CN1145912A - 用新的引发剂体系生产聚异烯烃的方法 - Google Patents
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Abstract
用本发明的方法，通过将异烯烃可选地与共轭或非共轭二烯和/或可阳离子聚合的、一或多不饱和化合物聚合可获得聚异烯烃，聚合反应在-100℃至+100℃的温度和0.1-100巴的压力下，在溶液、悬浮液或气相中，在由某些碳氢化合物和开链和/或环状铝氧烷化合物的组成的引发剂体系存在下进行。
Description
本发明涉及通过将异烯烃在溶液、悬浮液或气相中，可选地在共轭或非共轭二烯和/或可阳离子聚合的一或多不饱和化合物存在下聚合来生产聚异烯烃的方法。本发明还涉及异烯烃聚合用的新的引发剂体系。
人们早已知道异烯烃、特别是异丁烯的阳离子聚合，并且在许多先有技术文献中有述(参见，例如J.P.Kennedy，E.Marechal，Carbocationic Polymerisation，1982，A.Dandini&H.Cheradame inAdvances in Polymer Science，第34/35卷(1980))。在先有技术中使用路易斯酸或质子酸作该聚合的引发剂。聚合优选在卤代烃例如甲基氯、二氯甲烷或四氯化碳的存在下进行。
但是，该已知的方法具有缺点：常常仅得到低分子量聚合物，并且只有在低温下在极性、特别是卤代的溶剂中才能成功地进行。
本发明的目的是提供一种方法，按照该方法异烯烃可以在比迄今为止常规聚合的温度高的温度下均聚或共聚，得到高分子量产物。
业已发现，如果在基于铝氧烷化合物和通式R3，R4，R5 C-X(特别是X代表卤素)的一或多官能碳氢化合物的新引发剂体系存在下聚合，则可在升高的温度下制备高分子量聚异烯烃。
因此，本发明提供生产聚异烯烃的生产方法，该方法的特征在于使R1代表甲基、R2代表C1-C10烷基或C3-C10环烷基的式CH2＝CR1，R2异烯烃可选地与具有4-20个碳原子的共轭或非共轭二烯和/或阳离子可聚合的、一或多不饱和的、具有4-20个碳原子的化合物聚合可获得聚异烯烃，聚合反应在-100℃至+100℃的温度和0.1-100巴的压力下，在溶液、悬浮液或气相中，在由下述成分组成的引发剂体系存在下进行：a)式(I)碳氢化合物
式中，X代表卤素、SCN、CN、OH、OR5、OCOR5或COOR5，其中R5代表C1-C10烷基或C3-C10环烷基；R3、R4、R5相同或不同，代表C1-C10烷基、C3-C10环烷基、C6-C18芳基、C3-C10链烯基或C3-C10炔，可选地被X取代，和b)式(II)或(III)开链和/或环状铝氧烷化合物：
RxRyAl[O-AlRz]mRw (II)
式中，Rx、Ry、Rz、RW是C1-C12烷基；m代表5-30的一个整数。
优选使用的异烯烃是那些R1代表Me、R2代表C1-C6烷基如甲基、乙基、丙基。优选异丁烯和2-甲基-1-丁烯，特别优选异丁烯。可以在本发明中考虑使用的具有4-20、优选4-10、特别优选4-6个碳原子的共轭和非共轭二烯是：丁二烯、异戊二烯、1，3-异戊二烯、2，3-二甲基丁二烯、2，4-二甲基-1，3-戊二烯、环戊二烯、甲基环戊二烯、1，8-萜二烯、杨梅烯和1，3-环己二烯，优选异戊烯、1，3-异戊二烯和2，3-二甲基丁二烯，特别优选异戊二烯。其它适用于本发明方法的最好具有4-10个碳原子的、可共聚的、一或多不饱和有机化合物是：苯乙烯、对甲基苯乙烯和二乙烯基苯，特别优选二乙烯基苯。
在本发明的方法中，共轭或非共轭的和/或一或多不饱和有机化合物是以0.01-20％(摩尔)的量、优选1-10％(摩尔)的量共聚的，其中二烯和多不饱和有机化合物可以相互之间以任意的混合比共聚。
本发明的聚合是以已知的方式在溶液、悬浮液或在气相中连续或非连续地一步或分为多步进行的，聚合温度为-100℃至+200℃，优选-100℃至+100℃，特别优选-50℃至+50℃，压力为0.1-100巴，优选1-50巴。
在该方法中，引发剂成分a)的使用浓度为每升反应器体积10-3至10-7摩尔。
引发剂成分b)(铝氧烷)的用量应使得相对于成分a)的摩尔比为1∶100至104∶1，优选1∶10至102∶1，特别优选1∶1至10∶1(成分b)：成分a))。
被认为是引发剂体系的成分a)的式(I)碳氢化合物具体是那些X代表氯或溴，特别是氯，R3、R4、R5相同或不同并且是指氢、C1-C10烷基、C3-C10环烷基、C6-C8芳基、C3-C10链烯基或C3-C10炔，特别是C1-C10烷基的式(I)化合物。特别优选甲基氯、氯乙烷和2-氯丙烷。
