CN114573782B - 一种阴-阳离子水性聚氨酯的制备方法及制备的水性聚氨酯 - Google Patents
一种阴-阳离子水性聚氨酯的制备方法及制备的水性聚氨酯 Download PDFInfo
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Abstract
本发明涉及高分子聚合技术领域，具体涉及一种阴‑阳离子水性聚氨酯的制备方法及制备的水性聚氨酯。该方法包括S1.阴离子亲水扩链剂与阳离子亲水扩链剂成盐溶解，获得组分A；S2.获得具有组分A的聚氨酯预聚体；S3.使用有机碱或无机碱取代，获得带阴离子基团的聚氨酯分子链；S4.使用弱酸中和，获得带有阴‑阳离子的聚氨酯分子链；S5.聚氨酯分子链乳化，减压脱去溶剂，获得阴‑阳离子型水性聚氨酯乳液。本发明制备了同时具有阴离子和阳离子基团的水性聚氨酯乳液，不仅具有阴离子水性聚氨酯树脂的高强度的特性，同时具有阳离子水性聚氨酯的离子特性。
Description
技术领域
本发明涉及高分子聚合技术领域，具体涉及一种阴-阳离子水性聚氨酯的制备方法及利用该方法制备的阴-阳离子水性聚氨酯。
背景技术
水性聚氨酯作为近年来发展迅速的一种环保材料，在越来越多的领域得到广泛的应用。目前工业上最常用的水性聚氨酯树脂为阴离子型水性聚氨酯树脂，其在力学性能和耐黄变等性能方面优于阳离子型水性聚氨酯。
阳离子水性聚氨酯的特色来自其阳离子特性，但在有些应用领域是阴离子型水性聚氨酯不能取代的。如真皮封底涂饰领域、木器封闭涂层、吸墨涂层等。如果可以在水性聚氨酯分子链上同时引入阴离子和阳离子基团，并保证乳液稳定，不仅可以赋予阴离子水性聚氨酯阳离子特性，同时可以提高阳离子水性聚氨酯力学性能。
专利CN104371085B公布了一种两性离子水性聚氨酯的制备方法，使用两性离子型聚酯二元醇合成；CN102942678B公布了一种甜菜碱基团改性阳离子型水性聚氨酯及其制备方法。上述专利的核心均为利用N-甲基二乙醇胺与丙磺酸内酯发生季氨化反应，获得含有两亲离子的水性聚氨酯树脂。这种方法虽然可以获得含有阴阳离子的水性聚氨酯，但存在以下缺点：一是利用丙磺酸内酯进行离子化，可能会存在丙磺酸内酯单体残余，具有致癌性；二是这种亲水基团侧链较长，存在较明显的内增塑作用，影响强度；三是这种水性聚氨酯树脂中阴离子和阳离子基团比例为1：1，且阴离子基团的电负性更强，树脂的离子状态呈现为阴离子特性。
发明内容
为了解决现有技术中的问题，本发明提供了一种阴-阳离子水性聚氨酯树脂的制备方法，利用该方法制备的阴-阳离子水性聚氨酯性能好，且无致癌性的丙磺酸内酯单体的残留。
本发明采用的技术方案为：
一种阴-阳离子水性聚氨酯树脂的制备方法，包括以下步骤：
S1.将10份的双羟基阴离子亲水扩链剂与3～10份的含叔胺基团的阳离子亲水扩链剂在10～30份的溶剂中成盐溶解，获得组分A；
S2.将大分子多元醇投入反应釜，并投入二异氰酸酯、S1中的组分A、小分子扩链剂和丙酮进行反应，获得具有组分A的聚氨酯预聚体；所述大分子多元醇为聚酯多元醇、聚醚多元醇和或聚碳酸酯多元醇；
S3.使用0.1～3份的有机碱或无机碱加入上述S2所获得的聚氨酯预聚体中，取代组分A上含有叔胺基团的阳离子亲水扩链剂，获得带有阴离子基团的聚氨酯分子链，所述有机碱或无机碱碱性强于所述阳离子亲水扩链剂；
S4.使用0.1～5份的弱酸加入上述S3中，中和被取代的含有叔胺基团的阴离子亲水扩链剂，最终获得带有阴-阳离子的聚氨酯分子链；
S5.将S4中获得的聚氨酯分子链转移至分散设备中，在转速为1000～5000r/min条件下将20～100份的冰水混合物加入聚氨酯分子链中乳化，然后在40～60℃，-0.1MPa的条件下减压脱去溶剂，获得阴-阳离子型水性聚氨酯乳液。
优选的，S2中，具体方法为：将10～20份的大分子多元醇投入反应釜，在90～110℃、-0.1MPa的条件下真空脱水1～2小时后，降温至60℃；继续投入3～10份的二异氰酸酯、3～20份的组分A、0～3份的小分子扩链剂和2～5份的丙酮，搅拌升温至80℃，反应6～10小时，然后降温至60℃；最后加入5～20份的丙酮，搅拌均匀，继续降温至20℃，获得具有组分A的聚氨酯预聚体。
