活性自由基聚合法制备丙烯酰胺类聚合物的研究
发布时间：2019-04-11 19:45
【摘要】： 本文首先利用原子转移自由基聚合(ATRP)法研究了在完全的水溶液中丙烯酰胺的聚合。研究以2-氯丙酰胺(CPA)为引发剂,氯化亚铜(CuCl)/2,2’-联吡啶(bpy)为催化剂体系,用ATRP法制备了丙烯酰胺的聚合物。探讨了聚合反应中不同温度、不同的单体浓度等因素对单体转化率的影响,并对聚合反应动力学进行了一定的分析。其次,利用ATRP法制备了N-异丙基丙烯酰胺(NIPAM)与丙烯酸叔丁酯(tBA)的共聚物水凝胶,进而研究讨论了各种因素对ATRP法制备P(NIPAM-co-tBA)水凝胶聚合反应的影响。最后,对聚合物结构进行了一定的分析检测,用红外光谱仪分析表征了聚合物的结构及组成,用凝胶渗透色谱仪测定了聚合物的数均分子量(Mn)及分子量分布(PDI)。 在丙烯酰胺水溶液聚合中,研究了不同温度、不同的单体浓度、不同的单体与引发剂的配比([M]∶[I])及不同的催化剂与引发剂配比([C]∶[I])对聚合反应的影响。研究发现在聚合过程中,随温度的升高,聚合反应速率有所加快,但聚合反应的可控性降低;当增大反应体系中单体的浓度时,聚合反应速率增大,ln([M]0/[M])～t有较好的线性相关性;聚合反应速率也随引发剂用量的加大而增大,但加大引发剂的用量,反应的可控性降低;研究还发现当[C]∶[I]为1:1时聚合反应的可控性较好。通过对聚合反应进行动力学分析发现,反应过程符合活性聚合反应的基本特征,并且聚合物的分子量分布较窄(小于1.5)及实际分子量与理论分子量的偏差较小,聚合反应具有一定的可控性。 本文还以NIPAM为主单体,tBA为共聚单体,CPA为引发剂,N,N’-亚甲基双丙烯酰胺(MBA)为交联剂,采用ATRP法在水与二甲基甲酰胺(DMF)的混合溶液中制备了具有均相网络结构的P(NIPAM-co-tBA)水凝胶。实验同时也研究了不同的单体浓度、引发剂用量、交联剂用量及共聚单体的组成对水凝胶溶胀率(SR)和体积相转变温度(VPTT)的影响,并对聚合反应过程进行了动力学分析。研究发现,在较宽的范围内,P(NIPAM-co-tBA)水凝胶的VPTT可以由共聚单体tBA的用量进行调节,随着tBA用量的增加,所制备的水凝胶的温敏性和溶胀率下降。与传统的自由基聚合法合成的P(NIPAM-co-tBA)水凝胶相比,利用ATRP法制得的凝胶具有VPTT低,溶胀速率快等优点。
[Abstract]:In this paper, the polymerization of acrylamide in complete aqueous solution has been studied by means of atom transfer radical polymerization (ATRP). Acrylamide polymers were prepared by ATRP method using 2-chloro-propionamide (CPA) as initiator, cuprous chloride (CuCl) / 2,2-bipyridine (bpy) as catalyst system. The effects of different temperature and concentration of monomer on monomer conversion were discussed, and the kinetics of polymerization was analyzed. Secondly, the copolymer hydrogels of N-isopropylacrylamide (NIPAM) and tert-butyl acrylate (tBA) were prepared by ATRP method, and the effects of various factors on the polymerization of P (NIPAM-co-tBA) hydrogels prepared by ATRP were discussed. The structure and composition of the polymer were characterized by infrared spectroscopy. The molecular weight (Mn) and molecular weight distribution (PDI).) of the polymer were determined by gel permeation chromatography (GPC). In aqueous polymerization of acrylamide, different temperature and different monomer concentration were studied. The effects of different monomer / initiator ratio ([M]: [I]) and catalyst / initiator ratio ([C]: [I]) on the polymerization. It was found that the rate of polymerization increased with the increase of temperature, but the controllability of polymerization decreased. When the concentration of monomer in the reaction system increased, the polymerization rate increased by, ln ([M] 0 / [M]) t had a good linear correlation. The polymerization rate also increased with the increase of the amount of initiator, but the controllability of the polymerization decreased with increasing the amount of initiator, and it was found that the polymerization reaction had better controllability when the ratio of [C]: [I] was 1: 1. Through the kinetic analysis of the polymerization reaction, it is found that the reaction process accords with the basic characteristics of the active polymerization reaction, and the molecular weight distribution of the polymer is narrow (less than 1.5) and the deviation between the actual molecular weight and the theoretical molecular weight is small. The polymerization has certain controllability. In this paper, NIPAM was used as main monomer, tBA as comonomer, CPA as initiator, N, N-methylenebisacrylamide (MBA) as cross-linking agent, P (NIPAM-co-tBA) hydrogels with homogeneous network structure were prepared by ATRP method in the mixed solution of water and dimethylformamide (DMF). At the same time, the effects of different monomer concentration, initiator, crosslinking agent and comonomer composition on the swelling ratio (SR) and volume phase transition temperature (VPTT) of hydrogel were also studied. The kinetics of the polymerization process was also analyzed. It was found that the VPTT of, P (NIPAM-co-tBA) hydrogels could be regulated by the amount of co-monomer tBA in a wide range, and the temperature sensitivity and swelling ratio of the hydrogels decreased with the increase of the amount of tBA. Compared with the P (NIPAM-co-tBA) hydrogel synthesized by free radical polymerization, the gel prepared by ATRP method has the advantages of lower VPTT and faster swelling rate.
