大分子单体法合成反应性双亲聚合物
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摘要
本文合成了疏水缔合型聚氨酯大分子单体(HTP)，研究了大单体的溶液性
质，发现其在溶液中的形态对温度和浓度甚为敏感，在适宜的条件下，该大单
体可以形成胶束结构，并且其单端疏水双键蜷曲于胶束内部，有利于与增溶于
其中的小单体实施共聚。尝试了乳液、微乳和溶剂三种聚合方法实现小单体与
亲水大单体共聚。讨论了种子乳液聚合工艺及后处理对乳胶膜亲水性能的影响。
探索了微乳聚合工艺，合成了单分散双亲聚合物微球。以双亲性溶剂丙二醇甲
醚(PM)进行溶剂聚合，合成了大单体接枝的双亲聚合物。采用粘度法研究了大
单体与双亲聚合物在溶液中的形态及聚集态结构。差热扫描量热法(DSC)研究了
大单体及双亲聚合物热行为，证实了合成双亲聚合物存在微观相分离；透射电
镜(TEM)观察了乳胶型貌。
A water-soluble HTP macromonomer is synthesized starting from polyethylene glycol oxide, 2,4-toluene diisocyanate, using hydroxyethyl acrylate as end chain termination agent. It is revealed that the intrinsic viscosity of its aqueous solution and cloud point will be lower, and association of macromonomer will be apparent as hydrophobic mass fraction of the macromonomer is increased. It is also found that the conformation of HTP macromonomer in aqueous solution is dependent on temperature and concentration. Hydrophobic association occurs between macromonomer itself as the concentration of aqueous solution is increased. At higher temperature the HLB value of the macromonomer becomes lower, and micelle forms at the temperature over 75.
Micromonomer and hydrophilic macromonomer is copolymerized by using emulsification, microemulsification, and solution polmerization. Polymerization technics and the effect of neutralization and curing on hydrophilicity and long-term hydrophilicity of latex are studied in this paper. Polymerization technics is also studied for microemulsification. Synthesis of amphiphilic copolymer by using propylene glycol methyl ether and its solution's properties have been studied.
质，发现其在溶液中的形态对温度和浓度甚为敏感，在适宜的条件下，该大单
体可以形成胶束结构，并且其单端疏水双键蜷曲于胶束内部，有利于与增溶于
其中的小单体实施共聚。尝试了乳液、微乳和溶剂三种聚合方法实现小单体与
亲水大单体共聚。讨论了种子乳液聚合工艺及后处理对乳胶膜亲水性能的影响。
探索了微乳聚合工艺，合成了单分散双亲聚合物微球。以双亲性溶剂丙二醇甲
醚(PM)进行溶剂聚合，合成了大单体接枝的双亲聚合物。采用粘度法研究了大
单体与双亲聚合物在溶液中的形态及聚集态结构。差热扫描量热法(DSC)研究了
大单体及双亲聚合物热行为，证实了合成双亲聚合物存在微观相分离；透射电
镜(TEM)观察了乳胶型貌。
A water-soluble HTP macromonomer is synthesized starting from polyethylene glycol oxide, 2,4-toluene diisocyanate, using hydroxyethyl acrylate as end chain termination agent. It is revealed that the intrinsic viscosity of its aqueous solution and cloud point will be lower, and association of macromonomer will be apparent as hydrophobic mass fraction of the macromonomer is increased. It is also found that the conformation of HTP macromonomer in aqueous solution is dependent on temperature and concentration. Hydrophobic association occurs between macromonomer itself as the concentration of aqueous solution is increased. At higher temperature the HLB value of the macromonomer becomes lower, and micelle forms at the temperature over 75.
Micromonomer and hydrophilic macromonomer is copolymerized by using emulsification, microemulsification, and solution polmerization. Polymerization technics and the effect of neutralization and curing on hydrophilicity and long-term hydrophilicity of latex are studied in this paper. Polymerization technics is also studied for microemulsification. Synthesis of amphiphilic copolymer by using propylene glycol methyl ether and its solution's properties have been studied.
