CN110283524B - 一种多羧酸酯光催化自清洁水性聚氨酯涂料及其制备和应用 - Google Patents
一种多羧酸酯光催化自清洁水性聚氨酯涂料及其制备和应用 Download PDFInfo
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Abstract
本发明涉及一种多羧酸酯光催化自清洁型水性聚氨酯涂料及其制备和应用。该制备方法包括：将大分子聚二元醇、聚二苯甲酮多羧酸酯多元醇、二异氰酸酯及催化剂反应，得到水性聚氨酯预聚物；加入溶剂和亲水扩链剂反应，加入小分子扩链剂继续反应；加入溶剂和成盐剂反应，中和后加水分散乳化。该涂料具有光学活性，在光诱导下，产生超氧自由基，具有优良的自清洁性能，可以清除沾污在其表面的染料或其他化合物。
Description
技术领域
本发明属于聚氨酯涂料及其制备和应用领域，特别涉及一种多羧酸酯光催化自清洁水性聚氨酯涂料及其制备和应用。
背景技术
随着当今绿色友好、无毒环保的要求越来越严格，传统的溶剂型聚氨酯体系中挥发性有机物的排放使其应用受到了很大的限制，而水性聚氨酯在合成过程中以水代替有机溶剂，避免了有机溶剂的挥发，因此无毒无污染的水性聚氨酯涂料逐渐成为聚氨酯材料领域研究的主要方向。随着人们对水性聚氨酯更深入的研究和其更广泛的应用，对其性能也提出了更高的要求，水性聚氨酯要朝着高性能、多功能方向发展。
在使用过程中，聚氨酯制品不可避免的会受到有机污渍及细菌的侵扰，给消费者带来许多麻烦。因此，发明自清洁型水性聚氨酯涂料具有重大意义。现有的自清洁型水性聚氨酯涂料多是采用二氧化钛、二氧化硅、氧化镧等纳米粒子与水性聚氨酯乳液混合制备得到的，会有自清洁效果不佳的问题。
发明内容
本发明所要解决的技术问题是提供一种多羧酸酯光催化自清洁水性聚氨酯涂料及其制备和应用，解决了现有技术中聚氨酯涂料自清洁效果不佳的缺陷。
本发明提供了一种多羧酸酯光催化自清洁型水性聚氨酯涂料，由大分子聚二元醇、具有光活性的聚二苯甲酮多羧酸酯多元醇PEG-BPTCD、二异氰酸酯及催化剂预聚后，加入第一溶剂和亲水扩链剂反应，再加入小分子扩链剂继续反应，然后加入第二溶剂和成盐剂反应获得。
所述大分子聚二元醇为聚己二酸丁二醇酯二醇、聚碳酸酯二元醇、聚己内酯二醇、聚四氢呋喃二醇、聚己二酸新戊二醇酯二醇中的一种或两种。
所述具有光活性的聚二苯甲酮多羧酸酯多元醇PEG-BPTCD是由光活性化合物BPTCD和不同分子量的PEG以摩尔比1.0:1.1～1.0:2.0在100-110℃下反应1-3小时制得；PEG-BPTCD的结构式为：
式中m为1-50的整数，n为1-10的整数。
所述二异氰酸酯为异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、甲苯二异氰酸酯、二苯甲烷二异氰酸酯或4,4'-二环己基甲烷二异氰酸酯。
所述催化剂为辛酸亚锡、二月桂酸二丁基锡、有机铋盐催化剂、有机锌盐催化剂中的一种或几种。
所述第一溶剂为N-甲基吡咯烷酮。
所述亲水扩链剂为2,2'-二羟甲基丙酸或2,2'-二羟甲基丁酸。
所述小分子扩链剂为1,4-丁二醇、1,6-己二醇、二甘醇或丙二醇。
所述第二溶剂为丙酮或丁酮。
所述成盐剂为三乙胺、三乙醇胺、N,N-二甲基乙醇胺、氢氧化钠或氢氧化钾。
本发明还提供一种水性聚氨酯涂料制备方法，包括：
(1)将20-60重量份的大分子聚二元醇、0.5-10重量份的具有光活性的聚二苯甲酮多羧酸酯多元醇PEG-BPTCD、10-30重量份二异氰酸酯及0.05-1.0重量份的催化剂反应，得到水性聚氨酯预聚物；
