CN107698731A - 一种poss/b 改性的高硬度丙烯酸‑聚氨酯乳液 - Google Patents
一种poss/b 改性的高硬度丙烯酸‑聚氨酯乳液 Download PDFInfo
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Abstract
本发明涉及一种POSS/B改性的高硬度丙烯酸‑聚氨酯乳液,其制备方法为:采用低聚物多元醇、硼酸衍生物、异氰酸酯单体先合成改性聚氨酯,再加入交联型丙烯酸单体、六丙烯酸酯基POSS在催化剂作用下醇扩链剂合成POSS/B丙烯酸‑聚氨酯预聚体,最后通过中和、乳化、胺扩链剂等合成所述的POSS/B改性的高硬度丙烯酸‑聚氨酯乳液。本发明制得的一种POSS/B改性的高硬度丙烯酸‑聚氨酯乳液,具有高硬度和贮存稳定性,制成的涂膜具有优异的附着力、耐磨性、耐水性、耐老化性、耐沾污性、柔韧性、耐腐蚀性和自阻燃性。
Description
技术领域
本发明涉及一种丙烯酸-聚氨酯乳液,尤其涉及到一种POSS/B改性的高硬度丙烯酸-聚氨酯乳液,属于水性树脂技术领域。
技术背景
国内外相继制定了严厉的环保法规来限制挥发性有机化合物(VOC)向大气排放,高性能、环保化已成为涂料发展的方向。聚氨酯树脂的合成由传统的溶剂型向水性聚氨酯转变,水性聚氨酯涂料以水为溶剂,具有无污染、安全可靠、机械性能优良、相容性好、易于改性等优点,以其耐久性和耐化学性而著名,在木器漆领域与汽车涂料领域由于其优异的性能,受到用户的青睐。
但聚氨酯乳液存在固含量较小、成膜时间长、涂层可燃点低等缺点,专利和文章中存在大量有关改性水性聚氨酯研究与应用的发表。
中国专利CN105461863A公开了一种丙烯酸酯改性水性聚氨酯乳液及其制备方法,利用丙烯酸酯对水性聚氨酯进行改性,得到综合性能优异的聚氨酯材料,利用丙烯酸酯参与反应将双键引入到聚氨酯主链,随后引发丙烯酸单体的聚合,能够形成复杂的网状结构,相比较传统水性聚氨酯来说,耐水性、耐热性、力学性能有了明显的提高。
另一方面,随着人们生活水平的提高,阻燃建筑涂料、阻燃饰面涂料受到消费者的欢迎。中国专利CN105238245A公开了一种环氧树脂改性的水性聚氨酯阻燃涂料及其制备方法,通过加入阻燃剂达到涂料阻燃标准,其优点为水性聚氨酯阻燃涂料不仅涂膜硬度高、耐水性好,而且它耐火时间长、发烟量少、阻燃性好、无毒无害。但由于加入阻燃剂聚磷酸铵、三聚氰胺和季戊四醇等小分子、可溶性化合物或有害物,因此存在阻燃剂易游离于涂料表面、阻燃时效短、涂层对人体有害等缺点。
发明内容
本发明旨在提供一种POSS/B改性的高硬度丙烯酸-聚氨酯乳液及其制备方法。
POSS又称笼型聚倍半硅氧烷,是由Si-O交替连接的硅氧骨架组成的无机内核,其形状如同一个“笼子”,属于纳米化合物。POSS基团的多样性、高活性以及较好的聚合物相容性使之既可以通过物理共混又可以通过化学共聚的方法将其引入到聚合物材料中。
POSS改性聚合物能显著改善聚合物材料的表面光滑性、耐磨性、透明性和柔韧性;利用POSS的八臂结构和具有反应活性的官能团以及高度对称性,制备的树脂是一种星形树枝状聚合物,获得更高的交联密度,提高涂膜的致密性、耐水性和硬度。
