CN118496470B - 一种抗菌uv固化水性生物基树脂及在甲油胶中的应用 - Google Patents
一种抗菌uv固化水性生物基树脂及在甲油胶中的应用 Download PDFInfo
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Abstract
本发明公开了一种抗菌UV固化水性生物基树脂及在甲油胶中的应用，涉及聚氨酯技术领域,本发明利用二乙二醇双氯乙酯与聚氨酯主链中的环氧大豆油的叔胺结构发生季铵化反应，将亲水性的季铵盐基团和醚键引入到聚氨酯的侧链，提高了聚氨酯的亲水性，改善了在水中的分散性和树脂贮存稳定性，并且可以提高树脂固化膜的拉伸强度和硬度。二乙二醇双氯乙酯与改性环氧大豆油的多个叔胺基团发生季铵化反应，生成大量的季铵盐抗菌基团，可以有效抑制和杀灭大肠杆菌、金黄色葡萄球菌等细菌，起到优异的抗菌性能。抗菌UV固化水性生物基树脂绿色环保，固化速度快，同时力学性能高，具有很好的抗菌性能，在甲油胶、抗菌涂料等领域有广阔的应用前景。
Description
技术领域
本发明涉及聚氨酯技术领域，具体为一种抗菌UV固化水性生物基树脂及在甲油胶中的应用。
背景技术
UV固化水性树脂具有绿色环保，固化速度快，施工便捷等优点，主要有聚氨酯丙烯酸树脂、环氧丙烯酸树脂等。其中聚氨酯是由多元醇和多异氰酸酯经缩聚反应得到的高分子聚合物，弹性高，耐磨性能优良，隔热性能强；提高聚氨酯的力学强度、抗菌等性能，可以使聚氨酯在甲油胶、涂料、油墨等领域有更好的实际应用。
环氧大豆油作为一种生物基原料，具有无毒、绿色环保、耐热性能好、增塑效果优良等特点，在聚氯乙烯、聚氨酯、环氧树脂等高分子材料中应用十分广泛。申请号为201710579612.4的中国专利公开了一种基于可降解生物基类的环保型水性聚氨酯树脂及其制备方法，利用异山梨醇与环氧大豆油开环氧制得可降解生物基类多元醇，可以作为聚氨酯的扩链剂，得到的聚氨酯具有力学性能好，可生物降解、不污染环境等优点，但是该聚氨酯不具有抗菌性能，无法满足聚氨酯在抗菌涂层等领域中的实际应用。因此发展力学性能高，具有抗菌性能的水性聚氨酯有着重要的意义。
发明内容
本发明解决如下技术问题：本发明解决了聚氨酯强度不佳，不具有抗菌性能的问题，使聚氨酯树脂在甲油胶等领域有更好的实际应用。
本发明的技术方案：一种抗菌UV固化水性生物基树脂，包括78-91重量份阳离子生物基水性聚氨酯、0.4-0.8重量份消泡剂、2-4重量份增稠剂、0.2-0.6重量份分散剂和6-16重量份色浆。
其中，阳离子生物基水性聚氨酯的制备方法为：
（1）、在氮气氛围中，将真空脱水的二元醇、N,N-二甲基乙二胺改性环氧大豆油、异佛尔酮二异氰酸酯加入到反应瓶中，升温至70-80℃中，进行预聚反应1.5-2h，接着将温度降至50-55℃，加入丙酮、2,2-二羟甲基丙酸，进行扩链反应40-60min，加入三乙胺进行中和，最后加入丙烯酸羟乙酯，封端反应3-4h，减压蒸馏除去丙酮，得到叔胺生物基水性聚氨酯。
（2）、将叔胺生物基水性聚氨酯、N,N-二甲基甲酰胺加入到反应瓶中，混匀后加入二乙二醇双氯乙酯（CAS登录号为638-56-2），升温至90-120℃，反应18-24h，反应后减压蒸馏除去N,N-二甲基甲酰胺，得到阳离子生物基水性聚氨酯。
其中，二元醇、N,N-二甲基乙二胺改性环氧大豆油、异佛尔酮二异氰酸酯的摩尔比为1:（0.04-0.12）:（2.4-2.7）。
其中，二元醇包括聚乙二醇、聚四氢呋喃醚二醇中的至少一种。
其中，（2）中叔胺生物基水性聚氨酯、二乙二醇双氯乙酯的质量比为1:（0.05-0.15）。
