃树脂可以从粘稠的液体变化到硬的、脆的固体,其颜色依所使用的单体和特定的反应条件,可以从水白色变化到浅黄色,琥珀色,或深棕色。通常,纯单体的树脂倾向于是水白色,C9单体树脂倾向于为棕色,而C5单体树脂倾向于为黄色。
烃树脂作为改性剂,广泛应用于粘合剂,橡胶,热溶胶,印刷油墨,涂料,地板,和其它应用。这类树脂通常用来改性其它材料。
纯单体烃树脂可以通过苯乙烯基单体,例如苯乙烯,α-甲基苯乙烯,乙烯基甲苯,和其它烷基取代苯乙烯,使用Friedel-Crafts聚合催化剂,例如路易斯酸(例如三氟化硼(BF3),三氟化硼配合物,三氯化铝(AlCl3),烷基氯化铝),进行阳离子聚合而制备。
类似地,脂肪族C5烃树脂可以由含有C5和C6链烷烃,烯烃,和二烯烃的裂解石油原料,也称作“C5单体”,进行阳离子聚合而制备。这些单体物料包括可进行阳离子聚合的单体,例如作为主要反应组分的1,3-戊二烯,及环戊烯,戊烯,2-甲基-2-丁烯,2-甲基-2-戊烯,环戊二烯,和二环戊二烯。使用Friedel-Crafts聚合催化剂,例如路易斯酸(例如三氟化硼(BF3),三氟化硼配合物,三氯化铝(AlCl3),烷基氯化铝)催化聚合反应。除反应组分外,在原料中的不聚合组分包括可以与不饱和组分共蒸馏的饱和烃,例如戊烷,环戊烷,或2-甲基戊烷。该单体原料可以与作为链转移剂的C4或C5烯烃或二聚体共聚。
芳香族C9烃树脂,也可以用由石脑油裂解得到的石油馏出物衍生的芳香族C8,C9,和/或C10不饱和单体,也称作“C9单体”,进行阳离子聚合而制备。这些单体物料包括可进行阳离子聚合的单体,例如苯乙烯,α-甲基苯乙烯,β-甲基苯乙烯,乙烯基甲苯,茚,二环戊二烯,二乙烯基苯,和这些组分的其它烷基取代衍生物。使用Friedel-Crafts聚合催化剂,例如路易斯酸(例如三氟化硼(BF3),三氟化硼配合物,三氯化铝(AlCl3),烷基氯化铝)催化聚合反应。除反应组分外,不聚合组分包括芳香烃,例如二甲苯,乙苯,异丙基苯,乙基甲苯,1,2-二氢化茚,甲基二氢化茚,萘和其它类似物种。原料中的这些不聚合组分可以通过烷基化反应结合进树脂。
尽管路易斯酸是制备烃树脂的阳离子聚合反应的有效催化剂,但它们有一些不足。传统的路易斯酸是仅使用一次的催化剂,它要求淬灭反应和中和酸的生产步骤。
另外,传统的路易斯酸还要求从得到的树脂产品中除去催化剂盐残余物。在除去催化剂中和产生的盐残余物后,处理这些残余物又要求额外的费用。所以,减少催化剂残余物的量,特别是在这些反应中产生的含卤物种的量,是特别令人感兴趣的。
使用传统的路易斯酸催化剂,例如AlCl3和BF3所带来的另一问题是,它们是危险材料。这些传统的路易斯酸催化剂在暴露于湿气时产生高度腐蚀性的酸气(例如HF,HCl)。
除通常的路易斯酸外,人们还做了一些固体酸催化剂方面的工作。BITTLES等,“烯烃的粘土催化反应I.苯乙烯的聚合”,Journalof Polymer Science:A部分,第2卷,1221-31页(1964),和BITTLES等,“烯烃的粘土催化反应II.催化剂的酸性及测量”,Journal ofPolymer Science:A部分,第2卷,1847-62页(1964),其所公开的全部内容结合在此作为参考,它们一起公开了用酸性粘土催化剂催化苯乙烯聚合,得到分子量为440~2000的聚合物,分子量是用苯溶液的凝固点降低方法测定的。这些文件指出,用在真空下加热的方法制备聚合催化剂,并且如果催化剂吸收了湿气,通过在真空下再次加热,可以恢复催化剂的活性。
SALT,“活化粘土在聚合过程中作为催化剂的应用,特别涉及α-甲基苯乙烯的聚合物”,Clay Minerals Bulletin,第2卷,55-58页(1948),其所公开的全部内容结合在此作为参考,该文献公开了使用粘土催化剂,使苯乙烯和/或α-甲基苯乙烯聚合,得到从二聚体到分子量约为3000的聚合物。
CHEN等的U.S.5,561,095所公开的全部内容结合在此作为参考,该专利公开了一种负载的路易斯酸催化剂,用于烯烃,包括C3~C23的α-烯烃的聚合,得到数均分子量(Mn)为约300~300,000的聚合物。典型的路易斯酸载体包括二氧化硅,二氧化硅-氧化铝,沸石,和粘土。CHEN等的实施例1公开了在真空下加热一种负载在二氧化硅上的路易斯酸。
WHEELER等的U.S.3,799,913所公开的全部内容结合在此作为参考,该专利公开了Friedel-Crafts催化剂用于可聚合组分,包括α-甲基苯乙烯,茚,乙烯基甲苯,和苯乙烯的聚合,得到数均分子量(Mn)为约350~1200的聚合物。氯化锌作为一种Friedel-Crafts催化剂被公开。
SAINES的U.S.3,652,707所公开的全部内容结合在此作为参考,该专利公开了Friedel-Crafts金属卤化物催化剂用于烯烃,包括戊烯,苯乙烯和甲基苯乙烯的聚合,得到分子量为约700~2500的聚合物。氯化锌作为一种Friedel-Crafts金属卤化物催化剂被公开。
PENG等,“Electrophilic Polymerization of 1,3-PentadieneInitiated by Aluminum Triflate”,Eur.Polym.J,第30卷,第1册,69-77页(1994),所公开的全部内容结合在此作为参考,公开了aluminum triflate用于1,3-戊二烯的聚合,得到各种分子量的聚合物。
欧洲专利申请0 352 856 A1所公开的全部内容结合在此作为参考,该专利公开了aluminum triflate,cerium triflate等用于C3~C6烯烃的寡聚,得到含有6~24个碳原子的寡聚体。
GANDINI等.,“The Heterogeneous Cationic Polymerization ofAromatic Monomers by Aluminum Triflate”,Polymer Preprints,American Chemical Society,359-360页(1996),所公开的全部内容结合在此作为参考,公开了aluminum triflate用于C9相关单体的聚合,得到数均分子量(Mn)约为3000的聚合物。该文件还指出,aluminum triflate可用于由特定石油馏分得到的芳香单体和溶剂的混合物的直接“树脂化”。
其它公开固体酸催化剂用于单体聚合制备树脂的文件包括:LEPERT的U.S.4,068,062,LEPERT的U.S.4,130,701,LEPERT的U.S.4,245,075,和LUVINH的U.S.4,824,921,它们所公开的全部内容结合在此作为参考。
发明概述
本发明涉及烃树脂的制备。更具体而言,本发明涉及使用金属氧化物固体酸催化剂,使烃单体原料聚合。
由纯单体,C5单体,和C9单体中的至少一种,使用相对环境友好的,可再循环的金属氧化物固体酸催化剂制备烃树脂,其中可以除去固体酸催化剂中自由缔合的水。在本发明中,通过阳离子聚合(例如Friedel-Crafts)制备烃树脂,其中用金属氧化物固体酸催化剂处理含有纯单体,C5单体,和C9单体中至少一种的原料。
在使用前,处理金属氧化物固体酸催化剂以除去缔合到固体上的自由缔合水,以使催化剂酸性和聚合活性最高。例如,在使用前,煅烧催化剂足够长的时间,以除去自由缔合水,和/或使催化剂处于减压下。例如,煅烧最高可在约700℃的温度下进行,优选在50~500℃的温度下进行。煅烧可在减压下进行最长约8小时,优选约1~4小时。
按照一个方面,本发明涉及烃树脂的制备方法,包括在金属氧化物固体酸催化剂存在下,使包括选自纯单体,C5单体,和C9单体中至少之一的原料聚合生产烃树脂,其中基本上所有的自由缔合水都被从金属氧化物固体酸催化剂上除去。
在本发明的一个方面,所述金属氧化物固体酸催化剂包括嵌入杂多酸的粘土。
按照本发明的另一方面,所述金属氧化物固体酸催化剂包括选自杂多酸及其盐中至少之一,所述杂多酸及其盐包括选自磷钨酸,硅钨酸,磷钼酸,硅钼酸,混合金属杂多酸及其盐中至少之一。杂多酸及其盐可以是CsnH(3-n)PW12O40,其中n=2~小于3,优选2.50~2.98。
按照本发明的一个方面,所述金属氧化物固体酸催化剂包括选自负载杂多酸及其盐中至少一种,所述负载杂多酸及其盐包括选自二氧化硅负载的杂多酸及其盐,溶胶-凝胶结合的杂多酸及其盐,阳离子交换树脂负载的杂多酸及其盐,粘土负载的杂多酸及其盐,粘土嵌入的杂多酸及其盐,中孔二氧化硅负载的杂多酸及其盐,和中孔二氧化硅-氧化铝负载的杂多酸及其盐中至少之一。
按照本发明的另一方面,所述金属氧化物固体酸催化剂可以包括硫酸锆,钨酸锆,硫酸钛,硫酸钨,酸官能化的有机桥联聚倍半硅氧烷,或铌酸。
按照本发明的一个方面,所述金属氧化物固体酸催化剂包括混合氧化物,该混合氧化物包括选自下列物质中至少之一:
B2O3.Al2O3,Cr2O3.Al2O3,MoO3.Al2O3,ZrO2.SiO2,Ga2O3.SiO2,BeO2.SiO2,MgO.SiO2,CaO.SiO2,SrO.SiO2,Y2O3.SiO2,La2O3.SiO2,SnO.SiO2,PbO.SiO2,MoO3.Fe(MoO4)3,MgO.B2O3,和TiO2.ZnO。
按照本发明的另一方面,所述金属氧化物固体酸催化剂包括无机酸,所述无机酸包括选自下列物质中至少之一:
ZnO,Al2O3,TiO2,CcO2,As2O3,V2O5,Cr2O3,MoO3,ZnS,CaS,CaSO4,MnSO4,NiSO4,CuSO4,CoSO4,CdSO4,SrSO4,ZnSO4,MgSO4,FeSO4,BaSO4.KHSO4,K2SO4,(NH4)2SO4,Al2(SO4)3,Fe2(SO4)3,Cr2(SO4)3,Ca(NO3)2,Bi(NO3)3,Zn(NO3)2,Fe(NO3)3,CaCO3,BPO4,FePO4,CrPO4,Ti3(PO4)4,Zr3(PO4)4,Cu3(PO4)2,Ni3(PO4)2,AlPO4,Zn3(PO4)2,和Mg3(PO4)2。
