CN105801810B - 一种高光高透水性聚氨酯树脂的制备方法 - Google Patents

一种高光高透水性聚氨酯树脂的制备方法 Download PDF

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CN105801810B
CN105801810B CN201610332554.0A CN201610332554A CN105801810B CN 105801810 B CN105801810 B CN 105801810B CN 201610332554 A CN201610332554 A CN 201610332554A CN 105801810 B CN105801810 B CN 105801810B
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吴广峰
杨智慧
刘雪雁
陈天琪
尹浩宇
韩冰冰
张会轩
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Changchun University of Technology
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Abstract

本发明的一种高光高透水性聚氨酯树脂的制备方法，先制备水性聚氨酯预聚体，再用十八胺对预聚体进行部分封端，然后将预聚体在去离子水中分散同时滴入亲水扩链剂2‑[(2‑氨基乙基)氨基]乙磺酸钠水溶液进行后扩链，之后在真空条件下脱去体系内丙酮或丁酮，制得一种高光泽高透水性聚氨酯树脂。本发明的方法工艺简单，不需要加很多有机溶剂，不需加消泡剂，得到的高光高透水性聚氨酯树脂的固含量高，固含量为41‑46%；拉伸强度达39.8‑42.2MPa，断裂伸长率为789‑857%。光泽度（60︒）为90，透光率为89%，定性好，胶膜耐水性好，耐溶剂性好，胶膜的机械性能，光泽度，透光率均较高。

Description

一种高光高透水性聚氨酯树脂的制备方法
技术领域
本发明涉及一种高光高透水性聚氨酯树脂的制备方法。
背景技术
目前高光泽树脂可以用于皮革涂料，织物整理，PVC塑胶涂层等。丙烯酸树脂，虽然有较好的光泽度，硬度高，耐候性也较好，但是质脆，弹性差。醇酸树脂渗透性好，但是抗粘连性差，干燥慢也限制了它的使用。一般的阴离子型高光泽性水性聚氨酯，在制备方法上，要保证高光泽度，高透光率，前扩链时要使用较多亲水扩链剂，至少在3-4%以上，例如二羟甲基丙酸或二羟甲基丁酸，但是这种羧酸型亲水扩链剂随着使用量的增多，预聚体的粘度会变大，调节粘度用的有机溶剂用量会增多，脱除丙酮时困难，丙酮脱除不彻底直接影响水性聚氨酯分散体成膜。分散体粘度变大，水分散困难，容易凝胶，固含量一般不会超过40%。羧酸型扩链剂加入量大，胶膜的耐水性变差。另外，这样的水性聚氨酯一般采用胺类小分子扩链剂进行后扩链，如乙二胺等，胺类扩链剂挥发性较大，在使用过程中对环境和人体健康带来危害。以上这些高光泽度树脂，以60︒的反射光泽为例，除了一般的阴离子水性聚氨酯树脂光泽>80%，其它两种树脂的光泽只能达到80—90%，虽然溶剂型树脂也具有较高的光泽，但是它使用大量有机溶剂，对环境和人体健康带来不利影响。
发明内容
为了克服现有高光泽水性聚氨酯制备技术上的缺陷，本发明的目的在于公开一种高光高透水性聚氨酯树脂的制备方法。
