CN111909346A - 高温自交联聚氨酯水分散体的制备 - Google Patents

高温自交联聚氨酯水分散体的制备 Download PDF

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CN111909346A
CN111909346A CN202010853878.5A CN202010853878A CN111909346A CN 111909346 A CN111909346 A CN 111909346A CN 202010853878 A CN202010853878 A CN 202010853878A CN 111909346 A CN111909346 A CN 111909346A
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nco
weight
parts
polyol
hydroxyl
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CN111909346B (zh
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韦子遨
韦雨春
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Shanghai Sisheng Polymer Material Co ltd
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Shanghai Sisheng Polymer Material Co ltd
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Priority to US17/108,688 priority patent/US11655331B2/en
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Abstract

本发明涉及一种高温自交联聚氨酯水分散体的制备。通过使用异氰酸酯(NCO)封闭剂封闭部分NCO,以及在后扩链阶段使用羟烷基乙二胺扩链剂引入羟基使其聚合物大分子结构上同时含有封闭的NCO基团和羟基基团。施工时,它不需要再外加其它水性树脂和交联剂,在100‑150℃、20‑30min固化条件下释放出的NCO与自身聚合物大分子链上的羟基发生充分的交联反应,形成高密度的交联结构,从而得到高性能的可以单组份使用的水性涂料。

Description

高温自交联聚氨酯水分散体的制备
技术领域
本发明涉及高分子材料领域,尤其是一种高温自交联聚氨酯水分散体的制备,以及由其制备的高温固化的单组份水性涂料。
背景技术
水性聚氨酯由于其环保性和优异的综合性能在涂料、油墨以及胶粘剂领域得到越来越广泛的应用,具有非常广阔的市场应用前景。双组份水性聚氨酯性能优异,但施工不方便,在很多应用上难以使用。单组份水性聚氨酯虽然施工方便,但性能存在较大缺陷,对于许多应用而言,单组份水性涂料体系在耐溶剂和耐化学品性方面很难达到高质量溶剂型涂料的水平,不能满足很多应用的要求。
