聚醚型聚氨酯胶粘剂的制备与性能研究
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摘要
本文以聚氧化丙烯二元醇(PPG2000、PPG600),聚氧化乙烯二元醇(PEG400、PEG1000)与二异氰酸酯(甲苯二异氰酸酯、异佛尔酮二异氰酸酯)以及扩链剂(1,4—丁二醇、异佛尔酮二胺)为主要原料,通过不同组合,在异丙醇/乙酸乙酯混合溶剂中合成出一系列硬段含量不同的醇溶型聚氨酯(PU)和聚氨酯脲(PUU)胶粘剂。采用不同分子量的混合聚醚、增加异氰酸酯与扩链剂的含量等方法调节硬段含量。用傅立叶红外光谱(FTIR)研究了PU和PUU的化学结构;用计算机分峰方法分析了它们的氢键化程度的影响因素;通过T型剥离强度测试,研究并比较了PU和PUU对不同材料的粘接性能。
1.使用PPG600/PPG2000混合聚醚时,随着PPG600含量的增大,聚氨酯中不完善氢键化的氨酯羰基含量有明显提高,PU中完善氢键化的氨酯羰基含量稍有增加,软段和硬段相容性增强;使用PEG400/PPG2000混合聚醚时,随着PEG400含量的增大,PUU中完全氢键化的脲羰基含量升高,当PEG400含量高于一定数量后,体系中完善氢键化的脲羰基含量降低,不完善氢键化的脲羰基含量增加,而氨酯羰基氢键化程度变化不明显。
2.增加异氰酸酯与扩链剂的用量时,PU和PUU中中更趋向于形成长硬段,此时完善氢键化的羰基含量变大,软硬段微相分离程度提高,不完善氢键化的羰基含量也有一定提高,
3.对BOPP、PET、PA三种薄膜的粘接研究中,含有脲基的PUU对于带有极性的材料(PET、PA)有较好的剥离强度,而以IPDI、丁二醇扩链制成的PU则对BOPP有较好的剥离强度。
In this paper, polypropylene glycol (PPG2000,PPG600),polyethylene glycol(PEG1000,PEG400)were used as the main polyether diol, toluene diisocyanate isophorone and diisocyanate were used as the main diisocyanate ,and isophorone diamine,1,4-BD were used as the main chain extender to synthesize ethanol-soluble polyurethane with different material in the solvent that mixed by isopropanol and ethyl acetate.Adjusted the hard segment content by mixing polyether diol, changing the amount of diisocynate and chain extender. The chemical structure of PU and PUU were studied by FTIR, the degree of hydrogen bonding of PU and PUU were studied by computer peak fitting,the adhesive property of PU and PUU to different material were studied by test of T peel strength.
1.When used mixed polyether diol PPG600/PPG2000, the degree of disordered hydrogen bonding of urethane carbonyl groups increased with increasing of PPG600 conten,the amount of ordered hydrogen bonding urethane carbonyl groups increased.There is a better compatibility between soft segment and hard segment. When used mixed polyeter diol PEG400 /PPG2000, the amount of ordered hydrogen bonding urea carbonyl groups increased ,but then the degree of ordered hydrogen bonding for urea carbonyl groups decreased and the degree of disordered hydrogen bonding increased with the increase of PEG400 content . The change in degree of hydrogen bonding for urethane carbonyl groups was not evident.
2.When the amount of diisocyanate and chain extender was increased ,PU was tend to has long hard segment.The degree of ordered hydrogen bonding and disordered hydrogen bonding were both increased, separation of hard segment and soft segment was increased.
3.Study on the adhesion of PU with PET, Nylon, BOPP. PUU which had urea carbonyl had greater peel strength(PET, Nylon) than PU.PU that synthesized with IPDI,1,4-BD had good peel strength to BOPP.
1.使用PPG600/PPG2000混合聚醚时,随着PPG600含量的增大,聚氨酯中不完善氢键化的氨酯羰基含量有明显提高,PU中完善氢键化的氨酯羰基含量稍有增加,软段和硬段相容性增强;使用PEG400/PPG2000混合聚醚时,随着PEG400含量的增大,PUU中完全氢键化的脲羰基含量升高,当PEG400含量高于一定数量后,体系中完善氢键化的脲羰基含量降低,不完善氢键化的脲羰基含量增加,而氨酯羰基氢键化程度变化不明显。
2.增加异氰酸酯与扩链剂的用量时,PU和PUU中中更趋向于形成长硬段,此时完善氢键化的羰基含量变大,软硬段微相分离程度提高,不完善氢键化的羰基含量也有一定提高,
3.对BOPP、PET、PA三种薄膜的粘接研究中,含有脲基的PUU对于带有极性的材料(PET、PA)有较好的剥离强度,而以IPDI、丁二醇扩链制成的PU则对BOPP有较好的剥离强度。
In this paper, polypropylene glycol (PPG2000,PPG600),polyethylene glycol(PEG1000,PEG400)were used as the main polyether diol, toluene diisocyanate isophorone and diisocyanate were used as the main diisocyanate ,and isophorone diamine,1,4-BD were used as the main chain extender to synthesize ethanol-soluble polyurethane with different material in the solvent that mixed by isopropanol and ethyl acetate.Adjusted the hard segment content by mixing polyether diol, changing the amount of diisocynate and chain extender. The chemical structure of PU and PUU were studied by FTIR, the degree of hydrogen bonding of PU and PUU were studied by computer peak fitting,the adhesive property of PU and PUU to different material were studied by test of T peel strength.
