一种提高PDA胶体相对分子质量的新方法探索
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摘要
本文以二甲基二烯丙基氯化铵与丙烯酰胺为原料，分别从活泼单体补加法和提高单体纯度方面入手，合成一种水溶性阳离子型共聚物PDA。对影响以活泼单体补加法合成的30％阳离子度PDA产物性能的工艺条件作了研究，所得产物PDA特征粘度为6.6～7.1dL／g，阳离子单体转化率为65％左右。同时，借助仪器分析的结果，提出一种精制方法提纯阳离子单体，并对精制工艺作了研究，获得了较好的工艺条件。随后，采用精制后的阳离子单体合成30％阳离子度的PDA(加助剂EDTA-4Na)，通过正交实验优化工艺条件，所得产物PDA的特征粘度达7.2dL／g，并对各影响产物性能的因素分别作了研究。研究结果初步实现了活泼单体补加法的合成工艺应用于不同批次的阳离子单体时的工艺过程和结果的可重复性，为进一步的研究和该工艺的产业化奠定了基础。研究得到的阳离子单体精制工艺是一种通过提纯单体来提高PDA相对分子质量的有效方法。
In this paper, a kind of water-soluble cationic copolymer PDA of diallyldimethylammonium chloride (DMDAAC) and acrylamide (AM) was prepared by stage-addition of a major portion of the acrylamide monomer and by improving cationic monomer's purity. The effects of reaction conditions on copolymerization of preparing PDA with 30% cationicity by stage-addition were studied, and under a good reaction condition the intrinsic viscosity of the product PDA with 30% cationicity was 6.6 ~ 7.1dL/g and cationic monomer DMDAAC conversion was about 65%. Meanwhile, a refining method of the cationic monomer was provided and researched after impurities were analyzed through instruments. And then,the refined cationic monomer DMDAAC was used to synthesize PDA with 30% cationicity. After orthonormal experiments, a better reaction condition was founded and the intrinsic viscosity of PDA with 30% cationicity reached 7.2dL/g, and all the important factors on copolymerization were also researched. The results illustrated th
at the reaction conditions on preparing PDA with 30% cationicity by stage-addition was testified to be appropriate to different batch cationic monomers in copolymerization of preparing PDA and it settled a base for advanced research. And a useful method was obtained to improve the intrinsic viscosity of PDA by improving cationic monomer's purity.
In this paper, a kind of water-soluble cationic copolymer PDA of diallyldimethylammonium chloride (DMDAAC) and acrylamide (AM) was prepared by stage-addition of a major portion of the acrylamide monomer and by improving cationic monomer's purity. The effects of reaction conditions on copolymerization of preparing PDA with 30% cationicity by stage-addition were studied, and under a good reaction condition the intrinsic viscosity of the product PDA with 30% cationicity was 6.6 ~ 7.1dL/g and cationic monomer DMDAAC conversion was about 65%. Meanwhile, a refining method of the cationic monomer was provided and researched after impurities were analyzed through instruments. And then,the refined cationic monomer DMDAAC was used to synthesize PDA with 30% cationicity. After orthonormal experiments, a better reaction condition was founded and the intrinsic viscosity of PDA with 30% cationicity reached 7.2dL/g, and all the important factors on copolymerization were also researched. The results illustrated th
at the reaction conditions on preparing PDA with 30% cationicity by stage-addition was testified to be appropriate to different batch cationic monomers in copolymerization of preparing PDA and it settled a base for advanced research. And a useful method was obtained to improve the intrinsic viscosity of PDA by improving cationic monomer's purity.
