CN109608587A - 一种复合改性聚氨酯乳液及其制备方法 - Google Patents

一种复合改性聚氨酯乳液及其制备方法 Download PDF

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CN109608587A
CN109608587A CN201811511657.9A CN201811511657A CN109608587A CN 109608587 A CN109608587 A CN 109608587A CN 201811511657 A CN201811511657 A CN 201811511657A CN 109608587 A CN109608587 A CN 109608587A
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管莹
陆小辉
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CHENGDU JIESHENG SHUBANG NEW MATERIAL TECHNOLOGY Co Ltd
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Abstract

本发明公开了一种复合改性聚氨酯乳液,其特征在于:包括以下原料组份,以重量份数计为,大分子多元醇35‑65份;羟烷基封端聚硅氧烷4‑20份;环氧树脂2.5‑15份;三羟甲基丙烷1.5‑2份;二异氰酸酯35‑60份;2,2‑二羟甲基丁酸7‑15份;乙烯基单体70‑100份;丙烯酸羟基酯8‑18份;三乙胺7‑12份;乳化剂1.0‑1.5份;去离子水430‑600份;自交联功能单体0.5‑3份;过硫酸铵水溶液17‑20份。本发明采用乙烯基单体作为溶剂,不需要加入丙酮或其他惰性溶剂来稀释,避免了后期真空脱溶剂,回收溶剂等步骤,绿色环保。

Description

一种复合改性聚氨酯乳液及其制备方法
技术领域
本发明属于水性乳液技术领域,具体涉及一种复合改性聚氨酯乳液。
背景技术
传统的水性聚氨酯合成方法包括,(1)丙酮法,该方法需后期抽出溶剂,工艺复杂,成本高,且VOC较高;(2)预聚体法,该方法中,不需加入惰性溶剂来降低体系粘度,但需在低温下用高活性二元胺扩链来达到所需的高分子量,分子量控制难度较大,且还存在扩链剂残留问题,一般常用扩链剂(如乙二胺)具有一定的毒性。传统合成方法都无法满足绿色环保的需求。
发明内容
本发明的目的在于:解决上述现有技术中的不足,提供一种复合改性聚氨酯乳液。
为了实现上述目的,本发明采用的技术方案为:一种复合改性聚氨酯乳液,其特征在于:包括以下原料组份,以重量份数计为,
大分子多元醇35-65份;
羟烷基封端聚硅氧烷4-20份;
环氧树脂2.5-15份;
三羟甲基丙烷1.5-2份;
二异氰酸酯35-60份;
2,2-二羟甲基丁酸7-15份;
乙烯基单体70-100份;
丙烯酸羟基酯8-18份;
三乙胺7-12份;
乳化剂1.0-1.5份;
去离子水430-600份;
自交联功能单体0.5-3份;
过硫酸铵水溶液17-20份。
进一步的,所述二异氰酸酯为异佛尔酮二异氰酸酯、二环己基甲烷二异氰酸酯或1,6-六亚甲基二异氰酸酯中的一种或几种。
进一步的,所述大分子多元醇为分子量1000-2000的聚己内酯二醇或聚碳酸酯二醇。
进一步的,所述羟烷基封端聚硅氧烷为分子量1000-2000的羟丙基封端聚硅氧烷或羟丁基封端聚硅氧烷。
进一步的,所述环氧树脂为环氧值在0.41-0.56的双酚A型环氧树脂中的一种或多种的混合。