(2)向步骤(1)得到的聚氨酯预聚物中加入2-15重量份的溶剂和1-10重量份的亲水扩链剂反应，加入0.5-5重量份的小分子扩链剂，继续反应；
(3)向步骤(2)中继续反应后的体系中加入5-20重量份的溶剂和1-15重量份的成盐剂反应，中和后加50-300重量份的水分散乳化，将溶剂除去，得到水性聚氨酯涂料。
所述步骤(1)中反应温度为80-90℃，反应时间为2-6h。
所述步骤(2)中反应和继续反应的温度为70-80℃，反应和继续反应的时间为2-6h。
所述步骤(3)中反应温度为25-40℃，反应时间为0.5-2h；乳化时间为0.5-2h。
本发明还提供一种水性聚氨酯涂料的应用。例如用于各种基质的涂层和整理。
本发明将光活性化合物3,3',4,4'-二苯甲酮四甲酸二酐(BPTCD)通过缩合反应引入聚乙二醇分子链中，合成有光活性的聚二苯甲酮多羧酸酯多元醇(PEG-BPTCD)，再以此为预聚体用于合成水性聚氨酯，制备的水性聚氨酯涂料具有高效的自清洁效果。
有益效果
本发明提供了一种基于聚乙二醇和有光活性的聚二苯甲酮多羧酸酯多元醇(PEG-BPTCD)，将此自清洁型聚多元醇为预聚体引入水性聚氨酯分子链段中，制备得到包含光学活性基团的、具有自清洁功能的水性聚氨酯。本发明提供的光催化自清洁型水性聚氨酯，通过聚氨酯涂膜的自由基测试及其对亚甲基蓝的降解测试，表明该涂膜具备光催化自清洁功能。
附图说明
图1为实施例1制备的光催化自清洁聚氨酯与亚甲基蓝混合形成涂膜的光催化降解效果图；
图2为实施例1-6制备的光催化自清洁聚氨酯自由基含量测试结果。
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
(1)将20重量份的聚己二酸丁二醇酯二醇、2重量份有光活性的聚二苯甲酮多羧酸酯多元醇(PEG-BPTCD)、10重量份异佛尔酮二异氰酸酯及0.1重量份的辛酸亚锡于80℃反应2小时，得到水性聚氨酯预聚物；
其中，聚二苯甲酮多羧酸酯多元醇(PEG-BPTCD)为BPTCD与PEG(Mw:2000)以1.0:1.1的摩尔比在105℃下反应2小时制得。反应过程不用加入溶剂。
(2)向步骤(1)得到的聚氨酯预聚物中加入3重量份的N-甲基吡咯烷酮和3重量份的2,2'-二羟甲基丙酸，于70℃反应2小时后加入1重量份的1,4-丁二醇，70℃继续反应2小时；
(3)向上述体系中加入10重量份的丙酮和2重量份的三乙胺，于30℃进行中和反应1小时；中和后加100重量份的水分散乳化1小时，最后将溶剂旋转蒸发除去，制得自清洁型水性聚氨酯，获得的水性聚氨酯的分子量(Mw)为53000daltons。
取1g获得的水性聚氨酯聚合物，加入0.002g亚甲基蓝染料(0.2％w/w)，搅拌，混合均匀，然后慢慢倒入聚四氟乙烯磨具中，自然蒸发，获得水性聚氨酯膜。图1表明：本实施例得到的水性聚氨酯成膜后，在光诱导下，在自由基作用下，染料自动褪色，起到自清洁作用。
实施例2
(1)将30重量份的聚碳酸酯二元醇、2重量份有光活性的聚二苯甲酮多羧酸酯多元醇(PEG-BPTCD)、10重量份六亚甲基二异氰酸酯、及0.2重量份的二月桂酸二丁基锡于80℃反应2小时，得到水性聚氨酯预聚物；
其中，聚二苯甲酮多羧酸酯多元醇(PEG-BPTCD)为BPTCD与PEG(Mw:2000)以1.0:1.5的摩尔比在110℃下反应2小时制得。反应过程不用加入溶剂。
