CN107722217A - 一种阴离子与非离子混合型水性聚氨酯分散体及其制备方法 - Google Patents

一种阴离子与非离子混合型水性聚氨酯分散体及其制备方法 Download PDF

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CN107722217A
CN107722217A CN201710851111.7A CN201710851111A CN107722217A CN 107722217 A CN107722217 A CN 107722217A CN 201710851111 A CN201710851111 A CN 201710851111A CN 107722217 A CN107722217 A CN 107722217A
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aqueous polyurethane
polyurethane dispersion
anion
chain extender
nonionic
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戴家兵
郑广鹏
王浩志
严正祥
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Lnzhou Ketian Aqueous Polymer Material Co Ltd
Hefei Scisky Technology Co Ltd
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Lnzhou Ketian Aqueous Polymer Material Co Ltd
Hefei Scisky Technology Co Ltd
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Abstract

本发明提供一种阴离子与非离子混合型水性聚氨酯分散体及其制备方法，包括以下原料组分及重量百分比：大分子多元醇80‑150份；异氰酸酯35‑50份；双羟基聚环氧乙烷10‑20份；羧酸型亲水扩链剂2‑4份；中和剂2‑5份；小分子多元醇扩链剂2‑10份；小分子胺后扩链剂2‑10份。本发明在制备水性聚氨酯分散体的过程中无需加入有机溶剂，避免了环境污染，本发明制备的阴离子与非离子混合型水性聚氨酯分散体主链含有Y形侧链非离子型亲水组分，使得水性聚氨酯分散体的亲水链分布均匀，性能优良，增加了水性聚氨酯分散体的稳定性；水性聚氨酯分散体的侧链含有羧酸型亲水组分优化了水性聚氨酯分散体的耐水性能。