本发明的一种高光高透水性聚氨酯树脂的制备方法，步骤和条件如下：材料和质量百分比如下:多元醇49.2—66%；二异氰酸酯24.5—38.4%；催化剂0.8-1%；羧酸型亲水扩链剂2.5—3.1%；中和剂1.9-2.3%；前扩链剂1.1—4.2%；封端剂1.4—2.2%；后扩链剂1.1—1.7%；
所述的多元醇为聚四氢呋喃醚二醇、聚丙二醇和聚己二酸丁二醇酯中的一种或两种，分子量Mn均为2000；
所述的二异氰酸酯为异氟尔酮二异氰酸酯；
所述的催化剂为有机铋；
所述的羧酸型亲水扩链剂为二羟甲基丙酸和二羟甲基丁酸中的一种或两种；
所述的前扩链剂为1,4丁二醇和乙二醇中的一种或两种；
所述的后扩链剂为质量浓度为50%的2-[(2-氨基乙基)氨基]乙磺酸钠水溶液；
所述的封端剂为十八烷基胺；
制备的步骤和条件如下：
（1）按配比加料，将多元醇、催化剂的混合体系在40℃水浴加热及搅拌下，搅拌速度180rd/min,将二异氰酸酯加入混合体系中，继续搅拌，搅拌速度250rd/min,升温至85℃，保温反应1.5小时；
（2）按配比加料，将水浴温度降至75℃，搅拌速度升至300rd/min后，向反应体系中加入羧酸型亲水扩链剂，继续保温反应1.5小时；之后继续降温至53℃，向反应体系中加入1,4丁二醇保温反应1h，当体系中NCO质量分数达到34-53%时，向体系中加预聚体的质量的20%的丙酮稀释，并加入三乙胺，以100%中和度将羧酸型亲水扩链剂中和成盐，再加入十八烷基胺对预聚体进行封端改性，得到NCO端基的预聚体；
（3）水浴温度降至30℃，将得到的NCO端基的预聚体在水中进行分散，搅拌速度为2000rd/min，同时将质量浓度为5%的2-[(2-氨基乙基)氨基]乙磺酸钠水溶液以2-3g/min的滴加速度滴入水性聚氨酯分散体中进行后扩链和内交联；
（4）在温度40℃，真空度-0.08MPa的条件下脱去体系内丙酮或丁酮，得到高光高透水性聚氨酯树脂。
有益效果：本发明的一种高光高透水性聚氨酯树脂的制备方法的优点如下：（1）在后扩链时，使用一种磺酸盐亲水扩链剂2-[(2-氨基乙基)氨基]乙磺酸钠替代一般常用的小分子胺类扩链剂。这种扩链剂使用较少的量就能使聚氨酯乳液获得很优异的亲水性，水分散乳化时变的更容易，使用它能减少另一种羧酸型亲水扩链剂二羟甲基丙酸的使用量，即可以降低预聚体粘度，减少调节体系粘度的有机溶剂的使用量，在后期脱除有机溶剂时更容易。（2）亲水扩链剂2-[(2-氨基乙基)氨基]乙磺酸钠是制备高固含量、低粘度水性聚氨酯的重要单体。使用此亲水扩链剂后扩链，即可以达到较高的交联度还能降低乳液粘度，分散时加水量相对减少，即增加聚氨酯分散体最终的固含量。用此种亲水扩链剂作为后扩链剂制备水性聚氨酯时，加相对少的量就能使聚氨酯胶膜的光泽度和透光率很大的提高。另外，胺类小分子扩链剂挥发性很强，对环境和人体健康产生不利影响，而2-[(2-氨基乙基)氨基]乙磺酸钠扩链剂即安全环保，又能使聚氨酯树脂达到较高的交联度。（3）通过封端剂十八烷基胺改性的水性聚氨酯应用在织物整理和皮革涂饰时，赋予它们优良的手感及抗皱性能。（4）制作工艺简单，不需要加更多的有机溶剂，不需要加消泡剂，得到的高光高透水性聚氨酯树脂的固含量高，固含量为41-46%；拉伸强度达39.8-42.2MPa，断裂伸长率为789-857%。光泽度（60︒）为90，透光率为89%，定性好，胶膜耐水性好，耐溶剂性好，胶膜的机械性能，光泽度，透光率均较高。
具体实施方式
实施例1 一种高光高透水性聚氨酯树脂的制备方法，步骤和条件如下：材料和质量百分比如下:
多元醇49.2%，二异氰酸酯38.4%，催化剂0.8%，羧酸型亲水扩链剂2.5%,中和剂2.1%，前扩链剂4.2%，封端剂1.7%，后扩链剂1.1%；
