CN113912818A - 一种可光固化水性聚氨酯的制备方法 - Google Patents
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Abstract
本发明公开了一种可光固化水性聚氨酯的制备方法,解决光固化水性涂料中部分难题。该方法是将至少一种多羟基低聚物多元醇、多异氰酸酯和小分子亲水扩链剂反应,得到末端带有异氰酸酯基团的聚氨酯预聚物,然后和小分子多元醇反应生成聚合物溶液,在40℃加入小分子中和剂,然后加入去离子水分散,待温度降至25℃以下时,加入光引发剂2‑羟基‑2‑甲基‑1‑苯基丙酮,即得可光固化水性聚氨酯分散体。本发明还提供上述制备方法得到的水性聚氨酯分散体。本发明涉及水性聚氨酯制备技术领域,该发明所采用的方法在制备过程中不易出现凝胶等现象,生产过程更易控制,可操作性更强,节省人力物力,提高生产效率,从而节省成本。
Description
技术领域
本发明属于水性聚氨酯制备技术领域,具体涉及一种水性聚氨酯分散体及其制备方法。
背景技术
水性聚氨酯具有优异的弹性、柔韧性、耐低温性、粘附性等性质。由于其是以水为分散剂,具有低VOC,异氰酸酯残留低等特点受到了越来越多的关注,并逐步取代传统油性聚氨酯。目前水性聚氨酯已被广泛应用于橡胶、薄膜、皮革、家具、纺织品等领域。
然而,大多数水性聚氨酯是线性热塑性聚合物,其两相分离的微观形态,赋予其极好的成膜性。但相较于传统油性聚氨酯,具有不耐磨、耐水耐溶剂性差等缺点,这限制了其应用范围。为了改善这些缺点,研究人员发展了一些策略,如共混、枝接、交联、共聚等,其中交联是最重要的改性策略之一。目前研究的交联改性分为单组分和双组分,双组分虽然可以极大的提高水性聚氨酯的性能,但对操作,施工,运输都有一定的要求,且适用期短。因此,单组分水性聚氨酯在生产和应用上具有一定的优势,并获得了研究人员的广泛研究。
通常单组分的交联改性方法分为三种,①在制备预聚体时引进多官能度醇/异氰酸酯,如三羟甲基丙烷、HDI三聚体。②后扩链时使用多官能度胺进行扩链,例如二乙烯三胺、三乙烯四胺等。③通过丙烯酸羟乙酯等单体进行封端,在成膜后进行光固化交联。虽然三种方法都能成功交联,但也都存在一些不利影响。如预聚体中引入过多多官能度单体,会使预聚体粘度增大,甚至在生产过程中凝胶。后扩链时加入过多多官能度扩链剂会使乳液胶体变的不稳定,缩短其储存期。通过引入丙烯酸酯,在成膜后进行光固化,则会使得水性聚氨酯的分子量大大下降,出现流挂、粘黏、不能收卷等缺点。
本发明使用自制不饱和聚酯二元醇为交联剂合成水性聚氨酯,在水性聚氨酯成膜后进行光固化交联,避免实际操作中的不利影响,提升聚氨酯的耐水性、强度等性能。
发明内容
本发明的目的是提供一种可光固化水性聚氨酯及其制备方法,以解决现有技术中的问题。
本发明的目的是通过以下技术方案来实现的:
步骤一:在氮气保护下,将多羟基低聚物多元醇、至少一种多异氰酸酯、至少一种溶剂和小分子亲水扩链剂在75℃反应2-3h,得到末端带有异氰酸酯基团的聚氨酯预聚体。
步骤二:将步骤一得到的预聚体与小分子多元醇反应2-3h,得到聚合物溶液。
步骤三:将步骤二所得到的聚合物溶液降温至40℃,加入小分子中和剂,然后加入去离子水,分散后减压蒸馏,除去多余丙酮和丁酮,得到水性聚氨酯分散体,待温度降至25℃以下时,加入光引发剂2-羟基-2-甲基-1-苯基丙酮,即得可光固化水性聚氨酯分散体。
其中,所述的多羟基低聚物、多异氰酸酯、小分子亲水扩链剂、小分子中和剂、小分子多元醇的重量份数比为(40-80):(10-40):(0-16):(0-13):(0-20)。
优选的是,所述步骤一的多羟基低聚物多元醇为聚酯多元醇和聚醚多元醇,所述聚酯多元醇质量占多羟基低聚物多元醇的总质量的1/3-1。
