[1]杨宏军,孙爱斌,柴晨琼,等.膦腈碱催化甲基丙烯酸烯丙酯的基团转移聚合反应[J].常州大学学报(自然科学版),2018,30(04):1-6.[doi:10.3969/j.issn.2095-0411.2018.04.001]
 YANG Hongjun,SUN Aibin,CHAI Chenqiong,et al.Phosphazene Bases Catalyzed Group Transfer Polymerization of Allyl Methacrylate[J].Journal of Changzhou University(Natural Science Edition),2018,30(04):1-6.[doi:10.3969/j.issn.2095-0411.2018.04.001]
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膦腈碱催化甲基丙烯酸烯丙酯的基团转移聚合反应()
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常州大学学报(自然科学版)[ISSN:2095-0411/CN:32-1822/N]

卷:
30
期数:
2018年04期
页码:
1-6
栏目:
材料科学与工程
出版日期:
2018-07-28

文章信息/Info

Title:
Phosphazene Bases Catalyzed Group Transfer Polymerization of Allyl Methacrylate
作者:
杨宏军孙爱斌柴晨琼黄文艳薛小强蒋必彪
江苏环境友好高分子材料重点实验室,常州大学 材料科学与工程学院,江苏省光伏科学与工程协同创新中心,江苏 常州 213164
Author(s):
YANG Hongjun SUN Aibin CHAI Chenqiong HUANG Wenyan XUE Xiaoqiang JIANG Bibiao
Jiangsu Key Laboratory of Environmental Friendly Polymer Materials, School of Materials Science and Engineering, Jiangsu Collaborative Innovation Center of Photovoltaic Science and Engineering, Changzhou University, Changzhou 213164, China
关键词:
甲基丙烯酸烯丙酯 膦腈碱 基团转移聚合 悬垂双键
Keywords:
group transfer polymerization phosphazene bases allyl methacrylate pendent allyl group
分类号:
TQ 316.34
DOI:
10.3969/j.issn.2095-0411.2018.04.001
文献标志码:
A
摘要:
利用膦腈碱(t-BuP4)为催化剂在室温下催化甲基丙烯酸烯丙酯(AMA)的进行基团转移聚合(GTP)反应,制备含悬垂双键的线型聚合物,并通过核磁(1H NMR)、红外(FTIR)、凝胶渗透色谱(GPC)等对其进行分析和表征。结果表明t-BuP4催化AMA的GTP反应1 h内,单体转化率就接近100%; 聚合反应是通过AMA上的甲基丙烯酸酯双键进行,烯丙基双键不参与聚合反应; 所得聚合物Mark-Houwink常数为0.75; 使用极性溶剂更有利于加强聚合反应的可控性。
Abstract:
Vinyl functional polymers have received significant attention due to their high reactivity of double bonds. However their syntheses still present challenges to keep one reactive vinyl group in each repeat unit. Here, these polymers were successfully synthesized by the phosphazene bases(t-BuP4)catalyzed group transfer polymerization(GTP)of allyl methacrylate(AMA). The synthesized polymers were characterized by Fourier transform infrared spectroscopy(FTIR), nuclear magnetic resonance spectrometer(NMR), and triple detection size exclusion chromatography(TD-SEC). The results show that nearly 100% conversion of AMA was achieved within 1h for the t-BuP4 catalyzed system. The polymerization was processed by the reaction of the methacrylate double bonds in AMA. The Mark-Houwink parameter for the synthesized polymer is 0.75. The use of polar solvent helps to improve the level of control over the polymerization.

