CN110540629A - 一种有机硅改性阳离子水性聚氨酯防水剂的制备方法 - Google Patents
一种有机硅改性阳离子水性聚氨酯防水剂的制备方法 Download PDFInfo
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Abstract
本发明公开了一种有机硅改性阳离子水性聚氨酯防水剂的制备方法,先称取如下原料:多元醇,羟基硅油,多异氰酸酯,阳离子扩链剂,封端剂,水;再将上述多元醇和羟基硅油进行混合搅拌均匀,得到羟基硅油的醇类混合物;在其中添加上述多异氰酸酯并在水浴中搅拌均匀后,得到含有端异氰酸酯基团的预聚体;再将上述阳离子扩链剂添加到含有端异氰酸酯基团的预聚体中搅拌均匀后,得到扩链混合物料;在其中添加上述封端剂并在水浴中搅拌均匀后,得到封端混合物料;再将封端混合物料添加到水中,在水浴中搅拌均匀后,得到有机硅改性阳离子水性聚氨酯。本发明有机硅改性阳离子水性聚氨酯防水剂的制备方法具有工艺简单,制备的防水剂薄膜耐水性好的特点。
Description
技术领域
本发明涉及防水剂技术领域,具体涉及一种有机硅改性阳离子水性聚氨酯防水剂的制备方法。
背景技术
水性聚氨酯是以水代替有机溶剂作为分散介质的新型聚氨酯体系,也称水分散聚氨酯、水系聚氨酯或水基聚氨酯。水性聚氨酯以水为溶剂,无污染、安全可靠、机械性能优良、相容性好、易于改性等优点。随着环保法律法规的健全和人们环保意识的加强,聚氨酯材料的水性化日益受到重视。但由于亲水单体的加入以及氨基甲酸酯、脲键等的亲水性,使得其耐水性较差,具体表现为吸水率较大,水接触角较小。为了更好地提高水性聚氨酯的耐水性,扩大应用范围,改性聚氨酯的研究成为研究热点之一。
发明内容
本发明的目的提供一种有机硅改性阳离子水性聚氨酯防水剂的制备方法,具有工艺简单,制备的防水剂薄膜耐水性好的特点。
本发明所采用的技术方案是一种有机硅改性阳离子水性聚氨酯防水剂的制备方法,具体按照以下步骤实施:
步骤1、按照质量百分比分别称取如下原料:
多元醇40%~60%,羟基硅油2~6%,多异氰酸酯15%~20%,阳离子扩链剂2%~5%,封端剂3%~11%,水18%~38%,以上各组分的含量总和为100%;
步骤2、将步骤1中称取的多元醇和羟基硅油进行混合,搅拌均匀,得到羟基硅油的醇类混合物;
步骤3、将步骤1中称取的多异氰酸酯添加到羟基硅油的醇类混合物中,在水浴中搅拌均匀后,得到含有端异氰酸酯基团的预聚体;
步骤4、将步骤1中称取的阳离子扩链剂添加到含有端异氰酸酯基团的预聚体中,在水浴中搅拌均匀后,得到扩链混合物料;
步骤5、将步骤1中称取的封端剂添加到扩链混合物料中,在水浴中搅拌均匀后,得到封端混合物料;
步骤6、将封端混合物料添加到步骤1中称取的水中,在水浴中搅拌均匀后,得到有机硅改性阳离子水性聚氨酯。
本发明的特点还在于:
多元醇为聚酯多元醇、聚酰胺多元醇、聚缩醛多元醇、聚烯烃多元醇或聚醚多元醇中的任意一种。
多异氰酸酯为二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、六次亚甲基二异氰酸酯或异佛尔酮二异氰酸酯中的任意一种。
阳离子扩链剂为R基-环氧丙基-二羟乙基季铵盐,所述R基为甲基、乙基、丙基或苯基中的任意一种。
封端剂为内酰胺或亚硫酸氢钠中的任意一种。
步骤2中,搅拌时间为0.5h~2.5h。
步骤3中,水浴温度控制在55℃~95℃,搅拌时间为2h~4h。
