CN111875774A - 一种织物用水性阻燃耐水压聚氨酯乳液制备方法 - Google Patents

一种织物用水性阻燃耐水压聚氨酯乳液制备方法 Download PDF

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CN111875774A
CN111875774A CN202010776268.XA CN202010776268A CN111875774A CN 111875774 A CN111875774 A CN 111875774A CN 202010776268 A CN202010776268 A CN 202010776268A CN 111875774 A CN111875774 A CN 111875774A
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CN111875774B (zh
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陈剑冰
唐丽
荣星
陈龙
李瑶
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Liaoning Fixed Star Fine Chemical Co ltd
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Abstract

本发明一种水性阻燃耐水压聚氨酯乳液制备方法，由异佛尔酮二异氰酸酯、氢化苯基甲烷二异氰酸酯、聚氧化丙烯三醇、三（一缩二丙二醇）亚磷酸酯、线性双羟烷基硅氧烷、氰尿酸三聚氰胺、二羟甲基丙酸、2‑甲基‑1,3‑丙二醇、三乙胺、水合肼、去离子水经预聚反应、中和反应、乳化反应、扩链反应制成。具有手感硬挺、干爽、高弹性、高牢度、耐寒、高耐水压、阻燃性好、并环保、生产成本低。

Description

一种织物用水性阻燃耐水压聚氨酯乳液制备方法
技术领域
本发明涉及一种织物用水性阻燃耐水压聚氨酯乳液制备方法，特别是一种涤纶牛津帐篷布织物涂层用，具有手感硬挺、干爽、高弹性、高牢度、耐寒、高耐水压、阻燃性好、并环保、生产成本低的水性聚氨酯乳液制备方法。
背景技术
市场上阻燃、耐水压涂层纺织品都是通过在耐水压涂层胶中加入大量添加型阻燃剂，如溴系阻燃剂、三氧化二锑、氯化石蜡等，虽然能够达到优异的阻燃性能，但是耐水压、耐寒性等其它特性会大幅下降，并且这类物质已经被欧盟列入限制物质。
专利CN110629561A公开了“一种织物涂层用无锑耐烧穿型水性阻燃胶的制备方法”，该发明是在水性树脂中通过后添加的方式加入添加型阻燃填料、添加型磷酸酯类阻燃剂等实现耐烧穿的阻燃性能。后添加阻燃剂与合成过程中接枝改性阻燃性相比，前者在高牢度这一特性上大大低于后者；而且，该发明体系中虽然不含有锑，但是含有溴这类禁用物质，依然不符合环保的特点。
专利CN101498105A公开了一种“纺织品用水性发泡阻燃涂层胶及其制备方法”，该发明是通过向水性聚氨酯乳液、水性聚丙烯酸酯乳液中添加溴系阻燃剂和磷系阻燃剂以及三氧化二锑等物质实现织物涂层的阻燃效果，该发明应用于家纺类织物的涂层具有阻燃性优异、手感柔软的特点。但是该发明由于通过加入添加型阻燃剂实现阻燃性，在牢度方面无法达到高牢度的特点，且该发明不仅使用了溴系阻燃剂，还在配方中加入了三氧化二锑，其含有一定的铅、镉等重金属物质，这些物质不利于人体健康。
目前，市场上具备耐水压功能水性聚氨酯乳液和水性阻燃聚氨酯乳液虽然存在技术公开，但是同时具有耐水压功能和阻燃功能且具备干爽、高弹性、高牢度、耐寒、环保特点的产品未见技术公开。
