星状多臂共聚物h-PCMS-g-PEMA-b-PMMA的合成
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摘要
在Cu Cl/bpy催化体系下,通过对氯甲基苯乙烯(CMS)自引发制得球状超支化聚对氯甲基苯乙烯(h-PCMS),再以h-PCMS作为大分子引发剂,通过两步原子转移自由基聚合(ATRP)成功在球状h-PCMS表面接枝二嵌段聚合物聚甲基丙烯酸乙酯-b-聚甲基丙烯酸甲酯(PEMA-b-PMMA),合成了星状多臂共聚物h-PCMS2700-g-PEMA41000-b-PMMA15000(下标为分子量),分子量分布为1. 6,其结构和性能经1H NMR、IR、GPC和DSC表征。通过1H NMR定量分析表明,h-PCMS中的苄基氯具有活性,可进一步引发接枝反应,次苄基氯不能引发ATRP反应。在每一个h-PCMS表面有接近三分之一的苄基氯参与接枝反应,接枝臂数为6。
Spherical hyperbranched poly( chloromethyl styrene)( h-PCMS) was prepared by self-initiated polymerization of chloromethyl styrene( CMS) catalyzed by CuCl/bpy. A two-block polymer,polymethyl methacrylate-b-polymethyl methacrylate( PEMA-b-PMMA),was grafted on the surface of h-PCMS by two steps of atom transfer radical polymerization( ATRP) initiated by h-PCMS,to afford the star-shaped multi-arm copolymers h-PCMS2700-g-PEMA41000-b-PMMA15000( subscripts refering to molecular weight),the molecular weight distribution is about 1. 6. The structure and properties were characterized by1 H NMR,IR,GPC and DSC. It was confirmed by1 H NMR that benzyl chloride in h-PCMS was active,which could lead to further graft reaction,and secondary benzyl chloride could not initiate ATRP reaction. Approximately one-third of the benzyl chloride was involved in the grafting reaction on each h-PCMS surface resulting in a graft arm number of 6.
Spherical hyperbranched poly( chloromethyl styrene)( h-PCMS) was prepared by self-initiated polymerization of chloromethyl styrene( CMS) catalyzed by CuCl/bpy. A two-block polymer,polymethyl methacrylate-b-polymethyl methacrylate( PEMA-b-PMMA),was grafted on the surface of h-PCMS by two steps of atom transfer radical polymerization( ATRP) initiated by h-PCMS,to afford the star-shaped multi-arm copolymers h-PCMS2700-g-PEMA41000-b-PMMA15000( subscripts refering to molecular weight),the molecular weight distribution is about 1. 6. The structure and properties were characterized by1 H NMR,IR,GPC and DSC. It was confirmed by1 H NMR that benzyl chloride in h-PCMS was active,which could lead to further graft reaction,and secondary benzyl chloride could not initiate ATRP reaction. Approximately one-third of the benzyl chloride was involved in the grafting reaction on each h-PCMS surface resulting in a graft arm number of 6.
引文
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[5]JIA Z,HUANG W,YAN D.Synthesis and characterization of highly branched polymethacrylates[6]via self-condensing oxyanionic copolymerization[J].E-Polymers,2005,5(1):172-181.
[6]RAN J,WU L,ZHANG Z,et al.Atom transfer radical polymerization(ATRP):A versatile and forceful tool for functional membranes[J].Progress in Polymer Science,2014,39(1):124-144.
[7]王成龙.改性超支化聚合物制备及其在蚕丝活性染料染色中的应用[D].浙江:浙江理工大学,2014.
[8]姚军善,赵庸,张勇林,等.借助ATRP法合成两亲性星状多臂h-PCMS-g-m PEG接枝共聚物[J].现代化工,2014,34(5):108-112.
[9]孙跃文,吉虎,魏珂瑶,等.新型超支化接枝共聚物的合成[J].合成化学,2016,(12):1060-1065.
[10]王国建,刘琳,夏平.两亲性星状共聚物的合成、表征和性能[J].同济大学学报(自然科学版),2004,32(1):127-133.
[11]王勋.核壳结构多臂星状聚合物的制备及其客体包裹能力的研究[D].天津:天津大学,2007.
[12]ADELI M,HAAG R.Multiarm star nanocarriers containing a poly(ethylene imine)core and polylactide arms[J].Journal of Polymer Science Part A Polymer Chemistry,2006,44(19):5740-5749.
[13]张华林,刘竞超,万金涛,等.超支化聚酯/尼龙6接枝共聚改性环氧树脂的研究[J].绝缘材料,2004,37(6):27-29.
[14]KIM Y H.Hyperbranched polyarylene:US 4857630[P].1857.
[15]KIM Y H.Hyperbranched polymers 10 years after[J].J Polym Sci Part A Polym Chem,1998,36(11):1685-1698.
[16]BAUER B J,RAMZI A,LIU D,et al.Blends of fatty-acid-modified dendrimers with polyolefins[J].Journal of Polymer Science:Part B:Polymer Physics,2000,38:95-100.
[17]DVORNIC P R,HU J,MEIER D J,et al.Hyperbranched polyureas,polyurethanes,polyamidoamines,polyamides and polyesters:US 6534600[P].2003.
[18]BRAUNECKER W A,MATYJASZEWSKI K.Controlled/living radical polymerization:Features,developments,and perspectives[J].Progress in Polymer Science,2007,32(1):93-14650.