多烯烃单体的可控聚合-北京大学化学与分子工程学院
多烯烃单体的可控聚合
报告人:王文新
查尔斯皮肤医学科学研究中心,都柏林大学医学院,爱尔兰
经典理论长期认为多烯烃单体的聚合会直接导致不可溶的交联聚合物材料,这在70 年前就被高分子
科学界的先驱P. Flory (高分子科学的奠基人之一)和W. Stockmayer 所定义(F-S 理论)并且
1,
已被无数次的实验观察证实。因此,多烯烃单体的聚合一直被认为是链式增长聚合中难以控制的反
应。在过去的几十年中,可控活性自由基聚合推动了高分子化学和高分子物理的极大发展,其中包
括原子转移自由基聚合、可逆加成断裂链转移聚合等。目前,我们通过开发利用了多种不同可控活
性聚合的方法,已经证实以前这种看似常识性的理解和认知是不正确的,多烯烃单体的聚合是可以
实现的。并且成功将廉价易得的多烯烃单体合成为前所未有的多功能三维结构功能聚合物材料。我
们利用休眠增强的可控活性自由基聚合的方法,可将多烯烃单体通过控制线性/环化增长的方式合成
出单链环化结构也可将其通过烯烃低聚物加成的方式合成出名副其实的超支化结构
2,3,4。
示图1 由多烯烃单体均聚形成的结构迥异的高分子
我们的突破在于,通过控制动力学链长及调节链增长环境,从而改变了高分子链增长的方式,形成
了两种迥异的新型高分子结构。其中之一是高度环化的单链高分子结构,另一个是由短初级链加成
得到的真正的高度枝化结构。与此同时,由于这些材料有很多残余双键,因此还具有进一步功能化
的潜力。
参考文献
[1] P. J. Flory, J. Am. Chem. Soc. 1941; 63, 3083.
[2] Y. Zheng, H. Cao, B. Newland, Y. Dong, A. Pandit, W. Wang , J. Am. Chem. Soc. 2011; 133, 13130.
[3] T. Zhao, Y. Zheng, J. Poly, W. Wang , Nature Communications. 2013, 4, 1873
[4] T. Zhao, H. Zhang, B. Newland, A. Aied, D. Zhou, W. Wang, Angewandte Chemie, 2014, 53(24), 6095.
Controlled Multivinyl Polymerisation
Presentation given by Dr Wenxin Wang
Charles Institute of Dermatology, School of Medicine and Medical Science, University College Dublin, Irelande
Classical theory has long claimed that the polymerizations of multi-vinyl monomers (MVM) lead to insoluble
cross-linked materials, as defined by P. Flory and W. Stockmayer nearly 70 years ago (F-S theory)1, and has
since been numerously observed experimentally. Therefore, the (homo)polymerization of MVMs is still
considered as a formidable task in chain growth polymerization. In recent decades, the introduction of
controlled/living radical polymerizations (CRP) including atom transfer radical polymerization (ATRP) and
reversible addition fragmentation chain transfer (RAFT) etc., has led to a significant advance in both synthetic
polymer chemistry and physics. We have developed different strategies that allow facile syntheses of
unprecedented 3D structured multifunctional materials from commercial available multi-vinyl monomers
(MVMs). The syntheses by deactivation enhanced controlled/living radical polymerization can build the MVMs
up into either ‘Single Cyclized‘ polymer structures2 via linear/cyclization growth strategy, or via ‘vinyl oligomer
combination’ strategy to yield veritable hyperbranched polymers3, 4 (Scheme 1).
Scheme 1 Homopolymerization of MVM towards distinct polymeric architecture
Our breakthrough lies in the ability to alter the growth manner of polymerization by controlling the kinetic chain
length together with manipulating chain growth conditions to achieve two clearly different polymer structures.
The first a single chain which is linked repeatedly, creates a dense but soluble interlaced knot structure and the
second a combination of short chains to create a veritable dendritic structure which possesses a highly branched
structure. These materials also have the capability of further functionalisation because of numerous residual
vinyl functional groups.
References
[1] P. J. Flory, J. Am. Chem. Soc. 1941; 63, 3083.
[2] Y. Zheng, H. Cao, B. Newland, Y. Dong, A. Pandit, W. Wang, J. Am. Chem. Soc. 2011; 133, 13130.
[3] T. Zhao, Y. Zheng, J. Poly, W. Wang, Nature Communications. 2013, in press
[4] T. Zhao, H. Zhang, B. Newland, A. Aied, D. Zhou, W. Wang, Angewandte Chemie,
2014, 53(24), 6095.
