CN105482074B - 一种阴离子型聚氨酯改性有机硅乳液及其制备方法 - Google Patents
一种阴离子型聚氨酯改性有机硅乳液及其制备方法 Download PDFInfo
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Abstract
本发明涉及纺织助剂领域，尤其涉及一种阴离子型聚氨酯改性有机硅乳液及其制备方法。本发明采用十二烷基苯磺酸为阴离子乳化剂和催化剂，脂肪醇聚氧乙烯醚为非离子乳化剂，将含氨烃基偶联剂与有机硅单体进行乳液共聚，再加入聚氨酯预聚体进行改性，得到阴离子型聚氨酯改性有机硅乳液。本发明制得的阴离子有机硅乳液中不仅含有聚氨酯和有机硅链段，使整理后织物具有高弹、滑爽、防水等优异性能；而且可与其它阴离子型乳液复配，进一步增加功能。
Description
技术领域
本发明涉及一种纺织助剂领域，尤其是涉及一种阴离子型聚氨酯改性有机硅乳液及其制备方法。
背景技术
阴离子有机硅乳液作为织物整理剂，可以改善纺织品的手感，赋予织物柔软、滑爽等性能。由于其离子型与大多数纺织助剂相同，所以能较好的与阴离子型助剂同浴使用。通过与不同硅烷偶联剂的共聚反应，能够获得各种官能团改性的有机硅乳液，以满足不同风格的整理要求。随着人们生活水平的提高，单一偶联剂改性已经不能满足要求，且耐久性不佳，多种偶联剂改性的产品耐久性好，风格多样化，但产品工艺控制要求较高，产品性能不稳定。
水性聚氨酯由于其特殊结构，使其具有良好的弹性和特殊的手感风格，应用领域涵盖皮革、造纸、纺织以及涂料等。国外已有研究者将水性聚氨酯乳液与羟基硅油乳液进行共混，并发现这种共混体系具有良好的耐冻融和耐热稳定性。国内研究者在此基础上将这种共混乳液应用于纺织品整理中，使整理后的织物不仅柔软、滑爽、弹性好，而且具有一定的抗静电、抗起毛起球效果。不过这种共混乳液只是简单的物理混合，很难起到耐久的作用。
发明内容
本发明目的是客服现有技术的不足，提供一种高弹、滑爽、防水且耐久性好的阴离子聚氨酯改性有机硅整理剂，使整理后的织物既有有机硅整理剂的手感风格，又具有聚氨酯的特殊手感。
为了实现上述目的，本发明采用以下技术方案：
一种阴离子型聚氨酯改性有机硅乳液及其制备方法，按如下步骤进行：
(1)、将聚丙二醇、2,2-二羟甲基丙酸投入至反应容器中，开启搅拌，加热至105～110℃，在-0.05～-0.09MPa下抽真空除水1～2h，降温至80～85℃，滴加二异氰酸酯，滴加完后在80～85℃下保温3～4h；降温至50℃以下加入三乙胺中和0.5～1h，得到聚氨酯预聚体A，其结构通式如下；
其中，(2)、将去离子水、十二烷基苯磺酸、脂肪醇聚氧乙烯醚投入至反应容器中，启动搅拌，升温至50～55℃，保温1～1.5h后开始滴加氨烃基偶联剂与八甲基环四硅氧烷，滴加时间为1～2h，然后缓慢升温至70～80℃，保温4～6h后，降温至30～40℃，中和pH至6.0～7.0，加入步骤(1)得到的聚氨酯预聚体A，继续反应0.5～1h后过滤出料，得到阴离子型聚氨酯改性有机硅，其结构通式如下；
其中，
其中，步骤(1)中所用的原料及其质量百分含量为：聚丙二醇65％～68％，2,2-二羟甲基丙酸4％～6％，二异氰酸酯25％～27％，三乙胺3％～5％；
步骤(2)中所用的原料及其质量百分含量为：八甲基环四硅氧烷11％～13％，含氨烃基偶联剂0.3％～0.6％，十二烷基苯磺酸4％～6％，脂肪醇聚氧乙烯醚2％～3％，预聚体A 0.8％～1.0％，其余为去离子水。
作为优选，所述的聚丙二醇为聚丙二醇600、1000、1500中的一种；
所述的二异氰酸酯为异佛尔酮二异氰酸酯、甲苯二异氰酸酯、六亚甲基二异氰酸酯中的一种；
所述的氨烃基偶联剂为γ-氨丙基三乙氧基硅烷、N-氨乙基-3-氨丙基甲基二甲氧基硅烷中的一种；
所述的脂肪醇聚氧乙烯醚为AEO-3、AEO-7、AEO-9中的一种。
作为优选，所得氨酯改性有机硅乳液外观为带蓝光半透明状，固含量为18～20％，pH值为6.0～7.0。
由于上述技术方案的运用，本发明同现有技术相比，具有如下优点：
1、采用水性聚氨酯预聚体对阴离子有机硅乳液进行改性，预聚体中剩余的异氰酸基团能与有机硅链上的氨基发生反应，形成三维互穿的网状结构，提高乳液在纤维上的成膜性和膜的耐久性，使整理后的织物既有有机硅整理剂的手感风格，又具有聚氨酯的特殊手感。