步骤4中,水浴温度控制在30℃~70℃,搅拌时间为0.5h~2.5h。
步骤5中,水浴温度控制在50℃~90℃,搅拌时间为1h~3h。
步骤6中,水浴温度控制在10℃~50℃,搅拌时间为0.5h~2.5h。
本发明的有益效果是:
(1)有机硅具有极性,且表面能低,用于水性聚氨酯的改性可解决水性聚氨酯中亲水基团引入导致耐水性能下降的问题;而且有机硅氧烷链段具有柔软、润滑作用,同时阳离子聚氨酯上所带的电荷可以和皮革有较好的结合,不需要借助大量的树脂来提高粘合性,并且具有一定的可成膜性;故将有机硅氧烷和阳离子水性聚氨酯结合用于皮革涂饰,可以赋予其良好的柔软性和耐水性;
(2)本发明有机硅改性阳离子水性聚氨酯防水剂的制备方法中,采用原位聚合的方法将有机硅引入到水性聚氨酯中,并且采用合成的环氧基阳离子扩链剂,得到具有疏水功能的有机硅改性阳离子水性聚氨酯乳液;
(3)本发明选用的封端剂相比于传统的封端剂,具有较低的解封温度,同时具耐过烘黄变、耐酸蚀性的性能;
(4)本发明有机硅改性阳离子水性聚氨酯制备的制备方法,不仅具有安全环保的优点,而且结合了水性聚氨酯和聚硅氧烷的两者的优点,提高了水性聚氨酯防水剂的综合性能,在皮革涂饰上有广泛的应用前景。
附图说明
图1是无涂饰的皮革、本发明制备的有机硅改性阳离子水性聚氨酯防水剂涂饰的皮革的拉伸强度、断裂伸长率的测量结果图;
图2是无涂饰的皮革、本发明制备的有机硅改性阳离子水性聚氨酯防水剂涂饰的皮革的接触角的测量结果图。
具体实施方式
下面结合附图和具体实施方式对本发明进行详细说明。
本发明提出了一种有机硅改性阳离子水性聚氨酯防水剂的制备方法,具体按照以下步骤实施:
步骤1、按照质量百分比分别称取如下原料:
多元醇40%~60%,羟基硅油2~6%,多异氰酸酯15%~20%,阳离子扩链剂2%~5%,封端剂3%~11%,水18%~38%,以上各组分的含量总和为100%;
其中,多元醇为聚酯多元醇、聚酰胺多元醇、聚缩醛多元醇、聚烯烃多元醇或聚醚多元醇中的任意一种;
多异氰酸酯为二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、六次亚甲基二异氰酸酯或异佛尔酮二异氰酸酯中的任意一种;
阳离子扩链剂为R基-环氧丙基-二羟乙基季铵盐,所述R基为甲基、乙基、丙基或苯基中的任意一种;
封端剂为内酰胺或亚硫酸氢钠中的任意一种。
步骤2、将步骤1中称取的多元醇和羟基硅油进行混合,搅拌均匀,得到羟基硅油的醇类混合物;其中,搅拌时间为0.5h~2.5h。
步骤3、将步骤1中称取的多异氰酸酯添加到羟基硅油的醇类混合物中,在水浴中搅拌均匀后,得到含有端异氰酸酯基团的预聚体;其中,水浴温度控制在55℃~95℃,搅拌时间为2h~4h。
步骤4、将步骤1中称取的阳离子扩链剂添加到含有端异氰酸酯基团的预聚体中,在水浴中搅拌均匀后,得到扩链混合物料;其中,水浴温度控制在30℃~70℃,搅拌时间为0.5h~2.5h。
步骤5、将步骤1中称取的封端剂添加到扩链混合物料中,在水浴中搅拌均匀后,得到封端混合物料;其中,水浴温度控制在50℃~90℃,搅拌时间为1h~3h。
步骤6、将封端混合物料添加到步骤1中称取的水中,在水浴中搅拌均匀后,得到有机硅改性阳离子水性聚氨酯;其中,水浴温度控制在10℃~50℃,搅拌时间为0.5h~2.5h。
实施例1
一种有机硅改性阳离子水性聚氨酯防水剂的制备方法:
(1)按照质量百分比分别称取如下原料:
