CN114805735A - 一种水性聚氨酯树脂乳液的无溶剂合成方法 - Google Patents
一种水性聚氨酯树脂乳液的无溶剂合成方法 Download PDFInfo
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Abstract
本发明公开了一种水性聚氨酯树脂乳液的无溶剂合成方法：在反应器内加入5‑30份多元醇、0.5‑8份亲水单体和0‑1份催化剂，升温至100‑150℃，加入5‑30份二异氰酸酯、0‑5份扩链剂、0‑5份助剂，搅拌反应3‑5h，得到聚氨酯预聚物；将所得聚氨酯预聚物加入到高速搅拌的50‑80份水中，并加入0‑5份扩链剂和0‑5份助剂，混合均匀后，得到水性聚氨酯树脂乳液产物；本发明的水性聚氨酯树脂乳液合成过程不使用溶剂，工艺简单，适用性广，制得的水性聚氨酯树脂乳液品质稳定，性能优秀，可以应用在皮革、油墨、粘结剂、涂料等多个场合。
Description
技术领域
本发明涉及水性聚氨酯的合成方法，具体涉及一种无溶剂的水性聚氨酯合成工艺方法。
背景技术
水性聚氨酯树脂材料在皮革、油墨、粘结剂、涂料等行业有非常广泛的应用。传统的水性聚氨酯生产是在溶剂的存在下合成得到预聚物，再将预聚物分散在水中，根据最终产品的应用需要，脱除溶剂或者保留溶剂在最终产品中。常用的水性聚氨酯生产的溶剂有丙酮、丁酮、N,N-二甲基甲酰胺、N-甲基吡咯烷酮等。溶剂的使用是为了在反应后期降低体系粘度，以利于反应的搅拌混合、传热、和水分散的过程。这些溶剂的使用，既增加了生产步骤，降低了生产效率，也增加了能耗，提高了生产成本；并且，由于残留溶剂的存在，限制了产品的应用范围。
近年来，多个研究机构也开发了新的无溶剂型的水性聚氨酯生产工艺。这些生产工艺采用了降低分子量的方式控制反应后期的体系粘度，以达到克服了生产过程中的困难的目的。但低分子量的树脂材料也带来了产品性能不好，应用场合受限的问题。
发明内容
本发明目的是克服现有的水性聚氨酯生产工艺的技术缺陷，提供了一种改进的合成工艺。利用本发明的技术工艺，在水性聚氨酯生产过程中不使用溶剂，采用高温(100-150℃)反应的方式合成高分子量的水性聚氨酯预聚物，从而既减少了生产步骤，提高了生产效率，也降低了生产能耗和生产成本；而且扩大了最终的水性聚氨酯产品的应用范围。
本发明的技术方案如下：
一种水性聚氨酯树脂乳液的无溶剂合成方法，所述方法为(以下份数为质量份)：
在反应器内加入5-30份多元醇、0.5-8份亲水单体和0-1份催化剂，升温至100-150℃，加入5-30份二异氰酸酯、0-5份扩链剂、0-5份助剂，搅拌反应3-5h，得到聚氨酯预聚物；将所得聚氨酯预聚物加入到高速搅拌(加入过程中维持搅拌转速500-2000RPM)的50-80份水中，并加入0-5份扩链剂和0-5份助剂，混合均匀后，得到水性聚氨酯树脂乳液产物；
其中，
所述多元醇选自聚酯多元醇、聚醚多元醇、聚碳酸酯多元醇中的一种或两种以上任意比例的混合物；多元醇的分子量在200-10000g/mol；
所述亲水单体选自阴离子型的羧酸多元醇(例如二羟甲基丙酸)、磺酸多元醇(例如对苯二酚磺酸)、阳离子型的叔胺多元醇(例如N-甲基二乙醇胺)中的一种或两种以上任意比例的混合物；
所述催化剂选自有机锡或有机铋类化合物(例如二月桂酸二丁基锡)或者叔胺类化合物(例如三乙二胺)；
所述二异氰酸酯选自芳香族二异氰酸酯(例如甲苯二异氰酸酯、亚甲基二苯基二异氰酸酯)，脂肪族或脂环族二异氰酸酯(例如六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、氢化MDI)中的一种或两种以上任意比例的混合物；
所述扩链剂选自小分子二元醇(例如乙二醇、丙二醇)或者小分子二元胺(例如乙二胺、丙二胺)；
所述助剂包括中和剂、表面活性剂等；中和剂例如氨水、三乙胺、碳酸氢钠等；表面活性剂例如十二烷基苯磺酸钠、十六烷基三甲基溴化铵、聚乙烯醇等。
本发明的有益效果在于：
本发明提供了一种水性聚氨酯树脂乳液的无溶剂合成的方法，先采用高温反应的方式合成高分子量的聚氨酯预聚物，然后将该聚氨酯预聚物分散到高速搅拌的水中，充分混合后，得到水性聚氨酯树脂乳液产物。本发明的水性聚氨酯树脂乳液合成过程不使用溶剂，工艺简单，适用性广，制得的水性聚氨酯树脂乳液品质稳定，性能优秀，可以应用在皮革、油墨、粘结剂、涂料等多个场合。
具体实施方式
下面通过具体实施例进一步描述本发明，但本发明的保护范围并不仅限于此。
以下实施例中，聚酯多元醇购自斯泰潘化工，牌号
