CN111040660A - 一种纺织品用水性透湿、阻燃聚氨酯膜及制备方法 - Google Patents

一种纺织品用水性透湿、阻燃聚氨酯膜及制备方法 Download PDF

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CN111040660A
CN111040660A CN201911372653.1A CN201911372653A CN111040660A CN 111040660 A CN111040660 A CN 111040660A CN 201911372653 A CN201911372653 A CN 201911372653A CN 111040660 A CN111040660 A CN 111040660A
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parts
agent
reaction
flame
molecular weight
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唐丽
赫荣君
陈剑冰
荣星
陈龙
孙海娥
张于
盛艳霞
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Liaoning Fixed Star Fine Chemical Co ltd
Dandong Unik Textile Ltd
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Dandong Unik Textile Ltd
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Abstract

本发明一种纺织品用水性防水透湿、阻燃聚氨酯膜及制备方法,由异佛尔酮二异氰酸酯、氢化MDI、环氧乙烷和四氢呋喃共聚醚多元醇、聚已内酯多元醇、阻燃聚酯多元醇、环氧乙烷和四氢呋喃共聚醚多元醇、扩链剂、小分子扩链剂、有机硅多元醇、去离子水经预聚反应、扩链反应、乳化反应、扩链反应、封闭反应制成乳液,在复配消泡剂、润湿流平剂、滑爽剂、增稠剂、消光剂、脱模剂、交联剂制成膜胶,涂层在离型纸或OPP上烘干,制得纺织品用水性透湿阻燃聚氨酯膜制品。其成膜柔软、弹性好、干爽,同时达到透湿好、阻燃好、耐寒好、耐水压高、断裂强力大、耐洗牢度好、断裂伸长率高。

Description

一种纺织品用水性透湿、阻燃聚氨酯膜及制备方法
技术领域
本发明涉及的是一种纺织品用水性透湿、阻燃聚氨酯膜及制备方法;该聚氨酯乳液成膜柔软、弹性好、干爽,同时达到透湿好、阻燃好、耐寒好、耐水压高、断裂强力大、断裂伸长率高、耐洗牢度好特性。
使用离型纸或OPP制成膜制品,使用热熔胶贴合在纺织品面料上使用。
其主要应用于户外服装、行业服装、帐篷、汽车内饰、包装袋等面料处理,以提高面料的透湿性和阻燃性能。
背景技术
聚氨酯类产品实现阻燃需要外添加阻燃剂来实现。
目前,聚氨酯类产品实现防水透湿性和阻燃性能是在具有透湿性能的溶剂型聚氨酯中加入阻燃添加剂来实现。阻燃添加剂主要为含卤素的溴、锑及氯化石蜡等类型物质。
溶剂型聚氨酯本身含有甲苯、N、N二甲基甲酰胺,生产和使用过程会对环境和人体产生伤害,而且添加卤素的阻燃剂欧盟已经列入限制物质。