引文
1 奚旦立，孙裕生，刘秀英．环境监测．北京：高等教育出版社．1997：19～20
2 严瑞碹．水处理剂应用手册．北京：化学工业出版社．2000：4～45
3 许保玖．给水处理．北京：中国建筑工业出版社．1979：7～33
4 顾夏声，黄铭荣，王占生．水处理工程．北京：中国建筑工业出版社．1980：53～67
5 杨巍．美国水处理化学品现状与展望．工业水处理．1999，18(2)：7～11
6 甘光奉，甘莉．高分子絮凝剂研究的进展．工业水处理．1999，19(2)：6～7
7 陈秉栓，白玉文．高分子絮凝剂的开发和应用．山西化工．1983，(3)：28～32
8 Butler G B, Goette R L. Preparation and polymerization of unsaturated quaternary ammonium compounds. J.Am.Chem.Soc. 1954, 76:2418～2421
9 马喜平．聚丙烯酰胺类阳离子聚合物的合成及应用．化学世界．1995(1)：588～591
10 陈秉铨，白玉文．阳离子聚丙烯酰胺絮凝剂的合成．太原工学院学报．1983(3)：75～83
11 谭业邦，张黎明．用高分子化学反应合成阳离子聚合物．精细石油化学．1998(4)：41～42
12 杨通在，刘亦农．阳离子型改性絮凝剂的结构及其性能．塑料工业．1998，26(2)：116～118
13 Huang S S. Evaluation of chemical structural heterogeneity of cationic acrylamide copolymers by high-performance liquid chromatography. Journal Chromatogr. 1991,536(1-2): 203～209
14 赵华章，高宝玉，岳钦艳．二甲基二烯丙基氯化铵(DMDAAC)聚合物的研究进展．工业水处理．1999，19(6)：1～4
15 Jaeger W, Hahn M. Polymerization of water-soluble cationic vinyl monomers. Macromol Symposium. 1996,111:95～106
16 张跃军，顾学芳．二甲基二烯丙基氯化铵与丙烯酰胺共聚物的研究进展．精细化工．2002，19(9)：521～527
17 Walter H S, Walter M T. Composition comprising a linear copolymer of a quaternary ammonium compound and an ethylenically unsaturated copolymerizable compound. US: 2 923 701,1960
18 许振举．二甲基二烯丙基氯化铵的制备方法．CN：1 051 169A，1990
19 权艳梅．DMDAAC合成及分析方法的改进．油田化学．1997，14(2)：159～161
20 Jerry E B. Synthesis of dimethyldiallyammonium chloride. US:3 461 169, 1969
21 郭四虎，宋建军．二甲基二烯丙基氯化铵的合成．山西化工．2001，21(4)：4～5，10
22 Algner H S. Continuous process for the preparation ofdimethyldially ammonium chloride. DE: 3 528 985,1987
23 王雅琼，王保成．二甲基二烯丙基氯化铵的合成．太原工业大学学报．1996，27(2)：86～89
24 Walter H S, Price J A, Moore S T.Soluble copolymers of diallyl monomers. Journal Chemical Engineering Data. 1959,4:273～276
25 Hawthorne D G, Solomn D H. Cyclopolymerization effect of β-substituents on the cyclopolymerization of diallylamines.Journal Macromolecule Science and Chemistry. 1976,A10:923
26 Wandrey C, Jaeger W, Reinisch G. The stucture studies of polydiallyl-dimethylammonium chloride. Acta Polymers. 1982,32:177
27 愈益平．二烯丙基胺类聚合物的研制和在石油开采中的应用．油田化学．1991，8(3)：194～199
28 潘祖仁．高分子化学．北京：化学工业出版社．1997：18～90
29 林尚生，陆耘，梁兆熙．高分子化学．北京：科学出版社．1998：583～655
30 摩西R B，卡拉赫C E．聚合物化学导论．河北：科技时代出版社．1988：37～87
31 Butler G B. Method of enhancing polymerization of diallyl dimethyl armnonium compounds to produce high-molecular-weight polymers. US: 4 742 134, 1998
32 顾学芳，张跃军．阳离子絮凝剂的合成与应用(1)．工业水处理．2001，1：22～25
33 吴全才．反相乳液聚合合成DMDAAC／AM阳离子型共聚物．沈阳化工学院学报．1996，10(1)：57～62
34 Keil K H, Engelhardt F. Copolymer process for its preparation and its use. EP: 232 519, 1987
35 Gartner H A, Herbert A. Process for the production of high molecular weight copolymers of diallylammonium monomers and acrylamide monomers in solution. US: 5 110 883, 1992