聚酯多元醇50%,羟基硅油2%,二苯基甲烷二异氰酸酯15%,甲基-环氧丙基-二羟乙基季铵盐2%,内酰胺3%,水28%,以上各组分的含量总和为100%;
(2)将上述称取的聚酯多元醇和羟基硅油进行混合,搅拌均匀,得到羟基硅油的醇类混合物;其中,搅拌时间为0.5h;
(3)将上述称取的二苯基甲烷二异氰酸酯添加到羟基硅油的醇类混合物中,在水浴中搅拌均匀后,得到含有端异氰酸酯基团的预聚体;其中,水浴温度控制在55℃,搅拌时间为4h;
(4)将上述称取的甲基-环氧丙基-二羟乙基季铵盐添加到含有端异氰酸酯基团的预聚体中,在水浴中搅拌均匀后,得到扩链混合物料;其中,水浴温度控制在30℃,搅拌时间为2.5h;
(5)将上述称取的内酰胺添加到扩链混合物料中,在水浴中搅拌均匀后,得到封端混合物料;其中,水浴温度控制在50℃,搅拌时间为3h;
(6)将封端混合物料添加到步骤1中称取的水中,在水浴中搅拌均匀后,得到有机硅改性阳离子水性聚氨酯;其中,水浴温度控制在50℃,搅拌时间为2.5h。
实施例2
一种有机硅改性阳离子水性聚氨酯防水剂的制备方法:
(1)按照质量百分比分别称取如下原料:
聚酰胺多元醇45%,羟基硅油3%,甲苯二异氰酸酯15%,乙基-环氧丙基-二羟乙基季铵盐2.7%,内酰胺4.3%,水30%,以上各组分的含量总和为100%;
(2)将上述称取的聚酰胺多元醇和羟基硅油进行混合,搅拌均匀,得到羟基硅油的醇类混合物;其中,搅拌时间为1h;
(3)将上述称取的甲苯二异氰酸酯添加到羟基硅油的醇类混合物中,在水浴中搅拌均匀后,得到含有端异氰酸酯基团的预聚体;其中,水浴温度控制在65℃,搅拌时间为3.5h;
(4)将上述称取的乙基-环氧丙基-二羟乙基季铵盐添加到含有端异氰酸酯基团的预聚体中,在水浴中搅拌均匀后,得到扩链混合物料;其中,水浴温度控制在40℃,搅拌时间为2h;
(5)将上述称取的内酰胺添加到扩链混合物料中,在水浴中搅拌均匀后,得到封端混合物料;其中,水浴温度控制在60℃,搅拌时间为2.5h;
(6)将封端混合物料添加到步骤1中称取的水中,在水浴中搅拌均匀后,得到有机硅改性阳离子水性聚氨酯;其中,水浴温度控制在40℃,搅拌时间为2h。
实施例3
一种有机硅改性阳离子水性聚氨酯防水剂的制备方法:
(1)按照质量百分比分别称取如下原料:
聚缩醛多元醇40%,羟基硅油5%,六次亚甲基二异氰酸酯18%,丙基-环氧丙基-二羟乙基季铵盐2%,亚硫酸氢钠5%,水30%,以上各组分的含量总和为100%;
(2)将上述称取的聚缩醛多元醇和羟基硅油进行混合,搅拌均匀,得到羟基硅油的醇类混合物;其中,搅拌时间为1.5h;
(3)将上述称取的六次亚甲基二异氰酸酯添加到羟基硅油的醇类混合物中,在水浴中搅拌均匀后,得到含有端异氰酸酯基团的预聚体;其中,水浴温度控制在75℃,搅拌时间为3h;
(4)将上述称取的丙基-环氧丙基-二羟乙基季铵盐添加到含有端异氰酸酯基团的预聚体中,在水浴中搅拌均匀后,得到扩链混合物料;其中,水浴温度控制在50℃,搅拌时间为1.5h;
(5)将上述称取的亚硫酸氢钠添加到扩链混合物料中,在水浴中搅拌均匀后,得到封端混合物料;其中,水浴温度控制在70℃,搅拌时间为2h;
(6)将封端混合物料添加到步骤1中称取的水中,在水浴中搅拌均匀后,得到有机硅改性阳离子水性聚氨酯;其中,水浴温度控制在30℃,搅拌时间为1.5h。
实施例4
一种有机硅改性阳离子水性聚氨酯防水剂的制备方法:
(1)按照质量百分比分别称取如下原料:
