CN107857859B - 一种用于纺织涂层的生物基高光水性聚氨酯树脂及其制备方法 - Google Patents
一种用于纺织涂层的生物基高光水性聚氨酯树脂及其制备方法 Download PDFInfo
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Abstract
本发明提供一种用于纺织涂层的生物基高光水性聚氨酯分散体及其制备方法，该水性聚氨酯分散体包括以下原料组分及重量份：多元醇25‑70份；多异氰酸酯10‑30份；羧酸型亲水扩链剂4‑6份；中和剂3‑5份；生物基扩链剂5‑15份；小分子胺后扩链剂2‑10份；所述多元醇由石油基多元醇和生物基多元醇按照重量比(20‑40)：(5‑30)组成，生物基多元醇包括大豆油多元醇、棕榈油多元醇和松香酯多元醇中的任意一种或多种。本发明采用生物基多元醇替代部分石油基多元醇，有效的提高了产品的自然降解性，并且价格低廉，降低水性聚氨酯的生产成本，本发明还采用蓖麻油作为扩链剂，能够有效提高产品的光泽度和防腐性，有利于将该水性聚氨酯分散体广泛应用于纺织涂层。
Description
技术领域
本发明涉及高分子聚合物技术领域，具体公开了一种用于纺织涂层的生物基高光水性聚氨酯树脂及其制备方法。
背景技术
水性聚氨酯以水为分散介质，根据粒子尺寸，可分为水乳化型、水分散型和水溶型三种。它不含或含有少量有机溶剂、不燃、无毒、不污染环境、易运输、易运输、易保存、使用方便，且具有聚氨酯固有的高强度、耐磨损等优良特性。
水性聚氨酯与溶剂聚氨酯一样，是由多异氰酸酯与多羟基化合物反应，生成物的主链上含有氨基甲酸酯单元的聚合物节构。但溶剂型聚氨酯的光泽一般能达到95％以上，而水性聚氨酯的光泽一般只能在80％-85％之间。
并且传统的聚氨酯材料都是有机高分子产品，使用废弃后很难在自然环境中降解，会对环境造成一定的污染。
发明内容
本发明的目的在于克服现有的缺陷，提供一种用于纺织涂层的生物基高光水性聚氨酯树脂及其制备方法，由该水性聚氨酯树脂制备的纺织涂层不仅机械强度高，并且具有优异的耐低温性及较高的光泽度。
为了实现以上目的，本发明通过包括以下技术方案实现的：第一方面，本发明公开一种生物基高光水性聚氨酯分散体，包括以下原料组分及重量份：
优选地，所述多元醇为45-55份。
优选地，所述异氰酸酯为25-30份。
优选地，所述羧酸型亲水扩链剂为5-6份。
优选地，所述中和剂为4-5份。
优选地，所述生物基多元醇扩链剂为10-15份。
优选地，所述小分子胺后扩链剂1-2份。
优选地，所述多元醇由石油基多元醇和生物基多元醇按照重量比(20-40)：(5-30)组成。
更优选地，所述多元醇由石油基多元醇和生物基多元醇按照重量比(40-45)：(5-10)组成。
优选地，所述生物基多元醇包括大豆油多元醇、棕榈油多元醇和松香酯多元醇中的任意一种或多种。本发明采用生物基多元醇代替部分石油基多元醇，使得获得水性聚氨酯分散体具有优良的化学和物理性能，尤其是良好的耐水解性和热稳定性；由于生物基的存在聚合物容易自然降解，有利于降低环境污染。
优选地，所述大分子多元醇包括聚己内酯二醇、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，所述多异氰酸酯包括六亚甲基二异氰酸酯、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，所述生物基多元醇扩链剂为蓖麻油或蓖麻油衍生物多元醇。本发明采用蓖麻油或蓖麻油衍生物多元醇作为生物基多元醇，使得获得水性聚氨酯分散体具有较好的低温性能，耐水解性和防腐性，以及高光泽度。蓖麻油或蓖麻油衍生物多元醇通过所具有的OH基、双键以及酯键进行扩链反应，提高水性聚氨酯分散体的综合性能。
第二方面，本发明提供一种制备如上述所述的生物基高光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、所述生物基多元醇与所述多异氰酸酯在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，加入所述生物基多元醇扩链剂在80-100℃下搅拌1-2h，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，获得生物基高光水性聚氨酯分散体。
优选地，加入所述羧酸型亲水扩链剂、所述生物基多元醇扩链剂、所述小分子胺后扩链剂同时分别加入用于调节溶液浓度的溶剂。