按照本发明的另一方面,原料中包括约20重量%~80重量%的单体和约80重量%~20重量%的溶剂。原料中优选包括约30重量%~70重量%的单体和约70重量%~30重量%的溶剂。原料中更优选包括约50重量%~70重量%的单体和约50重量%~30重量%的溶剂。所述溶剂可以包括芳香族溶剂。芳香族溶剂可以包括选自甲苯,二甲苯,和芳香族石油溶剂中的至少一种。所述溶剂可以包括脂肪族溶剂。本发明还可以包括循环使用溶剂。
按照本发明的一个方面,原料中至少包括C5单体。所述原料中可以至少包括C5单体,其中通过在100~160℃的温度下加热并蒸馏分级,除去环戊二烯和甲基环戊二烯。C5单体可以包括选自异丁烯,2-甲基-2-丁烯,1-戊烯,2-甲基-1-戊烯,2-甲基-2-戊烯,2-戊烯,环戊烯,环己烯,1,3-戊二烯,1,4-戊二烯,异戊二烯,1,3-己二烯,1,4-己二烯,环戊二烯和二环戊二烯中的至少之一。所述原料中可以至少包括C5单体,其中原料中包括至少约70重量%的可聚合单体,其中含有至少约50重量%的1,3-戊二烯。C5原料可以含有低含量的异戊二烯,通常含有一部分2-甲基-2-丁烯,并且可以含有一种或多种环二烯烃。
所述原料中可以至少包括C5单体,其中原料中还包括最高达约40重量%的链转移剂,优选最高达约20重量%的链转移剂。所述链转移剂可以包括选自C4烯烃,C5烯烃,C4烯烃二聚体,和C5烯烃二聚体中至少之一。所述链转移剂可以包括选自异丁烯,2-甲基-1-丁烯,2-甲基-2-丁烯,其二聚体,及其寡聚体中至少之一。
按照本发明的一个方面,原料中包括约30重量%~95重量%的C5单体,和约70重量%~5重量%的辅助原料,该辅助原料包括选自纯单体,C9单体,和萜烯中的至少一种。优选地,原料中包括约50重量%~85重量%的C5单体,和约50重量%~15重量%的辅助原料,该辅助原料包括选自纯单体,C9单体,和萜烯中的至少一种。
按照本发明的另一方面,所述原料中至少包括C9单体。该C9单体可以包括选自苯乙烯,乙烯基甲苯,茚,二环戊二烯,及其烷基化衍生物中的至少一种。所述C9单体可以包括至少约20重量%的可聚合不饱和烃。所述C9单体可以包括约30重量%~75重量%的可聚合不饱和烃。所述C9单体可以包括约35重量%~70重量%的可聚合不饱和烃。
按照本发明的一个方面,原料中包括约30重量%~95重量%的C9单体,和约70重量%~5重量%的辅助原料,该辅助原料包括选自纯单体,C5单体,和萜烯中的至少一种。优选地,原料中包括约50重量%~85重量%的C9单体,和约50重量%~15重量%的辅助原料,该辅助原料包括选自纯单体,C5单体,和萜烯中的至少一种。
在单体原料中控制量的水的存在下,许多金属氧化物固体酸催化剂最有效地发挥作用。按照本发明的这一特点,原料中应包括低于约500ppm的水,优选低于约200ppm的水,更优选低于约100ppm的水,最优选低于约50ppm的水。
按照本发明的另一方面,在间歇反应器内,使原料与基于单体重量的约0.5重量%~30重量%,优选约1重量%~20重量%,更优选约3重量%~15重量%,最优选约0.5重量%~5重量%的金属氧化物固体酸催化剂接触。
按照本发明的一个方面,将金属氧化物固体酸催化剂加入到原料中。
按照本发明的另一方面,将原料加入到金属氧化物固体酸催化剂与溶剂形成的淤浆中。所述原料可以流经固定床金属氧化物固体酸催化剂。
按照本发明的另一方面,原料与金属氧化物固体酸催化剂淤浆一起加入到反应器内。
按照本发明的一个方面,采用连续法或间歇法进行聚合反应。间歇法的反应时间为约30分钟~8小时,优选在反应温度下约1~4小时。
按照本发明的一个方面,原料在约-50℃~150℃,优选约-20℃~100℃,更优选约0℃~70℃的反应温度下聚合。
按照本发明的另一方面,通过从烃树脂中除去金属氧化物固体酸催化剂而使聚合反应终止。可以通过过滤从烃树脂中除去金属氧化物固体酸催化剂。可以从包括金属氧化物固体酸催化剂的固定床反应器中移出烃树脂。
按照本发明的一个方面,汽提烃树脂以除去未反应的单体,溶剂和低分子量寡聚体。未反应的单体,溶剂和低分子量寡聚体可以回收使用。
按照本发明的一个方面,从烃树脂溶液中分离出烃树脂。
按照本发明的一个方面,原料至少包括纯单体,并且得到的烃树脂的软化点为约5℃~170℃,所述软化点是采用ASTM-E28“环球仪软化点标准测试方法”测定的。原料可以至少包括C5单体,其中得到的烃树脂的软化点为约50℃~150℃。原料可以至少包括C9单体,其中得到的烃树脂的软化点为约70℃~160℃。
按照本发明的一个方面,原料至少包括纯单体,其中烃树脂的数均分子量(Mn)为约400~2000,重均分子量(Mw)为约500~5000,Z均分子量(Mz)为约500~10,000,并且由Mw/Mn量度的多分散性(PD)为约1.2~3.5,其中Mn,Mw,和Mz是用尺寸排阻色谱(SEC)测定的。
按照本发明的一个方面,原料至少包括C5单体,其中烃树脂的数均分子量(Mn)为约400~2000,重均分子量(Mw)为约500~3500,Z均分子量(Mz)为约700~15,000,并且由Mw/Mn量度的多分散性(PD)为约1.2~5,其中Mn,Mw,和Mz是用尺寸排阻色谱(SEC)测定的。
按照本发明的另一方面,原料至少包括C9单体,其中烃树脂的数均分子量(Mn)为约400~1200,重均分子量(Mw)为约500~2000,Z均分子量(Mz)为约700~6000,并且由Mw/Mn量度的多分散性(PD)为约1.2~3.5,优选1.2~2.5,其中Mn,Mw,和Mz是用尺寸排阻色谱(SEC)测定的。
按照本发明的另一方面,烃树脂是氢化的。
发明详述
在此所阐释的内容,仅仅是举些例子,目的是举例讨论本发明的各种实施方案,并且只有那些相信是最有用的,并且容易理解的对本发明的原则和概念方面的描述才被提出。在这一点上,我们所阐释的本发明细节仅仅是满足从根本上理解本发明的需要,所公开的内容是使本领域技术人员了解在实践中如何实现本发明的数种形式。
除非特别指出,在本申请中的所有百分值,均是以所给样品重量为100%所测定的值(重量)。这样,例如30%表示在每100份(重量)样品中的30份(重量)。
除非特别指出,提到的化合物或组分包括该化合物或组分本身,及与其它化合物或组分的组合,例如化合物的混合物。
在进一步讨论前,定义下列术语以帮助理解本发明。
固体酸(SOLID ACID):一种固体,它能够使碱性Hammett指示剂改变颜色,其pKa<0。
金属氧化物固体酸(METAL OXIDE SOLID ACID):包含金属的固体酸,除硅铝酸盐外,所述金属全部以共价键与氧键合,例如磷酸金属盐,硝酸金属盐,硫酸金属盐。
杂多酸(HETEROPOLYACID):包括杂多酸平衡离子和具有互补电荷的杂多酸阴离子的固体酸。
杂多酸平衡离子(HETEROPOLYACID COUNTERION):阳离子物种,例如H+,Na+,K+,Cs+,Al3+,或NH4 +。
杂多酸阴离子(HETEROPOLYACID ANION):具有通式XxMmOy Z-的阴离子,其中X=不同于M的杂原子或中心原子;M=最高氧化态的前过渡金属;O=氧;z-=阴离子的电荷;而x,m,和y分别表示组成原子X,M,O的摩尔比;并且其中M是例如Mo,W,V,Nb,或Ta;并且其中X是例如P,Si,或As。
KEGGIN杂多酸(KEGGIN HETEROPOLYACID):一种其中的阴离子具有通式XM12O40 3-的杂多酸,其中四个氧原子在杂原子X周围构成一个中心四面体,并且12个末端氧原子和24个桥连氧原子构成金属原子M的12个八面体。
烃树脂(HYDROCARBON RESIN):一种低分子量(即数均分子量为约200~小于约3000,由尺寸排阻色谱(SEC)测得)的热塑性聚合物,由裂解石油蒸馏物,萜烯,煤焦油馏分,或纯的烯烃单体的热或催化聚合合成,其中一种单体至少是C5或更高碳数的单体。
纯单体(PURE MONOMER):一种包括由合成生产的或高度纯净的单体物种的组分,例如,由乙苯得来的苯乙烯,或由枯烯得来的α-甲基苯乙烯。
纯单体原料(PURE MONOMER FEED STREAM):包括任意数目纯单体物种的组合物。
C5单体(C5 MONOMERS):由石油加工,例如裂解衍生而来的组分,含有包括C5和/或C6烯烃物种的不饱和烃,在环境压力下于约20~100℃沸腾。
C9单体(C9 MONOMERS):由石油加工,例如裂解衍生而来的组分,含有不饱和芳香族C8,C9,和/或C10烯烃物种,在环境压力下于约100~300℃沸腾。
自由缔合水(FREELY-ASSOCIATED WATER):通过化学吸附和/或物理吸附缔合到固体酸催化剂上的水。
作为本发明的概述,烃树脂的制备是通过使用金属氧化物固体酸作为催化剂,使含有纯单体(例如苯乙烯基单体),C5单体,和C9单体中至少一种的原料进行阳离子聚合。制备的树脂的软化点(环球法)优选为约5~170℃,更优选为约30~150℃。这些催化剂比传统的路易斯酸聚合催化剂好,因为酸性位点是固体的组成部分。
更详细地看一下本发明,烃树脂是通过聚合反应制备的,其中含有纯单体,C5单体,和C9单体中至少一种的原料在溶剂中与金属氧化物固体酸催化剂接触。可用在本发明中的金属氧化物固体酸催化剂包括但不局限于如下种类。嵌入杂多酸的粘土(即杂多酸作为粘土层间的支柱)杂多酸及其盐,例如:
磷钨酸及其盐,包括例如
CsnH(3-n)PW12O40,例如其中n=2~小于3,更优选2.50~2.98
钨硅酸及其盐
磷钼酸及其盐
硅钼酸及其盐
混合金属杂多酸及其盐负载的杂多酸及其盐,例如
负载在二氧化硅上,例如
负载在二氧化硅上的H3PW12O40
结合进溶胶-凝胶中,例如
结合进溶胶-凝胶中的CsnH(3-n)PW12O40
负载在阳离子交换树脂上,例如
负载在阳离子交换树脂上的H3PW12O40
负载在粘土上,例如
负载在粘土上的H3PW12O40
嵌入粘土的杂多酸,例如
嵌入粘土的H3PW12O40
负载在中孔二氧化硅上,例如
负载在中孔二氧化硅上的H3PW12O40
负载在中孔二氧化硅-氧化铝上,例如
负载在中孔二氧化硅-氧化铝上的H3PW12O40硫酸锆钨酸锆硫酸钛硫酸钨酸官能化的有机桥联聚倍半硅氧烷铌酸混合氧化物
B2O3.Al2O3
Cr2O3.Al2O3
MoO3.Al2O3
ZrO2.SiO2
Ga2O3.SiO2
BeO2.SiO2
MgO.SiO2
CaO.SiO2
SrO.SiO2
Y2O3.SiO2