优选的，S1中，所述双羟基阴离子亲水扩链剂为二羟甲基丙酸和/或二羟甲基丁酸；所述含叔胺基团的阳离子亲水扩链剂为N-甲基二乙醇胺N-MDEA、N-乙基二乙醇胺N-EDEA、N-丙基二乙醇胺N-PDEA、N-苄基二乙醇胺N-BDEA、叔丁基二乙醇胺N-t-BuDEA中的任意一种或多种。
优选的，S1中，所述溶剂为丙酮、丁酮、N—甲基氨基甲酸甲酯、碳酸二甲酯、N，N-二甲基乙酰胺、N,N—二乙基甲酰胺中的任意一种或多种。
优选的，S2中，所述大分子多元醇分子量为1000～5000g/mol；所述二异氰酸酯为脂肪族或芳香族二异氰酸酯。
优选的，所述脂肪族或芳香族二异氰酸酯包括六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯中的一种或多种。
优选的，S2中，所述小分子扩链剂为含有两个羟基的小分子醇。
优选的，S3中，所述取代条件为20℃搅拌30min，所述有机碱或无机碱为氢氧化钠、氢氧化钾、三乙胺中的任意一种或多种混合。
优选的，S4中，所述中和条件为20℃搅拌30min，所述弱酸为乙酸、乳酸、苯甲酸、甲酸、草酸中的任意一种或多种混合。
本发明还提供一种利用上述阴-阳离子水性聚氨酯树脂的制备方法制备得到的阴-阳离子水性聚氨酯树脂。
本发明的有益效果在于：
利用本发明提供的制备方法可以获得同时具有阴离子和阳离子基团的水性聚氨酯乳液，同时制备的阴-阳离子水性聚氨酯中不含有致癌性的丙磺酸内酯单体的残留。由于阴、阳离子分别分布在聚氨酯分子链的不同位置，本发明所获得的阴-阳离子水性聚氨酯树脂不仅具有阴离子水性聚氨酯树脂的高强度的特性，同时具有阳离子水性聚氨酯的离子特性。
相比于现有技术中的水性聚氨酯，本发明提供的阴-阳离子水性聚氨酯在真皮封底涂饰领域、木器封闭涂层、吸墨涂层等领域具有更加优异的性能，且由于阴阳离子间相互的作用力，可以赋予材料更好的回弹性。
具体实施方式
下面结合实施例对本发明的技术方案进行说明，以便于本领域的技术人员理解。
实施例1
一种阴-阳离子水性聚氨酯树脂的制备方法，步骤如下：
S1.将10份的二羟甲基丙酸与8份的N-甲基二乙醇胺在18份的丙酮中成盐溶解，获得澄清透明的组分A；
S2.将15份的聚己二酸新戊二醇酯2000投入反应釜，在90～110℃，-0.1MPa的条件下真空脱水1～2小时后，降温至60℃；投入7份的异佛尔酮二异氰酸酯、5份的组分A和5份的丙酮，搅拌升温至80℃，反应6～10小时，然后降温至60℃，加入15份的丙酮，继续降温至20℃，获得具有组分A的聚氨酯预聚体；
S3.使用0.4份的氢氧化钠取代上述S2所获得聚氨酯预聚体中组分A上面的叔胺基团即N-甲基二乙醇胺，获得带有阴离子基团的聚氨酯分子链；
S4.使用1份的乳酸中和上述S3中被取代的N-甲基二乙醇胺，获得带有阴-阳离子的聚氨酯分子链；
S5.将S4中获得的聚氨酯分子链转移至分散设备中，在转速为4000r/min条件下将50份的冰水混合物加入聚氨酯分子链中乳化，然后在40～60℃，-0.1MPa的条件下减压脱去溶剂，获得阴-阳离子型水性聚氨酯乳液。
实施例2
一种阴-阳离子水性聚氨酯树脂的制备方法，步骤如下：
S1.将10份的二羟甲基丙酸与N-乙基二乙醇胺在18份的丙酮中成盐溶解，获得澄清透明的组分A；
S2.将15份的聚四氢呋喃醚二醇2000投入反应釜，在90～110℃，-0.1MPa的条件下真空脱水1～2小时，降温至60℃，投入7份的异佛尔酮二异氰酸酯、5份的组分A和5份的丙酮，搅拌升温至80℃，反应6～10小时，然后降温至60℃，加入15份的丙酮，继续降温至20℃，获得具有组分A的聚氨酯预聚体；
S3.使用0.6份的三乙胺取代上述S2所获得聚氨酯预聚体中组分A上面的叔胺基团，获得带有阴离子基团的聚氨酯分子链；
S4.使用1份的乙酸中和上述S3中被取代的N-乙基二乙醇胺，获得带有阴—阳离子的聚氨酯分子链；
S5.将S4中获得的聚氨酯分子链转移至分散设备中，在转速为4000r/min条件下将50份的冰水混合物加入聚氨酯分子链中乳化，然后在40～60℃，-0.1MPa的条件下减压脱去溶剂，获得阴-阳离子型水性聚氨酯乳液。
实施例3
一种阴-阳离子水性聚氨酯树脂的制备方法，步骤如下：
S1.将10份的二羟甲基丙酸与6份的N-甲基二乙醇胺在16份的丙酮中成盐溶解，获得澄清透明的组分A；
