CN109608608A - 一种环保无溶剂型水性聚氨酯乳液及其制备方法 - Google Patents

一种环保无溶剂型水性聚氨酯乳液及其制备方法 Download PDF

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CN109608608A
CN109608608A CN201811495174.4A CN201811495174A CN109608608A CN 109608608 A CN109608608 A CN 109608608A CN 201811495174 A CN201811495174 A CN 201811495174A CN 109608608 A CN109608608 A CN 109608608A
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chain extender
aqueous polyurethane
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王辉
黄芳芳
杜芳琪
汤德芳
李海锋
宣润泉
杨皓
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China Tobacco Zhejiang Industrial Co Ltd
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Abstract

本发明提供一种环保无溶剂型水性聚氨酯乳液，解决传统聚氨酯合成对溶剂的依赖，提供一种具有低VOC性的水性聚氨酯产品，同时能兼顾耐温性、柔韧性和耐溶剂性，且与其他水性聚氨酯(聚酯型、聚醚型)、水性丙烯酸乳液相容性良好。具体的技术方案为：一种环保无溶剂型水性聚氨酯乳液由水和树脂组成，所述树脂按照重量百分比计算由30～50％脂肪族二异氰酸酯，25～46％聚酯二元醇，6～12％2‑[(2‑氨基乙基)氨基]乙磺酸钠盐、1～6％交联扩链剂、1～6％短链扩链剂和0～3％后扩链剂组成。