水性聚氨酯添加阻燃剂虽能达到阻燃效果,但透湿性、耐水压达不到使用要求,即满足不了透湿好、阻燃好、耐水压高的特性,并且不环保。
专利CN201110119112.5公开了一种水性阻燃聚氨酯树脂及制备方法,其作为织物处理的阻燃涂层胶,其是一种含溴阻燃聚醚的水性聚氨酯树脂,固含量在20~40%。制备方法由制备含溴聚醚的聚氨酯预聚体A、制备含溴聚醚的封闭异氰酸酯的聚氨酯B,把上述的预聚体A和聚氨酯B进行乳化扩链反应,制得水性阻燃聚氨酯树脂。其具有校好的阻燃性能和水洗牢度,但其只是单纯的阻燃,并没有具体表述产品树脂具有透湿、耐水压特性,更不能制成具防水透湿阻燃特性的膜。
专利CN201611260755.0公开了一种三聚氰胺改性水性聚氨酯阻燃树脂及制备方法,其由多异氰酸酯、多元醇、多元胺类扩链剂、低聚物多元醇、二羟甲基丙酸、三聚氰胺、中和剂和去离子水通过化学反应制得,具有优良的阻燃性,良好的附着力、保色性、耐腐蚀性、耐水性、耐碱性、耐磨性、极低的VOC环保。并表明其用于水性防火涂料、水性阻燃涂料、水性防腐涂料、水性防水防潮涂料、水性工程特种涂料、水性木器涂料等,还可用于皮革鞣皮剂、合成防火层板的粘接剂、混凝土的防水剂等。但并没有提到可用于纺织品上,更没有提到做成膜。
专利CN201611232607.8公开了一种水性阻燃聚合物的制备方法,特别是一种水性聚氨酯阻燃物的制备方法。其采用两种聚多元醇、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯为单体,并加入磷硅复合阻燃剂,通过预聚合、中和、乳化、扩链来制备聚合物,表明其制备的水性阻燃聚合物具有无卤、低烟、低毒性等优点,并且保持了其力学性能,产品具有很好的高分子材料相容性和环境友好性。其产品通过复配添加磷硅复合阻燃剂,并不是接枝改性产品。而且也没有表述用于哪个领域及产品具体特点,没有表述可用于纺织品,也没有提到做成膜。
目前未见有环保的水性聚氨酯同时具备防水透湿性和阻燃性的聚氨酯膜产品技术文献公开。
发明内容
本发明涉及的是一种纺织品用水性透湿、阻燃聚氨酯膜及制备方法;该聚氨酯乳液成膜柔软、弹性好、干爽,同时达到透湿好、阻燃好、耐寒好、耐水压高、断裂强力大、耐洗牢度好、断裂伸长率高;
使用离型纸或OPP制成膜制品,使用热熔胶贴合在纺织品面料上使用;
其主要应用于户外服装、行业服装、帐篷、汽车内饰、包装袋等面料处理,以提高面料的透湿性和阻燃性能。
本发明纺织品用水性透湿、阻燃聚氨酯膜制备方法:
原料按重量配比:
(1)预聚反应:将异佛尔酮二异氰酸酯30-48份、氢化MDI 25-55 份、分子量为1000-3000的环氧乙烷和四氢呋喃共聚醚多元醇50-80份、分子量为100-500的聚已内酯多元醇5-15份、分子量为1000-3000的阻燃聚酯多元醇30-70份、分子量为100-800的环氧乙烷和四氢呋喃共聚醚多元醇10-30份加入反应釜中,升温至85-90℃搅拌反应3.5-4小时;
(2)扩链反应:加入分子量为200-550的扩链剂10-20份,在85-90℃反应3-4小时;
(3)乳化反应:加入去离子水180-500份,快速分散,然后在50-70℃保温反应1-1.5小时;
(4)扩链反应:控温40-60℃加入小分子扩链剂6-15份,40-60℃保温反应3-4小时;
(5)封闭反应:控温在40-45℃,加入分子量为1000-3000的有机硅多元醇30-50份,反应2-2.5小时,降温至20-35℃放料,得乳液;
