CN114933681A - 一种异氰酸酯改性聚丙烯酸酯无氟防水剂及其制备方法 - Google Patents
一种异氰酸酯改性聚丙烯酸酯无氟防水剂及其制备方法 Download PDFInfo
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Abstract
本发明提供一种异氰酸酯改性聚丙烯酸酯无氟防水剂及其制备方法，该制备方法包括以下步骤：A：将异氰酸十八酯与丙烯酸羟乙酯按摩尔比为1:1～1.1混合，在四甲基丙二胺的催化下，反应后得到中间体；B：再将将上述中间体与丙烯酸十八酯、乙烯基硅油、水、乳化剂混合均匀后在引发剂偶氮二异丁脒盐酸盐作用下，进行乳液聚合得到异氰酸酯改性聚丙烯酸酯无氟防水剂。该防水剂通用性强，防水性能优异；异氰酸酯基的引入有效平衡了整理剂对纤维的吸附性，较好地解决了纺织品整理加工过程中连续浸轧时头尾性能差异问题。
Description
技术领域
本发明涉及一种无氟防水剂，尤其是涉及一种异氰酸酯改性聚丙烯酸酯无氟防水剂及其制备方法，用于印染助剂领域。
背景技术
无氟防水剂近年来成为许多研究者的研究重点，尤其是以丙烯酸十八酯为主要原料的乳液聚合体系。
如公开号CN110669165A中公开了一种阳离子型聚丙烯酸酯无氟防水剂，以长链丙烯酸脂肪醇酯、甲基丙烯酸甲酯和反应性阳离子乳化剂为原料进行制备，乳液稳定性好，粒径分布小，与固色剂配伍性好，但甲基丙烯酸甲酯玻璃化温度较高，会导致整理后织物柔软性下降；公开号为CN110699961A、CN106087420A、CN110452361A公开了在无氟防水剂中引入有机硅链段的技术，目的用于改善整理后织物的手感，但制备过程过于复杂，生产成本较高；公开号为CN105671967A、CN111040105A、CN111535035A、CN112281493A中均采用了封端异氰酸酯与长链脂肪酸/脂肪醇的复配技术，通过高温解封交联达到防水效果，但所用长链脂肪酸/脂肪醇为单分子化合物，难以达到聚合物的防水效果，且吸附平衡性欠佳，纺织品连续浸轧整理加工过程中容易出现头尾差。
发明内容
本发明目的是客服现有技术的不足，提供一种异氰酸酯改性聚丙烯酸酯无氟防水剂及其制备方法。
为了实现上述目的，本发明采用以下技术方案：
一种异氰酸酯改性聚丙烯酸酯无氟防水剂及其制备方法，其制备包括如下合成方法与步骤：
A：将摩尔比为1:1～1.1的异氰酸十八酯与丙烯酸羟乙酯加入到装有冷凝回流装置和温度计的反应容器中，开启搅拌，加入占反应物总质量0.3～0.5％的四甲基丙二胺，在80～85℃下保温反应3～4h，得到中间体Y；
B：按质量份进行配比，在装有冷凝回流装置的反应容器中加入20～30份丙烯酸十八酯、2～5份乙烯基硅油、2～5份中间体Y、0.1～2份阳离子乳化剂、0.1～2份非离子乳化剂、10～15份溶剂、0.1～1份正十二烷基硫醇和50～70份去离子水，开启搅拌，升温至40～60℃，搅拌均匀后转入高压均质机，在20-30MPa下混合均匀得到预乳液；将预乳液装入装有冷凝回流装置和温度计的反应容器中，搅拌升温至60～80℃，加入0.1～1份偶氮二异丁脒盐酸盐，在60～80℃下保温反应3～5h，得到异氰酸酯改性聚丙烯酸酯无氟防水剂。
