CN114232347B - 一种氨基改性有机硅整理剂及其制备方法 - Google Patents

一种氨基改性有机硅整理剂及其制备方法 Download PDF

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CN114232347B
CN114232347B CN202111555483.8A CN202111555483A CN114232347B CN 114232347 B CN114232347 B CN 114232347B CN 202111555483 A CN202111555483 A CN 202111555483A CN 114232347 B CN114232347 B CN 114232347B
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施长年
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Abstract

本案涉及一种氨基改性有机硅整理剂及其制备方法，所述氨基改性有机硅整理剂包括组分A、组分B和乳化剂；其中组分A是采用含丰富的聚醚和氨基活性官能团的聚氨酯与有机硅通过化学接枝反应制得；组分B首先采用D4和3‑氨丙基甲基二甲氧基硅烷合成得到侧链含氨基的有机硅，然后利用氨基与氯化苄的取代反应引入苯环结构，之后通过与γ‑氯丙基甲基二甲氧基硅烷季铵化反应获得有机硅季铵盐。本发明的有机硅整理剂用于纺织物时能有效提高柔软性，减少织物间的摩擦系数，提高抗起毛球性，手感较好；该有机硅整理剂与常用阴、非离子表面活性剂均具有较好的相容性，与其它功能助剂配合使用可提高织物的多功能性。

