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1、河北科技大学 硕士学位论文 阳离子聚丙烯酰胺共聚行为及性能的研究 姓名：王磊 申请学位级别：硕士 专业：材料学 指导教师：肖继君 20100528 摘 要 I 摘 要 本文以丙烯酰胺（AM） 、阳离子单体丙烯酰氧乙基三甲基氯化铵（DAC）及甲 基丙烯酰氧乙基三甲基氯化铵（DMC）为主要原料，采用紫外光引发自由基聚合制 备二元共聚阳离子聚丙烯酰胺（CPAM） 。 采用红外光谱法（IR） 、氢核磁共振法（1H NMR）对 CPAM 的结构进行测定。 结果表明，AM 与 DAC 可以共聚生成 P（AM-DAC） ；AM 与 DMC 可以共聚生成 P （AM-DMC） ；AM-DAC 共聚反应的竞聚率
2、为 r1=1.051，r2=0.838；AM-DMC 共聚反 应的竞聚率为 r1=0.617， r2=2.142； AM-DMC、 AM-DAC 的共聚过程均为非理想共聚。 本文探讨了阳离子单体、固含量、单体摩尔配比、紫外光照时间、引发剂种类 及用量等因素对 CPAM 合成的影响。结果表明，单体转化率随合成条件和配方的改 变变化较小；随固含量的增加，CPAM 的特性粘数先增大后减小，而阳离子度先减 小后增加；随单体摩尔比的增大，CPAM 的特性粘数增大，阳离子度减小；随光照 时间的延长，P（AM-DMC）的特性粘数先增大后减小，P（AM-DAC）的特性粘数 呈增长趋势，CPAM 的阳离子度值变
3、化较小；随引发剂用量的增加，CPAM 的特性 粘数和阳离子度先增加后减小。 采用乌氏粘度计、可见光分光光度计、凝胶渗透色谱法（GPC）分别对 CPAM 的特性粘数、絮凝效果及 CPAM 的分子量及分子量分布进行测定，根据 1H NMR 谱图计算 CPAM 的阳离子度。结果表明，制备 P（AM-DMC）的工艺条件为：紫外 光照射时间为 6 min，固含量为 20wt%，AM：DMC=4：1，引发剂为光引发剂 184， 引发剂用量为 1，此条件制备的 P（AM-DMC）的阳离子度为 31.17%，特性粘数 为 151.31 ml/g， 粘均分子量分布在 280 万460 万之间， 絮凝过程中有较大
4、团状物出 现，易分层，上层清液的吸光度为 57.3%；制备 P（AM-DAC）的工艺条件为：紫外 光照射时间为 6 min，固含量为 20wt%，AM：DAC=4：1，引发剂为光引发剂 184， 引发剂用量为 1，此条件制备的 P（AM-DAC）的阳离子度为 17.75%，特性粘数 为 167.46 ml/g， 粘均分子量分布在 125 万300 万之间， 絮凝过程中有较大团状物出 现，易分层，上层清液的吸光度为 52.8%。 关键词 阳离子聚丙烯酰胺；竞聚率；阳离子度；氢核磁共振；共聚行为；絮凝性 能 河北科技大学硕士学位论文 II Abstract In this paper the bi
5、nary cationic polyacrylamide copolymers were prepared from acrylamide (AM) with cationic monomer acryloyloxyethyl trimethyl ammonium chloride (DAC) and methyl-acryloyloxyethyl trimethyl ammonium chloride (DMC), respectively. UV-induced free radical polymerization was used. The structure of CPAM was
6、determined by Fourier Transform Infrared Spectroscopy (IR) and 1H Nuclear Magnetic Resonance (1H NMR). The results show that P(AM-DAC) could be obtained by the copolymerization of AM and DAC; P(AM-DMC) could be obtained by the copolymerization of AM and DMC; the monomer reactivity-ratio of AM-DAC wa
7、s r1=1.051, r2=0.838; that of AM-DMC was r1=0.617, r2=2.142, the copolymerization of AM-DMC and AM-DAC were non-ideal copolymerization. Effecting factors for synthesis of the process of CPAM, such as cationic monomers, solid content, the molar ratio of monomer, UV irradiation time, type and dosage o
8、f photoinitiator were investigated in this paper. The results show that the monomer conversion rate had small change with the changes of synthesis condition and formulation; as the increase of solid content, the intrinsic viscosity of CPAM increased first and then decreased, while the cationic degre
