80%、90%阳离子度PDA制备工艺初步研究
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摘要
本文对80%、90%阳离子度PDA制备工艺进行了初步研究。以丙烯酰胺(AM)和工业单体二甲基二烯丙基氯化铵(DMDAAC)为原料,过硫酸铵(APS)为引发剂,采用一次加料方式,水溶液聚合法制备80%、90%阳离子度PDA共聚物。以文献已有的阳离子均聚物PDMDAAC制备工艺为基础,研究了单体起始总用量、引发剂用量、助剂Na_4EDTA用量以及聚合反应温度对聚合反应的影响。通过前期探索和正交优化的实验方法,得到了80%、90%阳离子度PDA最佳制备工艺。90%阳离子度PDA最佳制备工艺条件为:单体起始总用量以质量分数计为67.5%,引发剂用量为总单体质量的0.020%,助剂Na_4EDTA用量为总单体质量的0.0066%,保温方式为40℃3h、53℃3h和75℃3h,可得到产物最高特征黏度为3.90dL·g~(-1),残余双键总含量为4.31%。80%阳离子度PDA最佳制备工艺条件为:单体起始总用量以质量分数计为65.0%,引发剂用量为总单体质量的0.015%,助剂Na_4EDTA用量为总单体质量的0.0139%,保温方式为40℃3h、50℃3h和75℃3h,可得到产物最高特征黏度为4.12dL·g~(-1),残余双键总含量为7.98%。同时,在最佳制备工艺条件下考察各影响因素的变化对产物特征黏度的影响趋势。上述研究得到了高特征黏度的高阳离子度PDA产物,丰富了PDA制备工艺方面的理论及认识,为其机理研究和工业化生产打下一定的基础。
The process of preparing poly DMDAAC-AM(PDA)was studied in this paper.Using acrylamide(AM)and dimethyldiallylammonium chloride(DMDAAC)as raw materials and ammonium persulfate(APS)as initiator,PDA copolymers with cationicity of 80%and 90%were synthesized by aqueous solution polymerization and the method of adding all raw materials in one step.Based on present polymerization process of poly-DMDAAC in our research group,the effects of various factors such as monomer concentration,the amount of initiator and Na_4EDTA and temperatures were researched respectively.The optimal conditions of synthesizing PDA with cationicity of 80%and 90%were obtained via a series of preliminary and orthonormal experiments.The optimal processing conditions of PDA with cationicity of 90%were:m(DMDAAC and AM)%=67.5%, w(APS):w(DMDAAC and AM)=0.020%,w(Na_4EDTA):w(DMDAAC and AM)=0.0066%, and the copolymerization was carried out by maintaining the reaction temperature of 40℃,53℃,75℃each for 3 hours,the highest value of intrinsic viscosity was 3.90dL·g~(-1) and its correspongding residual double bond percent was 4.3 1%.The optimal processing conditions of PDA with cationicity of 80%were:m(DMDAAC and AM)%=65.0%, w(APS):w(DMDAAC and AM)=0.015%,w(Na_4EDTA):w(DMDAAC and AM)=0.0139%, and the copolymerization was carried out by maintaining the reaction temperature of 40℃,50℃,75℃each for 3 hours,the highest value of intrinsic viscosity was 4.12dL·g~(-1) and its correspongding residual double bond percent was 7.98%.Meanwhile,on the basis of the optimal processing conditions,the factors which affected the product intrinsic viscosity were studied respectively.The studies of the preparation of PDA with high intrinsic viscosity could enrich the recognization of process in preparing PDA theoritically and be a good foundation for its further mechanism researches and industrial production.
The process of preparing poly DMDAAC-AM(PDA)was studied in this paper.Using acrylamide(AM)and dimethyldiallylammonium chloride(DMDAAC)as raw materials and ammonium persulfate(APS)as initiator,PDA copolymers with cationicity of 80%and 90%were synthesized by aqueous solution polymerization and the method of adding all raw materials in one step.Based on present polymerization process of poly-DMDAAC in our research group,the effects of various factors such as monomer concentration,the amount of initiator and Na_4EDTA and temperatures were researched respectively.The optimal conditions of synthesizing PDA with cationicity of 80%and 90%were obtained via a series of preliminary and orthonormal experiments.The optimal processing conditions of PDA with cationicity of 90%were:m(DMDAAC and AM)%=67.5%, w(APS):w(DMDAAC and AM)=0.020%,w(Na_4EDTA):w(DMDAAC and AM)=0.0066%, and the copolymerization was carried out by maintaining the reaction temperature of 40℃,53℃,75℃each for 3 hours,the highest value of intrinsic viscosity was 3.90dL·g~(-1) and its correspongding residual double bond percent was 4.3 1%.The optimal processing conditions of PDA with cationicity of 80%were:m(DMDAAC and AM)%=65.0%, w(APS):w(DMDAAC and AM)=0.015%,w(Na_4EDTA):w(DMDAAC and AM)=0.0139%, and the copolymerization was carried out by maintaining the reaction temperature of 40℃,50℃,75℃each for 3 hours,the highest value of intrinsic viscosity was 4.12dL·g~(-1) and its correspongding residual double bond percent was 7.98%.Meanwhile,on the basis of the optimal processing conditions,the factors which affected the product intrinsic viscosity were studied respectively.The studies of the preparation of PDA with high intrinsic viscosity could enrich the recognization of process in preparing PDA theoritically and be a good foundation for its further mechanism researches and industrial production.
引文
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[13]吕生华,马建忠,吕建强,等.二甲基二烯丙基氯化铵-丙烯酰胺共聚物的结构表征与应用[J].精细化工,2000,17(7):386-388
[14]赵华章,岳钦艳,高宝玉,等.阳离子型高分子絮凝剂PDMDAAC与P(DMDAAC-AM)的合成及分析[J].精细化工,2001,18(17):645-650
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[19]Haruki T,Takashi Y,Toshihiko T.Hofmann rearrangement products of acrylamide polymers as paper strengthening agents[P].US:4 057 994,1992-05-17
[20]Okawa A,Nishimura M,Nagasaki S.Manufacture of ink-jet printing inks and ink-jet print media[P].JP:2007 237 589,2007-09-20
[21]Tooru F,Nobuyuki H.Cationic and anionic copolymer surfactants for petroleum recovery by flooding[P].JP:03 212 593,1991-09-18.
[22]Goddinger D,Schulze Z W.Conditioning preparations for hair and skin containing purine or purine derivatives and hydantoin[P].DE:2006 010 867,2006-03-07
[23]Koyagi T,Osugi T,Kageyama M.Conditioning shampoos containing cationic polymers and polysiloxanes[p].JP:2007 153 791,2007-06-21
[24]Shibata K,Kawada E,Uemura M.Urea-containing pretreatment agents for improved dyeability and fastness of acidic hair dyes[P].JP:2007 126 384,2007-05-04
[25]Lawrence K,Roger L.Indirect food additive:adjuvants,production adis and sanitizers,antioxidants and/or stabilizers for polymers[J].Fed.Regist.,1982,47(169):38274
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[27]郑昌仁.高聚物分子量及其分布[M].第3版.北京:化学工业出版社,1986
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[39]徐雄立.AM-DMDAAC共聚物的合成[J].合成化学,2003,5(11):509-512
[40]游纪萍,陈少平,凌永泰.DADMAC-AM共聚物的合成及其对细小纤维的絮凝作用[J].造纸科学与技术,2005,24(5):1-4
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