CN106543395A - 一种高粘度的水性聚氨酯胶粘剂及其制备方法 - Google Patents

一种高粘度的水性聚氨酯胶粘剂及其制备方法 Download PDF

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CN106543395A
CN106543395A CN201611134765.XA CN201611134765A CN106543395A CN 106543395 A CN106543395 A CN 106543395A CN 201611134765 A CN201611134765 A CN 201611134765A CN 106543395 A CN106543395 A CN 106543395A
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羊梦诗
廖平永
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Jiaxing Deyang Biotechnology Co Ltd
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Abstract

一种高粘度的水性聚氨酯胶粘剂及其制备方法，其制备步骤为：用聚酯多元醇、半导体纳米氧化物、亲水性单体和二异氰酸酯反应，生成‑NCO端基的水性聚氨酯预聚体；再用小分子二元胺、小分子三元胺进行扩链；最后用有机溶剂调节粘度，碱调节pH值，用去离子水将其分散成白色半透明乳液；真空出去有机溶剂，即得到高粘度水性聚氨酯胶粘剂。该水性聚氨酯胶粘剂具有高粘度的特性，在室温条件下初粘度高，粘接力强，涂覆性能良好，能够广泛使用在箱包、仪表盘、船舶夹板、汽车前后门等领域。

Description

一种高粘度的水性聚氨酯胶粘剂及其制备方法
技术领域
本发明属于胶粘剂技术领域，具体涉及一种高粘度的水性聚氨酯胶粘剂及其制备方法。
背景技术
聚氨酯是由多异氰酸酯(尤其以二异氰酸酯为主)和低聚物多元醇通过缩聚反应聚合，交联，扩链而成的一类高聚物。聚氨酯表现出的良好的粘结性能、柔韧性和耐冲击性能，与其分子链中含有异氰基(-NCO)和氨基甲酸酯基(-NH-C00-)是密切相关的。聚氨酯无论是与泡沫、纸张、织物、陶瓷、皮革等多孔粗糙材料，还是与金属、玻璃、橡胶等表面光洁的材料都有优良的化学粘接力。改变亲水性多羟基化合物的分子量、碳链的长短、化学结构等，可以调节聚氨酯材料的稳定性、初粘性、耐水耐热性和贮存稳定性等性能，使其更加广泛的应用于日常生活和工农业生产制造的各个领域。
近年来，随着“环保绿色化”深入人心，各国相继出台各项法律法规要求化学产品必须向着无毒、无害化、环境友好的方向发展。传统的有机溶剂型聚氨酯胶粘剂含有有机溶剂及其他有毒的助剂，由于其污染与毒性，在使用中日益受到限制。而水性聚氨酯材料由于使用水代替了有机溶剂，具有安全、无毒、无污染、绿色环保的特点，克服了有机溶剂型聚氨酯的缺陷，具有广阔的发展前景。
目前，未改性的水性聚氨酯胶粘剂的初粘性差，将胶粘剂涂覆在多孔泡沫材料表面时需多次涂覆，且胶粘剂会渗入材料导致施工困难，这就限制了水性聚氨酯胶粘剂的应用。因此，提高聚氨酯胶粘剂的粘度以扩大其应用领域，有着非常重大的现实意义。此外，如专利CN 104861917等的水性聚氨酯胶粘剂由于需要添加固化剂、消泡剂等添加剂，操作较为繁琐，不便于应用。本发明引入了纳米氧化物半导体微粒，由于纳米氧化物半导体微粒表面具有丰富的羟基官能团，能够与聚氨酯分子链端基反应形成交联网状结构，提高胶粘剂的粘度。本发明制备的聚氨酯胶粘剂粘度大，具有初粘性好，涂覆性能好的特点。制备过程中无需添加固化剂、消泡剂等添加剂，简化了合成工艺，操作简单，便于应用。
发明内容
