【摘要】： 本文首先利用原子轉(zhuǎn)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)為引發(fā)劑,氯化亞銅(CuCl)/2,2’-聯(lián)吡啶(bpy)為催化劑體系,用ATRP法制備了丙烯酰胺的聚合物。探討了聚合反應(yīng)中不同溫度、不同的單體濃度等因素對(duì)單體轉(zhuǎn)化率的影響,并對(duì)聚合反應(yīng)動(dòng)力學(xué)進(jìn)行了一定的分析。其次,利用ATRP法制備了N-異丙基丙烯酰胺(NIPAM)與丙烯酸叔丁酯(tBA)的共聚物水凝膠,進(jìn)而研究討論了各種因素對(duì)ATRP法制備P(NIPAM-co-tBA)水凝膠聚合反應(yīng)的影響。最后,對(duì)聚合物結(jié)構(gòu)進(jìn)行了一定的分析檢測(cè),用紅外光譜儀分析表征了聚合物的結(jié)構(gòu)及組成,用凝膠滲透色譜儀測(cè)定了聚合物的數(shù)均分子量(Mn)及分子量分布(PDI)。 在丙烯酰胺水溶液聚合中,研究了不同溫度、不同的單體濃度、不同的單體與引發(fā)劑的配比([M]∶[I])及不同的催化劑與引發(fā)劑配比([C]∶[I])對(duì)聚合反應(yīng)的影響。研究發(fā)現(xiàn)在聚合過(guò)程中,隨溫度的升高,聚合反應(yīng)速率有所加快,但聚合反應(yīng)的可控性降低;當(dāng)增大反應(yīng)體系中單體的濃度時(shí),聚合反應(yīng)速率增大,ln([M]0/[M])～t有較好的線性相關(guān)性;聚合反應(yīng)速率也隨引發(fā)劑用量的加大而增大,但加大引發(fā)劑的用量,反應(yīng)的可控性降低;研究還發(fā)現(xiàn)當(dāng)[C]∶[I]為1:1時(shí)聚合反應(yīng)的可控性較好。通過(guò)對(duì)聚合反應(yīng)進(jìn)行動(dòng)力學(xué)分析發(fā)現(xiàn),反應(yīng)過(guò)程符合活性聚合反應(yīng)的基本特征,并且聚合物的分子量分布較窄(小于1.5)及實(shí)際分子量與理論分子量的偏差較小,聚合反應(yīng)具有一定的可控性。 本文還以NIPAM為主單體,tBA為共聚單體,CPA為引發(fā)劑,N,N’-亞甲基雙丙烯酰胺(MBA)為交聯(lián)劑,采用ATRP法在水與二甲基甲酰胺(DMF)的混合溶液中制備了具有均相網(wǎng)絡(luò)結(jié)構(gòu)的P(NIPAM-co-tBA)水凝膠。實(shí)驗(yàn)同時(shí)也研究了不同的單體濃度、引發(fā)劑用量、交聯(lián)劑用量及共聚單體的組成對(duì)水凝膠溶脹率(SR)和體積相轉(zhuǎn)變溫度(VPTT)的影響,并對(duì)聚合反應(yīng)過(guò)程進(jìn)行了動(dòng)力學(xué)分析。研究發(fā)現(xiàn),在較寬的范圍內(nèi),P(NIPAM-co-tBA)水凝膠的VPTT可以由共聚單體tBA的用量進(jìn)行調(diào)節(jié),隨著tBA用量的增加,所制備的水凝膠的溫敏性和溶脹率下降。與傳統(tǒng)的自由基聚合法合成的P(NIPAM-co-tBA)水凝膠相比,利用ATRP法制得的凝膠具有VPTT低,溶脹速率快等優(yōu)點(diǎn)。
[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.
【學(xué)位授予單位】：重慶大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2010
【分類號(hào)】：O631.3

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