其中，N,N-二甲基乙二胺改性环氧大豆油的制备方法为：将摩尔比为1:（6-6.6）的环氧大豆油、N,N-二甲基乙二胺（CAS登录号为108-00-9）加入到反应瓶中，升温至50-65℃，反应6-12h，减压蒸馏除去低沸物，得到N,N-二甲基乙二胺改性环氧大豆油。
其中，抗菌UV固化水性生物基树脂的制备方法，其特征在于，将阳离子生物基水性聚氨酯、消泡剂、增稠剂、分散剂、色浆、蒸馏水加入到高剪切分散机中，剪切分散，得到抗菌UV固化水性生物基树脂。
其中，抗菌UV固化水性生物基树脂在甲油胶中的应用。
本发明的技术效果：本发明利用N,N-二甲基乙二胺的氨基与环氧大豆油的环氧基团进行开环反应，得到含有多个羟基和叔胺基团的N,N-二甲基乙二胺改性环氧大豆油，与二元醇和异佛尔酮二异氰酸酯发生交联反应，形成交联网络的聚氨酯；同时二乙二醇双氯乙酯含有两个氯乙基，可以与改性环氧大豆油的多个叔胺基团发生交联反应，从而使聚氨酯分子链形成双网络交联的空间结构，有利于提高固化膜的力学强度，表现出更高的拉伸强度和硬度。
本发明利用二乙二醇双氯乙酯与聚氨酯主链中的环氧大豆油的叔胺结构发生季铵化反应，从而将亲水性的季铵盐基团和醚键引入到聚氨酯的侧链，进一步提高了聚氨酯的亲水性，改善了在水中的分散性和树脂贮存稳定性。
本发明利用含有两个氯乙基的二乙二醇双氯乙酯，与改性环氧大豆油的多个叔胺基团发生季铵化反应，生成大量的季铵盐抗菌基团，可以有效抑制和杀灭大肠杆菌、金黄色葡萄球菌等细菌，起到优异的抗菌性能。
本发明以阳离子生物基水性聚氨酯作为基体，与色浆、消泡剂等复配，得到的抗菌UV固化水性生物基树脂具有绿色环保，固化速度快，同时力学性能高，具有很好的抗菌性能，在甲油胶、抗菌涂料等领域有广阔的应用前景。
具体实施方式
实施例1
将5mmol的环氧大豆油、30mmol N,N-二甲基乙二胺加入到反应瓶中，升温至50℃，反应12h，减压蒸馏除去低沸物，得到N,N-二甲基乙二胺改性环氧大豆油。
在氮气氛围中，将100mmol真空脱水的聚乙二醇2000、4mmol N,N-二甲基乙二胺改性环氧大豆油、240mmol异佛尔酮二异氰酸酯加入到反应瓶中，升温至70℃中，进行预聚反应2h，接着将温度降至50℃，加入80mL丙酮、57mmol 2,2-二羟甲基丙酸，进行扩链反应60min，加入三乙胺进行中和，最后加入18mmol丙烯酸羟乙酯，封端反应3h，减压蒸馏除去丙酮，得到叔胺生物基水性聚氨酯。
将60g叔胺生物基水性聚氨酯、800mL N,N-二甲基甲酰胺加入到反应瓶中，混匀后加入3g 二乙二醇双氯乙酯，升温至90℃，反应24h，反应后减压蒸馏除去N,N-二甲基甲酰胺，得到阳离子生物基水性聚氨酯。
将810g阳离子生物基水性聚氨酯、6g消泡剂DAPRO DF1760、30g增稠剂RM2020、6g分散剂RKZ9014、150g红色色浆UR236、900mL蒸馏水加入到高剪切分散机中，剪切分散，得到抗菌UV固化水性生物基树脂。
实施例2
将5mmol的环氧大豆油、33mmol N,N-二甲基乙二胺加入到反应瓶中，升温至55℃，反应12h，减压蒸馏除去低沸物，得到N,N-二甲基乙二胺改性环氧大豆油。
在氮气氛围中，将100mmol真空脱水的聚乙二醇2000、7mmol N,N-二甲基乙二胺改性环氧大豆油、250mmol异佛尔酮二异氰酸酯加入到反应瓶中，升温至70℃中，进行预聚反应2h，接着将温度降至50℃，加入80mL丙酮、57mmol 2,2-二羟甲基丙酸，进行扩链反应60min，加入三乙胺进行中和，最后加入18mmol丙烯酸羟乙酯，封端反应4h，减压蒸馏除去丙酮，得到叔胺生物基水性聚氨酯。