发明内容
本发明目的是提供一种织物用水性阻燃耐水压聚氨酯乳液制备方法，特别是用于涤纶牛津帐篷布涂层聚氨酯乳液，具有手感硬挺、干爽、高弹性、高牢度、耐寒、高耐水压、阻燃性好、并环保、生产成本低。
本发明一种水性阻燃耐水压聚氨酯乳液：
原料按重量配比
异佛尔酮二异氰酸酯（IPDI） 50-60
氢化苯基甲烷二异氰酸酯（H12MDI） 60-70
聚氧化丙烯三醇（分子量3000） 70-85
三（一缩二丙二醇）亚磷酸酯（分子量430） 30-40
线性双羟烷基硅氧烷（分子量1000） 15-30
氰尿酸三聚氰胺（MCA，分子量255） 4-6
二羟甲基丙酸 2-3
2-甲基-1,3-丙二醇 1-2
三乙胺 1.3-2.0
水合肼 7.5-10
去离子水 220-240
经预聚反应、中和反应、乳化反应、扩链反应制成；
产品化学指标如下：
外观：乳白色液体
离子性：阴
pH值：7±1
固含量：（50±1）%。
本发明一种水性阻燃耐水压聚氨酯乳液制备方法：
原料按重量配比：
（1）预聚反应：将分子量为3000的聚氧化丙烯三醇70-85、分子量为430的三（一缩二丙二醇）亚磷酸酯30-40、分子量为1000的线性双羟烷基硅氧烷15-30、异佛尔酮二异氰酸酯50-60、氢化苯基甲烷二异氰酸酯60-70加入反应釜中，升温至80-90℃，反应1-1.5小时，然后加入氰尿酸三聚氰胺4-6，保温80-90℃，反应1-1.5小时，然后加入2-甲基-1,3-丙二醇1-2、二羟甲基丙酸2-3反应1.5-2小时；
（2）中和反应：降温至45-55℃，加入三乙胺1.3-2.0，反应30-40分钟；
（3）乳化反应：加入去离子水220-240，搅拌10-20分钟至预聚体完全溶解；
（4）扩链反应：加入水合肼7.5-10，反应2-2.5小时，得水性阻燃耐水压聚氨酯乳液；
产品化学指标如下：
外观：乳白色液体
离子性：阴
pH值：7±1
固含量：（50±1）%。
本发明一种水性阻燃耐水压聚氨酯乳液制备方法生产工艺简单，成膜手感硬挺、干爽，具有高弹性、高牢度、高耐水压、阻燃、耐寒、环保、生产成本低的特点。
本发明可以复配消泡剂、增稠剂等助剂制成水性聚氨酯阻燃耐水压涂层胶，涂覆于涤纶牛津帐篷布织物表面，达到高牢度、高效阻燃性、高耐水压等特点。
本发明选用异佛尔酮二异氰酸酯具有环状结构，其环状结构上有侧甲基基团，具有位阻效应，可使分子间结合产生空隙，能够改善产品的成膜厚度以及蓬松感；且异佛尔酮二异氰酸酯具有顺式和反式不对称结构，此结构能够增加分子间斥力并形成空间位阻，使聚氨酯形成交联网状结构，赋予产品优良的弹性、干爽度及牢度。
本发明选用氢化苯基甲烷二异氰酸酯和异佛尔酮二异氰酸酯均具有环状结构，氢化苯基甲烷二异氰酸酯是直链环状结构，刚性较强，成膜强度较大；异佛尔酮二异氰酸酯的异氰酸酯基团是异构结构，可以自由旋转，能够增强产品柔韧性；所以氢化苯基甲烷二异氰酸酯与异佛尔酮二异氰酸酯搭配使用，能够降低聚氨酯乳液成膜刚性，提高柔润性，增加成膜后断裂伸长率，提高成膜弹性，使产品成膜后不易断裂。同时异佛尔酮二异氰酸酯的两个异构结构反应速度不同，保证了反应过程的稳定性，防止反应体系低温凝聚，使分子低温保持运动，增加成膜的柔顺性、降低产品刚性，使聚氨酯乳液能够达到良好的耐寒性、弹性，耐水、耐溶剂、耐磨性能，且有效改善聚氨酯乳液牢度。
本发明选用线性双羟烷基硅氧烷能够提供柔滑链段，其主链由硅氧键组成，键距长、键角和键能大，当温度降低至-136℃时还存在链段运动，故耐低温、耐寒性特好；由于线性双羟烷基硅氧烷主链上无不饱和键，而Si-O-Si键对氧、臭氧及紫外线等十分稳定，因而具有良好的耐候性；线性双羟烷基硅氧烷中羟基以σ键与主链上的硅原子相连，增加了自由旋转的空间体积，羟基的氢原子和水氢原子相互排斥，使水分子难以与亲水的氧结合，能够赋予产品成膜后优异的疏水性，提高耐水洗牢度。