(6)取上述乳液100份、消泡剂0.1-0.3份、润湿流平剂0.1-0.5份、滑爽剂1-5份、增稠剂1-3份依次加入釜中混合搅拌均匀,然后加入消光剂2-5份、脱模剂1-3份、交联剂1-5份搅拌均匀制成膜胶,粘度为2000-2500cps/25℃。
(7)在离型纸或OPP上涂覆膜胶,80-100℃烘干2-4分钟,膜厚0.15-0.18mm,制得纺织品用水性透湿、阻燃聚氨酯膜制品。
扩链剂:为羟基磺酸盐和氨基磺酸盐其一或混合使用;
小分子扩链剂:为2,4-二乙基-1,5-戊二醇(DEPD)、1,4-二羟甲基环己烷(CHDM)、乙二胺、异佛尔酮二胺、三乙烯二胺其一或几种混合使用;
消泡剂:为有机硅类消泡剂;
润湿流平剂:为炔二醇类润湿流平剂;
滑爽剂:为改性有机硅类滑爽剂;
增稠剂:为改性丙烯酸酯类型增稠剂;
消光剂:为亲水硅蜡改性的二氧化硅消光粉;
脱模剂:为亲水聚醚改性有机硅类脱模剂;
交联剂:为封闭型异氰酸酯交联剂。
本发明生产工艺简单方便,具有良好的工艺实施性,生产成本低,水性环保无污染,而且固体含量高,不但减少了合成工序、降低了生产成本。
本发明聚氨酯乳液成膜柔软、弹性好、干爽,同时达到透湿好、阻燃好、耐寒好、耐水压高、断裂强力大、断裂伸长率高、耐洗牢度好的特性。
本发明纺织品用水性透湿阻燃聚氨酯乳液是利用接枝嫁接改性技术方法,聚氨酯聚合物分子链段嫁接亲水聚醚改性烃羟基有机硅和环氧乙烷和四氢呋喃共聚醚多元醇,两种多元醇均具有亲水基团,亲水基团的引入满足了透湿性能;使用含有N、P两种元素的阻燃聚酯多元醇参与反应,N、P元素与硅元素产生协同效应,达到阻燃效果,使水性聚氨酯乳液即具透湿性,又具有阻燃性能。
众所周知,水性聚氨酯乳液由不同结构的异氰酸酯和聚酯多元醇、聚醚多元醇及扩链剂等原料加成反应而得。
本发明异氰酸酯原料选择了异佛尔酮二异氰酸酯和氢化MDI两种,两种异氰酸酯合理比例搭配使用不但能使反应顺利进行并且能使耐水压、耐洗性、成膜强度、干爽度等性能得到保证。
异佛尔酮二异氰酸酯具有环状结构且含有顺式和反式不对称结构,此结构增加分子间斥力且形成位阻,在合成过程中环状结构稳定,形成高聚物后仍能存在,增加了产品分子间斥力,产品微观粒子不易产生团聚,有效降低乳液粘度,可以得到高固含量的乳液,此结构可以增加产品成膜刚性,弹性好,耐磨性、干爽度及牢度能得到增强。而异佛尔酮二异氰酸酯的异构体环状结构,除具上述特性外,两个环上的异氰酸酯基团活性不同,反应速度不同,相差8-10倍,使反应过程更平稳;氢化MDI是直链环状结构,反应速度平稳,具有刚性,能够增加产品耐磨及耐水压性能;引入直链结构和异构结构的异氰酸酯二者合适比例的搭配,产品的断裂强度、耐洗性更好。如本发明选用其它类型异氰酸酯如六亚甲基异氰酸酯链段柔性会增强,但耐磨、耐水、断裂强力会降低,手感干爽度也会下降;如选用TDI或MDI异氰酸酯,二者具黄变性,做成膜时间久了会产生黄变和降解。因此不适合本发明。
本发明的多元醇选用了不同结构、不同分子量的环氧乙烷和四氢呋喃共聚醚多元醇、有机硅多元醇、聚己内酯多元醇、阻燃聚酯多元醇。
本发明采用环氧乙烷和四氢呋喃共聚醚多元醇两类不同官能团及分子量且不同比例的的共聚醚多元醇,大分子量选用两官能,而小分子量选用三官能,达到透湿,耐寒目的同时,三官能增加自交联性,利于强度、牢度提升。如果全部选用大分子量多元醇会使产品结晶度增加,耐寒性降低;全部选用小分子量多元醇透湿量会下降,满足不了高透湿要求。
