CN1097062C - 生产高度支化的聚异烯烃的方法 - Google Patents
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Abstract
本发明提供生产高度支化的聚异烯烃的方法，该方法的特征在于在含有至少一个能够进行阳离子聚合的基团和至少一个起异烯烃的阳离子聚合引发剂作用的基团的二官能单体(引发单体)的存在下，在+20℃至-100℃的温度下，可选地在惰性有机溶剂存在下，并且在烷基铝氧烷(共引发剂)存在下，将异烯烃在溶液、悬浮液或气相中一步聚合。
Description
本发明涉及生产高度支化的聚异烯烃的方法，该方法包括将异烯烃，可选地与共轭或非共轭二烯和/或可阳离子聚合的单或多不饱和化合物一起，在溶液、悬浮液或气相中一步聚合。
很久以来，人们已经知道了阳离子聚合，例如J.P.Kennedy和B.Ivan在Carbocationic Macromolecular Egineering(1991)中有述。就其物理性能而言，以这种方式生产的丁基橡胶和卤代丁基橡胶被用于工业，特别是用于轮胎内胎和轮胎的衬里。在这方面，这样制得的丁基橡胶在混炼、捏炼、压出和压延中的加工性能是非常重要的。加工性能特别与橡胶的格林强度和应力松弛有关。这可以通过例如将不同分子量的对应的聚合物共混，形成具有常规的、宽分子量分布的产品而实现。然而，该方法颇费人工。表现出宽分子量分布和无规长支链并且具有期望的加工性能的丁基橡胶的直接合成可以通过例如在二官能单体(例如二乙烯基苯、2，5-己二烯或乙烯基苄基氯)存在下使异丁烯与异戊二烯共聚合来完成。然而，该共聚合的一个重要缺点是在橡胶中生成高比例的凝胶(参见：例如H.-C.Wang，K.W.Powers，J.V.Fusco，ACS Meeting，1989年5月第21号论文)。
因此，又介绍了另一种引入长支链的方法，即在多官能支化剂存在下将异丁烯与异戊二烯共聚。后者应当理解为含有官能团的可溶性聚合物，它在加工条件下会引发聚合(通过叔烷基基团“从该处接枝”)或者与生长的聚合物链的阳离子终端反应(通过反应性双键“接枝”)。关于多官能支化剂，可以提及盐酸化苯乙烯-异戊二烯共聚物、氯化聚苯乙烯、聚异戊二烯或苯乙烯-丁二烯嵌段共聚物(H.C.Wang，K.W.Powers，J.V.Fusco，ACS Meeting，9-12.05.1989；EP-A 320263)。所得聚合物混合物称为“星形支化丁基橡胶”。该方法的一个缺点是必须进行分离步骤、附加的聚合步骤或支化剂的卤化步骤。该方法的特征在于在聚合期间同时生成线型或支化的聚合物。
在Polymer Bull.31(1993)中描述了通过活性聚丁二烯聚合物与二乙烯基苯的反应生产“多臂星形”聚异丁烯的方法。这些聚异丁烯是通过“先臂后核”的方法生产的(参见US 5458796的解释)。另一种生产支化丁基橡胶的可能性是使用多功能引发剂，如US 5084522所述。该方法也称为“先核后臂”法。考虑到生产多功能引发剂的分离步骤和转移反应生成均聚物的情况，该方法也有一些缺点。
因此，本发明的目的是提供生产高度支化的聚异烯烃的一步法，其特征在于在含有至少一个能够进行阳离子聚合的基团和至少一个起异烯烃的阳离子聚合引发剂作用的基团的二官能单体[引发单体(inimer)]的存在下，在+20℃至-100℃的温度下，可选地在惰性有机溶剂存在下，并且在烷基铝氧烷(共引发剂)存在下，将异烯烃(可选地与共轭或非共轭二烯一起)在溶液、悬浮液或气相中一步聚合。
优选使用的异烯烃是下式异烯烃：其中，R1＝Me，R2代表C1-C6烷基，例如甲基、乙基或丙基。特别优选异丁烯和2-甲基丁烯-1，尤其是异丁烯。适用于本发明方法的共轭或非共轭二烯是含有4-20个、优选4-10个、最优选4-6个碳原子的二烯，例如丁二烯、异戊二烯、1，3-戊二烯、2，3-二甲基丁二烯、2，4-二甲基戊二烯-1，3、环戊二烯、甲基环戊二烯、苎烯、月桂烯和/或1，3-环己二烯，优选异戊二烯、1，3-戊二烯和/或二甲基丁二烯，最优选异戊二烯。
本发明的方法特别优选用于丁基橡胶的生产，即异丁烯与异戊二烯的共聚。
适宜的二官能单体(引发单体)是通式(I)至(III)的芳族和/或脂族乙烯基和异戊二烯化合物：式中F 对应于官能有机基团-CR3 2X，其中X对应于OR，Cl，Br，I，CN，N3
或SCN，R3对应于H和/或C1-C20烷基，并且Ar 对应于C6H4或C10H8。
下面的基团是特别适宜的C1-C20烷基基团：甲基、乙基、丙基、丁基、己基、辛基、癸基和二十烷基，优选甲基、乙基和丙基，最优选甲基。
在本发明方法中，优选使用下式(IV)的引发单体：
式中，F 具有上述的意义。
最优选将下面的化合物用作引发单体：4-乙烯基苄基氯和/或4-异戊二烯基苄基氯。
