CN108570281B - 一种双组分改性水性聚氨酯阻燃涂层胶及其制备方法 - Google Patents
一种双组分改性水性聚氨酯阻燃涂层胶及其制备方法 Download PDFInfo
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- CN108570281B CN108570281B CN201810258693.2A CN201810258693A CN108570281B CN 108570281 B CN108570281 B CN 108570281B CN 201810258693 A CN201810258693 A CN 201810258693A CN 108570281 B CN108570281 B CN 108570281B
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Classifications
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- D06N2203/068—Polyurethanes
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- D06N2209/06—Properties of the materials having thermal properties
- D06N2209/067—Flame resistant, fire resistant
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Abstract
本发明公开了一种双组分改性水性聚氨酯阻燃涂层胶的制备方法;该制备方法先使用含双羟基的季铵盐插层剂对蒙脱土进行接枝改性,使无机蒙脱土有机化;在反应设备中加入多异氰酸酯和低聚物多元醇反应,然后加入小分子扩链剂反应和改性蒙脱土进行改性;加丙酮降低黏度并再加入亲水性扩链剂反应得到改性聚氨酯预聚体;加水高速剪切分散得到改性水性聚氨酯分散体;向该分散体中加入增稠剂和固化剂,得到双组分改性水性聚氨酯阻燃涂层胶。本发明制得的高固含改性胶粘剂具有优异的阻燃性能、力学性能、热稳定性能、粘接性能、耐水性能、耐候性,制成的双组分改性水性聚氨酯阻燃胶以水作为溶剂,安全环保,性能优异,可用于阻燃纺织物领域。
Description
技术领域
本发明涉及一种水性聚氨酯阻燃涂层胶,特别是涉及一种双组分改性水性聚氨酯阻燃涂层胶及其制备方法;该聚氨酯阻燃涂层胶具有阻燃性好、耐高温、高粘接性能的特点。
背景技术
随着石油化工和纺织工业的迅猛发展,各种纤维应运而生,因纤维易着火,由纺织品引起的火灾近年来有上升趋势,其中以床上用品、装饰用织物和衣着用织物为起火的主要原因。因此,国内外十分重视对纺织品阻燃的研究。
聚氨酯作为一种可常温固化的胶黏剂,以其优异的成型工艺性和良好的综合使用性能受到人们的普遍青睐。水性聚氨酯具有耐低温性能好、柔韧性好、不污染环境、节约环保等优点。
目前的水性聚氨酯胶黏剂普遍存在耐水、耐碱、耐温性不好,将其贴合衣物放在洗衣机用洗衣粉洗涤时容易造成发泡和脱落,而一些贴合强度好的胶一般是油性聚氨酯,不环保。
公开号为CN 10059796A的中国发明专利申请公开了一种采用NCO封闭二异氰酸酯-TMP体系,添加磷脂类阻燃剂的水性聚氨酯胶黏剂,虽然耐水性,耐化学性以及阻燃性都有所提高,但其力学性能较差,且在加工中磷脂类不可避免的会散发出难闻的气味,难以应用于高端材料中。
发明内容