36 罗文利．高分子阳离子聚合物的制备．CN：1 246 487A，2000
37 Hurlock J R, Murphy C J. Improved DMDAAC-AM copolymers by radical copolymerisation of diallydimethylammonium chloride and acrylamide in water-in-oil. DE: 4 203 818, 1992
38 焦书科．聚合反应工程进展．杭州：浙江大学出版社，1993：21～45
39 吴全才．PDA阳离子型絮凝剂合成及应用的研究．工业水处理．1997，17(4)：
40～42
40 Welcher R P. Controlled polymerization of dimethyldiallylammonium halides by the use of alkali metal or ammonium bisulfiter or metabisufites. US: 4 092 467, 1978
41 Bhat T, Bhupat R. High molecular weight DMDA.AC polymers by inverse emulsion technology. US: 4 713 431,1987
42 Lipp D N, Kozakiewicz J J. Cationic microemulsified polymers.EP:374 457, 1990
43 Huang S Y, Duplaise D L, Kozakiewicz J J. Emulsified functionalized polymers. EP: 374 478, 1990
44 Kiyoshis S H, Toshio V. Polymer or copolymers from at least one diallylamine derivative. Ger Often: 2 416 675, 1975
45 Subramanian R, Zhu S, Pelton R H. Synthesis and flocculation performance of graft and random copolymer microgels of acrylamide and diallyldimethyl ammonium chloride. Colloid Polymer Science. 1999,277(10): 939～946
46 Hunter W E, Craun G P. Process for the manufacture of high solids, free-flowing, granular poly(dimethyldiallyl ammonium chloride). US: 4 654 378, 1999
47 Sinquin A,Velly M,Durand J P.Process for inhibiting or retarding the formation or hydrates in a production effluent such as natural gas or petroleum gases. EP: 807 806,1997
48 Allen S D; Lyman L R. Wastewater treatment process and apparatus for high flow impurity removal. WO: 98 23 538,1998
49 Sivakumar A,Muray P. Use of hydrophilic dispersion polymers for oily wastewater clarification. WO:00 04 970, 2000
50 Hasse R A. Method for dewatering of sludge. US: 5 846 435,1998
51 Guerro G, Dauplaise D.Methods and agents for improving paper print- ability and strength. US: 5 824 190, 1998
52 Malhotra S L, Naik K N. Coated xerographic photographic paper. EP: 877 298, 1998
53 Nguyen D T. Method for inhibiting deposition in pulp and papermaking systems using a composition comprising of polyvinyl alcohol, gelation and cationic polymer. US: 5 723 021,1998
54 Sutman F J, Chascin K J. Process for making a uniform dispersion of aramid fibers and polymer. WO: 99 02 770,1999
55 Henderson K F. Polyampholyte coagulant in the papermaking process. WO: 00 34
55 Henderson K F Polyampholyte coagulant in the papermaking process. WO: 00 34 581,2000
56 Kevv E M. Polymeric combinations used as copper and precious metal heap leaching agglomeration aids. US: 5 833 937,1998