本发明选用三（一缩二丙二醇）亚磷酸酯为无卤结构的主链接枝磷的聚酯三醇，较高的含磷量能够有效改善聚氨酯膜的阻燃性；且其结构中含有端羟基，能与异佛尔酮二异氰酸酯及氢化苯基甲烷二异氰酸酯发生交联反应，赋予聚氨酯优良的力学性能，使成膜具有优异的蓬厚度、弹性以及牢度。
本发明选用氰尿酸三聚氰胺（MCA）是由三聚氰胺和三聚氰酸在水中合成的盐，为环状结构，其结构上具有羰基，具有优良的力学性能、耐水解性及热稳定性，其在320℃依然保持稳定，所以能够赋予赋予聚氨酯乳液良好的阻燃性能；且氰尿酸三聚氰胺（MCA）含氮量高、容易吸水，因此可以在高温环境下脱水成碳，有利于在材料表面进行焦炭泡沫化过程，生成具有阻燃性能的焦炭保护层；且氰尿酸三聚氰胺（MCA）中活泼氨基可以与异氰酸酯反应提供N元素接枝到大分子结构中，可使涂层后织物燃烧过程中释放氮气，有效冲淡氧气和高分子化合物分解产生的可燃气的浓度，减缓燃烧速度进而提高涂层织物阻燃性。
本发明选用线性双羟烷基硅氧烷、三（一缩二丙二醇）亚磷酸酯以及氰尿酸三聚氰胺三者分别提供Si、P、N元素，三者通过氢化苯基甲烷二异氰酸酯和异佛尔酮二异氰酸酯相连，能够达到协同阻燃效果，既提高了聚氨酯成膜的阻燃性，又赋予了聚氨酯成膜的蓬厚度及弹性等特点。
本发明选用聚氧化丙烯三醇作为聚氨酯的软段，其具有偶碳结构，具有较低的玻璃化温度，使其在低温环境下，分子链能够自由旋转，从而使聚氨酯保持较好的柔软度；并且其主链含有三个活泼羟基，与异氰酸酯反应能够形成空间网状结构，使分子具有极高的内交联度，提高聚氨酯的成膜牢度及成膜连续性，赋予涂层织物较高的耐水压特性；其主链含有醚键，能为聚氨酯的制备提供优异的耐水解性。
本发明选用聚氧化丙烯三醇、三（一缩二丙二醇）亚磷酸酯、线性双羟烷基硅氧烷作为聚氨酯的软段，三者与氰尿酸三聚氰胺通过异佛尔酮二异氰酸酯和氢化苯基甲烷二异氰酸酯相连，三官能体系提高了分子内交联度及成膜刚性，Si、P、N元素的协同作用使聚氨酯乳液具有良好阻燃性及成膜柔软度，提高了聚氨酯分子间斥力，使其产生位阻效应，增加了分子的旋转空间且提高了分子的内交联度，使制得的水性聚氨酯乳液同时具有耐水压、阻燃性、蓬厚硬挺手感等多种特点。
本发明扩链剂选用2-甲基-1,3-丙二醇，侧链的甲基可增加水性聚氨酯分子间斥力，产生位阻效应，能够提高聚氨酯成膜耐水性及牢度；选用二羟甲基丙酸，其含有亲水基团羧基和两个伯羟基，能够有效改善聚氨酯亲水性能，降低乳化过程中预聚体的粘度，为制备高含量水性聚氨酯乳液提供反应环境；二羟甲基丙酸提供的阴离子亲水基团与2-甲基-1,3-丙二醇提供的非离子亲水基团协同扩链，能有效提高成膜连续性，进而提高聚氨酯乳液与基材的结合牢度。
本发明经过大量对比实验及重复性实验，将异氰酸酯基与羟基比例控制在2.0左右；若异氰酸酯基比例太大，由于它和小分子扩链剂组成聚氨酯硬段，比例太大会形成难以舒展的刚性键，虽然耐磨性、牢度增强，但是会导致手感变硬、成膜变脆、弹性下降，伸长率下降；若异氰酸酯基比例太小，大分子聚酯多元醇、聚醚多元醇等软段比例过大，会导致聚氨酯成膜牢度及成膜连续性降低，成膜干爽度下降，耐磨性等性能降低。
本发明具有生产工艺简单、生产成本低，制得的水性聚氨酯乳液环保、无污染。
具体实施方式
实施例1
原料按重量配比：
