CN107353384A - 含有侧链苯的水性聚氨酯及其制备方法 - Google Patents

含有侧链苯的水性聚氨酯及其制备方法 Download PDF

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CN107353384A
CN107353384A CN201710575637.7A CN201710575637A CN107353384A CN 107353384 A CN107353384 A CN 107353384A CN 201710575637 A CN201710575637 A CN 201710575637A CN 107353384 A CN107353384 A CN 107353384A
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polyurethane prepolymer
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benzene
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CN107353384B (zh
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陶灿
徐杰
王继印
戎佳萌
贾娟
潘轸
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Anhui Cenxing Material Technology Co ltd
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HEFEI SIJINGQI CHEMICAL MATERIALS Co Ltd
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Abstract

本发明公开了一种含有侧链苯水性聚氨酯及其制备方法,该方法包括以下步骤:将大分子二元醇、二异氰酸酯、聚合侧链苯单体于90~100℃反应2~4h,得到聚氨酯预聚物a1;向其中加入小分子扩链剂、亲水扩链剂I、溶剂、催化剂,于60~80℃反应4~7h,得到水性聚氨酯预聚体a2;再加入溶剂和亲水扩链剂II,于50~60℃反应0.5~1h,得到水性聚氨酯预聚体a3;再加入溶剂,高速剪切下加入成盐剂,搅拌1~5min后加入水高速分散乳化5~10min后在真空下脱除溶剂,即得含有侧链苯水性聚氨酯。本发明通过在聚氨酯上引入侧链苯,使得水性聚氨酯对PET、PP、PE等难粘材料具有优异的附着力;另外,本发明制得的水性聚氨酯具有优异的耐热性,可以在不添加固化剂下保持80℃不发粘,并且乳液具有优异的耐研磨性。

Description

含有侧链苯的水性聚氨酯及其制备方法
技术领域
本发明涉及水性聚氨酯领域,尤其涉及一种含有侧链苯水性聚氨酯及其制备方法。
背景技术
水性聚氨酯是由含羟基、羧基、氨基等官能团的化合物与含异氰酸酯基化合物反应得到的高分子化合物,分子主链中除含有许多重复的氨基甲酸酯键外,还含有醚键、酯键等。水性聚氨酯被誉为性能最优异的树脂,如高硬度、耐磨损、柔韧性好、耐化学品、附着力强、成膜温度低、可在室温固化等,已在涂料,皮革涂饰,胶黏剂行业得到广泛应用。。但是,水性聚氨酯对PET,PP以及PE等难粘材料的附着力是目前难以解决的问题之一。