(2)向步骤(1)得到的聚氨酯预聚物中加入2重量份的N-甲基吡咯烷酮和2重量份的2,2'-二羟甲基丙酸，于70℃反应3小时后加入1重量份的1,6-己二醇，75℃继续反应3小时；
(3)向上述体系中加入5重量份的丁酮和2重量份的三乙胺，于室温下进行中和反应2小时；中和后加100重量份的水分散乳化1小时，最后将溶剂旋转蒸发除去，制得自清洁型水性聚氨酯，获得的自清洁型水性聚氨酯分子量(Mw)为54000daltons。
实施例3
(1)将40重量份的聚己内酯二醇、5重量份有光活性的聚二苯甲酮多羧酸酯多元醇(PEG-BPTCD)、10重量份甲苯二异氰酸酯及0.2重量份的新癸酸铋催化剂于85℃反应4小时，得到水性聚氨酯预聚物；
其中，聚二苯甲酮多羧酸酯多元醇(PEG-BPTCD)为BPTCD与PEG(Mw:2000)以1.0:2.0的摩尔比在110℃下反应2小时制得。反应过程不用加入溶剂。
(2)向步骤(1)得到的聚氨酯预聚物中加入5重量份的N-甲基吡咯烷酮和2重量份的2,2'-二羟甲基丙酸，于80℃反应2小时后加入2重量份的二甘醇，75℃继续反应3小时；
(3)向上述体系中加入10重量份的丁酮和3重量份的三乙胺，于30℃进行中和反应1小时；中和后加200重量份的水分散乳化2小时，最后将溶剂旋转蒸发除去，制得自清洁型水性聚氨酯。获得的自清洁型水性聚氨酯分子量(Mw)为51200daltons。
实施例4
(1)将40重量份的聚四氢呋喃二醇、2重量份有光活性的聚二苯甲酮多羧酸酯多元醇(PEG-BPTCD)、20重量份二苯甲烷二异氰酸酯及0.05重量份的异辛酸锌催化剂催化剂于80℃反应3小时，得到水性聚氨酯预聚物；
其中，聚二苯甲酮多羧酸酯多元醇(PEG-BPTCD)为BPTCD与PEG(Mw:1000)以1.0:1.1的摩尔比在110℃下反应2小时制得。反应过程不用加入溶剂。
(2)向步骤(1)得到的聚氨酯预聚物中加入10重量份的N-甲基吡咯烷酮和3重量份的2,2'-二羟甲基丙酸，于75℃反应4小时后加入0.5重量份的丙二醇，80℃继续反应2小时；
(3)向上述体系中加入15重量份的丙酮和5重量份的三乙醇胺，于40℃进行中和反应0.5小时；中和后加200重量份的水分散乳化1小时，最后将溶剂旋转蒸发除去，制得自清洁型水性聚氨酯。获得的自清洁型水性聚氨酯分子量(Mw)为52500daltons。
实施例5
(1)将50重量份的聚己二酸新戊二醇酯二醇、10重量份有光活性的聚二苯甲酮多羧酸酯多元醇(PEG-BPTCD)、10重量份4,4'-二环己基甲烷二异氰酸酯及0.5重量份的辛酸亚锡于80℃反应2小时，得到水性聚氨酯预聚物；
其中，聚二苯甲酮多羧酸酯多元醇(PEG-BPTCD)为BPTCD与PEG(Mw:600)以1.0:1.1的摩尔比在110℃下反应2小时制得。反应过程不用加入溶剂。
(2)向步骤(1)得到的聚氨酯预聚物中加入5重量份的N-甲基吡咯烷酮和5重量份的2,2'-二羟甲基丙酸，于70℃反应6小时后加入2重量份的1,4-丁二醇，80℃继续反应2小时；
(3)向上述体系中加入10重量份的丁酮和10重量份的三乙醇胺，于30℃反应1小时；中和后加200重量份的水分散乳化2小时，最后将溶剂旋转蒸发除去，制得自清洁型水性聚氨酯，获得的自清洁型水性聚氨酯分子量(Mw)为53000daltons。
实施例6
(1)将60重量份的聚碳酸酯二元醇、10重量份有光活性的聚二苯甲酮多羧酸酯多元醇(PEG-BPTCD)、10重量份异佛尔酮二异氰酸酯及0.05重量份的二月桂酸二丁基锡于85℃反应5小时，得到水性聚氨酯预聚物；
