CN116289217A - 一种纺织品用无氟防水防油污整理剂及制备方法和应用 - Google Patents
一种纺织品用无氟防水防油污整理剂及制备方法和应用 Download PDFInfo
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Abstract
本发明涉及纺织品功能整理剂技术领域，且公开了一种纺织品用无氟防水防油污整理剂及制备方法和应用，包括质量百分比如下的组分：无氟共聚物15‑25％、表面活性剂1‑5％、酸调节剂0.1‑0.5％、有机溶剂1‑5％，其余为水。通过乳液聚合的方式实现含反应基的有机硅、封端异氰酸酯和纳米粒子之间的共聚，制备了可以赋予纺织品较好的防水防油污性能的无氟整理剂，乳液稳定性好，经焙烘后，解封的异氰酸酯基可与纺织纤维上的活性基团形成共价结合，增强耐久性。同时，本发明提供了上述整理剂的应用方法，通过纺织行业传统的浸‑轧‑烘加工方式即可赋予纺织品较好的防水和防油污效果，工艺环保、简单、高效。
Description
技术领域
本发明涉及纺织品功能整理剂技术领域，具体为一种纺织品用无氟防水防油污整理剂及制备方法和应用。
背景技术
防水防油防污是纺织品的一项重要的附加功能，由氟碳类整理剂加工得以实现，但由于PFOA/PFOS的危害性，欧美国家已明确禁止C8防水剂的使用。而继C8之后，PFAS也受到了国际社会的重视，因此，含氟类化合物的使用也逐步受到限制，更加环保、安全的无氟防水剂将成为防水整理领域的主流。
然而，由于较高的表面张力，市面上的无氟防水剂，无论是丙烯酸酯类、聚氨酯类，还是有机硅类的防水剂，都无法实现对油的防护。因此，无氟防水剂整理后的纺织品只能够进行防水以及防水性污渍，而在其它场景的应用受到限制，如对油性、酒精类等污渍的防护。
目前，已有高校开展了具有防油污性能的无氟类物质的研究，如专利CN110799596A公开了一种无氟疏油涂层，由多层聚二甲基硅氧烷树脂结合纳米粒子构造的粗糙表面制得，具有较为理想的防油效果。
遗憾的是，该方法中，疏油树脂的制备为溶剂聚合，织物预处理以及疏油整理的工艺过程复杂冗长，并不适用于目前纺织行业环保、高效、低耗的的加工模式。此外，该发明使用的无机纳米粒子，与树脂或织物之间没有牢固的键合，因此其稳定性和耐久性没有保证。
发明内容
(一)解决的技术问题
针对现有技术的不足，本发明提供了一种纺织品用无氟防水防油污整理剂及制备方法和应用。针对现有无氟防水剂无法赋予纺织品防油性、醇类等污渍防护功能的缺陷，提供了一种无氟防水防油污整理剂的制备及应用方法。通过环保的乳液聚合方式制备了防水防油污整理剂，整理剂的各组分以及整理剂与纺织纤维之间实现共价结合，稳定性和耐久性得以保证，且通过纺织行业传统的浸-轧-烘加工方式即可赋予纺织品较好的防水和防油污效果，工艺环保、简单、高效。
(二)技术方案
为实现上述目的，本发明提供如下技术方案：一种纺织品用无氟防水防油污整理剂及制备方法和应用，包括质量百分比如下的组分：无氟共聚物15-25％、表面活性剂1-5％、酸调节剂0.1-0.5％、有机溶剂1-5％，其余为水。
优选的，所述无氟共聚物由以下单体在引发剂和链转移剂的作用下聚合而得，具体包括：
含反应基的有机硅单体(a)，
含反应基的封端异氰酸酯单体(b)，
含反应基的纳米粒子(c)，
所述单体(a)为功能单体，具有以下通式：
其中，Z1为反应基，具体可以为，(甲基)丙烯酰氧基、(甲基)丙烯酰胺基和乙烯基中的一种，R1为可以含O、S、N的烃基，R2为甲基或其它烷基或苯基；
所述单体(b)由具有以下通式的化合物封端反应后获得：
Z2-R3-N＝C＝O，
其中，Z2为反应基，具体可以为，(甲基)丙烯酰氧基、(甲基)丙烯酰胺基和乙烯基中的一种，R3为以含O、S、N的烃基。
优选的，所述单体(b)所用的封端剂选自酚类、己内酰胺、乙酰丙酮、甲乙酮肟、咪唑类和吡唑类物质，优选为甲乙酮肟和吡唑类。
优选的，所述纳米粒子(c)选自含反应基的纳米二氧化硅、纳米二氧化钛和笼型聚倍半硅氧烷中的一种或多种，其反应基可以为甲基)丙烯酰氧基、(甲基)丙烯酰胺基和乙烯基中的一种。
优选的，所述无氟共聚物中各单体的质量组成比例为组分(a)75-95％，组分(b)1-10％，组分(c)5-15％。