57 Harmalker S, Klewsaat G, Aldrich T. Skin Cleansing composition com-prising a mixture of thinkening polymers. US: 6 150 313, 2000
58 Gosselink E P, Panandiker R K. Laundry detergent compositions with a cationically charged dye maintenance polymer. WO: 00 22 077, 2000
59 United states food and drug administration. Indirect food additive: adjuvants,production adis and sanitizers; antioxidants and/or stabili-zers for polymers. Fed Regist. 1982, 47(169):38274
60 Anon. Food additives. Fed Regist. 1971, 36(118): 11723～11724
61 Smerbeck R V, Johnson J R. Method and composition for protecting against jellyfish stings. US: 5 958 397, 1999
62 Hwang M H. Electro conductive polymer composition. US: 4 282 118, 1981
63 张爱华，许振举．二甲基二烯丙基氯化铵-丙烯酰胺共聚物．CN：1 051 366 1992
64 张德慧，许易安．阳离子型有机高分子絮凝剂DMDAAC的制备及应用．河南化工．1998，(10)：12～14
65 谭明乾，张跃军．DMDAAC／AM共聚物合成及其絮凝性能．化工时刊．1999，(12)：15～17
66 吕生华．二甲基二烯丙基氯化铵与丙烯酰胺共聚物的结构表征及应用．精细化工．2000，17(7)：386～387
67 赵华章．阳离子型高分子絮凝剂PDMDAAC与P(DMDAAC-AM)的合成及分析．精细化工．2001，18(11)：645～649
68 永泽满．高分子水处理剂(下)第一版．北京：化学工业出版社．1983：35～78
69 邢云杰．几种阳离子度PDA合成工艺的初步研究．南京理工大学硕士学位论．2001
70 刘瑛．20％阳离子度PDA聚合工艺及引发剂体系的初步研究．南京理工大学硕士学位论．2001
71 谭明乾．阳离子聚丙烯酰胺有机高分子絮凝剂的合成及应用研究．南京理工大学硕士论文．1999
72 顾学芳．30％阳离子度PDA的合成及应用研究．南京理工大学硕士学位论．2000
73 马喜平．聚丙烯酰胺类阳离子聚合物的合成及应用．化学世界．1995，(1)：
588～591
74 陈伟忠．阳离子单体二甲基二烯丙基氯化铵制备工艺的改进．南京理工大学硕士学位论文．2000
75 Ynopsis. Copolymerization of cationic monomers with acrylamide in an aqueous solution. Journal of polymer science.1986(24):29～36
76 王海鹰．博士论文学期阶段实验小结．2002．
2 严瑞碹．水处理剂应用手册．北京：化学工业出版社．2000：4～45
3 许保玖．给水处理．北京：中国建筑工业出版社．1979：7～33
4 顾夏声，黄铭荣，王占生．水处理工程．北京：中国建筑工业出版社．1980：53～67
5 杨巍．美国水处理化学品现状与展望．工业水处理．1999，18(2)：7～11
6 甘光奉，甘莉．高分子絮凝剂研究的进展．工业水处理．1999，19(2)：6～7
7 陈秉栓，白玉文．高分子絮凝剂的开发和应用．山西化工．1983，(3)：28～32
8 Butler G B, Goette R L. Preparation and polymerization of unsaturated quaternary ammonium compounds. J.Am.Chem.Soc. 1954, 76:2418～2421
9 马喜平．聚丙烯酰胺类阳离子聚合物的合成及应用．化学世界．1995(1)：588～591
10 陈秉铨，白玉文．阳离子聚丙烯酰胺絮凝剂的合成．太原工学院学报．1983(3)：75～83
11 谭业邦，张黎明．用高分子化学反应合成阳离子聚合物．精细石油化学．1998(4)：41～42
12 杨通在，刘亦农．阳离子型改性絮凝剂的结构及其性能．塑料工业．1998，26(2)：116～118
13 Huang S S. Evaluation of chemical structural heterogeneity of cationic acrylamide copolymers by high-performance liquid chromatography. Journal Chromatogr. 1991,536(1-2): 203～209
14 赵华章，高宝玉，岳钦艳．二甲基二烯丙基氯化铵(DMDAAC)聚合物的研究进展．工业水处理．1999，19(6)：1～4
15 Jaeger W, Hahn M. Polymerization of water-soluble cationic vinyl monomers. Macromol Symposium. 1996,111:95～106
16 张跃军，顾学芳．二甲基二烯丙基氯化铵与丙烯酰胺共聚物的研究进展．精细化工．2002，19(9)：521～527
17 Walter H S, Walter M T. Composition comprising a linear copolymer of a quaternary ammonium compound and an ethylenically unsaturated copolymerizable compound. US: 2 923 701,1960
18 许振举．二甲基二烯丙基氯化铵的制备方法．CN：1 051 169A，1990
