CN110685170B - 具有保暖功能的羊毛角蛋白/水性聚氨酯复合乳液涂层剂及其制备方法 - Google Patents
具有保暖功能的羊毛角蛋白/水性聚氨酯复合乳液涂层剂及其制备方法 Download PDFInfo
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Abstract
本发明涉及具有保暖功能的羊毛角蛋白/水性聚氨酯复合乳液涂层剂及其制备方法。该涂层剂可由下述制备方法制得:以废旧羊毛为原料,从中提取羊毛角蛋白;然后将角蛋白制备为O/W型羊毛角蛋白乳液;制备了水性聚氨酯乳液,将羊毛角蛋白乳液与水性聚氨酯乳液进行复配混合,制得具有保暖功能的羊毛角蛋白/水性聚氨酯复合乳液涂层剂。本发明制备的羊毛角蛋白/水性聚氨酯复合乳液涂层剂用于棉织物的涂层整理后,棉织物的保温率从24.7%升到66%以上,说明涂层剂具有很好的保暖功能。本发明制备工艺简单,生产过程对环境无污染,有利于进一步推广和应用。
Description
技术领域
本发明属于涂层剂技术领域,具体涉及具有保暖功能的羊毛角蛋白/水性聚氨酯复合乳液涂层剂及其制备方法。
背景技术
涂层剂是一种纺织助剂,其涂覆在纺织物的表面,其可以使纺织物具有很多特性,如:保暖、防风、疏水、抗紫外线和防静电等。当前,市场上的涂层剂主要有聚丙烯酸酯类和聚氨酯类二大类,它们在使用时各有优劣。随着人们对纺织服装品质需求的提高,各种新型纺织物涂层剂被不断研发和生产出来,以满足市场的需求。
在羊皮制革时,会有大量的羊毛废弃余料,此外,在服装毛纺业也有大量的羊毛产品废弃物。羊毛废弃余料中可以提炼羊毛角蛋白,羊毛角蛋白是一种天然生物高分子聚合物,其具有羊毛优异的保暖性能,此外,其还具有良好的生物降解能力。由此可见,羊毛角蛋白在被用于涂层剂领域具有很好的潜力。
当前,很多新的天然材料被广泛应用于涂层剂领域,如:中国专利申请号200710145401.6公布了一种防水透湿涂层剂组合物及其应用,该专利在聚氨酯涂层剂中添加微孔木质素微细粉。文献调研发现,羊毛角蛋白用于制备涂层剂的研究鲜有报道,本发明拟在该领域有所突破。
发明内容
本发明的目的在于提供具有保暖功能的羊毛角蛋白/水性聚氨酯复合乳液涂层剂,以解决现有技术中存在的不足,该涂层剂对纺织品进行涂覆后,纺织品具有较好的保暖功能。
本发明的目的在于提供具有保暖功能的羊毛角蛋白/水性聚氨酯复合乳液涂层剂,该涂层剂可由下述制备方法制得:以废旧羊毛为原料,从中提取羊毛角蛋白;然后将角蛋白制备为O/W型羊毛角蛋白乳液;制备了水性聚氨酯乳液,将羊毛角蛋白乳液与水性聚氨酯乳液进行复配混合,制得具有保暖功能的羊毛角蛋白/水性聚氨酯复合乳液涂层剂。
本发明的另一个目的在于提供上述所述具有保暖功能的羊毛角蛋白/水性聚氨酯复合乳液涂层剂的制备方法,其制备方法如下:
(1)废旧羊毛的选取:选择以羊毛为材料的废旧衣物,用衣用清洗剂进行清洗,然后用大量水进行清洗,干燥。
(2)羊毛角蛋白溶液的制备:在60~80℃下,将步骤(1)处理的废旧衣物溶解在三羧基乙基膦和尿素的混合溶液,溶解过程不断搅拌,溶解时间为4~6h,过滤,浓缩得到羊毛角蛋白溶液,羊毛角蛋白溶液的固含量为40~60%。