其中，聚二苯甲酮多羧酸酯多元醇(PEG-BPTCD)为BPTCD与PEG(Mw:800)以1.0:1.1的摩尔比在110℃下反应2小时制得。反应过程不用加入溶剂。
(2)向步骤(1)得到的聚氨酯预聚物中加入10重量份的N-甲基吡咯烷酮和10重量份的2,2'-二羟甲基丁酸，于80℃反应3小时后加入3重量份的二甘醇，70℃继续反应5小时；
(3)向上述体系中加入10重量份的丁酮和5重量份的三乙醇胺，于40℃进行中和反应0.5小时；中和后加300重量份的水分散乳化2小时，最后将溶剂旋转蒸发除去，制得自清洁型水性聚氨酯。
图2是实施例1-6获得的基于聚二苯甲酮多羧酸酯多元醇光催化自清洁型水性聚氨酯涂料在光诱导下产生的自由基比例。可以看出，实施例1-6均可以得到光诱导产生大量自由基，起到高效的自清洁作用。
对比例1
(1)将20重量份的聚己二酸丁二醇酯二醇、10重量份异佛尔酮二异氰酸酯及0.1重量份的辛酸亚锡于80℃反应2小时，得到水性聚氨酯预聚物；
(2)向步骤(1)得到的聚氨酯预聚物中加入3重量份的N-甲基吡咯烷酮和3重量份的2,2'-二羟甲基丙酸，于70℃反应2小时后加入1重量份的1,4-丁二醇，70℃继续反应2小时；
(3)向上述体系中加入10重量份的丙酮和2重量份的三乙胺，于30℃进行中和反应1小时；加100重量份的水分散乳化1小时，最后将溶剂旋转蒸发除去，制得传统水性聚氨酯
(4)在上述水性聚氨酯体系中，加入10重量的纳米二氧化钛，搅拌均匀，获得纳米二氧化钛掺杂的水性聚氨酯。
将该聚合物混合体系按照实施例1的方法制成含亚甲基蓝染料的膜，在500W的紫外灯照射下，4.5小时才能褪色。与实施例1中，40分钟相比，效果大大降低。
Claims (10)
1.一种多羧酸酯光催化自清洁水性聚氨酯涂料，其特征在于，由大分子聚二元醇、具有光活性的聚二苯甲酮多羧酸酯多元醇PEG-BPTCD、二异氰酸酯及催化剂预聚后，加入第一溶剂和亲水扩链剂反应，再加入小分子扩链剂继续反应，然后加入第二溶剂和成盐剂反应获得，其中具有光活性的聚二苯甲酮多羧酸酯多元醇PEG-BPTCD是由光活性化合物3, 3', 4,4'-二苯甲酮四甲酸二酐BPTCD和不同分子量的PEG以摩尔比1.0:1.1～1.0:2.0在100-110℃下反应1-3小时制得。
2.根据权利要求1所述涂料，其特征在于，所述大分子聚二元醇为聚己二酸丁二醇酯二醇、聚碳酸酯二元醇、聚己内酯二醇、聚四氢呋喃二醇、聚己二酸新戊二醇酯二醇中的一种或两种；催化剂为辛酸亚锡、二月桂酸二丁基锡、有机铋盐催化剂、有机锌盐催化剂中的一种或几种。
3. 根据权利要求1所述涂料，其特征在于，所述PEG-BPTCD的结构式为：
，式中m为1-50的整数，n为1-10的整数。
4.根据权利要求1所述涂料，其特征在于，所述二异氰酸酯为异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、甲苯二异氰酸酯、二苯甲烷二异氰酸酯或4,4'-二环己基甲烷二异氰酸酯；第一溶剂为N-甲基吡咯烷酮；亲水扩链剂为2,2'-二羟甲基丙酸或2,2'-二羟甲基丁酸。
5.根据权利要求1所述涂料，其特征在于，所述小分子扩链剂为1,4-丁二醇、1,6-己二醇、二甘醇或丙二醇；第二溶剂为丙酮或丁酮；成盐剂为三乙胺、三乙醇胺、N,N-二甲基乙醇胺、氢氧化钠或氢氧化钾。
6.一种多羧酸酯光催化自清洁型水性聚氨酯涂料的制备方法，包括：
