Semicrystalline rubber diblock copolymers via cyclooctene ROMP and chain transfer with vinyl‐terminated isotactic polystyrene
Semicrystalline rubber diblock copolymers via cyclooctene ROMP and chain transfer with vinyl‐terminated isotactic polystyrene
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通过环辛烯 ROMP 和乙烯基封端等规聚苯乙烯的链转移制备半结晶橡胶二嵌段共聚物
DOI：
10.1002/pola.28135
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发表时间：
2016
期刊：
影响因子：
--
通讯作者：
Mülhaupt
中科院分区：
文献类型：
--
作者：
Kirschvink;Barbara T;Vielhauer;Maximilian;Pierre J;Mülhaupt
前言开环歧化聚合(ROMP)是一种用途广泛的合成方法，可用于多种聚合物材料的分子工程。1，2由于Ru基格拉布斯催化剂的稳定性，3，4在ROMP过程中可以容忍非极性环烯烃单体和带有官能团的单体。最常见的ROMP单体包括环辛烯、5-9和降冰片烯衍生物等环烯烃。10-12今天，ROMP工艺在嵌段和接枝共聚物的合成中特别重要。3分子共聚物结构可通过加入大单体、11、13-15顺序单体添加、16、17或通过将ROMP与其他聚合方法相结合来定制。传统上，ROMP端基功能化和ROMP摩尔质量控制是通过添加链转移剂(CTA)同时实现的，其中短链转移剂分别是1-辛烯和1-己烯或官能化的烯烃。3，19-22当以摩尔质量较高的1-烯烃作为大分子CTA时，ROMP通过链转移反应生成两嵌段共聚物。例如，Janssen等人。将端乙烯基聚(3-己基噻吩基)作为大分子CTA用于ROMP两嵌段共聚物的合成。23此外，Hillmyer等人。开发了一种无规聚苯乙烯-b-多环辛烯-b-无规聚苯乙烯的ROMP链转移工艺，以制备ABA型三嵌段共聚物。24他们利用阴离子苯乙烯聚合设计了封端烯烃的无规聚苯乙烯作为环辛烯催化的CTA。由于无规聚苯乙烯不结晶，因此通过催化后聚合加氢将无定形聚环辛烯嵌段转化为半结晶的线型低聚低聚乙烯和聚乙烯嵌段，从而使非晶态三嵌段共聚物变为半结晶。同样，Bishop和Register将活性环辛烯ROMP与随后的催化氢化相结合，以量身定制非晶态PS基质中含有结晶-玻璃态硬质聚乙烯结构域的热塑性弹性体。25值得注意的是，自由基聚合和阴离子聚合均可产生无定形无规聚苯乙烯，应用范围从聚苯乙烯商品热塑性塑料到苯乙烯工程塑料，如HIPS、SAN、ABS，甚至热塑性弹性体，如SBS和SEBS。26、27关于分别含有可结晶等规聚苯乙烯(IPS)或间同立构聚苯乙烯链段的半结晶橡胶嵌段共聚物的已知要少得多。在最近的研究中，Capacchione et al.28、29和Okuda等人。30以丁苯和丁二烯为原料，在等规钛酸络合物上进行活性苯乙烯/丁二烯共聚反应，制备了半结晶聚丁二烯-丁二烯-等规聚苯乙烯(IPs)半结晶橡胶嵌段共聚物。本文报道了以端乙烯基聚异辛烯(乙烯-iPS)为CTA，通过环辛烯缩聚反应合成聚环辛烯-b-iPS(PCO-b-iPS)的方法。
INTRODUCTION Ring-opening metathesis polymerization (ROMP) represents a versatile synthetic method enabling molecular engineering of a wide variety of polymeric materials for diversified applications. 1, 2 Owing to the robustness of the ruthenium-based Grubbs’ catalysts, 3, 4 both non-polar cyclic olefin monomers and monomers bearing functional groups are tolerated in the ROMP process. The most common ROMP monomers include cyclic olefins such as cyclooctene, 5–9 and norbornene derivatives. 10–12 Today, the ROMP process is of particular interest in block and graft copolymer synthesis. 3 Molecular copolymer architectures are tailored by incorporation of macromonomers, 11, 13–15 sequenced monomer addition, 16, 17 or by combining ROMP with other polymerization methods. 18 Traditionally, ROMP end group functionalization and ROMP molar mass control are simultaneously achieved by the addition of chain transfer agents (CTAs), among them short acyclic olefins such 1-octene and 1-hexene or functionalized olefins, respectively. 3, 19–22 When using higher molar mass 1-olefins as macromolecular CTA, ROMP produces diblock copolymers by chain transfer reaction. For example, Janssen et al. employed vinyl-terminated poly (3-hexylthiophene) as macromolecular CTA in ROMP diblock copolymer synthesis. 