聚烯烃多元醇45%,羟基硅油6%,异佛尔酮二异氰酸酯15%,苯基-环氧丙基-二羟乙基季铵盐2%,内酰胺5%,水27%,以上各组分的含量总和为100%;
(2)将上述称取的聚烯烃多元醇和羟基硅油进行混合,搅拌均匀,得到羟基硅油的醇类混合物;其中,搅拌时间为2h;
(3)将上述称取的多异氰酸酯添加到羟基硅油的醇类混合物中,在水浴中搅拌均匀后,得到含有端异氰酸酯基团的预聚体;其中,水浴温度控制在85℃,搅拌时间为2.5h;
(4)将上述称取的苯基-环氧丙基-二羟乙基季铵盐添加到含有端异氰酸酯基团的预聚体中,在水浴中搅拌均匀后,得到扩链混合物料;其中,水浴温度控制在60℃,搅拌时间为1h;
(5)将上述称取的内酰胺添加到扩链混合物料中,在水浴中搅拌均匀后,得到封端混合物料;其中,水浴温度控制在60℃,搅拌时间为1h;
(6)将封端混合物料添加到步骤1中称取的水中,在水浴中搅拌均匀后,得到有机硅改性阳离子水性聚氨酯;其中,水浴温度控制在80℃,搅拌时间为1.5h。
实施例5
一种有机硅改性阳离子水性聚氨酯防水剂的制备方法:
(1)按照质量百分比分别称取如下原料:
聚醚多元醇40%,羟基硅油3%,异佛尔酮二异氰酸酯16%,苯基-环氧丙基-二羟乙基季铵盐3%,亚硫酸氢钠5%,水33%,以上各组分的含量总和为100%;
(2)将上述称取的聚醚多元醇和羟基硅油进行混合,搅拌均匀,得到羟基硅油的醇类混合物;其中,搅拌时间为2.5h;
(3)将上述称取的异佛尔酮二异氰酸酯添加到羟基硅油的醇类混合物中,在水浴中搅拌均匀后,得到含有端异氰酸酯基团的预聚体;其中,水浴温度控制在95℃,搅拌时间为2h;
(4)将上述称取的苯基-环氧丙基-二羟乙基季铵盐添加到含有端异氰酸酯基团的预聚体中,在水浴中搅拌均匀后,得到扩链混合物料;其中,水浴温度控制在70℃,搅拌时间为0.5h;
(5)将上述称取的亚硫酸氢钠添加到扩链混合物料中,在水浴中搅拌均匀后,得到封端混合物料;其中,水浴温度控制在90℃,搅拌时间为1h;
(6)将封端混合物料添加到步骤1中称取的水中,在水浴中搅拌均匀后,得到有机硅改性阳离子水性聚氨酯;其中,水浴温度控制在10℃,搅拌时间为0.5h。
实验验证:
图1是无涂饰的皮革、实施例5制备的有机硅改性阳离子水性聚氨酯防水剂涂饰的皮革的拉伸强度、断裂伸长率的测量结果图;图2是无涂饰的皮革、实施例5制备的有机硅改性阳离子水性聚氨酯防水剂涂饰的皮革的接触角的测量结果图。其中,实施例5为最佳实施例;图1和图2中,皮革1表示无涂饰的皮革,皮革2表示本发明制备的有机硅改性阳离子水性聚氨酯防水剂涂饰的皮革。
由图1和图2可得出:直接喷涂本发明制备的有机硅改性阳离子水性聚氨酯防水剂乳液的皮革与不涂饰的皮革相比,其力学性能和防水性能显著提高;未经涂饰的皮革试样的拉伸强度只有7.30N/mm2,断裂伸长率只有59.82%,接触角为79°;直接采用本发明制备的有机硅改性阳离子水性聚氨酯防水剂涂饰的皮革试样的拉伸强度为8.73N/mm2,断裂伸长率为78.62%,接触角为99°。这说明本发明制备的有机硅改性阳离子水性聚氨酯防水剂作为涂饰剂涂饰在革试样表面,提高了革试样的力学性能及水接触角。
同时也说明了本发明制备得到的有机硅改性阳离子水性聚氨酯防水剂具有乳液粒径小、贮存稳定,分布窄,且乳胶粒表面带正电荷易于皮革结合,所成薄膜耐水性好、手感优良的优点;应用于皮革涂饰中不仅手感丰满爽滑、回弹良好,而且在基体上的牢固性极佳,并且具有优异的耐水性。
Claims (10)
1.一种有机硅改性阳离子水性聚氨酯防水剂的制备方法,其特征在于,具体按照以下步骤实施:
步骤1、按照质量百分比分别称取如下原料:
多元醇40%~60%,羟基硅油2~6%,多异氰酸酯15%~20%,阳离子扩链剂2%~5%,封端剂3%~11%,水18%~38%,以上各组分的含量总和为100%;
步骤2、将步骤1中称取的所述多元醇和羟基硅油进行混合,搅拌均匀,得到羟基硅油的醇类混合物;
步骤3、将步骤1中称取的所述多异氰酸酯添加到所述羟基硅油的醇类混合物中,在水浴中搅拌均匀后,得到含有端异氰酸酯基团的预聚体;
步骤4、将步骤1中称取的所述阳离子扩链剂添加到所述含有端异氰酸酯基团的预聚体中,在水浴中搅拌均匀后,得到扩链混合物料;
步骤5、将步骤1中称取的所述封端剂添加到所述扩链混合物料中,在水浴中搅拌均匀后,得到封端混合物料;
步骤6、将所述封端混合物料添加到步骤1中称取的所述水中,在水浴中搅拌均匀后,得到有机硅改性阳离子水性聚氨酯。
2.根据权利要求1所述的一种有机硅改性阳离子水性聚氨酯防水剂的制备方法,其特征在于,所述多元醇为聚酯多元醇、聚酰胺多元醇、聚缩醛多元醇、聚烯烃多元醇或聚醚多元醇中的任意一种。
3.根据权利要求1所述的一种有机硅改性阳离子水性聚氨酯防水剂的制备方法,其特征在于,所述多异氰酸酯为二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、六次亚甲基二异氰酸酯或异佛尔酮二异氰酸酯中的任意一种。
4.根据权利要求1所述的一种有机硅改性阳离子水性聚氨酯防水剂的制备方法,其特征在于,所述阳离子扩链剂为R基-环氧丙基-二羟乙基季铵盐,所述R基为甲基、乙基、丙基或苯基中的任意一种。
5.根据权利要求1所述的一种有机硅改性阳离子水性聚氨酯防水剂的制备方法,其特征在于,所述封端剂为内酰胺或亚硫酸氢钠中的任意一种。
6.根据权利要求1所述的一种有机硅改性阳离子水性聚氨酯防水剂的制备方法,其特征在于,步骤2中,所述搅拌时间为0.5h~2.5h。
7.根据权利要求1所述的一种有机硅改性阳离子水性聚氨酯防水剂的制备方法,其特征在于,步骤3中,所述水浴温度控制在55℃~95℃,所述搅拌时间为2h~4h。
8.根据权利要求1所述的一种有机硅改性阳离子水性聚氨酯防水剂的制备方法,其特征在于,步骤4中,所述水浴温度控制在30℃~70℃,所述搅拌时间为0.5h~2.5h。
9.根据权利要求1所述的一种有机硅改性阳离子水性聚氨酯防水剂的制备方法,其特征在于,步骤5中,所述水浴温度控制在50℃~90℃,所述搅拌时间为1h~3h。
10.根据权利要求1所述的一种有机硅改性阳离子水性聚氨酯防水剂的制备方法,其特征在于,步骤6中,所述水浴温度控制在10℃~50℃,所述搅拌时间为0.5h~2.5h。
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Cited By (2)
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CN115679703A (zh) * | 2022-11-15 | 2023-02-03 | 五邑大学 | 一种防水剂及其制备方法和应用 |
CN116948137A (zh) * | 2023-06-30 | 2023-10-27 | 江苏米尔化工科技有限公司 | 一种软硬段阻燃水性聚氨酯的制备方法 |
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