进一步的,所述丙烯酸羟基酯为甲基丙烯酸羟乙酯、丙烯酸羟丙酯中的一种或两种的混合。
进一步的,所述乳化剂为月桂醇聚氧乙烯醚、烷基醇聚氧乙烯硫酸铵盐中的一种或两种的混合。
进一步的,所述乙烯基单体为甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸羟乙酯或丙烯酸羟丙酯中的一种或几种。
进一步的,所述自交联功能单体为甲基丙烯酸缩水甘油酯、γ-(甲基丙烯酰氧)丙基三甲氧基硅烷中的一种或两种的混合。
一种制备复合改性聚氨酯乳液的方法,包括以下步骤,
S1:将大分子多元醇、所述羟烷基封端聚硅氧烷、环氧树脂、三羟甲基丙烷、二异氰酸酯、2,2-二羟甲基丁酸和乙烯基单体搅拌混合均匀,得到混合物;
S2:将步骤S1中得到的混合物升温至73-83℃,搅拌反应1.5-3h,得聚氨酯预聚体;其中,聚氨酯预聚体的NCO的含量为3-4%;
S3:向步骤S2中的得到的聚氨酯预聚体中加入丙烯酸羟基酯,在73-83℃下搅拌反应0.5-1.0h,得丙烯酸羟基酯封端的聚氨酯预聚体;其中,聚氨酯预聚体NCO的含量为1.5-2.5%。
S4:向上述S3步骤中得到的预聚体中加入三乙胺,在73-83℃下搅拌反应0.5h;
S5:将乳化剂溶解在去离子水中,再加入至步骤S4中得到的预聚体中,高速分散5-10min,得预乳液;
S6:将上述步骤S5中得到的所述预乳液升温至73-83℃,同时滴加乙烯基单体、自交联功能单体和过硫酸铵水溶液,其中,乙烯基单体和自交联功能单体在1-2.5h内滴完;过硫酸铵水溶液在1.5-3.5h内滴完;随后再保温0.5-1h,得聚氨酯乳液。
由于采用了上述技术方案,本发明的有益效果是:
本发明采用乙烯基单体作为溶剂,不需要加入丙酮或其他惰性溶剂来稀释,避免了后期真空脱溶剂,回收溶剂等步骤,绿色环保。
与现有预聚体法技术相比,本发明中,在得到聚氨酯预聚体后,无需再通过添加小分子量二元醇或二元胺扩链来达到所需分子量。而是通过在加入丙烯酸羟基酯封端前,加入三羟甲基丙烷来控制分子量,分子量易控,原料残留低,毒性低。预聚体封端完成预乳化后加入过硫酸铵水溶液和单体进行自由基聚合,反应生成改性的聚氨酯乳液。整个反应过程中,温度都在73-83℃,无需反复升降温,且反应时间短,可操作性强,经济效益高。
本发明中的乙烯基单体改性聚氨酯乳液,提高了乳液成膜的干燥性以及不返粘性。自交联功能单体的引入,可提高室温干燥下的交联密度,配合环氧改性,涂膜具有更高的拉伸强度和耐磨性。在合成聚氨酯预聚体阶段,引入的羟基封端聚硅氧烷,能显著的提高耐水性和韧性,且低温耐性好。自交联功能单体和羟基封端聚硅氧烷的加入,使乳液在合成和存储过程中,增加胶凝的倾向。通过在预乳化时加入少量乳化剂来提高稳定性,同时得到粒径更小的乳胶粒,提高涂膜的透明度和光泽,耐水性得到了较大的提升。
具体实施方式
实施例1:
常温下将聚己内酯二醇(Mw=1000)60份、二羟丙基封端聚硅氧烷(Mw=1000)6份、环氧树脂E44 5份、三羟甲基丙烷1.5份、异佛尔酮二异氰酸酯42份、2,2-二羟甲基丁酸11份以及甲基丙烯酸甲酯2.5份,丙烯酸丁酯60份投入干燥的反应釜中,搅拌混合均匀;
将混合物升温至73℃,搅拌反应3h,得聚氨酯预聚体,聚氨酯预聚体中NCO的含量3-4%;加入甲基丙烯酸羟乙酯12份,在73℃下搅拌反应1h,得甲基丙烯酸羟基酯封端的聚氨酯预聚体,该聚氨酯预聚体的NCO的含量降低至1.5-2.5%,再向反应釜中加入8份三乙胺,在73℃搅拌反应0.5h;