Description

一种阴离子与非离子混合型水性聚氨酯分散体及其制备方法
技术领域
本发明涉及高分子树脂技术领域，具体公开了一种阴离子与非离子混合型水性聚氨酯分散体及其制备方法。
背景技术
目前水性聚氨酯分散体基本以内乳化的工艺进行制备，在聚氨酯树脂结构中引入亲水扩链剂，使聚氨酯树脂具有亲水性，然后高速分散在水中从而制备出水性聚氨酯分散体。水性聚氨酯分散体以水作为分散介质，安全环保无毒，广泛用于合成革、纺织涂层和粘合剂中。
目前水性聚氨酯分散体有离子型和非离子型两种。相对于非离子型来说，离子型水性聚氨酯分散体具有优良的耐热性、相对较好的耐水性和优异的机械强度。但是，离子型水性聚氨酯分散体耐酸碱盐介质稳定性差，耐冻融稳定性较差。而相对于离子型来说，非离子型水性聚氨酯的耐水性很差，机械强度低。但是，非离子型水性聚氨酯分散体耐酸碱盐介质稳定性非常优异，耐冻融稳定性也较佳。
专利CN102408536A使用两端带有羟基基团的聚乙二醇和端氨基磺酸盐制备混合型水性聚氨酯分散体，制备的分散体固体含量高，机械性能优异。但是磺酸盐本身耐水性很差，这种结构的混合型水性聚氨酯分散体耐水性不好。按照专利CN104910343A公布的方法制备出的分散体也同样存在耐水性不好的弊端。
发明内容
本发明的目的在于克服现有的缺陷，提供一种阴离子与非离子混合型水性聚氨酯分散体及其制备方法，该水性聚氨酯分散体储存稳定性好，耐水性佳，机械性能优异。
为了实现以上目的，本发明通过包括以下技术方案实现的：本发明第一方面提供一种阴离子与非离子混合型水性聚氨酯分散体，包括以下原料组分及重量百分比：
优选地，所述大分子多元醇为120-140份。
优选地，所述异氰酸酯为35-40份。
优选地，所述双端羟基非离子型亲水扩链剂为13-17份。
优选地，所述羧酸型亲水扩链剂为2-4份。
优选地，所述中和剂为1-2份。
优选地，所述小分子多元醇扩链剂为2-5份。
优选地，所述小分子胺后扩链剂3-6份。
优选地，所述双端羟基非离子型亲水扩链剂为含有两个端羟基的Y形侧链非离子型亲水扩链剂，所述双端羟基非离子型亲水扩链剂为双端羟基聚环氧乙烷。
优选地，所述双端羟基非离子型亲水扩链剂的分子式为：
其中，-R-为-CH2-、-CH2-CH2-、-CH2-COO-NH-；-R′-为-CH3；为其中，n为15-50的整数。
优选地，所述大分子多元醇包括聚环氧丙烷、聚己内酯二醇、聚四氢呋喃二醇、聚碳酸酯二醇和聚己二酸丁二醇酯二醇中的任意一种或多种。
优选地，所述异氰酸酯包括六亚甲基二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、异氟尔酮二异氰酸酯和二环己基甲烷二异氰酸酯中的任意一种或多种。
优选地，所述羧酸型亲水扩链剂为二羟甲基丙酸。
优选地，所述中和剂包括三乙胺、二乙醇胺和三乙醇胺中的任意一种或多种。
优选地，所述小分子多元醇扩链剂包括三羟甲基丙烷、甘油、丁二醇、乙二醇和环己二甲醇中的任意一种或多种。
优选地，所述小分子胺后扩链剂包括乙二胺、异氟尔酮二胺、甲苯二胺和二氨基二环己基甲烷中的任意一种或多种。
本发明第二方面提供一种制备如上述所述的阴离子与非离子混合型水性聚氨酯分散体的方法，包括以下步骤：
1)将所述大分子多元醇、所述双羟基聚环氧乙烷与所述异氰酸酯在80-100℃下搅拌1-3h，然后加入所述羧酸型亲水扩链剂在80-100℃下搅拌1-2h，继续加入所述小分子多元醇扩链剂在80-100℃下搅拌1-2h，得到获得水性聚氨酯预聚体；
2)将所述水性聚氨酯预聚体降温至1-20℃，加入所述中和剂后转移至高速分散机内，高速搅拌下加入去离子水；然后加入所述小分子胺后扩链剂低速搅拌1-10min，得到获得阴离子与非离子混合型水性聚氨酯分散体。
本发明的反应机理为：首先使得异氰酸酯单体与含有两个端羟基的Y形侧链非离子型亲水扩链剂及大分子多元醇进行反应，得到低粘度具有一定乳化能力的反应物，然后依次加入羧酸型亲水扩链剂、小分子多元醇扩链剂搅拌均匀后乳化分散，形成稳定的细乳液，使得异氰酸酯与羧酸型亲水扩链剂、小分子多元醇扩链剂在乳化后的乳液粒子内进行反应，提高分子量，从而制备出储存稳定性好，耐热、耐冷、耐水性能优良，机械强度高的水性聚氨酯分散体。
本发明第三方面提供一种如上述所述的阴离子与非离子混合型水性聚氨酯分散体在制备织物涂饰层的应用。
优选地，将所述阴离子与非离子混合型水性聚氨酯分散体经增稠、流平、消泡处理后，以0.3～0.6mm的厚度均匀涂布离型纸上，置于140～150℃的烘箱中干燥30～60s，得到半干的有一定拉丝状的粘合树脂层；将粘合树脂层贴于基布上，置于140～150℃的干燥箱中干燥1～2min，揭去离型纸，获得织物涂饰层。
综上所述，本发明提供一种阴离子与非离子混合型水性聚氨酯分散体及其制备方法，本发明的有益效果：
本发明在制备水性聚氨酯分散体的过程中无需加入有机溶剂，避免了环境污染，达到了低碳、环保、节能的目标；本发明制备的阴离子与非离子混合型水性聚氨酯分散体主链含有Y形侧链非离子型亲水组分，使得水性聚氨酯分散体的亲水链分布均匀，性能优良，增加了水性聚氨酯分散体的稳定性；水性聚氨酯分散体的侧链含有羧酸型亲水组分优化了水性聚氨酯分散体的耐水性能，进一步提高了水性聚氨酯分散体的综合性能。
进一步，本发明制备的水性聚氨酯分散体操作简单，分散更容易，合成过程易控制。
进一步，本发明获得的阴离子与非离子混合型水性聚氨酯分散体在耐水性测试中吸水率低至14％，并且，阴离子与非离子混合型水性聚氨酯分散体还具有优良的机械性能、储存稳定性、冻融性能以及耐电解质稳定性。
具体实施方式