所用的引发单体与单体的摩尔比在1∶104至1∶10的范围内，优选1∶103至1∶50，最优选1∶10至1∶20。
在异烯烃与能够与异烯烃共聚的二烯的共聚过程中，异烯烃与可共聚单体的摩尔比通常为1∶103至1∶10，优选1∶102至1∶50。
本发明的方法可以在惰性有机溶剂例如直链或支链烃和/或直链和支链卤代烃(例如戊烷、己烷和/或二氯甲烷)存在下进行。在这一方面，惰性溶剂的用量并不关键。最适宜的用量可以通过适当的初步试验容易地测定。
除了引发单体外，还必须用烷基铝氧烷作本发明方法的共引发剂。适当的、优选的烷基铝氧烷是甲基铝氧烷、乙基铝氧烷和/或丁基铝氧烷，特别是甲基铝氧烷，例如Polyhedron，Vol.7，No.22/23(1988)，第2375等页所述的那些。
在本发明的方法中，所用的铝氧烷与所述引发单体的摩尔比在1∶104至1∶103的范围内，优选1∶103至1∶3，最优选1∶102至1∶2。
在本发明的聚合中也可以加入其它适宜的添加剂。适宜的添加剂的实例包括给电子体例如二甲基乙酰胺和/或二甲基亚砜，或质子接受体例如二叔丁基吡啶(例如参见US 5169914)。
引发单体和共引发剂可以同时、依次、连续或分批加到待聚合的单体混合物中。当然铝氧烷也可以通过相应烷基铝的水解以已知的方式就地制备。
本发明的方法可以在+20℃至-100℃的温度范围内进行，优选在-20℃至-90℃的温度范围内进行，特别是在-40℃至-80℃的温度范围内进行。
本发明的方法可以在溶液、悬浮液或在气相中进行。优选在溶液中进行。也可以以分批法、流动法或连续法来进行本发明的过程，其中反应时间或停留时间为2秒至20小时，优选60秒至1小时，特别是15-40分钟。
如上所述，本发明的方法产生高度支化的聚异烯烃，其中支化度尤其取决于引发单体的反应性、共引发剂、共引发剂的浓度、单体与引发剂的摩尔比、反应温度和反应时间。因此，可以通过适当变化上述参数来分别调节待生产的聚异烯烃的支化度和分子量。
例如，本发明的方法可以以下述方式进行，在冷却至反应温度的反应器中投入纯化的溶剂和单体，在将反应器的温度调节至所需的反应温度后，加入所需量的引发单体，与其中的单体混合物一起搅拌。随后加入所需量的共引发剂。将反应器的内容物剧烈和充分地搅拌。所有操作都是在惰性气氛中进行的。聚合过程通过产生的热来监控。放热反应完成后，用例如溶解在乙醇中的2，5-二叔丁基-4-甲氧基苯酚终止反应。然后以有效的方法例如汽提处理所得聚合物。
本发明方法的优点特别是由一步法反应程序产生的，获得确定的、表现出优异的加工性能的、高度支化的聚异烯烃(优选丁基橡胶)。
实施例
用凝胶渗透色谱/粘度计联合表征聚合物的分子量分布和支化度。GPC-粘度计联合装置装有八个尺寸为100，1000(2x)，104(2x)，105(2x)和106埃的总长度为976厘米的Styragel柱。以0.5毫升/分钟的流速泵送四氢呋喃洗脱介质。在30℃下用乌氏粘度计在线测定1.93毫升的级分。用常数K＝5×10-4dl/g和α＝0.6计算Mv值。实施例1
将1000毫升无水己烷投入装有搅拌器和温度计的2升圆底烧瓶中，冷却至-60℃，与100毫摩尔异戊二烯和100毫摩尔乙烯基苄基氯(INIMER)混合。随后将200克异丁烯冷凝于其中。通过在-60℃下加入12毫摩尔甲基铝氧烷(30％的甲苯溶液)引发聚合。在-60℃下搅拌3小时后，通过加入乙醇终止反应。分离得到134克(转化率：64.8％)聚合物。用GPC/粘度计表征得知分子量分布Mn＝11kg/mol，支化度为大约73％。Staudinger指数为0.3dl/g。凝胶含量为2.7％。实施例2
按照类似于实施例1的方法进行本实施例，但这次用220克异丁烯和200毫摩尔乙烯基苄基氯(INIMER)。3小时后的转化率为18.3％。Staudinger指数为0.23dl/g。凝胶含量为4.6％。用GPC/粘度计表征得知分子量分布Mn＝13kg/mol，Mw＝58kg/mol，支化度为大约80％。
Claims (5)
1.生产高度支化的聚异烯烃的方法，其特征在于在含有至少一个能够进行阳离子聚合的基团和至少一个起异烯烃的阳离子聚合引发剂作用的基团的二官能单体的存在下，在+20℃至-100℃的温度下，可选地在惰性有机溶剂存在下，并且在烷基铝氧烷存在下，将异烯烃在溶液、悬浮液或气相中一步聚合。
2.根据权利要求1的方法，其特征在于将异丁烯和/或2-甲基丁烯-1用作异烯烃。
3.根据权利要求1或2的方法，其特征在于所用的二官能单体是下式(I)至(III)的单体：
式中
F对应于官能有机基团-CR3 2X，其中X对应于OR，Cl，Br，I，CN，N3或SCN，R3对应于H和/或C1-C20烷基，并且
Ar对应于C6H4或C10H8。