将0.5份月桂醇聚氧乙烯醚和0.8份烷基醇聚氧乙烯硫酸铵盐,溶解在485份去离子中,再加入到聚氨酯预聚体中,随后高速分散反应体系10min,得预乳液;
将所述预乳液升温至73℃,在2.5h内,在搅拌条件下,将5份甲基丙烯酸羟乙酯、13份丙烯酸羟丙酯和1份甲基丙烯酸缩水甘油酯滴加到预乳液中;在滴加的同时,将18.45份过硫酸铵水溶液在3.0h内,滴加到预乳液中,滴加完成后,再保温0.5h。保温完后立即降温至40℃以下,得到聚氨酯乳液。
实施例2
在常温下将聚碳酸酯二醇(Mw=1000)42份、二羟丁基封端聚硅氧烷(Mw=1000)5份、环氧树脂E51 8份、三羟甲基丙烷1.8份、异佛尔酮二异氰酸酯31份、1,6-六亚甲基二异氰酸酯12.8份、2,2-二羟甲基丁酸11份以及甲基丙烯酸甲酯2.5份,丙烯酸丁酯60份投入干燥的反应釜中,搅拌混合均匀;
将反应釜中的混合物升温至78℃,搅拌反应2h,得聚氨酯预聚体,其中,聚氨酯预聚体的NCO的含量3-4%
再向反应釜中加入13份甲基丙烯酸羟乙酯,在78℃下搅拌反应0.8h,得甲基丙烯酸羟基酯封端的聚氨酯预聚体,其中,NCO的含量1.5-2.5%,向反应釜中加入8三乙胺份,在78℃搅拌反应0.5h;
将0.6份月桂醇聚氧乙烯醚和0.8份烷基醇聚氧乙烯硫酸铵盐,溶解在460去离子水中,再加入聚氨酯预聚体中,随后将反应体系高速分散10min,得预乳液;
将所述预乳液升温至78℃,在搅拌条件下,同时将5份甲基丙烯酸羟乙酯、13份丙烯酸羟丙酯、1份γ-(甲基丙烯酰氧)丙基三甲氧基硅烷、0.5份甲基丙烯酸缩水甘油酯滴加在预乳液中,在1.5h内滴加完成;在滴加的同时,将18.45份过硫酸铵水溶液同时滴加在预乳液中,在2h内滴完,滴完后再保温0.5h。保温完后立即降温至40℃以下。得到聚氨酯乳液。
实施例3
常温下将聚己内酯二醇(Mw=1000)55份、二羟丁基封端聚硅氧烷(Mw=2000)5份、环氧树脂E51 2.5份、三羟甲基丙烷1.5份、异佛尔酮二异氰酸酯38份、二环己基甲烷二异氰酸酯9.5份、2,2-二羟甲基丁酸13份以及甲基丙烯酸甲酯5份,丙烯酸丁酯75份投入到干燥的反应釜中,搅拌混合均匀;
将反应釜中的混合物升温至83℃,搅拌反应1.5h,得聚氨酯预聚体,其中,聚氨酯预聚体的NCO的含量3-4%;
将11份加入甲基丙烯酸羟乙酯加入到聚氨酯预聚体中,在83℃下搅拌反应0.8h,得甲基丙烯酸羟基酯封端的聚氨酯预聚体,其中,NCO的含量1.5-2.5%;
向反应釜中加入8.9份三乙胺,在83℃搅拌反应0.5h;
将0.7份月桂醇聚氧乙烯醚和0.8份烷基醇聚氧乙烯硫酸铵盐,溶解在490去离子水中,再加入到加入聚氨酯预聚体中,随后将反应体高速分散10min,得预乳液;
将预乳液升温至83℃,在搅拌条件下,同时将3份甲基丙烯酸羟乙酯、8份丙烯酸羟丙酯、0.5份γ-(甲基丙烯酰氧)丙基三甲氧基硅烷滴加至预乳液中,在1h滴加完,在滴加的同时,将20份过硫酸铵水溶液滴加到预乳液中,在1.5h滴加完成,随后保温0.5h。保温完后立即降温至40℃以下,得到聚氨酯乳液。
实施例4
在常温下,将聚己内酯二醇(Mw=1000)45.5份、二羟丙基封端聚硅氧烷(Mw=1000)10份、环氧树脂E51 2.5份、三羟甲基丙烷1.5份、异佛尔酮二异氰酸酯38份、1,6-六亚甲基二异氰酸酯4份、2,2-二羟甲基丁酸12份以及甲基丙烯酸甲酯2.5份,丙烯酸丁酯60份投入干燥的反应釜中,搅拌混合均匀;
将反应釜中的混合物升温至78℃,搅拌反应2h,得聚氨酯预聚体,其中,聚氨酯预聚体的NCO的含量3-4%;