本发明目的在于提供一种改性的双组分水性聚氨酯阻燃涂层胶的制备方法,所得的双组分水性聚氨酯阻燃涂层胶的胶粘剂固含量高,乳液稳定性好,具有优异阻燃性、耐水性能和热稳定性。
本发明利用聚氨酯成膜能力强且能赋予织物弹性的性能,可使织物涂层阻燃整理后具有较好的耐搓揉性和手感,通过用带有羟基的插层剂改性蒙脱土,使改性蒙脱土分子链上有羟基,可以与聚氨酯分子链的NCO基团发生化学反应,形成网状结构,提高了蒙脱土在聚氨酯中的分散性,从而使阻燃剂能均匀分布且牢固粘附在织物表面。
无机纳米粒子改性有机聚合物既可以增强又可以增韧。无机纳米粒子不会产生大的伸长变形,在大的拉应力作用下,基体和填料会在纳米微粒的界面首先产生界面脱粘,形成空穴,聚合物分子链纤维化,其局部区域可产生屈服提前现象。应力集中产生屈服和界面脱粘都需要消耗更多的能量,这就是无机刚性粒子的增韧作用。而且将纳米材料应用于高分子材料改性中,得到无机/有机杂化材料,还会明显提高高分子材料的力学性能、热稳定性,并能赋予高分子材料一些特殊的性能,如阻燃性、耐高温性、耐水性、高阻隔性、高导电性、和优良的光学性能等,具有广阔的应用前景。
蒙脱土因层间有大量无机离子,对有机化合物呈疏性,利用蒙脱土晶层间金属离子的可交换性,以有机阳离子交换金属离子,使蒙脱土有机化,蒙脱土被有机阳离子处理后,与插层有机聚合物或有机小分子化合物有了良好的亲和性,这样有机化合物可以比较容易地插层到蒙脱土层间,这样的有机阳离子叫做插层剂。聚合物/蒙脱土纳米复合材料,由于具有纳米蒙脱土结构使得复合材料的力学性能,阻隔性能,热稳定性能以及阻燃性能等都有很大的提高,被很多专家认为是一类具有良好发展前景的新型阻燃材料。本发明通过用带有羟基的插层剂改性蒙脱土,使改性蒙脱土分子链上有羟基,可以与聚氨酯分子链的NCO基团发生化学反应,形成网状结构,一方面提高了蒙脱土在聚氨酯中的分散性,另一方面,蒙脱土属于黏土,一种含水层状硅酸盐,加入聚合物中,能提高聚合物的阻燃性能和力学性能,是一种很优异的成炭剂,因此可以提高材料阻燃性。
因此,本发明一方面采用磺酸盐型亲水性扩链剂取代原有的羧酸盐型扩链剂,提高水性聚氨酯的固含量和结晶性能,提高了水性聚氨酯胶粘剂的稳定性和粘接强度。另一方面采用含羟基的插层剂改性蒙脱土,再将带有羟基的改性蒙脱土引入到水性聚氨酯分子链中,使蒙脱土与聚氨酯分子链发生化学键合,提高了水性聚氨酯胶粘剂的热稳定性、力学性能、耐水和耐溶剂性能。层状硅酸盐增加了炭化层,而且蒙脱土片层中的结构性铁起着自由基捕捉剂的作用,一定程度的阻碍了有机聚合物基体的热降解,降低其热释放速率,从而达到阻燃作用。
为实现本发明目的,采取了如下技术方案:
一种双组分改性水性聚氨酯阻燃涂层胶的制备方法,包括以下步骤:
(1)改性蒙脱土的制备:将蒙脱土和无水乙醇混合,在室温下超声分散,加热至70~80℃,向反应体系中加入含羟基的季铵盐作为插层剂,搅拌反应6~8h后,冷却、离心,沉淀物用无水乙醇反复洗涤,真空干燥后得到改性蒙脱土;其中蒙脱土和含羟基的季铵盐的质量比为2:0.5~1;
(2)改性聚氨酯预聚体的合成:将真空脱水的低聚物多元醇、多异氰酸酯和催化剂混合,在60~80℃下反应2~3h,然后降低温度至50~60℃,滴加用溶剂稀释的多元醇小分子扩链剂,反应1~2h,升温至65~75℃后加入改性蒙脱土和N-甲基吡咯烷酮的混合溶液反应1~2h,得到蒙脱土改性的聚氨酯预聚体;其中多异氰酸酯、低聚物多元醇和多元醇小分子扩链剂的物质的量之比为10:3~6:1~2,多异氰酸酯和改性蒙脱土的质量比为10:1~2.5;