23 Moreover, Hillmyer et al. developed a ROMP chain transfer process for preparing atactic polystyrene-b-polycyclooctene-b-atactic polystyrene as an ABA-type triblock copolymer. 24 They employed anionic styrene polymerization to design olefin-terminated atactic polystyrene as CTA for cyclooctene ROMP. Since atactic polystyrene does not crystallize, the resulting amorphous triblock copolymers were rendered semicrystalline by catalytic postpolymerization hydrogenation, which converts the amorphous polycyclooctene blocks into semicrystalline linear oligoethylene and polyethylene blocks. Similarly, Bishop and Register combined living cyclooctene ROMP with subsequent catalytic hydrogenation to tailor thermoplastic elastomers containing crystalline-glassy hard polyethylene domains within the amorphous PS matrix. 25 Notably, both free-radical and anionic styrene polymerizations yield amorphous atactic polystyrenes with applications ranging from polystyrene commodity thermoplastics to styrenic engineering plastics such as HIPS, SAN, ABS, and even thermoplastic elastomers such as SBS and SEBS. 26, 27 Much less is known with respect to semicrystalline rubber block copolymers containing crystallizable isotactic polystyrene (iPS) or syndiotactic polystyrene segments, respectively. In recent advances, Capacchione et al. 28, 29 and Okuda et al. 30 prepared semicrystalline polybutadiene-block-isotactic polystyrene (iPS) as semicrystalline rubber block copolymers by means of the living styrene/butadiene copolymerization on isospecific titanate complexes using sequenced feed of styrene and butadiene. Herein, we report on the synthesis of polycyclooctene-b-iPS (PCO-b-iPS) copolymers prepared by means of cyclooctene ROMP using vinyl-terminated iPS (vinyl-iPS) as the CTA, which is readily available by isospecific styrene polymerization in the presence of 1, 9-decadiene.
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影响因子：
5.5
作者：
M. Vielhauer;S. Bodendorfer;P. Lutz;C. Friedrich;R. Mülhaupt
通讯作者：
M. Vielhauer;S. Bodendorfer;P. Lutz;C. Friedrich;R. Mülhaupt
影响因子：
4.6
作者：
Diallo, Abdou K.;Annunziata, Liana;Carpentier, Jean-Francois
通讯作者：
Carpentier, Jean-Francois
链转移开环易位聚合合成α-三烷氧基甲硅烷基官能化聚环辛烯
影响因子：
5.5
作者：
A. Diallo;X. Michel;S. Fouquay;G. Michaud;F. Simon;Jean;J. Carpentier;Sophie M. Guillaume
通讯作者：
Sophie M. Guillaume
聚苯乙烯和苯乙烯共聚物
DOI：
10.1002/apmc.1997.052440102
发表时间：
1997
期刊：
Angewandte Makromolekulare Chemie
影响因子：
--
作者：
Hermann Gausepohl;V. Warzelhan
通讯作者：
V. Warzelhan
影响因子：
5.5
作者：
Martinez, Henry;Hillmyer, Marc A.
通讯作者：
Hillmyer, Marc A.