9、e decreased and then increased; as the increase of molar ratio of monomer, the intrinsic viscosity of CPAM increased, while the cationic degree decreased; as the extension of illumination time, the intrinsic viscosity of P (AM-DMC) increased first and then decreased, the intrinsic viscosity of P (AM
10、-DAC) showed a rising trend, the cationic degree of CPAM had small change; with the increase of dosage of photoinitiator, the intrinsic viscosity and cationic degree of CPAM increased first and then decreased. The intrinsic viscosity , flocculation property, molecular weight and its distribution of
11、CPAM were determined by Ubbelohde Viscometer, Visible Range Spectrophotometer and Gel Permeation Chromatography (GPC), respectively, the cation degree of CPAM was calculated according to 1H NMR spectra. The results show that the synthesizing process conditions of P(AM-DMC) was UV irradiation time of
12、 6 min, solid content of 20wt%, AM: DMC of 4:1, initiator of photoinitiators of 184, dosage of initiator 1. The cationic degree of P(AM-DMC) preparated was 17.75% and intrinsic viscosity is 151.31 ml/g, the viscosity-average molecular weight distribution of P(AM-DMC) was 2.8 million to 4.6 million,
13、lager flocculation constituent were formed during the process of flocculation, and seperated easily, the absorbance of the upper clear liquid was 57.3%; the process Abstract III synthesizing condition of P(AM-DAC) was UV irradiation time of 6 min, solid content of 20wt%, AM: DMC of 4:1, initiator of
14、 photoinitiators was 184, dosage of initiator 1, the cationic degree of P(AM-DMC) preparated was 31.17% and intrinsic viscosity was 167.46 ml/g, the viscosity-average molecular weight distribution of P(AM-DAC) was 1.25 million to 3 million, lager flocculation constituent were appeared in the process
15、 of flocculation, and seperated easily, the absorbance of the upper clear liquid was 52.8%. Keywords polyacrylamide; reactivity-ratio; cationic-degree;1H NMR; copolymerization; flocculation 第 1 章 绪 论 1 第 1 章 绪 论 1.1 简 述 聚丙烯酰胺（Polyacrylamide，简称 PAM）是丙烯酰胺（Acrylamide，简称 AM） 的均聚物及丙烯酰胺与其它单体共聚物的统称1。 它是一类新
16、型的精细功能高分子产 品，是水溶性合成高聚物中最重要的品种之一，更是应用最为广泛的品种之一25。 聚丙烯酰胺可以作为絮凝剂、增稠剂、纸张增强剂、三次除水剂、土壤改良剂、 泥浆处理剂、水土保失剂、表面活性剂等化学助剂广泛的应用在化工、冶金、地质、 煤炭、石油开采、造纸、纺织、水处理等生产部门，有“百业助剂”之称6。 聚丙烯酰胺最早在 1893 年由实验室制得7，它是一种水溶性的多功能线性高聚 物8。 依据聚丙烯酰胺分子链上的官能基团在水中离解性质的不同， 可将其分为阳离 子型（CPAM） 、阴离子型（HPAM） 、两性离子型（AmPAM 或 ZPAM）和非离子型 （NPAM）等类型。其中阳离子聚丙烯酰胺作为一种重要高效的絮凝剂，广泛应用于 工业污水以及城市综合污水处理领域，其共聚合产品更以电荷度的可控性、电荷分 布的均匀性以及制造工艺的简单易操作而备受人们的关注912。 随着社会的发展和经济的进步，含有机物质和胶体等微粒的污泥及废水量也越 来越大，由于这些微粒的表面带有负电荷，使得非离子型 PAM 或者阴离子聚丙烯酰 胺不能达到理