(3)改性水性聚氨酯分散体的制备:向步骤(2)得到的改性聚氨酯预聚体中加入溶剂降低乳液粘度,再加入磺酸盐型亲水性扩链剂反应,加水用高速分散机分散乳化,得到改性水性聚氨酯杂合分散体,所述的水的质量为该改性水性聚氨酯杂合分散体的固含量的40~50%,磺酸盐型亲水性扩链剂的质量为该改性水性聚氨酯分散体固含量的2.5~3.5%;
(4)双组分改性水性聚氨酯复合阻燃涂层胶的配胶:向步骤(3)得到的改性水性聚氨酯分散体中加入增稠剂和固化剂,混合均匀,得到双组分改性的水性聚氨酯阻燃涂层胶;所述的改性水性聚氨酯复合乳液、增稠剂和固化剂的质量比为100:0.1~0.5:0.1~1。
为进一步实现本发明目的,优选地,步骤(2)所述的含羟基的季铵盐为十二烷基双羟乙基甲基氯化铵、十六烷基二羟乙基溴化铵、二羟基丙基二甲基十二烷基氯化铵和甲基油脂基二(2-羟基)乙基季铵盐中的一种。
优选地,步骤(2)所述的多异氰酸酯为六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、1,4-环己烷二异氰酸酯或三甲基1,6-亚己基二异氰酸酯中的一种或多种。
优选地,步骤(2)所述的低聚物多元醇为相对分子量为1000~3000的聚酯多元醇或聚醚多元醇;所述聚醚多元醇为聚氧化丙烯二醇、聚氧化丙烯三醇、聚四氢呋喃二醇或四氢呋喃-氧化丙烯共聚二醇;所述聚酯多元醇是聚己二酸乙二醇酯二醇、聚己二酸一缩二乙二醇酯二醇、聚己二酸-1,4-丁二醇酯二醇、一缩二乙二醇酯二醇、聚碳酸酯二醇和聚己内酯二醇中的一种或多种混合物。
优选地,步骤(2)所述的多元醇小分子扩链剂为1,4-丁二醇、2,3-丁二醇、1,3-丙二醇和1,6-己二醇中的一种或两种。
优选地,步骤(3)所述的亲水性扩链剂为乙二胺基乙磺酸钠、1,4-丁二醇-2-磺酸钠和1,2-二羟基-3-丙磺酸钠中的一种。
优选地,步骤(4)所述的增稠剂为聚丙烯酸类碱类增稠剂,包括型号为WZA-120或WZA-121的增稠剂;多异氰酸酯固化剂包括型号为PUDS80、PUDS81或PUDS82的多异氰酸酯固化剂。
优选地,步骤(2)和步骤(3)所述的溶剂为乙酸乙酯、乙酸丁酯、二氯甲烷、丙酮、甲苯、邻苯二甲酸二丁酯、N,N-二甲基甲酰胺和邻苯二甲酸二丁酯中的一种。
优选地,步骤(1)所述在室温下超声分散的时间为0.5~1h;步骤(1)所述蒙脱土和无水乙醇的质量比是1:10~15;
步骤(2)所述的滴加的时间为15~30min;步骤(2)所述的多元醇小分子扩链剂的相对分子质量为60~150;步骤(2)所述的改性蒙脱土和N-甲基吡咯烷酮的质量比为1:5~10;
步骤(3)所述的改性聚氨酯预聚体中加入溶剂降低乳液粘度至50~150mPa·s;步骤(3)所述的加入磺酸盐型亲水性扩链剂反应的时间为10~20min;步骤(3)所述的加水用高速分散机分散乳化是加水用高速分散机以4000~6000rpm/min的转速分散乳化15~30min。
一种双组分改性水性聚氨酯阻燃涂层胶,由上述制备方法制得,以质量百分比计,该阻燃涂层胶固含量为40-50%,乳液储存时间为6个月以上,能均匀地涂覆在织物表面,形成涂层,涂覆后织物的防水等级达到5级,续燃时间降低至0.3s,损毁长度减少至35nm,抗静水压达到8.46kPa,断裂强力达到1340N,抗扭曲弯挠为0级。
相对于现有技术,本发明具有如下优点:
1)采用含有羟基的季铵盐插层剂对蒙脱土进行改性,使改性后的蒙脱土的有机化程度增加,提高了蒙脱土与聚合物之间的相容性,同时,改性蒙脱土片层表面接枝的有机分子链含有双羟基,可与聚氨酯分子链上的端-NCO基发生反应,从而以化学键的形式将蒙脱土引入到聚氨酯分子链中,进一步增强蒙脱土与聚氨酯的相容性。