作为优选，所述乙烯基硅油为聚合度10～15的直链型双端乙烯基聚硅氧烷，所述阳离子乳化剂为十八烷基三甲基氯化铵、十八烷基二甲基苄基氯化铵、双十八烷基二甲基氯化铵、十六烷基三甲基氯化铵、十六烷基三甲基溴化铵中的一种或几种的混合；所述非离子乳化剂为平平加O，且结构中的平均聚氧乙烯重复单元数为40～70；所述溶剂为二丙二醇、三丙二醇、二丙二醇甲醚、丙二醇、己二醇中的一种或几种的混合。
由于上述技术方案的运用，本发明具有如下优点：
采用丙烯酸羟乙酯与异氰酸十八酯反应生成中间体Y，其结构中引入乙烯基，可更好的与丙烯酸十八酯共聚；结构中氨基甲酸酯基可提升防水剂与化纤织物的结合能力，并与长链烷烃、酯基一起协同增效，平衡吸附性，改善浸轧整理过程中的头尾差问题。双端乙烯基硅油不仅可以改善整理后织物的柔软性，而且双乙烯基结构可增加聚合物分子结构的交联度，提高产品的耐磨性与防水性能。
具体实施方式
下面通过具体实施方式，对本发明做进一步的描述。
实施例1：A：将摩尔比为1:1的异氰酸十八酯与丙烯酸羟乙酯加入到装有冷凝回流装置和温度计的反应容器中，开启搅拌，加入占反应物总质量0.5％的四甲基丙二胺，在80℃下保温反应3h，得到中间体Y；
B：按质量份进行配比，在装有冷凝回流装置的反应容器中加入25g丙烯酸十八酯、2.5g聚合度10的乙烯基硅油、5g中间体Y、1g十八烷基三甲基氯化铵、1g平平加O(平均聚氧乙烯重复单元数为40)、10g三丙二醇、0.3g正十二烷基硫醇和55g去离子水，开启搅拌，升温至55℃，搅拌均匀后转入高压均质机，在20MPa下混合均匀得到预乳液；将预乳液装入装有冷凝回流装置和温度计的反应容器中，搅拌升温至60℃，加入0.5g偶氮二异丁脒盐酸盐，在60℃下保温反应5h，得到异氰酸酯改性聚丙烯酸酯无氟防水剂。
实施例2：A：将摩尔比为1:1的异氰酸十八酯与丙烯酸羟乙酯加入到装有冷凝回流装置和温度计的反应容器中，开启搅拌，加入占反应物总质量0.5％的四甲基丙二胺，在80℃下保温反应3h，得到中间体Y；
B：按质量份进行配比，在装有冷凝回流装置的反应容器中加入25g丙烯酸十八酯、3g聚合度15的乙烯基硅油、4.5g中间体Y、1.5g十八烷基二甲基苄基氯化铵、2g平平加O(平均聚氧乙烯重复单元数为50)、10g二丙二醇甲醚、0.2g正十二烷基硫醇和55g去离子水，开启搅拌，升温至60℃，搅拌均匀后转入高压均质机，在25MPa下混合均匀得到预乳液；将预乳液装入装有冷凝回流装置和温度计的反应容器中，搅拌升温至70℃，加入0.5g偶氮二异丁脒盐酸盐，在70℃下保温反应5h，得到异氰酸酯改性聚丙烯酸酯无氟防水剂。
实施例3：A：将摩尔比为1:1.05的异氰酸十八酯与丙烯酸羟乙酯加入到装有冷凝回流装置和温度计的反应容器中，开启搅拌，加入占反应物总质量0.5％的四甲基丙二胺，在85℃下保温反应4h，得到中间体Y；
B：按质量份进行配比，在装有冷凝回流装置的反应容器中加入20g丙烯酸十八酯、5g聚合度10的乙烯基硅油、5g中间体Y、2g十八烷基三甲基氯化铵、2g平平加O(平均聚氧乙烯重复单元数为65)、15g三丙二醇、0.3g份正十二烷基硫醇和50g去离子水，开启搅拌，升温至60℃，搅拌均匀后转入高压均质机，在25MPa下混合均匀得到预乳液；将预乳液装入装有冷凝回流装置和温度计的反应容器中，搅拌升温至60℃，加入0.5g偶氮二异丁脒盐酸盐，在60℃下保温反应5h，得到异氰酸酯改性聚丙烯酸酯无氟防水剂。