将60g叔胺生物基水性聚氨酯、800mL N,N-二甲基甲酰胺加入到反应瓶中，混匀后加入5g 二乙二醇双氯乙酯，升温至100℃，反应24h，反应后减压蒸馏除去N,N-二甲基甲酰胺，得到阳离子生物基水性聚氨酯。
将890g阳离子生物基水性聚氨酯、5g消泡剂DAPRO DF1760、28g增稠剂RM2020、3g分散剂RKZ9014、75g红色色浆UR236、900mL蒸馏水加入到高剪切分散机中，剪切分散，得到抗菌UV固化水性生物基树脂。
实施例3
将5mmol的环氧大豆油、30mmol N,N-二甲基乙二胺加入到反应瓶中，升温至65℃，反应6h，减压蒸馏除去低沸物，得到N,N-二甲基乙二胺改性环氧大豆油。
在氮气氛围中，将100mmol真空脱水的聚四氢呋喃醚二醇2000、10mmol N,N-二甲基乙二胺改性环氧大豆油、260mmol异佛尔酮二异氰酸酯加入到反应瓶中，升温至75℃中，进行预聚反应2h，接着将温度降至55℃，加入80mL丙酮、57mmol 2,2-二羟甲基丙酸，进行扩链反应40min，加入三乙胺进行中和，最后加入18mmol丙烯酸羟乙酯，封端反应3h，减压蒸馏除去丙酮，得到叔胺生物基水性聚氨酯。
将60g叔胺生物基水性聚氨酯、800mL N,N-二甲基甲酰胺加入到反应瓶中，混匀后加入7g 二乙二醇双氯乙酯，升温至120℃，反应18h，反应后减压蒸馏除去N,N-二甲基甲酰胺，得到阳离子生物基水性聚氨酯。
将910g阳离子生物基水性聚氨酯、4g消泡剂DAPRO DF1760、20g增稠剂RM2020、2g分散剂RKZ9014、60g红色色浆UR236、1000mL蒸馏水加入到高剪切分散机中，剪切分散，得到抗菌UV固化水性生物基树脂。
实施例4
将5mmol的环氧大豆油、33mmol N,N-二甲基乙二胺加入到反应瓶中，升温至65℃，反应6h，减压蒸馏除去低沸物，得到N,N-二甲基乙二胺改性环氧大豆油。
在氮气氛围中，将100mmol真空脱水的聚乙二醇2000、12mmol N,N-二甲基乙二胺改性环氧大豆油、270mmol异佛尔酮二异氰酸酯加入到反应瓶中，升温至80℃中，进行预聚反应1.5h，接着将温度降至55℃，加入80mL丙酮、57mmol 2,2-二羟甲基丙酸，进行扩链反应40min，加入三乙胺进行中和，最后加入18mmol丙烯酸羟乙酯，封端反应3h，减压蒸馏除去丙酮，得到叔胺生物基水性聚氨酯。
将60g叔胺生物基水性聚氨酯、800mL N,N-二甲基甲酰胺加入到反应瓶中，混匀后加入9g 二乙二醇双氯乙酯，升温至120℃，反应18h，反应后减压蒸馏除去N,N-二甲基甲酰胺，得到阳离子生物基水性聚氨酯。
将780g阳离子生物基水性聚氨酯、8g消泡剂DAPRO DF1760、40g增稠剂RM2020、6g分散剂RKZ9014、150g红色色浆UR236、900mL蒸馏水加入到高剪切分散机中，剪切分散，得到抗菌UV固化水性生物基树脂。
对比例1
将5mmol的环氧大豆油、30mmol N,N-二甲基乙二胺加入到反应瓶中，升温至50℃，反应12h，减压蒸馏除去低沸物，得到N,N-二甲基乙二胺改性环氧大豆油。
在氮气氛围中，将100mmol真空脱水的聚乙二醇2000、4mmol N,N-二甲基乙二胺改性环氧大豆油、240mmol异佛尔酮二异氰酸酯加入到反应瓶中，升温至70℃中，进行预聚反应2h，接着将温度降至50℃，加入80mL丙酮、57mmol 2,2-二羟甲基丙酸，进行扩链反应60min，加入三乙胺进行中和，最后加入18mmol丙烯酸羟乙酯，封端反应3h，减压蒸馏除去丙酮，得到叔胺生物基水性聚氨酯。
将810g叔胺生物基水性聚氨酯、6g消泡剂DAPRO DF1760、30g增稠剂RM2020、6g分散剂RKZ9014、150g红色色浆UR236、900mL蒸馏水加入到高剪切分散机中，剪切分散，得到UV固化水性生物基树脂。