2)采用“分子复合技术”将含有双羟基的改性蒙脱土通过化学键的形式引入到聚氨酯分子链中,形成交联网络结构,提高了聚氨酯胶粘剂的热稳定性、力学性能和耐水解性能。
3)采用含磺酸基的扩链剂作为亲水性扩链剂,由于其离子化强度高,它的引入会使分子内的库仑力和氢键作用增强,从而提高软硬段的相分离程度;同时在乳胶粒间形成较强的静电斥力,提高乳液的稳定性。用含磺酸盐型亲水性扩链剂所制备的水性聚氨酯胶粘剂储存稳定性好,粘接强度高。
4)本发明方法不用外加中和剂中和,操作方便、工艺简单、生产周期短,环保节能且易于推广和应用。
5)蒙脱土作为一种含水层状硅酸盐,加入聚氨酯胶粘剂中,能提高聚氨酯的阻燃性能和力学性能。是一种很优异的成炭剂,可以提高材料阻燃性。
具体实施方式
为更好理解本发明,下面结合实施例对本发明进一步地说明,但本发明要求保护的范围并不局限于实施例表示的范围。
实施例中有关测试说明如下:
阻燃涂层涂布:将适量的水性聚氨酯阻燃胶均匀的涂布在涤纶牛津帐篷布上(600D×600D,300g/m2),烘焙干燥后,裁剪为25cm×25cm的样片,检测涂覆水性聚氨酯阻燃胶后样片水洗前后的防水性、阻燃性、静水压、抗扭曲弯挠性等性能。
防水性:按GB/T 4745-1997eqv ISO 4920:1981(纺织织物表面抗湿性测定沾水试验)方法测试;
阻燃性能:按GB/T 5455-1997eqv ISO 6941:1992(纺织品燃烧性能垂直方向试样火焰蔓延性能的测定)方法测试:
断裂强力和断裂伸长率:按GB/T 392.1-1997(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件)方法测试;
抗扭曲弯挠性:按FZ/T 01052-1998(涂层织物抗扭曲弯挠性能的测定)方法测试。评定分5级:0级为无折痕,1级为有折痕、小裂纹、浅脱色,2级为深脱色、有龟裂,但没有到中间层;3级为有起壳或龟裂、穿达底布;4级为有剥落、完全穿达底布;
静水压:按GB/T 4744-1997eqv ISO 811:1981(纺织织物抗渗水性测定静水压试验)方法测试;
耐水洗性:洗涤条件为:织物25cm×25cm,洗涤剂JFC 2g/L,浴比1:30,温度45℃,时间10min,烘干(60℃)重复5次。
实施例1
取10g蒙脱土和120mL质量分数为50%乙醇的水溶液混合,在室温下超声分散0.5h后,加热至75℃,向反应体系中加入4g十二烷基双羟乙基甲基氯化铵,反应6h后,进行冷却、离心沉淀,用无水乙醇进行反复洗涤,真空干燥后得到改性蒙脱土。
将50gHDI、371g分子量为3000的聚丁二烯二醇在75℃下反应2.5h,然后降低温度至55℃,将3.2g的1,4-丁二醇用50g丙酮溶解滴加20min,再继续反应1.5h,然后再升温到70℃后加入6g改性蒙脱土和60mL的N-甲基吡咯烷酮的混合溶液反应1.5h,得到聚氨酯预聚体。
将550g丙酮加入到改性聚氨酯预聚体中,降低乳液粘度呈滴状,再加入22.5g质量分数为50%的乙二胺基乙磺酸钠反应15min,加500g水用高速分散机以4000rpm/min的转速分散乳化20min,得到改性水性聚氨酯杂合分散体。
取100g上述制得的改性水性聚氨酯复合乳液,加入0.2g增稠剂WZA-120和0.5g固化剂剂PUDS80,混合均匀,得到双组分改性的水性聚氨酯胶粘剂。