Description

一种氨基改性有机硅整理剂及其制备方法
技术领域
本发明涉及纺织品助剂领域，具体为一种氨基改性有机硅整理剂及其制备方法。
背景技术
纺织助剂作为纺织品生产加工过程中一种必须的化学品，对于赋予纺织品柔软、防皱、抗静电、抗菌、阻燃等性能，提高纺织工业的整体水平起着至关重要的作用。其中，有机硅整理剂因其可以显著改善织物的手感，应用最为广泛。用于纺织品整理的有机硅通常是指室温下为液态的线型聚硅氧烷，分子主链为重复的Si-O链节，有机基团直接与硅原子相连的一类高分子材料。
虽然有机硅整理剂用于纺织物中时能够赋予纺织物一定的滑爽性、柔软性和蓬松性等，但在防水性上还存在着不足；与防水剂配合使用时，相容性差，易分层，连续生产易产生白斑。
发明内容
针对现有技术中的不足之处，本发明提出了一种由组分A和组分B混合而成的有机硅整理剂，具有优异的柔软性和防水性，易可与其它功能助剂混用，相容性好，稳定性高，可丰富整理后的织物的多功能性。
为实现上述目的，本发明提供如下技术方案：
一种氨基改性有机硅整理剂的制备方法，包括如下步骤：
一、制备组分A
1)在搅拌釜中加入一定量的三官能聚丙二元醇，升温至100℃并持续抽真空60min，降温至50℃，加入异佛尔酮异氰酸酯和催化剂，通入氮气保护，升温至80℃，搅拌反应3h；冷却至50℃以下，加入丙烯酸羟乙酯和丙酮，升温至80℃，反应2h，得到末端双键的三臂聚氨酯预聚物；
2)采用四甲基二氢基二硅氧烷(HMM)和八甲基环四硅氧烷(D4)为原料制得双端氢硅氧烷；
3)在反应釜中加入末端双键的三臂聚氨酯预聚物和双端氢硅氧烷，搅拌均匀后升温至80℃，加入催化量的氯铂酸，继续升温到100℃，搅拌反应5-6h；得组分A；
二、制备组分B
1)将一定量的八甲基环四硅氧烷(D4)和3-氨丙基甲基二甲氧基硅烷加入到反应釜中，加入氢氧化钾水溶液，升温至120～130℃，保温反应3～4h，反应完成后加入适量六甲基二硅氧烷进行封端反应1～2h，得到侧链氨基改性有机硅；
2)将侧链氨基改性有机硅加入到反应瓶中，加入无水乙腈加热回流，滴加氯化苄，回流反应20h，旋蒸除去溶剂；之后向其中加入乙二醇搅拌使其溶解，转移至反应瓶中升温至110℃，滴加γ-氯丙基甲基二甲氧基硅烷，密闭反应40h，冷却至室温后旋蒸除去有机溶剂，得到组分B；
三、制备氨基改性有机硅整理剂
将组分A和组分B按照55～70:30～45的质量比投入到搅拌釜中，然后加入该混合物质量5％～15％的乳化剂，加热至60℃，搅拌状态下逐步加水使固含量在30～35％之间，继续搅拌30min即得。
优选地，所述三官能聚丙二元醇的分子量为3000g/mol，所述催化剂为二月桂酸酯二丁基锡。
优选地，所述三官能聚丙二元醇、异佛尔酮异氰酸酯和丙烯酸羟乙酯的摩尔比为2:6-7:1。
优选地，所述末端双键的三臂聚氨酯预聚物和双端氢硅氧烷的摩尔比为1:2～2.5。
优选地，所述八甲基环四硅氧烷和3-氨丙基甲基二甲氧基硅烷的质量比为15～25:1，氢氧化钾的质量为八甲基环四硅氧烷质量的0.2％～0.4％。
优选地，所述侧链氨基改性有机硅与氯化苄、γ-氯丙基甲基二甲氧基硅烷的摩尔比为1:1.2～1.5:3。
优选地，所述乳化剂选自AEO-9、AEO-4、AEO-7、TO-3和TO-5中的一种。
本发明进一步提供一种如上所述的制备方法制得的氨基改性有机硅整理剂。
本案中有机硅整理剂由聚醚和聚氨酯改性的有机硅组分A和新型的阳离子型有机硅整理剂组分B乳化而成，含氨基和聚醚改性的有机硅与含苯环和季铵盐改性的有机硅之间形成协同作用，形成的有机硅整理剂具有优秀的防水性和柔软性。
具体而言，组分A是采用含丰富的聚醚和氨基活性官能团的聚氨酯与有机硅通过化学接枝反应制得，有效提高产物的韧性和滑爽性；丰富的活性官能团与纤维之间易形成牢固的共价键和氢键等作用力，因而可以有效提升整理后织物的柔软性和整理效果的耐久性；且本案以三官能度的PPG作为起始原料改性有机硅获得三臂的聚合物链，相较于线性有机硅，提供更丰富的活性官能团，锚固效应高，也易形成交联网状结构；虽然超支化结构的聚合物链可以形成更丰富的活性官能团，但其分子量较高，粘度较大，易导致成膜效果不理想。
阳离子型有机硅整理剂具有低温韧性、耐水性和抗静电性等，本案的组分B首先采用D4和3-氨丙基甲基二甲氧基硅烷合成得到侧链含氨基的有机硅，然后利用氨基与氯化苄的取代反应引入苯环结构，之后通过与γ-氯丙基甲基二甲氧基硅烷季铵化反应获得有机硅季铵盐。其中季铵盐基团的存在使其还具有优良的抗菌活性和表面活性；苯环结构引入到有机硅的侧链中，增加光泽度，同时提高耐水性。结构中的甲氧基硅烷与组分A中有机硅之间产生相互作用，从而对组分A进行协同补强；进而在保持优异的柔软性的同时还具有耐水性。
