新型结构调节剂制备溶聚丁苯橡胶的研究
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摘要
目前世界上合成溶聚丁苯橡胶(SSBR)，普遍采用烷基锂作引发剂，通过添加极性结构调节剂来控制产物微观结构的阴离子溶液聚合技术，其关键是结构调节剂的选择，它对合成高性能溶聚丁苯橡胶至关重要，直接影响产品的结构及性能，然而目前生产中所常用的结构调节剂或调节能力低(THF)，调节剂用量大，不易回收或容易导致活性链失活(2G)，偶联效率降低，影响产品质量。论文在参考相关美国专利的基础上，针对这些问题采用Darzens缩合法合成了两种不对称醚：乙基四氢糠基醚(ETE)和乙氧基乙基吗啉(EOEM)以及两种烷氧基碱金属化合物：四氢糠醇钠(THFAONa)和吗啉乙醇钠(MEONa)。以正丁基锂(n-BuLi)为引发剂、环己烷和正己烷混合溶液为溶剂，将合成得到的四类新型结构调节剂应用于丁二烯／苯乙烯溶液阴离子聚合，全面考察了他们对聚合反应动力学、聚合产物以及后续偶联反应的影响规律。
研究了不同调节剂用量、不同引发温度下的聚合动力学行为以及共聚物组成与单体转化率的关系，并分别求取了不同条件下的各单体表观竞聚率。动力学研究表明，调节剂的加入能显著提高聚合反应速率；调节剂用量增加，聚合反应速率加快，丁二烯表观竞聚率(r_1)减小而苯乙烯表观竞聚率(r_2)增大，反应趋向于无规共聚。产物微观结构的研究表明，四种调节剂对SSBR均具有很强的1，2-结构调节能力和无规化调节能力，控制引发温度在30～70℃之间变化，改变调节剂用量，可以控制SSBR中的1，2-结构含量在20％～80％之间灵活变化；其无规化调节能力大小依次为：THFAONa＞MEONa＞ETE＞EOEM；引发温度升高，调节剂的1，2-结构调节能力以及无规化调节能力均减弱，且ETE体系和THFAONa体系受温度的影响要小于EOEM体系和MEONa体系。对SSBR分子量及其分布的研究表明，不对称醚体系以及MEONa体系对分子量及其分布的影响很小，而THFAONa的加入对分子量及其分布的影响较为明显，70℃引发时，THFAONa／Li=5.0的情况下，聚合产物的分子量分布能增至1.65。对SSBR后续偶联反应的研究表明，调节剂加入量的增加或引发温度的升高，均能降低偶联效率，四种调节剂对SSBR后续偶联反应的影响大小依次为：THFAONa＞MEONa＞ETE＞EOEM。
SSBR硫化胶的研究结果表明，四种调节体系下均能得到具有优异物理机械性能的SSBR产品，且MEONa体系和THFAONa体系下制得的SSBR产品，兼具高抗湿滑性和低滚动力的特点，综合性能优良；ETE体系下制得的SSBR产品具有优异的抗湿滑性能，但滚动阻力偏高。
It is well known that the solution styrene and butadiene rubber(SSBR) is produced fromanionic polymerization by organolithium initiators in the presence ofpolar modifiers, such asamines、ethers or alkoxyl metal compounds which are needed to adjust the vinyl content ofthe diene polymers. The key synthesis technology of SSBR is the selection of structuremodifiers which is increasingly attracted extensive attentions, and it has a direct effect onstructure and properties of SSBR.
In this thesis, self-made asymmetric ethers and sodium alkoxides are used as modifiers inanionic copolymerization of styrene and butadiene in the cyclohexane and hexane mixingsolution with n-butyllithium as the initiator, in which asymmetric ethers are synthesizedfollowing the Darzens method include ethyl morpholinoethyl ether(EOEM) andtetrahydrofufury ethyl ether(ETE), sodium alkoxides include sodium salts of tetrahydrofufuryalcohol and sodium salts of morpholinoethoI. Furthermore, this thesis studies systematicallythe kinetic behavior of the copolymerization and the coupling reaction. The microstructure,molecular weight and its distribution of the copolymers are well discussed in detail. Inaddition, the physical mechanical properties and the dynamic mechanical analysis(DMA) arealso investigated.
The kinetic behaviors of the copolymerization、the relationship between polymercomposition and conversion at different modifier dosages、different initiation temperature arestudied. And the value of the monomer apparent reactivity ratios under different conditions isobtained. The kineties research indicates that the polymerization speed increases fast with theadding of the modifiers, and the value of the butadiene apparent reactivity ratios(r_1) declinesand the styrene apparent reactivity ratios (r_2) augments accordingly when the dosage ofmodifiers increased, so the styrene monomer is randomized along the polymer chain to formrandom SSBR. However, the value of r_1 augments and that of r_2 declines when the initiationtemperature rises from 50℃to 70℃.
The microstructure research shows that the regulation ability of the modifiers are sostrong that the 1,2-content of polybutadiene in SSBR can be modified from 20％to 80％easily by altering the modifier concentration and the initiation temperature ranges from 30℃to 70℃; And the randomizers regulation ability decreased in following order: THFAONa＞ MEONa＞ETE＞EOEM; The regulation ability of the modifiers is getting smaller as theinitiation temperature rises, and the initiation temperature has more significant influence onthe regulation ability of EOEM and MEONa than that of ETE and THFAONa. The researchshows that the adding of the modifiers, such as ETE、EOEM and MEONa, have littleinfluence on the molecular weight and its distribution. However, THFAONa has a significantinfluence on them, and the molecular weight distribution of SSBR ranges from 1.04 to 1.65with the changing of THFAONa/BuLi(mol ratio) ranges from 0 to 5.0 at 50℃. It is found thatcoupling efficiency decreased with increasing modifier dosages or raising the initiationtemperature, and the sequence to the effect of the coupling efficiency is as follows:THFAONa＞MEONa＞ETE＞EOEM.