甲基、乙基或丁基铝氧烷，特别是例如Polyhedron，第7卷，no.22/23(1988)，pp.2375 et seq.所述的甲基铝氧烷特别适宜用作成分b)。
异烯烃聚合的新引发剂体系特别优选包含下述成分a)：甲基氯、乙基氯和/或苄基氯和下述成分b)：甲基铝氧烷。
引发剂成分a)和b)可以同时或陆续地、连续或不连续地加到单体混合物中。铝氧烷也可以通过适当的烷基铝化合物的水解就地产生。此外，还可以使用预处理形式的引发剂成分。预处理被认为是在无待用单体条件下各成分的陈化。
本发明的聚合优选在溶液或悬浮液中进行。可以考虑的溶剂或悬浮剂是那些在反应条件下为惰性的有机溶剂或悬浮剂，例如己烷、异戊烷和/或甲苯，优选己烷。
溶剂或悬浮剂的合适用量可以容易地通过适当的初步试验来确定。该用量通常为溶剂或悬浮剂与单体之和的80-95％(体积)。
本发明的方法可以例如如下进行：将反应器冷却至反应温度，例如投入纯化的溶剂和单体。在反应器被调节至所需的反应温度后，立即按比例加入一小部分引发剂成分b)并与单体混合物一起搅拌。然后按比例加入引发剂成分a)和剩余的引发剂成分b)并将反应器的内容物剧烈混合。在一个优选的实施方案中，引发剂成分a)和剩余的引发剂成分b)在加到反应器混合物中之前预混合一段时间。所用操作均在保护性气体例如氮气或氩气下进行。反应过程通过热的释放来监控。当放热反应完全之后，用例如溶解在乙醇中的2，5-二叔丁基-4-甲基苯酚使其突然中止。然后将反应器卸压，将所得聚合物溶液以汽提的常规方式后处理，或者必要时将其送入随后反应的卤化步骤中。可以将这种形式的所得聚合物直接官能化，即卤化。
本发明还提供用于异烯烃聚合的新的引发剂体系，该体系由下述成分组成：a)式(I)碳氢化合物
式中，X代表卤素、SCN、CN、OH、OR5、OCOR5或COOR5，其中R5代表C1-C10烷基或C3-C10环烷基；R3、R4、R5相同或不同，代表氢、C1-C10烷基、C3-C10环烷基、C6-C18芳基、C2-C10炔基或C3-C10炔，可选地被X取代，和b)式(II)或(III)开链和/或环状铝氧烷化合物：
RxRyAl[O-AlRz]mRw (II)，
式中，Rx、Ry、Rz、Rw是C1-C12烷基；m代表5-30的一个整数。
特别令人惊讶的是，按照本发明可以将例如伯烷基卤化物例如甲基氯与铝氧烷的组合用于异烯烃的聚合，因为迄今为止仅将共引发剂可活化的叔烷基化合物用于异烯烃的聚合。另一个惊人的发现是能够利用本发明的新引发剂体系生产分子量比先有技术的高得多的聚异烯烃。
用本发明方法生产的聚异烯烃的平均分子量Mw为2-20000kg/mol，优选20-1000kg/mol，非常特别优选200-800kg/mol。收率通常超过理论值的90％(重力法测定)。
实施例聚合试验的总体描述
首先的纯化和干燥的溶剂引入在保护性气体(氩气)下的反应器中，冷却至-78℃。然后将异丁烯引入反应器中，冷凝并称重测定其数量。然后，用吸移管引入适当摩尔比的引发剂成分，通过加入共引发剂使反应开始进行。
所用的共引发剂是甲基铝氧烷(30％的甲苯溶液)(MAO)。
转化完全后，立即用1％的2，6-二叔丁基甲酚的乙醇溶液使反应中止。分离出聚合物并以常规方式干燥。所用的引发剂成分示于表1中。聚合实施例：表1
| 实施例 | 引发剂 | 溶剂(ml) | 引发剂(a) | 共引发剂(b)(mmol/l)MAO＝IEt2AlCl＝(II)* | 转化率(％) | Mw(kg/-mol) | |||
| 1 | 2-氯丙烷 | 甲苯(15) | 5.95 | 59.5(I) | 90.4 | 351 | |||
| 2 | 新戊基氯 | 甲苯(15) | 5.95 | 59.5(I) | 100 | 396 | |||
| 3 | 叔丁基氯 | 甲苯(15) | 5.95 | 59.5(I) | 87.6 | 30 | |||
| 4 | 叔丁基氯 | 己烷(15) | 5.95 | 59.5(I) | 79.2 | 115 | |||
| 5* | 叔丁基氯 | 甲苯(15) | 5.95 | 59.5(II) | 94.2 | 35* | |||
| 6 | 1-氯戊烷 | 甲苯(15) | 5.95 | 59.5(I) | 56.8 | 740 | |||
| 7 | 1-氯戊烷 | 己烷(15) | 5.95 | 59.5(I) | 37.5 | 941 | |||
| 8 | 1-氯己烷 | 甲苯(15) | 5.95 | 59.5(I) | 45.2 | 715 | |||
| 9 | 氯甲烷 | 己烷(15) | 5.95 | 59.5(I) | 6I.5 | 496 | |||
