一种新的可控/活性自由基聚合方法——DPETTX调节苯乙烯自由基聚合研究
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摘要
可控/活性自由基聚合(CLRP)自20世纪末以来获得了非常迅猛的发展,但由于已有方法的缺陷和局限,限制了其工业化规模应用.因此,开发可控、活性程度更高、更加简单实用且环境友好的CLRP新方法具有重要意义.本文制备了一种芳香环状硫醚化合物9-(1-苯乙基)-9-((1-苯乙基)硫基)-9H-硫杂蒽DPETTX,对其单独引发和与少量偶氮二异庚腈(ABVN)共同引发苯乙烯(St)聚合的行为进行了系统评价.结果表明,DPETTX可在高温(100℃)下单独引发St聚合,但引发效率较低;当其与少量ABVN共用时,可使St在低温下(55℃)聚合,聚苯乙烯(PS)的数均分子量(M_n)随转化率升高而不断增大,如摩尔比ABVN/DPETTX=0.05/1时,M_n从2.7万增长到4.6万.该基于DPETTX和少量ABVN的共引发体系,打开了一条开发新可控/活性自由基聚合体系的路径.
Rapid progress in controlled/living radical polymerization(CLRP) has been achieved since the end of the last century. However, the demerits and limitations of existed methods impede their industrial applications on a large scale.Therefore, it is prominent to develop new CLRP methods that are better in controlled/living features, more simple,feasible and environmental-friendly. In this article, a new thioether, 9-(1-phenylethyl)-9-((1-phenylethyl)thio)-9 Hthioxanthene(DPETTX) was synthesized. Then, the polymerization behavior of St initiated by DPETTX and both DPETTX and a small amount of 2,2′-azobisisoheptonitrile(ABVN) was studied. Results show that DPETTX can initiated the polymerization of St at a high temperature(100 °C) with low initiation efficiency, while St polymerization at a low temperature(55 °C) was possible in the presence of a small amount of ABVN and number average molecular weight(M_n) increased continuously with increasing conversion of St. M_nincreased from 27 k to 46 k when a molar ratio of ABVN/DPETTX=0.05/1 was adopted. This co-initiating system based on DPETTX and a small amount of ABVN paves a new way for developing new CLRP methods.
Rapid progress in controlled/living radical polymerization(CLRP) has been achieved since the end of the last century. However, the demerits and limitations of existed methods impede their industrial applications on a large scale.Therefore, it is prominent to develop new CLRP methods that are better in controlled/living features, more simple,feasible and environmental-friendly. In this article, a new thioether, 9-(1-phenylethyl)-9-((1-phenylethyl)thio)-9 Hthioxanthene(DPETTX) was synthesized. Then, the polymerization behavior of St initiated by DPETTX and both DPETTX and a small amount of 2,2′-azobisisoheptonitrile(ABVN) was studied. Results show that DPETTX can initiated the polymerization of St at a high temperature(100 °C) with low initiation efficiency, while St polymerization at a low temperature(55 °C) was possible in the presence of a small amount of ABVN and number average molecular weight(M_n) increased continuously with increasing conversion of St. M_nincreased from 27 k to 46 k when a molar ratio of ABVN/DPETTX=0.05/1 was adopted. This co-initiating system based on DPETTX and a small amount of ABVN paves a new way for developing new CLRP methods.