向聚氨酯预聚体中加入8份丙烯酸羟丙酯,在78℃下,搅拌反应1h,得丙烯酸羟基酯封端的聚氨酯预聚体,NCO的含量1.5-2.5%,再加入8.2份三乙胺,在78℃下,搅拌反应0.5h;
将0.6份月桂醇聚氧乙烯醚和0.8份烷基醇聚氧乙烯硫酸铵盐,溶解在435份去离子水中,再加入到聚氨酯预聚体中,随后反应体系高速分散8min,得预乳液;
将所述预乳液升温至78℃,在搅拌的条件下,同时将8份甲基丙烯酸羟乙酯、10份丙烯酸羟丙酯、1.5份γ-(甲基丙烯酰氧)丙基三甲氧基硅烷、0.5份甲基丙烯酸缩水甘油酯滴加至预乳液中,在1.5h内滴加完成;在滴加的同时,将18.45份硫酸铵水溶液滴加至预乳液中,在2h滴加完成,随后保温0.5h。保温完后,立即降温至40℃以下。得到聚氨酯乳液。
实施例5
在常温下,将聚己内酯二醇(Mw=2000)65份、二羟丙基封端聚硅氧烷(Mw=2000)20份、环氧树脂E51 2.5份、三羟甲基丙烷2份、1,6-六亚甲基二异氰酸酯4份、二环己基甲烷二异氰酸酯50份、2,2-二羟甲基丁酸14.6份以及甲基丙烯酸甲酯10份,丙烯酸丁酯70份投入干燥的反应釜中,搅拌混合均匀;
将反应釜中的混合物升温至83℃,搅拌反应1.5h,得聚氨酯预聚体,其中,聚氨酯预聚体的NCO的含量3-4%;
向聚氨酯预聚体中加入8份丙烯酸羟丙酯,在83℃下,搅拌反应0.5h,得丙烯酸羟基酯封端的聚氨酯预聚体,NCO的含量1.5-2.5%,再加入10份三乙胺,在83℃下,搅拌反应0.5h;
将0.6份月桂醇聚氧乙烯醚和0.9份烷基醇聚氧乙烯硫酸铵盐,溶解在600份去离子水中,再加入到聚氨酯预聚体中,随后反应体系高速分散5min,得预乳液;
将所述预乳液升温至83℃,在搅拌的条件下,同时将5份甲基丙烯酸羟乙酯、15份丙烯酸羟丙酯、2份γ-(甲基丙烯酰氧)丙基三甲氧基硅烷、0.5份甲基丙烯酸缩水甘油酯滴加至预乳液中,在1.5h内滴加完成;在滴加的同时,将20份硫酸铵水溶液滴加至预乳液中,在2h滴加完成,随后保温0.5h。保温完后,立即降温至40℃以下。得到聚氨酯乳液。
对于上述实施例1-5中得到的聚氨酯乳液,测定固含量、PH值、粘度等性能参数,其结果如下表所示:
上述实施例1-5中,得到的聚氨酯乳液均呈半透乳液状。上表中,聚氨酯乳液固含量的测试条件为105℃,时间为1h;实施例1-5中,聚氨酯稳定性的检测方法为:在60℃下,将聚氨酯乳液放置于容器中,静置,记录聚氨酯乳液保持均一性的时间。
向上述实施例1-5中的聚氨酯乳液中分别加入8%的WL72-100水性HDI固化剂混合后,再倒入聚四氟乙烯模具(150mm*40mm*10mm)中,室温放置一段时间至基本干燥,再于80℃干燥24h,最后在真空度0.08MPa下70℃干燥72h,制成胶膜。再将胶膜冲压成为30mm*3mm哑铃状长条,以200mm/min的拉伸速度,测试聚氨酯胶膜的力学性能,其结果如下表所示:
实施例1 实施例2 实施例3 实施例4 实施例5
拉伸强度 20MPa 23MPa 18MPa 22MPa 24MPa
拉断生长率 65% 71% 69% 77% 74%
采用GB/T 23982中的测试方法,测试实施例1-5中聚氨酯乳液制备的膜的抗粘连性(500g,(50±2)℃/4h),实施例1-5中的膜为A-0级。
采用JC/T 2327-2015中的测试方法,测试聚氨酯乳液漆膜性能,实施例1-5中的漆膜的附着力(划格间距2mm)均为≤1级,耐水性(不起泡、无剥落、无裂纹):>7d,耐磨性(750g/500r)/g:≤0.015,耐冲击均能达到60cm,在0℃下,测定聚氨酯的低温柔韧,均≤1mm。