本发明采用有机硅多元醇为2官能亲水聚醚改性烃羟基有机硅,烃羟基不会水解,增加了产品稳定性;且羟基接在了一端,因此,耐水、耐寒性好,同时亲水聚醚改性有机硅多元醇和环氧乙烷和四氢呋喃共聚醚多元醇能够协同作用,对透湿提供了进一步保证。
本发明聚己内酯多元醇采用三官能产品,增加交联牢度的同时其玻璃化温度低,低温环境下,链段可以自由旋转,耐寒性好,低温环境下仍能保持良好柔软度。
本发明选用环氧乙烷和四氢呋喃共聚醚多元醇具有偶碳结构,产品成膜粘结牢度好。具有优良的力学性能、耐水解性、耐热性、耐氧化性及耐磨性,因此产品成膜牢度、弹性、耐热性、耐水解性、耐磨性、干爽度得到很大加强。
本发明选用的阻燃聚酯多元醇侧链含有P、N结构,且P、N含量高,达40%,接枝改性水性聚氨酯中达到阻燃效果,由于存在于侧链部位克服了聚酯易水解的缺点,产品性能稳定,另外,有机硅多元醇接入,Si、P、N协同作用,阻燃性能更好。
本发明的扩链剂选用羟基磺酸盐和氨基磺酸盐其一或混合使用;
选用两种磺酸盐(羟基磺酸盐和氨基磺酸盐)作为亲水扩链剂,氨基磺酸盐反应速度快,而羟基磺酸盐反应速度相对较慢,两种磺酸盐反应速度不同,保证了产品反应过程的平稳,另外磺酸盐聚氨酯耐强酸、强碱、耐电解质性能好,产品的应用更加广泛,对添加剂的耐受性优异,而羧酸型扩链剂耐电解质和耐强酸、强碱性均不好,无法满足本发明耐洗要求。
本发明小分子扩链剂选用2,4-二乙基-1,5-戊二醇(DEPD)、1,4-二羟甲基环己烷(CHDM)、乙二胺、异佛尔酮二胺、三乙烯二胺其一或几种混合使用。
由于2,4-二乙基-1,5-戊二醇、1,4-二羟甲基环己烷二者均含有侧链结构,增加分子间斥力,降低合成乳液粘度,利于高含量乳液实现;侧链结构利于牢度、耐水性增强,进一步保证了粘结牢度、耐水压、耐水洗性;而乙二胺、异佛尔酮二胺、三乙烯二胺的参与反应形成脲键,提高产品刚性,提高牢度、耐水洗、耐水、断裂强力。
本发明选用的有机硅多元醇采取最后加入,进行最综封闭反应,为了使有机硅链段接在聚氨酯外层,除了具有上述的透湿、阻燃协同性能,还能增加手感滑爽度以及耐寒、耐水性能;
本发明选用有机硅多元醇羟基在同一端,反应时位阻大,只能一个羟基参与反应,如反应开始加入,会是阻止加成反应顺利进行,会影响产品的最综性能,如选用两侧羟基有机硅多元醇两个羟基的活性相同,反应速度一致,达不到封闭目的,还会产生凝胶。
本发明水性透湿阻燃聚氨酯乳液复配消泡剂、润湿流平剂、脱模剂、消光剂、增稠剂、手感剂等使用离型纸或OPP做成不同风格特色膜制品,通过热熔胶贴合在面料上,使面料具有透湿、阻燃功能。
本发明消泡剂采用有机硅类消泡剂,具长效特性,不但能消除膜胶制作过程产生的气泡,还能迅速消除制膜涂覆过程运动产生的气泡,如采用矿物油类消泡剂会产生油斑,会影响膜连续性。
本发明润湿流平剂采用炔二醇类润湿流平剂,该润湿流平剂有效降低表面张力,使膜胶在离型纸或OPP上能润展开,不产生缩孔鱼眼;还具有动态消泡的作用,和消泡剂协同作用,膜更均匀,而其它类型润湿流平剂不具备动态效果,在离型纸或OPP上达不到好的流平效果。
本发明滑爽剂采用改性有机硅类滑爽剂,具有高滑爽度。
本发明增稠剂采用改性丙烯酸酯类增稠剂,增稠同时改善膜胶的流平性能,保证膜的均匀性实现。
本发明消光剂采用亲水硅蜡改性的二氧化硅消光粉,其与本发明水性乳液相溶性好,均匀分散,不会产生团聚颗粒,给膜提供干爽手感。