为解决上述问题,国内外许多公司制备了水性封闭型聚异氰酸酯固化剂和封闭型聚氨酯水分散体。在施工过程中,通过加热烘烤使得被封闭的异氰酸酯(NCO)解封,再通过解封的NCO与树脂上的活性基团发生交联反应,从而获得高性能的单组份水性涂料。美国专利US9404020B2使用封闭剂封闭多异氰酸酯的部分NCO,然后用带有羧酸或羧酸盐亲水基团的多胺与之反应,实现该封闭多异氰酸酯固化剂的水性化。中国专利CN101649036B先使用异氰酸酯单体和小分子多元醇合成多异氰酸酯,然后使用二羟甲基丙酸作为亲水基团,最后用封闭剂封闭剩余的NCO,通过用三乙胺中和得到水性封闭多异氰酸酯固化剂。中国专利CN102417598B、CN102731749A和CN102978943A通过使用过量的异氰酸酯单体和聚合物多元醇、二羟甲基丙酸或磺酸盐二醇等带有亲水基团的单体反应,先合成NCO封端的大分子链聚合物,再用封闭剂封闭NCO,最后得到封闭型聚氨酯水分散体。中国专利CN101381446A和CN1238398C制备了可紫外和加热双重固化的含有封闭NCO和-C=C-双键的聚氨酯丙烯酸酯共聚物分散体,通过紫外光固化可进一步提升该类产品的性能。
就以上单纯的水性封闭型聚异氰酸酯固化剂和封闭型聚氨酯水分散体而言,其本身缺乏与NCO发生反应的活性基团,单独使用时很难形成高密度的交联结构。以上封闭型聚氨酯在实际使用过程中通常作为交联剂配合其它水性树脂使用。当加热解封时,释放出的NCO与水性树脂上的活性基团,尤其是羟基发生交联反应。以上封闭型聚氨酯在和其它水性树脂混合使用时,由于组成、结构和相分离等问题,通常会存在相容性和贮存稳定性等诸多问题。为克服以上问题,本发明设计了本身既带有封闭NCO又带有羟基基团的聚氨酯水分散体,它不需要拼混其它水性树脂和交联剂。实际使用时,加热释放出的NCO与自身聚合物大分子链上的羟基发生充分的交联反应,形成高密度的交联结构,从而得到高性能的可以单组份使用的水性涂料。
发明内容
本发明所要解决的技术问题在于提供一种高温自交联聚氨酯水分散体的制备方法,其大分子结构上同时含有封闭的NCO基团和羟基基团,使用时不需要添加其它水性树脂。
本发明所要解决的另一技术问题在于提供由上述聚氨酯水分散体制备的单组份水性涂料。
为实现以上发明目的,本发明通过下述技术方案实现:
一种高温自交联聚氨酯水分散体,其特征在于:按重量百分比计,由以下各组分组成:
含封闭NCO的羟基聚氨酯 20~40%
去离子水 60~80%
有机溶剂 0~8%
PH值调节剂 适量;
其中,在所述的含封闭NCO的羟基聚氨酯中,封闭NCO含量按干固体份计为1.8-5.0%,羟基含量按干固体份计为0.5~2.0%,其计算方法如下:
Figure DEST_PATH_IMAGE001
NCO%为如上所述的封闭NCO含量,OH%为如上所述的羟基含量,MNCO为封闭NCO的摩尔数,MOH为接入羟基的摩尔数,W为聚氨酯乳液的重量(单位为克),w%为聚氨酯乳液的固含量百分数。
其中,所述的含封闭NCO的羟基聚氨酯由按重量百分比计的下述组分制备得到:
聚合物多元醇 30~50重量份
三羟甲基丙烷或三羟甲基乙烷 0.5~3
异氰酸酯单体 30~50重量份
二羟甲基丙酸或二羟甲基丁酸 3.0~6.0重量份
NCO封闭剂 5.0~15.0重量份
羟烷基乙二胺扩链剂 4.0~10.0重量份
催化剂 0.01~0.05重量份;
针对上述的聚氨酯水分散体的制备方法,其特征包括以下步骤:
(a)先将聚合物多元醇、三羟甲基丙烷或三羟甲基乙烷、异氰酸酯单体、二羟甲基丙酸或二羟甲基丁酸、催化剂、有机溶剂按配方量加入反应釜中,其中异氰酸酯单体过量,在50~90℃反应至NCO含量达到或小于理论值。由于加入了三官能度的三羟甲基丙烷或三羟甲基乙烷,此时得到至少三官能度NCO封端的预聚体。如下所示:
Figure 24685DEST_PATH_IMAGE002
(b)在以上预聚体中加入配方量的NCO封闭剂,对NCO进行部分封闭。在50~90℃继续反应至NCO含量达到或小于理论值。RBH代表封闭剂,如下所示:
Figure DEST_PATH_IMAGE003
(c)将以上聚合物降温至20-40℃,加入配方量的PH值调节剂,再将上述反应物高速分散至配方量的去离子水中。
(d)随后加入配方量的羟烷基乙二胺扩链剂,在10~40℃反应30分钟。通过NCO与-NH2和-NH的反应引入羟基基团,同时也进一步增大聚合物的分子量。如下所示:
Figure 348350DEST_PATH_IMAGE004
(e)在步骤(a)中如果加入的有机溶剂是N-甲基吡咯烷酮等高沸点溶剂,溶剂不需分离,如果加入的溶剂是丙酮或丁酮,最后需加热减压分离。
在上述方案的基础上,所述聚合物多元醇是常规的聚酯多元醇、聚四氢呋喃醚多元醇(PTMG)、环氧乙烷聚醚多元醇(PEG)、环氧丙烷聚醚多元醇(PPG)、聚己内酯多元醇(PCL)、聚碳酸酯多元醇(PCD)和聚丙烯酸酯多元醇(PA),其分子量为400~3000,优选为1000-2000,官能度为2~3,它们可单独或作为混合物使用。
在上述方案的基础上,所述的异氰酸酯单体为异佛尔酮二异氰酸酯(IPDI)、六亚甲基二异氰酸酯(HDI)、二环己基甲烷二异氰酸酯(HMDI)、四甲基苯二亚甲基二异氰酸酯(TMXDI)、苯二亚甲基二异氰酸酯(XDI)、二苯基甲烷二异氰酸酯(MDI)、甲苯二异氰酸酯(TDI)中的一种或其几种的混合物。优选异佛尔酮二异氰酸酯(IPDI)和二环己基甲烷二异氰酸酯(HMDI)。
在上述方案的基础上,所述的NCO封闭剂为咪唑、2-甲基咪唑、3,5-二甲基吡唑、甲乙酮肟、丙酮肟、乙酰苯胺、丙二酸二乙酯、苯酚、乙酰乙酸乙酯、乙酰丙酮中的一种或其几种的混合物,优选3,5-二甲基吡唑、甲乙酮肟和丙二酸二乙酯。
在上述方案的基础上,所述的羟烷基乙二胺扩链剂为羟乙基乙二胺、N,N-二羟乙基乙二胺、羟丙基乙二胺和乙二胺二丁醇中的一种或其几种的混合物。优选羟乙基乙二胺和N,N-二羟乙基乙二胺。
在上述方案的基础上,所述的封闭NCO与扩链剂接入羟基的摩尔数比为1:1~1.5:1。
在上述方案的基础上,所述的有机溶剂为N-甲基吡咯烷酮、N-乙基吡咯烷酮、二甲基乙酰胺、二甲基甲酰胺、丙酮或丁酮中的一种或其几种的混合物。优选丙酮和N-甲基吡咯烷酮。
在上述方案的基础上,所述的PH值调节剂为三乙胺、N-甲基吗啉、二甲基乙醇胺等,优选三乙胺。
在上述方案的基础上,所述的催化剂为有机锡、有机铋和有机银等,优选环保高效的有机铋。
针对上述聚氨酯水分散体的用途,由其制备的水性涂料在不需添加外加交联剂或其它树脂的情况下,在100-150℃、20-30min固化条件下可得到优异物理化学性能的涂层。被封闭的NCO基团在加热解封后,与自身聚合物大分子链上羟基基团反应形成充分的交联结构。
NCO基团的解封过程如下所示:
Figure DEST_PATH_IMAGE005
聚合物大分子链上NCO基团与羟基基团的交联反应如下所示:
Figure 800191DEST_PATH_IMAGE006
本发明的有益效果是:本发明获得了同时含有封闭NCO和羟基基团的聚氨酯水分散体,它不需要添加其它水性树脂和交联剂,在高温烘烤条件下即可获得具有优异物理化学性能的单组份水性涂料。
具体实施方式
实施例1