如表1所示,本实施例将改性蒙脱土引入到改性水性聚氨酯胶粘剂中,加入增稠剂和固化剂混合均匀后,得到双组分改性水性聚氨酯阻燃胶。本实施例制备的产品涂覆在帐篷布上之后,帐篷布的防水性能、阻燃性能、耐静水压、抗扭曲弯挠性能都达到了较高的要求,且各项指标耐水洗性较好,织物经阻燃涂层整理后其强力略有提高。
表1
实施例2
取10g蒙脱土和120mL质量分数为50%乙醇的水溶液混合,在室温下超声分散1h后,加热至70℃,向反应体系中加入3g十六烷基二羟乙基溴化铵,反应8h后,进行冷却、离心沉淀,用无水乙醇进行反复洗涤,真空干燥后得到改性蒙脱土;
将50gIPDI、225g分子量为2000的聚己内酯二醇在80℃下反应3h,然后降低温度至50℃,将4g2,3-丁二醇用60g丙酮溶解滴加30min,再继续反应2h,然后再升温到75℃后加入9g改性蒙脱土和80mL的N-甲基吡咯烷酮的混合溶液反应1.5h,得到聚氨酯预聚体;
将350g丙酮加入到改性聚氨酯预聚体中降低乳液粘度呈滴状,再加入16.2g质量分数为50%的1,4-丁二醇-2-磺酸钠反应15min,加300g水用高速分散机以5000rpm/min的转速分散乳化15min,得到改性水性聚氨酯杂合分散体;
取100g上述制得的改性水性聚氨酯复合乳液,加入0.5g增稠剂WZA-121和0.8g固化剂剂PUDS81,混合均匀,得到双组分改性的水性聚氨酯胶粘剂。
表2
如表2所示,本实施例将改性蒙脱土的添加量加大,将制得的聚氨酯胶粘剂涂覆在帐蓬布上之后,帐篷布的防水性能、阻燃性能、耐静水压、抗扭曲弯挠性能都有所提高,且各项指标耐水洗性好,织物经阻燃涂层整理后其强力略有提高。
实施例3
取20g蒙脱土和120mL质量分数为50%乙醇的水溶液混合,在室温下超声分散0.5h后,加热至80℃,向反应体系中加入5g二羟基丙基二甲基十二烷基氯化铵,反应7h后,进行冷却、离心沉淀,用无水乙醇进行反复洗涤,真空干燥后得到改性蒙脱土;
将50g1,4-环己烷二异氰酸酯、540g分子量为3000的聚己二酸-1,4-丁二醇酯二醇在75℃下反应2h,然后降低温度至60℃,将4.1g1,3-丙二醇用60g丙酮溶解滴加15min,再继续反应1.5h,然后再升温到65℃后加入12g改性蒙脱土和100mL的N-甲基吡咯烷酮的混合溶液反应2h,得到改性聚氨酯预聚体;
将800g丙酮加入到改性聚氨酯预聚体中降低乳液粘度呈滴状,再加入36.2g质量分数为50%的乙二胺基乙磺酸钠反应25min,加850g水用高速分散机以6000rpm/min的转速分散乳化30min,得到改性水性聚氨酯杂合分散体;
取100g上述制得的改性水性聚氨酯复合乳液,加入0.1g增稠剂WZA-120和0.9g固化剂剂PUDS82,混合均匀,得到双组分改性的水性聚氨酯胶粘剂。
表3
实施例4
取20g蒙脱土和120mL质量分数为50%乙醇的水溶液混合,在室温下超声分散1h后,加热至75℃,向反应体系中加入4.5g甲基油脂基二(2-羟基)乙基季铵盐,反应7.5h后,进行冷却、离心沉淀,用无水乙醇进行反复洗涤,真空干燥后得到改性蒙脱土;
将35gHDI和15IPDI、180g分子量为2000的聚氧化丙烯二醇在70℃下反应2.5h,然后降低温度至55℃,将3.5g1,6-己二醇用55g丙酮溶解滴加20min,再继续反应2h,然后再升温到75℃后加入改性蒙脱土和70mL的N-甲基吡咯烷酮的混合溶液反应1h,得到改性聚氨酯预聚体;
将300g丙酮加入到改性聚氨酯预聚体中降低乳液粘度,再加入16.4g质量分数为50%的1,2-二羟基-3-丙磺酸钠反应10min,加250g水用高速分散机以5000rpm/min的转速分散乳化18min,得到改性水性聚氨酯杂合分散体;