优选地，所述溶剂为丙酮、丁酮和甲乙酮的一种或多种。
第三方面，本发明公开一种如上述所述的生物基高光水性聚氨酯分散体在制备纺织涂层的用途。
综上所述，本发明提供一种用于纺织涂层的生物基高光水性聚氨酯分散体及其制备方法，本发明的有益效果：
本发明先采用异氰酸酯单体与生物基多元醇及大分子多元醇进行反应，得到低粘度的反应物，然后依次加入羧酸型亲水扩链剂、生物基多元醇扩链剂进行反应，充分反应后，乳化分散，从而制备出储存稳定性好，耐热、耐冷、耐水性能优良，且具有较高光泽的水性聚氨酯分散体。本发明采用生物基多元醇替代部分石油基多元醇，有效的提高了产品的自然降解性，并且价格低廉，降低水性聚氨酯的生产成本，本发明还采用的蓖麻油作为扩链剂，能够有效提高产品的光泽度、耐低温性和防腐性，有利于将该水性聚氨酯分散体广泛应用于纺织涂层。
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43g聚己内酯二醇(PCL2000，相对分子质量为2000)和7.4g生物基多元醇(HM10100，相对分子质量为2500)，放入反应器中，搅拌下加入25g异氟尔酮二异氰酸酯，保持温度90℃，搅拌2小时。降温至80℃加入5.7g二羟甲基丙酸(DMPA)，11g蓖麻油，并保持80℃搅拌2小时，然后降温到65℃加入催化剂和20g丙酮，恒温反应3h，制得水性聚氨酯预聚体。
将水性聚氨酯预聚体降温至15℃，加入4.3g三乙胺，搅拌1分钟，然后转移至高速乳化机内，在1400r/min的转速下加入184g去离子水，相转变后缓慢加入1.5g乙二胺后扩链试剂，制得生物基高光水性聚氨酯分散体。
实施例2
称取30g聚己内酯二醇(PCL2000，相对分子质量为2000)和14.7g生物基多元醇(HM10100，相对分子质量为2500)，放入反应器中，搅拌下加入25g异氟尔酮二异氰酸酯，保持温度90℃，搅拌2小时。降温至80℃加入5.7g二羟甲基丙酸(DMPA)，11g蓖麻油，并保持80℃搅拌2小时，然后降温到65℃加入催化剂和20g丙酮，恒温反应3h，制得水性聚氨酯预聚体。
将水性聚氨酯预聚体降温至15℃，加入4.3g三乙胺，搅拌1分钟，然后转移至高速乳化机内，在1400r/min的转速下加入180g去离子水，相转变后缓慢加入1.5g乙二胺后扩链试剂，制得生物基高光水性聚氨酯分散体。
实施例3
称取30g聚四氢呋喃二醇(PTMG2000，相对分子质量为2000)和14.7g生物基多元醇(HM10100，相对分子质量为2500)，放入反应器中，搅拌下加入25g异氟尔酮二异氰酸酯，保持温度90℃，搅拌2小时。降温至80℃加入5.7g二羟甲基丙酸(DMPA)，11g蓖麻油，并保持80℃搅拌2小时，然后降温到65℃加入催化剂和20g丙酮，恒温反应3h，制得水性聚氨酯预聚体。
将水性聚氨酯预聚体降温至15℃，加入4.3g三乙胺，搅拌1分钟，然后转移至高速乳化机内，在1400r/min的转速下加入180g去离子水，相转变后缓慢加入1.5g乙二胺后扩链试剂，制得生物基高光水性聚氨酯分散体。
实施例4
称取30g聚己二酸丁二醇酯二醇(PAA2000，相对分子质量为2000)和14.7g生物基多元醇(HM10100，相对分子质量为2500)，放入反应器中，搅拌下加入25g异氟尔酮二异氰酸酯，保持温度90℃，搅拌2小时。降温至80℃加入5.7g二羟甲基丙酸(DMPA)，11g蓖麻油，并保持80℃搅拌2小时，然后降温到65℃加入催化剂和20g丙酮，恒温反应3h，制得水性聚氨酯预聚体。
将水性聚氨酯预聚体降温至15℃，加入4.3g三乙胺，搅拌1分钟，然后转移至高速乳化机内，在1400r/min的转速下加入180g去离子水，相转变后缓慢加入1.5g乙二胺后扩链试剂，制得生物基高光水性聚氨酯分散体。
对比例1
称取50.4g聚己内酯二醇(PCL2000，相对分子质量为2000)，放入反应器中，搅拌下加入25g异氟尔酮二异氰酸酯，保持温度90℃，搅拌2小时。降温至80℃加入16.7g二羟甲基丙酸(DMPA)，并保持80℃搅拌2小时，然后降温到65℃加入催化剂和20g丙酮，恒温反应3h，制得水性聚氨酯预聚体。
将水性聚氨酯预聚体降温至15℃，加入4.3g三乙胺，搅拌1分钟，然后转移至高速乳化机内，在1400r/min的转速下加入184g去离子水，相转变后缓慢加入1.5g乙二胺后扩链试剂，制得水性聚氨酯分散体。