优选的是,所述聚酯多元醇为马来酸酐系聚酯多元醇、衣康酸系聚酯多元醇中的至少一种,所述聚醚多元醇为聚氧化丙烯二元醇,聚四氢呋喃二元醇中的至少一种。
优选的是,所述步骤一的多异氰酸酯为甲苯二异氰酸酯(TDI)、异佛尔酮二异氰酸酯(IPDI)、二苯基甲烷二异氰酸酯(MDI)、二环己基甲烷二异氰酸酯(HMDI)、六亚甲基二异氰酸酯(HDI)、赖氨酸二异氰酸酯(LDI)中的至少一种。
优选的是,所述步骤一的小分子亲水扩链剂为二羟甲基丁酸、二羟甲基丙酸、N-甲基二乙醇胺、N-丁基二乙醇胺中的至少一种。
优选的是,所述步骤二的小分子多元醇为一缩二乙二醇、新戊二醇、三缩四乙二醇、二缩三乙二醇、1,2-丙二醇、1,4-丁二醇中的至少一种。
优选的是,所述步骤三的小分子中和剂为三乙胺、氢氧化钠、氨水。
本发明还提供上述制备方法得到的水性聚氨酯分散体。
本发明的有益效果
1.本发明首先提供一种可光固化水性聚氨酯的制备方法,该方法采用的是水性聚氨酯成膜后再交联的策略,相较于在水性聚氨酯预聚体制备过程中引入交联剂而言,本发明所采用的方法在制备过程中不易出现凝胶等现象,生产过程更易控制,可操作性更强,节省人力物力,提高生产效率,从而节省成本。
2.本发明采用的光固化交联来源于不饱和聚酯多元醇中的双键,相较于使用丙烯酸羟乙酯、甲基丙烯酸羟乙酯等含双建化合物,制备含有双键的水性聚氨酯而言,本发明所制备的水性聚氨酯分散体分子量较大,在光固化前不会出现流挂、厚度不均等现象。应用于布料时,收卷不粘,可操作性更强。
附图说明
图1为本发明实施例一中各组分按质量成分表;
图2为本发明实施例二中各组分按质量成分表;
图3为本发明的拉伸测试及耐水解性能试验表;
图4为本发明的光固化交联后拉伸强度测试表;
图5为本发明中的自制不饱和聚酯多元醇UPR的核磁共振氢谱图;
图6为本发明实施例1中聚合物的核磁共振氢谱图。
具体实施方式
下面结合实施例对本发明做更进一步的说明。所描述的实施例为本发明较佳的实施方式,但本发明的实施方式并不受实施例的限制,其他的任何未背离本发明的精神实质,都包含在本发明的保护范围之内。
下列实施例中所用试剂的简称如下:
BDO为1,4-丁二醇;HMDI为二环己基甲烷二异氰酸酯;IPDI为异佛尔酮二异氰酸酯;DMF为N,N-二甲基甲酰胺;DMPA为二羟甲基丙烷;
UPR为自制分子量为1150的不饱和聚酯多元醇,所用原料为马来酸酐、己二酸、3-甲基-1,5-戊二醇。具体为:将马来酸酐、己二酸、3-甲基-1,5-戊二醇按照摩尔比1:1:2.2加入到装有磁籽、温度计、精馏管的500mL四口烧瓶中,通入氮气。在氮气保护下逐步升温至体系温度至190℃(在升温的同时保持馏头温度低于100℃),待酸值降低至50mgKOH/g后,进行减压蒸馏除水,待酸值小于1mgKOH/g后,开始降温,待体系降至室温后,取少量聚合物测定羟值,经计算分子量为1150g/mol。
实施例1
所述水性聚氨酯分散体的制备方法如下:
在反应釜中加入IPDI、UPR、DMF,将温度升至75℃,保温反应3h,将体系降温至45℃,加入DMPA、BDO、丁酮,升温至75℃,保温反应3h,即得聚氨酯溶液。将体系降温至50℃,加入丙酮降低物料体系黏度。待温度将至40℃后,加入三乙胺中和至pH为7-8,加入去离子水并高速搅拌,使得聚氨酯在水中乳化。乳化完成后减压蒸馏,除去多余丁酮、丙酮,冷却后加入光引发剂即得可光固化水性聚氨酯分散体。
实施例2
所述水性聚氨酯分散体的制备方法如下:
在反应釜中加入HMDI、UPR、DMF,将温度升至75℃,保温反应3h,将体系降温至45℃,加入DMPA、BDO、丁酮,升温至75℃,保温反应3h,即得聚氨酯溶液。将体系降温至50℃,加入丙酮降低物料体系黏度。待温度将至40℃后,加入三乙胺中和至pH为7-8,加入去离子水并高速搅拌,使得聚氨酯在水中乳化。乳化完成后减压蒸馏,除去多余丁酮、丙酮,冷却后加入光引发剂即得可光固化水性聚氨酯分散体。