本发明通过纳米氧化物半导体对聚氨酯胶粘剂进行改性，目的是提供一种高粘度的水性聚氨酯胶粘剂及其制备方法。
本发明提供的一种高粘度的水性聚氨酯胶粘剂及其制备方法，其制备步骤为：用聚酯多元醇、半导体纳米氧化物、亲水性单体和二异氰酸酯反应，生成-NCO端基的水性聚氨酯预聚体；再用小分子二元胺、小分子三元胺进行扩链；最后用有机溶剂调节粘度，碱调节pH值，用去离子水将其分散成白色半透明乳液；真空出去有机溶剂，即得到高粘度水性聚氨酯胶粘剂。
本发明提供的一种高粘度的水性聚氨酯胶粘剂及其制备方法，具体制备步骤为：
⑴ 将聚酯多元醇与半导体纳米氧化物混合，升温至110 ~ 125 ℃，真空脱水30 ~ 90min，降温至60 ~ 80 ℃后，依次加入二异氰酸酯、亲水性单体和占聚酯多元醇重量0.01 ~0.05%的辛酸亚锡催化剂，反应2 ~ 5 h，生成-NCO端基的水性聚氨酯预聚体；其中，聚酯多元醇与半导体纳米氧化物的质量比为1 : 0.01 ~ 0.2，聚酯多元醇与亲水性单体的摩尔数比为1 : 0.5 ~ 2；
⑵ 将小分子二元胺与小分子三元胺按照一定比例加入到水性聚氨酯预聚体中，然后加入聚酯多元醇质量20 %的有机溶剂降低体系粘度，并于60 ~ 80 ℃反应0.5 ~ 2 h；其中，聚酯多元醇与小分子二元胺摩尔数比为1 : 0.2 ~ 2；聚酯多元醇与小分子三元胺摩尔数比为1 : 0.2 ~ 2；
⑶ 滴加碱，调节反应的pH值为6 ~ 7，按照质量比固体物料量：去离子水= 1 : 1 ~ 10加入去离子水，在高速搅拌下分散成白色半透明乳液；
⑷ 真空减压除去有机溶剂，得到高粘度的水性聚氨酯胶粘剂。
所述的聚酯多元醇是聚己二酸-1,4-丁二醇、聚己二酸乙二醇、聚己二酸一缩二乙二醇、聚己二酸己二醇中的一种，或者多种的任意比例混合物。
本发明中所述的半导体纳米氧化物是纳米氧化铁、纳米氧化钴、纳米氧化钨、纳米氧化锡或者掺杂有氯化钾的纳米二氧化钛。
本发明中所述的二异氰酸酯是甲苯二异氰酸酯、1,4-四亚甲基二异氰酸酯、1,6-己二异氰酸酯、异氟尔酮二异氰酸酯、苯二亚甲基二异氰酸酯、甲基环己基二异氰酸酯中的一种，或者多种的任意比例混合物。
本发明中所述的亲水性单体是2,2-二羟甲基丙酸、2,2-二羟甲基丁酸、2,2-二羟甲基戊酸、2,2-二羟甲基己酸中的一种，或者多种的任意比例混合物。
本发明中所述的小分子二元胺是乙二胺、1,3-丙二胺、1,4-丁二胺、1,5-戊二胺或1,6-己二胺。
本发明中所述的小分子三元胺是二乙烯三胺、三聚氰胺或者三氨基丙烷。
本发明中所述的有机溶剂是N-甲基吡咯烷酮、乙酸乙酯、丙酮、丁酮、四氢呋喃、1,4-二氧六环中的一种，或者多种的任意比例混合物。
本发明中所述的碱是二乙胺、三乙胺、二异丙基乙基胺、吡啶、氢氧化钠、氢氧化钾或氢氧化锂。
本发明的有益效果：本发明提供的高粘度水性聚氨酯胶粘剂制备工艺简单，有机溶剂使用少，减少了减压蒸除有机溶剂的能耗。本发明提供的水性聚氨酯胶粘剂具有高粘度的特性，在室温条件下初粘度好、粘接力强、涂覆性能良好，能够广泛使用在箱包、仪表盘、船舶夹板、汽车前后门玻璃等领域。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1
三口烧瓶中加入50 g聚己二酸-1,4-丁二醇和0.5 g纳米氧化铁，加热至110 ℃抽真空1.5 h，降温到60 ℃，依次加入32 g甲苯二异氰酸酯和2 g 2,2-二羟甲基丙酸，逐滴加入辛酸亚锡催化剂10滴，反应4 h；加入0.6 g乙二胺、1.2 g二乙烯三胺和10 mL N-甲基吡咯烷酮于65℃反应1 h，用2 g二异丙基乙基胺中和反应，加入100 g去离子水分散乳化，抽真空脱去N-甲基吡咯烷酮，即得到高粘度的水性聚氨酯胶粘剂。该产品为白色半透明乳液（胶粘剂1）。
实施例2