取100g上述制得的改性水性聚氨酯复合乳液,加入0.3g增稠剂WZA-121和0.6g固化剂剂PUDS80,混合均匀,得到双组分改性的水性聚氨酯胶粘剂。
表4
对比例5
为对比市面上的阻燃胶与所制备的改性蒙脱土水性聚氨酯阻燃胶的优缺点,从北京洁儿爽高科技有限公司购得阻燃胶SCJ-969,从力合粉体科技有限公司购得纤维阻燃胶,与实施例1-4所得的样品相对比,所得各项性能见表5。同样的,将相同质量的阻燃胶均匀的涂布在涤纶牛津帐篷布上(600D×600D,300g/m2),烘焙干燥后,裁剪为25cm×25cm的样片,检测涂覆阻燃胶后样片防水性、阻燃性、静水压、抗扭曲弯挠性等性能。
通过对比实施例2和实施例3可知,将改性蒙脱土在水性聚氨酯胶黏剂中的添加量加大,所制得的聚氨酯胶粘剂涂覆在帐蓬布上之后,帐篷布的防水性能、阻燃性能、耐静水压、抗扭曲弯挠性较实施例2并没与太大的改变,而实施例4继续增大水性聚氨酯中改性蒙脱土的含量,将所制备的水性聚氨酯乳液涂覆到帐篷布上,帐篷布的防水性能、阻燃性能、耐静水压、抗扭曲弯挠性均有所下降,原因是,纳米无机材料添加量的增多,导致所得水性聚氨酯乳液的稳定性变差,涂覆在帐篷布后易出现分层和无机材料析出,水洗后,帐篷布表面的涂层易脱落,导致各项性能都有所下降。
表5
通过表5可以看到,按照实例3的步骤所得样品各项性能都优于其他实施例。市面上买来的两种阻燃胶的防水等级和阻燃效果较好,但是其耐静水压、抗扭曲弯挠性和断裂强力等性能稍显不足,这说明将改性蒙脱土掺杂在水性聚氨酯胶黏剂中所得的阻燃胶不仅有更好阻燃性,也有优良的机械性能和力学性能。
本发明采用含有羟基的季铵盐插层剂对蒙脱土进行改性,使改性后的蒙脱土的有机化程度增加,提高了蒙脱土与聚合物之间的相容性,同时,改性蒙脱土片层表面接枝的有机分子链含有双羟基,可与聚氨酯分子链上的端-NCO基发生反应,从而以化学键的形式将蒙脱土引入到聚氨酯分子链中,进一步增强蒙脱土与聚氨酯的相容性。
采用含磺酸基的扩链剂作为亲水性扩链剂,由于其离子化强度高,它的引入会使分子内的库仑力和氢键作用增强,从而提高软硬段的相分离程度;同时在乳胶粒间形成较强的静电斥力,提高乳液的稳定性。用含磺酸盐型亲水性扩链剂所制备的水性聚氨酯胶粘剂储存稳定性好,粘接强度高。采用“分子复合技术”将含有双羟基的改性蒙脱土通过化学键的形式引入到聚氨酯分子链中,形成交联网络结构,提高了聚氨酯胶粘剂的力学性能和抗扭曲弯挠性能。
蒙脱土作为一种含水层状硅酸盐,加入聚氨酯胶粘剂中,是一种很优异的成炭剂,可以提高材料阻燃性能提高聚氨酯的阻燃性能。
Claims (9)
1.一种双组分改性水性聚氨酯阻燃涂层胶的制备方法,其特征在于由以下步骤组成:
(1)改性蒙脱土的制备:将蒙脱土和无水乙醇混合,在室温下超声分散,加热至70~80℃,向反应体系中加入含羟基的季铵盐作为插层剂,搅拌反应6~8h后,冷却、离心,沉淀物用无水乙醇反复洗涤,真空干燥后得到改性蒙脱土;其中蒙脱土和含羟基的季铵盐的质量比为2:0.5~1;所述含羟基的季铵盐为十二烷基双羟乙基甲基氯化铵、十六烷基二羟乙基溴化铵、二羟基丙基二甲基十二烷基氯化铵和甲基油脂基二(2-羟基)乙基季铵盐中的一种;
(2)改性聚氨酯预聚体的合成:将真空脱水的低聚物多元醇、多异氰酸酯和催化剂混合,在60~80℃下反应2~3h,然后降低温度至50~60℃,滴加用溶剂稀释的多元醇小分子扩链剂,反应1~2h,升温至65~75℃后加入改性蒙脱土和N-甲基吡咯烷酮的混合溶液反应1~2h,得到蒙脱土改性的聚氨酯预聚体;其中多异氰酸酯、低聚物多元醇和多元醇小分子扩链剂的物质的量之比为10:3~6:1~2,多异氰酸酯和改性蒙脱土的质量比为10:1~2.5;