1.When used mixed polyether diol PPG600/PPG2000, the degree of disordered hydrogen bonding of urethane carbonyl groups increased with increasing of PPG600 conten,the amount of ordered hydrogen bonding urethane carbonyl groups increased.There is a better compatibility between soft segment and hard segment. When used mixed polyeter diol PEG400 /PPG2000, the amount of ordered hydrogen bonding urea carbonyl groups increased ,but then the degree of ordered hydrogen bonding for urea carbonyl groups decreased and the degree of disordered hydrogen bonding increased with the increase of PEG400 content . The change in degree of hydrogen bonding for urethane carbonyl groups was not evident.
2.When the amount of diisocyanate and chain extender was increased ,PU was tend to has long hard segment.The degree of ordered hydrogen bonding and disordered hydrogen bonding were both increased, separation of hard segment and soft segment was increased.
3.Study on the adhesion of PU with PET, Nylon, BOPP. PUU which had urea carbonyl had greater peel strength(PET, Nylon) than PU.PU that synthesized with IPDI,1,4-BD had good peel strength to BOPP.
引文
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[2]陈竹生.高分子材料科学与工程,1990,(3):26
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[12]孟舒献,温晓娜,邱训高等.化学工业与工程,2002,19(1):129
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[26]E.Potocka.Polymer,1968,2:895
[27]G.L.Wilkes.Macromolecules.1974,10:203
[28]H.Ighinara.Macromolecules,1974,10:591
[29]Wilkes.G.L.etal.Macromolecules,1981,14:456
[30]陶颖,朱景凤.河南化工,1999,(3):28
[31]汤嘉陵,张崇照,张蓉等.高分子材料科学与工程,1999,15(2):147
[32]武中正.聚氨酯工业,1996,2:11-13
[33]孟舒献,温晓娜,邱训高等.化学工业与工程,2002,19(1):129
[34]Macknight.Etal.Anal,Cacorimetry,Proc,Am,Chem,Soc,Symp,99(1998)
[35]杲云,张志平,应圣康等.合成橡胶工业,1995,18(1):19
[36]修玉英,罗钟瑜,王得宁等.华南理工大学学报(自然科学版),1997,25(8):44
[37]Katsuhiko Nakamae,Takashi Nishino,Seiji Asaoka.Adhesion and Adhesives,1996,16:233
[38]James T.Garrett,Ruijian Xu,Jaedong Cho.Polymer,2003,44:2711
[39]Matthew J.O'Sickey,Bruce D.Lawrey,Garth L.Wilkes.Polymer,2002,43:7399
[40]程时远等.聚氨酯工业,1992(10):3-6
[41]李绍雄,刘益君.聚氨酯胶粘剂,1998:231-307
[42]Bonart.Macromolecules.1969,3(2):337
[43]李建宗,李士杰.中国胶粘剂,2001,6(5):44
[44]胡巧玲,朱永群.中国胶粘剂,1996,6(6):7-11
[45]林道昌.聚氨酯工业,1999,14(2):47-49
[46]何曼君,陈维孝,董西侠.高分子物理.上海:复旦大学出版社,1990
[47]杨娟,王贵友,胡春圃.高分子学报,2003,6(6):794
[48]罗宁,王得宁,应圣康.合成橡胶工业,1995,18(4):200
[49]刘检仔,潘肇琦,华东理工大学科学学报(自然科学版).2006,32(10):1187-1191
[50]刘喜军,杨秀英,王慧敏.高分子实验教程.齐齐哈尔大学出版社,1995
[51]詹中贤,朱长春.聚氨酯工业.2005,20(1):17-20
[52]倪余伟,张松,冷静.涂料工业.2005,35(7):10-12
[53]李公峰.聚氨酯工业.1994,2:11-13
[54]王雪晨,应福麟.聚氨酯工业.1994,2:39-41
[55]邹德荣.合成材料老化与应用.2002,2:13-15