本发明脱模剂采用亲水聚醚改性有机硅类脱模剂,具有滑爽特性,使膜容易从离型纸或OPP上剥离。
本发明交联剂采用封闭型异氰酸酯交联剂,解闭温度低,解闭后释放活性异氰酸酯基团增加膜的断裂强力及耐水性。
具体实施方式
实施例1
原料按重量配比:
(1)预聚反应:将异佛尔酮二异氰酸酯40份、氢化MDI 55份、分子量为1800的环氧乙烷和四氢呋喃共聚醚多元醇60份、分子量为200的聚已内酯多元醇8份、分子量为2000的阻燃聚酯多元醇35份、分子量为400的环氧乙烷和四氢呋喃共聚醚多元醇 18份加入反应釜中,升温至86℃搅拌反应4小时;
(2)扩链反应:加入分子量为250的羟基磺酸盐10份,分子量为490的氨基磺酸盐5份,在85℃反应3.5小时;
(3)乳化反应:加入去离子水280份,快速分散,然后在55℃保温反应1.5小时;
(4)扩链反应:控温50℃加入2,4-二乙基-1,5-戊二醇10份,1,4-二羟甲基环己烷3份,乙二胺2份,50℃保温反应3.5小时;
(5)封闭反应:控温至42℃,加入分子量为1900有机硅多元醇35份,搅拌反应2.5小时,再降温25℃放料得乳液;
(6)取上述乳液100份、消泡剂0.15份、润湿流平剂0.2份、滑爽剂1.5份、增稠剂1.5份依次加入釜中混合搅拌均匀,然后加入消光剂2.5份、脱模剂1份、交联剂1.5份搅拌均匀制成膜胶,粘度为2200cps/25℃;
(7)在离型纸上涂覆膜胶,100℃烘干2.5分钟,膜厚0.15mm,制得纺织品用水性透湿阻燃聚氨酯膜制品。
该实施例中氢化MDI和小分子扩链剂用量较大,断裂强力增强,手感会更干爽。
实施例2
原料按重量配比:
(1)预聚反应:将异佛尔酮二异氰酸酯48份、氢化MDI 35 份、分子量为2000的环氧乙烷和四氢呋喃共聚醚多元醇80份、分子量为200的聚已内酯多元醇10份、分子量为1500的阻燃聚酯多元醇50份、分子量为500的环氧乙烷和四氢呋喃共聚醚多元醇 18份加入反应釜中,升温至85℃搅拌反应3.5小时;
(2)扩链反应:加入分子量为300的羟基磺酸盐7.5份,加入分子量为360的氨基磺酸盐7.5份,在86℃反应4小时;
(3)乳化反应:加入去离子水315份,快速分散,然后在60℃保温反应1小时;
(4)扩链反应:控温60℃,加入2,4-二乙基-1,5-戊二醇4份,1,4-二羟甲基环己烷2份,异佛尔酮二胺1份,在60℃保温反应3小时;
(5)封闭反应:控温至40℃,加入分子量为2000的有机硅多元醇50份,搅拌反应2小时,再降温25℃放料得乳液;
(6)取上述乳液100份、消泡剂0.2份、润湿剂流平剂0.2份、滑爽剂2份、增稠剂2份依次加入釜中混合搅拌均匀,然后加入消光剂3份、脱模剂2份、交联剂3份搅拌均匀制成膜胶,粘度为2100cps/25℃;
(7)在离型纸上涂覆膜胶,80℃烘干3分钟,膜厚0.16mm,制得纺织品用水性透湿阻燃聚氨酯膜制品。
该实施例产品由于原料配比中有机硅多元醇、环氧乙烷和四氢呋喃共聚多元醇使用量较大,因此透湿、耐寒性会更优异。
实施例3
原料按重量配比:
(1)预聚反应:将异佛尔酮二异氰酸酯43份、氢化MDI 35 份、分子量为3000的环氧乙烷和四氢呋喃共聚醚多元醇55份、分子量为200的聚已内酯多元醇8份、分子量为2500的阻燃聚酯多元醇60份、分子量为400的环氧乙烷和四氢呋喃共聚醚多元醇 10份加入反应釜中,升温至87℃搅拌反应3.5小时;