本发明所述的POSS/B改性的高硬度丙烯酸-聚氨酯乳液,是在丙烯酸-聚氨酯分子结构上引入硼酸衍生物和六丙烯酸酯基POSS,使得丙烯酸-聚氨酯分子骨架中含有硼氧键、硅氧键,具有星形树枝状结构,有效提高丙烯酸乳液的耐水性、自洁性、耐磨性、耐腐蚀性和阻燃性。
为克服现有技术的缺点和不足,本发明采取以下技术方案,所述的一种POSS/B改性的高硬度丙烯酸-聚氨酯乳液,按重量份数计,其成分为:10.0~20.0份低聚物多元醇、6.0~12.0份硼酸衍生物、30.0~40.0份异氰酸酯单体、5.0~10.0份交联型丙烯酸单体、5.0~10.0份六丙烯酸酯基POSS、1.0~3.0份催化剂、0.02~0.5份引发剂、2.0~10.0份醇扩链剂、2.0~5.0份三乙胺、1.0~3.0份胺扩链剂、100.0~180.0份去离子水。
其中,所述的低聚物多元醇为聚酯多元醇或聚醚多元醇;所述的聚酯多元醇为聚己二酸丁二醇酯二元醇、聚碳酸酯二元醇或聚己内酯二元醇中的至少一种,Mn为1000~3000;所述的聚醚多元醇为聚四氢呋喃醚二醇、聚四亚甲基醚二醇或聚环氧丙烷醚二醇中的至少一种,Mn为1000~3000。
所述的硼酸衍生物为硼酸三乙酯、硼酸三甲酯、硼酸三异丙酯、苯基硼酸、3-氟苯基硼酸、仲丁基硼酸、4-氟苯基硼酸、3-甲氧基苯基硼酸、正丁基硼酸、2-甲氧基苯基硼酸、苯乙基硼酸、对乙基苯硼酸、2-氟吡啶-3-硼酸、4-溴苯硼酸、4-氯苯硼酸、正丙基硼酸、4-正丙基苯硼酸或对羧基苯基硼酸中的至少一种。
所述的异氰酸酯单体为HDI、MDI、IPDI或HMDI中的至少一种。
所述的催化剂为碱性金属羧酸盐、有机金属化合物、含磷化合物或胺类;进一步的,优选为二月桂酸二丁基锡、醋酸锂、三正丁基磷、辛酸亚锡、环烷酸锡、环烷酸铅、环烷酸钴、马来酸二丁基锡或二乙酸二丁基锡中的至少一种。
所述的交联型丙烯酸单体为N-羟乙基丙烯酰胺、N-羟甲基丙烯酰胺或N-羟丙基丙烯酰胺中的至少一种。
所述的六丙烯酸酯基POSS,其分子结构式如下:
所述的引发剂为过硫酸铵、过硫酸钾或过硫酸钠中的至少一种。
所述的醇扩链剂为乙二醇、1,2-丙二醇、1,4-丁二醇、1,6-己二醇、1,5-戊二醇、三羟甲基丙烷、新戊二醇或甘醇中的至少一种。
所述的胺扩链剂为乙二胺、二乙烯三胺、己二胺或哌嗪中的至少一种。
所述的POSS/B改性的高硬度丙烯酸-聚氨酯乳液,其制备方法如下:
a)、合成POSS/B-丙烯酸改性聚氨酯预聚体:将10.0~20.0份低聚物多元醇、6.0~12.0份硼酸衍生物、30.0~40.0份异氰酸酯单体、1.0~3.0份催化剂加入到反应釜中,通N2保护,在300~600rpm转速搅拌下,升温到80~100℃反应1~2h;然后逐滴滴加5.0~10.0份交联型丙烯酸单体、5.0~10.0份六丙烯酸酯基POSS和0.02~0.1份引发剂的混合液,保持在80~100℃继续反应1~3h;降温至60~80℃,加入20.0~30.0份溶剂稀释调节体系粘度,再加入2.0~10.0份醇扩链剂、0.02~0.1份催化剂继续反应1~3h,得所述的POSS/B-丙烯酸改性聚氨酯预聚体;