发明内容
有鉴于此,本发明的目的是提供一种含有侧链苯水性聚氨酯及其制备方法,对PET,PP以及PE等难粘材料的附着力。
为了实现上述目的,本发明提供如下技术方案:
一种含有侧链苯水性聚氨酯的制备方法,包括以下步骤:
a)将大分子二元醇、二异氰酸酯、聚合侧链苯单体于90~100℃反应2~4h,得到聚氨酯预聚物a1
b)向步骤a)得到的聚氨酯预聚物a1中加入小分子扩链剂、亲水扩链剂I、溶剂、催化剂,于60~80℃反应4~7h,得到水性聚氨酯预聚体a2
c)向步骤b)得到的水性聚氨酯预聚体a2中加入溶剂和亲水扩链剂II,于 50~60℃反应0.5~1h,得到水性聚氨酯预聚体a3
d)向步骤c)得到的水性聚氨酯预聚体a3中加入溶剂,高速剪切下加入成盐剂,搅拌1~5min后加入水高速分散乳化5~10min后在真空下脱除溶剂,即得含有侧链苯水性聚氨酯。
优选地,所述大分子多元醇选自苯酐聚酯二元醇、聚碳酸酯二元醇、聚己内酯二元醇、端羟基聚丁二烯二元醇、聚己二酸新戊二醇酯二醇、聚己二酸-3- 甲基-1,5-戊二醇酯二醇中的一种或几种。
优选地,所述聚合侧链苯单体选自 中的一种或多种。
优选地,所述二异氰酸酯为甲苯二异氰酸酯、异佛尔酮二异氰酸酯、1,6-六亚甲基二异氰酸酯、4,4`-二苯基甲烷二异氰酸酯或4,4'-二环己基甲烷二异氰酸酯。
优选地,所述小分子扩链剂为1,6环己二甲醇、1,6-己二醇、3-甲基-1,5-戊二醇、1,4丁二醇、新戊二醇或三甲基戊二醇。
优选地,所述亲水扩链剂I为二羟甲基丙酸或二羟甲基丁酸;
所述亲水扩链剂II为乙二胺基磺酸钠。
优选地,所述催化剂选自辛酸亚锡、二月桂酸正丁基锡、有机Bi盐催化剂、有机Zn盐催化剂中的一种或几种。
优选地,所述成盐剂为三乙胺、N,N二甲基乙醇胺、氢氧化钠或氢氧化钾。
优选地,步骤b)、步骤c)和步骤d)中,所述溶剂均独立地选自丙酮或丁酮。
本发明还提供了一种含有侧链苯水性聚氨酯,采用上述含有侧链苯水性聚氨酯及其制备方法制得。
本发明提供的一种含有侧链苯水性聚氨酯及其制备方法,该方法包括以下步骤:将大分子二元醇、二异氰酸酯、聚合侧链苯单体于90~100℃反应2~4h,得到聚氨酯预聚物a1;向其中加入小分子扩链剂、亲水扩链剂I、溶剂、催化剂,于60~80℃反应4~7h,得到水性聚氨酯预聚体a2;再加入溶剂和亲水扩链剂II,于50~60℃反应0.5~1h,得到水性聚氨酯预聚体a3;再加入溶剂,高速剪切下加入成盐剂,搅拌1~5min后加入水高速分散乳化5~10min后在真空下脱除溶剂,即得含有侧链苯水性聚氨酯。本发明通过在聚氨酯上引入侧链苯,使得水性聚氨酯对PET、PP、PE等难粘材料具有优异的附着力;另外,本发明制得的水性聚氨酯具有优异的耐热性,可以在不添加固化剂下保持80℃不发粘,并且乳液具有优异的耐研磨性。
具体实施方式
为了进一步了解本发明,下面结合实施例对本发明的优选实施方案进行描述,但是应当理解,这些描述只是为进一步说明本发明的特征和优点而不是对本发明专利要求的限制。
本发明提供了一种含有侧链苯水性聚氨酯及其制备方法,包括以下步骤:
a)将大分子二元醇、二异氰酸酯、聚合侧链苯单体于90~100℃反应2~4h,得到聚氨酯预聚物a1
b)向步骤a)得到的聚氨酯预聚物a1中加入小分子扩链剂、亲水扩链剂I、溶剂、催化剂,于60~80℃反应4~7h,得到水性聚氨酯预聚体a2
c)向步骤b)得到的水性聚氨酯预聚体a2中加入溶剂和亲水扩链剂II,于 50~60℃反应0.5~1h,得到水性聚氨酯预聚体a3