(2)扩链反应:加入分子量为300的羟基磺酸盐15份,加入分子量为360的氨基磺酸盐3份,在86℃反应3.5小时;
(3)乳化反应:加入去离子水285份,快速分散,然后在60℃保温反应1小时;
(4)扩链反应:控温55℃,加入2,4-二乙基-1,5-戊二醇4份,1,4-二羟甲基环己烷2份,乙二胺8份,在55℃保温反应3.5小时;
(5)封闭反应:控温至43℃,加入分子量为3000的有机硅多元醇50份,搅拌反应2.5小时,再降温26℃放料得乳液;
(6)取上述乳液100份、消泡剂0.3份、润湿剂流平剂0.5份、滑爽剂5份、增稠剂3份依次加入釜中混合搅拌均匀,然后加入消光剂5份、脱模剂3份、交联剂2份搅拌均匀制成膜胶,粘度为2500cps/25℃;
(7)在离型纸上涂覆膜胶,85℃烘干3分钟,膜厚0.15mm,制得纺织品用水性透湿阻燃聚氨酯膜制品。
该实施例产品由于原料组份阻燃聚酯多元醇和有机硅多元醇加入量较大,因此阻燃性会好,润湿流平剂、消光剂用量较大,进一步保证膜的厚度均匀度及干爽度。
实施例4
原料按重量配比:
(1)预聚反应:将异佛尔酮二异氰酸酯40份、氢化MDI 35 份、分子量为3000的环氧乙烷和四氢呋喃共聚醚多元醇55份、分子量为200的聚已内酯多元醇15份、分子量为1500的阻燃聚酯多元醇50份、分子量为500的环氧乙烷和四氢呋喃共聚醚多元醇 10份加入反应釜中,升温至88℃搅拌反应4小时;
(2)扩链反应:加入分子量为330的羟基磺酸盐12份,分子量为390的氨基磺酸盐3份,在89℃反应3.5小时;
(3)乳化反应:加入去离子水280份,快速分散,然后在60℃保温反应1小时;
(4)扩链反应:控温60℃,加入2,4-二乙基-1,5-戊二醇1份,1,4-二羟甲基环己烷4份,在60℃保温反应4小时;
(5)封闭反应:控温至45℃,加入分子量为1500的有机硅多元醇元醇50份,搅拌反应2.5小时,再降温29℃放料得乳液;
(6)取上述乳液100份、消泡剂0.2份、润湿剂流平剂0.15份、滑爽剂3份、增稠剂2份依次加入釜中混合搅拌均匀,然后加入消光剂2份、脱模剂2份、交联剂2.5份搅拌均匀制成膜胶,粘度为2500cps/25℃;
(7)在OPP上涂覆膜胶,90℃烘干2.5分钟,膜厚0.17mm,制得纺织品用水性透湿阻燃聚氨酯膜制品。
该实施例产品由于原料组份氢化MDI用量较大,弹性、刚性好,断裂强力增大;采用分子量为3000的环氧乙烷和四氢呋喃共聚醚多元醇分子量较大,且共聚醚中环氧乙烷比例较大,因此透湿性好,且乳液粒子更细,稳定性更佳。
实施例5
原料按重量配比:
(1)预聚反应:将异佛尔酮二异氰酸酯48份、氢化MDI 30 份、分子量为2500的环氧乙烷和四氢呋喃共聚醚多元醇60份、分子量为230的聚已内酯多元醇9份、分子量为2000的阻燃聚酯多元醇70份、分子量为600的环氧乙烷和四氢呋喃共聚醚多元醇 15份加入反应釜中,升温至89℃搅拌反应3.5小时;
(2)扩链反应:加入分子量为330的羟基磺酸盐12份,分子量为550的氨基磺酸盐6份,在85℃反应4小时;
(3)乳化反应:加入去离子水300份,快速分散,然后在50℃保温反应1.5小时;
(4)扩链反应:控温55℃,加入2,4-二乙基-1,5-戊二醇3份,1,4-二羟甲基环己烷3份,三乙烯二胺3份,在55℃保温反应3.5小时;
