丙烯酰胺多面体低聚倍半硅氧烷在超临界CO2中的RAFT聚合

doi:10.7503/cjcu20150377

高等学校化学学报 ›› 2015, Vol. 36 ›› Issue (10): 2067.doi: 10.7503/cjcu20150377

丙烯酰胺多面体低聚倍半硅氧烷在超临界CO₂中的RAFT聚合

程龙, 边仲轩, 丁敏源, 赵萌, 李慧()

华东理工大学材料科学与工程学院, 上海 200237

收稿日期:2015-05-11 出版日期:2015-10-10 发布日期:2015-09-06
作者简介:联系人简介: 李慧, 女, 博士, 教授, 主要从事聚合方法等研究. E-mail:lihui@ecust.edu.cn
基金资助:
国家科技部国际合作项目(批准号: 2010DFB70470)资助

RAFT Polymerization of Acrylamide Polyhedral Oligometic Silsesquioxane in Supercritical CO₂⁺

CHENG Long, BIAN Zhongxuan, DING Minyuan, ZHAO Meng, LI Hui^*()

School of Materials Science and Engineering,East China University of Science and Technology, Shanghai 200237, China

Received:2015-05-11 Online:2015-10-10 Published:2015-09-06
Contact: LI Hui E-mail:lihui@ecust.edu.cn

摘要/Abstract

摘要：

以超临界CO₂为聚合介质, 硫代苯甲酰基特丁基硫酯(TTBT)为链转移剂, 通过可逆加成-断裂链转移(RAFT)聚合制备了聚丙烯酰胺多面体低聚倍半硅氧烷(PAMPOSS)均聚物及其与甲基丙烯酸甲酯(PMMA)的嵌段共聚物(PAMPOSS-b-PMMA). 对产物结构组成和分子量及其分布进行表征. 结果表明, 在TTBT的控制下, POSS的均聚物和嵌段共聚物具有高分子量及窄分子量分布. 含POSS单体在超临界CO₂中为均相聚合, POSS聚合物的结晶性在一定程度上影响其在超临界CO₂中溶解性.

关键词: 超临界CO2, 低聚倍半硅氧烷(POSS), 硫代苯甲酰基特丁基硫酯(TTBT), 可逆加成-断裂转移(RAFT)聚合

Abstract:

Polyacrylamide(PAM) isobutyl-polyhedral oligometic silsesquioxane(POSS)(PAMPOSS) homopolymer and PAMPOSS-b-PMMA(polymethyl methacrylate) block copolymers were prepared via reversible addition-fragmentation transfer(RAFT) polymerization using benzenecarbodithioic acid 1,1-dimethylethyl ester as the RAFT agent in supercritical CO₂. The products were characterized. The results show that polymerization reaction in supercritical CO₂ is well controlleded. Both of PAMPOSS and PAMPOSS-b-PMMA have high degree of polymerization(DP) and low polydispersity index(PDI). It can be also found that the polymerization of AM-POSS is a homogeneous reaction, and the solubility of POSS containing polymers in supercritical CO₂ is effected by the crystallinity of POSS.

Key words: Supercritical CO2, Polyhedral oligometic silsesquioxane(POSS), Benzenecarbodithioic acid 1, 1-dimethylethyl ester(TTBT), Reversible addition fragmentation transfer(RAFT) polymerization

中图分类号:

O631

TrendMD:

程龙, 边仲轩, 丁敏源, 赵萌, 李慧. 丙烯酰胺多面体低聚倍半硅氧烷在超临界CO₂中的RAFT聚合. 高等学校化学学报, 2015, 36(10): 2067.

CHENG Long, BIAN Zhongxuan, DING Minyuan, ZHAO Meng, LI Hui. RAFT Polymerization of Acrylamide Polyhedral Oligometic Silsesquioxane in Supercritical CO₂⁺. Chem. J. Chinese Universities, 2015, 36(10): 2067.

图/表 11

Scheme 1 Synthesis of polymers PAMPOSS and PAMPOSS-b-PMMA

Fig.1 1H NMR spectrum of AM-POSS^Peaks a—i are the same as compound AM-POSS in Scheme 1.

Fig.2 FTIR spectrum of AM-POSS

Table 1 Conversion and molecular weight of PAMPOSS

Time/h	Conversion of monomer(%)	ln([M₀]/[M])	10^-3M_n,NMR	10^-3M_n,th	10^-3M_n,GPC	PDI
12	32.1	0.39	5.57	5.96	2.32	1.12
24	44.9	0.60	8.35	8.34	3.20	1.11
36	63.4	1.01	12.06	11.77	5.12	1.13
48	72.6	1.29	13.92	13.47	6.60	1.30
72	83.3	1.79	15.78	15.47	8.34	1.36

Fig.3 1H NMR spectra of PAMPOSS(a) and PAMPOSS-b-PMMA(b)

Fig.4 Dependence of Mn on AM-POSS conversion(c)

Table 2 Effect of pressure on conversion and molecular weight of PAMPOSS*

Pressure/MPa	Conversion of monomer(%)	10^-3M_n,NMR	10^-3M_n,th	10^-3 M_n,GPC	PDI
20	72.6	13.92	13.47	6.60	1.30
25	71.4	13.74	13.25	6.45	1.26
30	70.1	13.56	13.01	6.23	1.20

Fig.5 Reaction kinetics curve of PAMPOSS

Fig.6 FTIR spectra of PAMPOSS(a) and PAMPOSS-b-PMMA(b)

Table 3 Molecular weight of PAMPOSS and PAMPOSS-b-PMMA

Structure	10^-3M_n,NMR	10^-3M_n,th	10^-3M_n,GPC	PDI
PAMPOSS	13.92	13.47	6.60	1.30
PAMPOSS-b-PMMA	443.60	450.30	480.20	1.35

Fig.7 GPC spectra of PAMPOSS homopolymer(a) and PAMPOSS-b-PMMA block copolymer(b)

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丙烯酰胺多面体低聚倍半硅氧烷在超临界CO₂中的RAFT聚合

RAFT Polymerization of Acrylamide Polyhedral Oligometic Silsesquioxane in Supercritical CO₂⁺

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