本发明的聚氨酯乳液VOC极低,将本发明的聚氨酯乳液应用于地坪涂料、跑道球场照面等领域。该聚氨酯涂料具备优异的附着力、耐候耐磨性,耐水抗污性,低温抗冲击性,高温抗回粘性。并且本发明的聚氨酯乳液采用有机硅-环氧-丙烯酸复合改性,将环氧树脂高模量、高强度,丙烯酸树脂较好的耐候性,有机硅较好的耐水抗污性、优异的低温耐性结合在一起,提高聚氨酯涂料的综合性能;聚氨酯乳液的制备工艺绿色环保,聚氨酯的分子量易控。

Claims (10)

1.一种复合改性聚氨酯乳液,其特征在于:包括以下原料组份,以重量份数计为,
大分子多元醇35-65份;
羟烷基封端聚硅氧烷4-20份;
环氧树脂2.5-15份;
三羟甲基丙烷1.5-2份;
二异氰酸酯35-60份;
2,2-二羟甲基丁酸7-15份;
乙烯基单体70-100份;
丙烯酸羟基酯8-18份;
三乙胺7-12份;
乳化剂1.0-1.5份;
去离子水430-600份;
自交联功能单体0.5-3份;
过硫酸铵水溶液17-20份。
2.根据权利要求1所述的复合改性聚氨酯乳液,其特征在于:所述二异氰酸酯为异佛尔酮二异氰酸酯、二环己基甲烷二异氰酸酯或1,6-六亚甲基二异氰酸酯中的一种或几种。
3.根据权利要求1所述的复合改性聚氨酯乳液,其特征在于:所述大分子多元醇为分子量1000-2000的聚己内酯二元醇或聚碳酸酯二元醇。
4.根据权利要求1所述的复合改性聚氨酯乳液,其特征在于:所述羟烷基封端聚硅氧烷为分子量1000-2000的羟丙基封端聚硅氧烷或羟丁基封端聚硅氧烷。
5.根据权利要求1所述的复合改性聚氨酯乳液,其特征在于:所述环氧树脂为环氧值在0.41-0.56的双酚A型环氧树脂中的一种或多种的混合。
6.根据权利要求1所述的复合改性聚氨酯乳液,其特征在于:所述丙烯酸羟基酯为甲基丙烯酸羟乙酯、丙烯酸羟丙酯中的一种或两种的混合。
7.根据权利要求1所述的复合改性聚氨酯乳液,其特征在于:所述乳化剂为月桂醇聚氧乙烯醚、烷基醇聚氧乙烯硫酸铵盐中的一种或两种的混合。
8.根据权利要求1所述的复合改性聚氨酯乳液,其特征在于:所述乙烯基单体为甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸羟乙酯或丙烯酸羟丙酯中的一种或几种。
9.根据权利要求1所述的复合改性聚氨酯乳液,其特征在于:所述自交联功能单体为甲基丙烯酸缩水甘油酯、γ-(甲基丙烯酰氧)丙基三甲氧基硅烷中的一种或两种的混合。
10.一种制备如权利要求1-9任一所述的复合改性聚氨酯乳液的方法,其特征在于:包括以下步骤,
S1:将大分子多元醇、羟烷基封端聚硅氧烷、环氧树脂、三羟甲基丙烷、二异氰酸酯、2,2-二羟甲基丁酸和乙烯基单体搅拌混合均匀,得到混合物;
S2:将步骤S1中得到的混合物升温至73-83℃,搅拌反应1.5-3h,得聚氨酯预聚体;
S3:向步骤S2中的得到的聚氨酯预聚体中加入丙烯酸羟基酯,在73-83℃下搅拌反应0.5-1.0h,得丙烯酸羟基酯封端的聚氨酯预聚体;
S4:向上述步骤S3中得到的预聚体中加入三乙胺,在73-83℃下搅拌反应0.5h;
S5:将乳化剂溶解在去离子水中,再加入至步骤S4中得到的预聚体中,高速分散5-10min,得预乳液;
S6:将上述步骤S5中得到的所述预乳液升温至73-83℃,同时滴加乙烯基单体、自交联功能单体和过硫酸铵水溶液,其中,乙烯基单体和自交联功能单体在1-2.5h内滴完;过硫酸铵水溶液在1.5-3.5h内滴完;随后再保温0.5-1h,得聚氨酯乳液。
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Application publication date: 20190412