三口烧瓶中加入50 g聚己二酸乙二醇和0.5 g纳米氧化钴，加热至120 ℃抽真空1.5h，降温到60 ℃，依次加入32 g 1,6-己二异氰酸酯和2g 2,2-二羟甲基丁酸，逐滴加入辛酸亚锡催化剂10滴，反应4 h；加入0.6 g 1,3-丙二胺、1.2 g三聚氰胺和10 mL 丙酮于65 ℃反应1 h，用2 g二异丙基乙基胺中和反应，加入100 g去离子水分散乳化，抽真空脱去丙酮，即得到高粘度的水性聚氨酯胶粘剂。该产品为白色半透明乳液（胶粘剂2）。
实施例3
三口烧瓶中加入50 g聚己二酸一缩二乙二醇和0.5 g纳米氧化锡，加热至120 ℃抽真空1.5 h，降温到70 ℃，依次加入32 g异氟尔酮二异氰酸酯和2 g 2,2-二羟甲基己酸，逐滴加入辛酸亚锡催化剂10滴，反应3 h；加入0.6 g 1,5-戊二胺、1.2 g二乙烯三胺和10 mL 四氢呋喃于65 ℃反应1 h，用2 g三乙胺中和反应，加入100 g去离子水分散乳化，抽真空脱去四氢呋喃，即得到高粘度的水性聚氨酯胶粘剂。该产品为白色半透明乳液（胶粘剂3）。
实施例4
三口烧瓶中加入50 g聚己二酸一缩二乙二醇和0.5 g纳米氧化锡，加热至120 ℃抽真空1.5 h，降温到70 ℃，依次加入32 g甲基环己基二异氰酸酯和2 g 2,2-二羟甲基丁酸，逐滴加入辛酸亚锡催化剂10滴，反应3 h；加入0.6 g 1,6-己二胺、1.2 g二乙烯三胺和10 mL四氢呋喃于65 ℃反应1 h，用2 g三乙胺中和反应，加入100 g去离子水分散乳化，抽真空脱去四氢呋喃，即得到高粘度的水性聚氨酯胶粘剂。该产品为白色半透明乳液（胶粘剂4）。
实施例5
三口烧瓶中加入50 g聚己二酸己二醇和0.5 g纳米氧化钨，加热至120 ℃抽真空1.5h，降温到70 ℃，依次加入32 g甲基环己基二异氰酸酯和2 g 2,2-二羟甲基戊酸，逐滴加入辛酸亚锡催化剂10滴，反应3 h；加入0.6 g 1,5-戊二胺、1.2 g二乙烯三胺和10 mL丁酮于75 ℃反应1 h，用2 g三乙胺中和反应，加入100 g去离子水分散乳化，抽真空脱去丁酮，即得到高粘度的水性聚氨酯胶粘剂。该产品为白色半透明乳液（胶粘剂5）。
实施例6
三口烧瓶中加入50 g聚己二酸己二醇和0.5 g纳米氧化钨，加热至120 ℃抽真空1.5h，降温到70 ℃，依次加入32 g苯二亚甲基二异氰酸酯和2 g 2,2-二羟甲基己酸，逐滴加入辛酸亚锡催化剂10滴，反应3 h；加入0.6 g 1,5-戊二胺、1.2 g二乙烯三胺和10 mL 乙酸乙酯于75 ℃反应1 h，用2 g吡啶中和反应，加入100 g去离子水分散乳化，抽真空脱去乙酸乙酯，即得到高粘度的水性聚氨酯胶粘剂。该产品为白色半透明乳液（胶粘剂6）。
实施例7
分别将胶粘剂1、胶粘剂2、胶粘剂3、胶粘剂4、胶粘剂5、胶粘剂6和国内市售产品进行初粘度检测、粘接力检测，每个样品测3次，求平均值，测试结果如表1。
初粘度检测：分别将10 g胶黏剂均匀涂抹在两片经丙酮处理过的PVC片（25 mm×20 mm）上，放入40℃烘箱10 min，将两片PVC贴合，0.2 MPa压力粘合10 s，测其剥离力就是初粘强度。
粘接力测试：将胶黏剂涂抹在ABS塑料件上，涂抹量为180 ~ 220 g/m2，60℃烘箱放置3 min后，将ABS塑料件上和贴有无纺布的聚氨酯泡沫贴合在一起，0.2 MPa压力粘合10s，测其剥离力就是粘接力。
表1
测试项目 胶黏剂1 胶黏剂2 胶黏剂3 胶黏剂4 胶黏剂5 胶黏剂6 市售产品
初粘度 （N/cm） 61 59 64 62 60 65 25
粘接力 （N/cm） 70 73 72 73 71 70 31
从表1中可以看出，国内关于水性聚氨酯胶粘剂的市售产品的初粘度在25 N/cm，本发明的高粘度的水性聚氨酯胶粘剂的初粘度在60 N/cm以上；国内关于水性聚氨酯胶粘剂的市售产品的粘接力多在31 N/cm，本发明的高粘度的水性聚氨酯胶粘剂的粘接力在70 N/cm以上。说明本发明提供的水性聚氨酯胶粘剂具有高粘度、初粘度好的特性。