制备方法为:(a)先将聚己二酸-1,6-己二醇二元醇(2000分子量)41.4重量份、三羟甲基丙烷2.2重量份、二羟甲基丙酸4.1重量份、异佛尔酮二异氰酸酯36.9重量份、丙酮22重量份(不计入最后产品的总重量份中)、有机铋催化剂0.02重量份加入反应釜中,在65-70℃反应3hr至NCO含量略低于理论值;(b)在以上反应物中加入封闭剂3,5-二甲基吡唑6.8重量份,在65-70℃继续反应2hr至NCO含量达到或小于理论值;(c)将以上聚合物降温至20-40℃,加入PH值调节剂三乙胺3.1重量份,搅拌均匀后将上述反应物高速分散至184.6重量份的去离子水中;(d)以上加入羟乙基乙二胺扩链剂4.9重量份,在10~40℃反应30分钟;(e)以上产物在加热和负压条件下分离丙酮,制得含有封闭NCO和羟基基团的聚氨水分散体。
以上产品固含量35.0%。按干固体份计,封闭NCO含量3.0%,羟基含量0.8%。封闭NCO与扩链剂接入羟基的摩尔数比为1.5:1。
实施例2
制备方法为:(a)先将聚四氢呋喃醚二元醇(1000分子量)38.1重量份、三羟甲基丙烷0.69重量份、二羟甲基丙酸4.4重量份、异佛尔酮二异氰酸酯39.6重量份、N-甲基吡咯烷酮15.0重量份、有机铋催化剂0.02重量份加入反应釜中,在70℃反应3hr至NCO含量略低于理论值;(b)在以上反应物中加入封闭剂3,5-二甲基吡唑7.3重量份,在70℃继续反应2hr至NCO含量达到或小于理论值;(c)将以上聚合物降温至20-40℃,加入PH值调节剂三乙胺3.3重量份,搅拌均匀后将上述反应物高速分散至169.8重量份的去离子水中;(d)以上加入羟乙基乙二胺扩链剂6.1重量份,在10~40℃反应30分钟,制得含有封闭NCO和羟基基团的聚氨酯水分散体。
以上产品固含量35.0%。按干固体份计,封闭NCO含量3.2%,羟基含量1.00%。封闭NCO与扩链剂接入羟基的摩尔数比为1.3:1。
实施例3
制备方法为:(a)先将聚碳酸酯二元醇(1000分子量)37.0重量份、三羟甲基丙烷0.68重量份、二羟甲基丙酸4.3重量份、异佛尔酮二异氰酸酯38.0重量份、丙酮20重量份(不计入最后产品的总重量份中)、有机铋催化剂0.02重量份加入反应釜中,在70℃反应3hr至NCO含量略低于理论值;(b)在以上反应物中加入封闭剂3,5-二甲基吡唑8.8重量份,在70℃继续反应2hr至NCO含量达到或小于理论值;(c)将以上聚合物降温至20-40℃,加入PH值调节剂三乙胺3.2重量份,搅拌均匀后将上述反应物高速分散至183重量份的去离子水中;(d)以上加入N,N-二羟乙基乙二胺扩链剂6.6重量份,在10~40℃反应30分钟;(e)以上产物在加热和负压条件下分离丙酮。制得含有封闭NCO和羟基基团的聚氨酯水分散体。
以上产品固含量35.0%。按干固体份计,封闭NCO含量3.9%,羟基含量1.5%。封闭NCO与扩链剂接入羟基的摩尔数比为1:1。
应用例
耐水性的测定方法:常温浸水试验法,按GB/T1733-1993。
耐溶剂的测定方法:用乙醇和丁酮擦拭,按GB/T23989-2009。
耐酸碱的测定方法:常温浸泡法,按GB/T9274-88。
取实施例1、实施例2和实施例3制得的含封闭NCO和羟基的聚氨酯水分散体,涂膜在120℃烘烤30min,并于室温放置24hr后进行以上耐性测试。
测试结果如下:
实施例1 实施例2 实施例3
耐水性 48hr无异常 72hr无异常 72hr无异常
耐乙醇 20次 20次 100次
耐丁酮 20次 20次 100次
耐酸性(5%H<sub>2</sub>SO<sub>4</sub>) 12hr无异常 48hr无异常 48hr无异常