引文
1 Matyjaszewski K,Tsarevsky NV.J Am Chem Soc,2014,136:6513–6533
2 Georges MK,Veregin RPN,Kazmaier PM,Hamer GK.Macromolecules,1993,26:2987–2988
3 Hawker CJ.J Am Chem Soc,1994,116:11185–11186
4 Wang JS,Matyjaszewski K.J Am Chem Soc,1995,117:5614–5615
5 Kato M,Kamigaito M,Sawamoto M,Higashimura T.Macromolecules,1995,28:1721–1723
6 Chiefari J,Chong YKB,Ercole F,Krstina J,Jeffery J,Le TPT,Mayadunne RTA,Meijs GF,Moad CL,Moad G,Rizzardo E,Thang SH.Macromolecules,1998,31:5559–5562
7 Percec V,Guliashvili T,Ladislaw JS,Wistrand A,Stjerndahl A,Sienkowska MJ,Monteiro MJ,Sahoo S.J Am Chem Soc,2006,128:14156–14165
8 Yamago S,Iida K,Yoshida J.J Am Chem Soc,2002,124:2874–2875
9 Yamago S,Ray B,Iida K,Yoshida JI,Tada T,Yoshizawa K,Kwak Y,Goto A,Fukuda T.J Am Chem Soc,2004,126:13908–13909
10 Yamago S,Kayahara E,Kotani M,Ray B,Kwak Y,Goto A,Fukuda T.Angew Chem Int Ed,2007,46:1304–1306
11 Zheng X,Yue M,Yang P,Li Q,Yang W.Polym Chem,2012,3:1982–1986
12 Huang X,Wang L,Yang W.Polym Chem,2015,6:6664–6670
13 Yao CR,Wang L,Yang WT.RSC Adv,2016,6:69743–69747
14 Rizzardo E,Solomon DH.Polym Bull,1979,1:529–534
15 Toy AA,Chaffey-Millar H,Davis TP,Stenzel MH,Izgorodina EI,Coote ML,Barner-Kowollik C.Chem Commun,2006,58:835–837
16 Junkers T,Stenzel MH,Davis TP,Barner-Kowollik C.Macromol Rapid Commun,2007,28:746–753
17 Günzler F,Junkers T,Barner-Kowollik C.J Polym Sci A,2009,47:1864–1876
18 Junkers T,Delaittre G,Chapman R,Günzler F,Chernikova E,Barner-Kowollik C.Macromol Rapid Commun,2012,33:984–990
19 Li XE.Fractural carbon-carbon bond radical initiators:design,synthesis and application.Dissertation for the Doctoral Degree.Beijing:Beijing University of Chemical Technology,2014.23–120(in Chinese)[李雪娥.几种C–C键断裂自由基引发剂的设计合成和应用的初步研究.博士学位论文.北京:北京化工大学,2014.23–120]
2 Georges MK,Veregin RPN,Kazmaier PM,Hamer GK.Macromolecules,1993,26:2987–2988
3 Hawker CJ.J Am Chem Soc,1994,116:11185–11186
4 Wang JS,Matyjaszewski K.J Am Chem Soc,1995,117:5614–5615
5 Kato M,Kamigaito M,Sawamoto M,Higashimura T.Macromolecules,1995,28:1721–1723
6 Chiefari J,Chong YKB,Ercole F,Krstina J,Jeffery J,Le TPT,Mayadunne RTA,Meijs GF,Moad CL,Moad G,Rizzardo E,Thang SH.Macromolecules,1998,31:5559–5562
7 Percec V,Guliashvili T,Ladislaw JS,Wistrand A,Stjerndahl A,Sienkowska MJ,Monteiro MJ,Sahoo S.J Am Chem Soc,2006,128:14156–14165
8 Yamago S,Iida K,Yoshida J.J Am Chem Soc,2002,124:2874–2875
9 Yamago S,Ray B,Iida K,Yoshida JI,Tada T,Yoshizawa K,Kwak Y,Goto A,Fukuda T.J Am Chem Soc,2004,126:13908–13909
10 Yamago S,Kayahara E,Kotani M,Ray B,Kwak Y,Goto A,Fukuda T.Angew Chem Int Ed,2007,46:1304–1306
11 Zheng X,Yue M,Yang P,Li Q,Yang W.Polym Chem,2012,3:1982–1986
12 Huang X,Wang L,Yang W.Polym Chem,2015,6:6664–6670
13 Yao CR,Wang L,Yang WT.RSC Adv,2016,6:69743–69747
14 Rizzardo E,Solomon DH.Polym Bull,1979,1:529–534
15 Toy AA,Chaffey-Millar H,Davis TP,Stenzel MH,Izgorodina EI,Coote ML,Barner-Kowollik C.Chem Commun,2006,58:835–837
16 Junkers T,Stenzel MH,Davis TP,Barner-Kowollik C.Macromol Rapid Commun,2007,28:746–753
17 Günzler F,Junkers T,Barner-Kowollik C.J Polym Sci A,2009,47:1864–1876
18 Junkers T,Delaittre G,Chapman R,Günzler F,Chernikova E,Barner-Kowollik C.Macromol Rapid Commun,2012,33:984–990
19 Li XE.Fractural carbon-carbon bond radical initiators:design,synthesis and application.Dissertation for the Doctoral Degree.Beijing:Beijing University of Chemical Technology,2014.23–120(in Chinese)[李雪娥.几种C–C键断裂自由基引发剂的设计合成和应用的初步研究.博士学位论文.北京:北京化工大学,2014.23–120]