b)、制备POSS/B改性的丙烯酸-聚氨酯乳液:将所述的POSS/B-丙烯酸改性聚氨酯预聚体降温到35~45℃,加入2.0~5.0份中和剂三乙胺,搅拌5~10min;接着加入80.0~150.0份去离子水,在1000~1200rpm高速下乳化15~30min;然后在300~500rpm低速下滴加2.5~13.0%胺扩链剂水溶液20.0~45.0份,在15~30min内滴加完毕,保持扩链反应1~2h,然后减压蒸馏出溶剂,得所述的POSS/B改性的丙烯酸-聚氨酯乳液。
其中,所述的溶剂为丙酮、丁酮、环己酮中的至少一种。
所述的2.5~13.0%胺扩链剂水溶液:将1.0~3.0份胺扩链剂溶解在20.0~40.0份的去离子水中。
本发明制得的一种POSS/B改性的高硬度丙烯酸-聚氨酯乳液,具有高硬度和贮存稳定性,制成的涂膜具有优异的附着力、耐磨性、耐水性、耐老化性、耐沾污性、柔韧性、耐腐蚀性和自阻燃性。
具体实施方式
下面结合实施例对本发明的一种POSS/B改性的高硬度丙烯酸-聚氨酯乳液做进一步的描述。可以理解的是,此处所描述的具体实施例仅仅用于解释相关发明,而非对该发明的限定。
实施例1
一种POSS/B改性的高硬度丙烯酸-聚氨酯乳液,由以下步骤制备:
a)、合成POSS/B-丙烯酸改性聚氨酯预聚体:将20.0份聚己二酸丁二醇酯二元醇(Mn1000)、12.0份硼酸三甲酯、32.0份MDI、2.0份二月桂酸二丁基锡加入到反应釜中,通N2保护,在500rpm转速搅拌下,升温到95℃反应1.6h;然后逐滴滴加8.0份N-羟乙基丙烯酰胺、6.0份六丙烯酸酯基POSS和0.1份过硫酸铵的混合液,保持在80℃继续反应3h;降温至60℃,加入30.0份丁酮稀释调节体系粘度,再加入6.0份1,4-丁二醇、0.04份二月桂酸二丁基锡继续反应2h,得所述的POSS/B-丙烯酸改性聚氨酯预聚体;
b)、制备POSS/B改性的丙烯酸-聚氨酯乳液:将所述的POSS/B改性的丙烯酸-聚氨酯预聚体降温到35℃,加入4.0份中和剂三乙胺,搅拌10min;接着加入130.0份去离子水,在1200rpm高速下乳化25min;然后在300rpm低速下滴加7.5%的二乙烯三胺水溶液27.0份,在30min内滴加完毕,保持扩链反应1.8h,然后减压蒸馏出溶剂丁酮,得所述POSS/B改性的丙烯酸-聚氨酯乳液。
实施例2
一种POSS/B改性的高硬度丙烯酸-聚氨酯乳液,由以下步骤制备:
a)、合成POSS/B-丙烯酸改性聚氨酯预聚体:将10.0份聚环氧丙烷醚二醇(Mn1500)、6.0份对乙基苯硼酸、40.0份IPDI、3.0份环烷酸钴加入到反应釜中,通N2保护,在300rpm转速搅拌下,升温到80℃反应2h;然后逐滴滴加10.0份N-羟甲基丙烯酰胺、5.0份六丙烯酸酯基POSS和0.02份过硫酸钾的混合液,保持在80℃继续反应3h;降温至60℃,加入30.0份丙酮稀释调节体系粘度,再加入2.0份1,6-己二醇、0.02份环烷酸钴继续反应3h,得所述的POSS/B-丙烯酸改性聚氨酯预聚体;
b)、制备POSS/B改性的丙烯酸-聚氨酯乳液:将所述的POSS/B改性的丙烯酸-聚氨酯预聚体降温到45℃,加入2.0份中和剂三乙胺,搅拌5min;接着加入120.0份去离子水,在1200rpm高速下乳化10min;然后在200rpm低速下滴加7.0%的二乙烯三胺水溶液43.0份,在10min内滴加完毕,保持扩链反应1h,然后减压蒸馏出溶剂丙酮,得所述POSS/B改性的丙烯酸-聚氨酯乳液。