La2O3.SiO2
SnO.SiO2
PbO.SiO2
MoO3.Fe(MoO4)3
MgO.B2O3
TiO2.ZnO无机酸
ZnO
Al2O3
TiO2
CeO2
As2O3
V2O5
Cr2O3
MoO3
CaSO4
MnSO4
NiSO4
CuSO4
CoSO4
CdSO4
SrSO4
ZnSO4
MgSO4
FeSO4
BaSO4
KHSO4
K2SO4
(NH4)2SO4
Al2(SO4)3
Fe2(SO4)3
Cr2(SO4)3
Ca(NO3)2
Bi(NO3)3
Zn(NO3)2
Fe(NO3)3
CaCO3
BPO4
FePO4
CrPO4
Ti3(PO4)4
Zr3(PO4)4
Cu3(PO4)2
Ni3(PO4)2
AlPO4
Zn3(PO4)2
Mg3(PO4)2
如前面所提到的,上面所列出的金属氧化物固体酸催化剂,并不是彻底列举。在选择其它可用于本发明的金属氧化物固体酸催化剂时,通常金属氧化物固体酸催化剂的酸性应比Hammett标度的约-3更大。
关于杂多酸,需要的平衡离子包括例如铯,铝,钾,钠,和铵。
关于磷钨酸盐,应注意到n应小于3,因为为具有催化作用,应存在质子。
关于负载的杂多酸及其盐,在开发负载的催化剂体系过程中,第一步是证明一个纯的催化剂在一个催化工艺中,可以催化需要的转变过程。一旦证明了一个催化剂体系,一个关键的开发策略是将该催化剂负载在载体上,以使活性催化剂组分分散在大的表面上。该策略的实例包括将贵金属催化剂负载在碳或类似的惰性材料的表面上,用作氢化催化剂。在杂多酸的微晶大小为8nm(纳米)的情况下,通常只有该微晶的表面原子能催化反应。这样,为提高使用杂多酸的效率,将杂多酸负载在具有高表面积的固体上。尽管优选的非负载催化剂是盐,例如Cs2.9H0.1PW12O40,但优选的负载杂多酸是母体杂多酸H3PW12O40。可参考OKUHARA等,“Catalytic Chemistry ofHeteropoly Compounds”,Advances in Catalysis,第41卷,113-252页(1996),和MISONO等,“Solid Superacid Catalysts”,Chemtech,23-29页(1993年11月);它们所公开的全部内容结合在此作为参考。
用于负载金属氧化物的载体包括粘土。粘土包括天然存在的粘土矿物,例如高岭土,膨润土,硅镁土,蒙脱土,clarit,漂白土,水辉石,和beidellite.粘土还包括合成粘土,例如滑石粉和氢化滑石。粘土还包括用硫酸或盐酸处理的蒙脱土粘土。粘土甚至还包括改性粘土(即骨架元素置换改性的粘土),例如氧化铝作为支柱的粘土,铈改性的氧化铝作为支柱的粘土,和金属氧化物作为支柱的粘土。除粘土外,其它载体包括二氧化硅,二氧化硅-氧化铝,中孔二氧化硅,中孔二氧化硅-氧化铝,和离子交换树脂。其它类型的载体包括天然或合成沸石,例如沸石Y,沸石β(即BEA),MFI(例如“Zeolite Sacony Mobil-5”(ZSM-5)),MEL(例如“Zeolite SaconyMobil-11”(ZSM-11)),NaX,NaY,八面沸石(即FAU),和丝光沸石(即MOR)。名称BEA,MFI,MEL,FAU,和MOR是IUPAC定义的沸石框架结构类型。
酸官能化的有机桥联聚倍半硅氧烷的例子可见BRANDVOLD等的U.S.5,475,162和BRANDVOLD等的U.S.5,371,154,它们所公开的全部内容结合在此作为参考。
在使用前,处理金属氧化物固体酸催化剂,以除去自由缔合水,以使催化剂酸性和聚合活性最高。可以采用各种技术除去自由缔合水,包括热处理,减压处理,干气例如氮气或空气处理,或它们的组合。尽管不希望被理论所束缚,但除去自由缔合水使金属氧化物固体酸催化剂的酸强度最大,并使聚合反应重现性更好。
通过煅烧除去金属氧化物固体酸催化剂上的自由缔合水,这通常意味着将金属氧化物固体酸催化剂加热到较高的温度,而不使催化剂熔化。可在惰性气氛下,例如氮气或干燥空气下,或在减压下,煅烧金属氧化物固体酸催化剂。煅烧优选进行最长约8小时或更长,更优选约1~4小时,优选最高在约700℃,更优选在约100~400℃温度下进行。
从金属氧化物固体酸催化剂上除去的自由缔合水,可以衍生自与金属氧化物固体酸催化剂缔合的水(物理吸附水)或羟基(化学吸附水)。除去基本上所有自由缔合水意味着除去所有或基本上所有物理吸附水,并除去至少大部分化学吸附水。
可以预见,通过控制金属氧化物固体酸催化剂的煅烧条件,例如控制煅烧步骤进行的温度或时间,可以裁剪得到的树脂的物理性能,例如其软化点或其分子量。
在单体原料中控制量的水的存在下,许多金属氧化物固体酸催化剂最有效地发挥作用。例如原料中可以包括低于约500ppm的水,优选低于约200ppm的水,更优选低于约100ppm的水,最优选低于约50ppm的水。
纯单体原料可以含有相对纯净的苯乙烯基单体,例如苯乙烯,α-甲基苯乙烯,β-甲基苯乙烯,4-甲基苯乙烯,和乙烯基甲苯馏分。单体可以以纯组分的形式,或者以两种或多种单体原料的混合物的形式使用,以给出需要的树脂性能。优选的混合物包括约20~90重量%的α-甲基苯乙烯,和约80~10重量%的一种或多种共聚单体,优选苯乙烯,乙烯基甲苯,4-甲基苯乙烯,或这些组分的混合物。另外,本发明的单体也可以使用其它烷基化的苯乙烯,例如叔丁基苯乙烯或苯基苯乙烯。如果需要,原料可以进行干燥,并且优选含有少于约200ppm的水,更优选少于约100ppm的水,最优选少于约50ppm的水。
在C5树脂的情况下,石油原料中含有在约20~100℃,优选约30~70℃下沸腾的不饱和C5和/或C6烯烃,及二烯烃。在某些情况下,通过在100~160℃的温度下徐徐加热并蒸馏分级,除去原料中的环戊二烯和甲基环戊二烯组分。在这些原料中的单体可以包括但不限于:烯烃,例如异丁烯,2-甲基-2-丁烯,1-戊烯,2-甲基-1-戊烯,2-甲基-2-戊烯,和2-戊烯;环烯烃,例如环戊烯和环己烯;二烯烃,例如1,3-戊二烯,1,4-戊二烯,异戊二烯,1,3-己二烯,和1,4-己二烯;环二烯烃,例如环戊二烯,二环戊二烯,和这些环二烯烃的烷基取代衍生物及共二聚体。商业化的这类原料包括但不局限于:“Naphtha Petroleum 3,1,3-戊二烯”,由LyondellPetrochemical Company,Houston,TX获得,普通的“1,3-戊二烯浓缩物”或“高级1,3-戊二烯浓缩物”,两者都由Shell NederlandChemie B.V.,Hoogvilet,the Netherlands获得。C5原料通常含有至少约70重量%的可聚合单体,其中含有至少约50重量%的1,3-戊二烯。C5原料可以含有低含量的异戊二烯,通常含有2-甲基-2-丁烯,并且可以含有一种或多种环二烯烃。
还是关于C5单体原料,除反应组分外,在原料中的不可聚合组分包括与不饱和组分共蒸馏的饱和烃,例如戊烷,环戊烷,或2-甲基戊烷。该单体原料可以与作为链转移剂的C4或C5烯烃,或其二聚体共聚。加入链转移剂可以使得到的树脂比仅使用单体制备的树脂具有更低的分子量和更窄的分子量分布。链转移剂通过再生一个聚合物引发点而使链终止,从而使聚合物的链增长停止。在这些反应中可作为链转移剂的组分包括但不局限于:异丁烯,2-甲基-1-丁烯,2-甲基-2-丁烯,及这些物种的二聚体或寡聚体。链转移剂可以以纯的形式,或者在溶剂中稀释后加入到反应中。如果需要,原料可以进行干燥,并且优选含有少于约500ppm的水,更优选少于约200ppm的水,最优选少于约50ppm的水。
在C9单体树脂的情况下,原料中含有在环境压力下在约100~300℃沸腾的不饱和芳香族C8,C9和/或C10单体。芳香族C8-C10原料(也称作C9原料)可由石油馏分的蒸汽裂解得到。在这些原料中的单体可以包括但不局限于苯乙烯,乙烯基甲苯,茚,二环戊二烯,和这些组分的烷基化衍生物。商业化的这类原料包括但不局限于由Lyondell Petrochemical Company,Houston,TX获得的“LRO-90”,由DSM,Geleen,the Netherlands获得的“DSM C9 ResinfeedClassic”,由Dow Chemical Company of Midland,Michigan获得的“RO-60”和“RO-80”,和由Dow Chemical Company of Terneuzen,the Netherlands获得的“Dow Resin Oil 60-L”。C9原料通常含有至少约20重量%,优选约30~75重量%,最优选约35~70重量%的可聚合不饱和烃。其余通常是烷基取代的芳香族化合物,它们可以通过烷基化反应结合到树脂中。如果需要,原料可以进行干燥,并且优选含有少于约500ppm的水,更优选少于约200ppm的水,最优选少于约50ppm的水。
原料可以限定为纯单体,C5单体,或C9单体。作为一种替代方式,可以与纯单体,C5单体,或C9单体构成的主要原料结合使用辅助原料。依主要原料的不同,纯单体,C5单体,C9单体,或甚至萜烯,及其任意组合,都可用作辅助原料。萜烯原料包括但不局限于α-苎烯,α-和β-蒎烯,及二戊烯。由主要原料和辅助原料的混合物得来的树脂,可以由约30~95重量%的主要原料与约70~5重量%的辅助原料,优选由约50~85重量%的主要原料与约50~15重量%的辅助原料制备。
聚合原料优选含有约20~80重量%的单体,更优选含有约30~70重量%的单体,最优选含有约40~70重量%的单体。在C5树脂的情况下,原料可以含有最高达约40重量%的链转移剂,更优选含有最高达约20重量%的链转移剂,所述链转移剂讨论如上。原料还含有约80~20重量%的溶剂,例如甲苯,辛烷,高沸点芳香溶剂,脂肪族溶剂,或混合溶剂。
关于溶剂,对于纯单体聚合,优选的溶剂是芳香族溶剂。通常可以使用甲苯,二甲苯,或轻芳香族石油溶剂,例如可由ExxonChemical Company,Houston,TX获得的“Aromatic 100”,可由AshlandChemical Incorporated,Columbus,OH获得的“HiSol 10”,和可由Shell Chemical Company,Houston,TX获得的“Cyclosol 53”。这些溶剂可以使用新鲜的,也可以使用加工回收的。所述溶剂通常含有少于约200ppm的水,更优选少于约100ppm的水,最优选少于约50ppm的水。