与现有技术相比，本发明的有益效果是：本发明的有机硅整理剂用于棉、麻、绒等纺织物时能有效提高柔软性，减少织物间的摩擦系数，提高抗起毛球性，手感较好；同时用于人造纤维时也能产生很好的柔软和蓬松效果；该有机硅整理剂与常用阴、非离子表面活性剂均具有较好的相容性，与其它功能助剂配合使用可提高织物的多功能性，尤其在与有机氟防水剂的复配使用可进一步提高织物的防水性。
具体实施方式
下面将结合实施例对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
此外，下面所描述的本发明不同实施方式中所涉及的技术特征只要彼此之间未构成冲突就可以相互结合。
实施例1：
一、制备组分A
1)在搅拌釜中加入10mmol三官能PPG-3000，升温至100℃并持续抽真空60min，降温至50℃，加入30mmol异佛尔酮异氰酸酯和50ppm二月桂酸酯二丁基锡，通入氮气保护，升温至80℃，搅拌反应3h；冷却至50℃以下，加入50mmol丙烯酸羟乙酯和适量丙酮，升温至80℃，反应2h，得到末端双键的三臂聚氨酯预聚物(Mn＝9100g/mol)；
Figure BDA0003418491920000051
2)采用四甲基二氢基二硅氧烷和八甲基环四硅氧烷为原料制得双端氢硅氧烷(Mn＝4300g/mol)；
3)在反应釜中加入1mmol末端双键的三臂聚氨酯预聚物和2.2mmol双端氢硅氧烷，搅拌均匀后升温至80℃，加入催化量的氯铂酸，继续升温到100℃，搅拌反应5-6h；得组分A；
二、制备组分B
1)将15g八甲基环四硅氧烷和1g 3-氨丙基甲基二甲氧基硅烷加入到反应釜中，将0.03g氢氧化钾加适量水溶解后加入到反应釜中，升温至120～130℃，保温反应3～4h，反应完成后加入适量六甲基二硅氧烷进行封端反应1～2h，得到侧链氨基改性有机硅；
Figure BDA0003418491920000052
2)将侧链氨基改性有机硅加入到反应瓶中，加入无水乙腈加热回流，滴加氯化苄，回流反应20h，旋蒸除去溶剂；之后向其中加入乙二醇搅拌使其溶解，转移至反应瓶中升温至110℃，滴加γ-氯丙基甲基二甲氧基硅烷，密闭反应40h，冷却至室温后旋蒸除去有机溶剂，得到组分B；
Figure BDA0003418491920000053
三、制备氨基改性有机硅整理剂
将组分A和组分B按照55:45的质量比投入到搅拌釜中，然后加入该混合物质量5％的AEO-9乳化剂，加热至60℃，搅拌状态下逐步加水使固含量在30～35％之间，继续搅拌30min即得。
实施例2：
将组分A和组分B按照60:40的质量比投入到搅拌釜中，然后加入该混合物质量6％的AEO-7乳化剂，加热至60℃，搅拌状态下逐步加水使固含量在30～35％之间，继续搅拌30min即得。
实施例3：
将组分A和组分B按照70:30的质量比投入到搅拌釜中，然后加入该混合物质量6％的TO-5乳化剂，加热至60℃，搅拌状态下逐步加水使固含量在30～35％之间，继续搅拌30min即得。
对比例1：
将组分A和占组分A质量6％的TO-5乳化剂，加热至60℃，搅拌状态下逐步加水使固含量在30～35％之间，继续搅拌30min即得。
对比例2：
同实施例1，区别在于组分A采用二官能PPG代替三官能PPG。
对比例3：
同实施例1，区别在于组分B中未使用氯化苄进行氯取代，而是采用碘甲烷直接与侧链氨基改性有机硅进行季铵化反应。
整理工艺：
织物→浸轧(二浸二轧，轧余率80％)→预烘(90℃，60s)→焙烘(140～170℃，60～180s)
氨基改性有机硅整理剂的化学特性和表征：
1、固含量，采用失重法计算
2、稳定性，通过置于高速离心机中，以2000r/min的转速离心20min，观察乳液是否出现分层等异常现象。
3、织物手感，原布手感定为1级，手感评定最高分为5级，最低分为1级，五人一组取其平均值。
4、白度，参照GB/T 8424.2-2001标准测定
5、防水性，喷淋法进行评定防水等级
上述表征数据记录在如下表1中。
表1
实施例1 实施例2 实施例3 对比例1 对比例2 对比例3
固含量％ 32.5 33.1 32.6 33.0 33.3 32.4
离心稳定性 稳定 稳定 稳定 较稳定 分层 较稳定
静置稳定性 稳定 稳定 稳定 稳定 稳定 稳定
织物手感 5级 4级 5级 3级 2级 4级
白度％ 84.5 82.1 81.3 74.5 79.3 74.8
防水效果 90 90 90 50- 70+ 60-
从表1中数据可知本案实施例1-3的各项性能优异，组分A和组分B的配合使用使整理后的织物在手感、外观以及防水效果上均具有不错的提升。
尽管本发明的实施方案已公开如上，但其并不仅仅限于说明书和实施方式中所列运用，它完全可以被适用于各种适合本发明的领域，对于熟悉本领域的人员而言，可容易地实现另外的修改，因此在不背离权利要求及等同范围所限定的一般概念下，本发明并不限于特定的细节。