Description

一种环保无溶剂型水性聚氨酯乳液及其制备方法
技术领域
本发明属于水性油墨领域，涉及一种环保无溶剂型水性聚氨酯分散体及其制备方法，该树脂不含羧基，有出色的低VOC性，同时也能保持传统水性聚氨酯所具备的耐温性、柔韧性和耐溶剂性，而且与其他水性聚氨酯(聚酯型、聚醚型)、水性丙烯酸乳液等混合均有良好的相容性，可混合后用于更广泛的领域。
背景技术
聚氨酯是一种性能介于橡胶与塑料之间的高分子合成材料，其特点是硬度调整范围宽，既有橡胶的弹性又有塑料的硬度，因此拥有良好的力学性能和回弹性能，特别适用于涂层领域。水性聚氨酯涂料，即用水代替有机溶剂作为分散介质的聚氨酯体系，无污染、安全可靠、性能优良、相容性好、易于改性。
随着人们环保安全意识的增强，环保法规要求亦日趋严格，很多客户要求在包装行业所用及低VOC甚至零VOC的水性化产品。在传统的水性聚氨酯中，采用了如DMF、NMP、丙酮等溶剂进行预聚体的合成，这些溶剂会残留在包装材料商，形成了日后慢慢释放VOC的污染源。因此对完全无溶剂水性聚氨酯的开发和应用需求越来越多，市场潜力巨大。
为了解决溶剂残留的问题，现有文献资料主要提及除去水性聚氨酯合成中所用到的DMF、NMP等高沸点溶剂，用其他安全性较高的溶剂如三丙二醇甲醚等进行代替。但这种合成工艺未能彻底解决聚氨酯合成对溶剂的依赖，且使用传统的亲水扩链剂如二羟甲基丙酸、二羟甲基丁酸等，在无高沸点溶剂DMF、NMP等存在下，也会出现难以溶解，难以在聚氨酯合成中混合均匀等现实问题。因此彻底解决聚氨酯合成时对溶剂的依赖，对整个行业的发展都有重要意义。
发明内容
第一方面，本发明提供一种环保无溶剂型水性聚氨酯乳液，解决传统聚氨酯合成对溶剂的依赖，提供一种具有低VOC性的水性聚氨酯产品，同时能兼顾耐温性、柔韧性和耐溶剂性，且与其他水性聚氨酯(聚酯型、聚醚型)、水性丙烯酸乳液相容性良好。
具体的技术方案为：一种环保无溶剂型水性聚氨酯乳液由水和树脂组成，所述树脂按照重量百分比计算由30～50％脂肪族二异氰酸酯，25～46％聚酯二元醇，6～12％2-[(2-氨基乙基)氨基]乙磺酸钠盐、1～6％交联扩链剂、1～6％短链扩链剂和1～3％后扩链剂组成；其中，所述脂肪族二异氰酸酯为四甲基苯二甲基二异氰酸酯和异佛尔酮二异氰酸酯的混合物；所述的交联扩链剂为三羟甲基丙烷或三羟甲基乙烷；所述的短链扩链剂选自乙二醇、丁二醇、新戊二醇中的一种或多种；所述的后扩链剂为乙二胺、异佛尔酮二胺、二乙烯基三胺、三乙烯基四胺中的一种或多种。
在本发明一些优选的实施方式中，其中，所述脂肪族二异氰酸酯为四甲基苯二甲基二异氰酸酯和异佛尔酮二异氰酸酯混合比例9:1～6:4；此比例若高于这个范围，会造成最终分子量过小，乳液性能不足；若低于这个范围，又会导致合成粘度过大易凝结。
其中，所述的2-[(2-氨基乙基)氨基]乙磺酸钠盐(AAS)的含量优选为6～12％，若高于此范围会导致合成粘度大，乳液固含低；若低于此范围会导致乳液稳定性差，流平变差。
所述的交联扩链剂含量优选为1～6％，若高于此范围均会导致乳液合成稳定性差；若低于此范围会导致乳液各方面性能不足。
所述的短链扩链剂含量优选为1～6％，若高于或低于此范围均会导致乳液合成稳定性差。
所述的后扩链剂含量优选为1～3％，若高于此范围会导致乳化困难；若低于此范围会导致乳液稳定性变差。
作为优选，所述的聚酯二元醇选自聚己二酸-丁二醇酯多元醇、聚碳酸酯多元醇、聚己内酯多元醇中的一种或多种，其均分子量为2000～5000。
作为优选，所述水与树脂的质量比为7：3。
本发明采用功能型脂肪族二异氰酸酯混合液做主原料，配合普通聚酯二元醇和扩链剂合成低粘度的预聚体，解决了传统聚氨酯合成对溶剂的依赖。经乳化分散后的聚氨酯乳液，低VOC，不必经蒸馏除去传统溶剂丙酮，节省工时能耗。
第二方面，本发明还提供上述所述的环保无溶剂型水性聚氨酯乳液的制备方法，该方法包括如下步骤：
步骤1)选用的聚酯二元醇在真空条件下搅拌脱水，直到聚酯二元醇中的含水量小于200ppm后，去真空到达常压；
步骤2)保持搅拌并加入脂肪族二异氰酸酯，保温至90℃反应3h；
步骤3)保持搅拌并加入交联扩链剂，降温至80℃并保温反应1h；
步骤4)保持搅拌并加入短链扩链剂，降温至75℃继续反应1h；
步骤5)降温至55℃，保持搅拌，加入质量分数为50％的2-[(2-氨基乙基)氨基]乙磺酸钠盐的水溶液，保温50-55℃反应0.5h；
步骤6)出料将合成的树脂在高速分散机下进行分散，转速1200rpm，分散的同时加入水和后扩链剂，乳化分散0.5h，得到成品乳液。
与现有技术相比，本发明具有如下优点：
(1)本树脂主链结构不含羧基，有出色的低VOC；
(2)本树脂可以兼顾耐温性、柔韧性和耐溶剂性能；
(3)本树脂与其他水性聚氨酯(聚酯型、聚醚型)、水性丙烯酸乳液等混合均有良好的相容性，可混合后用于更广泛的领域。
具体实施方式
下面结合具体实施例对本发明予以详细说明，但不用来限制本发明的范围。
实施例1
本实施例聚氨酯乳液采用以下组分及含量的原料进行制备：
a 聚酯二元醇(分子量3000) 210g
b 四甲基苯二甲基二异氰酸酯 275.7g
c 异佛尔酮二异氰酸酯 66.6g
d 三羟甲基丙烷 27.5g
e 丁二醇 41g
f 2-[(2-氨基乙基)氨基]乙磺酸钠盐 60.8g
g 乙二胺 12g