对于C5聚合,优选的溶剂是芳香族溶剂。通常未反应的树脂油组分通过加工回收用作溶剂。除回收的溶剂外,可以使用甲苯,二甲苯,或芳香族石油溶剂,例如可由Exxon Chemical Company,Houston,TX获得的“Solvesso 100”,和可由Shell Chemical Company,Houston,TX获得的“Shellsol A”。这些溶剂可以使用新鲜的,也可以使用加工回收的。所述溶剂通常含有少于约500ppm的水,更优选少于约200ppm的水,最优选少于约50ppm的水。
对于C9聚合,优选的溶剂是芳香族溶剂。通常未反应的树脂油组分通过加工回收用作溶剂。除回收的溶剂外,可以使用甲苯,二甲苯,或芳香族石油溶剂,例如可由Exxon Chemical Company,Houston,TX获得的“Solvesso 100”,和可由Shell Chemical Company,Houston,TX获得的“Shellsol A”。这些溶剂可以使用新鲜的,也可以使用加工回收的。所述溶剂通常含有少于约200ppm的水,更优选少于约100ppm的水,最优选少于约50ppm的水。
关于聚合反应条件,第一重要的变量是金属氧化物固体酸催化剂的用量。基于单体重量,金属氧化物固体酸的用量优选为约0.1~30重量%。对于纯单体树脂,金属氧化物固体酸的浓度优选为约0.1~15重量%,更优选为约0.5~10重量%,最优选为约0.5~8重量%。对于C5单体,金属氧化物固体酸的浓度优选为约0.5~30重量%,更优选为约1~20重量%,最优选为约3~15重量%。对于C9单体,金属氧化物固体酸的浓度优选为约0.5~30重量%,更优选为约1~20重量%,最优选为约3~15重量%。
在反应中第二重要的变量是反应顺序,即反应物彼此结合的次序和方式。在一种反应顺序中,可以将催化剂逐渐加入到单体溶液中,同时控制反应温度。作为一种可以选择的方式,在另一种反应顺序中,可以将单体逐渐加入到金属氧化物固体酸催化剂在溶剂中形成的浆液中。对于一定的催化剂量和反应温度,当将单体加入到催化剂浆液中,基本上得到软化点较低的树脂。如将在下面段落中所详细讨论的那样,将单体加入到催化剂溶液中所得到的树脂,与将催化剂加入到单体中所得到的树脂相比,具有较低的分子量和窄的多分散性,即Mw/Mn,这些数据由尺寸排阻色谱测定。
树脂的平均分子量用尺寸排阻色谱,即SEC测定。分析用的色谱柱组由四个Waters“Ultrastyrogel”柱按顺序组成,其孔大小分别为500,500,1000,和100埃,(分别为Part Nos.WAT010571,010571,010572,010570),可由Waters Corporation,Milford,MA获得。由一组标准的窄分子量分布聚苯乙烯聚合物的峰洗脱时间计算标定分子量。标准组包括18个标准物,其峰值分子量从162直到43,900。窄分子量标准物的峰值分子量定义为(MwMn)1/2(ASTM测试方法D3536-76)。标准曲线定义为一个三度多项式曲线,即logMw对Vc/Vr的曲线,其中Vc是标准物的洗脱容积,而Vr是参考峰的洗脱容积,参考峰是以溶解空气形式存在于注射溶液中的氧气所形成的。柱子和检测池(惠普差示折光计)保持在40℃。溶剂(流动相)为四氢呋喃,含有250ppm的丁基化羟基甲苯(BHT,2,6-二叔丁基-4-甲基苯酚)作为稳定剂(所述含有BHT的四氢呋喃可由Burdick and Jackson,Muskegon,MI获得)。流动相储存器用氦保护,并保持流速为1毫升/分钟。在这样的条件下,BHT的洗脱时间为35.86分钟。样品溶解在四氢呋喃中,0.25% wt/vol,并在注射(200微升)进色谱仪之前,通过一个孔大小为0.45微米的“TEFLON”(聚四氟乙烯)膜过滤器过滤。报告的分子量是“聚苯乙烯相当物”的分子量,由标准曲线计算得到。
对于纯单体树脂,用本发明方法制备的树脂的数均分子量(Mn)为约400~2000,重均分子量(Mw)为约500~5000,Z均分子量(Mz)为约500~10,000,并且由Mw/Mn量度的多分散性(PD)为约1.2~3.5,典型为约1.2~2.5。对于C5烃树脂,用本发明方法制备的树脂的数均分子量(Mn)为约400~2000,重均分子量(Mw)为约500~3500,Z均分子量(Mz)为约700~15,000,并且由Mw/Mn量度的多分散性(PD)为约1.2~5,典型为约1.2~3.5。对于C9烃树脂,用本发明方法制备的树脂的数均分子量(Mn)为约400~1200,重均分子量(Mw)为约500~2000,Z均分子量(Mz)为约700~6000,并且由Mw/Mn量度的多分散性(PD)为约1.2~3.5,典型为约1.2~2.5。
如前面所提到的,将单体加入到催化剂溶液中,比将催化剂加入到单体中,得到更窄的多分散性(PD)和更低的分子量。考虑反应顺序的影响,如果需要,使用金属氧化物固体酸比使用传统的路易斯酸Friedel-Crafts催化剂,可以得到更窄的多分散性(PD)。例如,当将纯单体用20分钟时间,在-6~-2℃温度下,加入到0.8重量%的Cs2.9H0.1PW12O40催化剂中,烃树脂产品的Mw为1540,Mn为720,Mz为3920,并且多分散性(PD=Mw/Mn)为2.2。与之相比,当将0.8重量%的Cs2.9H0.1PW12O40催化剂用1分钟时间,在0℃下,加入到纯单体中,烃树脂产品的Mw为3100,Mn为1170,Mz为7080,并且多分散性(PD=Mw/Mn)为2.7。上述数据是实施例4和13得到的,如上面所指出的,它们具有相似但不同的反应条件。
按上面的观点,如果需要,使用金属氧化物固体酸比使用传统的路易斯酸Friedel-Crafts催化剂,可以得到更窄的多分散性(PD)。为确保树脂与最终应用中的聚合物的相容性,窄的多分散性是重要的。
第三重要的反应变量是反应温度。在这些反应中,聚合反应温度可以为-50~150℃,但是,反应温度更优选为约-20~100℃,最优选为约0~70℃。对于纯单体,反应温度优选为约-50~100℃,更优选为约-20~75℃,最优选为约-10~60℃。对于C5单体,反应温度优选为约-50~100℃,更优选为约-20~75℃,最优选为约-10~70℃。对于C9单体,反应温度优选为约0~150℃,更优选为约10~120℃,最优选为约20~110℃。温度对最终树脂的性能有很大影响。在较低的反应温度下,制备出具有较高分子量和高软化点的树脂。在反应温度下的反应时间优选为约30分钟~8小时,更优选为约1~4小时。
聚合工艺可以是连续,半连续,或间歇工艺,在连续的,间歇的,半连续的,固定床,流化床,和活塞流这样的反向反应器内进行。例如,在连续工艺中,使单体溶液通过固定床催化剂,或使单体和催化剂浆液一起进料到连续反应器内。
通过从产品中用物理方法分离出固体催化剂可以使反应终止。物理分离可以使反应溶液呈中性。另外,通过简单过滤,或通过从催化剂固定床中分离出树脂溶液,可以实现物理分离。结果,物理分离容易而且完全,使得对于某些金属氧化物固体酸催化剂,在树脂产品中没有留下酸和残余催化剂。
这样,使用金属氧化物固体酸催化剂,使得采取额外的工艺步骤来淬灭反应,中和催化剂,和从最终产品中过滤掉催化剂盐残余物的需要变得很小,或变得不需要。
一旦金属氧化物固体酸催化剂与树脂溶液分离开,就可以汽提树脂溶液以除去未反应的烃,溶剂,和低分子量寡聚物,它们可以通过加工回收使用。当使纯单体反应时,由本发明可以得到水白色树脂,基于起始单体的量,收率最高可达约99%。
由本发明得到的树脂的软化点,通常优选为约5℃~170℃,更优选为约30~150℃,所述软化点是采用ASTM-E28“环球仪软化点标准测试方法”(1996年修订)测定的。对于纯单体,软化点优选为约5℃~170℃,更优选为约50℃~150℃。对于C5烃树脂,软化点优选为约5℃~170℃,更优选为约50℃~150℃,最优选为约70~130℃。对于C9烃树脂,软化点优选最高达约170℃,并且软化点最优选为约70~160℃。如果需要,使用合适的反应条件,还可以制备可流动树脂或那些在室温下为液体的树脂。
树脂制备后,随后可以进行氢化以降低色度并改善色稳定性。树脂的氢化在现有技术中是广为所知的。关于氢化的讨论,可以参考DAUGHENBAUGH等的U.S.5,491,214,它所公开的全部内容结合在此作为参考。
本发明树脂可以用作改性剂,用在粘合剂,密封剂,印刷油墨,保护性涂料,塑料制品,路标,地板,和用作干洗再整理剂。
本发明的金属氧化物固体酸催化剂,比路易斯酸(例如AlCl3,AlBr3,BF3,BF3的配合物,TiCl4,及其它通常用于Friedel-Crafts聚合的路易斯酸)具有一些优势。许多这种优势是由于酸性位点是固体催化剂的组成部分。
因为酸性位点是固体催化剂的组成部分,残余催化剂对树脂产品或溶剂的污染极小。结果,金属氧化物固体酸催化剂不会由于残余催化剂而使烃树脂具有颜色。如果使用纯的苯乙烯基单体,得到的树脂可以是水白色的。
本发明的金属氧化物固体酸催化剂通常可以再生并循环使用,因此减少了使用过的催化剂的废物处理量。相反,路易斯酸通常是使用一次的催化剂。
另外,与传统的路易斯酸催化剂,例如BF3和AlCl3相比,本发明的金属氧化物固体酸催化剂是不危险的。本发明的催化剂在暴露于湿气时通常不产生腐蚀性或危险性的液态或气态酸。
下面还将用实施例进一步举例说明本发明,在实施例前是实施例所采用催化剂的制备方法。实施例1-26涉及纯单体树脂,实施例41-55涉及C5树脂,实施例56涉及C9树脂。这些实施例是非限定性的,不限定本发明的范围。
除非另外指出,在实施例中所出现的所有百分数,份数等,都是指重量。
催化剂制备
在250℃,在干燥的氮气流下,通过煅烧水合盐制备H3PW12O40。