（1）预聚反应：将分子量为3000的聚氧化丙烯三醇80、分子量为430的三（一缩二丙二醇）亚磷酸酯35、分子量为1000的线性双羟烷基硅氧烷20、异佛尔酮二异氰酸酯55、氢化苯基甲烷二异氰酸酯65加入反应釜中，升温至80-90℃，反应1-1.5小时，然后加入氰尿酸三聚氰胺5，保持温度80-90℃，反应1-1.5小时，然后加入2-甲基-1,3-丙二醇1.5、二羟甲基丙酸2.5反应1.5-2小时；
（2）中和反应：降温至45-55℃，加入三乙胺1.7，反应30-40分钟；
（3）乳化反应：加入去离子水230，搅拌10-20分钟至预聚体完全溶解；
（4）扩链反应：加入水合肼8.8，反应2-2.5小时，得水性阻燃耐水压聚氨酯乳液。
该实施例原料组分线性双羟烷基硅氧烷、三（一缩二丙二醇）亚磷酸酯用量较大，产品成膜后牢度好、耐寒性好且阻燃性优。
实施例2
（1）预聚反应：将分子量为3000的聚氧化丙烯三醇85、分子量为430的三（一缩二丙二醇）亚磷酸酯40、分子量为1000的线性双羟烷基硅氧烷15、异佛尔酮二异氰酸酯60、氢化苯基甲烷二异氰酸酯70加入反应釜中，升温至80-90℃，反应1-1.5小时，然后加入氰尿酸三聚氰胺6，保持温度80-90℃，反应1-1.5小时，然后加入2-甲基-1,3-丙二醇1、二羟甲基丙酸3反应1.5-2小时；
（2）中和反应：降温至45-55℃，加入三乙胺2.0，反应30-40分钟；
（3）乳化反应：加入去离子水240，搅拌10-20分钟至预聚体完全溶解；
（4）扩链反应：加入水合肼9.6，反应2-2.5小时，得水性阻燃耐水压聚氨酯乳液。
该实施例原料组分聚氧化丙烯三醇和氢化苯基甲烷二异氰酸酯用量较大，阻燃协同作用更好，弹性、刚性更好。
实施例3
（1）预聚反应：将分子量为3000的聚氧化丙烯三醇70、分子量为430的三（一缩二丙二醇）亚磷酸酯40、分子量为1000的线性双羟烷基硅氧烷20、异佛尔酮二异氰酸酯60、氢化苯基甲烷二异氰酸酯65加入反应釜中，升温至80-90℃，反应1-1.5小时，然后加入氰尿酸三聚氰胺5，保持温度80-90℃，反应1-1.5小时，然后加入2-甲基-1,3-丙二醇2、二羟甲基丙酸2反应1.5-2小时；
（2）中和反应：降温至45-55℃，加入三乙胺1.3，反应30-40分钟；
（3）乳化反应：加入去离子水230，搅拌10-20分钟至预聚体完全溶解；
（4）扩链反应：加入水合肼9.1，反应2-2.5小时，得水性阻燃耐水压聚氨酯乳液。
该实施例原料组分扩链剂2-甲基1,3-丙二醇用量较大，产品耐水性更好；三（一缩二丙二醇）亚磷酸酯用量较大，因此产品中磷占比更大，制得的聚氨酯阻燃性更好。
实施例4
（1）预聚反应：将分子量为3000的聚氧化丙烯三醇75、分子量为430的三（一缩二丙二醇）亚磷酸酯30、分子量为1000的线性双羟烷基硅氧烷25、异佛尔酮二异氰酸酯55、氢化苯基甲烷二异氰酸酯65加入反应釜中，升温至80-90℃，反应1-1.5小时，然后加入氰尿酸三聚氰胺5，保持温度80-90℃，反应1-1.5小时，然后加入2-甲基-1,3-丙二醇1.5、二羟甲基丙酸2.5反应1.5-2小时；
（2）中和反应：降温至45-55℃，加入三乙胺1.7，反应30-40分钟；
（3）乳化反应：加入去离子水220，搅拌10-20分钟至预聚体完全溶解；
（4）扩链反应：加入水合肼7.9，反应2-2.5小时，得水性阻燃耐水压聚氨酯乳液。
该实施例原料组分异佛尔酮二异氰酸酯、氢化苯基甲烷二异氰酸酯与多元醇比例较小，产品分子量较大，产品弹性、手感更好。
实施例5
（1）预聚反应：将分子量为3000的聚氧化丙烯三醇80、分子量为430的三（一缩二丙二醇）亚磷酸酯30、分子量为1000的线性双羟烷基硅氧烷30、异佛尔酮二异氰酸酯50、氢化苯基甲烷二异氰酸酯65加入反应釜中，升温至80-90℃，反应1-1.5小时，然后加入氰尿酸三聚氰胺4，保持温度80-90℃，反应1-1.5小时，然后加入2-甲基-1,3-丙二醇1.5、二羟甲基丙酸3反应1.5-2小时；