王文新教授现就职于爱尔兰都柏林大学医学院查尔斯皮肤科学研究中心,是爱尔兰科
学基金会(SFI)的首席科学家。王文新教授目前带领他的研究团队(4 名博士后,11
名博士研究生)主要从事皮肤疑难病和伤口愈合方面的学术研究。1990 年王教授获得
四川大学本科学士学位后,先后在天津造纸技术研究所及天津大港油田钻井采油研究
院从事新产品的研发工作。1993 年王教授入读上海交通大学,并于1996 及1999 年先
后获得上海交通大学的硕士和博士学位,师从颜德岳院士。1999 年王教授在上海塑料
工业有限公司科技部任职一年,然后他开始了他的海外学术职业生涯。2000 年,王教
授时任比利时烈日大学的大分子教育研发中心(CERM)研究员,2001-2007 年王教授
在英国诺丁汉大学化学系任高级研究员,2007-2008 年王教授在英国诺丁汉大学药学
院任高级研究员,2008 年九月王教授被爱尔兰国立高威大学(NUIG)生物工程系聘任
为讲师(助里教授),2009 年被提拔为终身副教授教职。2013 年王文新教授被都柏林
大学医学院查尔斯皮肤科学研究中心聘任至今。王教授在爱尔兰国立高威大学(NUIG)
担任《高分子科学技术》的本科生教学工作及《组织修复和再生工程》的本科,研究
生和博士研究生的教学工作,现于都柏林大学仍担任《组织修复和再生工程》的教学。
他的研究方向主要有:皮肤伤口愈合及基因治疗、心血管及神经衰老性疾病研究,涉
及到从枝化高分子到智能高分子在组织工程和药物运载方面的广泛应用、从新型胶束
高分子颗粒到有机/无机复合纳米材料,从生物降解高分子到含氟和含硅高分子合成。
他在科学研究方面的贡献和成就已经被国内外广泛认可,并有着丰硕的成果,包括
109 篇论文发表于高水平科技杂志上,如《自然:通讯》《美国化学协会会刊》《德
国应用化学》《先进材料》等,以及2 个书的章节,89 篇会议论文,7 项已获专利,4
项申请中的专利和一项申请中的公开发明。不仅如此,作为创立者之一,王教授创建
了一个运转良好的生物材料公司:Vornia Biomaterials。目前,王教授担任该公司的董
事长和首席技术负责人。王教授曾先后于2010 和2011 年获得享有高度声誉的‘爱尔
兰科学基金会再生药物奖’和爱尔兰科学基金会首席科学家奖。王教授还被聘选为多
个研究委员会和基金会的专业评审专家,其中包括比利时科学研究基金会-Bio4 佛兰德
斯委员会、欧盟FP7 框架和Horizon2020 的玛丽居里基金会、加拿大渥太华研究基金
会、罗马尼亚研究委员会、葡萄牙科学基金会和英国医疗研究委员会。王教授已先后
25 次被国际会议和大学邀请作为主要报告人,并作为顾问、组织者、会议主席或召集
人,共主办了11 次国际大型会议。
Dr Wenxin Wang is a Senior Lecturer in Skin Research and Wound Healing and a Science
Foundation Ireland (SFI) Principle Investigator at the Charles Institute of Dermatology,
University College Dublin. Dr Wang received his B.S. degree at Sichuan University, China and
his M.S. and Ph.D. at Shanghai Jiao Tong University, China. Dr Wang has several years of
industrial working experience in china before he started his academic career overseas. He
worked in Tianjin Institute of Paper (1990) and Tianjin Dagang Oilfield Institute of Drilling
and Extraction (1991) as a Research Scientist, he also worked in Shanghai Plastics Industry
Corporation in 1999 as Technology Officer. Following academic appointments in Belgium (at
the Centre for Education and Research on Macromolecules (CERM), University of Liege as a
Research Fellow) in 2000 and in UK from 2001-2008 (at the School of Chemistry, University
of Nottingham and, at the School of Pharmacy, University of Nottingham as a Senior
Research Fellow), Dr Wang took his University Lecturer appointment in Ireland in 2008 and
then became a SFI Stokes Lecturer at the National University of Ireland, Galway (NUIG) in
2009. Dr Wang has been teaching the undergraduate courses including ‘Polymer Technology’
and ‘Tissue Engineering’, and also teaching ‘Tissue Engineering’ course for postgraduate
students at NUI Galway. His scientific interests are in the areas of skin wound healing and
gene therapy, new treatments of cardiovascular and neural degenerative disease, extend
from dendritic polymers to smart polymers for a wide range of applications particularly for
tissue engineering and drug delivery, from new colloidal polymer particles to
organic/inorganic hybrid nanomaterials, and from biodegradable to fluorinated and silicone
polymers. His scientific contribution and achievements have been recognized extensively.
This is reflected in his productive track record as a publishing author that includes 109 peer-
reviewed scientific journal papers such as Nature Communication, JACS, Angewandte
Chemie, Advanced Materials, 2 book chapters, 89 conference associated publications, 7
patents, 4 filed patent applications and 1 filed invention disclosure form. Dr Wang has been
invited 25 times as a keynote speaker or invited speaker at international conferences and
Universities and hosted 11 conferences as a member of the advisory board, organizer, chair
or convenor around the world. Moreover, as one of the founders, Dr Wang has launched a
spin-out company: Vornia Biomaterials. Currently, Dr Wang is the Chairman of Director
Board and CSO of this company. Dr Wang has won the highly prestigious “The Science
Foundation Ireland (SFI) prize in Regenerative Medicine” in 2010 and the SFI Principle
Investigator award in 2011. Dr Wang has also been selected as an expert reviewer and panel
member by a variety of research councils and funding bodies, including the evaluation
expert and panel member for the Belgium Scientific Review Board at the Scientific Research
Foundation – Flanders (FWO) Commission Bio4, European Commission FP7 and Horizon2020
- Marie Curie Fellowship, Canada Ontario Research Fund, Romania Research Council, the
Portuguese Foundation for Science FCT mission and Medical Research Council, UK.
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