实验方法：
(一)织物与助剂：
织物：70D斜纹白色涤塔夫
对比助剂
对比例1：无氟防水剂DM-3696(广东德美精细化工集团股份有限公司)
对比例2：无氟防水剂RUCO-DRY ECO Plus(德国鲁道夫)
(二)应用工艺：
1、浸扎工艺：30-50g/L，100℃预烘，定型150℃-180℃*90sec。
2、浸渍工艺：2％-5％(o.w.f)。温度25℃-50℃*20-30min，脱水，烘干，定型150-180℃-90sec。
(三)测试指标与方法：
1、防水性能：
参照GB4745-1997织物防水沾水实验，通过人眼观看判断织物的沾水情况，防水效果分为5级，5级最好，1级最差。
2、连续性：
根据目标织物的带液率配制对应数量的防水剂溶液且防水剂用量为20g/L，通过连续浸扎10块相同的织物并定型后，根据GB4745-1997织物防水沾水实验，将每一块织物进行防水性能测试。
实验结果：
表1连续性测试结果
表2 20g/L耐洗测试结果
| 初始防水 | 水洗10次 | |
| 实施例1 | 5 | 4.5 |
| 实施例2 | 5 | 4.5 |
| 实施例3 | 5 | 4 |
| 对比例1 | 5 | 3.5 |
| 对比例2 | 4.5 | 2 |
表3 40g/L耐洗测试结果
由以上数据可知，本发明各实施例在白色涤塔夫中的防水性能、连续性均优于市场样对比例；最后，应当指出，以上实施例仅是本发明较有代表性的例子。显然，本发明的技术方案不限于上述实施例，还可以有许多变形。凡是从本发明公开的内容直接导出或联想到的所有变形，均应认为是本发明的保护范围。
Claims (2)
1.一种异氰酸酯改性聚丙烯酸酯无氟防水剂及其制备方法，其特征在于：其制备包括如下合成方法与步骤：
A：将摩尔比为1:1～1.1的异氰酸十八酯与丙烯酸羟乙酯加入到装有冷凝回流装置和温度计的反应容器中，开启搅拌，加入占反应物总质量0.3～0.5％的四甲基丙二胺，在80～85℃下保温反应3～4h，得到中间体Y；
B：按质量份进行配比，在装有冷凝回流装置的反应容器中加入20～30份丙烯酸十八酯、2～5份乙烯基硅油、2～5份中间体Y、0.1～2份阳离子乳化剂、0.1～2份非离子乳化剂、10～15份溶剂、0.1～1份正十二烷基硫醇和50～70份去离子水，开启搅拌，升温至40～60℃，搅拌均匀后转入高压均质机，在20-30MPa下混合均匀得到预乳液；将预乳液装入装有冷凝回流装置和温度计的反应容器中，搅拌升温至60～80℃，加入0.1～1份偶氮二异丁脒盐酸盐，在60～80℃下保温反应3～5h，得到异氰酸酯改性聚丙烯酸酯无氟防水剂。
2.根据权利要求1所述的一种异氰酸酯改性聚丙烯酸酯无氟防水剂及其制备方法，其特征在于：所述乙烯基硅油为聚合度10～15的直链型双端乙烯基聚硅氧烷，所述阳离子乳化剂为十八烷基三甲基氯化铵、十八烷基二甲基苄基氯化铵、双十八烷基二甲基氯化铵、十六烷基三甲基氯化铵、十六烷基三甲基溴化铵中的一种或几种的混合；所述非离子乳化剂为平平加O，且结构中的平均聚氧乙烯重复单元数为40～70；所述溶剂为二丙二醇、三丙二醇、二丙二醇甲醚、丙二醇、己二醇中的一种或几种的混合。
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