(3)改性水性聚氨酯分散体的制备:向步骤(2)得到的改性聚氨酯预聚体中加入溶剂降低乳液粘度,再加入磺酸盐型亲水性扩链剂反应,加水用高速分散机分散乳化,得到改性水性聚氨酯杂合分散体,所述的水的质量为该改性水性聚氨酯杂合分散体的固含量的40~50%,磺酸盐型亲水性扩链剂的质量为该改性水性聚氨酯分散体固含量的2.5~3.5%;
(4)双组分改性水性聚氨酯复合阻燃涂层胶的配胶:向步骤(3)得到的改性水性聚氨酯分散体中加入增稠剂和固化剂,混合均匀,得到双组分改性的水性聚氨酯阻燃涂层胶;所述的改性水性聚氨酯复合乳液、增稠剂和固化剂的质量比为100:0.1~0.5:0.1~1。
2.根据权利要求1所述的制备方法,其特征在于,步骤(2)所述的多异氰酸酯为六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、1,4-环己烷二异氰酸酯或三甲基1,6-亚己基二异氰酸酯中的一种或多种。
3.根据权利要求1所述的制备方法,其特征在于,步骤(2)所述的低聚物多元醇为相对分子量为1000~3000的聚酯多元醇或聚醚多元醇;所述聚醚多元醇为聚氧化丙烯二醇、聚氧化丙烯三醇、聚四氢呋喃二醇或四氢呋喃-氧化丙烯共聚二醇;所述聚酯多元醇是聚己二酸乙二醇酯二醇、聚己二酸一缩二乙二醇酯二醇、聚己二酸-1,4-丁二醇酯二醇、一缩二乙二醇酯二醇、聚碳酸酯二醇和聚己内酯二醇中的一种或多种混合物。
4.根据权利要求1所述的制备方法,其特征在于,步骤(2)所述的多元醇小分子扩链剂为1,4-丁二醇、2,3-丁二醇、1,3-丙二醇和1,6-己二醇中的一种或两种。
5.根据权利要求1所述的制备方法,其特征在于,步骤(3)所述的亲水性扩链剂为乙二胺基乙磺酸钠、1,4-丁二醇-2-磺酸钠和1,2-二羟基-3-丙磺酸钠中的一种。
6.根据权利要求1所述的制备方法,其特征在于,步骤(4)所述的增稠剂为聚丙烯酸类碱类增稠剂,包括型号为WZA-120或WZA-121的增稠剂;多异氰酸酯固化剂包括型号为PUDS80、PUDS81或PUDS82的多异氰酸酯固化剂。
7.根据权利要求1所述的制备方法,其特征在于,步骤(2)和步骤(3)所述的溶剂为乙酸乙酯、乙酸丁酯、二氯甲烷、丙酮、甲苯、邻苯二甲酸二丁酯、N,N-二甲基甲酰胺和邻苯二甲酸二丁酯中的一种。
8.根据权利要求1所述的制备方法,其特征在于,步骤(1)所述在室温下超声分散的时间为0.5~1h;步骤(1)所述蒙脱土和无水乙醇的质量比是1:10~15;
步骤(2)所述的滴加的时间为15~30min;步骤(2)所述的多元醇小分子扩链剂的相对分子质量为60~150;步骤(2)所述的改性蒙脱土和N-甲基吡咯烷酮的质量比为1:5~10;
步骤(3)所述的改性聚氨酯预聚体中加入溶剂降低乳液粘度至50~150mPa·s;步骤(3)所述的加入磺酸盐型亲水性扩链剂反应的时间为10~20min;步骤(3)所述的加水用高速分散机分散乳化是加水用高速分散机以4000~6000rpm/min的转速分散乳化15~30min。
9.一种双组分改性水性聚氨酯阻燃涂层胶,其特征在于,其由权利要求1-8任一项所述制备方法制得,以质量百分比计,该阻燃涂层胶固含量为40-50%,乳液储存时间为6个月以上,能均匀地涂覆在织物表面,形成涂层,涂覆后织物的防水等级达到5级,续燃时间降低至0.3s,损毁长度减少至35nm,抗静水压达到8.46kPa,断裂强力达到1340N,抗扭曲弯挠为0级。
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