Reversible-deactivation Radical Polymerization of Methyl Methacrylate Mediated by Carbodiimide Catalysts

Yan-An Wang; Xiao-Tao Zhang; Yan Shi; Zhi-Feng Fu; Wan-tai Yang

doi:10.11777/j.issn1000-3304.2018.18046

您当前的位置：

首页 >

文章列表页 >

Reversible-deactivation Radical Polymerization of Methyl Methacrylate Mediated by Carbodiimide Catalysts

Research Article | 更新时间：2021-01-26

- Reversible-deactivation Radical Polymerization of Methyl Methacrylate Mediated by Carbodiimide Catalysts
- Acta Polymerica Sinica Vol. 0, Issue 10, Pages: 1287-1296(2018)
- 作者机构：
  
  化工资源有效利用国家重点实验室北京化工大学　北京 100029
- 作者简介：
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2018.18046
  CLC：
- Published：2018-10，
  
  Received：5 February 2018，
  
  Revised：9 March 2018，
扫描看全文
Yan-An Wang, Xiao-Tao Zhang, Yan Shi, Zhi-Feng Fu, Wan-tai Yang. Reversible-deactivation Radical Polymerization of Methyl Methacrylate Mediated by Carbodiimide Catalysts. [J]. Acta Polymerica Sinica 0(10):1287-1296(2018)
DOI：

Yan-An Wang, Xiao-Tao Zhang, Yan Shi, Zhi-Feng Fu, Wan-tai Yang. Reversible-deactivation Radical Polymerization of Methyl Methacrylate Mediated by Carbodiimide Catalysts. [J]. Acta Polymerica Sinica 0(10):1287-1296(2018) DOI： 10.11777/j.issn1000-3304.2018.18046.

摘要

首次采用2种碳二亚胺(二环己基碳二亚胺(DCC)和

′-二异丙基碳二亚胺(DIC))作为催化剂、碘(I

)与偶氮二异庚腈(ABVN)原位生成烷基碘化物为引发剂，实现了甲基丙烯酸甲酯(MMA)的可逆-失活自由基聚合. 首先，对比了2种催化剂对该体系催化活性的大小，发现DCC作为催化剂时对聚合的可控程度优于DIC. 然后详细考察了DCC用量、引发剂用量和不同溶剂对聚合反应的影响. 结果表明，在反向碘转移聚合(RITP)的基础之上添加DCC或DIC，均可以有效降低聚合物的分子量多分散指数(PDI =

). [MMA]

:[I

]

:[ABVN]

:[DCC]

= 200:1:1.7:4时具有最佳的可控效果，凝胶渗透色谱(GPC)测定的分子量与理论分子量吻合，且数均分子量随转化率增加呈线性增长，分子量多分散指数较小(PDI

1.26). 在甲苯、苯、四氢呋喃(THF)、苯甲醚4种溶剂中均有很好的可控聚合特征. 最后，通过

H-NMR对所得聚合物结构进行表征，证明为碘原子封端，端基保有度达到97.5%，并成功进行了聚甲基丙烯甲酯的扩链反应；通过自由基捕捉实验、紫外等对碳二亚胺调控MMA聚合的机理进行了讨论.

Abstract

The reversible-deactivation radical polymerization (RDRP) of methyl methacrylate (MMA) was carried out utilizing an alkyl iodide

in situ

formed as initiator and dicyclohexylcarbodiimide (DCC) or

′-diisopropylcarbodiimide (DIC) as highly efficient organic catalysts for the first time. Firstly

the catalytic activity of the two catalysts was demonstrated and compared. The control of the polymerization by DCC was better than that by DIC under the same experimental conditions. Then the influence of the amount of catalyst DCC

the amount of traditional initiators and the type of solvents on the polymerization was investigated in detail. The results show that the addition of DCC or DIC catalyst can effectively reduce the polydispersity index (PDI =

)

as compared with the reverse iodine chain transfer polymerization (RITP). The catalytic performance is excellent with the ratio of [MMA]

:[I

]

:[ABVN]

:[DCC]

= 200:1:1.7:4. The measured molecular weight by GPC is consistent with the theoretical molecular weight

and the molecular weight increases linearly with the increase in conversion rate. The molecular weight polydispersity index is small (PDI