检测结果：
1、对上述实施例1～4中制备的生物基高光水性聚氨酯分散体以及对比例1制备的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。
2、将实施例1～4制备的生物基高光水性聚氨酯分散体以及对比例1制备的水性聚氨酯分散体经过增稠、流平、消泡，然后涂覆至纺织布的表层，置于120℃的干燥箱中干燥1～2分钟即得纺织涂层，根据国家标准GB/T 28463-2012《纺织品装饰用涂层织物》对实施例1～4以及对比例1制备的水性聚氨酯分散体进行性能评价，其测试结果见表1。
3、光泽度：测试纺织涂饰层的光泽度，测试结果如表2所示。
表1 实施例1～4以及对比例1制备的水性聚氨酯分散体的性能结果
| 实施例1 | 实施例2 | 实施例3 | 实施例4 | 对比例1 | |
| 外观 | 透明 | 透明 | 半透明 | 透明 | 半透明 |
| 粘度/s | 43 | 35 | 45 | 52 | 47 |
| 模量/MPa | 3.6 | 4.0 | 3.5 | 3.2 | 3.2 |
| 机械强度/MPa | 27.53 | 30.16 | 29.25 | 28.73 | 25.23 |
| 伸长率/％ | 426 | 456 | 527 | 420 | 447 |
| 储存稳定性(50℃，3周) | 无异常 | 无异常 | 无异常 | 无异常 | 无异常 |
| 耐低温性(-20℃) | 不脆裂 | 不脆裂 | 不脆裂 | 不脆裂 | 脆裂 |
表2 实施例1～4以及对比例1制备的水性聚氨酯分散体的光泽度结果
| 项目 | 实施例1 | 实施例2 | 实施例3 | 实施例4 | 对比例1 |
| 光泽度(°) | 90.21 | 91.35 | 91.35 | 92.13 | 82.17 |
从表1、表2可以看出，与对比例1相比，实施例1～4制得的生物基高光水性聚氨酯分散体的外观、粘度、储存稳定性、伸长率相当，但实施例1～4制备的生物基高光水性聚氨酯分散体的机械强度和耐低温性更加优良，并且光泽度较高，有利于将生物基高光水性聚氨酯分散体广泛应用于制备纺织涂层。
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 (6)
1.一种制备用于纺织涂层的生物基高光水性聚氨酯分散体的方法，其特征在于：所述用于纺织涂层的生物基高光水性聚氨酯分散体，包括以下原料组分及重量份：
其中，所述多元醇由石油基多元醇和生物基多元醇按照重量比(40-45)：(5-10)组成，所述生物基多元醇为HM10100型号，所述生物基多元醇的相对分子质量为2500，所述多异氰酸酯为异氟尔酮二异氰酸酯，所述生物基扩链剂为蓖麻油或蓖麻油衍生物多元醇；
所述方法包括以下步骤：
1)将所述石油基多元醇、所述生物基多元醇与所述多异氰酸酯在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，加入所述生物基扩链剂在80-100℃下搅拌1-2h，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，搅拌下加入去离子水；然后加入所述小分子胺后扩链剂搅拌1-10min，获得生物基高光水性聚氨酯分散体。
2.如权利要求1所述用于纺织涂层的生物基高光水性聚氨酯分散体的制备方法，其特征在于：所述石油基多元醇包括聚己内酯二醇、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。
3.如权利要求1所述的用于纺织涂层的生物基高光水性聚氨酯分散体的制备方法，其特征在于：所述羧酸型亲水扩链剂为二羟甲基丙酸。
4.如权利要求1所述的用于纺织涂层的生物基高光水性聚氨酯分散体的制备方法，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。
5.如权利要求1所述的用于纺织涂层的生物基高光水性聚氨酯分散体的制备方法，其特征在于：加入所述羧酸型亲水扩链剂、所述生物基多元醇扩链剂、所述小分子胺后扩链剂同时分别加入用于调节溶液浓度的溶剂。
6.如权利要求5所述的用于纺织涂层的生物基高光水性聚氨酯分散体的制备方法，其特征在于：所述溶剂为丙酮、丁酮和甲乙酮的一种或多种。
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