d)向步骤c)得到的水性聚氨酯预聚体a3中加入溶剂,高速剪切下加入成盐剂,搅拌1~5min后加入水高速分散乳化5~10min后在真空下脱除溶剂,即得含有侧链苯水性聚氨酯。
上述技术方案中,通过在聚氨酯上引入侧链苯,使得水性聚氨酯对PET、 PP、PE等难粘材料具有优异的附着力;另外,本发明制得的水性聚氨酯具有优异的耐热性,可以在不添加固化剂下保持80℃不发粘还具有优异的耐研磨性。
将大分子二元醇、二异氰酸酯、聚合侧链苯单体于90~100℃反应2~4h,得到聚氨酯预聚物a1
在本发明的实施例中,大分子多元醇选自苯酐聚酯二元醇、聚碳酸酯二元醇、聚己内酯二元醇、端羟基聚丁二烯二元醇、聚己二酸新戊二醇酯二醇、聚己二酸-3-甲基-1,5-戊二醇酯二醇中的一种或几种;在其实施例中,大分子多元醇的相对分子量为1000~4000;在另外的实施例中,大分子多元醇的相对分子量为2000。
在本发明的实施例中,二异氰酸酯为甲苯二异氰酸酯、异佛尔酮二异氰酸酯、1,6-六亚甲基二异氰酸酯、4,4`-二苯基甲烷二异氰酸酯或4,4'-二环己基甲烷二异氰酸酯。
在本发明的实施例中,聚合侧链苯单体选自 中的一种或多种。
得到聚氨酯预聚物a1后,向其中加入小分子扩链剂、亲水扩链剂I、溶剂、催化剂,于60~80℃反应4~7h,得到水性聚氨酯预聚体a2
在本发明的实施例中,小分子扩链剂为1,6环己二甲醇、1,6-己二醇、3-甲基-1,5-戊二醇、1,4丁二醇、新戊二醇或三甲基戊二醇;在其他实施例中,小分子扩链剂的重量份数为3-甲基-1,5-戊二醇。
在本发明的实施例中,亲水扩链剂I为二羟甲基丙酸或二羟甲基丁酸;在其他实施例中,亲水扩链剂为二羟甲基丙酸。
在本发明的实施例中,催化剂选自辛酸亚锡、二月桂酸正丁基锡、有机Bi 盐催化剂、有机Zn盐催化剂中的一种或几种;在其他实施例中,有机Bi盐催化剂为异辛酸铋,月桂芁酸铋或新癸酸铋;有机Zn盐催化剂为二甲基锌或二乙基锌。
在本发明的实施例中,步骤b)中,溶剂为丙酮或丁酮。
得到的水性聚氨酯预聚体a2后,向其中加入溶剂和亲水扩链剂II,于 50~60℃反应0.5~1h,得到水性聚氨酯预聚体a3
在本发明的实施例中,溶剂同上所述,在此不再赘述。
在本发明的实施例中,亲水扩链剂II为乙二胺基磺酸钠。
得到水性聚氨酯预聚体a3后,向其中加入溶剂,高速剪切下加入成盐剂,搅拌1~5min后加入水高速分散乳化5~10min后在真空下脱除溶剂,即得含有侧链苯水性聚氨酯。
在本发明的实施例中,溶剂同上所述,在此不再赘述。
在本发明的实施例中,成盐剂为三乙胺、N,N二甲基乙醇胺、氢氧化钠或氢氧化钾;在其他实施例中,成盐剂为三乙胺。
在本发明的实施例中,大分子二元醇、二异氰酸酯、聚合侧链苯单体、小分子扩链剂、亲水扩链剂I、催化剂、亲水扩链剂II、成盐剂与水的质量比为 (40~60):(20~30):(6~20):(2~15):(2~5):(0.1~0.3):(1~5): (0.8~5):(80~100)。
在本发明的实施例中,步骤b)中溶剂、步骤c)中溶剂、步骤d)中溶剂与二异氰酸酯的质量比为(2~3):(0.8~1.2):(1.6~2.8):1。
本发明还提供了一种含有侧链苯水性聚氨酯,采用上述方法制得。
本发明提供的水性聚氨酯对PET、PP、PE等难粘材料具有优异的附着力,还具有优异的耐热性,可以在不添加固化剂下保持80℃不发粘还具有优异的耐研磨性。
说明本发明,下面结合实施例对本发明提供的含有侧链苯水性聚氨酯及其制备方法进行详细地描述,但不能将它们理解为对本发明保护范围的限定。
