CN110983784B - 一种改进的环保阻燃剂组合物及其制备方法 - Google Patents
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Abstract
本发明公开了一种改进的环保阻燃剂组合物及其制备方法。该环保阻燃剂组合物包括55‑70重量%磷系阻燃剂、0.5‑2重量%杂多酸、1‑5重量%端羟基超支化聚酰胺和25‑40重量%水,以所述环保阻燃剂组合物的总重量为基准。本发明的改进的环保阻燃剂组合物的阻燃性能好,耐水洗,经其整理后的棉织物甲醛含量低,更环保。
Description
技术领域
本发明涉及一种改进的环保阻燃剂组合物及其制备方法,特别是一种棉织物改进的环保阻燃剂组合物及其制备方法。
背景技术
随着纺织工业的发展,纺织品的品种和应用越来越广泛,从我们的日常生活扩展到交通运输、卫生、军事等领域,大部分纺织品本身不具备阻燃性而存在潜在的火灾危险,为了我们的生命和财产安全,阻燃纺织品显得尤为重要。生产阻燃纺织品一般有两种加工方法,一种是将阻燃剂混入纺丝原液中,直接制备阻燃纤维,这种加工方法只适用于合成纤维纺织品;另一种是阻燃后整理法,采用阻燃剂对织物进行阻燃整理,对于棉纤维等天然纤维纺织品,只能采用此种加工方法。
棉纺织品的耐久阻燃剂可分为卤系、磷系等。卤系阻燃剂在燃烧过程中会产生HCl、HBr等刺激性有毒气体,许多国家已禁止使用,逐渐被磷系阻燃剂取代,美国农业部南方地区研究所开发了以四羟甲基氯化磷为主的一系列棉耐久阻燃剂,后来英国Albright–wilson公司在此基础上开发了著名的Proban阻燃整理工艺;接着瑞士Ciba公司研制出了新型的耐久性阻燃剂Pyrovatex CP阻燃剂,学名为N–羟甲基–3–(二甲氧基磷羧基)丙酰胺(缩写为MDPPA),以上阻燃剂对棉纺织品耐久阻燃整理效果好,但因结构本身含有N-羟甲基或整理过程中加入缩醛类交联剂,使整理后棉纺织品上的甲醛含量严重超标,严重危害环境和身体健康,目前市场上销售和应用的棉用耐久阻燃剂仍以上述几种磷系阻燃剂为主。
因此,对上述磷系阻燃剂进行改进,开发一种改进的环保阻燃剂,使得阻燃效果更加优异,并减少甲醛等带来的健康和环境问题,具有非常重要的现实意义。
发明内容
本发明在于提供一种改进的环保阻燃剂组合物及其制备方法。与现已公开的棉用耐久阻燃剂及其制备方法相比,该发明独创性表现在如下几个方面:(1)本发明采用杂多酸,能够催化磷系阻燃剂与纤维素的羟基发生反应;(2)加入端羟基超支化聚酰胺,一方面吸收甲醛,另一方面与纤维素发生反应,提升耐久性,还一方面,它与磷系阻燃剂具有协同增效作用,大大提升阻燃性能。本发明制备的改进的环保阻燃剂组合物阻燃性能好,耐水洗,经其整理后的棉织物甲醛含量低,更环保。
在本发明的一个方面,本发明提供一种改进的环保阻燃剂组合物,它包括以下组分:
磷系阻燃剂 55-70重量%,
杂多酸 0.5-2重量%,
端羟基超支化聚酰胺 1-5重量%,
去离子水 25-40重量%,
以所述环保阻燃剂组合物的总重量为基准。
在本发明的另一个方面,本发明提供一种改进的环保阻燃剂组合物的制备方法,该方法包括以下几个步骤:
1)将水和磷系阻燃剂加入反应釜,室温搅拌20-30分钟;
2)加入杂多酸,室温搅拌10-20分钟;
3)加入端羟基超支化聚酰胺,室温搅拌10分钟,制得所述改进的环保阻燃剂组合物。
按本发明制备的改进的环保阻燃剂组合物阻燃性能好,耐水洗,经其整理后的棉织物甲醛含量低,更环保。
具体实施方式
在一个优选的实施方式中,本发明提供一种改进的环保阻燃剂组合物,它包括以下组分:
磷系阻燃剂 60-65重量%,
杂多酸 0.5-1.5重量%,
端羟基超支化聚酰胺 2-4.5重量%,
去离子水 30-35重量%,
以所述环保阻燃剂组合物的总重量为基准。
在一个优选的实施方式中,所述磷系阻燃剂包含N–羟甲基–3–(二甲氧基磷羧基)丙酰胺、四羟甲基氯化磷或其组合;