（1）将20-60重量份的大分子聚二元醇、0.5-10重量份的具有光活性的聚二苯甲酮多羧酸酯多元醇PEG-BPTCD、10-30重量份二异氰酸酯及0.05-1.0重量份的催化剂反应，得到水性聚氨酯预聚物，其中具有光活性的聚二苯甲酮多羧酸酯多元醇PEG-BPTCD是由光活性化合物3, 3', 4, 4'-二苯甲酮四甲酸二酐BPTCD和不同分子量的PEG以摩尔比1.0:1.1～1.0:2.0在100-110 ℃下反应1-3小时制得；
（2）向步骤（1）得到的聚氨酯预聚物中加入2-15重量份的溶剂和1-10重量份的亲水扩链剂反应，加入0.5-5重量份的小分子扩链剂，继续反应；
（3）向步骤（2）中继续反应后的体系中加入5-20重量份的溶剂和1-15重量份的成盐剂反应，中和后加50-300重量份的水分散乳化，将溶剂除去，得到水性聚氨酯涂料。
7. 根据权利要求6所述的制备方法，其特征在于，步骤（1）中反应温度为80-90 ℃，反应时间为2-6h。
8. 根据权利要求6所述的制备方法，其特征在于，步骤（2）中反应和继续反应的温度为70-80 ℃，反应和继续反应的时间为2-6h。
9. 根据权利要求6所述的制备方法，其特征在于，步骤（3）中反应温度为25-40 ℃，反应时间为0.5-2h；乳化时间为0.5-2h。
10.一种如权利要求1所述涂料的应用。
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| WO2007070801A2 (en) * | 2005-12-12 | 2007-06-21 | Allaccem, Inc. | Methods and systems for preparing antimicrobial films and coatings |
| CN106902876A (zh) * | 2017-03-06 | 2017-06-30 | 中国石油大学(华东) | 一步共聚合法制备氮化碳基高效选择性光催化剂 |
| CN107522621A (zh) * | 2017-10-10 | 2017-12-29 | 东华大学 | 一种光诱导抗菌整理剂二苯甲酮四甲酸酯的制备方法 |
| CN107522833A (zh) * | 2017-08-02 | 2017-12-29 | 合肥思敬齐化工材料有限责任公司 | 一种自清洁型水性聚氨酯的制备方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007070801A2 (en) * | 2005-12-12 | 2007-06-21 | Allaccem, Inc. | Methods and systems for preparing antimicrobial films and coatings |
| CN106902876A (zh) * | 2017-03-06 | 2017-06-30 | 中国石油大学(华东) | 一步共聚合法制备氮化碳基高效选择性光催化剂 |
| CN107522833A (zh) * | 2017-08-02 | 2017-12-29 | 合肥思敬齐化工材料有限责任公司 | 一种自清洁型水性聚氨酯的制备方法 |
| CN107522621A (zh) * | 2017-10-10 | 2017-12-29 | 东华大学 | 一种光诱导抗菌整理剂二苯甲酮四甲酸酯的制备方法 |
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