单电子转移活性自由基聚合法制备水溶性聚合物

发布时间：2018-07-10 07:39

  本文选题：单电子转移活性自由基聚合 + 星形聚丙烯酰胺　； 参考：《东北石油大学》2011年硕士论文

【摘要】：本文采用SET-LRP方法,分别在水溶液和离子液体中合成了具有反聚电解质溶液行为的线性丙烯酰胺(AM)与甲基丙烯酰氧乙基-N,N-二甲基-N-丁磺酸铵盐(DMBS)共聚物和四臂星形聚丙烯酰胺(SPAM),并考察了溶剂、催化剂、引发剂和温度等因素对聚合反应动力学的影响,其主要内容如下: 1、以季戊四醇为原料,在改良实验条件的情况下反应制得高产率、高纯度的2,2-二溴甲基-1,3-二溴丙烷(PEBr_4)四官能团引发剂,并以此为核引发AM的SET-LRP;且参照文献成功合成了电子供体配位能力较强且高度自旋多齿配体Me6-TREN和电中性的磺基甜菜碱型两性离子功能单体;并通过IR和~1H NMR等表征手段对产物进行了结构分析,证实为目标产物,且纯度较高。 2、以Cu~0/Me_6-TREN[三(N,N-二甲基氨基乙基)胺]为催化剂,2-氯丙酰胺(CPA)为引发剂,在25℃水溶液中通过SET-LRP实现了AM与DMBS的共聚合,制备出线性的、具有反聚电解质溶液行为的共聚物。通过~1H NMR、GPC对所合成的P(AM-co-DMBS)进行了分析表征,证明所制备的聚合物确为目标产物,并具有较窄的分子量分布M_w/M_n=1.33(M_n~(GPC)=3.01×10~4,转化率为82%),且聚合物链端保留了α-Br端基。考察了溶剂、催化剂、引发剂和温度对聚合反应的影响;并研究了AM和DMBS共聚物的盐溶液性质,两性离子聚合物与三种盐溶液都表现出很好的反聚电解质溶液行为,随盐浓度的增加聚合物溶液的表观粘度增加。 3、以Cu~0/Me_6-TREN为催化剂,季戊四溴为引发剂,在40℃离子液体中实现了丙烯酰胺(AM)的单电子转移活性自由基聚合(SET-LRP),得到了窄分子量分布的四官能度星形PAM,M_w/M_n≈1.26(M_n~(GPC)=14.1×103,转化率为43.4%)。采用1H NMR对SPAM结构进行表征,并采用GPC测定了SPAM的分子量及分子量分布;考察了水、催化剂和引发剂用量对聚合反应的影响。
[Abstract]:The SET-LRP method is used in this paper. The copolymers of linear acrylamide (AM) and methacryloxy ethoxyethyl N-dimethyl-n-butylammonium sulfonate (DMBS) and four-arm star-shaped polyacrylamide (SPAM) were synthesized in aqueous solution and ionic liquid respectively. The main contents of the effects of catalyst, initiator and temperature on the kinetics of polymerization are as follows: 1. Using pentaerythritol as raw material, the high yield was obtained under improved experimental conditions. High purity 2-dibromomethyl-1-tribromopropane (PEBr4) tetrafunctional initiator, The SET-LRPwas used as the nucleus to initiate AM, and the highly spin polydentate ligand Me6-TREN and the electrically neutral sulfobetaine amphoteric functional monomer were successfully synthesized by referring to the literature. The product was characterized by IR and 1H NMR. The product was confirmed to be the target product with high purity. 2. Cu0 / Mex 6-TREN [tris (N- (N- (N-dimethyl aminoethyl) amine)] as catalyst was used as initiator, and 2-chloropropionamide (CPA) was used as initiator. The copolymerization of AM and DMBS was carried out by SET-LRP in aqueous solution at 25 鈩，

本文编号：2112662