| 10 | 氯乙烷 | 己烷(15) | 5.95 | 59.5(I) | 100 | 610 | |||
| 11 | 氯乙烷 | 己烷(15) | 11.92 | 59.5(I) | 39.5 | 986 | |||
| 12* | 氯乙烷 | 甲苯(15) | 5.96 | 59.6(II) | 32.8 | 375* | |||
| 13 | 氯乙烷 | 己烷(15) | 5.95 | 59.5(I) | 100 | 580 | |||
| 14 | 1-氯丁烷 | 己烷(15) | 5.95 | 59.5(I) | 89.4 | 598 | |||
*比较例反应条件：在T反应器＝-40℃下，t反应＝5h；在-33℃下24h(试验1至9)或者在-40℃下24h(试验10至14)(未搅拌)；单体浓度：5.95mol/l表2比较例(不用共引发剂)
结果：
| 实施例 | 引发剂 | 浓度(mmol/l) | 溶剂(ml) | 转化率(％) |
| 1 | MAO | 5.95 | 己烷(15) | 0 |
| 2 | Et2AlCl | 5.95 | 己烷(15) | 0 |
| 3 | 氯乙烷 | 5.95 | 己烷(15) | 0 |
显然在未用共引发剂的比较例(表2)中，在所述条件下MAO、氯化二乙基铝和氯代烷烃均不能引发异丁烯聚合。
当以MAO为共引发剂，同时以烷基卤化物为引发剂时，可以以较高的转化率获得比先有技术高得多的分子量(表1中的实施例5和12)，从而可以利用分子量的温度依赖性在更高的温度下进行聚合。
Claims (6)
1.生产聚异烯烃的方法，其特征在于使R1代表甲基、R2代表C1-C10烷基或C3-C10环烷基的式CH2＝CR1R2异烯烃可选地与具有4-20个碳原子的共轭或非共轭二烯和/或可阳离子聚合的、一或多不饱和的、具有4-20个碳原子的化合物聚合可获得聚异烯烃，聚合反应在-100℃至+100℃的温度和0.1-100巴的压力下，在溶液、悬浮液或气相中，在由下述成分组成的引发剂体系存在下进行：a)式(I)碳氢化合物式中，X代表卤素、SCN、CN、OH、OR5、OCOR5或COOR5，其中R5代表C1-C10烷基或C3-C10环烷基；R3、R4、R5相同或不同，代表氢、C1-C10烷基、C3-C10环烷基、C6-C18芳基、C2-C10炔基或C3-C10炔，可选地被X取代，和b)式(II)或(III)开链和/或环状铝氧烷化合物：
RxRyAl[O-A1Rz]mRw (II)，
式中，Rx、Ry、Rz、Rw是C1-C12烷基；m代表5-30的一个整数。
2.根据权利要求1的方法，其特征在于该方法在-100至+100℃的温度下进行。
3.根据权利要求1的方法，其特征在于该方法在1至50巴的压力下进行。
4.根据权利要求1至3的方法，其特征在于引发剂成分a)的使用浓度为每升反应体积10-2至10-7摩尔。
5.根据权利要求1至4的方法，其特征在于所用的引发剂成分b)的相对于成分a)的摩尔比为1∶100至104∶1。
6.用于异烯烃聚合的新引发剂体系，该体系的组成为：a)式(I)碳氢化合物
式中，X代表卤素、SCN、CN、OH、OR5、OCOR5或COOR5，其中R5代表C1-C10烷基或C3-C10环烷基；R3、R4、R5相同或不同，代表氢、C1-C10烷基、C3-C10环烷基、C6-C18芳基、C2-C10炔基或C3-C10炔，可选地被X取代，和b)式(II)或(III)开链和/或环状铝氧烷化合物：
RxRyAl[O-AlRz]mRw (II).
式中，Rx、Ry、Rz、Rw是C1-C12烷基；m代表5-30的一个整数。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19525035A DE19525035A1 (de) | 1995-07-10 | 1995-07-10 | Verfahren zur Herstellung von Polyisoolefinen mittels neuer Initiatorsysteme |
| DE19525035.4 | 1995-07-10 |
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| CN1145912A true CN1145912A (zh) | 1997-03-26 |
| CN1087307C CN1087307C (zh) | 2002-07-10 |
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| US (1) | US5668232A (zh) |
| EP (1) | EP0757997B1 (zh) |