对比例2
在氮气氛围中，将100mmol真空脱水的聚乙二醇2000、240mmol异佛尔酮二异氰酸酯加入到反应瓶中，升温至70℃中，进行预聚反应2h，接着将温度降至50℃，加入80mL丙酮、57mmol 2,2-二羟甲基丙酸，进行扩链反应60min，加入三乙胺进行中和，最后加入18mmol丙烯酸羟乙酯，封端反应3h，减压蒸馏除去丙酮，得到水性聚氨酯。
将810g水性聚氨酯、6g消泡剂DAPRO DF1760、30g增稠剂RM2020、6g分散剂RKZ9014、150g红色色浆UR236、900mL蒸馏水加入到高剪切分散机中，剪切分散，得到UV固化水性生物基树脂。
UV固化水性生物基树脂的贮存稳定性按GB/T 6753.3-1986方法进行测试。测试结果如表1内容。
表1 UV固化水性生物基树脂性能测试
| 实施例1 | 实施例2 | 实施例3 | 实施例4 | 对比例1 | 对比例2 | |
| 贮存稳定性（月） | ≧9 | ≧9 | ≧12 | ≧10 | ≧6 | ≧8 |
由表1可知，实施例1至实施例4的抗菌UV固化水性生物基树脂的贮存稳定性达到9-12个月，这归功于二乙二醇双氯乙酯的氯原子，与聚氨酯主链中的环氧大豆油的叔胺结构发生季铵化反应，从而将亲水性的季铵盐基团和醚键引入到聚氨酯的侧链，进一步提高了聚氨酯的亲水性，改善了在水中的分散性和树脂贮存稳定性。
对比例1以叔胺生物基水性聚氨酯作为树脂基体，对比例2的水性聚氨酯作为树脂基体，二者均没有与二乙二醇双氯乙酯发生季铵化反应，聚氨酯不含有季铵盐亲水基团，并且亲水性醚键的含量少于实施例1。导致聚氨酯的亲水性和在水中的分散性低于实施例1。树脂的贮存稳定性不佳。
向50mLUV固化水性生物基树脂中加入1.1g光引发剂1173，搅拌混匀，将溶液倒在马口铁表面，在功率为36W的紫外光固化机中进行固化30s，光照距离为10cm。得到UV固化水性生物基树脂固化膜。
固化膜的拉伸性能按照 GB/T 528-2009方法进行测试。铅笔硬度按GB/T 6736-2006进行测试。测试结果如表2内容。
表2固化膜拉伸性能测试
| 实施例1 | 实施例2 | 实施例3 | 实施例4 | 对比例1 | 对比例2 | |
| 拉伸强度（MPa） | 23.5 | 29.7 | 30.2 | 31.5 | 19.0 | 14.4 |
| 铅笔硬度 | 4H | 5H | 5H | 5H | 3H | 2H |
由表2可知，实施例1-4的树脂固化膜的拉伸强度达到23.5-31.5MPa，铅笔硬度达到4-5H，这归功于N,N-二甲基乙二胺改性环氧大豆油含有多个羟基，与二元醇和异佛尔酮二异氰酸酯发生交联反应，形成交联网络；同时二乙二醇双氯乙酯含有两个氯乙基，可以与改性环氧大豆油的多个叔胺基团发生交联反应，从而使聚氨酯分子链形成双网络交联的空间结构，有利于提高固化膜的力学强度，表现出更高的拉伸强度和硬度。
固化膜的抗菌性能按GB/T 21866-2008方法进行测试，以大肠杆菌或金黄色葡萄球菌作为测试菌种；以实施例1至实施例4，以及对比例1的UV固化水性生物基树脂固化膜作为实验组，以对比例2的UV固化水性生物基树脂固化膜作为空白对照组，进行抗菌性能测试。抗菌率=（B-C）/B×100%。C为实验组培养24h后的平均回收菌数（cfu/片）。B为空白对照组培养24h后的平均回收菌数（cfu/片）。测试结果如表3内容。
表3固化膜抗菌性能测试
| 实施例1 | 实施例2 | 实施例3 | 实施例4 | 对比例1 | |
| 大肠杆菌抑菌率（%） | 93.5 | 98.2 | 99.9 | 99.9 | 1.6 |