优选地,所述废旧羊毛(g)、三羧基乙基膦(mL)和尿素(g)的体积质量比为1∶10~20∶1~2。
(3)羊毛角蛋白粉体的制备:将步骤(2)制备的羊毛角蛋白溶液在冷冻干燥机上进行冷冻干燥,制得羊毛角蛋白粉体。
优选地,所述冷冻温度为:-50~-60℃,干燥时间为:10~18h。
(4)O/W乳液的制备:取羊毛角蛋白固体至圆底烧瓶,加入N-甲基吗啉,使其在恒温电磁搅拌器上于40℃下持续搅拌并完全溶解;当羊毛角蛋白完全溶解后,将混合溶液加入司班60,搅拌使其混合均匀;将以上混合液加入饱和的十二烷基磺酸钠水溶液中,用磁力转子均匀搅拌,得到O/W型羊毛角蛋白乳液。
优选地,所述羊毛角蛋白(g)与N-甲基吗啉(mL)的固液比为:1∶5~10;司班60占N-甲基吗啉的用量比为:1~3%;混合液(mL)与饱和的十二烷基磺酸钠水溶液(mL)的用量比例为1∶2~4。
(5)预聚:在反应釜中加入聚丙二醇和二羟甲基丙酸,在100~120℃下真空脱水1~2h,缓慢降温至50~60℃,滴加甲苯二异氰酸酯、丁酮和催化剂辛酸亚锡的混合溶液,升温至80~90℃,反应3~4h。
优选地,所述聚丙二醇的分子量为200,聚丙二醇、二羟甲基丙酸、甲苯二异氰酸酯的摩尔比为1∶1~3∶3~5,辛酸亚锡(mL)与丁酮(mL)的体积质量比为1∶20~30。
(6)扩链:将步骤(5)的反应釜降温至40~45℃,于1~1.5h内分2~4次加入单羟基丙烯酸,升温至60~80℃,保温反应1~2h。
优选地,所述单羟基丙烯酸与二羟甲基丙酸的摩尔比为1∶1~2。
(7)乳化:在乳化泵中,对步骤(6)的溶液在高剪切力作用下加入一定量的去离子水,进行反向乳化,同时滴加三乙胺中和。
优选地,乳化泵的剪切速率为6000~15000r/min;
(8)脱溶剂:对步骤(7)的乳液采用减压低温蒸馏法脱除丁酮,即得到水性聚氨酯乳液。
(9)乳液的混合:将步骤(4)制备的O/W型羊毛角蛋白乳液与步骤(8)制备的水性聚氨酯乳液混合,将混合后的溶液在高速分散匀质机上搅拌0.5~1h,搅拌温度为40~45℃,即可得到具有保暖功能的羊毛角蛋白/水性聚氨酯复合乳液涂层剂。
优选地,所述步骤(4)制备的O/W型羊毛角蛋白乳液与步骤(8)制备的水性聚氨酯乳液的体积比为1︰5~7。
本发明具有如下显著特点:
(1)本发明制备的羊毛角蛋白/水性聚氨酯复合乳液涂层剂用于棉织物的涂层整理后,棉织物的保温率从24.7%升到66%以上,说明涂层剂具有很好的保暖功能。
(2)本发明将羊毛角蛋白乳液与水性聚氨酯乳液进行混合,制得的羊毛角蛋白/水性聚氨酯复合乳液涂层剂性能稳定,放置90天不分层。
(3)本发明中的羊毛角蛋白/水性聚氨酯复合乳液涂层剂的原料来源广泛,将废旧羊毛实现高效应用;此外,对水性聚氨酯涂层剂也是进一步的改性,明显提升了水性聚氨酯涂层剂性能。
(4)本发明制备工艺简单,生产过程对环境无污染,有利于进一步推广和应用。
具体实施方式
以下所述实施例详细说明了本发明。
实施例1
在本实施例中,具有保暖功能的羊毛角蛋白/水性聚氨酯复合乳液涂层剂采用如下方法制备而成,包括如下步骤:
(1)废旧羊毛的选取:选择以羊毛为材料的废旧衣物,用衣用清洗剂进行清洗,然后用大量水进行清洗,干燥。