按照如下程序制备钾和铵盐。由热解重量分析法,测量在300℃的失重,并考虑水的当量,确定缔合水的数目,从而计算出杂多钨酸H3PW12O40·xH2O的分子量。钾或铵盐,K3PW12O40·xH2O或(NH4)3PW12O40·xH2O的制备,是通过将20g,6.1mmol酸H3PW12O40·xH2O(Aldrich,Milwaukee,WI)加入到装有磁搅拌棒的500ml单口圆底烧瓶中。使酸溶解在125ml蒸馏水中。将1.26g,9.15mmol碳酸钾(Aldrich,Milwaukee,WI)或0.88g,9.15mmol碳酸铵(Aldrich,Milwaukee,WI)溶解在25ml蒸馏水中,并用约12分钟滴加到剧烈搅拌的杂多酸溶液中。得到的溶液在室温下搅拌2小时,并在100℃,0.25mmHg压力下减压直到干燥。产品为细的白色粉末。类似地,通过改变磷钨酸与金属碳酸盐的比例,可以制备一系列的化学式为(阳离子)nH(3-n)PW12O40的盐,其中(阳离子)为任何平衡阳离子。在使用前,磷钨酸盐在250℃(除非在表1中另外注明),在氮气流下,预处理30分钟,以除去吸附的水。
按照如下程序制备磷钨酸铯盐。由热解重量分析法,测量在300℃的失重,并考虑水的当量,确定缔合水的数目,从而计算出杂多钨酸H3PW12O40·xH2O的分子量。杂多钨酸铯盐,Cs2.9H0.1PW12O40的制备,是通过将30g,9.2mmol酸H3PW12O40·xH2O(Aldrich,Milwaukee,WI)加入到装有磁搅拌棒的500ml单口圆底烧瓶中。使酸溶解在185ml蒸馏水中。将4.32g,13.3mmol碳酸铯(Aldrich,Milwaukee,WI)溶解在35ml蒸馏水中,并用25分钟时间滴加到剧烈搅拌的杂多酸溶液中。得到的溶液在室温下搅拌2小时,并在100℃,0.25mmHg下减压直到干燥。产品为细的白色粉末。通过改变磷钨酸与碳酸铯的比例,例如表3所示,可以制备一系列铯盐。
按照如下程序制备铝盐。由热解重量分析法,测量在300℃的失重,并考虑水的当量,确定缔合水的数目,从而计算出杂多钨酸H3PW12O40·xH2O的分子量。杂多钨酸铝盐,AlPW12O40的制备,是通过将20g,6.1mmol酸H3PW12O40·xH2O(Aldrich,Milwaukee,WI)加入到装有磁搅拌棒的500ml单口圆底烧瓶中。使酸与60ml乙醚(Aldrich,Milwaukee,WI)混合。1.25g,6.1mmol三(异丙氧基)铝,Al(OCH(CH)2)3(Aldrich,Milwaukee,WI)与40ml乙醚混合,并滴加到搅拌的杂多酸溶液中。得到的溶液在25℃搅拌12小时。从反应溶液中过滤出沉淀的固体,用25ml乙醚洗涤数次,并在80℃,在真空下(0.15mmHg)干燥直到恒重。产品为细的白色粉末。
实施例1-10
这些实施例举例说明使用Keggin杂多酸作为催化剂,用于苯乙烯基纯单体的聚合。Keggin磷钨酸盐被发现是活性催化剂,可用于由苯乙烯基纯单体制备烃树脂。
一个250ml三口烧瓶,装配有顶搅拌器,回流冷凝器,气体进口和出口,温度计,和加料滴液漏斗。向烧瓶中加入86.6g α-甲基苯乙烯(试剂级,Aldrich,Milwaukee,WI),36.6g苯乙烯(试剂级,Aldrich,Milwaukee,WI),和36.6g甲苯(试剂级,Aldrich,Milwaukee,WI)。在使用前溶剂和单体都用氧化铝干燥。
用冰浴将反应混合物冷却到0℃。将1.0g(除非另外指出)表1中所注明的催化剂,用约1分钟加入到搅拌着的反应烧瓶内。通常可以观察到最高达5℃的放热。在0℃搅拌反应溶液6小时。
然后在低温下,真空过滤出得到的树脂溶液中的催化剂。用约100ml甲苯洗涤反应瓶和催化剂滤饼。在0.25mmHg压力下,逐渐将温度升高到170℃,并保持在该温度下15分钟,汽提树脂中的溶剂和挥发性产物,以完全除去挥发性组分。
使用各种磷钨酸盐制备的树脂的性能列于表1。
表1
a.在400℃煅烧催化剂 b.使用0.5g催化剂
实施例 | 催化剂 | 产率 | 软化点(环球法R&B) | 分子量 | |||
Mn | Mw | Mz | PD | ||||
1 | H3PW12O40 | 10% | - | 510 | 1320 | 6470 | 2.6 |
2 | Cs3PW12O40 | 40% | 134℃ | 1460 | 3430 | 6680 | 2.3 |
3 | Cs2.9H0.1PW12O40 | 54% | 115℃ | 880 | 1680 | 3330 | 1.9 |
4 | Cs2.9H0.1PW12O40 a | 52% | 139℃ | 1170 | 3100 | 7080 | 2.7 |
5 | (NH4)3PW12O40 | 43% | 40℃ | 440 | 810 | 2470 | 1.8 |
6 | K3PW12O40 | 5% | - | 770 | 1850 | 4270 | 2.4 |
7 | K2.5H0.5PW12O40 | 48% | 43℃ | 450 | 1010 | 3270 | 2.2 |
8 | AlPW12O40 | 42% | 71℃ | 620 | 1390 | 3680 | 2.3 |
9 | AlPW12O40 a | 42% | 125℃ | 990 | 3650 | 13610 | 3.7 |
10 | AlPW12O40 b | 27% | 76℃ | 600 | 1520 | 4190 | 2.6 |
在实施例2,5,8,9和10中,全部取代的杂多酸显示形成的树脂比对全部酸性位点被取代的催化剂所预期的树脂更高。这表明,这些催化剂的制备,没有从H3PW12O40基材中完全取代所有的质子,在催化剂上留下残余的酸官能度,而这些残余的酸官能度使其表现出观察到的催化行为。如上面所指出的,应存在质子,使催化剂具有催化活性。若使用过量的平衡离子(例如见实施例20)来使反应进行,则如预期的那样,催化剂活性降低。
实施例11-13
下面的实施例举例说明在使用杂多酸催化剂由苯乙烯基纯单体制备烃树脂时,将单体加入到催化剂在溶剂中形成的浆液中的影响。这些实施例还用来说明钼基杂多酸的应用。
将50ml二甲苯(Aldrich,Milwaukee,WI)和0.5g已在真空下于250℃煅烧1小时的H3PMo12O40和Na3PW12O40(Osram SylvaniaInc.,Towanda,PA)的两者之一,加入到用氮气吹扫的装有磁搅拌棒和热点偶温度计的反应器内。将该催化剂浆液冷却到-5℃,并用2分钟,将单体α-甲基苯乙烯(25g,0.19mol)和苯乙烯(25g,0.22mol)(两者都由Aldrich,Milwaukee,WI得到)加入到该搅拌着的溶液中。两个反应都可以观察到约10℃的放热。所述溶液在0℃搅拌10~15分钟,然后使其升至室温。该反应溶液在室温下搅拌约15小时。反应溶液过滤出固体催化剂,并在一台旋转蒸发器内,在100℃,0.5mmHg压力下,除去溶剂和挥发性产物。
制备的树脂的性能列于表2。
表2
实施例 | 催化剂 | 产率 | 分子量 | |||
Mn | Mw | Mz | PD | |||
11 | H3PMo12O40 | 78% | 320 | 450 | 780 | 1.5 |
12 | Na3PW12O40 | 66% | 330 | 540 | 1890 | 1.6 |
对于实施例13,一个带夹套的250ml三口烧瓶,装配有顶搅拌器,回流冷凝器,气体进口和出口,温度计,和加料滴液漏斗。用氮气吹扫烧瓶,向其中加入已经用活化过的4埃分子筛干燥过的36.3g甲苯溶剂(Aldrich,Milwaukee,WI),和1.0g杂多钨酸铯Cs2.9H0.1PW12O40,该铯盐如上面在实施例1-10所描述的方法制备,并在400℃煅烧30分钟。通过反应器夹套,用循环冷浴将催化剂浆液冷却到约-2℃。将单体61.6g α-甲基苯乙烯和61.6g苯乙烯(两者都是试剂级,由Aldrich,Milwaukee,WI得到)用氧化铝干燥,并加入到装在反应瓶上的滴液漏斗中。用约20分钟,将单体滴加到催化剂浆液中,同时保持反应温度为-6.0~-2.0℃。然后将反应溶液保持在-2.0℃,总共反应2小时。
得到的树脂溶液在室温下真空过滤出催化剂。用约50ml甲苯洗涤反应瓶和催化剂滤饼。在0.06mmHg压力下,逐渐将溶液加热到175℃,并保持在该温度下15分钟,汽提树脂中的溶剂和挥发性产物,以完全除去挥发性组分。
实施例13制备的树脂具有如下性能。
树脂产率 21%
软化点 97℃
分子量
Mn 720
Mw 1540
Mz 3920
PD 2.2
由于实施例13与实施例4的反应类似,涉及单体加入到催化剂的实施例13的树脂性能,可以与涉及催化剂加入到单体的实施例4的树脂性能进行比较。如前面所指出的,将单体加入到催化剂溶液,比将催化剂加入到单体中,得到更窄的多分散性(PD)和更低的分子量。在实施例13中,当将纯单体用20分钟,在-6~-2℃温度下,加入到0.8重量%的Cs2.9H0.1PW12O40催化剂中,烃树脂产品的Mw为1540,Mn为720,Mz为3920,多分散性(PD=Mw/Mn)为2.2。与之相比较,在实施例4中,当将0.8重量%的Cs2.9H0.1PW12O40催化剂用1分钟时间,在0℃温度下,加入到纯单体中,烃树脂产品的Mw为3100,Mn为1170,Mz为7080,多分散性(PD=Mw/Mn)为2.7。
实施例14-20
这些实施例举例说明使用Keggin杂多酸铯盐作为催化剂,用于苯乙烯基纯单体聚合制备烃树脂。
一个带夹套的500ml三口烧瓶,装配有顶搅拌器,回流冷凝器,气体进口和出口,温度计,和加料滴液漏斗。向烧瓶加入86.6g α-甲基苯乙烯(试剂级,Aldrich,Milwaukee,WI),36.6g苯乙烯(试剂级,Aldrich,Milwaukee,WI),和36.6g甲苯(试剂级,Aldrich,Milwaukee,WI)。在使用前溶剂和单体都用氧化铝干燥。磷钨酸铯盐催化剂在250℃,在氮气流下,预处理30分钟,以除去吸附的水。通过反应器夹套,用从一个冰浴来的循环水将反应混合物冷却到0℃。基于单体的量,将0.5~1.0重量%的催化剂加入到搅拌着的反应瓶内。通常有5℃的放热。反应溶液在0℃搅拌2.5小时。
得到的树脂溶液在室温下真空过滤出催化剂。用约100ml甲苯洗涤反应瓶和催化剂滤饼。在0.5mmHg压力下,逐渐将溶液加热到185℃,并保持在该汽提温度下15分钟,汽提树脂中的溶剂和挥发性产物,以完全除去挥发性组分。