19 权艳梅．DMDAAC合成及分析方法的改进．油田化学．1997，14(2)：159～161
20 Jerry E B. Synthesis of dimethyldiallyammonium chloride. US:3 461 169, 1969
21 郭四虎，宋建军．二甲基二烯丙基氯化铵的合成．山西化工．2001，21(4)：4～5，10
22 Algner H S. Continuous process for the preparation ofdimethyldially ammonium chloride. DE: 3 528 985,1987
23 王雅琼，王保成．二甲基二烯丙基氯化铵的合成．太原工业大学学报．1996，27(2)：86～89
24 Walter H S, Price J A, Moore S T.Soluble copolymers of diallyl monomers. Journal Chemical Engineering Data. 1959,4:273～276
25 Hawthorne D G, Solomn D H. Cyclopolymerization effect of β-substituents on the cyclopolymerization of diallylamines.Journal Macromolecule Science and Chemistry. 1976,A10:923
26 Wandrey C, Jaeger W, Reinisch G. The stucture studies of polydiallyl-dimethylammonium chloride. Acta Polymers. 1982,32:177
27 愈益平．二烯丙基胺类聚合物的研制和在石油开采中的应用．油田化学．1991，8(3)：194～199
28 潘祖仁．高分子化学．北京：化学工业出版社．1997：18～90
29 林尚生，陆耘，梁兆熙．高分子化学．北京：科学出版社．1998：583～655
30 摩西R B，卡拉赫C E．聚合物化学导论．河北：科技时代出版社．1988：37～87
31 Butler G B. Method of enhancing polymerization of diallyl dimethyl armnonium compounds to produce high-molecular-weight polymers. US: 4 742 134, 1998
32 顾学芳，张跃军．阳离子絮凝剂的合成与应用(1)．工业水处理．2001，1：22～25
33 吴全才．反相乳液聚合合成DMDAAC／AM阳离子型共聚物．沈阳化工学院学报．1996，10(1)：57～62
34 Keil K H, Engelhardt F. Copolymer process for its preparation and its use. EP: 232 519, 1987
35 Gartner H A, Herbert A. Process for the production of high molecular weight copolymers of diallylammonium monomers and acrylamide monomers in solution. US: 5 110 883, 1992
36 罗文利．高分子阳离子聚合物的制备．CN：1 246 487A，2000
37 Hurlock J R, Murphy C J. Improved DMDAAC-AM copolymers by radical copolymerisation of diallydimethylammonium chloride and acrylamide in water-in-oil. DE: 4 203 818, 1992
38 焦书科．聚合反应工程进展．杭州：浙江大学出版社，1993：21～45
39 吴全才．PDA阳离子型絮凝剂合成及应用的研究．工业水处理．1997，17(4)：
40～42
40 Welcher R P. Controlled polymerization of dimethyldiallylammonium halides by the use of alkali metal or ammonium bisulfiter or metabisufites. US: 4 092 467, 1978
41 Bhat T, Bhupat R. High molecular weight DMDA.AC polymers by inverse emulsion technology. US: 4 713 431,1987
42 Lipp D N, Kozakiewicz J J. Cationic microemulsified polymers.EP:374 457, 1990
43 Huang S Y, Duplaise D L, Kozakiewicz J J. Emulsified functionalized polymers. EP: 374 478, 1990
44 Kiyoshis S H, Toshio V. Polymer or copolymers from at least one diallylamine derivative. Ger Often: 2 416 675, 1975
45 Subramanian R, Zhu S, Pelton R H. Synthesis and flocculation performance of graft and random copolymer microgels of acrylamide and diallyldimethyl ammonium chloride. Colloid Polymer Science. 1999,277(10): 939～946
46 Hunter W E, Craun G P. Process for the manufacture of high solids, free-flowing, granular poly(dimethyldiallyl ammonium chloride). US: 4 654 378, 1999