h 去离子水 1600g
上述聚氨酯乳液按以下工艺步骤制备：
组分a在85℃，真空条件下搅拌脱水，搅拌速度为200rpm。直到组分a中的含水量小于200ppm后，结束抽真空恢复常压，升温至90℃。保持搅拌并加入组分b和c的混合液，保持90℃反应3h。降温至80℃，保持搅拌并加入组分d，80℃反应1h。降温至75℃，保持搅拌并加入组分e，继续反应1h。冷却至55℃，保持搅拌且匀速滴加组分f的50％固含水溶液，反应0.5h后出料。将合成的树脂在1200rpm转速下高速分散，加入组分h，待完全搅拌开成乳液，加入组分g，随后保持0.5h，得到成品乳液。
性能测试：
固含量：采用GB/T 2793-1995标准进行。
VOCs：采用YC 263-2008标准进行，用气相色谱检测。
耐温性：将制备乳液用线棒涂布于PET薄膜，然后真空镀铝，获得样张。放入设定好温度的烘箱中烘烤60s，最高不变色温度即为测试结果。
柔韧性：按上述方法获得样张，通过水性胶水复合到卡纸上，将复合材料反复对折，直至折口处出现明显缺陷即为测试结果。
耐溶剂性：按照国标GB/T 1690-2010进行，选用溶剂为环己酮。
漆膜硬度：按照国标GB/T 6739-2006进行，用铅笔硬度计测试。
储存稳定性：按照国标GB/T 6753.3-1986进行，条件选择50℃烘箱。
实施例2
本实施例聚氨酯乳液采用以下组分及含量的原料进行制备：
a 聚碳酸酯二元醇(分子量3000) 370g
b 四甲基苯二甲基二异氰酸酯 268.4g
c 异佛尔酮二异氰酸酯 33.3g
d 三羟甲基丙烷 28.1g
e 丁二醇 11g
f 2-[(2-氨基乙基)氨基]乙磺酸钠盐 95g
g 异佛尔酮二胺 17g
h 去离子水 1800g
上述聚氨酯乳液按实施例1工艺步骤制备。
实施例3
本实施例聚氨酯乳液采用以下组分及含量的原料进行制备：
a 聚四氢呋喃二元醇(分子量2000) 370g
b 四甲基苯二甲基二异氰酸酯 209.8g
c 异佛尔酮二异氰酸酯 88.8g
d 三羟甲基丙烷 28.1g
e 丁二醇 25g
f 2-[(2-氨基乙基)氨基]乙磺酸钠盐 76g
g 二乙烯基三胺 10.7g
h 去离子水 1800g
上述聚氨酯乳液按实施例1工艺步骤制备。
实施例4
本实施例聚氨酯乳液采用以下组分及含量的原料进行制备：
a 聚己内酯二元醇(分子量2000) 350g
b 四甲基苯二甲基二异氰酸酯 234.2g
c 异佛尔酮二异氰酸酯 66.6g
d 三羟甲基乙烷 40g
e 乙二醇 9g
f 2-[(2-氨基乙基)氨基]乙磺酸钠盐 85.5g
g 三乙烯基四胺 10g
h 去离子水 1800g
上述聚氨酯乳液按实施例1工艺步骤制备。
对比例1
本对比例聚氨酯乳液采用以下组分及含量的原料进行制备：
上述聚氨酯乳液按以下工艺步骤制备：
组分a在85℃，真空条件下搅拌脱水，搅拌速度为200rpm。直到组分a中的含水量小于200ppm后，结束抽真空恢复常压，升温至90℃。保持搅拌并加入组分b和c的混合液，保持90℃反应3h。降温至80℃，保持搅拌并加入组分d，80℃反应1h，粘度偏大补入适量丙酮降粘。降温至75℃，保持搅拌并加入组分e和f，75℃继续反应1h，粘度偏大补入适量丙酮降粘。冷却至50℃，保持搅拌并加入组分g，反应0.5h后出料。将合成的树脂在1200rpm转速下高速分散，加入组分i，待完全搅拌开成乳液，加入组分h，随后保持0.5h。通过旋蒸除去乳液中的丙酮，得到成品乳液。
对比例2
本对比例聚氨酯乳液采用以下组分及含量的原料进行制备：
a 聚碳酸酯二元醇(分子量3000) 370g
b 四甲基苯二甲基二异氰酸酯 268.3g
c 异佛尔酮二异氰酸酯 33.3g
d 二羟甲基丙酸 40.2g
e 三羟甲基丙烷 27.1g
f 丁二醇 11g
g N,N-二甲基乙醇胺 26.7g
h 异佛尔酮二胺 17g
i 去离子水 1700g
上述聚氨酯乳液按对比例1工艺步骤制备。
对比例3
本对比例聚氨酯乳液采用以下组分及含量的原料进行制备：
a 聚四氢呋喃二元醇(分子量2000) 370g
b 四甲基苯二甲基二异氰酸酯 209.8g
c 异佛尔酮二异氰酸酯 88.8g
d 二羟甲基丙酸 40.2g
e 三羟甲基丙烷 28.1g
f 丁二醇 25g
g N,N-二甲基乙醇胺 26.7g
h 二乙烯基三胺 12g
i 去离子水 1700g
上述聚氨酯乳液按对比例1工艺步骤制备。
对比例4
本对比例聚氨酯乳液采用以下组分及含量的原料进行制备：
a 聚己内酯二元醇(分子量2000) 350g
b 四甲基苯二甲基二异氰酸酯 234.2g
c 异佛尔酮二异氰酸酯 66.6g
d 二羟甲基丙酸 40.2g
e 三羟甲基乙烷 40g
f 乙二醇 9g
g N,N-二甲基乙醇胺 26.7g
h 三乙烯基四胺 10g
i 去离子水 1700g
上述聚氨酯乳液按对比例1工艺步骤制备。
对实施例1～4和对比例1～4制备的乳液，进行各项性能测试，结果如下：
表1乳液脂性能测试结果
由表1可知，实施例1-4乳液的性能相对与对比例1-4的性能，VOC含量低，耐温性、柔韧性和耐溶剂性能好，且本树脂与其他水性聚氨酯(聚酯型、聚醚型)、水性丙烯酸乳液等混合均有良好的相容性，解决了传统聚氨酯合成对溶剂的依赖，可混合后用于更广泛的领域。