实施例1
a)将相对分子量为1000苯酐聚酯二元醇、异佛尔酮二异氰酸酯、于90℃反应4h,得到聚氨酯预聚物a1
b)向步骤a)得到的聚氨酯预聚物a1中加入3-甲基-1,5-戊二醇、二羟甲基丙酸、丙酮、辛酸亚锡,于60℃反应7h,得到水性聚氨酯预聚体a2
c)向步骤b)得到的水性聚氨酯预聚体a2中加入丙酮和乙二胺基磺酸钠,于50℃反应1h,得到水性聚氨酯预聚体a3
d)向步骤c)得到的水性聚氨酯预聚体a3中加入丁酮,高速剪切下加入N,N 二甲基乙醇胺,搅拌5min后加入水高速分散乳化7min,然后在真空下脱除溶剂,即得含有侧链苯水性聚氨酯;
苯酐聚酯二元醇、异佛尔酮二异氰酸酯、3-甲基-1,5-戊二醇、二羟甲基丙酸、辛酸亚锡、乙二胺基磺酸钠、N,N二甲基乙醇胺与水的质量比为40:30:6:15:2:0.1:1:5:80;
步骤b)中丙酮、步骤c)中丙酮、步骤d)中丁酮与异佛尔酮二异氰酸酯的质量比为2:0.8:1.6:1。
实施例2
a)将相对分子量为2000聚碳酸酯二元醇、相对分子量为3000聚己内酯二元醇、4,4'-二环己基甲烷二异氰酸酯、于100℃反应2h,得到聚氨酯预聚物a1
b)向步骤a)得到的聚氨酯预聚物a1中加入3-甲基-1,5-戊二醇、二羟甲基丁酸、丁酮、二月桂酸正丁基锡,于80℃反应4h,得到水性聚氨酯预聚体a2
c)向步骤b)得到的水性聚氨酯预聚体a2中加入丙酮和乙二胺基磺酸钠,于60℃反应0.5h,得到水性聚氨酯预聚体a3
d)向步骤c)得到的水性聚氨酯预聚体a3中加入丙酮,高速剪切下加入氢氧化钠,搅拌1min后加入水高速分散乳化5min后,然后在真空下脱除溶剂,即得含有侧链苯水性聚氨酯;
聚碳酸酯二元醇、聚己内酯二元醇、4,4'-二环己基甲烷二异氰酸酯、3-甲基-1,5-戊二醇、二羟甲基丁酸、二月桂酸正丁基锡、乙二胺基磺酸钠、氢氧化钠与水的质量比为30:30:28:8:13:2.5:0.12: 1.5:4.5:90;
步骤b)中丁酮、步骤c)中丙酮、步骤d)中丙酮与4,4'-二环己基甲烷二异氰酸酯的质量比为3:1.2:2.5:1。
实施例3
a)将相对分子量为3000的端羟基聚丁二烯二元醇、相对分子量为3000的聚己二酸新戊二醇酯二醇、1,6-六亚甲基二异氰酸酯、于 100℃反应3h,得到聚氨酯预聚物a1
b)向步骤a)得到的聚氨酯预聚物a1中加入三甲基戊二醇、二羟甲基丙酸、丙酮、异辛酸铋、二甲基锌,于70℃反应5h,得到水性聚氨酯预聚体a2
c)向步骤b)得到的水性聚氨酯预聚体a2中加入丁酮和乙二胺基磺酸钠,于60℃反应1h,得到水性聚氨酯预聚体a3
d)向步骤c)得到的水性聚氨酯预聚体a3中加入丁酮,高速剪切下加入氢氧化钾,搅拌3min后加入水高速分散乳化10min后,然后在真空下脱除溶剂,即得含有侧链苯水性聚氨酯;
端羟基聚丁二烯二元醇、聚己二酸新戊二醇酯二醇、1,6-六亚甲基二异氰酸酯、三甲基戊二醇、二羟甲基丙酸、异辛酸铋、二甲基锌、乙二胺基磺酸钠、氢氧化钾与水的质量比为21:21:26:10:11:3:0.14: 2:4:100;
步骤b)中丙酮、步骤c)中丁酮、步骤d)中丁酮与1,6-六亚甲基二异氰酸酯的质量比为2.3:1:2:1。
实施例4
a)将相对分子量为4000聚己内酯二元醇、异佛尔酮二异氰酸酯、于90℃反应3h,得到聚氨酯预聚物a1
b)向步骤a)得到的聚氨酯预聚物a1中加入1,4丁二醇、二羟甲基丁酸I、丁酮、二乙基锌,于80℃反应6h,得到水性聚氨酯预聚体a2