1.26). The polymerizations of MMA in different solvents were carried out. The induction period is shortened and the polymerization rate is increased with the increase of catalyst or initiator amount. The polymerizations have good control effect in toluene

benzene

tetrahydrofuran (THF)

anisole. The structure and the iodine-end-capped structure of the obtained PMMA was demonstrated by

H-NMR spectrum. The calculated

NMR

was in good agreement with

GPC

and the fraction of iodine chain end of the PMMA chains was up to 97.5%

and the iodine terminus could be efficiently reactivated for chain extension. Last

the mechanism of the polymerization mediated by carbodiimide is discussed based on free radical trapping experiments and ultraviolet absorption. The high conversion of CP-I to CPo radical catalyzed by DIC and the complexation peak of I

/carbodiimide detected by ultraviolet absorption spectroscopy demonstrate that the polymerization catalyzed by carbodiimide proceeds according to the reversible complexation mediated polymerization mechanism.

关键词

甲基丙烯酸甲酯二环己基碳二亚胺NN′-二异丙基碳二亚胺可逆-失活自由基聚合反向碘转移聚合

Keywords

Methyl methacrylateDicyclohexylcarbodiimideNN′-diisopropylcarbodiimideReversible-deactivation radical polymerizationReverse chain transfer polymerization

references

Jenkins D, Jones R G, Moad G . Pure Appl Chem , 2010 . 82 ( 5 ): 483 - 491.

Otsu T, Matyjaszewski K . Macromol Rapid Commun , 1982 . 26 ( 3 ): 127 - 132.

Hawker C J, Bosman A W, Harth E . Chem Rev , 2001 . 101 ( 12 ): 3661 - 3688.

Xia J H, Matyjaszewski K . Macromolecules , 1997 . 30 ( 26 ): 8161 - 8164.

Moad G, Rizzardo E, hang S H . Aust J Chem , 2006 . 59 ( 6 ): 669 - 692.

Wolpers A, Vana P . Macromolecules , 2014 . 47 ( 3 ): 954 - 963.

Goto A, Ohno K, Fukuda T . Macromolecules , 1998 . 31 ( 9 ): 2809 - 2814.

Matyjaszewski K, Gaynor S, Wang J . Macromolecules , 1995 . 28 ( 6 ): 2093 - 2095.

Ohtsuki A, Lei L, Tanishima M, Goto A, Kaji H . J Am Chem Soc , 2015 . 137 ( 16 ): 5610 - 5617.

Goto A, Zushi H, Hirai N, Wakada T, Kwak Y, Fukuda T . Macromol Symp , 2007 . 248 ( 1 ): 126 - 131.

Tanishima M, Goto A, Lei L, Ohtsuki A, Kaji A, Nomura A, Tsujii Y, Yamaguchi Y, Komatsu H, Miyamoto M . Polymers , 2014 . 6 ( 2 ): 311 - 326.

Lei L, Tanishima M, Goto A, Kaji H . Polymers , 2014 . 6 ( 3 ): 860 - 872.

David G, Boyer C, Tonnar J, Ameduri B, Lacroix-Desmazes P, Boutevin B . Chem Rev , 2006 . 37 ( 51 ): 3936 - 3962.

Tonnar J, Lacroix-Desmazes P . Polymer , 2016 . 106 ( 2 ): 267 - 274.

Boyer C, Lacroix-Desmazes P, Robin J J, Boutevin B . Macromolecules , 2006 . 39 ( 12 ): 4044 - 4053.

Enriquez-Medrano F J, Maldonado-Textle H, Hernandez-Valdez M, Lacroix-Desmazes P, Guerrero-Santos R . Polym Chem , 2013 . 4 ( 4 ): 978 - 985.

Goto A, Zushi H, Hirai N, Wakada T, Tsujii Y, Fukuda T . J Am Chem Soc , 2007 . 129 ( 43 ): 13347 - 13354.

Goto A, Zushi H, Hirai N, Wakada T, Kwak Y, Fukuda T . Macromol Symp , 2007 . 248 ( 1 ): 126 - 131.

Bai L J, Zhang L F, Liu Y, Pan X Q, Cheng Z P, Zhu X L . Polym Chem , 2013 . 4 ( 10 ): 3069 - 3076.

Goto A, Tsujii Y, Kaji H . ACS Symp Ser , 2012 . 1100 305 - 315.

