CN104962192A - 耐水、耐候聚酯型水性聚氨酯乳液及其制备方法 - Google Patents
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Abstract
本发明公开了一种耐水、耐候聚酯型水性聚氨酯乳液及其制备方法,所述乳液包括聚酯二元醇、二异氰酸酯、催化剂、扩链剂、有机溶剂、有机硅与去离子水等。制备方法包括将二异氰酸酯、催化剂和扩链剂,加入脱水后的聚酯二元醇中反应,加入有机溶剂和氨基硅油,得有机硅改性接枝聚氨醋,加入封端剂、中和剂和水反应,即得。本发明所述的乳液物质存储稳定,涂膜具有理想的硬度、粘附力、耐水性和耐候性。
Description
技术领域
本发明属于水性聚氨酯涂料技术领域,具体涉及一种耐水、耐候聚酯型水性聚氨酯乳液及其制备方法。
背景技术
水性聚氨酯以水为分散介质,具有不燃、气味小和不污染环境等优点。近年来随着人们对环境保护关注程度的日益加深,使水性聚氨酯在各个行业得以广泛应用。多数水性聚氨酯是由自乳化法制备,由于此法制备的聚氨酯结构中存在亲水基团,使得涂膜的耐水性、耐溶剂性和耐候性较差,限制了其使用范围。虽然聚酯型水性聚氨酯涂膜的硬度、粘附力优于聚醚型水性聚氨酯,但是聚酯多元醇的酯基易水解,聚酯型水性聚氨酯的耐水性较聚醚型水性聚氨酯差,目前国内企业生产的水性聚氨酯主要是聚醚型水性聚氨酯。因此,对聚酯型水性聚氨酯的耐水性进行改进具有现实意义。
目前,国内聚氨酯领域工作者对聚酯型水性聚氨酯做了一定的研究工作并给与了报道。如专利申请号“02136168.1”,名称为“耐水解的聚酯型聚氨酯胶粘剂的制备方法”,是采用增加直链聚酯二元醇的分子量和引入带侧基的二元醇对酯基进行保护,从而提高水性聚酯型聚氨酯胶粘剂的耐水性。另如专利号为:201110442843.3,发明名称为一种耐水、耐候的聚酯聚氨酯-聚丙烯酸酯水分散体及其制备方法,是采用丙烯酸单体和聚酯型聚氨酯预聚体共聚,在聚氨酯中引入丙烯酸改进聚酯水性聚氨酯的耐水性。
在现有的技术资料中,还未见采用大分子有机硅对聚酯型水性聚氨酯进行改性提高聚氨酯耐水性、耐候性的研究报道及应用范例。
发明内容
本发明的目的在于克服上述现有技术的不足,提供一种固含量高、柔软性好的耐水、耐候聚酯型水性聚氨酯乳液及其制备方法。
本发明提供的耐水、耐候聚酯型水性聚氨酯乳液,按质量百分比计算,由以下原料反应而成:
其中,所述聚酯二元醇为聚己二酸聚酯二元醇、聚碳酸酯二元醇或聚己内酯二元醇。
其中,所述二异氰酸酯为甲苯二异氰酸酯、4,4'-二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、1,6-己二异氰酸酯或二环己基甲烷二异氰酸酯。
其中,所述催化剂为二月桂酸二丁基锡或辛酸亚锡。
其中,所述扩链剂为阴离子扩链剂及非离子扩链剂,阴离子扩链剂为二轻甲基丙酸;非离子扩链剂为1,4-丁二醇或乙二醇。
其中,所述有机溶剂为丙酮、N甲基毗咯烷酮或异丙醇。
其中,所述有机硅为氨基硅油或三元嵌段硅油,氨基硅油为含有氨基或含亚氨基的聚硅氧烷中的一种。
其中,所述中和剂为三乙胺。
其中,所述封端剂为乙醇。
本发明提供的耐水、耐候聚酯型水性聚氨酯乳液的制备方法,包括以下步骤:
(1)、按上述的质量百分比分别称取各原料;
(2)、将聚酯二元醇升温至100-120℃,真空脱水处理15-3Omin,降温至30-50℃,得到脱水后的聚酯二元醇;