4.根据权利要求1或2的方法，其特征在于将甲基铝氧烷、乙基铝氧烷和/或丁基铝氧烷用作烷基铝氧烷。
5.根据权利要求1或2的方法，其特征在于烷基铝氧烷和二官能单体用量的摩尔比为1∶104至1∶103。
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| Application Number | Priority Date | Filing Date | Title |
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| DE19628450.3 | 1996-07-15 | ||
| DE19628450A DE19628450A1 (de) | 1996-07-15 | 1996-07-15 | Verfahren zur Herstellung von hochverzweigten Polyisoolefinen |
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| US (1) | US6156859A (zh) |
| EP (1) | EP0819707B1 (zh) |
| JP (1) | JPH1060050A (zh) |
| CN (1) | CN1097062C (zh) |
| BR (1) | BR9703977A (zh) |
| CA (1) | CA2210274C (zh) |
| DE (2) | DE19628450A1 (zh) |
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| US6274689B1 (en) | 1998-10-07 | 2001-08-14 | Exxon Chemical Patents, Inc. | Random isomonoolefin/allyl styrene copolymers and functionalized derivatives thereof |
| CA2446866C (en) * | 2001-05-29 | 2011-05-03 | The University Of Western Ontario | Arborescent thermoplastic elastomers and products therefrom |
| CA2448337A1 (en) * | 2003-11-03 | 2005-05-03 | Bayer Inc. | Butyl-type rubber with high viscosity |
| CN101010377B (zh) * | 2004-06-15 | 2010-11-24 | 埃克森美孚化学专利公司 | 弹性体组合物、气密层及其制备方法 |
| WO2007136700A2 (en) | 2006-05-17 | 2007-11-29 | The University Of Akron | Method of purifying block copolymers |
| EP2079844B1 (en) * | 2006-10-04 | 2015-01-07 | The University of Akron | Synthesis of inimers and hyperbranched polymers |
| US20100059452A1 (en) * | 2008-09-11 | 2010-03-11 | Lanxess, Inc. | Method of purifying block copolymers |
| BR112012009358A2 (pt) | 2009-10-30 | 2016-11-22 | Rhodia China Co Ltd | compostos de fosfinato de dieno conjugado, método para sua preparação e uso. |
| CN104140484B (zh) * | 2013-05-08 | 2016-08-17 | 中国石油化工股份有限公司 | 一种支化稀土异戊橡胶及其制备方法和橡胶组合物 |
| US11981777B2 (en) | 2018-08-20 | 2024-05-14 | The University Of Akron | Synthesis of hyperbranched polymethacrylates and polyacrylates by a haloinimer approach |
| CN112646098B (zh) * | 2019-10-12 | 2022-09-20 | 中国石油化工股份有限公司 | 嵌段共聚物及其制备方法 |