47 Sinquin A,Velly M,Durand J P.Process for inhibiting or retarding the formation or hydrates in a production effluent such as natural gas or petroleum gases. EP: 807 806,1997
48 Allen S D; Lyman L R. Wastewater treatment process and apparatus for high flow impurity removal. WO: 98 23 538,1998
49 Sivakumar A,Muray P. Use of hydrophilic dispersion polymers for oily wastewater clarification. WO:00 04 970, 2000
50 Hasse R A. Method for dewatering of sludge. US: 5 846 435,1998
51 Guerro G, Dauplaise D.Methods and agents for improving paper print- ability and strength. US: 5 824 190, 1998
52 Malhotra S L, Naik K N. Coated xerographic photographic paper. EP: 877 298, 1998
53 Nguyen D T. Method for inhibiting deposition in pulp and papermaking systems using a composition comprising of polyvinyl alcohol, gelation and cationic polymer. US: 5 723 021,1998
54 Sutman F J, Chascin K J. Process for making a uniform dispersion of aramid fibers and polymer. WO: 99 02 770,1999
55 Henderson K F. Polyampholyte coagulant in the papermaking process. WO: 00 34
55 Henderson K F Polyampholyte coagulant in the papermaking process. WO: 00 34 581,2000
56 Kevv E M. Polymeric combinations used as copper and precious metal heap leaching agglomeration aids. US: 5 833 937,1998
57 Harmalker S, Klewsaat G, Aldrich T. Skin Cleansing composition com-prising a mixture of thinkening polymers. US: 6 150 313, 2000
58 Gosselink E P, Panandiker R K. Laundry detergent compositions with a cationically charged dye maintenance polymer. WO: 00 22 077, 2000
59 United states food and drug administration. Indirect food additive: adjuvants,production adis and sanitizers; antioxidants and/or stabili-zers for polymers. Fed Regist. 1982, 47(169):38274
60 Anon. Food additives. Fed Regist. 1971, 36(118): 11723～11724
61 Smerbeck R V, Johnson J R. Method and composition for protecting against jellyfish stings. US: 5 958 397, 1999
62 Hwang M H. Electro conductive polymer composition. US: 4 282 118, 1981
63 张爱华，许振举．二甲基二烯丙基氯化铵-丙烯酰胺共聚物．CN：1 051 366 1992
64 张德慧，许易安．阳离子型有机高分子絮凝剂DMDAAC的制备及应用．河南化工．1998，(10)：12～14
65 谭明乾，张跃军．DMDAAC／AM共聚物合成及其絮凝性能．化工时刊．1999，(12)：15～17
66 吕生华．二甲基二烯丙基氯化铵与丙烯酰胺共聚物的结构表征及应用．精细化工．2000，17(7)：386～387
67 赵华章．阳离子型高分子絮凝剂PDMDAAC与P(DMDAAC-AM)的合成及分析．精细化工．2001，18(11)：645～649
68 永泽满．高分子水处理剂(下)第一版．北京：化学工业出版社．1983：35～78
69 邢云杰．几种阳离子度PDA合成工艺的初步研究．南京理工大学硕士学位论．2001
70 刘瑛．20％阳离子度PDA聚合工艺及引发剂体系的初步研究．南京理工大学硕士学位论．2001
71 谭明乾．阳离子聚丙烯酰胺有机高分子絮凝剂的合成及应用研究．南京理工大学硕士论文．1999
72 顾学芳．30％阳离子度PDA的合成及应用研究．南京理工大学硕士学位论．2000
73 马喜平．聚丙烯酰胺类阳离子聚合物的合成及应用．化学世界．1995，(1)：
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