使用各种磷钨酸铯盐制备的树脂的性能列于表3。实施例14-18是本发明方法,而比较例19和20是用于比较目的。
表3
实施例 | 在制备铯盐时使用的Cs与H3PW12O40的摩尔比 | 产率 | 软化点(R&B) |
14 | 2.0 | 3% | 液体 |
15 | 2.2 | 13% | 液体 |
16 | 2.5 | 46% | 45℃ |
17 | 2.8 | 55% | 115℃ |
18 | 2.9 | 81% | 116℃ |
19 | 3.0 | 37% | 113℃ |
20 | 3.2 | 2% | 液体 |
实施例21-23
这些实施例用来举例说明在由苯乙烯基纯单体制备烃树脂时,重复使用磷钨酸铯盐催化剂。
反应装置和程序与在实施例14-20中所描述的相似,但有下列不同。在反应的起始30分钟,将催化剂分成相等的三份加入到反应溶液中。在每次聚合后,过滤收集起催化剂,在回流甲苯中洗涤,在氮气流下加热到150℃,维持30分钟,并再次使用。
制备的树脂的性能列于表4。
表4
实施例 | 催化剂 | 产率 | 软化点(R&B) |
21 | Cs2.9H0.1PW12O40 | 93% | 70℃ |
22(催化剂的第一次重复使用) | Cs2.9H0.1PW12O40 | 94% | 68℃ |
23(催化剂的第二次重复使用) | Cs2.9H0.1PW12O40 | 91% | 66℃ |
实施例24-26
这些实施例举例说明杂多酸用于纯单体的聚合。
对于比较例24,通过使用Cs3PW12O40,使50∶50的α-甲基苯乙烯/苯乙烯混合物在甲苯中,在0~10℃下聚合。实施例24制备的树脂具有如下性能。软化点(R&B) 68℃分子量
Mn 650
Mw 1349
Mz 3280
PD 2.08
对于比较例25,通过使用Cs3PW12O40,使净单体50∶50的α-甲基苯乙烯/苯乙烯混合物聚合。实施例25制备的树脂基本上是无色的,在室温下为脆性的固体,并具有如下性能。
软化点(R&B) 105℃
分子量
Mn 953
Mw 2315
Mz 5288
PD 2.42
对于实施例26,通过使用Cs2.5H0.5PW12O40,使50∶50的α-甲基苯乙烯/苯乙烯混合物在甲苯中,在0~10℃下聚合,产率基本上是定量的。实施例26制备的树脂在室温下为半固体,并具有如下性能。分子量
Mn 380
Mw 612
Mz 1582
PD 1.75
实施例27
本实施例说明铯改性的杂多酸用于纯单体聚合。
一个500ml三口烧瓶,带有冷却夹套,顶搅拌器,回流冷凝器,气体进口和出口,温度计,和加料滴液漏斗。向烧瓶中加入86.6g乙烯基甲苯(Deltech Corporation,Baton Rouge,LA),36.6gα-甲基苯乙烯(试剂级,Aldrich,Milwaukee,WI),和100g甲苯(试剂级,Aldrich,Milwaukee,WI)。在反应前,乙烯基甲苯用分子筛和无水氯化钙(试剂级,Aldrich,Milwaukee,WI)干燥。在反应前,甲苯也用3埃分子筛干燥。
1.48g Cs2.9H0.1PW12O40在200℃下干燥30分钟后,将该催化剂加入到反应混合物中。反应温度维持在-5±2℃下10分钟,然后升温到0±2℃,并在该温度再保持170分钟,总反应时间为180分钟。
在反应结束后,从树脂溶液中过滤出催化剂。在190℃的浴温和<5mmHg的压力的最终条件下,树脂溶液旋转蒸发45分钟。最终产率为68.3g或55%。树脂的软化点为92℃。由SEC测得的数均,重均,和z均分子量分别为809,2009,4888。
实施例28-31
这些实施例举例说明负载的铯改性或非改性的杂多酸用于纯单体聚合。负载催化剂制备
采用早期的湿法技术制备催化剂。按照如下技术,制备了三种不同的杂多酸在二氧化硅上的负载物。
将杂多酸,磷钨酸(Aldrich,Milwaukee,WI)溶解于150ml水中,然后慢慢加入到100g硅胶,“Davisil Grade 710”中。得到的湿硅胶在75℃的烘箱内干燥至少24小时。加入到100g硅胶中的杂多酸的量列于下表5中。
表5
聚合
实施例 | 杂多酸的量,克 | 干燥后产品的外观 |
28 | 5 | 白色粉末 |
29 | 10 | 浅棕色产品 |
30 | 15 | 浅棕色产品 |
一个500ml三口烧瓶,带有冷却夹套,顶搅拌器,回流冷凝器,气体进口和出口,温度计,和加料滴液漏斗。向烧瓶中加入36.6g苯乙烯(试剂级,Aldrich,Milwaukee,WI),86.6gα-甲基苯乙烯(试剂级,Aldrich,Milwaukee,WI),和100g甲苯(试剂级,Aldrich,Milwaukee,WI)。在反应前,苯乙烯和α-甲基苯乙烯用分子筛和氧化铝(试剂级,Aldrich,Milwaukee,WI)干燥。在使用前,甲苯也用3埃分子筛干燥。
5.0g负载的杂多酸在400℃下干燥60分钟后,将该催化剂加入到反应混合物中。反应温度维持在0±6℃下180分钟。
在反应结束后,从树脂溶液中过滤出催化剂。在190℃的浴温和小于5mmHg的压力的最终条件下,树脂溶液旋转蒸发45分钟。
得到的树脂性能列于表6。实施例28-30是本发明方法,而比较例31是用来比较的。
表6
实施例 | 催化剂 | 产率,% | 软化点(R&B) | 分子量 | ||
Mn | Mw | Mz | ||||
28 | 5%HPA在“Davisil”上 | 8.8 | 101.4℃ | 613 | 1286 | 4813 |
29 | 10%HPA在“Davisil”上 | 55 | 未测 | 387 | 888 | 2407 |
30 | 15%HPA在“Davisil”上 | 57 | 32.6℃ | 407 | 893 | 2392 |
31 | “Davisil” | 4.5 | 未测 | 600 | 1190 | 3410 |
实施例32-34
这些实施例举例说明负载的金属氧化物固体酸用于纯单体的聚合。负载催化剂的制备
采用早期的湿法技术制备催化剂。在研杵中研磨“Silica Grade57”(W.R.Grace,Boca Raton,Florida)。通过30目筛网,但通不过60目筛网的材料用于制备。将12.5g杂多酸,磷钨酸(Aldrich,Milwaukee,WI)溶解于73ml水中,然后慢慢加入到50g硅胶中。得到的湿硅胶在75℃的烘箱内干燥至少24小时。聚合
按照如下程序,使用上述催化剂制备树脂。每个实施例的不同在于催化剂的煅烧温度,如下表7中所列。
一个500ml三口烧瓶,带有冷却夹套,顶搅拌器,回流冷凝器,气体进口和出口,温度计,和加料滴液漏斗。向烧瓶中加入36.6g苯乙烯(试剂级,Aldrich,Milwaukee,WI),86.6gα-甲基苯乙烯(试剂级,Aldrich,Milwaukee,WI),和100g甲苯(试剂级,Aldrich,Milwaukee,WI)。在反应前,苯乙烯和α-甲基苯乙烯用分子筛和氧化铝(试剂级,Aldrich,Milwaukee,WI)干燥。在使用前,甲苯也用3埃分子筛干燥。
将催化剂加入到反应混合物中。反应温度维持在0±6℃下180分钟。
在反应结束后,从树脂溶液中过滤出催化剂。在190℃的浴温和小于5mmHg的压力的最终条件下,树脂溶液旋转蒸发45分钟。得到的树脂性能列于表7。
表7
实施例 | 煅烧温度 | 产率,% | 软化点(R&B) | 分子量 | ||
Mn | Mw | Mz | ||||
32 | 250℃ | 76 | 58℃ | 490 | 972 | 4340 |
33 | 325℃ | 67 | 54℃ | 474 | 991 | 3692 |
34 | 400℃ | 63 | 56℃ | 478 | 1028 | 3593 |
实施例35和36
这些实施例试图将杂多酸安置在二氧化硅载体孔隙的口上,并将这样的负载催化剂用于纯单体的聚合。催化剂制备
使用早期的湿法技术制备催化剂。
实施例35的催化剂制备
在研杵中研磨“Silica Grade 57”(W.R.Grace,Boca Raton,Florida)。通过30目筛网,但通不过60目筛网的材料用于制备。用28ml“RHS”使25g二氧化硅湿润(“RHS”的用量28ml,是基于实验选择的,这些实验表明,二氧化硅样品可以吸收36.5ml水,而不会留下液态水)。
将2.81g杂多酸,磷钨酸(Aldrich,Milwaukee,WI)溶解于20ml水中,并加入到硅胶/“RHS”混合物中。然后,该固体混合物在旋转蒸发器内转动2小时,接着在110℃,3mmHg压力下,旋转蒸发1小时。这些样品进一步在116℃的真空烘箱内干燥过夜。然后催化剂在200℃煅烧2小时。
实施例36的催化剂制备
在研杵中研磨“Silica Grade 57”(W.R.Grace,Boca Raton,Florida)。通过30目筛网,但通不过60目筛网的材料用于制备。用37ml“RHS”(Hercules Incorporated,Wilmington,Delaware)使25g二氧化硅湿润(37ml是基于实验选择的,这些实验表明,二氧化硅样品可以吸收36.5ml水,而不会留下液态水)。将2.81g杂多酸,磷钨酸(Aldrich,Milwaukee,WI)溶解于20ml水中,并加入到硅胶/“RHS”混合物中。然后,该固体混合物在旋转蒸发器内转动2小时,接着在110℃,3mmHg压力下,旋转蒸发1小时。这些样品进一步在116℃的真空烘箱内干燥过夜。然后催化剂在200℃煅烧2小时。聚合
按照实施例32-34的程序制备树脂。得到的烃树脂的性能列于表8。
表8
实施例 | 产率,% | 软化点(R&B) | 分子量 | ||
Mn | Mw | Mz | |||
35 | 71 | 57℃ | 519 | 1309 | 4421 |
36 | 81 | 44℃ | 446 | 1076 | 4527 |
实施例37-40
这些实施例试图将杂多酸安置在二氧化硅载体的孔隙壁上,并将这样的负载催化剂用于纯单体的聚合。催化剂制备