| CN113493556B (zh) * | 2020-04-08 | 2023-09-26 | 中国石油天然气股份有限公司 | 高支化丁基橡胶的制备方法 |
| CN113493546B (zh) * | 2020-04-08 | 2023-11-28 | 中国石油天然气股份有限公司 | 一种宽分子量分布丁基橡胶的制备方法 |
| CN113493550B (zh) * | 2020-04-08 | 2023-10-31 | 中国石油天然气股份有限公司 | 一种高宽分布高支化丁基橡胶的制备方法 |
| CN113493548B (zh) * | 2020-04-08 | 2023-09-26 | 中国石油天然气股份有限公司 | 支化丁基橡胶的制备方法 |
| CN113493549B (zh) * | 2020-04-08 | 2023-10-31 | 中国石油天然气股份有限公司 | 高宽分布、高支化丁基橡胶的制备方法 |
| CN113493547B (zh) * | 2020-04-08 | 2023-11-28 | 中国石油天然气股份有限公司 | 一种超支化丁基橡胶的制备方法 |
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| US3948868A (en) * | 1969-04-03 | 1976-04-06 | Exxon Research And Engineering Company | Homogeneous styrene/isoolefin copolymers |
| US4074035A (en) * | 1975-04-22 | 1978-02-14 | Exxon Research & Engineering Co. | Halomethylated aromatic interpolymers |
| US5071913A (en) * | 1987-12-11 | 1991-12-10 | Exxon Chemical Patents Inc. | Rubbery isoolefin polymers exhibiting improved processability |
| US5084522A (en) * | 1988-02-05 | 1992-01-28 | University Of Ottawa | Styrenic polymer containing pendant reactive tertiary structures and the preparation thereof |
| CA1338546C (en) * | 1988-05-27 | 1996-08-20 | Kenneth William Powers | Para-alkylstyrene/isoolefin copolymers |
| US5458796A (en) * | 1994-03-31 | 1995-10-17 | Shell Oil Company | Synthesis of polyisobutylene star-branched polymers via living carbocationic polymerization |
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| Publication number | Publication date |
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| CA2210274C (en) | 2006-02-07 |
| EP0819707A3 (de) | 1998-08-05 |
| JPH1060050A (ja) | 1998-03-03 |
| EP0819707B1 (de) | 2001-03-14 |
| CA2210274A1 (en) | 1998-01-15 |
| DE59703126D1 (de) | 2001-04-19 |
| US6156859A (en) | 2000-12-05 |
| ES2155225T3 (es) | 2001-05-01 |
| BR9703977A (pt) | 1998-09-01 |
| CN1172815A (zh) | 1998-02-11 |
| EP0819707A2 (de) | 1998-01-21 |
| RU2189991C2 (ru) | 2002-09-27 |
| DE19628450A1 (de) | 1998-01-22 |
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