具体的加入量如下：多元醇为聚己二酸丁二醇酯(Mn=2000)，质量43.48g；二异氰酸酯为异氟尔酮二异氰酸酯，质量33.9g；催化剂为有机铋，质量0.70g；羧酸型亲水扩链剂为二羟甲基丙酸，质量2.2g；中和剂为三乙胺，质量1.88g；前扩链剂为1,4丁二醇，质量3.74g；封端剂为十八烷基胺，质量1.52g；后扩链剂为质量分数为50%的2-[(2-氨基乙基)氨基]乙磺酸钠水溶液，2-[(2-氨基乙基)氨基]乙磺酸钠质量为1.0g；
制备的步骤和条件如下：以下步骤按配比加料；
（1）将聚己二酸丁二醇酯、催化剂有机铋的混合体系在40℃水浴加热及搅拌下，搅拌速度180rd/min,将异氟尔酮二异氰酸酯加入混合体系中，继续搅拌，搅拌速度250rd/min,升温至85℃保温反应1.5小时；
（2）将水浴温度降至75℃，搅拌速度升至300rd/min后，向反应体系中加入亲水扩链剂二羟甲基丙酸，继续保温反应1.5小时；之后继续降温至53℃，向反应体系中加入1,4丁二醇保温反应1h，当体系中NCO质量分数达到47%时，向体系中加预聚体的质量的20%的丙酮稀释，并加入三乙胺，以100%中和度将羧酸型亲水扩链剂中和成盐，再加入十八烷基胺对预聚体进行封端改性，得到的NCO端基的预聚体；
（3）水浴温度降至30℃，将得到的NCO端基的预聚体在水中进行分散，搅拌速度为2000rd/min，同时将质量浓度为5%的2-[(2-氨基乙基)氨基]乙磺酸钠水溶液以2-3g/min的滴加速度滴入水性聚氨酯分散体中进行后扩链和内交联；
（4）在温度40℃，真空度-0.08MPa条件下脱去体系内丙酮或丁酮，得到高光泽高透水性聚氨酯树脂。
实施例2 一种高光高透水性聚氨酯树脂的制备方法，步骤和条件如下：材料和质量百分比如下:
多元醇66%，二异氰酸酯24.5%，催化剂1%，羧酸型亲水扩链剂2.6%,中和剂1.9%，前扩链剂1.1%，封端剂1.4%，后扩链剂1.5%；
具体的加入量如下：多元醇为聚四氢呋喃醚二醇(Mn=2000)，质量50.21g；聚丙二醇(Mn=2000) ，质量20.45g； 二异氰酸酯为异氟尔酮二异氰酸酯，质量26.32g；催化剂为有机铋，质量1.06g；羧酸型亲水扩链剂为二羟甲基丙酸 ，质量2.8g;中和剂为三乙胺，质量2.11g；前扩链剂为1,4丁二醇，质量1.22g；封端剂为十八烷基胺，质量1.51g；后扩链剂为质量浓度为50%的2-[(2-氨基乙基)氨基]乙磺酸钠水溶液，2-[(2-氨基乙基)氨基]乙磺酸钠质量为1.64g；
制备的步骤和条件如下：以下步骤按配比加料；
（1）将多元醇聚四氢呋喃醚、聚丙二醇和催化剂有机铋的混合体系在40℃水浴加热及搅拌下，搅拌速度180rd/min,将异氟尔酮二异氰酸酯加入混合体系中，继续搅拌，搅拌速度250rd/min,升温至85℃保温反应1.5小时；
（2）将水浴温度降至75℃，搅拌速度升至300rd/min后，向反应体系中加入亲水扩链剂二羟甲基丙酸，继续保温反应1.5小时；之后继续降温至53℃，向反应体系中加入1,4丁二醇保温反应1h，当体系中NCO质量分数达到53%时，向体系中加预聚体的质量的20%的丙酮稀释，并加入三乙胺，以100%中和度将羧酸型亲水扩链剂中和成盐，再加入十八烷基胺对预聚体进行封端改性,得到NCO端基的预聚体；
（3）水浴温度降至30℃，将得到的NCO端基的预聚体在水中进行分散，搅拌速度为2000rd/min，同时将质量比为为5%的2-[(2-氨基乙基)氨基]乙磺酸钠水溶液以2-3g/min的滴加速度滴入水性聚氨酯分散体中进行后扩链和内交联；