在International Chemical Congress of Pacific BasinSocieties,Dec 17-22,1995,Y.Izumi发表的一篇论文提出了这些实施例的催化剂合成方法,该论文所公开的全部内容结合在此作为参考。该方法涉及使用一种溶胶凝胶技术,将杂多酸或铯改性的杂多酸结合到硅胶结构中。
向1L圆底烧瓶中加入10g Cs2.9H0.1PW12O40。杂多酸铯盐的制备采用在催化剂制备方法中指出的方法。加入250ml 200标准强度的乙醇,并混合溶液1小时。然后加入100ml水和0.07g 36%的盐酸。然后用60分钟,向该搅拌着的溶液中加入277g 98%的原硅酸四乙酯(Aldrich,Milwaukee,WI)。该溶液在40℃保持60分钟。然后在烧瓶上加上一个回流冷凝器,并使溶液回流4小时。
将得到的凝胶转移到另一个圆底烧瓶中,并且在50℃和50mmHg压力下,将该凝胶旋转蒸发脱水,直到不再有水/乙醇从凝胶中蒸发出来。该材料在管式炉中,在干燥氮气流下,于250℃煅烧16小时。
H3PW12O40,Cs2.5H0.5PW12O40,和Cs2.7H0.3PW12O40进行类似的制备。聚合
按照实施例32-34的程序制备树脂,但是如果反应放热,则催化剂逐渐加入,以控制放热在0±5℃。得到的烃树脂的性能列于表9。
表9
实施例 | 催化剂组分 | 产率% | 软化点(R&B) | 分子量 | ||
Mn | Mw | Mz | ||||
37 | H3PW12O40 | 2 | 未测 | 756 | 5345 | 26281 |
38 | Cs2.5H0.5PW12O40 | 6 | 97.4℃ | 608 | 1649 | 9402 |
39 | Cs2.7H0.3PW12O40 | 36 | 101.4℃ | 616 | 1125 | 3748 |
40 | Cs2.9H0.1PW12O40 | 30 | 98.6℃ | 511 | 1024 | 3284 |
实施例41-45
这些实施例举例说明使用Keggin杂多酸作为催化剂,用于1,3-戊二烯,一种C5单体原料的聚合。
基于单体用量,将2重量%的按照催化剂制备方法制备的催化剂,加入到一个配有橡胶隔片盖,并吹着氮气的8盎司反应器内。用注射器将用4埃分子筛干燥过的25ml甲苯(试剂级,Aldrich,Milwaukee,WI)加入到反应器内。将25ml 1,3-戊二烯(90%工业级,Aldrich,Milwaukee,WI)加入到在0℃搅拌的催化剂溶液中,保持放热在10℃以下(除非另外指出)。单体加入后,反应溶液在室温下(除非另外指出)搅拌16小时,然后过滤。将反应溶液在真空下(0.2-0.5mmHg)加热到90℃,除去其中的挥发性组分。
制备的树脂的性能列于表10。
表10
1.反应在55℃进行2.反应放热保持在5℃以下
实施例 | 催化剂组分 | 产率 | 分子量 | |||
Mn | Mw | Mz | PD | |||
41 | Cs2.5H0.5PW12O40 1 | 74% | 440 | 1440 | 16,530 | 3.3 |
42 | Cs2.5H0.5PW12O40 | 63% | 550 | 1610 | 12,670 | 3.0 |
43 | Cs2.5H0.5PW12O40 2 | 53% | 480 | 1410 | 8480 | 2.9 |
44 | Cs3PW12O40 | 4% | 850 | 2200 | 6230 | 2.6 |
45 | AlPW12O40 | 4% | - | - | - | - |
实施例46
本实施例举例说明在涉及C5单体原料时,将单体加入到催化剂在溶剂中形成的浆液中的影响。
一个500ml三口烧瓶,装配有顶搅拌器,回流冷凝器,气体进口和出口,温度计,和加料滴液漏斗。向烧瓶中加入60g甲苯(试剂级,Aldrich,Milwaukee,WI),和2.8g Cs2.9H0.1PW12O40催化剂,该催化剂按照实施例41-45的程序制备,并在375-400℃,在干燥氮气流下煅烧30分钟。将单体,140g 1,3-戊二烯浓缩物(NaphthaPetroleum 3“1,3-戊二烯”,Lyondell Petrochemical Company,Houston,TX)加入到加料滴液漏斗。在使用前,单体和溶剂用4埃分子筛干燥。将反应溶液加热到50℃,并用25分钟,将单体由加料滴液漏斗加入到反应瓶中。反应溶液在50℃搅拌4-5小时。
然后得到的树脂溶液在室温下真空过滤出杂多酸催化剂。用约100ml甲苯洗涤反应瓶和催化剂滤饼。在2-5mmHg压力下,缓慢将反应溶液加热到100℃,除去树脂溶液中的溶剂和挥发性组分。
制备的树脂具有如下性能。产率 14%分子量(SEC法)
630
Mw 1360
Mz 5240
实施例47和48
这些实施例举例说明在涉及C5单体原料时,将粉碎的催化剂逐渐加入到搅拌着的单体在溶剂中形成的溶液中的影响。
一个500ml三口烧瓶,装配有顶搅拌器,回流冷凝器,气体进口和出口,和温度计。用注射器向烧瓶中加入60g甲苯(试剂级,Aldrich,Milwaukee,WI)和140g 1,3-戊二烯浓缩物(NaphthaPetroleum 3“1,3-戊二烯”,Lyondell Petrochemical Company,Houston,TX)。在使用前,单体和溶剂用4埃分子筛干燥。催化剂Cs2.9H0.1PW12O40按照实施例41-45的程序制备,并在干燥氮气流下,如下表11中所列的条件进行煅烧。将该催化剂分成4等份,在氮气流保护下,彼此间隔1小时加入到反应瓶内。总反应时间为7小时。
然后得到的树脂溶液在室温下真空过滤出杂多酸催化剂。用约100ml甲苯洗涤反应瓶和催化剂滤饼。
过滤出催化剂后,将树脂油放在一个圆底烧瓶中,该烧瓶装配有配合入口管的带应接器蒸馏头,温度计,并连接到冷凝器和接收瓶。在氮气流下,将树脂油加热到235℃,随后在235-245℃通入蒸汽,以除去轻油产品。持续通入蒸汽,直到每100ml蒸汽冷凝物中收集的油少于1ml,或直到收集到1000ml蒸汽冷凝物。停掉蒸汽后,在235℃用氮气吹扫,以便除去剩余树脂中的水。
制备的树脂的性能列于表11。
表11
实施例 | 催化剂 | 产率 | 分子量 | |||
Mn | Mw | Mz | PD | |||
47 | Cs2.9H0.1PW12O402重量%375-400℃煅烧/30分钟,氮气 | 8% | 1400 | 2390 | 7650 | 1.7 |
48 | Cs2.9H0.1PW12O404.8重量%240-265℃煅烧/1小时,氮气 | 14% | 1210 | 2080 | 7920 | 1.7 |
实施例49-51
这些实施例举例说明在涉及C5单体原料时,Keggin杂多酸催化剂中铯与质子的比例对1,3-戊二烯浓缩物的聚合的影响。
一个500ml三口烧瓶,装配有顶搅拌器,回流冷凝器,气体进口和出口,温度计,液体加料漏斗,和固体加料漏斗。向烧瓶中加入60g甲苯(试剂级,Aldrich,Milwaukee,WI),和催化剂总量的约1/3。该催化剂按照实施例41-45的方法制备,并在250-265℃,在氮气流下煅烧1小时。将催化剂浆液加热到30℃。用15分钟,将140g 1,3-戊二烯浓缩物(Naphtha Petroleum 3“1,3-戊二烯”,Lyondell Petrochemical Company,Houston,TX),通过加料滴液漏斗加入到氮气保护的反应瓶内,同时保持反应温度在30℃,再于30℃搅拌30分钟。单体和溶剂用4埃分子筛干燥。催化剂总用量是单体总量的10重量%,将剩余的杂多酸催化剂分成7份,彼此间隔15分钟,由固体加料漏斗加入到反应溶液内,并保持反应温度在30℃。在最后一批催化剂加入后,使反应溶液在30℃再维持5小时。
然后得到的树脂溶液在室温下真空过滤出杂多酸催化剂。用约100ml甲苯洗涤反应瓶和催化剂滤饼。
过滤出催化剂后,将树脂油放在一个圆底烧瓶中,该烧瓶装配有配合入口管的带应接器蒸馏头,温度计,并连接到冷凝器和接收瓶。在氮气流下,将树脂油加热到235℃,随后在235-245℃通入蒸汽,以除去轻油产品。持续通入蒸汽,直到每100ml蒸汽冷凝物中收集的油少于1ml,或直到收集到1000ml蒸汽冷凝物。停掉蒸汽后,在235℃用氮气吹扫,以便除去剩余树脂中的水。
制备的树脂的性能列于表12。
表12
实施例 | 催化剂 | 产率 | 分子量 | |||
Mn | Mw | Mz | PD | |||
49 | Cs2.5H0.5PW12O40 | 16% | 1010 | 1630 | 5630 | 1.6 |
50 | Cs2.75H0.25PW12O40 | 28% | 990 | 1560 | 5450 | 1.6 |
51 | Cs2.9H0.1PW12O40 | 25% | 1160 | 1940 | 8370 | 1.7 |
实施例52-55
这些实施例举例说明在涉及C5单体原料时,重复将Keggin杂多酸铯盐用于1,3-戊二烯浓缩物的聚合。
程序类似于实施例49-51所公开的方法,只是催化剂量为单体量的11重量%,反应温度为50℃,在1,3-戊二烯加入反应溶液后,催化剂分5次加入,并且在最后一批催化剂加入后,反应溶液保持回流3小时。
通过反应溶液的离心分离,收集反应中的催化剂。用热甲苯洗涤固体催化剂4次,并在真空下,在100℃干燥1-1.5小时,然后再次使用。
制备的树脂的性能列于表13。
表13
实施例 | 催化剂 | 产率 | 软化点(R&B) | 分子量 | |||
Mn | Mw | Mz | PD | ||||
52 | Cs2.9H0.1PW12O40 | 31% | 19℃ | 1040 | 1720 | 7610 | 1.7 |
53 | 回收的Cs2.9H0.1PW12O40 | 26% | 27℃ | 1040 | 1880 | 12080 | 1.8 |
54 | Cs2.5H0.5PW12O40 | 10% | 59℃ | 950 | 1880 | 10680 | 2.0 |
55 | 回收的Cs2.5H0.5PW12O40 | 6% | 56℃ | 960 | 1690 | 7260 | 1.8 |
实施例56