(3)、将二异氰酸酯和催化剂加入脱水后的聚酯二元醇中,搅拌均匀,升温至78-80℃,保温反应60min-90min,得到初聚体;
(4)、将初聚体的温度控制在78-80℃,加入扩链剂,反应60-90min,得到聚氨酯预聚体;
(5)、将有机溶剂加入聚氨酯预聚体中,搅拌均匀,冰浴降温至0-5℃,然后滴入有机硅,反应60-90min,得到有机改性聚氨酯;
(6)、将封端剂加入有机硅改性聚氨酯中,室温条件下反应30min,然后加入中和剂,室温条件下,搅拌处理15-20min,加入去离子水,搅拌乳化分散15-30min,即得耐水、耐候聚酯型水性聚氨酯乳液。
本发明以聚酯二元醇为软段材料、以阴离子单体为亲水扩链剂和二异氰酸酯反应制备聚氨酯预聚体,并以大分子有机硅对聚氨酯预聚体进行侧链接枝改性,所制备出的有机硅改性聚酯型水性聚氨酯呈微乳液状态,存储稳定性好,在涂膜过程改性聚氨酯中的聚氨酯单元和硅氧烷链段产生微相分离,聚氨酯单元和涂膜的基材结合而硅氧烷在涂膜的表面富集,可赋予改性聚氨酯优良粘附力的同时,明显改善涂膜的耐水性和耐候性。
本发明产品兼具聚酯型聚氨酯和硅材料的优良特性,可用于木器、金属、陶瓷和塑料的涂膜剂,涂膜硬度4-5H(铅笔硬度)、粘附力4-5B,涂膜水浸24h吸水率低于15%,且涂膜具有理想的耐候性。
具体实施方式
以下结合具体实施例对发明作进一步详细的描述。
耐水、耐候聚酯型水性聚氨酯乳液,按质量百分比计算,由以下原料反应而成:
其中,聚酯二元醇为聚己二酸聚酯二元醇、聚碳酸酯二元醇或聚己内酯二元醇。
其中,二异氰酸酯为甲苯二异氰酸酯、4,4'-二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、1,6-己二异氰酸酯或二环己基甲烷二异氰酸酯。
其中,催化剂为二月桂酸二丁基锡或辛酸亚锡。
其中,扩链剂为阴离子扩链剂及非离子扩链剂。
优选地,阴离子扩链剂为二轻甲基丙酸;非离子扩链剂为1,4-丁二醇或乙二醇。
其中,有机溶剂为丙酮、N甲基毗咯烷酮或异丙醇。
其中,有机硅为氨基硅油或三元嵌段硅油。
优选地,氨基硅油为含有氨基或含亚氨基的聚硅氧烷中的一种。
其中,中和剂为三乙胺。
其中,封端剂为乙醇。
耐水、耐候聚酯型水性聚氨酯乳液的制备方法为:
(1)、按上述的质量百分比分别称取各原料;
(2)、将聚酯二元醇升温至100-120℃,真空脱水处理15-3Omin,降温至30-50℃,得到脱水后的聚酯二元醇;
(3)、将二异氰酸酯和催化剂加入脱水后的聚酯二元醇中,搅拌均匀,升温至78-80℃,保温反应60min-90min,得到初聚体;
(4)、将初聚体的温度控制在78-80℃,加入扩链剂,反应60-90min,得到聚氨酯预聚体;
(5)、将有机溶剂加入聚氨酯预聚体中,搅拌均匀,冰浴降温至0-5℃,然后滴入有机硅,反应60-90min,得到有机改性聚氨酯;
(6)、将封端剂加入有机硅改性聚氨酯中,室温条件下反应30min,然后加入中和剂,室温条件下,搅拌处理15-20min,加入去离子水,搅拌乳化分散15-30min,即得耐水、耐候聚酯型水性聚氨酯乳液。
实施例1
按质量百分比称取以下原料:聚酯二元醇(采用分子量1000的聚己二酸己二醇酯二醇)15.55%,异佛尔酮二异氰酸酯8.84%,二月桂酸二丁基锡0.02%,1,4-丁二醇0.41%,二轻甲基丙酸1.01%,丙酮10.00%,氨基硅油2.86%,乙醇1.46%,三乙胺0.99%,去离子水58.86%;