下面结合实施例进一步阐述本发明。应理解，实施例仅用于说明本发明，而非限制本发明的范围。
实施例1
称取120g聚环氧丙烷(PPG3000，相对分子质量为3000)和20g双端羟基聚环氧乙烷(相对分子质量为1000)，放入反应器中，搅拌下加入40g二苯基甲烷二异氰酸酯，保持温度85℃，搅拌2小时。降温至50℃加入3g二羟甲基丙酸(DMPA)，2g三羟甲基丙烷，升温至70℃，并保持70℃搅拌4小时，制得水性聚氨酯预聚体。
将水性聚氨酯预聚体降温至5℃，加入1.5g三乙胺，搅拌10分钟，然后转移至高速乳化机内，在1400r/min的转速下加入300g去离子水，相转变后缓慢加入4g乙二胺后扩链试剂，制得阴离子与非离子混合型水性聚氨酯分散体。
实施例2
称取160g聚环氧丙烷(PPG3000，相对分子质量为3000)和15g双端羟基聚环氧乙烷(相对分子质量为1500)，放入反应器中，搅拌下加入35g异氟尔酮二异氰酸酯，保持温度90℃，搅拌2小时。降温至50℃加入2.5g DMPA，1.5g丁二醇，2g三羟甲基丙烷，升温至70℃，并保持70℃搅拌5小时，制得水性聚氨酯预聚体。
将水性聚氨酯预聚体降温至30℃，加入1.25g三乙胺，搅拌10分钟，然后转移至高速乳化机内，在1400r/min的转速下加入400g去离子水，相转变后缓慢加入3.6g乙二胺后扩链试剂，制得阴离子与非离子混合型水性聚氨酯分散体。
实施例3
称取100g聚四氢呋喃二醇(PTMEG2000，相对分子质量为2000)和10g双端羟基聚环氧乙烷(相对分子质量为800)，放入反应器中，搅拌下加入30g甲苯二异氰酸酯，5g六亚甲基二异氰酸酯，保持温度85℃，搅拌2小时。降温至50℃加入3.2g DMPA，2g环己二甲醇，1g三羟基丙烷，升温至70℃，并保持75℃搅拌5小时，制得水性聚氨酯预聚体。
将水性聚氨酯预聚体降温至10℃，加入1.62g三乙胺，搅拌10分钟，然后转移至高速乳化机内，在1400r/min的转速下加入320g去离子水，相转变后缓慢加入6g异氟尔酮二胺后扩链试剂，制得阴离子与非离子混合型水性聚氨酯分散体。
实施例4
称取140g聚己二酸丁二醇酯二醇(PAA2000，相对分子质量为2000)，20gPPG2000(相对分子质量为2000)和15g双端羟基聚环氧乙烷(相对分子质量为1200)，放入反应器中，搅拌下加入42g氢化二苯基甲烷二异氰酸酯和12g甲苯二异氰酸酯，保持温度85℃，搅拌2小时。降温至50℃加入3.6g二羟甲基丙酸(DMPA)，2.1g丁二醇和0.2g三羟甲基丙烷，升温至65℃，并保持65℃搅拌5小时，制得水性聚氨酯预聚体。
将水性聚氨酯预聚体降温至0℃，加入1.7g三乙胺，搅拌10分钟，，然后转移至高速乳化机内，在1400r/min的转速下加入400g去离子水，相转变后缓慢加入3g乙二胺和2g环己二胺后扩链试剂，制得阴离子与非离子混合型水性聚氨酯分散体。
检测结果：
对上述实施例1～4中制备的阴离子与非离子混合型水性聚氨酯分散体进行性能测试：
(1)粘度：用涂料4号杯进行测试。粘度测试结果如表1所示。
(2)储存稳定性：将乳液放置在50℃的环境中，三周后，观察粘度及外观有无异常，比如粘度是否增大，外观是否变的更白更倾向不透明，是否有渣滓出现等异常情况。储存稳定性的测试结果如表1所示。
(3)冻融性：放在-10℃的环境，冷冻，然后放在室温(23-25℃)下解冻，此为一个循环，每24h一个循环，冻融3～5个循环，乳液状态是否有异常。冻融性的测试结果如表1所示。
(4)耐电解质稳定性：配制质量分数为5％的氯化钠、氯化钙、氯化铝水溶液，取100g乳液，搅拌下将上述溶液缓慢加入乳液中，直到有絮凝产生停止加入，记录加入的电解质体积。耐电解质稳定性测试结果如表2所示。
(5)参照GB/T 1040-92《塑料拉伸性能试验方法》对实施例1～4获得的阴离子与非离子混合型水性聚氨酯分散体进行模量、强度、伸长率性能评价，其测试结果见表1。
(6)耐水性测试：取实施例中的1～4获得的阴离子与非离子混合型水性聚氨酯分散体均匀涂覆在聚四氟乙烯板上，室温干燥7天成膜，将膜剪成2cm×2cm的小块，称重(W0)，然后在水中浸泡24h，取出后吸干表面上的液体，称重(W1)。计算膜的吸水率：吸水率(％)＝(W1-W0)/W0。吸水率的测试结果见表1。
表1实施例1～4制得的阴离子与非离子混合型水性聚氨酯分散体的性能结果
表2实施例1～4制得的阴离子与非离子混合型水性聚氨酯分散体的耐电解质稳定性
实施例1 实施例2 实施例3 实施例4
NaCl(mL) 20.7 21.4 24.8 20.5
CaCl2(mL) 9.1 8.2 7.9 8.4
AlCl3(mL) 5.4 5.9 4.9 4.5
从表1、表2可以看出，实施例1～4制得的阴离子与非离子混合型水性聚氨酯分散体的外观、粘度正常，还具有优良的机械性能、储存稳定性、冻融性能以及耐电解质稳定性。并且，实施例1～4中水性聚氨酯分散体的吸水率为14-16％，说明本发明获得阴离子与非离子混合型水性聚氨酯分散体具有优良的耐水性。
以上，仅为本发明的较佳实施例，并非对本发明任何形式上和实质上的限制，应当指出，对于本技术领域的普通技术人员，在不脱离本发明方法的前提下，还将可以做出若干改进和补充，这些改进和补充也应视为本发明的保护范围。凡熟悉本专业的技术人员，在不脱离本发明的精神和范围的情况下，当可利用以上所揭示的技术内容而做出的些许更动、修饰与演变的等同变化，均为本发明的等效实施例；同时，凡依据本发明的实质技术对上述实施例所作的任何等同变化的更动、修饰与演变，均仍属于本发明的技术方案的范围内。

