以乙基黄原酸丙酸乙酯为链转移剂的PMMA-b-PS的可逆加成断链转移自由基聚合
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摘要
将乙基黄原酸丙酸乙酯作为链转移剂,进行甲基丙烯酸甲酯(MMA)的可逆加成断链转移自由基聚合(RAFT),并将得到的产物作为大分子链转移剂,加入第二单体苯乙烯(St)进行扩链反应,制备了PMMA-b-PS嵌段共聚物。通过红外光谱、核磁共振、凝胶渗透色谱、热重分析和差示扫描量热等测试手段对制备的PMMA-b-PS嵌段共聚物进行分析表征。研究表明,第二单体St与大分子链转移剂发生了共聚,形成了嵌段共聚物;制备所得PMMA-b-PS嵌段共聚物的数均相对分子质量明显增加,相对分子质量分布变宽,初始热分解温度明显提高,玻璃化转变温度介于PMMA与PS的玻璃化转变温度之间。
Ethyl xanthate ethyl propionate was used as chain transfer agent for reversible addition – fragmentation chain transfer( RAFT) polymerization of methyl methacrylate( MMA). The PMMA-CTA was employed for the preparation of PMMA-b-PS block copolymer by adding the second monomer styrene( St). The PMMA and PMMA-b-PS block copolymer was characterized by FT-IR,1 H-NMR,GPC,TG and DSC. The results indicate that the PMMA macromolecular chain transfer is copolymerized with the second monomer St and the expected block copolymer is formed. The PMMA-b-PS block copolymer possesses a higher molecular weight and a wider molecular weight distribution. The initial decomposition temperature of the PMMA-b-PS block copolymer is significantly increased,while the glass transition temperature is between that of PMMA and PS.
Ethyl xanthate ethyl propionate was used as chain transfer agent for reversible addition – fragmentation chain transfer( RAFT) polymerization of methyl methacrylate( MMA). The PMMA-CTA was employed for the preparation of PMMA-b-PS block copolymer by adding the second monomer styrene( St). The PMMA and PMMA-b-PS block copolymer was characterized by FT-IR,1 H-NMR,GPC,TG and DSC. The results indicate that the PMMA macromolecular chain transfer is copolymerized with the second monomer St and the expected block copolymer is formed. The PMMA-b-PS block copolymer possesses a higher molecular weight and a wider molecular weight distribution. The initial decomposition temperature of the PMMA-b-PS block copolymer is significantly increased,while the glass transition temperature is between that of PMMA and PS.
引文
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[2]Toledano-Prados M,Lorenzo-Pesqueira M,González-Fonteboa B,et al.Effect of polycarboxylate superplasticizers on large amounts of fly ash cements[J].Constr.Build.Mater.,2013,48:628-635.
[3]Qiao J,Qi L,Ma H M,et al.A block copolymer covalent coating acting as surfactants in separation of 2-[hydroxy(4-nitrophenyl)methyl]-cyclopent-2-enone and 4-nitrobenzaldehyde by capillary electrophoresis[J].Talanta,2009,80:770-776.
[4]Daniel T,Agnieszka-Zofia W,Mathias D.Direct synthesis of double hydrophilic statistical di‐and triblock copolymers comprised of acrylamide and acrylic acid units via the MADIX process[J].Macromol.Rapid Commun.,2001,22:1497-1503.
[5]Charmot D,Corpart P,Adam H,et al.Controlled radical polymerization in dispersed media[J].Macromol.Symp.,2015,150:23-32.
[6]Destarac M,Charmot D,Franck X,et al.Dithiocarbamates as universal reversible addition-fragmentation chain transfer agents[J].Macromol.Rapid Commun.,2000,21:1035-1039.
[7]蒋波,易玲敏,詹晓力,等.新型链转移剂黄原酸酯调控的RAFT自由基聚合[J].化学进展,2008,20(7):1128-1135.Jiang B,Yi L M,Zhan X L,et al.Reversible addition fragmentation chain transfer polymerization mediated by xanthate[J].Progress in Chemistry,2008,20(7):1128-1135.
[8]Patel V K,Vishwakarma N K,Mishra A K,et al.Synthesis of alkyne-terminated xanthate RAFT agents and their uses for the controlled radical polymerization of N-vinylpyrrolidone and the synthesis of its block copolymer using click chemistry[J].J.Appl.Polym.Sci.,2013,127:4305-4317.
[9]Pound G,Eksteen Z,Pfukwa R,et al.Unexpected reactions associated with the xanthate-mediated polymerization of N-vinylpyrrolidone[J].J.Polym.Sci.Part A:Polym.Chem.,2008,46:6575-6593.
[10]Chen J,Zhao X N,Zhang L F,et al.Reversible additionfragmentation chain transfer polymerization of vinyl acetate under high pressure[J].J.Polym.Sci.Part A:Polym.Chem.,2015,53:1430-1436.
[11]Patel V K,Vishwakarma N K,Mishra A K,et al.(S)-2-(ethyl propionate)-(O-ethyl xanthate)-and(S)-2-(ethyl isobutyrate)-(O-ethyl xanthate)-mediated RAFT polymerization of vinyl acetate[J].J.Appl.Polym.Sci.,2012,125:2946-2955.
[12]Patel V K,Mishra A K,Vishwakarma N K,et al.(S)-2-(Ethyl propionate)-(O-ethyl xanthate)and(S)-2-(ethyl isobutyrate)-(Oethyl xanthate)-mediated RAFT polymerization of N-vinylpyrrolidone[J].Polym.Bull.,2010,65:97-110.
[13]钟玉鹏,刘景勃,龚桂胜,等.以黄原酸钾为链转移剂的甲基丙烯酸甲酯可逆加成断裂链转移聚合[J].高分子材料科学与工程,2015,31(11):15-18.Zhong Y P,Liu J B,Gong G S,et al.The RAFT polymerization of methyl methacrylate with potassium xanthate as chain transfer agent[J].Polymer Materials Science&Engineering,2015,31(11):15-18.
[14]王小燕,朱健,周弟,等.甲基丙烯酸二甲氨基乙酯的可逆加成断裂链转移自由基聚合及其嵌段共聚物的合成[J].石油化工,2005,34(6):536-540.Wang X Y,Zhu J,Zhou D,et al.Reversible addition-fragmentation chain transfer free-radical polymerization of 2-(dimethylamino)ethyl methacrylate and synthesis of derived block polymer[J].Petrochemical Technology,2005,34(6):536-540.
[15]Zhu J,Zhu X L,Cheng Z P,et al.Study on controlled free-radical polymerization in the presence of 2-cyanoprop-2-yl 1-dithionaphthalate(CPDN)[J].Polymer,2002,43:7037-7042.