其余的同实施例1。
实施例3 一种高光高透水性聚氨酯树脂的制备方法，步骤和条件如下：材料和质量百分比如下:多元醇57.8%，二异氰酸酯29%，催化剂0.9%，羧酸型亲水扩链剂3.1%,中和剂2.3%，前扩链剂3%，封端剂2.2%，后扩链剂1.7%
具体的加入量如下：多元醇为聚四氢呋喃醚二醇(Mn=2000) ，质量53.83g；二异氰酸酯为异氟尔酮二异氰酸酯，质量27g；
催化剂为有机铋，质量0.83g；羧酸型亲水扩链剂为二羟甲基丙酸 ，质量2.9g；中和剂为三乙胺，质量为2.18g；前扩链剂为1,4丁二醇，质量2.83g；封端剂为十八烷基胺，质量2.1g；后扩链剂为质量浓度为50%的2-[(2-氨基乙基)氨基]乙磺酸钠水溶液，2-[(2-氨基乙基)氨基]乙磺酸钠质量1.54g；
制备的步骤和条件如下：
（1）将多元醇聚四氢呋喃醚、催化剂有机铋的混合体系在40℃水浴加热及搅拌下，搅拌速度180rd/min,将异氟尔酮二异氰酸酯加入混合体系中，继续搅拌，搅拌速度250rd/min,升温至85℃保温反应1.5小时；
（2）将水浴温度降至75℃，搅拌速度升至300rd/min后，向反应体系中加入亲水扩链剂二羟甲基丙酸，继续保温反应1.5小时；之后继续降温至53℃，向反应体系中加入1,4丁二醇保温反应1h，当体系中NCO质量分数达到34%时，向体系中加预聚体的质量的20%的丙酮稀释，并加入三乙胺，以100%中和度将羧酸型亲水扩链剂中和成盐，再加入十八烷基胺对与预聚体进行封端改性,得到NCO端基的预聚体；
（3）水浴温度降至30℃，将得到的NCO端基的预聚体在水中进行分散，搅拌速度为2000rd/min，同时将质量比为为5%的2-[(2-氨基乙基)氨基]乙磺酸钠水溶液以2-3g/min的滴加速度滴入水性聚氨酯分散体中进行后扩链和内交联；
其余的同实施例1。
测定实施例1至3的一种高光高透水性聚氨酯树脂的物性和胶膜性能。结果见表1、2。
检测方法如下：
固含量测定：称取一定质量的乳液M1于一干燥的表面皿中，让其铺展于表面皿上，放进（60±5）℃ 的烘箱中干燥，称表面皿中剩余固形物的总质量至恒重M2。按照下式计算固含量：
C(%)=M2/ M1×100%
式中：C—固含量(%)；M1—试样的质量（g）；M2—固形物质量（g）
乳液粒径测试：用粒径分析仪采用动态光散射法测试粒径。取适量的乳液，用去离子水将其稀释至固含量为3‰的稀乳液。取稀释好的样品1ml，转移至石英比色皿中，再将装有稀释乳液的比色皿放入仪器光路中，在25℃的条件下，进行乳液粒径测试。
离心稳定性测定：取一定质量的乳液装在离心管里，放入离心机内，在25℃、转速为3000 r/min的条件下离心15 min，观察有无分层和沉淀，评价乳液的稳定性，若乳液无分层或沉淀则可认为在常温下放置6个月稳定。
力学性能测试：将聚氨酯胶膜剪成标准样品（哑铃状），测试温度为25℃，在电子拉伸试验机上进行测试，拉伸速度为200mm/min，每个样品测试3次取平均值。
吸水率测试：把干燥好的聚氨酯胶膜剪成1cm × 1cm的小方块，在25℃室温下测定样品小方块膜的质量，然后把小方块膜浸泡于25℃室温下的去离子水中24h后，用滤纸吸干其表面的水分，再称量其质量，依据两者的质量差求吸水率 ：
W =［(M2 －M1) / M1］× 100%
式中W为样品膜的吸水率（%），M1为样品膜浸泡前质量（g），M2为样品膜浸泡后的质量(g)。每张膜取3个小方块，取其平均值。
表1 为一种高光高透水性聚氨酯乳液性能表。
表2 为一种高光高透水性聚氨酯胶膜性能表。