引文
[1] Zhou Z, Chu B, Peiffer D G. Macromolecules[J], 1993, 26. 1 876;
[2] Nguyen D, Williams C E, Eisenbery A. Macromolecules [J], 1994, 27. 5090
[3] Yanhui M, Ti C, Webber S E. Macromolecules [J], 1998, 31. 1773
[4] QIU Yong-Xing(邱永兴), YU Xiao-Jie(俞小洁), FENG Lin-Xian(封麟先), et al. Acta Polymerica. Sinica(高分子学报)[J], 1994, (6): 694
[5] Meldal M. Tetrahedron Letter[J], 1996, 37:6185
[6] Qiu Yong-Xing(邱永兴), YU Xiao-Jie(俞小洁), FENG Lin-Xian(封麟先). Acta Polymerica. Sinica(高分子学报)[J], 1993 11(1): 67
[7] Rempp P F. Adv. Polym. Sci. [J], 1984, 58:42
[8] Baines F L, Dionsio S, Billingham N C. Macromolecules[J], 1996, 29:3096
[9] Wesslen B. Biomaterials[J], 1994, 15:278
[10] Wesslen B, Wesslen K B. dPolym Sci Part A[J], 1989, 27:3915
[11] Lundsted L G. US Pat 2 674 619
[12] Lee J H, et al. Prog Polym Sci[J], 1995, 20:1043
[13] Vaughn T H, et al. J Am Oil Chem Soc, 1951, 28:294
[14] Vaughn T H, Lundsted L G, et al. J Am Oil Chem Soc[J], 1952, 29:290
[15] Schrnolka I R. J Colloid Interface Sci [J], 1974, 46:518
[16] Riess G. Macromol Chen, Suppl [J], 1985, 13:157
[17] Shimura Y, Lin W S, J Polym Sci Part A[J], 1970, 8:2171
[18] Xie H Q, Chen X Y, Guo J S. Angew Makcromol Chem [J], 1992, 200:49
[19] Xie H Q, Tao X Q, Guo J S. J Appl Polym Sci [J], 1996, 61:407
[20] Vulic L, Loman A J B, Feijen K. J Polym Sci Part A, Polym Chem[J], 1990, 28: 1693
[21] Koyo H, Hirai H, Tsuruta T, et al. Macromol Chem Rapid Commun [J], 1993, 14: 195
[22] Yedlinski Z, Kurcok P, Walach W, et al. Macromol Chem [J], 1993, 194: 1681
[23] Kayiya T, Narisawa S, Maeda T, et al. J Polym Sci Part C, Polym Lett[J], 1996, 4: 257
[24] Kobayashi S. Prog Polym Sci [J], 1990, 15:751
[25] Schulz R. Macromol Chem, Macromol Symp [J], 1993, 73: 103
[26] Kobayashi S, Uyama H, Liu D R, et al. Macromoclecules [J], 1990, 23: 5075
[27] Liu Q, Wilson G R, Davis R M, et al. Polym [J], 1993, 34:3030
[28] Seung S, Young R. Polym Bull [J], 1979, 1:481
[29] Seung S, Young R. J Polym Sci Part C, Polym Lett [J], 1980, 18:89
[30] Percec V, Guhaniyogi S C, Kennedy J P, et al. Polym Bull [J], 1982, 1: 25
[31] Minoda M, Sawamoto M, Higashimura T. Macromolecules[J], 1987, 20: 2045
[32] Kanaoka S, Minoda M, et al. J Polym Sci Part A, Polym Chem[J], 1990, 28: 1127
[33] Sawamoto S, Higashimura T. Macromol Chem, Macromol Syrup [J], 1990, 32: 131