2、由于聚氨酯与聚硅氧烷溶解度相差较大，在高温焙烘的过程中，聚氨酯与有机硅易发生微相分离，可有效增加整理后织物的弹性。同时，由于成膜性的改善，也使得整理后织物的滑爽性和防水性进一步得到提高。
附图说明
图1为实施例1的红外图谱，其中曲线1为聚氨酯预聚体A，曲线2为聚氨酯改性有机硅；
图2为实施例2的红外图谱，其中曲线1为聚氨酯预聚体A，曲线2为聚氨酯改性有机硅；
图3为实施例3的红外图谱，其中曲线1为聚氨酯预聚体A，曲线2为聚氨酯改性有机硅。
具体实施方式
下面通过具体实施方式，结构附图，对本发明做进一步的描述。
实施例1：一种阴离子型聚氨酯改性有机硅乳液及其制备方法，按如下步骤进行：
(1)、将75.0g聚丙二醇1500、6.0g 2,2-二羟甲基丙酸投入反应容器中，开启搅拌，加热至110℃，在-0.08MPa下抽真空除水1h，降温至85℃，滴加29.5g异佛尔酮二异氰酸酯，滴加完后在85℃下保温3h；降温至50℃以下加入4.5g三乙胺中和0.5h，得到聚氨酯预聚体A；
(2)、将865.0g去离子水、50.0g十二烷基苯磺酸、30.0g AEO-3投入反应容器中，启动搅拌，升温至50℃，保温1.5h后开始滴加5.0gγ-氨丙基三乙氧基硅烷与120.0g八甲基环四硅氧烷，滴加时间为2h，然后缓慢升温至75℃，保温4h，降温至30℃，中和pH至6.5，加入10.0g预聚体A，继续反应1h后过滤出料，得到阴离子型聚氨酯改性有机硅乳液。
参见附图1，它是本实施例中聚氨酯改性有机硅乳液的红外图谱，曲线1为聚氨酯预聚体A的红外图谱，曲线2为聚氨酯改性有机硅的红外图谱。3321.2cm-1处的特征峰为氨基甲酸酯键中N-H的吸收峰，2260.9cm-1处为-NCO基团的特征吸收峰，1716.9cm-1和1520.5cm-1两处为-NH-COO-的特征吸收峰；与有机硅上的氨基反应之后，2260.9cm-1处的异氰酸酯基特征峰消失，在1260.2cm-1、960.8cm-1和800.6cm-1处出现三个新的吸收峰，为有机硅链段中Si-CH3、Si-OCH2CH3的特征吸收峰，1000cm-1～1130cm-1处为Si-O-Si的吸收峰，以上分析均表明预聚体A与有机硅反应较完全，目标产物成功获得。
实施例2：一种阴离子型聚氨酯改性有机硅乳液及其制备方法，按如下步骤进行：
(1)、将100.5g聚丙二醇1000、6.0g 2,2-二羟甲基丙酸投入反应容器中，开启搅拌，加热至105℃，在-0.09MPa下抽真空除水1h，降温至80℃，滴加异佛尔酮二异氰酸酯，滴加完后在80℃下保温3h；降温至50℃以下加入4.5g三乙胺中和0.5h，得到聚氨酯预聚体A；
(2)、将777.0g去离子水、40.0g十二烷基苯磺酸、25.0g AEO-7投入反应容器中，启动搅拌，升温至55℃，保温1h后开始滴加4.0gγ-氨丙基三乙氧基硅烷与110.0g八甲基环四硅氧烷，滴加时间为2h，然后缓慢升温至80℃，保温4h，降温至30℃，中和pH至6.6，加入9.0g预聚体A，继续反应1h后过滤出料，得到阴离子型聚氨酯改性有机硅乳液。
参见附图2，它是本实施例中聚氨酯改性有机硅乳液的红外图谱，曲线1为聚氨酯预聚体A的红外图谱，曲线2为聚氨酯改性有机硅的红外图谱。3334.2cm-1处的特征峰为氨基甲酸酯键中N-H的吸收峰，2258.8cm-1处为-NCO基团的特征吸收峰，1708.5cm-1和1513.2cm-1两处为-NH-COO-的特征吸收峰；与有机硅上的氨基反应之后，2258.8cm-1处的异氰酸酯基特征峰消失，在1259.1cm-1、952.2cm-1和799.1cm-1处出现三个新的吸收峰，为有机硅链段中Si-CH3、Si-OCH2CH3的特征吸收峰，1000cm-1～1130cm-1处为Si-O-Si的吸收峰，以上分析均表明预聚体A与有机硅反应较完全，目标产物成功获得。
实施例3：一种阴离子型聚氨酯改性有机硅乳液及其制备方法，按如下步骤进行：
(1)、将75.0g聚丙二醇1500、5.0g 2,2-二羟甲基丙酸投入反应容器中，开启搅拌，加热至105～110℃，在-0.085MPa下抽真空除水1h，降温至85℃，滴加异佛尔酮二异氰酸酯，滴加完后在85℃下保温3.5h；降温至50℃以下加入3.8g三乙胺中和0.5h，得到聚氨酯预聚体A；