Claims (9)

1.一种高粘度的水性聚氨酯胶粘剂及其制备方法，其特征在于，具体步骤为：
（1） 将聚酯多元醇与半导体纳米氧化物混合，升温至110 ~ 125 ℃，真空脱水30 ~ 90min，降温至60 ~ 80 ℃后，依次加入二异氰酸酯、亲水性单体和占聚酯多元醇重量0.01 ~0.05%的辛酸亚锡催化剂，反应2 ~ 5 h，生成-NCO端基的水性聚氨酯预聚体；其中，聚酯多元醇与半导体纳米氧化物的质量比为1 : 0.01 ~ 0.2；聚酯多元醇与亲水性单体的摩尔数比为1 : 0.5 ~ 2；
（2） 将小分子二元胺与小分子三元胺按照一定比例加入到水性聚氨酯预聚体中，然后加入聚酯多元醇质量20 %的有机溶剂降低体系粘度，并于60 ~ 80 ℃反应0.5 ~ 2 h；其中，聚酯多元醇与小分子二元胺摩尔数比为1 : 0.2 ~ 2；聚酯多元醇与小分子三元胺摩尔数比为1 : 0.2 ~ 2；
（3） 滴加碱，调节反应的pH值为6 ~ 7，按照质量比固体物料量：去离子水= 1 : 1 ~10加入去离子水，在高速搅拌下分散成白色半透明乳液；
（4） 真空减压除去有机溶剂，得到高粘度的水性聚氨酯胶粘剂。
2.如权利要求1所述的一种高粘度的水性聚氨酯胶粘剂及其制备方法，其特征在于，所述的聚酯多元醇是聚己二酸-1,4-丁二醇、聚己二酸乙二醇、聚己二酸一缩二乙二醇、聚己二酸己二醇中的一种，或者多种的任意比例混合物。
3.如权利要求1所述的一种高粘度的水性聚氨酯胶粘剂及其制备方法，其特征在于，所述的半导体纳米氧化物是纳米氧化铁、纳米氧化钴、纳米氧化钨、纳米氧化锡或者掺杂有氯化钾的纳米二氧化钛。
4.如权利要求1所述的一种高粘度的水性聚氨酯胶粘剂及其制备方法，其特征在于，所述的二异氰酸酯是甲苯二异氰酸酯、1,4-四亚甲基二异氰酸酯、1,6-己二异氰酸酯、异氟尔酮二异氰酸酯、苯二亚甲基二异氰酸酯、甲基环己基二异氰酸酯中的一种，或者多种的任意比例混合物。
5.如权利要求1所述的一种高粘度的水性聚氨酯胶粘剂及其制备方法，其特征在于，所述的亲水性单体是2,2-二羟甲基丙酸、2,2-二羟甲基丁酸、2,2-二羟甲基戊酸、2,2-二羟甲基己酸中的一种，或者多种的任意比例混合物。
6.如权利要求1所述的一种高粘度的水性聚氨酯胶粘剂及其制备方法，其特征在于，所述的小分子二元胺是乙二胺、1,3-丙二胺、1,4-丁二胺、1,5-戊二胺或1,6-己二胺。
7.如权利要求1所述的一种高粘度的水性聚氨酯胶粘剂及其制备方法，其特征在于，所述的小分子三元胺是二乙烯三胺、三聚氰胺或者三氨基丙烷。
8.如权利要求1所述的一种高粘度的水性聚氨酯胶粘剂及其制备方法，其特征在于，所述的有机溶剂是N-甲基吡咯烷酮、乙酸乙酯、丙酮、丁酮、四氢呋喃、1,4-二氧六环中的一种，或者多种的任意比例混合物。
9.如权利要求1所述的一种高粘度的水性聚氨酯胶粘剂及其制备方法，其特征在于，所述的碱是二乙胺、三乙胺、二异丙基乙基胺、吡啶、氢氧化钠、氢氧化钾或氢氧化锂。
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101235264A (zh) * 2007-01-30 2008-08-06 中国科学院福建物质结构研究所 一种水性聚氨酯胶粘剂及其制备方法
CN101824299A (zh) * 2010-04-30 2010-09-08 山西省应用化学研究所 一种单组份高固含量水性聚氨酯胶粘剂的制备方法
CN103232831A (zh) * 2013-05-15 2013-08-07 复旦大学 一种单组份水性聚氨酯胶粘剂及其制备方法
CN105820792A (zh) * 2016-05-11 2016-08-03 南京京锦元科技实业有限公司 一种高耐水性高强度水性聚氨酯胶粘剂及其应用

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101235264A (zh) * 2007-01-30 2008-08-06 中国科学院福建物质结构研究所 一种水性聚氨酯胶粘剂及其制备方法
CN101824299A (zh) * 2010-04-30 2010-09-08 山西省应用化学研究所 一种单组份高固含量水性聚氨酯胶粘剂的制备方法
CN103232831A (zh) * 2013-05-15 2013-08-07 复旦大学 一种单组份水性聚氨酯胶粘剂及其制备方法
CN105820792A (zh) * 2016-05-11 2016-08-03 南京京锦元科技实业有限公司 一种高耐水性高强度水性聚氨酯胶粘剂及其应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
余先纯等: "《木材胶黏剂与胶合技术》", 31 March 2011, 中国轻工业出版社 *

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