【学位授予单位】：重庆大学
【学位级别】：硕士
【学位授予年份】：2010
【分类号】：O631.3
本文编号：2456696
[Abstract]:In this paper, the polymerization of acrylamide in complete aqueous solution has been studied by means of atom transfer radical polymerization (ATRP). Acrylamide polymers were prepared by ATRP method using 2-chloro-propionamide (CPA) as initiator, cuprous chloride (CuCl) / 2,2-bipyridine (bpy) as catalyst system. The effects of different temperature and concentration of monomer on monomer conversion were discussed, and the kinetics of polymerization was analyzed. Secondly, the copolymer hydrogels of N-isopropylacrylamide (NIPAM) and tert-butyl acrylate (tBA) were prepared by ATRP method, and the effects of various factors on the polymerization of P (NIPAM-co-tBA) hydrogels prepared by ATRP were discussed. The structure and composition of the polymer were characterized by infrared spectroscopy. The molecular weight (Mn) and molecular weight distribution (PDI).) of the polymer were determined by gel permeation chromatography (GPC). In aqueous polymerization of acrylamide, different temperature and different monomer concentration were studied. The effects of different monomer / initiator ratio ([M]: [I]) and catalyst / initiator ratio ([C]: [I]) on the polymerization. It was found that the rate of polymerization increased with the increase of temperature, but the controllability of polymerization decreased. When the concentration of monomer in the reaction system increased, the polymerization rate increased by, ln ([M] 0 / [M]) t had a good linear correlation. The polymerization rate also increased with the increase of the amount of initiator, but the controllability of the polymerization decreased with increasing the amount of initiator, and it was found that the polymerization reaction had better controllability when the ratio of [C]: [I] was 1: 1. Through the kinetic analysis of the polymerization reaction, it is found that the reaction process accords with the basic characteristics of the active polymerization reaction, and the molecular weight distribution of the polymer is narrow (less than 1.5) and the deviation between the actual molecular weight and the theoretical molecular weight is small. The polymerization has certain controllability. In this paper, NIPAM was used as main monomer, tBA as comonomer, CPA as initiator, N, N-methylenebisacrylamide (MBA) as cross-linking agent, P (NIPAM-co-tBA) hydrogels with homogeneous network structure were prepared by ATRP method in the mixed solution of water and dimethylformamide (DMF). At the same time, the effects of different monomer concentration, initiator, crosslinking agent and comonomer composition on the swelling ratio (SR) and volume phase transition temperature (VPTT) of hydrogel were also studied. The kinetics of the polymerization process was also analyzed. It was found that the VPTT of, P (NIPAM-co-tBA) hydrogels could be regulated by the amount of co-monomer tBA in a wide range, and the temperature sensitivity and swelling ratio of the hydrogels decreased with the increase of the amount of tBA. Compared with the P (NIPAM-co-tBA) hydrogel synthesized by free radical polymerization, the gel prepared by ATRP method has the advantages of lower VPTT and faster swelling rate.
【学位授予单位】：重庆大学
【学位级别】：硕士
【学位授予年份】：2010
【分类号】：O631.3
【参考文献】
相关期刊论文 前7条
1 张先正,卓仁禧;快速温度敏感聚(N-异丙基丙烯酰胺-co-丙烯酰胺)水凝胶的制备及性能研究[J];高等学校化学学报;2000年08期
2 袁金颖,魏高原,王延梅,潘才元;ABA型两亲嵌段共聚物的合成及表征[J];高分子学报;2001年05期
3 岳玲,张晓宏,吴世康;两亲两嵌段共聚物PS-b-PAA合成及其在溶液中的形态和纳米聚集结构形成[J];高分子学报;2004年02期
4 蒋志飞;张立武;;原子转移自由基聚合在智能型水凝胶制备中的应用[J];高分子通报;2007年02期
5 郭建华,韩哲文,吴平平;原子转移自由基聚合的研究进展[J];高分子通报;1998年03期
6 朱麟勇,童晓峰,李妙贞,王尔鉴;新型线状-树枝状两亲嵌段共聚物的合成[J];化学学报;2000年06期
7 华静,荆雄科,陈滇宝;ATRP技术在新型高分子材料合成中的应用[J];化工科技;2001年04期
相关博士学位论文 前1条
1 江成发;原子转移自由基交联共聚合成水凝胶及其反应动力学研究[D];四川大学;2005年
相关硕士学位论文 前1条
1 熊邦虎;含氟丙烯酸酯共聚物的原子转移自由基聚合与分析[D];重庆大学;2009年
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