[34] Kanaoka S, Sawamotos S, Higashimura T. Macromolecules [J], 1991, 24: 5741
[35] Qiu YX, Yu XJ, Feng LX. Acta Polymerica Sinica, 1993, 11(1): 67[邱永兴，俞小洁，封麟先．高分子学报(Gaofenzi Xuebao)[J], 1993, 11(1): 67]
[36] Higashimara T, Nakamura T, Aoshita S. Polym Bull[J], 1993, 31:317
[37] Gao Bo, Wesslen B, Wesslen K B. J Polm Sci Part A, Polym Chem[J], 1992, 30: 1799
[38] Jannasch P, Wesslen B. J Polym Sci Part A, Polym Chem[J], 1993, 31: 1519
[39] Jannasch P, Gunnarsson O, Wesslen B. JPolym Sci Part A, Polym Chem [J], 1996, 59: 619
[40] 计剑，孙永红，全凤芹，等．高等化学学报[J]，1997，18：1899
[41] Wesslen B, Wesslen K B. J Polym Sci Part A, Polym Chem [J], 1989, 27: 3915
[42] Yamashita S, Kodama K, Ikeda Y, et at. J Polym Sci Part A, Polym Chen [J], 1993, 31: 2437
[43] Yuko Ikeda, et al. J Polym Sci Part A, Polym Chem[J], 1995, 33:387
[44] Xie Zhiyuan, et al. J Appl Polym Sci [J], 1996, 1:61
[45] Hallden A, Wesslen B, J Appl Polym Sci[J], 1996, 60:2495
[46] Kobayashi S, Kaku M, Sawada S, et al. Poly Bull [J], 1984, 11:253
[47] Kobayashi S, Uyama H, Narita Y. Macromolecules[J], 1992, 23:353
[48] Kobayashi S, Masuda E, Shoda S, et al. Macromolecules[J], 1989, 22:2878
[49] Shoda S, Masuda E, Kobayashi S, et al. J Polym Sci Part A, Polym, Chem [J], 1991, 30:1489
[50] Saegusa T, Kobayashi S, J Macromol Sci Chem [J], 1984, A21:1021
[51] Gnanou Y, Hild G, Rempp P. Macromolecules [J], 1984, 17:945
[52] Slowikowaka I, Danicwska I. J Polym Sci, Polym Symp [J], 1975, 53:187
[53] 姚康德．高技术有机高分子材料进展．化学工业出版社，1994
[54] Belcheva N, Zlatkov T, Panayotoy I, et al. Polym[J], 1993, 34:2213
[55] 周爱娟，等．铝亲水抗蚀有机膜的制备及亲水性表征[J]．沈阳化工学院学报，1996，(1)：21
[56] 史兴利．史兴利硕士论文[D]．长沙：中南工业大学，1998
[57] 关鲁雄，黄可龙，靳湘军，等．中南工业大学学报[J]，1997，28(3)：298
[58] 陈立新．涂料工业[J]，1999，(9)：10
[59] 东南大学，中国专利，1342732A
[60] 蒋惮杰，黄可龙，潘春跃．华侨大学学报(自然科学版)[J]，2002，23(1)：31
[61] 蒋惮杰，黄可龙，潘春跃．华侨大学学报(自然科学版)[J]，2002，23(2)：133
[62] Hill A, Candau F, Joeseph S. Macromolecules, 1993, 26:4521
[63] Turner S R, Jan Bock. U S Patent, 4528348, 1985
[64] 方治齐，陈宏伟，刘春华，等．高分子材料与工程[J]，2002，18(6)：196
[65] 方治齐，董其宝，刘春华，等．应用化学[J]，付印中
[66] Zana R. Surfactant Solutions, New Methods of Investigation [M]. New York and Basel: Marcel Deckker, Inc., 1987
[67] Anagopoulos D, Dondos A. Eur. Polym. J[J], 1995, 31(10): 977
[68] A. W. Adamson, Physical of Surfaces, John-Wiley, 1976.
