【作者】 丁伟；

【导师】 刘永建；

【作者基本信息】 大庆石油学院 ， 油气田开发工程， 2006， 博士

【摘要】 丙烯酰胺（AM）类聚合物是指丙烯酰胺的均聚物及丙烯酰胺与其它单体形成的共聚物的统称。聚丙烯酰胺（PAM）及其衍生物是一类新型的精细功能高分子产品,是水溶性聚电解质中最重要的品种之一。除了在石油工业中用于驱油剂外,它还广泛应用于化工、冶金、地质、煤炭、造纸、轻纺、水处理等工业部门。本论文主要研究丙烯酰胺类聚合物的合成及性能,分别合成了超高相对分子质量的部分水解聚丙烯酰胺、超高相对分子质量的阳离子型聚丙烯酰胺、具有反聚电解质溶液行为的两性聚合物、耐温抗盐型聚丙烯酰胺衍生物以及兼具梳形结构和两性离子结构的聚丙烯酰胺衍生物,并对它们的性能进行了评价,具体研究内容和结果如下:⒈采用自行研制的双官能度引发剂与还原剂和水溶性偶氮化合物组成的复合氧化还原引发体系,引发AM水溶液均聚,经微波后水解制备超高相对分子质量部分水解聚丙烯酰胺（HPAM）。结果表明:在AM浓度32%,双官能度引发剂浓度10mg/L,聚合温度6℃,偶氮化合物用量25mg/L,EDTA用量60 mg/L,甲酸钠用量5mg/L,尿素用量400 mg/L;得到PAM平均相对分子质量高达3.0×10⁷。优化水解工艺条件为:PAM浓度15%,微波反应器输出功率420W,水解时间8min,助溶剂NP-10用量100mg/L,得到的HPAM相对分子质量高达3.3×10⁷,水解度达到设计要求。采用浓度为800mg/L的HPAM水溶液在人造非均质岩心上进行驱油性能评价,可提高采收率15%以上,与相同条件下的国产HPAM（DQ2500）相比,采收率提高幅度达5%。⒉以丙烯酰胺（AM）和丙烯酰氧乙基三甲基氯化铵（AETMAC）作为共聚单体,采用新型复合氧化还原体系引发AM与AETMAC共聚合反应,合成超高相对分子质量（≥1.0×10⁷）、阳离子度可在1～50%范围内任意调控的超高相对分子质量阳离子聚丙烯酰胺。最佳工艺参数为:引发剂浓度60 mg/L（对单体）,单体浓度为20 %,pH值为8,引发温度为10℃,DA浓度为600 mg/L,尿素浓度为100 mg/L,EDTA浓度为100mg/L,Span-20浓度为100 mg/L,偶氮浓度为80 mg/L。分别采用F-R法、K-T法和YBR法三种方法对AETMAC与AM的竞聚率进行测定,结果表明应用K-T法和YBR法测定竞聚率比较准确,AETMAC与AM的竞聚率分别为r_AETMAC=0.3835,r_AM=2.2863。对合成的超高分子量阳离子絮凝剂CPAM（AETMAC-AM）絮凝评价试验结果表明,絮凝效更多还原

【Abstract】 Acrylamide-based polymers are the names of acrylamide homopolymer and copolymersof acrylamide with other monomers. Polyacrylamide(PAM), an important water-solublepolyelectrolyte, is widely used as flooding agent for EOR, chemical engineering, flocculants,paper-making additives and so on in industry.The main purpose of this paper is to investigate the synthesis and properties of acrylamide-basedpolymers.A super high molecular weight HPAM and a cationic PAM, zwitterionic polymers withantipolyelectrolyte behavior in solution, temperature-tolerant and salt resistant tetrapolymer and a novelcomb-like zwitterionic PAM derivative were synthesized, their properties were evaluated.By using a complex redox initiating system composed of a self-made difunctional peroxide initiator,a reductive agent and a water-soluble azo-compound, a kind of PAM with ultra high molecular weight of≥3.0×107 were obtained under conditions: concentration of monomer 32%, concentration of difunctionalperoxide 10mg/L, azo 25mg/L,EDTA 60 mg/L,sodium formate5mg/L, urea 400 mg/L andpolymerization temperature 6℃ . The PAM was hydrolyzed in a microwave reactor at optimizedconditions and HPAM was obtained at expected hydrolysis degree with good solubility and molecularweight over 3.3×107. In core flooding experiments the enhancement in oil recovery by 800mg/L ofHPAM solution injected was of over 15%, higher than that of HPAM(DQ2500).By using a complex initiating system of persulfate, NaSF, functional monomer DA and additives,cationic PAM was synthesized with AM and AETMAC as co-monomers. The polymerization iscontrolled under low temperature(10℃ )in aqueous solution, concentration of initiator 60 mg/L, totalmonomer concentration 20%, pH 8, concentration of DA 600mg/L, urea 100mg/L,EDTA100mg/L,Span-20 100mg/L, azo 80 mg/L, the molecular weight of CPAM was over 1.0×107.Under experimentalconditions, the reactivity ratios of AM and AETMAC are caculated by means of three methods: F-R,K-T, and YBR., they were rAETMAC=0.3835,rAM=2.2863. Through the flocculation experiments ofusing Poly(AETMAC-AM) disposing of bentonite suspension and urban waste water, the optimumcapacity is determined. The result showed the flocculant has good solubility and flocculation efficiency.Its efficiency is better than other flocculants, and as good as products abroad.Three kind of betaine zwitterionsic monomers were synthesized and copolymerized with AM toprepare zwitterionic polymers with antipolyelectrolyte behavior in solution. The results showed that thethree zwitterionic copolymers in 1000～4000mg/L salt solution, their solution viscosity increased withthe concentration of salt. In core flooding experiments the enhancement in oil recovery by 1000mg/L ofthe polymers solution injected was of over 10%.The synthesis of a tripolymer of acrylamide(AM), 2-acrylamido-2-methylpropanesulfonic acid(AMPS )and N,N-dimethylacrylamide(DMAM) as raw material was gained byfree radical micellar copolymerization. The optimum conditions was attained by the methodof orthogonal test. Under the optimized conditions, the intrinsic viscosity of the tripolymerwas reached 22.0dL/g. With microwave hydrolysis technology, a tetrapolymer ofAM-DMAM-AMPS-AA copolymer was obtained with intrinsic viscosity reached about27.0dL/g. The structures of the copolymers were characterized by FTIR. Solution propertiesof the tripolymer and tetrapolymer were studied, and showed that the two polymers had goodsolubility, viscositying effect and significant salt resistance. Under conditions of temperature45℃ , shear rate 2000rpm, maintaining ratio of viscosity was over 90%, in aging treatment at90℃ in more than 30 days standing, their maintaining ratio of viscosity was over 85%. It wasfound that the effect of concentration of SDS on polymers solution viscosity was muchstronger.A new betaine-type zwitterionic compound monomer with hydrophic long side chain which namedN,N-dimethyl-N-carboxynonyl-N-methacylolozylethyl ammonium bromide was synthesized bydimethyl aminoethyl methacrylate(DM )and 10-Bromodecanoic acid. At optimum conditions such asreaction temperature 55℃, DM∶10-Bromodecanoic acid=2∶1(molar ratio), reaction time 8h, the yieldof the monomer was 78%. The new monomer was copolymerized with AM to synthesize a comb-likezwitterionic copolymer. The properties of dilute solution of the copolymer was tested and showed thatthe copolymer solution had excellent shearing resistance, salt tolerance and viscoelastic characteristics.更多还原