[56]黄志雄,彭永利.武汉化工学院学报.2002,24(2):41-43
[57]郭青,吴蓁.中国胶粘剂.2000,10(4):32-34
[58]洛桂娥.科技情报开发与经济.2005,15(23):159-160
[59]杨娟,王贵友,胡春圃.化学学报.2006,16(64):1737-1742
[60]刘美荣.天津轻工业学院学报.2002,9(3):18-22
[61]田雨,张杰.聚氨酯工业.2001,16(1):40-43
[2]陈竹生.高分子材料科学与工程,1990,(3):26
[3]刘凉冰.聚氨酯工业,2003,18(4):6
[4]李绍雄,刘益军.聚氨酯胶粘剂.化学工业出版社,1998
[5]工孟钟,黄应昌.胶粘剂应用手册.化学工业出版社,1987
[6][G]·厄特尔.聚氨酯手册.中国石化出版社,1998
[7]刘凯.聚氨酯工业,1994,(2):3
[8]任伟,徐海涛,杨勇.聚氨酯工业,2005,20(3):28
[9]山西省化工研究所编.聚氨酯弹性体手册.北京:化学工业出版社,2001
[10]徐培林.聚氨酯材料手册.北京:化学工业出版社,2002
[11]杨娟.聚氨酯脲和聚脲材料的研究.华东理工大学硕士论文,2003
[12]孟舒献,温晓娜,邱训高等.化学工业与工程,2002,19(1):129
[13]詹天贤,朱长春.聚氨酯工业,2003,18(4):25
[14]孟舒献,温晓娜,邱训高等.化学工业与工程,2002,19(1):129
[15]陈福泰,多英全,罗善国等.高分子材料科学与工程,2001,17(3):1
[16]Frontin P M.J Appl Polym Sci,1993,48:2003
[17]Cooper S L.J Appl Polym Sci,1966,10(12):1837
[18]Heprum.Polyurethane Elastomors.Applied Sci Publishers,London and NewYork,1982
[19]陈清元.高分子材料科学与工程,1998,13(2):100
[20]赵孝彬,杜磊,张小平等.高分子材料科学与工程,2002,18(2):16
[21]赵孝彬,杜磊,张小平.聚氨酯工业,2001,16(1):4
[22]宋常春.合肥工业大学学报(自然科学版),2001,24(2):234
[23]Luo N,Wang D N,Ying S K.Polymer,1996,37(16):3577
[24]罗宁,王得宁,应圣康.高分子学报,1996,(4):423
[25]R.D.Andreas.Polymer,1965,38(16):3665
[26]E.Potocka.Polymer,1968,2:895
[27]G.L.Wilkes.Macromolecules.1974,10:203
[28]H.Ighinara.Macromolecules,1974,10:591
[29]Wilkes.G.L.etal.Macromolecules,1981,14:456
[30]陶颖,朱景凤.河南化工,1999,(3):28
[31]汤嘉陵,张崇照,张蓉等.高分子材料科学与工程,1999,15(2):147
[32]武中正.聚氨酯工业,1996,2:11-13
[33]孟舒献,温晓娜,邱训高等.化学工业与工程,2002,19(1):129
[34]Macknight.Etal.Anal,Cacorimetry,Proc,Am,Chem,Soc,Symp,99(1998)
[35]杲云,张志平,应圣康等.合成橡胶工业,1995,18(1):19
[36]修玉英,罗钟瑜,王得宁等.华南理工大学学报(自然科学版),1997,25(8):44
[37]Katsuhiko Nakamae,Takashi Nishino,Seiji Asaoka.Adhesion and Adhesives,1996,16:233
[38]James T.Garrett,Ruijian Xu,Jaedong Cho.Polymer,2003,44:2711
[39]Matthew J.O'Sickey,Bruce D.Lawrey,Garth L.Wilkes.Polymer,2002,43:7399
[40]程时远等.聚氨酯工业,1992(10):3-6
[41]李绍雄,刘益君.聚氨酯胶粘剂,1998:231-307
[42]Bonart.Macromolecules.1969,3(2):337
[43]李建宗,李士杰.中国胶粘剂,2001,6(5):44
[44]胡巧玲,朱永群.中国胶粘剂,1996,6(6):7-11
[45]林道昌.聚氨酯工业,1999,14(2):47-49
[46]何曼君,陈维孝,董西侠.高分子物理.上海:复旦大学出版社,1990
[47]杨娟,王贵友,胡春圃.高分子学报,2003,6(6):794
[48]罗宁,王得宁,应圣康.合成橡胶工业,1995,18(4):200
[49]刘检仔,潘肇琦,华东理工大学科学学报(自然科学版).2006,32(10):1187-1191
[50]刘喜军,杨秀英,王慧敏.高分子实验教程.齐齐哈尔大学出版社,1995
[51]詹中贤,朱长春.聚氨酯工业.2005,20(1):17-20
[52]倪余伟,张松,冷静.涂料工业.2005,35(7):10-12
[53]李公峰.聚氨酯工业.1994,2:11-13
[54]王雪晨,应福麟.聚氨酯工业.1994,2:39-41
[55]邹德荣.合成材料老化与应用.2002,2:13-15
[56]黄志雄,彭永利.武汉化工学院学报.2002,24(2):41-43
[57]郭青,吴蓁.中国胶粘剂.2000,10(4):32-34
[58]洛桂娥.科技情报开发与经济.2005,15(23):159-160
[59]杨娟,王贵友,胡春圃.化学学报.2006,16(64):1737-1742
[60]刘美荣.天津轻工业学院学报.2002,9(3):18-22
[61]田雨,张杰.聚氨酯工业.2001,16(1):40-43