(2)、将820.0g去离子水、50.0g十二烷基苯磺酸、25.0g AEO-9投入反应容器中，启动搅拌，升温至55℃，保温1h后开始滴加5.0gγ-氨丙基三乙氧基硅烷与115.0g八甲基环四硅氧烷，滴加时间为2h，然后缓慢升温至75℃，保温5h，降温至30℃，中和pH至6.8，加入10.0g预聚体A，继续反应1h后过滤出料，得到阴离子型聚氨酯改性有机硅乳液。
参见附图3，它是本实施例中聚氨酯改性有机硅乳液的红外图谱，曲线1为聚氨酯预聚体A的红外图谱，曲线2为聚氨酯改性有机硅的红外图谱。3330.5cm-1处的特征峰为氨基甲酸酯键中N-H的吸收峰，2263.0cm-1处为-NCO基团的特征吸收峰，1708.5cm-1和1517.4cm-1两处为-NH-COO-的特征吸收峰；与有机硅上的氨基反应之后，2263.0cm-1处的异氰酸酯基特征峰消失，在1259.2cm-1、948.8cm-1和805.4cm-1处出现三个新的吸收峰，为有机硅链段中Si-CH3、Si-OCH2CH3的特征吸收峰，1000cm-1～1130cm-1处为Si-O-Si的吸收峰，以上分析均表明预聚体A与有机硅反应较完全，目标产物成功获得。
将上述实施例所得到的产品对纺织品进行整理，主要测试整理后纺织品的弹性、滑爽性及防水性。
1、整理工艺：
所用织物：涤棉梭织布。
整理工艺流程：浸轧工作液(聚氨酯改性有机硅乳液50g/L，轧余率60％)→焙烘(190℃×40s)→回潮24h→测试
2.应用性能测试：
弹性用KESFB-AUTO-A织物风格仪测试整理后织物的压缩回弹性，数值越大，表明弹性越好。
滑爽性参考纺织标准FZ/T 01054-2012《织物表面摩擦性能的试验方法》进行测试，数值越小，表明滑爽性越好。
防水性参考GB/T 4745-1997《织物表面抗湿性测试：沾水试验》进行测试。
本发明的阴离子型聚氨酯改性有机硅乳液应用性能测试结果如表1所示：
表1阴离子型聚氨酯改性有机硅乳液应用性能测试结果
Claims (3)
1.一种阴离子型聚氨酯改性有机硅乳液的制备方法，其特征在于按如下步骤进行：
(1)、将聚丙二醇、2,2-二羟甲基丙酸投入至反应容器中，开启搅拌，加热至105～110℃，在-0.05～-0.09MPa下抽真空除水1～2h，降温至80～85℃，滴加二异氰酸酯，滴加完后在80～85℃下保温3～4h；降温至50℃以下加入三乙胺中和0.5～1h，得到聚氨酯预聚体A，其结构通式如下；
其中，
(2)、将去离子水、十二烷基苯磺酸、脂肪醇聚氧乙烯醚投入至反应容器中，启动搅拌，升温至50～55℃，保温1～1.5h后开始滴加氨烃基偶联剂与八甲基环四硅氧烷，滴加时间为1～2h，然后缓慢升温至70～80℃，保温4～6h后，降温至30～40℃，中和pH至6.0～7.0，加入步骤(1)得到的聚氨酯预聚体A，继续反应0.5～1h后过滤出料，得到阴离子型聚氨酯改性有机硅，其结构通式如下；
其中，
其中，步骤(1)中所用的原料及其质量百分含量为：聚丙二醇65％～68％，2,2-二羟甲基丙酸4％～6％，二异氰酸酯25％～27％，三乙胺3％～5％；
步骤(2)中所用的原料及其质量百分含量为：八甲基环四硅氧烷11％～13％，含氨烃基偶联剂0.3％～0.6％，十二烷基苯磺酸4％～6％，脂肪醇聚氧乙烯醚2％～3％，预聚体A0.8％～1.0％，其余为去离子水。
2.根据权利要求1所述的一种阴离子型聚氨酯改性有机硅乳液的制备方法，其特征在于：
所述的聚丙二醇为聚丙二醇600、1000、1500中的一种；
所述的二异氰酸酯为异佛尔酮二异氰酸酯、甲苯二异氰酸酯、六亚甲基二异氰酸酯中的一种；
所述的氨烃基偶联剂为γ-氨丙基三乙氧基硅烷、N-氨乙基-3-氨丙基甲基二甲氧基硅烷中的一种；
所述的脂肪醇聚氧乙烯醚为AEO-3、AEO-7、AEO-9中的一种。
3.根据权利要求1所述的一种阴离子型聚氨酯改性有机硅乳液的制备方法，其特征在于：所得氨酯改性有机硅乳液外观为带蓝光半透明状，固含量为18～20％，pH值为6.0～7.0。
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