Furthermore, the results of the physical properties show that the resulting productspossesse good physical and mechanical properties. The products in MEONa/BuLi system orTHFAONa/BuLi system have both high wet skidding-resistance and low rolling-resistanceproperties, which are valuable for using in making automobile tire treads, and the products inETE system have excellent wet skidding-resistance properties which are valuable for using inmaking race tire treads and rain tire treads.
研究了不同调节剂用量、不同引发温度下的聚合动力学行为以及共聚物组成与单体转化率的关系，并分别求取了不同条件下的各单体表观竞聚率。动力学研究表明，调节剂的加入能显著提高聚合反应速率；调节剂用量增加，聚合反应速率加快，丁二烯表观竞聚率(r_1)减小而苯乙烯表观竞聚率(r_2)增大，反应趋向于无规共聚。产物微观结构的研究表明，四种调节剂对SSBR均具有很强的1，2-结构调节能力和无规化调节能力，控制引发温度在30～70℃之间变化，改变调节剂用量，可以控制SSBR中的1，2-结构含量在20％～80％之间灵活变化；其无规化调节能力大小依次为：THFAONa＞MEONa＞ETE＞EOEM；引发温度升高，调节剂的1，2-结构调节能力以及无规化调节能力均减弱，且ETE体系和THFAONa体系受温度的影响要小于EOEM体系和MEONa体系。对SSBR分子量及其分布的研究表明，不对称醚体系以及MEONa体系对分子量及其分布的影响很小，而THFAONa的加入对分子量及其分布的影响较为明显，70℃引发时，THFAONa／Li=5.0的情况下，聚合产物的分子量分布能增至1.65。对SSBR后续偶联反应的研究表明，调节剂加入量的增加或引发温度的升高，均能降低偶联效率，四种调节剂对SSBR后续偶联反应的影响大小依次为：THFAONa＞MEONa＞ETE＞EOEM。
SSBR硫化胶的研究结果表明，四种调节体系下均能得到具有优异物理机械性能的SSBR产品，且MEONa体系和THFAONa体系下制得的SSBR产品，兼具高抗湿滑性和低滚动力的特点，综合性能优良；ETE体系下制得的SSBR产品具有优异的抗湿滑性能，但滚动阻力偏高。
It is well known that the solution styrene and butadiene rubber(SSBR) is produced fromanionic polymerization by organolithium initiators in the presence ofpolar modifiers, such asamines、ethers or alkoxyl metal compounds which are needed to adjust the vinyl content ofthe diene polymers. The key synthesis technology of SSBR is the selection of structuremodifiers which is increasingly attracted extensive attentions, and it has a direct effect onstructure and properties of SSBR.
In this thesis, self-made asymmetric ethers and sodium alkoxides are used as modifiers inanionic copolymerization of styrene and butadiene in the cyclohexane and hexane mixingsolution with n-butyllithium as the initiator, in which asymmetric ethers are synthesizedfollowing the Darzens method include ethyl morpholinoethyl ether(EOEM) andtetrahydrofufury ethyl ether(ETE), sodium alkoxides include sodium salts of tetrahydrofufuryalcohol and sodium salts of morpholinoethoI. Furthermore, this thesis studies systematicallythe kinetic behavior of the copolymerization and the coupling reaction. The microstructure,molecular weight and its distribution of the copolymers are well discussed in detail. Inaddition, the physical mechanical properties and the dynamic mechanical analysis(DMA) arealso investigated.
The kinetic behaviors of the copolymerization、the relationship between polymercomposition and conversion at different modifier dosages、different initiation temperature arestudied. And the value of the monomer apparent reactivity ratios under different conditions isobtained. The kineties research indicates that the polymerization speed increases fast with theadding of the modifiers, and the value of the butadiene apparent reactivity ratios(r_1) declinesand the styrene apparent reactivity ratios (r_2) augments accordingly when the dosage ofmodifiers increased, so the styrene monomer is randomized along the polymer chain to formrandom SSBR. However, the value of r_1 augments and that of r_2 declines when the initiationtemperature rises from 50℃to 70℃.
The microstructure research shows that the regulation ability of the modifiers are sostrong that the 1,2-content of polybutadiene in SSBR can be modified from 20％to 80％easily by altering the modifier concentration and the initiation temperature ranges from 30℃to 70℃; And the randomizers regulation ability decreased in following order: THFAONa＞ MEONa＞ETE＞EOEM; The regulation ability of the modifiers is getting smaller as theinitiation temperature rises, and the initiation temperature has more significant influence onthe regulation ability of EOEM and MEONa than that of ETE and THFAONa. The researchshows that the adding of the modifiers, such as ETE、EOEM and MEONa, have littleinfluence on the molecular weight and its distribution. However, THFAONa has a significantinfluence on them, and the molecular weight distribution of SSBR ranges from 1.04 to 1.65with the changing of THFAONa/BuLi(mol ratio) ranges from 0 to 5.0 at 50℃. It is found thatcoupling efficiency decreased with increasing modifier dosages or raising the initiationtemperature, and the sequence to the effect of the coupling efficiency is as follows:THFAONa＞MEONa＞ETE＞EOEM.
Furthermore, the results of the physical properties show that the resulting productspossesse good physical and mechanical properties. The products in MEONa/BuLi system orTHFAONa/BuLi system have both high wet skidding-resistance and low rolling-resistanceproperties, which are valuable for using in making automobile tire treads, and the products inETE system have excellent wet skidding-resistance properties which are valuable for using inmaking race tire treads and rain tire treads.
引文
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