优选的，所述表面活性剂为非离子表面活性剂或阳离子表面活性剂中的一种或几种，非离子表面活性剂包括但不限于：司盘40、司盘60、司盘80、聚氧乙烯单硬脂酸酯、脱水山梨糖醇单硬脂酸酯、脱水山梨糖醇单油酸酯、聚氧乙烯十八烷基醚等中的一种或几种；阳离子表面活性剂包括但不限于：十六烷基三甲基溴化铵、十八烷基三甲基氯化铵、二十二烷基三甲基氯化铵、烷基苄基二甲基氯化铵等中的一种或几种。
优选的，所述酸调节剂为冰醋酸，水为去离子水，有机溶剂选自甲基乙基酮、丙二醇甲醚醋酸酯、乙醇、异丙醇等。
一种纺织品用无氟防水防油污整理剂的制备方法，包括以下步骤：
S1：将上述组分按比例在60℃下化料，剪切均质，
S2：在60-80℃下以及引发剂和链转移剂的作用下反应3小时以上，得无氟防水防油污整理剂。
一种纺织品用无氟防水防油污整理剂的应用，通过将无氟防水剂加工而成的纺织品，将上述无氟防水剂用水以一定比例稀释成整理液，对纺织品进行浸-轧-烘整理，焙烘温度为130℃-180℃，优选为150℃-170℃，焙烘时间为0.5-2分钟，优选为1-1.5分钟。
(三)有益效果
与现有技术相比，本发明提供了一种纺织品用无氟防水防油污整理剂及制备方法和应用，具备以下有益效果：
该一种纺织品用无氟防水防油污整理剂及制备方法和应用，通过乳液聚合的方式实现含反应基的有机硅、封端异氰酸酯和纳米粒子之间的共聚，制备了可以赋予纺织品较好的防水防油污性能的无氟整理剂，乳液稳定性好，经焙烘后，解封的异氰酸酯基可与纺织纤维上的活性基团形成共价结合，增强耐久性。同时，本发明提供了上述整理剂的应用方法，通过纺织行业传统的浸-轧-烘加工方式即可赋予纺织品较好的防水和防油污效果，工艺环保、简单、高效。
附图说明
附图用来提供对本发明的进一步理解，并且构成说明书的一部分，与本发明的实施例一起用于解释本发明，并不构成对本发明的限制。在附图中：
图1为本发明实施例1和对比例4对酱油、20％异丙醇溶液和玉米油的防护效果图；
图2为本发明实施例与对比例的微观形貌图。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。
实施例1
将110g甲基丙烯酰氧丙基三(三甲基硅氧烷基)硅烷，5g 2-[(3,5-二甲基-1-H-吡唑基)羧氨基]乙基丙烯酸酯，11g丙烯酰氧丙基笼型聚倍半硅氧烷，6g司盘80，3.5g十八烷基三甲基氯化铵，1g冰醋酸，33g异丙醇，420g去离子水，在60℃恒温水浴中化料40分钟，高速剪切、均质，得预乳液。将预乳液加入到1L的反应釜中，加入正十二烷硫醇和引发剂V50，在持续搅拌和氮气保护下，60℃保温反应3小时以上，得无氟防水防油污整理剂。将上述的整理剂用水稀释至100g/L，对涤棉65/35织物进行浸-轧-烘处理，烘干条件为温度170℃，时间90s。
对比例1
将126g甲基丙烯酰氧丙基三(三甲基硅氧烷基)硅烷，6g司盘80，3.5g十八烷基三甲基氯化铵，1g冰醋酸，33g异丙醇，420g去离子水，在60℃恒温水浴中化料40分钟，高速剪切、均质，得预乳液。将预乳液加入到1L的反应釜中，加入正十二烷硫醇和引发剂V50，在持续搅拌和氮气保护下，60℃保温反应3小时以上，得无氟防水防油污整理剂。将上述的整理剂用水稀释至100g/L，对涤棉65/35织物进行浸-轧-烘处理，烘干条件为温度170℃，时间90s。
对比例2
将121g甲基丙烯酰氧丙基三(三甲基硅氧烷基)硅烷，5g 2-[(3,5-二甲基-1-H-吡唑基)羧氨基]乙基丙烯酸酯，6g司盘80，3.5g十八烷基三甲基氯化铵，1g冰醋酸，33g异丙醇，420g去离子水，在60℃恒温水浴中化料40分钟，高速剪切、均质，得预乳液。将预乳液加入到1L的反应釜中，加入正十二烷硫醇和引发剂V50，在持续搅拌和氮气保护下，60℃保温反应3小时以上，得无氟防水防油污整理剂。将上述的整理剂用水稀释至100g/L，对涤棉65/35织物进行浸-轧-烘处理，烘干条件为温度170℃，时间90s。
对比例3
将市售无氟防水剂RUCO-DRY ECO PLUS用水稀释至100g/L，对涤棉65/35织物进行浸-轧-烘处理，烘干条件为温度170℃，时间90s。
将上述实施例及对比例处理后的织物按以下测试标准进行性能评价，结果如表1所示。此外，对实施例1和对比例4对不同污渍的防护效果进行了实物拍摄，如图1所示。