c)向步骤b)得到的水性聚氨酯预聚体a2中加入丁酮和乙二胺基磺酸钠,于50℃反应0.8h,得到水性聚氨酯预聚体a3
d)向步骤c)得到的水性聚氨酯预聚体a3中加入丁酮,高速剪切下加入N,N 二甲基乙醇胺,搅拌4min后加入水高速分散乳化5min后,然后在真空下脱除溶剂,即得含有侧链苯水性聚氨酯;
二聚酸聚酯二元醇、异佛尔酮二异氰酸酯、1,4丁二醇、二羟甲基丁酸、二乙基锌、乙二胺基磺酸钠、N,N二甲基乙醇胺与水的质量比为45:24:12:10:3.5:0.16:2.5:3.5:85;
步骤b)中丁酮、步骤c)中丁酮、步骤d)中丁酮与异佛尔酮二异氰酸酯的质量比为2.7:1.1:1.6:1。
实施例5
a)将相对分子量为2000聚己二酸-3-甲基-1,5-戊二醇酯二醇、甲苯二异氰酸酯、于100℃反应3h,得到聚氨酯预聚物a1
b)向步骤a)得到的聚氨酯预聚物a1中加入1,6-己二醇、二羟甲基丙酸、丁酮、新癸酸铋,于70℃反应5h,得到水性聚氨酯预聚体a2
c)向步骤b)得到的水性聚氨酯预聚体a2中加入丁酮和乙二胺基磺酸钠,于50℃反应0.8h,得到水性聚氨酯预聚体a3
d)向步骤c)得到的水性聚氨酯预聚体a3中加入丙酮,高速剪切下加入三乙胺,搅拌3min后加入水高速分散乳化8min后,然后在真空下脱除溶剂,即得含有侧链苯水性聚氨酯;
聚己二酸-3-甲基-1,5-戊二醇酯二醇、甲苯二异氰酸酯、1,6-己二醇、二羟甲基丙酸、新癸酸铋、乙二胺基磺酸钠、三乙胺与水的质量比为48:22:14:8:4:0.18:3.5:3:95;
步骤b)中丁酮、步骤c)中丁酮、步骤d)中丙酮与甲苯二异氰酸酯的质量比为2.5:1.0:1.8:1。
实施例6
a)将相对分子量为2000的二聚酸聚酯二元醇、4,4`-二苯基甲烷二异氰酸酯、于90℃反应4h,得到聚氨酯预聚物a1
b)向步骤a)得到的聚氨酯预聚物a1中加入1,4丁二醇、二羟甲基丙酸、丁酮、月桂芁酸铋,于80℃反应6h,得到水性聚氨酯预聚体a2
c)向步骤b)得到的水性聚氨酯预聚体a2中加入丙酮和乙二胺基磺酸钠,于60℃反应1h,得到水性聚氨酯预聚体a3
d)向步骤c)得到的水性聚氨酯预聚体a3中加入丁酮,高速剪切下加入N,N 二甲基乙醇胺,搅拌5min后加入水高速分散乳化7min后,然后在真空下脱除溶剂,即得含有侧链苯水性聚氨酯;
苯酐聚酯二元醇、4,4`-二苯基甲烷二异氰酸酯、 1,4丁二醇、二羟甲基丙酸、月桂芁酸铋、乙二胺基磺酸钠、N,N二甲基乙醇胺与水的质量比为53:20:8:8:6:4.5:0.22:4: 2.5:90;
步骤b)中丁酮、步骤c)中丙酮、步骤d)中丁酮与4,4`-二苯基甲烷二异氰酸酯的质量比为2.3:0.9:2:1。
实施例7
a)将相对分子量为2000的苯酐聚酯二元醇、4,4`-二苯基甲烷二异氰酸酯、于90℃反应4h,得到聚氨酯预聚物a1
b)向步骤a)得到的聚氨酯预聚物a1中加入1,6环己二甲醇、二羟甲基丙酸、丁酮、月桂芁酸铋,于80℃反应6h,得到水性聚氨酯预聚体a2
c)向步骤b)得到的水性聚氨酯预聚体a2中加入丁酮和乙二胺基磺酸钠,于60℃反应1h,得到水性聚氨酯预聚体a3
d)向步骤c)得到的水性聚氨酯预聚体a3中加入丁酮,高速剪切下加入氢氧化钠,搅拌5min后加入水高速分散乳化7min后,然后在真空下脱除溶剂,即得含有侧链苯水性聚氨酯;
苯酐聚酯二元醇、4,4`-二苯基甲烷二异氰酸酯、 1,6环己二甲醇、二羟甲基丙酸、月桂芁酸铋、乙二胺基磺酸钠、氢氧化钠与水的质量比为57:25:9:9:4:5:0.24:4.5:2:80;