(5)封闭反应:控温至44℃,加入分子量为2000的有机硅多元醇50份,搅拌反应2.5小时,再降温31℃放料得乳液;
(6)取上述乳液100份乳液加入消泡剂0.13份、润湿剂流平剂0.15份、滑爽剂1.5份、增稠剂1.3份依次加入釜中混合搅拌均匀,然后加入消光剂2.5份、脱模剂2.3份、交联剂2.5份搅拌均匀制成膜胶,粘度为2400cps/25℃;
(7)在OPP上涂覆膜胶,100℃烘干2.5分钟,膜厚0.16mm,制得纺织品用水性透湿阻燃聚氨酯膜制品。
该实施例产品由于原料阻燃聚酯多元醇和有机硅多元醇用量较大,阻燃产生协同,阻燃效果更好,手感软,耐寒性更好;环氧乙烷和四氢呋喃共聚醚多元醇选用2官能2500分子量和和三官能600分子量,小分子量协同大分子量搭配使用,合理配比保证透湿实现。
实施例6
原料按重量配比:
(1)预聚反应:将异佛尔酮二异氰酸酯40份、氢化MDI 55 份、分子量为3000的环氧乙烷和四氢呋喃共聚醚多元醇75份、分子量为300的聚已内酯多元醇10份、分子量为1500的阻燃聚酯多元醇50份、分子量为600的环氧乙烷和四氢呋喃共聚醚多元醇 13份加入反应釜中,升温至90℃搅拌反应3.5小时;
(2)扩链反应:加入分子量为490的羟基磺酸盐6份,分子量为550的氨基磺酸盐12份,在90℃反应4小时;
(3)乳化反应:加入去离子水306份,快速分散,然后在58℃保温反应1.5小时;
(4)扩链反应:控温40℃,加入乙二胺4份,异氟尔酮二胺4份,三乙烯二胺3份,在40℃保温反应3小时;
(5)封闭反应:控温至41℃,加入分子量为2000的有机硅多元醇40份,搅拌反应2.5小时,再降温34℃放料得乳液;
(6)100份乳液加入消泡剂0.18份、润湿剂流平剂0.2份、滑爽剂3.5份、增稠剂2.3份依次加入釜中混合搅拌均匀,然后加入消光剂2.5份、脱模剂1.9份、交联剂4份搅拌均匀制成膜胶,粘度为2450cps/25℃;
(7)在离型纸上涂覆膜胶,90℃烘干3分钟,膜厚0.15mm,制得纺织品用水性透湿阻燃聚氨酯膜制品。
该实施例产品由于原料组份选用乙二胺、异佛尔酮二胺、三乙烯二胺扩链,弹性、刚性好,断裂强力增大;采用分子量为3000的环氧乙烷和四氢呋喃共聚醚多元醇,分子量较大,且占比较大,共聚醚中环氧乙烷比例较大,因此透湿性好,且乳液粒子更细,稳定性更佳。
上述实施例:
所述的消泡剂:为上海桑井化工有限公司产品EASYTECH DF-106;
所述的润湿流平剂:为空气化工产品有限公司产品104E;
所述的滑爽剂:为陶氏化学公司产品3289;
所述的增稠剂:为辽宁恒星精细化工有限公司产品FS-165;
所述的消光剂:为赢创特种化学有限公司产品OK-412;
所述的脱模剂:为辽宁恒星精细化工有限公司产品 8502A;
所述的交联剂:为辽宁恒星精细化工有限公司产品DF-819B。
试验检测1
对比例:选用PTFE膜、TPU膜进行检测对比。
表1.水性防水透湿阻燃聚氨酯膜、PTFE、TPU对比检测结果
Figure DEST_PATH_IMAGE002
透湿性测试:按照GB/T 12704.2-2009 纺织品 织物透湿性试验方法第2部分:蒸发法 进行测试;
断裂强力及断裂伸长率测试:按照GB/T 3923.1-2013 纺织品 织物拉伸性能 第1部分断裂强力和断裂伸长率的测定(条样法) 进行测试;
阻燃性测试:按照GB/T 5455-2014 纺织品 燃烧性能 垂直方向 损毁长度阴燃和续燃时间的测定 进行测试;