Claims (5)

1.一种高光高透水性聚氨酯树脂的制备方法，其特征在于，材料和质量百分比如下:多元醇49.2—66%；二异氰酸酯24.5—38.4%；催化剂0.8-1%；羧酸型亲水扩链剂2.5—3.1%；中和剂1.9-2.3%；前扩链剂1.1—4.2%；封端剂1.4—2.2%；后扩链剂1.1—1.7%；
所述的多元醇为聚四氢呋喃醚二醇、聚丙二醇和聚己二酸丁二醇酯中的一种或两种；
所述的二异氰酸酯为异氟尔酮二异氰酸酯；
所述的催化剂为有机铋；
所述的羧酸型亲水扩链剂为二羟甲基丙酸和二羟甲基丁酸中的一种或两种；
所述的前扩链剂为1,4丁二醇和乙二醇中的一种或两种；
所述的后扩链剂为质量浓度为50%的2-[(2-氨基乙基)氨基]乙磺酸钠水溶液；
所述的封端剂为十八烷基胺；
制备的步骤和条件如下：
（1）按配比加料，将多元醇、催化剂的混合体系在40℃水浴加热及搅拌下，搅拌速度180rd/min,将二异氰酸酯加入混合体系中，继续搅拌，搅拌速度250rd/min,升温至85℃，保温反应1.5小时；
（2）按配比加料，将水浴温度降至75℃，搅拌速度升至300rd/min后，向反应体系中加入羧酸型亲水扩链剂，继续保温反应1.5小时；之后继续降温至53℃，向反应体系中加入1,4丁二醇保温反应1h，当体系中NCO质量分数达到34-53%时，向体系中加预聚体的质量的20%的丙酮稀释，并加入三乙胺，以100%中和度将羧酸型亲水扩链剂中和成盐，再加入十八烷基胺对预聚体进行封端改性，得到NCO端基的预聚体；
（3）水浴温度降至30℃，将得到的NCO端基的预聚体在水中进行分散，搅拌速度为2000rd/min，同时将质量浓度为5%的2-[(2-氨基乙基)氨基]乙磺酸钠水溶液以2-3g/min的滴加速度滴入水性聚氨酯分散体中进行后扩链和内交联；
（4）在温度40℃，真空度-0.08MPa的条件下脱去体系内丙酮或丁酮，得到高光高透水性聚氨酯树脂。
2.如权利要求1所述的一种高光高透水性聚氨酯树脂的制备方法，其特征在于，材料和质量百分比如下:多元醇49.2%，二异氰酸酯38.4%，催化剂0.8%，羧酸型亲水扩链剂2.5%,中和剂2.1%，前扩链剂4.2%，封端剂1.7%，后扩链剂1.1%；所述的多元醇为聚己二酸丁二醇酯，Mn=2000；二异氰酸酯为异氟尔酮二异氰酸酯；催化剂为有机铋；羧酸型亲水扩链剂为二羟甲基丙酸；中和剂为三乙胺；前扩链剂为1,4丁二醇；封端剂为十八烷基胺；后扩链剂为质量浓度为50%的2-[(2-氨基乙基)氨基]乙磺酸钠水溶液；
所述的制备的步骤和条件如下：
（1）按配比加料，将聚己二酸丁二醇酯、催化剂有机铋的混合体系在40℃水浴加热及搅拌下，搅拌速度180rd/min,将异氟尔酮二异氰酸酯加入混合体系中，继续搅拌，搅拌速度250rd/min,升温至85℃保温反应1.5小时；
（2）将水浴温度降至75℃，搅拌速度升至300rd/min后，按配比加料，向反应体系中加入亲水扩链剂二羟甲基丙酸，继续保温反应1.5小时；之后继续降温至53℃，向反应体系中加入1,4丁二醇保温反应1h，当体系中NCO质量分数达到47%时，向体系中加预聚体的质量的20%的丙酮稀释，并加入三乙胺，以100%中和度将羧酸型亲水扩链剂中和成盐，再加入十八烷基胺对预聚体进行封端改性，得到NCO端基的预聚体；
（3）水浴温度降至30℃，将得到的NCO端基的预聚体在水中进行分散，搅拌速度为2000rd/min，同时将质量浓度为5%的2-[(2-氨基乙基)氨基]乙磺酸钠水溶液以2-3g/min的滴加速度滴入水性聚氨酯分散体中进行后扩链和内交联。