步骤b)中丁酮、步骤c)中丁酮、步骤d)中丁酮与4,4`-二苯基甲烷二异氰酸酯的质量比为2.6:1.1:2.2:1。
实施例8
a)将相对分子量为2000的苯酐聚酯二元醇、4,4'-二环己基甲烷二异氰酸酯、于90℃反应4h,得到聚氨酯预聚物a1
b)向步骤a)得到的聚氨酯预聚物a1中加入新戊二醇、二羟甲基丙酸、丙酮、月桂芁酸铋,于80℃反应6h,得到水性聚氨酯预聚体a2
c)向步骤b)得到的水性聚氨酯预聚体a2中加入丁酮和乙二胺基磺酸钠,于60℃反应1h,得到水性聚氨酯预聚体a3
d)向步骤c)得到的水性聚氨酯预聚体a3中加入丁酮,高速剪切下加入三乙胺,搅拌5min后加入水高速分散乳化7min后,然后在真空下脱除溶剂,即得含有侧链苯水性聚氨酯;
苯酐聚酯二元醇、4,4'-二环己基甲烷二异氰酸酯、 新戊二醇、二羟甲基丙酸、月桂芁酸铋、乙二胺基磺酸钠、三乙胺与水的质量比为50:27:10:10:2:2.8:0.26:5:1.5:100;
步骤b)中丙酮、步骤c)中丁酮、步骤d)中丁酮与4,4`-二苯基甲烷二异氰酸酯的质量比为2.1:1.2:2.4:1。
实施例9
a)将相对分子量为2000的苯酐聚酯二元醇、4,4'-二环己基甲烷二异氰酸酯、于90℃反应4h,得到聚氨酯预聚物a1
b)向步骤a)得到的聚氨酯预聚物a1中加入三甲基戊二醇、二羟甲基丙酸、丁酮、月桂芁酸铋,于80℃反应6h,得到水性聚氨酯预聚体a2
c)向步骤b)得到的水性聚氨酯预聚体a2中加入丙酮和乙二胺基磺酸钠,于60℃反应1h,得到水性聚氨酯预聚体a3
d)向步骤c)得到的水性聚氨酯预聚体a3中加入丙酮,高速剪切下加入三乙胺,搅拌5min后加入水高速分散乳化7min后,然后在真空下脱除溶剂,即得含有侧链苯水性聚氨酯;
苯酐聚酯二元醇、44'-二环己基甲烷二异氰酸酯、 三甲基戊二醇、二羟甲基丙酸、月桂芁酸铋、乙二胺基磺酸钠、三乙胺与水的质量比为55:23:7:8:12:4.2:0.3:3:0.8:90;
步骤b)中丁酮、步骤c)中丙酮、步骤d)中丙酮与4,4`-二苯基甲烷二异氰酸酯的质量比为2.5:1:2.6:1。
实施例10
a)将相对分子量为2000的苯酐聚酯二元醇、1,6-六亚甲基二异氰酸酯、于90℃反应4h,得到聚氨酯预聚物a1
b)向步骤a)得到的聚氨酯预聚物a1中加入1,6环己二甲醇、二羟甲基丙酸、丙酮、月桂芁酸铋,于80℃反应6h,得到水性聚氨酯预聚体a2
c)向步骤b)得到的水性聚氨酯预聚体a2中加入丙酮和乙二胺基磺酸钠,于60℃反应1h,得到水性聚氨酯预聚体a3
d)向步骤c)得到的水性聚氨酯预聚体a3中加入丙酮,高速剪切下加入三乙胺,搅拌5min后加入水高速分散乳化7min后,然后在真空下脱除溶剂,即得含有侧链苯水性聚氨酯;
苯酐聚酯二元醇、1,6-六亚甲基二异氰酸酯、1,6环己二甲醇、二羟甲基丙酸、月桂芁酸铋、乙二胺基磺酸钠、三乙胺与水的质量比为 50:25:13:8.5:3.5:0.2:3:2.9:90;
步骤b)中丙酮、步骤c)中丙酮、步骤d)中丙酮与4,4`-二苯基甲烷二异氰酸酯的质量比为2.5:1:2.2:1。
测试实施例1~10制得的含有侧链苯水性聚氨酯的附着力、耐热性和研磨稳定性,结果见表1。
表1实施例1~10的实验结果