静水压测试:按照GB/T 4744-2013 纺织品 防水性能的检测和评价 静水压法 进行测试;
耐寒性测试:按照FZ/T 01143-2018 涂层织物 低温耐折性能试验方法 进行测试;
水洗测试:按照GB/T 8629-2001 纺织品 实验用家庭洗涤和干燥程序 进行测试。
从以上测试结果可以看出,本发明产品耐水压、透湿、阻燃、耐寒性、耐水洗性好,性能明显优于其它膜产品。

Claims (3)

1.一种纺织品用水性透湿、阻燃聚氨酯膜制备方法,其特征是:
原料按重量配比:
(1)预聚反应:将异佛尔酮二异氰酸酯30-48份、氢化MDI 25-55 份、分子量为1000-3000的环氧乙烷和四氢呋喃共聚醚多元醇50-80份、分子量为100-500的聚已内酯多元醇5-15份、分子量为1000-3000的阻燃聚酯多元醇30-70份、分子量为100-800的环氧乙烷和四氢呋喃共聚醚多元醇10-30份加入反应釜中,升温至85-90℃搅拌反应3.5-4小时;
(2)扩链反应:加入分子量为200-550的扩链剂10-20份,在85-90℃反应3-4小时;
(3)乳化反应:加入去离子水180-500份,快速分散,然后在50-70℃保温反应1-1.5小时;
(4)扩链反应:控温40-60℃加入小分子扩链剂6-15份,40-60℃保温反应3-4小时;
(5)封闭反应:控温在40-45℃,加入分子量为1000-3000的有机硅多元醇30-50份,反应2-2.5小时,降温至20-35℃放料,得乳液;
(6)取上述乳液100份、消泡剂0.1-0.3份、润湿流平剂0.1-0.5份、滑爽剂1-5份、增稠剂1-3份依次加入釜中混合搅拌均匀,然后加入消光剂2-5份、脱模剂1-3份、交联剂1-5份搅拌均匀制成膜胶,粘度为2000-2500cps/25℃;
(7)在离型纸或OPP上涂覆膜胶,80-100℃烘干2-4分钟,膜厚0.15-0.18mm,制得纺织品用水性透湿阻燃聚氨酯膜制品;
扩链剂:为羟基磺酸盐和氨基磺酸盐其一或混合使用;
小分子扩链剂:为2,4-二乙基-1,5-戊二醇(DEPD)、1,4-二羟甲基环己烷(CHDM)、乙二胺、异佛尔酮二胺、三乙烯二胺其一或几种混合使用。
2.根据权利要求1所述的纺织品用水性防水透湿、阻燃聚氨酯膜制备方法,其特征是:
消泡剂:为有机硅类消泡剂;
润湿流平剂:为炔二醇类润湿流平剂;
滑爽剂:为改性有机硅类滑爽剂;
增稠剂:为改性丙烯酸酯类型增稠剂;
消光剂:为亲水硅蜡改性的二氧化硅消光粉;
脱模剂:为亲水聚醚改性有机硅类脱模剂;
交联剂:为封闭型异氰酸酯交联剂。
3.如权利要求1或2所述制备方法得到的纺织品用水性防水透湿、阻燃聚氨酯膜。
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CN113980610B (zh) * 2021-12-02 2023-03-03 东莞市墨田科技实业有限公司 一种诺美纸阻燃聚氨酯热压胶膜及其制备方法
CN114806143A (zh) * 2022-03-31 2022-07-29 广东盈通新材料有限公司 一种耐低温柔软pu阻隔膜及复合防水贴条

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Application publication date: 20200421