| JP (1) | JPH0931117A (zh) |
| CN (1) | CN1087307C (zh) |
| CA (1) | CA2180591A1 (zh) |
| DE (2) | DE19525035A1 (zh) |
| ES (1) | ES2140760T3 (zh) |
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| CA2252295C (en) * | 1998-10-30 | 2007-07-17 | Bayer Inc. | Improved process for preparation of butyl rubber utilizing activated alkylaluminum halides |
| US6252021B1 (en) * | 1998-11-23 | 2001-06-26 | Korea Kumho Petrochemical Co., Ltd. | Process for producing polyisobutene using a catalytic system comprising transition metal-benzene derivative compound-methylaluminoxane |
| DE10004048A1 (de) * | 2000-01-31 | 2001-08-02 | Bayer Ag | Hochmolekulare gelfreie Isobutencopolymere mit hohen Doppelbindungsgehalten |
| CA2329552C (en) * | 2000-12-22 | 2010-04-13 | Bayer Inc. | An improved process for the preparation of butyl rubber utilizing alkylaluminum dihalides and aluminoxanes |
| JP5016809B2 (ja) * | 2005-11-09 | 2012-09-05 | 出光興産株式会社 | ビニリデン化合物オリゴマーの製造方法 |
| US20100273964A1 (en) * | 2009-04-22 | 2010-10-28 | Stewart Lewis | Heterogeneous lewis acid catalysts for cationic polymerizations |
| US8883943B2 (en) | 2009-09-25 | 2014-11-11 | China Petroleum & Chemical Corporation | Isoolefin polymers and process for preparing the same |
| US8283427B2 (en) * | 2010-05-06 | 2012-10-09 | Lewis Stewart P | Heterogeneous perfluoroaryl substituted Lewis acid catalysts for cationic polymerizations |
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| GB1094728A (en) * | 1964-05-01 | 1967-12-13 | Exxon Research Engineering Co | Butyl rubber catalyst system |
| US3948868A (en) * | 1969-04-03 | 1976-04-06 | Exxon Research And Engineering Company | Homogeneous styrene/isoolefin copolymers |
| US3645920A (en) * | 1969-04-14 | 1972-02-29 | Goodrich Co B F | Process of polymerizing a 1 2-monoepoxide with a polymeric hydrocarbyl aluminum alkoxide catalyst |
| US3850897A (en) * | 1971-11-26 | 1974-11-26 | Snam Progetti | Procedure for the production of polymers and copolymers of isobutylene |