PC-1011-55，聚醚多元醇购自陶氏化学，牌号VORANOLTM2000LM。
实施例1
将167.7克聚酯多元醇、15.5克二羟甲基丙酸加入到反应釜里，搅拌加热到120℃。将69.4克甲苯二异氰酸酯加入到反应釜里，搅拌反应4小时。将12.0克三乙胺和9.0克乙二醇加入到反应釜里，搅拌均匀。将反应物倒入剧烈搅拌的476.6克水中，充分混合后，得到白色聚氨酯树脂乳液。
实施例2
将162.6克聚醚多元醇、15.0克二羟甲基丙酸、0.37克二月桂酸二丁基锡加入到反应釜里，搅拌加热到135℃。将77.3克异佛尔酮二异氰酸酯加入到反应釜里，搅拌反应4小时。将11.2克三乙胺和6.6克乙二胺加入到反应釜里，搅拌均匀。将反应物倒入剧烈搅拌的476.9克水中，充分混合后，得到白色聚氨酯树脂乳液。
实施例3
将95.7克聚醚多元醇、95.7克聚酯多元醇、16.3克二羟甲基丙酸、0.37克二月桂酸二丁基锡加入到反应釜里，搅拌加热到135℃。将46.1克异佛尔酮二异氰酸酯和46.1克亚甲基二苯基二异氰酸酯加入到反应釜里，搅拌反应4小时。将12.4克三乙胺和8.5克乙二胺加入到反应釜里，搅拌均匀。将反应物倒入剧烈搅拌的428.9克水中，充分混合后，得到白色聚氨酯树脂乳液。
实施例4
将95.7克聚醚多元醇、95.7克聚酯多元醇、16.3克二羟甲基丙酸、0.37克二月桂酸二丁基锡加入到反应釜里，搅拌加热到135℃。将105.2克异佛尔酮二异氰酸酯加入到反应釜里，搅拌反应4小时。将10.5克三乙胺加入到反应釜里，搅拌均匀。将反应物倒入剧烈搅拌的428.9克水中，充分混合后，加入8.5克乙二胺、4.5克氨水和0.3克十二烷基苯磺酸钠，最终得到白色聚氨酯树脂乳液。
水性聚氨酯树脂乳液性能指标及测试结果
本发明的水性聚氨酯树脂乳液的合成过程中，不使用溶剂，工艺简单，适用性广，制得的水性聚氨酯树脂乳液品质稳定，性能优秀，可以应用在皮革、油墨、粘结剂、涂料等多个场合。
上述实施例用来解释说明本发明，而不是对本发明进行限制，在本发明的精神和权利要求的保护范围内，对本发明做出的任何修改和改变，都落入本发明的保护范围。
Claims (8)
1.一种水性聚氨酯树脂乳液的无溶剂合成方法，其特征在于，所述方法为：
在反应器内加入5-30份多元醇、0.5-8份亲水单体和0-1份催化剂，升温至100-150℃，加入5-30份二异氰酸酯、0-5份扩链剂、0-5份助剂，搅拌反应3-5h，得到聚氨酯预聚物；将所得聚氨酯预聚物加入到高速搅拌的50-80份水中，并加入0-5份扩链剂和0-5份助剂，混合均匀后，得到水性聚氨酯树脂乳液产物；
其中，
所述多元醇选自聚酯多元醇、聚醚多元醇、聚碳酸酯多元醇中的一种或两种以上任意比例的混合物；
所述亲水单体选自阴离子型的羧酸多元醇、磺酸多元醇、阳离子型的叔胺多元醇中的一种或两种以上任意比例的混合物；
所述催化剂选自有机锡或有机铋类化合物或者叔胺类化合物；
所述二异氰酸酯选自芳香族二异氰酸酯，脂肪族或脂环族二异氰酸酯中的一种或两种以上任意比例的混合物；
所述扩链剂选自小分子二元醇或者小分子二元胺；
所述助剂选自中和剂、表面活性剂中的一种或多种。
2.如权利要求1所述的水性聚氨酯树脂乳液的无溶剂合成方法，其特征在于，聚氨酯预聚物加入水的过程中维持搅拌转速500-2000RPM。
3.如权利要求1所述的水性聚氨酯树脂乳液的无溶剂合成方法，其特征在于，所述多元醇的分子量在200-10000g/mol。
4.如权利要求1所述的水性聚氨酯树脂乳液的无溶剂合成方法，其特征在于，所述亲水单体选自二羟甲基丙酸、对苯二酚磺酸、N-甲基二乙醇胺中的一种或两种以上任意比例的混合物。
5.如权利要求1所述的水性聚氨酯树脂乳液的无溶剂合成方法，其特征在于，所述催化剂选自二月桂酸二丁基锡或三乙二胺。
6.如权利要求1所述的水性聚氨酯树脂乳液的无溶剂合成方法，其特征在于，所述二异氰酸酯选自甲苯二异氰酸酯、亚甲基二苯基二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、氢化MDI中的一种或两种以上任意比例的混合物。
7.如权利要求1所述的水性聚氨酯树脂乳液的无溶剂合成方法，其特征在于，所述扩链剂选自乙二醇、丙二醇、乙二胺或丙二胺。
8.如权利要求1所述的水性聚氨酯树脂乳液的无溶剂合成方法，其特征在于，所述助剂选自氨水、三乙胺、碳酸氢钠、十二烷基苯磺酸钠、十六烷基三甲基溴化铵、聚乙烯醇。
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