[69] 尹芬芳，史林启，安英丽，等．高等化学学报[J]，2003，24(1)：160
[70] 何曼君，陈维孝，董西侠．高分子物理，复旦大学出版社，1990
[71] 陈永春，陈超，曹红燕，等．应用化学[J]，2002，19(7)：662
[2] Nguyen D, Williams C E, Eisenbery A. Macromolecules [J], 1994, 27. 5090
[3] Yanhui M, Ti C, Webber S E. Macromolecules [J], 1998, 31. 1773
[4] QIU Yong-Xing(邱永兴), YU Xiao-Jie(俞小洁), FENG Lin-Xian(封麟先), et al. Acta Polymerica. Sinica(高分子学报)[J], 1994, (6): 694
[5] Meldal M. Tetrahedron Letter[J], 1996, 37:6185
[6] Qiu Yong-Xing(邱永兴), YU Xiao-Jie(俞小洁), FENG Lin-Xian(封麟先). Acta Polymerica. Sinica(高分子学报)[J], 1993 11(1): 67
[7] Rempp P F. Adv. Polym. Sci. [J], 1984, 58:42
[8] Baines F L, Dionsio S, Billingham N C. Macromolecules[J], 1996, 29:3096
[9] Wesslen B. Biomaterials[J], 1994, 15:278
[10] Wesslen B, Wesslen K B. dPolym Sci Part A[J], 1989, 27:3915
[11] Lundsted L G. US Pat 2 674 619
[12] Lee J H, et al. Prog Polym Sci[J], 1995, 20:1043
[13] Vaughn T H, et al. J Am Oil Chem Soc, 1951, 28:294
[14] Vaughn T H, Lundsted L G, et al. J Am Oil Chem Soc[J], 1952, 29:290
[15] Schrnolka I R. J Colloid Interface Sci [J], 1974, 46:518
[16] Riess G. Macromol Chen, Suppl [J], 1985, 13:157
[17] Shimura Y, Lin W S, J Polym Sci Part A[J], 1970, 8:2171
[18] Xie H Q, Chen X Y, Guo J S. Angew Makcromol Chem [J], 1992, 200:49
[19] Xie H Q, Tao X Q, Guo J S. J Appl Polym Sci [J], 1996, 61:407
[20] Vulic L, Loman A J B, Feijen K. J Polym Sci Part A, Polym Chem[J], 1990, 28: 1693
[21] Koyo H, Hirai H, Tsuruta T, et al. Macromol Chem Rapid Commun [J], 1993, 14: 195
[22] Yedlinski Z, Kurcok P, Walach W, et al. Macromol Chem [J], 1993, 194: 1681
[23] Kayiya T, Narisawa S, Maeda T, et al. J Polym Sci Part C, Polym Lett[J], 1996, 4: 257
[24] Kobayashi S. Prog Polym Sci [J], 1990, 15:751
[25] Schulz R. Macromol Chem, Macromol Symp [J], 1993, 73: 103
[26] Kobayashi S, Uyama H, Liu D R, et al. Macromoclecules [J], 1990, 23: 5075
[27] Liu Q, Wilson G R, Davis R M, et al. Polym [J], 1993, 34:3030
[28] Seung S, Young R. Polym Bull [J], 1979, 1:481
[29] Seung S, Young R. J Polym Sci Part C, Polym Lett [J], 1980, 18:89
[30] Percec V, Guhaniyogi S C, Kennedy J P, et al. Polym Bull [J], 1982, 1: 25
[31] Minoda M, Sawamoto M, Higashimura T. Macromolecules[J], 1987, 20: 2045
[32] Kanaoka S, Minoda M, et al. J Polym Sci Part A, Polym Chem[J], 1990, 28: 1127
[33] Sawamoto S, Higashimura T. Macromol Chem, Macromol Syrup [J], 1990, 32: 131