为了验证本发明制备所得到的产品在光固化交联后性能得到提升,对上诉实施例产品进行拉伸测试及耐水解性能试验(见附图3、4)。
备注:拉伸测试按照GB/T 1040-92实施,耐水解测试为肉眼观测以简单判断是否对其耐水性有提升。
需要说明的是,在本文中,诸如第一和第二等之类的关系术语仅仅用来将一个实体或者操作与另一个实体或操作区分开来,而不一定要求或者暗示这些实体或操作之间存在任何这种实际的关系或者顺序。而且,术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含,从而使得包括一系列要素的过程、方法、物品或者设备不仅包括那些要素,而且还包括没有明确列出的其他要素,或者是还包括为这种过程、方法、物品或者设备所固有的要素。
尽管已经示出和描述了本发明的实施例,对于本领域的普通技术人员而言,可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型,本发明的范围由所附权利要求及其等同物限定。
Claims (8)
1.一种可光固化水性聚氨酯的制备方法,其特征在于,该方法包括:
步骤一:在氮气保护下,将多羟基低聚物多元醇、至少一种多异氰酸酯、至少一种溶剂和小分子亲水扩链剂在75℃反应2-3h,得到末端带有异氰酸酯基团的聚氨酯预聚体;
步骤二:将步骤一得到的预聚体与小分子多元醇反应2-3h,得到聚合物溶液;
步骤三:将步骤二所得到的聚合物溶液降温至40℃,加入小分子中和剂,然后加入去离子水,分散后减压蒸馏,除去多余丙酮和丁酮,得到水性聚氨酯分散体,待温度降至25℃以下时,加入光引发剂2-羟基-2-甲基-1-苯基丙酮,即得可光固化水性聚氨酯分散体;
其中,所述的多羟基低聚物、多异氰酸酯、小分子亲水扩链剂、小分子中和剂、小分子多元醇的重量份数比为(40-80):(10-40):(0-16):(0-13):(0-20)。
2.根据权利要求1所述的一种可光固化水性聚氨酯分散体的制备方法,其特征在于,所述步骤一中的多羟基低聚物多元醇为聚酯多元醇和聚醚多元醇,所述聚酯多元醇质量占多羟基低聚物多元醇的总质量的1/3-1。
3.根据权利要求2所述的一种可光固化水性聚氨酯分散体的制备方法,其特征在于,所述聚酯多元醇为马来酸酐系聚酯多元醇、衣康酸系聚酯多元醇中的至少一种,所述聚醚多元醇为聚氧化丙烯二元醇,聚四氢呋喃二元醇中的至少一种。
4.根据权利要求1所述的一种可光固化水性聚氨酯分散体的制备方法,其特征在于,所述步骤一的多异氰酸酯为甲苯二异氰酸酯(TDI)、异佛尔酮二异氰酸酯(IPDI)、二苯基甲烷二异氰酸酯(MDI)、二环己基甲烷二异氰酸酯(HMDI)、六亚甲基二异氰酸酯(HDI)、赖氨酸二异氰酸酯(LDI)中的至少一种。
5.根据权利要求1所述的一种可光固化水性聚氨酯分散体的制备方法,其特征在于,所述步骤一的小分子亲水扩链剂为二羟甲基丁酸、二羟甲基丙酸、N-甲基二乙醇胺、N-丁基二乙醇胺中的至少一种。
6.根据权利要求1所述的一种可光固化水性聚氨酯分散体的制备方法,其特征在于,所述步骤二的小分子多元醇为一缩二乙二醇、新戊二醇、三缩四乙二醇、二缩三乙二醇、1,2-丙二醇、1,4-丁二醇中的至少一种。
7.根据权利要求1所述的一种可光固化水性聚氨酯分散体的制备方法,其特征在于,所述步骤三的小分子中和剂为三乙胺、氢氧化钠、氨水。
8.权利要求1-7任何一项所述的制备方法得到的可光固化的水性聚氨酯分散体。
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