Claims (8)

1.一种氨基改性有机硅整理剂的制备方法，其特征在于，包括如下步骤：
一、制备组分A
1)在搅拌釜中加入一定量的三官能聚丙二元醇，升温至100℃并持续抽真空60min，降温至50℃，加入异佛尔酮异氰酸酯和催化剂，通入氮气保护，升温至80℃，搅拌反应3h；冷却至50℃以下，加入丙烯酸羟乙酯和丙酮，升温至80℃，反应2h，得到末端双键的三臂聚氨酯预聚物；
2)采用四甲基二氢基二硅氧烷和八甲基环四硅氧烷为原料制得双端氢硅氧烷；
3)在反应釜中加入末端双键的三臂聚氨酯预聚物和双端氢硅氧烷，搅拌均匀后升温至80℃，加入催化量的氯铂酸，继续升温到100℃，搅拌反应5-6h；得组分A；
二、制备组分B
1)将一定量的八甲基环四硅氧烷和3-氨丙基甲基二甲氧基硅烷加入到反应釜中，加入氢氧化钾水溶液，升温至120～130℃，保温反应3～4h，反应完成后加入适量六甲基二硅氧烷进行封端反应1～2h，得到侧链氨基改性有机硅；
2)将侧链氨基改性有机硅加入到反应瓶中，加入无水乙腈加热回流，滴加氯化苄，回流反应20h，旋蒸除去溶剂；之后向其中加入乙二醇搅拌使其溶解，转移至反应瓶中升温至110℃，滴加γ-氯丙基甲基二甲氧基硅烷，密闭反应40h，冷却至室温后旋蒸除去有机溶剂，得到组分B；
三、制备氨基改性有机硅整理剂
将组分A和组分B按照55～70:30～45的质量比投入到搅拌釜中，然后加入该混合物质量5％～15％的乳化剂，加热至60℃，搅拌状态下逐步加水使固含量在30～35％之间，继续搅拌30min即得。
2.如权利要求1所述的氨基改性有机硅整理剂的制备方法，其特征在于，所述三官能聚丙二元醇的分子量为3000g/mol，所述催化剂为二月桂酸酯二丁基锡。
3.如权利要求1所述的氨基改性有机硅整理剂的制备方法，其特征在于，所述三官能聚丙二元醇、异佛尔酮异氰酸酯和丙烯酸羟乙酯的摩尔比为2:6-7:1。
4.如权利要求1所述的氨基改性有机硅整理剂的制备方法，其特征在于，所述末端双键的三臂聚氨酯预聚物和双端氢硅氧烷的摩尔比为1:2～2.5。
5.如权利要求1所述的氨基改性有机硅整理剂的制备方法，其特征在于，所述八甲基环四硅氧烷和3-氨丙基甲基二甲氧基硅烷的质量比为15～25:1，氢氧化钾的质量为八甲基环四硅氧烷质量的0.2％～0.4％。
6.如权利要求1所述的氨基改性有机硅整理剂的制备方法，其特征在于，所述侧链氨基改性有机硅与氯化苄、γ-氯丙基甲基二甲氧基硅烷的摩尔比为1:1.2～1.5:3。
7.如权利要求1所述的氨基改性有机硅整理剂的制备方法，其特征在于，所述乳化剂选自AEO-9、AEO-4、AEO-7、TO-3和TO-5中的一种。
8.一种如权利要求1-7中任一项所述的制备方法制得的氨基改性有机硅整理剂。
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