(2)羊毛角蛋白溶液的制备:在70℃下,将步骤(1)处理的10g废旧衣物溶解在150mL三羧基乙基膦和15g尿素的混合溶液,溶解过程不断搅拌,溶解时间为5h,过滤,浓缩得到羊毛角蛋白溶液,羊毛角蛋白溶液的固含量为48.7%。
(3)羊毛角蛋白粉体的制备:将步骤(2)制备的羊毛角蛋白溶液在冷冻干燥机上进行冷冻干燥,冷冻温度为:-55℃,干燥时间为:14h,制得羊毛角蛋白粉体。
(4)O/W乳液的制备:取10g羊毛角蛋白固体至圆底烧瓶,加入75mLN-甲基吗啉,使其在恒温电磁搅拌器上于40℃下持续搅拌并完全溶解;当羊毛角蛋白完全溶解后,将混合溶液加入1.5g司班60,搅拌使其混合均匀;将以上混合液加入225mL饱和的十二烷基磺酸钠水溶液中,用磁力转子均匀搅拌,得到O/W型羊毛角蛋白乳液。
(5)预聚:在反应釜中加入0.1mol分子量为200聚丙二醇和0.2mol二羟甲基丙酸,在110℃下真空脱水1.5h,缓慢降温至55℃,滴加0.4mol甲苯二异氰酸酯、25mL丁酮和1mL催化剂辛酸亚锡的混合溶液,升温至85℃,反应3.5h。
(6)扩链:将步骤(5)的反应釜降温至43℃,于1.2h内分3次加入0.13mol单羟基丙烯酸,升温至70℃,保温反应1.5h。
(7)乳化:在乳化泵中,乳化泵的剪切速率为9000r/min,对步骤(6)的溶液在高剪切力作用下加入300mL的去离子水,进行反向乳化,同时滴加三乙胺中和。
(8)脱溶剂:对步骤(7)的乳液采用减压低温蒸馏法脱除丁酮,即得到水性聚氨酯乳液。
(9)乳液的混合:将100mL步骤(4)制备的O/W型羊毛角蛋白乳液与600mL步骤(8)制备的水性聚氨酯乳液混合,将混合后的溶液在高速分散匀质机上搅拌0.75h,搅拌温度为43℃,即可得到具有保暖功能的羊毛角蛋白/水性聚氨酯复合乳液涂层剂a。
实施例2
在本实施例中,具有保暖功能的羊毛角蛋白/水性聚氨酯复合乳液涂层剂采用如下方法制备而成,包括如下步骤:
(1)废旧羊毛的选取:选择以羊毛为材料的废旧衣物,用衣用清洗剂进行清洗,然后用大量水进行清洗,干燥。
(2)羊毛角蛋白溶液的制备:在60℃下,将步骤(1)处理的10g废旧衣物溶解在100mL三羧基乙基膦和10g尿素的混合溶液,溶解过程不断搅拌,溶解时间为4h,过滤,浓缩得到羊毛角蛋白溶液,羊毛角蛋白溶液的固含量为43.5%。
(3)羊毛角蛋白粉体的制备:将步骤(2)制备的羊毛角蛋白溶液在冷冻干燥机上进行冷冻干燥,冷冻温度为:-50℃,干燥时间为:18h,制得羊毛角蛋白粉体。
(4)O/W乳液的制备:取10g羊毛角蛋白固体至圆底烧瓶,加入50mLN-甲基吗啉,使其在恒温电磁搅拌器上于40℃下持续搅拌并完全溶解;当羊毛角蛋白完全溶解后,将混合溶液加入0.5g司班60,搅拌使其混合均匀;将以上混合液加入120mL饱和的十二烷基磺酸钠水溶液中,用磁力转子均匀搅拌,得到O/W型羊毛角蛋白乳液。
(5)预聚:在反应釜中加入0.1mol分子量为200聚丙二醇和0.1mol二羟甲基丙酸,在110℃下真空脱水1.5h,缓慢降温至50℃,滴加0.3mol甲苯二异氰酸酯、20mL丁酮和1mL催化剂辛酸亚锡的混合溶液,升温至85℃,反应3h。
(6)扩链:将步骤(5)的反应釜降温至40℃,于1h内分2次加入0.1mol单羟基丙烯酸,升温至70℃,保温反应1.5h。