Claims (4)

1.一种环保无溶剂型水性聚氨酯乳液，该乳液由水和树脂组成，其特征在于：所述树脂按照重量百分比计算由30～50％脂肪族二异氰酸酯，25～46％聚酯二元醇，6～12％2-[(2-氨基乙基)氨基]乙磺酸钠盐、1～6％交联扩链剂、1～6％短链扩链剂和1～3％后扩链剂组成；
其中，所述脂肪族二异氰酸酯为四甲基苯二甲基二异氰酸酯和异佛尔酮二异氰酸酯的混合物，其混合比例9:1～6:4；所述的交联扩链剂为三羟甲基丙烷或三羟甲基乙烷；所述的短链扩链剂选自乙二醇、丁二醇、新戊二醇中的一种或多种；所述的后扩链剂为乙二胺、异佛尔酮二胺、二乙烯基三胺、三乙烯基四胺中的一种或多种。
2.根据权利要求1所述的环保无溶剂型水性聚氨酯乳液，其特征在于：所述的聚酯二元醇选自聚己二酸-丁二醇酯多元醇、聚碳酸酯多元醇、聚己内酯多元醇中的一种或多种，其均分子量为2000～5000。
3.根据权利要求1所述的环保无溶剂型水性聚氨酯乳液，其特征在于：所述水与树脂的质量比为7：3。
4.如权利要求1所述的环保无溶剂型水性聚氨酯乳液的制备方法，其特征在于：该方法包括如下步骤：
步骤1)选用的聚酯二元醇在真空条件下搅拌脱水，直到聚酯二元醇中的含水量小于200ppm后，去真空到达常压；
步骤2)保持搅拌并加入脂肪族二异氰酸酯，保温至90℃反应3h；
步骤3)保持搅拌并加入交联扩链剂，降温至80℃并保温反应1h；
步骤4)保持搅拌并加入短链扩链剂，降温至75℃继续反应1h；
步骤5)降温至55℃，保持搅拌，加入质量分数为50％的2-[(2-氨基乙基)氨基]乙磺酸钠盐的水溶液，保温50-55℃反应0.5h；
步骤6)出料将合成的树脂在高速分散机下进行分散，转速1200rpm，分散的同时加入水和后扩链剂，乳化分散0.5h，得到成品乳液。
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