耐碱性(10%NaOH) 12hr无异常 48hr无异常 48hr无异常

Claims (8)

1.一种高温自交联聚氨酯水分散体,其特征在于:按重量百分比计,由以下各组分组成:
含封闭NCO的羟基聚氨酯 20~40%
去离子水 60~80%
有机溶剂 0~8%
PH值调节剂 适量;
其中,所述的含封闭NCO的羟基聚氨酯中的封闭NCO含量按干固体份计为1.8-5.0%,羟基含量按干固体份计为0.5~2.0%;
其中,所述的含封闭NCO的羟基聚氨酯由按重量百分比计的下述组分制备得到:
聚合物多元醇 30~50重量份
三羟甲基丙烷或三羟甲基乙烷 0.5~3
异氰酸酯单体 30~50重量份
二羟甲基丙酸或二羟甲基丁酸 3.0~6.0重量份
NCO封闭剂 5.0~15.0重量份
羟烷基乙二胺扩链剂 4.0~10.0重量份
催化剂 0.01~0.05重量份;
所述的聚氨酯水分散体的制备方法,其特征包括以下步骤:(a)先将聚合物多元醇、三羟甲基丙烷或三羟甲基乙烷、异氰酸酯单体、二羟甲基丙酸或二羟甲基丁酸、催化剂、有机溶剂按配方量加入反应釜中,其中异氰酸酯单体过量,在50~90℃反应至NCO含量达到或小于理论值;(b)在以上反应物中加入配方量的NCO封闭剂,在50~90℃继续反应至NCO含量达到或小于理论值;(c)将以上聚合物降温至20-40℃,加入配方量的PH值调节剂,再将上述反应物高速分散至配方量的去离子水中;(d)随后加入配方量的羟烷基乙二胺扩链剂,在10~40℃反应30分钟;(e)在步骤(a)中如果加入的有机溶剂是高沸点溶剂,溶剂不需分离,如果加入的溶剂是丙酮或丁酮,最后需加热减压分离。
2.根据权利要求1所述的聚氨酯水分散体,其特征在于:所述聚合物多元醇是常规的聚酯多元醇、聚四氢呋喃醚多元醇(PTMG)、环氧乙烷聚醚多元醇(PEG)、环氧丙烷聚醚多元醇(PPG)、聚己内酯多元醇(PCL)、聚碳酸酯多元醇(PCD)和聚丙烯酸酯多元醇(PA),其分子量为400~3000,官能度为2~3,它们可单独或作为混合物使用。
3.根据权利要求1所述的聚氨酯水分散体,其特征在于:所述的异氰酸酯单体为异佛尔酮二异氰酸酯(IPDI)、六亚甲基二异氰酸酯(HDI)、二环己基甲烷二异氰酸酯(HMDI)、四甲基苯二亚甲基二异氰酸酯(TMXDI)、苯二亚甲基二异氰酸酯(XDI)、二苯基甲烷二异氰酸酯(MDI)、甲苯二异氰酸酯(TDI)中的一种或其几种的混合物。
4.根据权利要求1所述的聚氨酯水分散体,其特征在于:所述的NCO封闭剂为咪唑、2-甲基咪唑、3,5-二甲基吡唑、甲乙酮肟、丙酮肟、乙酰苯胺、丙二酸二乙酯、苯酚、乙酰乙酸乙酯、乙酰丙酮中的一种或其几种的混合物。
5.根据权利要求1所述的聚氨酯水分散体,其特征在于:所述的羟烷基乙二胺扩链剂为羟乙基乙二胺、N,N-二羟乙基乙二胺、羟丙基乙二胺和乙二胺二丁醇中的一种或其几种的混合物。
6.根据权利要求1所述的聚氨酯水分散体,其特征在于:所述的封闭NCO与扩链剂接入羟基的摩尔数比为1:1~1.5:1。
7.根据权利要求1所述的聚氨酯水分散体,其特征在于:所述的有机溶剂为N-甲基吡咯烷酮、N-乙基吡咯烷酮、二甲基乙酰胺、二甲基甲酰胺、丙酮或丁酮中的一种或其几种的混合物。
8.根据权利要求1所述的聚氨酯水分散体的用途,由其制备的水性涂料在不需添加外加交联剂或其它树脂的情况下,在100-150℃、20-30min固化条件下可得到优异物理化学性能的涂层。
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