(7)乳化:在乳化泵中,乳化泵的剪切速率为6000r/min,对步骤(6)的溶液在高剪切力作用下加入250mL的去离子水,进行反向乳化,同时滴加三乙胺中和。
(8)脱溶剂:对步骤(7)的乳液采用减压低温蒸馏法脱除丁酮,即得到水性聚氨酯乳液。
(9)乳液的混合:将100mL步骤(4)制备的O/W型羊毛角蛋白乳液与500mL步骤(8)制备的水性聚氨酯乳液混合,将混合后的溶液在高速分散匀质机上搅拌0.75h,搅拌温度为43℃,即可得到具有保暖功能的羊毛角蛋白/水性聚氨酯复合乳液涂层剂b。
实施例3
在本实施例中,具有保暖功能的羊毛角蛋白/水性聚氨酯复合乳液涂层剂采用如下方法制备而成,包括如下步骤:
(1)废旧羊毛的选取:选择以羊毛为材料的废旧衣物,用衣用清洗剂进行清洗,然后用大量水进行清洗,干燥。
(2)羊毛角蛋白溶液的制备:在80℃下,将步骤(1)处理的10g废旧衣物溶解在200mL三羧基乙基膦和20g尿素的混合溶液,溶解过程不断搅拌,溶解时间为6h,过滤,浓缩得到羊毛角蛋白溶液,羊毛角蛋白溶液的固含量为60.3%。
(3)羊毛角蛋白粉体的制备:将步骤(2)制备的羊毛角蛋白溶液在冷冻干燥机上进行冷冻干燥,冷冻温度为:-60℃,干燥时间为:18h,制得羊毛角蛋白粉体。
(4)O/W乳液的制备:取10g羊毛角蛋白固体至圆底烧瓶,加入100mLN-甲基吗啉,使其在恒温电磁搅拌器上于40℃下持续搅拌并完全溶解;当羊毛角蛋白完全溶解后,将混合溶液加入3g司班60,搅拌使其混合均匀;将以上混合液加入350mL饱和的十二烷基磺酸钠水溶液中,用磁力转子均匀搅拌,得到O/W型羊毛角蛋白乳液。
(5)预聚:在反应釜中加入0.1mol分子量为200聚丙二醇和0.3mol二羟甲基丙酸,在120℃下真空脱水1.5h,缓慢降温至55℃,滴加0.5mol甲苯二异氰酸酯、30mL丁酮和1mL催化剂辛酸亚锡的混合溶液,升温至90℃,反应4h。
(6)扩链:将步骤(5)的反应釜降温至45℃,于1.2h内分3次加入0.15mol单羟基丙烯酸,升温至70℃,保温反应1.5h。
(7)乳化:在乳化泵中,乳化泵的剪切速率为15000r/min,对步骤(6)的溶液在高剪切力作用下加入400mL的去离子水,进行反向乳化,同时滴加三乙胺中和。
(8)脱溶剂:对步骤(7)的乳液采用减压低温蒸馏法脱除丁酮,即得到水性聚氨酯乳液。
(9)乳液的混合:将100mL步骤(4)制备的O/W型羊毛角蛋白乳液与700mL步骤(8)制备的水性聚氨酯乳液混合,将混合后的溶液在高速分散匀质机上搅拌0.75h,搅拌温度为43℃,即可得到具有保暖功能的羊毛角蛋白/水性聚氨酯复合乳液涂层剂c。
应用性能实施例:
实施例1~3制备的羊毛角蛋白/水性聚氨酯复合乳液涂层剂a、b和c用于棉织物的涂层整理:在绷架上将棉织物紧绷,将涂层剂用刮刀均匀涂刮于棉织物上,涂布量干重为20~25g/m2,于90℃烘干2分钟,于150℃焙烘3分钟,制得经过羊毛角蛋白/水性聚氨酯复合乳液涂层剂a、b和c整理的棉织物。
保温性能测试:按照《纺织品保温性能试验方法》(GB 11048—89)中方法A的要求,采用YG606型平板式保温仪对羊毛角蛋白/水性聚氨酯复合乳液涂层剂a、b和c整理的棉织物的保温率进行测试。试验时将尺寸为300mm×300mm的样品覆盖在250mm×250mm的试验板上,以通断电的方式保持恒温,测定试验板在一定时间内保持恒温所需的加热时间,计算试样保温率。测试结果如下表所示:
由表可见,经过本发明制备的羊毛角蛋白/水性聚氨酯复合乳液涂层剂a、b和c整理的棉织物的保温率达到66%以上,明显高于未整理的棉织物。这表明:本发明制备的羊毛角蛋白/水性聚氨酯复合乳液涂层剂a、b和c具有很好的保暖功能。
Claims (1)
1.具有保暖功能的羊毛角蛋白/水性聚氨酯复合乳液涂层剂的制备方法,其特征在于,所述制备方法包括如下步骤:
(1)废旧羊毛的选取:选择以羊毛为材料的废旧衣物,用衣用清洗剂进行清洗,然后用大量水进行清洗,干燥;
(2)羊毛角蛋白溶液的制备:在60~80℃下,将步骤(1)处理的废旧衣物溶解在三羧基乙基膦和尿素的混合溶液,溶解过程不断搅拌,溶解时间为4~6h,过滤,浓缩得到羊毛角蛋白溶液,羊毛角蛋白溶液的固含量为40~60%;所述废旧羊毛、三羧基乙基膦和尿素的体积质量比为1g∶(10~20)mL∶(1~2)g;
(3)羊毛角蛋白粉体的制备:将步骤(2)制备的羊毛角蛋白溶液在冷冻干燥机上进行冷冻干燥,制得羊毛角蛋白粉体;冷冻温度为-50~-60℃,干燥时间为10~18h;
(4)O/W乳液的制备:取羊毛角蛋白固体至圆底烧瓶,加入N-甲基吗啉,使其在恒温电磁搅拌器上于40℃下持续搅拌并完全溶解;当羊毛角蛋白完全溶解后,将混合溶液加入司班60,搅拌使其混合均匀;将以上混合液加入饱和的十二烷基磺酸钠水溶液中,用磁力转子均匀搅拌,得到O/W型羊毛角蛋白乳液;所述羊毛角蛋白与N-甲基吗啉的固液比为1g∶(5~10)mL;所述司班60占N-甲基吗啉的用量比为1~3%;所述混合液与饱和的十二烷基磺酸钠水溶液的用量比例为1mL∶(2~4)mL;
(5)预聚:在反应釜中加入聚丙二醇和二羟甲基丙酸,在100~120℃下真空脱水1~2h,缓慢降温至50~60℃,滴加甲苯二异氰酸酯、丁酮和催化剂辛酸亚锡的混合溶液,升温至80~90℃,反应3~4h;所述聚丙二醇的分子量为200;所述聚丙二醇、二羟甲基丙酸、甲苯二异氰酸酯的摩尔比为1∶(1~3)∶(3~5);所述辛酸亚锡与丁酮的体积质量比为1mL∶(20~30)mL;
(6)扩链:将步骤(5)的反应釜降温至40~45℃,于1~1.5h内分2~4次加入单羟基丙烯酸,升温至60~80℃,保温反应1~2h;所述单羟基丙烯酸与二羟甲基丙酸的摩尔比为1∶(1~2);
(7)乳化:在剪切速率为6000~15000r/min的乳化泵中,对步骤(6)的溶液在高剪切力作用下加入一定量的去离子水,进行反向乳化,同时滴加三乙胺中和;
(8)脱溶剂:对步骤(7)的乳液采用减压低温蒸馏法脱除丁酮,即得到水性聚氨酯乳液;
(9)乳液的混合:将步骤(4)制备的O/W型羊毛角蛋白乳液与步骤(8)制备的水性聚氨酯乳液混合,将混合后的溶液在高速分散匀质机上搅拌0.5~1h,搅拌温度为40~45℃,即可得到具有保暖功能的羊毛角蛋白/水性聚氨酯复合乳液涂层剂;其中,所述步骤(4)制备的O/W型羊毛角蛋白乳液与步骤(8)制备的水性聚氨酯乳液的体积比为1︰(5~7)。
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