[34] Kanaoka S, Sawamotos S, Higashimura T. Macromolecules [J], 1991, 24: 5741
[35] Qiu YX, Yu XJ, Feng LX. Acta Polymerica Sinica, 1993, 11(1): 67[邱永兴，俞小洁，封麟先．高分子学报(Gaofenzi Xuebao)[J], 1993, 11(1): 67]
[36] Higashimara T, Nakamura T, Aoshita S. Polym Bull[J], 1993, 31:317
[37] Gao Bo, Wesslen B, Wesslen K B. J Polm Sci Part A, Polym Chem[J], 1992, 30: 1799
[38] Jannasch P, Wesslen B. J Polym Sci Part A, Polym Chem[J], 1993, 31: 1519
[39] Jannasch P, Gunnarsson O, Wesslen B. JPolym Sci Part A, Polym Chem [J], 1996, 59: 619
[40] 计剑，孙永红，全凤芹，等．高等化学学报[J]，1997，18：1899
[41] Wesslen B, Wesslen K B. J Polym Sci Part A, Polym Chem [J], 1989, 27: 3915
[42] Yamashita S, Kodama K, Ikeda Y, et at. J Polym Sci Part A, Polym Chen [J], 1993, 31: 2437
[43] Yuko Ikeda, et al. J Polym Sci Part A, Polym Chem[J], 1995, 33:387
[44] Xie Zhiyuan, et al. J Appl Polym Sci [J], 1996, 1:61
[45] Hallden A, Wesslen B, J Appl Polym Sci[J], 1996, 60:2495
[46] Kobayashi S, Kaku M, Sawada S, et al. Poly Bull [J], 1984, 11:253
[47] Kobayashi S, Uyama H, Narita Y. Macromolecules[J], 1992, 23:353
[48] Kobayashi S, Masuda E, Shoda S, et al. Macromolecules[J], 1989, 22:2878
[49] Shoda S, Masuda E, Kobayashi S, et al. J Polym Sci Part A, Polym, Chem [J], 1991, 30:1489
[50] Saegusa T, Kobayashi S, J Macromol Sci Chem [J], 1984, A21:1021
[51] Gnanou Y, Hild G, Rempp P. Macromolecules [J], 1984, 17:945
[52] Slowikowaka I, Danicwska I. J Polym Sci, Polym Symp [J], 1975, 53:187
[53] 姚康德．高技术有机高分子材料进展．化学工业出版社，1994
[54] Belcheva N, Zlatkov T, Panayotoy I, et al. Polym[J], 1993, 34:2213
[55] 周爱娟，等．铝亲水抗蚀有机膜的制备及亲水性表征[J]．沈阳化工学院学报，1996，(1)：21
[56] 史兴利．史兴利硕士论文[D]．长沙：中南工业大学，1998
[57] 关鲁雄，黄可龙，靳湘军，等．中南工业大学学报[J]，1997，28(3)：298
[58] 陈立新．涂料工业[J]，1999，(9)：10
[59] 东南大学，中国专利，1342732A
[60] 蒋惮杰，黄可龙，潘春跃．华侨大学学报(自然科学版)[J]，2002，23(1)：31
[61] 蒋惮杰，黄可龙，潘春跃．华侨大学学报(自然科学版)[J]，2002，23(2)：133
[62] Hill A, Candau F, Joeseph S. Macromolecules, 1993, 26:4521
[63] Turner S R, Jan Bock. U S Patent, 4528348, 1985
[64] 方治齐，陈宏伟，刘春华，等．高分子材料与工程[J]，2002，18(6)：196
[65] 方治齐，董其宝，刘春华，等．应用化学[J]，付印中
[66] Zana R. Surfactant Solutions, New Methods of Investigation [M]. New York and Basel: Marcel Deckker, Inc., 1987
[67] Anagopoulos D, Dondos A. Eur. Polym. J[J], 1995, 31(10): 977
[68] A. W. Adamson, Physical of Surfaces, John-Wiley, 1976.
[69] 尹芬芳，史林启，安英丽，等．高等化学学报[J]，2003，24(1)：160
[70] 何曼君，陈维孝，董西侠．高分子物理，复旦大学出版社，1990
[71] 陈永春，陈超，曹红燕，等．应用化学[J]，2002，19(7)：662