Claims (10)

1.一种阴离子与非离子混合型水性聚氨酯分散体，其特征在于：包括以下原料组分及重量百分比：
2.如权利要求1所述的阴离子与非离子混合型水性聚氨酯分散体，其特征在于：所述双端羟基非离子型亲水扩链剂的分子式为：
其中，-R-为-CH2-、-CH2-CH2-、-CH2-COO-NH-；-R′-为-CH3；为其中，n为15-50的整数。
3.如权利要求1所述的阴离子与非离子混合型水性聚氨酯分散体，其特征在于：所述大分子多元醇包括聚环氧丙烷、聚己内酯二醇、聚四氢呋喃二醇、聚碳酸酯二醇和聚己二酸丁二醇酯二醇中的任意一种或多种。
4.如权利要求1所述的阴离子与非离子混合型水性聚氨酯分散体，其特征在于：所述异氰酸酯包括六亚甲基二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、异氟尔酮二异氰酸酯和二环己基甲烷二异氰酸酯中的任意一种或多种。
5.如权利要求1所述的阴离子与非离子混合型水性聚氨酯分散体，其特征在于：所述羧酸型亲水扩链剂为二羟甲基丙酸。
6.如权利要求1所述的阴离子与非离子混合型水性聚氨酯分散体，其特征在于：所述中和剂包括三乙胺、二乙醇胺和三乙醇胺中的任意一种或多种。
7.如权利要求1所述的阴离子与非离子混合型水性聚氨酯分散体，其特征在于：所述小分子多元醇扩链剂包括三羟甲基丙烷、甘油、丁二醇、乙二醇和环己二甲醇中的任意一种或多种。
8.如权利要求1所述的阴离子与非离子混合型水性聚氨酯分散体，其特征在于：所述小分子胺后扩链剂包括乙二胺、异氟尔酮二胺、甲苯二胺和二氨基二环己基甲烷中的任意一种或多种。
9.一种制备如权利要求1至8任一所述的阴离子与非离子混合型水性聚氨酯分散体的方法，其特征在于：包括以下步骤：
1)将所述大分子多元醇、所述双端羟基非离子型亲水扩链剂与所述异氰酸酯在80-100℃下搅拌1-3h，然后加入所述羧酸型亲水扩链剂在80-100℃下搅拌1-2h，继续加入所述小分子多元醇扩链剂在80-100℃下搅拌1-2h，得到获得水性聚氨酯预聚体；
2)将所述水性聚氨酯预聚体降温至1-20℃，加入所述中和剂后转移至高速分散机内，高速搅拌下加入去离子水；然后加入所述小分子胺后扩链剂低速搅拌1-10min，得到获得阴离子与非离子混合型水性聚氨酯分散体。
10.一种如权利要求1至8任一所述的阴离子与非离子混合型水性聚氨酯分散体在制备织物涂饰层的应用。
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