实施例3
一种POSS/B改性的高硬度丙烯酸-聚氨酯乳液,由以下步骤制备:
a)、合成POSS/B-丙烯酸改性聚氨酯预聚体:将12.4份聚己内酯二元醇(Mn3000)、10.5份仲丁基硼酸、36.0份HMDI、1.8份马来酸二丁基锡加入到反应釜中,通N2保护,在450rpm转速搅拌下,升温到92℃反应1.5h;然后逐滴滴加8.5份N-羟甲基丙烯酰胺、8.0份六丙烯酸酯基POSS和0.05份过硫酸铵的混合液,保持在92℃继续反应2.5h;降温至80℃,加入28.0份丙酮稀释调节体系粘度,再加入6.0份新戊二醇、0.05份马来酸二丁基锡继续反应2.5h,得所述的POSS/B-丙烯酸改性聚氨酯预聚体;
b)、制备POSS/B改性的丙烯酸-聚氨酯乳液:将所述的POSS/B改性的丙烯酸-聚氨酯预聚体降温到40℃,加入4.0份中和剂三乙胺,搅拌10min;接着加入120.0份去离子水,在1000rpm高速下乳化20min;然后在400rpm低速下滴加4.0%的己二胺水溶液37.5份,在20min内滴加完毕,保持扩链反应1.5h,然后减压蒸馏出溶剂丙酮,得所述POSS/B改性的丙烯酸-聚氨酯乳液。
本发明实施例中的POSS/B改性的高硬度丙烯酸-聚氨酯乳液,其技术指标如表1所示:
表1 POSS改性高硬度耐水性醇酸树脂技术指标
固含量 | 粘度 | 玻璃化温度Tg | |
实施例1 | 36.8% | 355±10mPa·s | 45℃ |
实施例2 | 33.5% | 320±10mPa·s | 42℃ |
实施例3 | 36.0% | 315±10mPa·s | 47℃ |
将本发明的实施例的乳液配制成水性防火涂料与市面上的自阻燃型丙烯酸防火涂料(对比例)进行性能对比测试,按照相关标准进行检测,其测试数据如表2所示:
表2水性自阻燃型涂料性能技术指标
尽管本发明已作了详细说明并引用了实施例,但对于本领域的普通技术人员,显然可以按照上述说明而做出的各种方案、修改和改动,都应该包括在权利要求的范围之内。
Claims (9)
1.一种POSS/B改性的高硬度丙烯酸-聚氨酯乳液,其特征在于,所述的POSS/B改性的高硬度丙烯酸-聚氨酯乳液,按重量份数计,其成分为:10.0~20.0份低聚物多元醇、6.0~12.0份硼酸衍生物、30.0~40.0份异氰酸酯单体、5.0~10.0份交联型丙烯酸单体、5.0~10.0份六丙烯酸酯基POSS、1.0~3.0份催化剂、0.02~0.5份引发剂、2.0~10.0份醇扩链剂、2.0~5.0份三乙胺、1.0~3.0份胺扩链剂、100.0~180.0份去离子水;
其中,所述的六丙烯酸酯基POSS,其分子结构式如下:
所述的硼酸衍生物为硼酸三乙酯、硼酸三甲酯、硼酸三异丙酯、苯基硼酸、3-氟苯基硼酸、仲丁基硼酸、4-氟苯基硼酸、3-甲氧基苯基硼酸、正丁基硼酸、2-甲氧基苯基硼酸、苯乙基硼酸、对乙基苯硼酸、2-氟吡啶-3-硼酸、4-溴苯硼酸、4-氯苯硼酸、正丙基硼酸或4-正丙基苯硼酸或对羧基苯基硼酸中的至少一种;
所述的异氰酸酯单体为HDI、MDI、IPDI或HMDI中的至少一种;所述的交联型丙烯酸单体为N-羟乙基丙烯酰胺、N-羟甲基丙烯酰胺或N-羟丙基丙烯酰胺中的至少一种。