将称取的聚酯二元醇加入到连接有搅拌装置的反应容器中,将反应容器内的聚酯二元醇升温至100℃进行抽真空脱水处理,处理时间为30min,抽真空脱水处理完成后将聚酯二元醇降温至30℃,即得到脱水后的聚酯二元醇;
接着将称取的异佛尔酮二异氰酸酯和二月桂酸二丁基锡加入脱水后的聚酯二元醇中,搅拌均匀后升温至78-80℃,保温反应90min,即得到初聚体;
将初聚体的温度保持在78-80℃,加入称取的1,4-丁二醇和二轻甲基丙酸,保温反应90min,即制成聚氨酯预聚体;
将丙酮加入聚氨酯预聚体中搅拌均匀,并用冰浴将聚氨酯预聚体降温至0-5℃;再将氨基硅油于25min内滴加到聚氨酯预聚体,于0-5℃反应60min,即制得氨基硅油改性接枝聚氨酯,并撤离冰浴;
将制备出氨基硅油改性聚氨酯升温至室温后加入称取的三乙胺,快速搅拌,中和处理15min,之后加入称取的乙醇,封端反应30min,最后加入去离子水,高速搅拌乳化分散15min,即制备得到本发明所述的耐水、耐候聚酯型水性聚氨酯乳液。
实施例2
按质量百分比称取以下原料:聚酯二元醇(采用分子量1000的聚己二酸乙二醇-1,4-丁二醇酯二醇)9.33%,二月桂酸二丁基锡0.04%,异佛尔酮二异氰酸酯7.23%,二甲基丙酸1.06%,乙二醇0.50%,异丙醇7.30%,氨基硅油9.00%,乙醇1.20%,三乙胺1.03%,去离子水63.31%;
将称取的聚酯二元醇加入到连接有搅拌装置的反应容器中,将反应容器内的聚酯二元醇升温至110℃进行抽真空脱水处理,处理时间为30min,抽真空脱水处理完成后将聚酯二元醇降温至40℃,即得到脱水后的聚酯二元醇;
接着将称取的异佛尔酮二异氰酸酯和二月桂酸二丁基锡加入脱水后的聚酯二元醇中,搅拌均匀后升温至78-80℃,保温反应60min,即得到初聚体;
将初聚体的温度保持在78-80℃,加入称取的乙二醇和二轻甲基丙酸,保温反应90min,即制成聚氨酯预聚体;
将异丙醇加入聚氨酯预聚体中搅拌均匀,并用冰浴将聚氨酯预聚体降温至0-5℃;再将氨基硅油于35min内滴加到聚氨酯预聚体,于0-5℃反应90min,即制得氨基硅油改性接枝聚氨酯,并撤离冰浴;
将制备出的氨基硅油改性聚氨酯升温至室温后加入称取的三乙胺,快速搅拌,中和处理10min,之后加入称取的乙醇,封端反应30min再加入去离子水,高速搅拌乳化分散20min,即制备得到本发明所述的耐水、耐候聚酯型水性聚氨酯乳液。
实施例3
按质量百分比称取以下原料:聚酯二元醇(采用分子量2000的聚己内酯二醇)18.46%,辛酸亚锡0.03%,4,4-二苯基甲烷二异氰酸酯6.97%,1,4-丁二醇0.19%,二羟甲基丙酸0.70%,N-甲基毗咯烷酮5.50%,三元嵌段硅油3.58%,乙醇1.48%,三乙胺0.66%,去离子水62.43%;
将称取的聚酯二元醇加入到连接有搅拌装置的反应容器中,将反应容器内的聚酯二元醇升温至120℃进行抽真空脱水处理,处理时间为20min,抽真空脱水处理完成后将聚酯二元醇降温至40℃,即得到脱水后的聚酯二元醇;
接着将称取的4,4-二苯基甲烷二异氰酸酯和辛酸亚锡加入脱水后的聚酯二元醇中,搅拌均匀后升温至78-80℃,保温反应90min,即得到初聚体;
将初聚体的温度控制在78-80℃,加入称取的1,4-丁二醇和二轻甲基丙酸,保温反应90min,即制成聚氨酯预聚体;