S2.将10份的聚丙二醇2000投入反应釜，在90～110℃，-0.1MPa的条件下真空脱水1～2小时，降温至60℃，投入5份的甲苯二异氰酸酯、6份的组分A和5份的丙酮，搅拌升温至80℃，反应6～10小时，然后降温至60℃，加入15份的丙酮，继续降温至20℃，获得具有组分A的聚氨酯预聚体；
S3.使用0.6份的三乙胺取代上述S2所获得聚氨酯预聚体中组分A上面的叔胺基团，获得带有阴离子基团的聚氨酯分子链；
S4.使用0.8份的甲酸中和上述S3中被取代的N-甲基二乙醇胺，获得带有阴—阳离子的聚氨酯分子链；
S5.将S4中获得的聚氨酯分子链转移至分散设备中，在转速为4000r/min条件下将50份的冰水混合物加入聚氨酯分子链中乳化，然后在40～60℃，-0.1MPa的条件下减压脱去溶剂，获得阴-阳离子型水性聚氨酯乳液。
实施例4
选择结构与实施例1、2、3制备得到的阴-阳离子水性聚氨酯类似的阴离子水性聚氨酯KT620和阳离子水性聚氨酯树脂KT311，与实施例对比进行性能测试。
上述KT620使用聚己二酸新戊二醇酯、异佛尔酮二异氰酸酯、二羟甲基丙酸合成，使用丙酮作为溶剂；上述KT311使用聚己二酸新戊二醇酯、异佛尔酮二异氰酸酯、N—甲基二乙醇胺合成，丙酮作为溶剂。
性能测试包括粒径(马尔文激光粒度仪)、存储稳定性(50℃，14D)、拉伸至100％的模量mPa、断裂强度、伸长率、300％形变回复率(10次)和单宁酸封闭效果。测试结果如下表1所示。
从表格中可以看出，本发明制备的阴-阳离子水性聚氨酯粒径明显小于作为对比的KT620和KT311，表明本发明制备的水性聚氨酯同时具有阴-阳离子基团。且本发明制备的阴-阳离子水性聚氨酯100％模量和300％形变回复率均大于KT620和KT311，表明阴阳粒子基团在成膜过程中发生离子交联。实施例1～3的单宁酸封闭效果好于KT620，与KT311无明显差异，说明所制备的阴阳离子水性聚氨酯树脂具有较好的阳离子特性。
以上仅为本发明创造的较佳实施例而已，并不用以限制本发明创造；尽管参照前述实施方式对本发明进行了详细的说明，本领域的普通技术人员应当理解：凡在本发明创造的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明创造的保护范围之内。
Claims (9)
1.一种阴-阳离子水性聚氨酯树脂的制备方法，其特征在于，包括以下步骤：
S1.将10份的双羟基阴离子亲水扩链剂与3～10份的含叔胺基团的阳离子亲水扩链剂在10～30份的溶剂中成盐溶解，获得组分A；
所述双羟基阴离子亲水扩链剂为二羟甲基丙酸和/或二羟甲基丁酸；所述含叔胺基团的阳离子亲水扩链剂为N-甲基二乙醇胺N-MDEA、N-乙基二乙醇胺N-EDEA、N-丙基二乙醇胺N-PDEA、N-苄基二乙醇胺N-BDEA、叔丁基二乙醇胺N-t-BuDEA中的任意一种或多种；
S2.将大分子多元醇投入反应釜，并投入二异氰酸酯、S1中的组分A、小分子扩链剂和丙酮进行反应，获得具有组分A的聚氨酯预聚体；所述大分子多元醇为聚酯多元醇、聚醚多元醇和或聚碳酸酯多元醇；
S3.使用0.1～3份的有机碱或无机碱加入上述S2所获得的聚氨酯预聚体中，取代组分A上含有叔胺基团的阳离子亲水扩链剂，获得带有阴离子基团的聚氨酯分子链，所述有机碱或无机碱碱性强于所述阳离子亲水扩链剂；
S4.使用0.1～5份的弱酸加入上述S3中，中和被取代的含有叔胺基团的阴离子亲水扩链剂，最终获得带有阴-阳离子的聚氨酯分子链；
S5.将S4中获得的聚氨酯分子链转移至分散设备中，在转速为1000～5000r/min条件下将20～100份的冰水混合物加入聚氨酯分子链中乳化，然后在40～60℃，-0.1MPa的条件下减压脱去溶剂，获得阴-阳离子型水性聚氨酯乳液。
2.如权利要求1所述的一种阴-阳离子水性聚氨酯树脂的制备方法，其特征在于，S2中，具体方法为：将10～20份的大分子多元醇投入反应釜，在90～110℃、-0.1MPa的条件下真空脱水1～2小时后，降温至60℃；继续投入3～10份的二异氰酸酯、3～20份的组分A、0～3份的小分子扩链剂和2～5份的丙酮，搅拌升温至80℃，反应6～10小时，然后降温至60℃；最后加入5～20份的丙酮，搅拌均匀，继续降温至20℃，获得具有组分A的聚氨酯预聚体。