| 金黄色葡萄球菌抑菌率（%） | 90.4 | 95.7 | 98.7 | 99.9 | - |
由表3可知，实施例1-4的树脂固化膜对大肠杆菌抑菌率达到93.5-99.9%。对金黄色葡萄球菌抑菌率达到90.4-99.9%。这归功于二乙二醇双氯乙酯含有两个氯乙基，可以与改性环氧大豆油的多个叔胺基团发生季铵化反应，生成大量的季铵盐抗菌基团，可以有效抑制和杀灭大肠杆菌、金黄色葡萄球菌等细菌，起到优异的抗菌性能。
Claims (10)
1.一种抗菌UV固化水性生物基树脂，其特征在于，所述抗菌UV固化水性生物基树脂包括78-91重量份阳离子生物基水性聚氨酯、0.4-0.8重量份消泡剂、2-4重量份增稠剂、0.2-0.6重量份分散剂和6-16重量份色浆；
所述阳离子生物基水性聚氨酯的制备方法为：
（1）、在氮气氛围中，将真空脱水的二元醇、N,N-二甲基乙二胺改性环氧大豆油、异佛尔酮二异氰酸酯加入到反应瓶中，进行预聚反应，接着在50-55℃中，加入丙酮、2,2-二羟甲基丙酸，进行扩链反应40-60min，加入三乙胺进行中和，最后加入丙烯酸羟乙酯，封端反应3-4h，减压蒸馏除去丙酮，得到叔胺生物基水性聚氨酯；
（2）、将叔胺生物基水性聚氨酯、N,N-二甲基甲酰胺加入到反应瓶中，混匀后加入二乙二醇双氯乙酯，反应后减压蒸馏除去N,N-二甲基甲酰胺，得到阳离子生物基水性聚氨酯。
2.根据权利要求1所述的抗菌UV固化水性生物基树脂，其特征在于，所述预聚反应在70-80℃中进行1.5-2h。
3.根据权利要求1所述的抗菌UV固化水性生物基树脂，其特征在于，所述二元醇、N,N-二甲基乙二胺改性环氧大豆油、异佛尔酮二异氰酸酯的摩尔比为1:（0.04-0.12）:（2.4-2.7）。
4.根据权利要求3所述的抗菌UV固化水性生物基树脂，其特征在于，所述二元醇包括聚乙二醇、聚四氢呋喃醚二醇中的至少一种。
5.根据权利要求1所述的抗菌UV固化水性生物基树脂，其特征在于，所述（2）中叔胺生物基水性聚氨酯、二乙二醇双氯乙酯的质量比为1:（0.05-0.15）。
6.根据权利要求1所述的抗菌UV固化水性生物基树脂，其特征在于，所述（2）中反应在90-120℃中进行18-24h。
7.根据权利要求1所述的抗菌UV固化水性生物基树脂，其特征在于，所述N,N-二甲基乙二胺改性环氧大豆油的制备方法为：将环氧大豆油、N,N-二甲基乙二胺加入到反应瓶中，升温至50-65℃，反应6-12h，减压蒸馏除去低沸物，得到N,N-二甲基乙二胺改性环氧大豆油。
8.根据权利要求7所述的抗菌UV固化水性生物基树脂，其特征在于，所述环氧大豆油、N,N-二甲基乙二胺的摩尔比为1:（6-6.6）。
9.一种如权利要求1-8任一项所述的抗菌UV固化水性生物基树脂的制备方法，其特征在于，将阳离子生物基水性聚氨酯、消泡剂、增稠剂、分散剂、色浆、蒸馏水加入到高剪切分散机中，剪切分散，得到抗菌UV固化水性生物基树脂。
10.一种如权利要求9所述的制备方法得到的抗菌UV固化水性生物基树脂在甲油胶中的应用。
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| CN101967222B (zh) * | 2010-09-19 | 2012-04-25 | 中国林业科学研究院林产化学工业研究所 | 一种环氧化蓖麻油改性的水性聚氨酯的制备方法 |
| CN101967341B (zh) * | 2010-09-29 | 2013-02-20 | 中国科学院长春应用化学研究所 | 一种水性耐磨紫外光固化的上光油及其制法 |
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