将N-甲基毗咯烷酮加入聚氨酯预聚体中搅拌均匀,并用冰浴将聚氨酯预聚体降温至0-5℃;再将三元嵌段硅油于30min内滴加到聚氨酯预聚体,于0-5℃反应60min,即制得三元嵌段硅油改性接枝聚氨酯,并撤离冰浴;
将制备出的三元嵌段硅油改性聚氨酯升温至室温后加入称取的三乙胺,快速搅拌,中和处理15min,之后再加入乙醇,封端反应30min,最后加入去离子水,高速搅拌乳化分散30min,即制备得到本发明所述的耐水、耐候聚酯型水性聚氨酯。
实施例4
按质量百分比称取以下原料:聚酯二元醇(采用分子量2000的聚己二酸己二醇酯二醇)14.63%,二月桂酸二丁基锡0.02%,甲苯二异氰酸酯3.12%,二轻甲基丙酸0.71%,N-甲基毗咯烷酮7.65%,三元嵌段硅油11.34%,三乙胺0.64%,乙醇0.62%,去离子水61.27%;
将称取的聚酯二元醇加入到连接有搅拌装置的反应容器中,将反应容器内的聚酯二元醇升温至100℃进行抽真空脱水处理,处理时间为30min,抽真空脱水处理完成后将聚酯二元醇降温至50℃,即得到脱水后的聚酯二元醇;
接着将称取的甲苯二异氰酸酯和二月桂酸二丁基锡加入脱水后的聚酯二元醇中,搅拌均匀后升温至78-80℃,保温反应90min,即得到初聚体;
将初聚体的温度控制在78-80℃加入称取的二羟甲基丙酸,保温反应60min,即制成聚氨酯预聚体;
将N-甲基毗咯烷酮加入聚氨酯预聚体中搅拌均匀,并用冰浴将聚氨酯预聚体降温至0-5℃;再将三元嵌段硅油于35min内滴加到聚氨酯预聚体,保温反应90min,即制得三元嵌段硅油改性接枝聚氨酯,并撤离冰浴;
将制备出的三元嵌段硅油改性聚氨酯升温至室温后加入称取的三乙胺,快速搅拌,中和处理10min,之后再加入乙醇,封端反应30min,最后加入去离子水,高速搅拌乳化分散20min,即制备得到本发明所述的耐水、耐候聚酯型水性聚氨酯乳液。
实施例5
按质量百分比称取以下原料:聚酯二元醇(采用分子量2000的聚碳酯二元醇)16.38%,二月桂酸二丁基锡0.04%,1,6-己二异氰酸酯4.53%,1,4-丁二醇0.20%,二轻甲基丙酸1.50%,N-甲基毗咯烷酮9.50%,氨基硅油5.55%,三乙胺0.95%,乙醇0.93%,去离子水60.42%;
将称取的聚酯二元醇加入到连接有搅拌装置的反应容器中,将反应容器内的聚酯二元醇升温至110℃进行抽真空脱水处理,处理时间为30min,抽真空脱水处理完成后将聚酯二元醇降温至40℃,即得到脱水后的聚酯二元醇;
接着将称取的1,6-己二异氰酸酯和二月桂酸二丁基锡加入脱水后的聚酯二元醇中,搅拌均匀后升温至78-80℃,保温反应90min,即得到初聚体;
将初聚体的温度控制在78-80℃加入称取的1,4-丁二醇和二羟甲基丙酸,保温反应60min,即制成聚氨酯预聚体;
将N-甲基毗咯烷酮加入聚氨酯预聚体中搅拌均匀,并用冰浴将聚氨酯预聚体降温至0-5℃;再将氨基硅油于30min内滴加到聚氨酯预聚体,保温反应80min,即制得氨基硅油改性接枝聚氨酯;
将制备出的氨基硅油改性聚氨酯升温至室温后加入称取的三乙胺,快速搅拌,中和处理15min,之后再加入称取的乙醇,封端反应30min,最后加入去离子水,高速搅拌乳化分散30min,即制备得到本发明所述的耐水、耐候聚酯型水性聚氨酯乳液。
实施例6
分别对实施例1-5得到的耐水、耐候聚酯型水性聚氨酯乳液进行涂膜硬度、粘附力和涂膜水浸24小时吸水率测试。
以上检测项目数据如下表所示:
项目 | 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 |
涂膜硬度/H | 4.5 | 4.6 | 4.4 | 4.8 | 4.7 |
粘附力/B | 4.7 | 4.9 | 4.8 | 4.5 | 4.6 |
吸水率/% | 12 | 14 | 11 | 13 | 12 |
可以看出,本发明所述的耐水、耐候聚酯型水性聚氨酯乳液具有理想的硬度、粘附力及耐水性,可以作为木器、金属、陶瓷和塑料的涂膜剂
以上所述仅是本发明所述的优选实施方式,本发明所述的保护范围并不仅局限于上述实施例,凡属于本发明思路下的技术方案均属于本发明所述的保护范围。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前提下的若干改进和润饰,这些改进和润饰也应视为本发明所述的保护范围。
Claims (10)
1.一种耐水、耐候聚酯型水性聚氨酯乳液,其特征在于:
按质量百分比计算,由以下原料反应而成:
2.根据权利要求1所述的耐水、耐候聚酯型水性聚氨酯乳液,其特征在于:所述聚酯二元醇为聚己二酸聚酯二元醇、聚碳酸酯二元醇或聚己内酯二元醇。
3.根据权利要求1所述的耐水、耐候聚酯型水性聚氨酯乳液,其特征在于:所述二异氰酸酯为甲苯二异氰酸酯、4,4'-二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、1,6-己二异氰酸酯或二环己基甲烷二异氰酸酯。
4.根据权利要求1所述的耐水、耐候聚酯型水性聚氨酯乳液,其特征在于:所述催化剂为二月桂酸二丁基锡或辛酸亚锡。
5.根据权利要求1所述的耐水、耐候聚酯型水性聚氨酯乳液,其特征在于:所述扩链剂为阴离子扩链剂及非离子扩链剂,阴离子扩链剂为二轻甲基丙酸;非离子扩链剂为1,4-丁二醇或乙二醇。
6.根据权利要求1所述的耐水、耐候聚酯型水性聚氨酯乳液,其特征在于:所述有机溶剂为丙酮、N甲基毗咯烷酮或异丙醇。
7.根据权利要求1所述的耐水、耐候聚酯型水性聚氨酯乳液,其特征在于:所述有机硅为氨基硅油或三元嵌段硅油,氨基硅油为含有氨基或含亚氨基的聚硅氧烷中的一种。
8.根据权利要求1所述的耐水、耐候聚酯型水性聚氨酯乳液,其特征在于:所述中和剂为三乙胺。
9.根据权利要求1所述的耐水、耐候聚酯型水性聚氨酯乳液,其特征在于:所述封端剂为乙醇。
10.制备权利要求1~9任意一项所述的耐水、耐候聚酯型水性聚氨酯乳液的方法,其特征在于:包括以下步骤:
(1)、按上述的质量百分比分别称取各原料;
(2)、将聚酯二元醇升温至100-120℃,真空脱水处理15-3Omin,降温至30-50℃,得到脱水后的聚酯二元醇;
(3)、将二异氰酸酯和催化剂加入脱水后的聚酯二元醇中,搅拌均匀,升温至78-80℃,保温反应60min-90min,得到初聚体;
(4)、将初聚体的温度控制在78-80℃,加入扩链剂,反应60-90min,得到聚氨酯预聚体;
(5)、将有机溶剂加入聚氨酯预聚体中,搅拌均匀,冰浴降温至0-5℃,然后滴入有机硅,反应60-90min,得到有机改性聚氨酯;
(6)、将封端剂加入有机硅改性聚氨酯中,室温条件下反应30min,然后加入中和剂,室温条件下,搅拌处理15-20min,加入去离子水,搅拌乳化分散15-30min,即得耐水、耐候聚酯型水性聚氨酯乳液。
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