防水性能测试，按照AATCC-22喷淋实验进行；
防污性能测试，将约0.05mL的污渍从距离布面约0.6cm处滴落，从45°角方向观察污渍的润湿和芯吸现象，记录污渍从滴落布面到刚开始润湿或芯吸的时间。
表1防水性和防污性评价
| 实施例1 | 对比例1 | 对比例2 | 对比例3 | |
| 防水性/分 | 85 | 85 | 80 | 90 |
| 防酱油性/s | >1800s | >1800s | >1800s | >1800s |
| 防20％异丙醇溶液/s | >1800s | 600s | >1800s | 0s |
| 防玉米油 | >1800s | 30s | 1200s | 0s |
由表1的测试结果结合图2的微观形貌图可知，相比于对比例1，实施例1和对比例2由于封端异氰酸酯单体的作用，增强了与纤维的交联成膜，从而防水性和防污性能更佳；而实施例1相比于对比例1，由于纳米粒子构造的表面粗糙度，其对于油性和醇类污渍的防护作用进一步得到提升。此外，对比例3虽然具有较好的防水性和防水性污渍的性能，但对于醇类和油性污渍无任何防护作用。
Claims (9)
1.一种纺织品用无氟防水防油污整理剂及制备方法和应用，其特征在于：包括质量百分比如下的组分：无氟共聚物15-25％、表面活性剂1-5％、酸调节剂0.1-0.5％、有机溶剂1-5％，其余为水。
2.根据权利要求1所述的一种纺织品用无氟防水防油污整理剂，其特征在于：所述无氟共聚物由以下单体在引发剂和链转移剂的作用下聚合而得，具体包括：
含反应基的有机硅单体(a)，
含反应基的封端异氰酸酯单体(b)，
含反应基的纳米粒子(c)，
所述单体(a)为功能单体，具有以下通式：
其中，Z1为反应基，具体可以为，(甲基)丙烯酰氧基、(甲基)丙烯酰胺基和乙烯基中的一种，R1为可以含O、S、N的烃基，R2为甲基或其它烷基或苯基；
所述单体(b)由具有以下通式的化合物封端反应后获得：
Z2-R3-N＝C＝O，
其中，Z2为反应基，具体可以为，(甲基)丙烯酰氧基、(甲基)丙烯酰胺基和乙烯基中的一种，R3为以含O、S、N的烃基。
3.根据权利要求1所述的一种纺织品用无氟防水防油污整理剂及制备方法和应用，其特征在于：所述单体(b)所用的封端剂选自酚类、己内酰胺、乙酰丙酮、甲乙酮肟、咪唑类和吡唑类物质，优选为甲乙酮肟和吡唑类。
4.根据权利要求1所述的一种纺织品用无氟防水防油污整理剂，其特征在于：所述纳米粒子(c)选自含反应基的纳米二氧化硅、纳米二氧化钛和笼型聚倍半硅氧烷中的一种或多种，其反应基可以为甲基)丙烯酰氧基、(甲基)丙烯酰胺基和乙烯基中的一种。
5.根据权利要求1所述的一种纺织品用无氟防水防油污整理剂，其特征在于：所述无氟共聚物中各单体的质量组成比例为组分(a)75-95％，组分(b)1-10％，组分(c)5-15％。
6.根据权利要求1所述的一种纺织品用无氟防水防油污整理剂，其特征在于：所述表面活性剂为非离子表面活性剂或阳离子表面活性剂中的一种或几种，非离子表面活性剂包括但不限于：司盘40、司盘60、司盘80、聚氧乙烯单硬脂酸酯、脱水山梨糖醇单硬脂酸酯、脱水山梨糖醇单油酸酯、聚氧乙烯十八烷基醚等中的一种或几种；阳离子表面活性剂包括但不限于：十六烷基三甲基溴化铵、十八烷基三甲基氯化铵、二十二烷基三甲基氯化铵、烷基苄基二甲基氯化铵等中的一种或几种。
7.根据权利要求1所述的一种纺织品用无氟防水防油污整理剂，其特征在于：所述酸调节剂为冰醋酸，水为去离子水，有机溶剂选自甲基乙基酮、丙二醇甲醚醋酸酯、乙醇、异丙醇等。
8.一种纺织品用无氟防水防油污整理剂的制备方法，其特征在于，包括以下步骤：
S1：将上述组分按比例在60℃下化料，剪切均质，
S2：在60-80℃下以及引发剂和链转移剂的作用下反应3小时以上，得无氟防水防油污整理剂。
9.一种纺织品用无氟防水防油污整理剂的应用，其特征在于：通过将无氟防水剂加工而成的纺织品，将上述无氟防水剂用水以一定比例稀释成整理液，对纺织品进行浸-轧-烘整理，焙烘温度为130℃-180℃，优选为150℃-170℃，焙烘时间为0.5-2分钟，优选为1-1.5分钟。
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