以上对本发明提供的一种含有侧链苯水性聚氨酯及其制备方法进行了详细的介绍,本文中应用了具体个例对本发明的原理及实施方式进行了阐述,以上实施例的说明只是用于帮助理解本发明的方法及其核心思想,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以对本发明进行若干改进和修饰,这些改进和修饰也落入本发明权利要求的保护范围内。

Claims (10)

1.一种含有侧链苯水性聚氨酯的制备方法,其特征在于,包括以下步骤:
a)将大分子二元醇、二异氰酸酯、聚合侧链苯单体于90~100℃反应2~4h,得到聚氨酯预聚物a1
b)向步骤a)得到的聚氨酯预聚物a1中加入小分子扩链剂、亲水扩链剂I、溶剂、催化剂,于60~80℃反应4~7h,得到水性聚氨酯预聚体a2
c)向步骤b)得到的水性聚氨酯预聚体a2中加入溶剂和亲水扩链剂II,于50~60℃反应0.5~1h,得到水性聚氨酯预聚体a3
d)向步骤c)得到的水性聚氨酯预聚体a3中加入溶剂,高速剪切下加入成盐剂,搅拌1~5min后加入水高速分散乳化5~10min后在真空下脱除溶剂,即得含有侧链苯水性聚氨酯。
2.如权利要求1所述的制备方法,其特征在于,所述大分子多元醇选自苯酐聚酯二元醇、聚碳酸酯二元醇、聚己内酯二元醇、端羟基聚丁二烯二元醇、聚己二酸新戊二醇酯二醇、聚己二酸-3-甲基-1,5-戊二醇酯二醇中的一种或几种。
3.如权利要求1所述的制备方法,其特征在于,所述聚合侧链苯单体选自 中的一种或多种。
4.如权利要求1所述的制备方法,其特征在于,所述二异氰酸酯为甲苯二异氰酸酯、异佛尔酮二异氰酸酯、1,6-六亚甲基二异氰酸酯、4,4`-二苯基甲烷二异氰酸酯或4,4'-二环己基甲烷二异氰酸酯。
5.如权利要求1所述的制备方法,其特征在于,所述小分子扩链剂为1,6环己二甲醇、1,6-己二醇、3-甲基-1,5-戊二醇、1,4丁二醇、新戊二醇或三甲基戊二醇。
6.如权利要求1所述的制备方法,其特征在于,所述亲水扩链剂I为二羟甲基丙酸或二羟甲基丁酸;
所述亲水扩链剂II为乙二胺基磺酸钠。
7.如权利要求1所述的制备方法,其特征在于,所述催化剂选自辛酸亚锡、二月桂酸正丁基锡、有机Bi盐催化剂、有机Zn盐催化剂中的一种或几种。
8.如权利要求1所述的制备方法,其特征在于,所述成盐剂为三乙胺、N,N二甲基乙醇胺、氢氧化钠或氢氧化钾。
9.如权利要求1所述的制备方法,其特征在于,步骤b)、步骤c)和步骤d)中,所述溶剂均独立地选自丙酮或丁酮。
10.一种含有侧链苯水性聚氨酯,其特征在于,采用权利要求1~9任一项所述的含有侧链苯水性聚氨酯及其制备方法制得。
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CN108424505A (zh) * 2018-03-29 2018-08-21 苏州博莱特新材料有限公司 一种水性聚氨酯树脂
CN111019078A (zh) * 2019-12-31 2020-04-17 北京华腾新材料股份有限公司 一种水性聚氨酯固化剂及其制备方法和应用

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108424505A (zh) * 2018-03-29 2018-08-21 苏州博莱特新材料有限公司 一种水性聚氨酯树脂
CN111019078A (zh) * 2019-12-31 2020-04-17 北京华腾新材料股份有限公司 一种水性聚氨酯固化剂及其制备方法和应用

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