| DE3300155A1 (de) * | 1983-01-05 | 1984-07-05 | Basf Ag, 6700 Ludwigshafen | Verfahren zur kontinuierlichen herstellung von isobutylenpolymerisaten |
| DD225425A1 (de) * | 1984-07-09 | 1985-07-31 | Leuna Werke Veb | Halbzeuge aus thermoplast |
| US5032653A (en) * | 1988-06-28 | 1991-07-16 | Exxon Chemical Patents, Inc. | Direct synthesis by cationic polymerization of nitrogen-containing polymers |
| JP2936414B2 (ja) * | 1988-08-19 | 1999-08-23 | 鐘淵化学工業株式会社 | 官能性末端を有するイソブチレン系ポリマー |
| ES2020484A6 (es) * | 1990-06-29 | 1991-08-01 | Repsol Quimica Sa | Procedimiento de preparacion de homopolimeros de dienos conjugados y de copolimeros de dienos conjugados con otros dienos o compuestos vinil aromaticos. |
| JP2835779B2 (ja) * | 1990-11-17 | 1998-12-14 | 鐘淵化学工業株式会社 | 官能性末端を有するイソブチレン系ポリマーの製造法 |
| US5329032A (en) * | 1992-03-18 | 1994-07-12 | Akzo Chemicals Inc. | Polymethylaluminoxane of enhanced solution stability |
-
1995
- 1995-07-10 DE DE19525035A patent/DE19525035A1/de not_active Withdrawn
-
1996
- 1996-06-27 DE DE59603661T patent/DE59603661D1/de not_active Expired - Fee Related
- 1996-06-27 EP EP96110357A patent/EP0757997B1/de not_active Expired - Lifetime
- 1996-06-27 ES ES96110357T patent/ES2140760T3/es not_active Expired - Lifetime
- 1996-07-05 CA CA002180591A patent/CA2180591A1/en not_active Abandoned
- 1996-07-08 JP JP8195193A patent/JPH0931117A/ja active Pending
- 1996-07-08 US US08/677,638 patent/US5668232A/en not_active Expired - Fee Related
- 1996-07-10 CN CN96110528A patent/CN1087307C/zh not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| EP0757997A3 (de) | 1998-01-28 |
| US5668232A (en) | 1997-09-16 |
| CN1087307C (zh) | 2002-07-10 |
| JPH0931117A (ja) | 1997-02-04 |
| DE19525035A1 (de) | 1997-01-16 |
| EP0757997B1 (de) | 1999-11-17 |
| CA2180591A1 (en) | 1997-01-11 |
| EP0757997A2 (de) | 1997-02-12 |
| DE59603661D1 (de) | 1999-12-23 |
| ES2140760T3 (es) | 2000-03-01 |
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