本实施例说明用铯改性的杂多酸可以制备C9树脂。
一个500ml三口烧瓶,带有冷却夹套,顶搅拌器,回流冷凝器,气体进口和出口,温度计,和加料滴液漏斗。向烧瓶中加入66.2g“LRO-90”(Lyondell Petrochemical Company,Houston,TX),66.2g“RHS”(再循环氢化溶剂,Hercules Incorporated,Wilmington,Delaware)(RHS类似于“OMS”,Organic Mineral Spirits,ExxonChemical Company,Houston,TX),和100g甲苯(试剂级,Aldrich,Milwaukee,WI)。在反应前,将LRO与RHS混合,并用无水氯化钙(试剂级,Aldrich,Milwaukee,WI)干燥。在使用前,甲苯也用3埃分子筛干燥。
将6.12g Cs2.9H0.1PW12O40催化剂在200℃干燥30分钟。加入一部分催化剂3.0g,引发反应。反应温度维持在10℃,并且在45分钟和100分钟后,再分别加入另外的0.75g催化剂。140分钟后,将反应瓶加热并保持在40℃。总反应时间为345分钟。
在反应结束后,从树脂溶液中过滤出催化剂。在190℃的浴温和<5mmHg的压力的条件下,将树脂溶液旋转蒸发45分钟。最终收率为14.3g。树脂的软化点为65℃。由SEC测得的数均,重均,和z均分子量分别为421、729、1348。
尽管已经结合一些优选的实施方案公开了本发明,使其各方面可以被更全面地理解和领会,但并不是想将本发明限定在这些特定的实施方案中。相反,其目的是想在由附加的权利要求所限定的本发明范围内,覆盖所有可能包括的选择方案、改进和等同方案。
Claims (25)
1.一种制备烃树脂的方法,包括在金属氧化物固体酸催化剂的存在下,使包括选自纯单体、C5单体和C9单体中至少之一的原料聚合而制备烃树脂,其中基本上所有自由缔合水都被从金属氧化物固体酸催化剂上除去。
2.权利要求1的方法,其中从金属氧化物固体酸催化剂上除去水,包括在最高达约700℃的温度下煅烧。
3.权利要求1的方法,其中金属氧化物固体酸催化剂包括嵌入杂多酸的粘土。
4.权利要求1的方法,其中金属氧化物固体酸催化剂包括选自杂多酸及其盐中的至少之一,所述杂多酸及其盐包括选自磷钨酸,硅钨酸,磷钼酸,硅钼酸,混合金属杂多酸及其盐中的至少之一。
5.权利要求4的方法,其中杂多酸及其盐包括CsnH(3-n)PW12O40,其中n=2~小于3。
6.权利要求1的方法,其中金属氧化物固体酸催化剂包括选自负载杂多酸及其盐中的至少之一,所述负载杂多酸及其盐包括选自二氧化硅负载的杂多酸及其盐,溶胶-凝胶结合的杂多酸及其盐,阳离子交换树脂负载的杂多酸及其盐,粘土负载的杂多酸及其盐,粘土嵌入的杂多酸及其盐,中孔二氧化硅负载的杂多酸及其盐,和中孔二氧化硅-氧化铝负载的杂多酸及其盐中的至少之一。
7.权利要求1的方法,其中金属氧化物固体酸催化剂包括硫酸锆。
8.权利要求1的方法,其中金属氧化物固体酸催化剂包括钨酸锆。
9.权利要求1的方法,其中金属氧化物固体酸催化剂包括硫酸钛。
10.权利要求1的方法,其中金属氧化物固体酸催化剂包括硫酸钨。
11.权利要求1的方法,其中金属氧化物固体酸催化剂包括酸官能化的有机桥联聚倍半硅氧烷。
12.权利要求1的方法,其中金属氧化物固体酸催化剂包括铌酸。
13.权利要求1的方法,其中金属氧化物固体酸催化剂包括混合氧化物,所述混合氧化物包括选自下列物质中的至少之一:
B2O3.Al2O3,Cr2O3.Al2O3,MoO3.Al2O3,ZrO2.SiO2,Ga2O3.SiO2,BeO2.SiO2,MgO.SiO2,CaO.SiO2,SrO.SiO2,Y2O3.SiO2,La2O3.SiO2,SnO.SiO2,PbO.SiO2,MoO3.Fe(MoO4)3,MgO.B2O3,和TiO2.ZnO。
14.权利要求1的方法,其中金属氧化物固体酸催化剂包括无机酸,所述无机酸包括选自下列物质中的至少之一:
ZnO,Al2O3,TiO2,CcO2,As2O3,V2O5,Cr2O3,MoO3,ZnS,CaS,CaSO4,MnSO4,NiSO4,CuSO4,CoSO4,CdSO4,SrSO4,ZnSO4,MgSO4,FeSO4,BaSO4,KHSO4,K2SO4,(NH4)2SO4,Al2(SO4)3,Fe2(SO4)3,Cr2(SO4)3,Ca(NO3)2,Bi(NO3)3,Zn(NO3)2,Fe(NO3)3,CaCO3,BPO4,FePO4,CrPO4,Ti3(PO4)4,Zr3(PO4)4,Cu3(PO4)2.Ni3(PO4)2,AlPO4,Zn3(PO4)2,和Mg3(PO4)2。
15.权利要求1的方法,其中的原料至少包括纯单体,并且其中所述的纯单体包括选自苯乙烯,α-甲基苯乙烯,β-甲基苯乙烯,4-甲基苯乙烯,和乙烯基甲苯馏分中的至少之一。
16.权利要求1的方法,其中的原料至少包括C5单体,所述C5单体包括选自异丁烯,2-甲基-2-丁烯,1-戊烯,2-甲基-1-戊烯,2-甲基-2-戊烯,2-戊烯,环戊烯,环己烯,1,3-戊二烯,1,4-戊二烯,异戊二烯,1,3-己二烯,1,4-己二烯,环戊二烯和二环戊二烯中的至少之一。
17.权利要求1的方法,其中的原料至少包括C9单体,所述C9单体包括选自苯乙烯,乙烯基甲苯,茚,二环戊二烯,及其烷基化衍生物中的至少之一。
18.权利要求1的方法,其中使原料与基于单体重量的0.1重量%~30重量%的金属氧化物固体酸催化剂在间歇反应器内接触。
19.权利要求1的方法,其中将金属氧化物固体酸催化剂加入到原料中。
20.权利要求1的方法,其中将原料加入到金属氧化物固体酸催化剂在溶剂中形成的淤浆中。
21.权利要求1的方法,其中原料在约-50℃~150℃的反应温度下聚合。
22.权利要求1的方法,其中原料至少包括纯单体,并且其中烃树脂的数均分子量(Mn)为约400~2000,重均分子量(Mw)为约500~5000,Z均分子量(Mz)为约500~10,000,并且由Mw/Mn量度的多分散性(PD)为约1.2~3.5,其中Mn,Mw,和Mz是用尺寸排阻色谱(SEC)测定的。
23.权利要求1的方法,其中原料至少包括C5单体,并且其中烃树脂的数均分子量(Mn)为约400~2000,重均分子量(Mw)为约500~3500,Z均分子量(Mz)为约700~15,000,并且由Mw/Mn量度的多分散性(PD)为约1.2~5,其中Mn,Mw,和Mz是用尺寸排阻色谱(SEC)测定的。
24.权利要求1的方法,其中原料至少包括C9单体,并且其中烃树脂的数均分子量(Mn)为约400~1200,重均分子量(Mw)为约500~2000,Z均分子量(Mz)为约700~6000,并且由Mw/Mn量度的多分散性(PD)为约1.2~3.5,其中Mn,Mw,和Mz是用尺寸排阻色谱(SEC)测定的。
25.权利要求5的方法,其中n=2.50~2.98。
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- 1998-01-07 WO PCT/US1998/000009 patent/WO1998030519A1/en not_active Application Discontinuation
- 1998-01-07 EP EP98901163A patent/EP0970117A2/en not_active Withdrawn
- 1998-01-07 CA CA002277295A patent/CA2277295A1/en not_active Abandoned
- 1998-01-07 AU AU58134/98A patent/AU5813498A/en not_active Abandoned
- 1998-01-07 JP JP53096698A patent/JP2001511194A/ja active Pending
- 1998-01-07 US US09/003,879 patent/US6608155B2/en not_active Expired - Fee Related
- 1998-01-07 EP EP98901668A patent/EP0954516A1/en not_active Withdrawn
- 1998-01-07 KR KR1019997006219A patent/KR20000070004A/ko not_active Application Discontinuation
- 1998-01-07 WO PCT/US1998/000012 patent/WO1998030587A2/en not_active Application Discontinuation
- 1998-01-07 KR KR1019997006222A patent/KR20000070007A/ko not_active Application Discontinuation
- 1998-01-07 DE DE69818018T patent/DE69818018T2/de not_active Expired - Fee Related
- 1998-01-07 KR KR1019997006224A patent/KR20000070009A/ko not_active Application Discontinuation
- 1998-01-07 US US09/003,888 patent/US6133386A/en not_active Expired - Fee Related
- 1998-01-07 JP JP53096498A patent/JP2001509185A/ja active Pending
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CN111548806B (zh) * | 2020-05-12 | 2021-06-01 | 天津大学 | 一种两段式处理碳氢燃料裂解炉内表面积碳的方法 |
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