3.如权利要求1所述的一种阴-阳离子水性聚氨酯树脂的制备方法，其特征在于，S1中，所述溶剂为丙酮、丁酮、N—甲基氨基甲酸甲酯、碳酸二甲酯、N，N-二甲基乙酰胺、N,N—二乙基甲酰胺中的任意一种或多种。
4.如权利要求2所述的一种阴-阳离子水性聚氨酯树脂的制备方法，其特征在于，S2中，所述大分子多元醇分子量为1000～5000g/mol；所述二异氰酸酯为脂肪族或芳香族二异氰酸酯。
5.如权利要求4所述的一种阴-阳离子水性聚氨酯树脂的制备方法，其特征在于，所述脂肪族或芳香族二异氰酸酯包括六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯中的一种或多种。
6.如权利要求1所述的一种阴-阳离子水性聚氨酯树脂的制备方法，其特征在于，S2中，所述小分子扩链剂为含有两个羟基的小分子醇。
7.如权利要求1所述的一种阴-阳离子水性聚氨酯树脂的制备方法，其特征在于，S3中，所述取代条件为20℃搅拌30min，所述有机碱或无机碱为氢氧化钠、氢氧化钾、三乙胺中的任意一种或多种混合。
8.如权利要求1所述的一种阴-阳离子水性聚氨酯树脂的制备方法，其特征在于，S4中，所述中和条件为20℃搅拌30min，所述弱酸为乙酸、乳酸、苯甲酸、甲酸、草酸中的任意一种或多种混合。
9.一种利用权利要求1-8任一项所述的一种阴-阳离子水性聚氨酯树脂的制备方法制备得到的阴-阳离子水性聚氨酯树脂。
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| US4182828A (en) * | 1977-05-14 | 1980-01-08 | Bayer Aktiengesellschaft | Production of solutions or dispersions of polyisocyanate polyaddition products containing urethane and/or urea groups and containing both anionic and cationic groups |
| CN102585149A (zh) * | 2012-01-12 | 2012-07-18 | 温州大学 | 一种高固含量的磺酸盐型两性水性聚氨酯及其制备方法 |
| CN102796237A (zh) * | 2012-08-31 | 2012-11-28 | 合肥安科精细化工有限公司 | 双羟基阳离子亲水扩链剂及其在合成阳离子水性聚氨酯分散体中的应用 |
| CN105176363A (zh) * | 2015-09-17 | 2015-12-23 | 合肥思敬齐化工材料有限责任公司 | 一种水性聚氨酯木器底漆树脂及其制备方法 |
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| US4182828A (en) * | 1977-05-14 | 1980-01-08 | Bayer Aktiengesellschaft | Production of solutions or dispersions of polyisocyanate polyaddition products containing urethane and/or urea groups and containing both anionic and cationic groups |
| CN102585149A (zh) * | 2012-01-12 | 2012-07-18 | 温州大学 | 一种高固含量的磺酸盐型两性水性聚氨酯及其制备方法 |
| CN102796237A (zh) * | 2012-08-31 | 2012-11-28 | 合肥安科精细化工有限公司 | 双羟基阳离子亲水扩链剂及其在合成阳离子水性聚氨酯分散体中的应用 |
| CN105176363A (zh) * | 2015-09-17 | 2015-12-23 | 合肥思敬齐化工材料有限责任公司 | 一种水性聚氨酯木器底漆树脂及其制备方法 |
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