2.根据权利要求1所述的POSS/B改性的高硬度丙烯酸-聚氨酯乳液,其特征在于,所述的低聚物多元醇为聚酯多元醇或聚醚多元醇;所述的聚酯多元醇为聚己二酸丁二醇酯二元醇、聚碳酸酯二元醇或聚己内酯二元醇中的至少一种,Mn为1000~3000;所述的聚醚多元醇为聚四氢呋喃醚二醇、聚四亚甲基醚二醇或聚环氧丙烷醚二醇中的至少一种,Mn为1000~3000。
3.根据权利要求1所述的POSS/B改性的高硬度丙烯酸-聚氨酯乳液,其特征在于,所述的催化剂为碱性金属羧酸盐、有机金属化合物、含磷化合物或胺类。
4.根据权利要求1所述的POSS/B改性的高硬度丙烯酸-聚氨酯乳液,其特征在于,所述的催化剂为二月桂酸二丁基锡、醋酸锂、三正丁基磷、辛酸亚锡、环烷酸锡、环烷酸铅、环烷酸钴、马来酸二丁基锡或二乙酸二丁基锡中的至少一种。
5.根据权利要求1所述的POSS/B改性的高硬度丙烯酸-聚氨酯乳液,其特征在于,所述的引发剂为过硫酸铵、过硫酸钾或过硫酸钠中的至少一种。
6.根据权利要求1所述的POSS/B改性的高硬度丙烯酸-聚氨酯乳液,其特征在于,所述的醇扩链剂为乙二醇、1,2-丙二醇、1,4-丁二醇、1,6-己二醇、1,5-戊二醇、三羟甲基丙烷、新戊二醇或二甘醇中的至少一种;所述的胺扩链剂为乙二胺、二乙烯三胺、己二胺或哌嗪中的至少一种。
7.一种根据权利要求1所述的POSS/B改性的高硬度丙烯酸-聚氨酯乳液的制备方法,其特征在于,步骤如下:
a)、合成POSS/B-丙烯酸改性聚氨酯预聚体:将10.0~20.0份低聚物多元醇、6.0~12.0份硼酸衍生物、30.0~40.0份异氰酸酯单体、1.0~3.0份催化剂加入到反应釜中,通N2保护,在300~600rpm转速搅拌下,升温到80~100℃反应1~2h;然后逐滴滴加5.0~10.0份交联型丙烯酸单体、5.0~10.0份六丙烯酸酯基POSS和0.02~0.1份引发剂的混合液,保持在80~100℃继续反应1~3h;降温至60~80℃,加入20.0~30.0份溶剂稀释调节体系粘度,再加入2.0~10.0份醇扩链剂、0.02~0.1份催化剂继续反应1~3h,得所述的POSS/B-丙烯酸改性聚氨酯预聚体;
b)、制备POSS/B改性的丙烯酸-聚氨酯乳液:将所述的POSS/B-丙烯酸改性聚氨酯预聚体降温到35~45℃,加入2.0~5.0份中和剂三乙胺,搅拌5~10min;接着加入80.0~150.0份去离子水,在1000~1200rpm高速下乳化15~30min;然后在300~500rpm低速下滴加2.5~13.0%胺扩链剂水溶液20.0~45.0份,在15~30min内滴加完毕,保持扩链反应1~2h,然后减压蒸馏出溶剂,得所述的POSS/B改性的丙烯酸-聚氨酯乳液。
8.根据权利要求7所述的POSS/B改性的高硬度丙烯酸-聚氨酯乳液,其特征在于,所述的溶剂为丙酮、丁酮、环己酮中的至少一种。
9.根据权利要求7所述的POSS/B改性的高硬度丙烯酸-聚氨酯乳液,其特征在于,所述的2.5~13.0%胺扩链剂水溶液,将1.0~3.0份胺扩链剂溶解在20.0~40.0份的去离子水中。
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