Goto A, Ohtsuki A, Ohfuji H, Tanishima M, Kaji H . J Am Chem Soc , 2013 . 135 ( 30 ): 11131 - 11139.

Sarkar J, Xiao L, Goto A . Macromolecules , 2016 . 49 ( 14 ): 5033 - 5042.

Xiao L Q, Sakakibara K, Tsujii Y, Goto A . Macromolecules , 2017 . 50 ( 5 ): 1882 - 1891.

Goto A, Suzuki T, Ohfuji H, Tanishima M, Fukuda T, Tsujii Y, Kaji H . Macromolecules , 2011 . 44 ( 44 ): 8709 - 8715.

Wang W X, Bai L J, Chen H, Xu H, Niu Y Z, Tao Q, Cheng Z P . RSC Adv , 2016 . 6 ( 99 ): 97455 - 97462.

Wang Y A, Shi Y, Fu X F, Yang W T . Polym Chem , 2017 . 8 6073 - 6085.

Lei L, Tanishima M, Goto A, Kaji H, Yamaguchi Y, Komatsu H, JitsukawaT, Miyamoto M . Macromolecules , 2014 . 47 ( 9 ): 6610 - 6618.

Chen Kelong(陈珂龙), Hui Jia(惠嘉), Shi Yan(石艳), Yang Wantai(杨万泰), Fu Zhifeng(付志峰) . 高分子学报 , 2016 . ( 1 ): 112 - 117.

. Acta Polymerica Sinica , 2016 . ( 1 ): 112 - 117.

Lei L, Tanishima M, Goto A, Kaji H . Polymers , 2014 . 6 ( 3 ): 860 - 872.

Bai L J, Wang W X, Chen H, Wang M H, Cheng Z P . RSC Adv , 2015 . 5 ( 44 ): 34769 - 34776.

Iwasaki N . J Chem Soc Jpn Chem Ind , 1998 . ( 4 ): 231 - 239.

Wright T, Chirowodza H, Pasch H . Macromolecules , 2012 . 45 ( 7 ): 2995 - 3003.

Lacroix-Desmazes P, Severac B, Boutevin B . Macromolecules , 2005 . 38 ( 38 ): 6299 - 3609.

Pascual S, Coutin B, Tardi M, Polton A, Vairon J P . Macromolecules , 1999 . 32 ( 5 ): 1432 - 1437.

Robinson K L, Khan M A, M. de Paz Báñez M V, Wang X S, Armes S P. . Macromolecules , 2001 . 34 ( 10 ): 3155 - 3158.

Braunecker W A, Itami Y, Matyjaszewski K . Macromolecules , 2005 . 38 ( 23 ): 9402 - 9404.

Ando T, Kamigaito M, Sawamoto M . Macromolecules , 1997 . 30 ( 16 ): 4507 - 4510.

更多指标>

Views

下载量

CSCD

Alert me when the article has been cited

提交

Tools

Publicity Resources

Kinetics of Methyl Methacrylate Polymerization Mediated by 4, 4'-Dimethoxydiphenyl Nitroxide

Effect of Graphene Modified by P[MMA-IL] on the Crystallization and Dielectric Behavior of PVDF Composite Film

Magnetic Responsive Oil-absorbing Polymeric Resins Based on 4-Tert-butyl-styrene and Methyl Methacrylate

Preparation and Characterization of Oil/Water Separation Membranes via Grafting Methyl Methacrylate onto Poly(vinylidene fluoride)

Transformation of the Counterion of Active Species and Anionic Block Copolymerization of PBMA-b-PMMA

Related Author

No data

Related Institution

State Key Laboratory of Chemical Engineering(Zhejiang University), College of Chemical Engineering and Biochemical Engineering, Zhejiang University

School of Chemistry and Chemical Engineering, Hefei University of Technology

Key Laboratory of Advanced Functional Materials and Devices

The Center of New Energy Materials and Technology, School of Materials Science and Engineering, Southwest Petroleum University

Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences

Postal code：100190
Tel：010-62588927 Email：gfzxb@iccas.ac.cn
Technical support is provided by Beijing Founder electronics co., LTD 京ICP备05002797号-8 京公网安备11010802024621
It is recommended to read the content of this site in Chrome&IE9+. Please switch to extreme mode in browser 360.
Cookies We use cookies to help provide and enhance our service and tailor content. By continuing, you agree to the use of cookies.

⁰