（2）中和反应：降温至45-55℃，加入三乙胺2，反应30-40分钟；
（3）乳化反应：加入去离子水230，搅拌10-20分钟至预聚体完全溶解；
（4）扩链反应：加入水合肼8.4，反应2-2.5小时，得水性阻燃耐水压聚氨酯乳液。
该实施例原料组分聚氧化丙烯三醇用量较大，其分子量大且分子内交联度大，产品成膜牢度更好，耐水压性能更佳；线性双羟烷基硅氧烷用量较大，产品耐水洗性能更好，Si与P、N阻燃协同作用更佳。
上述实施例：
聚氧化丙烯三醇：选用上海高桥石化公司GMN-3050A，分子量为3000；
三（一缩二丙二醇）亚磷酸酯：选用青岛联美化工有限公司三（一缩二丙二醇）亚磷酸酯（P430），分子量为430；
试验例
涂层胶制备：取上述实施例1-5所得水性阻燃耐水压聚氨酯乳液100份，加入消泡剂0.2份（选用德国毕克化学产品BYK-024），增稠剂1-1.5份（选用万华化学集团股份有限公司产品Vesmody U705），制备成水性阻燃耐水压聚氨酯涂层胶，粘度4000-5000mPa·s。
对比例：浙江传化股份有限公司产品TF-687A（一种水性聚氨酯阻燃胶）。
将上述涂层胶分别对300D涤纶长丝牛津布、600D涤纶长丝牛津布进行刮涂，选用3.0mm厚度刮刀，刮一刀，160-175℃烘干1-2分钟。
性能测试指标如下：
具有手感硬挺、干爽、高弹性，高牢度、高耐寒性、高耐水压及阻燃性能优的技术特点。
Figure DEST_PATH_IMAGE002
Figure DEST_PATH_IMAGE004
测试标准：
阻燃性测试标准：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；
静水压测试标准：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；
耐寒性测试标准：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。
手感及表面膜感检测：通过手触摸测定。
通过以上检测结果可以看出，本发明一种织物用水性阻燃耐水压聚氨酯乳液具有手感硬挺、干爽、高弹性、高牢度、高耐水压、阻燃、耐寒的优点，与市场上现有阻燃涂层胶相比，各方面性能明显优于市场同类产品。

Claims (2)

1.发明一种水性阻燃耐水压聚氨酯乳液制备方法，其特征是：
原料按重量配比
（1）预聚反应：将分子量为3000的聚氧化丙烯三醇70-85、分子量为430的三（一缩二丙二醇）亚磷酸酯30-40、分子量为1000的线性双羟烷基硅氧烷15-30、异佛尔酮二异氰酸酯50-60、氢化苯基甲烷二异氰酸酯60-70加入反应釜中，升温至80-90℃，反应1-1.5小时，然后加入氰尿酸三聚氰胺4-6，保温80-90℃，反应1-1.5小时，然后加入2-甲基-1,3-丙二醇1-2、二羟甲基丙酸2-3反应1.5-2小时；
（2）中和反应：降温至45-55℃，加入三乙胺1.3-2.0，反应30-40分钟；
（3）乳化反应：加入去离子水220-240，搅拌10-20分钟至预聚体完全溶解；
（4）扩链反应：加入水合肼7.5-10，反应2-2.5小时，得水性阻燃耐水压聚氨酯乳液；
产品化学指标如下：
外观：乳白色液体
离子性：阴
pH值：7±1
固含量：（50±1）%。
2.如权利要求1所述制备方法得到的水性阻燃耐水压聚氨酯乳液。
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