3.如权利要求1所述的一种高光高透水性聚氨酯树脂的制备方法，其特征在于，材料和质量百分比如下:多元醇66%，二异氰酸酯24.5%，催化剂1%，羧酸型亲水扩链剂2.6%,中和剂1.9%，前扩链剂1.1%，封端剂1.4%，后扩链剂1.5%；
所述的多元醇为聚四氢呋喃醚二醇，Mn=2000；聚丙二醇，Mn=2000； 二异氰酸酯为异氟尔酮二异氰酸酯；催化剂为有机铋；羧酸型亲水扩链剂为二羟甲基丙酸；中和剂为三乙胺；前扩链剂为1,4丁二醇；封端剂为十八烷基胺；后扩链剂为质量浓度为50%的2-[(2-氨基乙基)氨基]乙磺酸钠水溶液；
所述的制备的步骤和条件如下：
（1）按配比加料，将多元醇聚四氢呋喃醚、聚丙二醇和催化剂有机铋的混合体系在40℃水浴加热及搅拌下，搅拌速度180rd/min,将异氟尔酮二异氰酸酯加入混合体系中，继续搅拌，搅拌速度250rd/min,升温至85℃保温反应1.5小时；
（2）按配比加料，将水浴温度降至75℃，搅拌速度升至300rd/min后，向反应体系中加入亲水扩链剂二羟甲基丙酸，继续保温反应1.5小时；之后继续降温至53℃，向反应体系中加入1,4丁二醇保温反应1h，当体系中NCO质量分数达到53%时，向体系中加预聚体的质量的20%的丙酮稀释，并加入三乙胺，以100%中和度将羧酸型亲水扩链剂中和成盐，再加入十八烷基胺对预聚体进行封端改性,得到NCO端基的预聚体；
（3）水浴温度降至30℃，将得到的NCO端基的预聚体在水中进行分散，搅拌速度为2000rd/min，同时将质量浓度为5%的2-[(2-氨基乙基)氨基]乙磺酸钠水溶液以2-3g/min的滴加速度滴入水性聚氨酯分散体中进行后扩链和内交联。
4.如权利要求1所述的一种高光高透水性聚氨酯树脂的制备方法，其特征在于，材料和质量百分比如下:多元醇57.8%，二异氰酸酯29%，催化剂0.9%，羧酸型亲水扩链剂3.1%,中和剂2.3%，前扩链剂3%，封端剂2.2%，后扩链剂1.7%；所述的多元醇为聚四氢呋喃醚二醇，Mn=2000；二异氰酸酯为异氟尔酮二异氰酸酯；催化剂为有机铋；羧酸型亲水扩链剂为二羟甲基丙酸；中和剂为三乙胺；前扩链剂为1,4丁二醇；封端剂为十八烷基胺；后扩链剂为质量浓度为50%的2-[(2-氨基乙基)氨基]乙磺酸钠水溶液；
所述的步骤（1）按配比加料，将多元醇聚四氢呋喃醚、催化剂有机铋的混合体系在40℃水浴加热及搅拌下，搅拌速度180rd/min, 将异氟尔酮二异氰酸酯加入混合体系中，继续搅拌，搅拌速度250rd/min,升温至85℃保温反应1.5小时；（2）将水浴温度降至75℃，搅拌速度升至300rd/min后，向反应体系中加入亲水扩链剂二羟甲基丙酸，继续保温反应1.5小时；之后继续降温至53℃，向反应体系中加入1,4丁二醇保温反应1h，当体系中NCO质量分数达到34%时，向体系中加预聚体的质量的20%的丙酮稀释，并加入三乙胺，以100%中和度将羧酸型亲水扩链剂中和成盐，再加入十八烷基胺对预聚体进行封端改性，得到NCO端基的预聚体；
所述的步骤（3）水浴温度降至30℃，将得到的NCO端基的预聚体在水中进行分散，搅拌速度为2000rd/min，同时将质量浓度为5%的2-[(2-氨基乙基)氨基]乙磺酸钠水溶液以2-3g/min的滴加速度滴入水性聚氨酯分散体中进行后扩链和内交联。
5.如权利要求1所述的一种高光高透水性聚氨酯树脂的制备方法，其特征在于，所述的多元醇为聚四氢呋喃醚二醇、聚丙二醇和聚己二酸丁二醇酯的分子量Mn均为2000。
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