参考文献/References:


[1]JONG L, STEIN R S. Synthesis characterization and rubber elasticity of end-linked poly(tetrahydrofuran)elastomer[J]. Macromolecules,1991,24(9):2323-2329.
[2]IWAHARA T, KUSAKABE M, CHIBA M, et al. Curing system involving SiH-containing organic oligomers[J]. J Appl Polym Sci,1993,50(5):825-833.
[3]YANG H J, ZHANG G Z, JIANG B B. A versatile strategy for synthesis of hyperbranched polymers with commercially available methacrylate inimer[J]. RSC Advances,2015,5,60401-60408
[4]杨宏军,柏涛,蒋必彪,等. 含悬垂双键超支化聚合物的一步法合成[J]. 常州大学学报(自然科学版),2016,28(2):14-19.
[5]YANG H J, BAI T,JIANG B B. Facile synthesis of functional copolymers with pendant vinyl groups by using asymmetrical divinyl monomers[J]. Journal of the Applied Polymer Science,2015,132:42758.
[6]CHEN G H,MA X S,GUAN Z B. Synthesis of functional olefin copolymers with controllable topologies using a chain-walking catalyst[J]. Journal of the American Chemical Society,2003,125:6697-6704.
[7]TAI H Y,TOCHWIN A,WANG W X. Thermoresponsive hyperbranched polymers via In Situ RAFT copolymerization of peg-based monomethacrylate and dimethacrylate monomers[J]. Journal of Polymer Science Part A: Polymer Chemistry,2013,51:3751-3761.
[8]YANG H J,BAI T,JIANG B B. A simple route to vinyl-functionalized hyperbranched polymers: self-condensing anionic copolymerization of allyl methacrylate and hydroxyethyl methacrylate[J].Polymer,2015,72:63-68.
[9]DONG Z M,LIU X H,TANG X L. Synthesis of hyperbranched polymers with pendent norbornene functionalities via RAFT polymerization of a novel asymmetrical divinyl monomer[J]. Macromolecules,2009,42:4596-4603.
[10]MOHAN Y M,RAGHUNADH V,BASKARAN D. Reactive polymers bearing styrene pendants through selective anionic polymerization of 4-vinylbenzyl methacrylate[J]. Macromolecules,2012,45:3387-3394.
[11]KAKUCHI T,CHEN Y G,KITAKADO J. Organic superbase as an efficient catalyst for group transfer polymerization of methyl methacrylate[J].Macromolecules,2011,44:4641-464.
[12]XU T Q,LIU J H,LU X B.Highly active half-metallocene yttrium catalysts for living methacrylate[J].Macromolecules,2015,48:7428-7434.
[13]杨宏军,钱小磊,蒋必彪等. 膦腈碱催化甲基丙烯酸烯丙酯与甲基丙烯酸甲酯的负离子共聚反应[J]. 高分子学报,2015(5):550-553.
[14]MATSUMOTO A,ASAI S,HIROYUKI A. Free-radical crosslinking polymerization ofunsymmetrical divinyl compounds 1.Gelation in the polymerization of allyl methacrylate[J]. Macromol Chem Phys,2000,201:2735-2741.
[15]MATSUMOTO A,ASAI S,HIROYUKI A. Free-radical cross-linking polymerization of unsymmetrical divinyl compounds 2.Steric effect on gelation in the copolymerizations of allyl methacrylate with several alkyl methacrylates[J]. Eur Polym J,2002,38:863-868.
[16]GUAN Z.Control of polymer topology through transition-metal catalysis: synthesis of hyperbranched polymers by cobalt-mediated free radical polymerization[J]. J AM Chem Soc,2002,124:5616-5617.

相似文献/References:

[1]杨宏军,柏涛,薛小强,等.含悬垂双键超支化聚合物的一步法合成[J].常州大学学报(自然科学版),2016,(02):14.[doi:10.3969/j.issn.2095-0411.2016.02.003]
 YANG Hongjun,BAI Tao,XUE Xiaoqiang,et al.OnePot Synthesis of Hyperbranched Polymers with Pendant Vinyl Bonds[J].Journal of Changzhou University(Natural Science Edition),2016,(04):14.[doi:10.3969/j.issn.2095-0411.2016.02.003]

备注/Memo

备注/Memo:
基金项目:国家自然科学青年基金项目(21304010); 江苏省自然科学青年基金项目(BK20130246)。
作者简介:杨宏军(1983—),男,山西阳泉人,博士,副教授。通讯联系人:蒋必彪(1964—),E-mail:jiangbibiao@cczu.edu.cn
更新日期/Last Update: 2018-07-30