在一个优选的实施方式中,所述杂多酸是无机杂多酸,包含磷钨酸、硅钨酸或其组合;
在一个优选的实施方式中,所述端羟基超支化聚酰胺的重均分子量为1000-3000、羟基数为5-30/mol。
在一个优选的实施方式中,所述的水是本行业中常用的水,优选是去离子水。
在一个优选的实施方式中,本发明提供一种改进的环保阻燃剂组合物的制备方法,它包括以下几个步骤:
1)将去离子水、磷系阻燃剂加入反应釜,室温搅拌20-30分钟;
2)加入杂多酸,室温搅拌10-20分钟;
3)加入端羟基超支化聚酰胺,室温搅拌10分钟,制得所述改进的环保阻燃剂组合物。
在一个优选的实施方式中,所述的室温为15-30℃。
在一个优选的实施方式中,所述的搅拌在100-400转/分钟下进行,优选在150-250转/分钟下进行。
按本发明制备的改进的环保阻燃剂组合物的阻燃性能好,耐水洗,经其整理后的棉织物甲醛含量低,更环保。
实施例
下面结合具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解,在阅读了本发明讲授的内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。
各实施例中,所有原料、织物均为市售。
所制得产品在纺织品上的应用与性能测定:
1)在纺织品的应用工艺:
试样:棉府绸
配方:阻燃剂280g/L、350g/L
阻燃整理工艺:浸轧(轧余率72%)→烘干(120℃*120s)→焙烘(170℃*150s)→水洗→烘干
2)织物性能测定标准:
织物燃烧性能测试:参照《GB/T5455-1997纺织品燃烧性能试验垂直燃烧法》测定;
阻燃织物性能评价:参照《GB/T 17591-2006阻燃织物》标准评定,B1级阻燃标准为:续燃时间≤5s,阴燃时间≤5s,损毁长度≤150mm;
阻燃织物的洗涤方法:按照《GB/T 17595-1998织物燃烧试验前的家庭洗涤过程》标准洗涤;
阻燃织物的布面甲醛含量:按照《GB/T 2912.1-1998纺织品甲醛的测定第1部分:游离水解的甲醛(水萃取法)》测定。
实施例1
在装有搅拌器、温度计的四口烧瓶中加入去离子水26g、N–羟甲基–3–(二甲氧基磷羧基)丙酰胺52g(商品名为Pyrovatex CP,购自亨斯迈公司),以220转/分钟左右的转速室温搅拌20-30分钟,然后加入磷钨酸0.6g(购自湖北巨胜科技有限公司),以180转/分钟左右的转速在室温下继续搅拌10-20分钟,最后加入端羟基超支化聚酰胺HyPer HPN202 2.2g(购自武汉超支化树脂科技有限公司,重均分子量2700,羟基数12/mol),以180转/分钟左右的转速在室温下继续搅拌10分钟,得所述环保阻燃剂组合物1。应用效果见表1。
实施例2
在装有搅拌器、温度计的四口烧瓶中加入去离子水30g、四羟甲基氯化磷55g,以230转/分钟左右的转速室温搅拌20-30分钟,然后加入硅钨酸0.8g(购自天门恒昌化工有限公司),以160转/分钟左右的转速在室温下继续搅拌10-20分钟,最后加入端羟基超支化聚酰胺HyPer HPN202 3.0g(购自武汉超支化树脂科技有限公司,重均分子量2700,羟基数12/mol),以160转/分钟左右的转速在室温下继续搅拌10分钟,得所述环保阻燃剂组合物2。应用效果见表1。
实施例3
在装有搅拌器、温度计的四口烧瓶中加入去离子水26g、N–羟甲基–3–(二甲氧基磷羧基)丙酰胺35g(商品名为Pyrovatex CP,购自亨斯迈公司),四羟甲基氯化磷20g,以240转/分钟左右的转速室温搅拌20-30分钟,然后加入磷钨酸0.8g(购自湖北巨胜科技有限公司),以180转/分钟左右的转速在室温下继续搅拌10-20分钟,最后加入端羟基超支化聚酰胺HyPer HPN202 3.5g(购自武汉超支化树脂科技有限公司,重均分子量2700,羟基数12/mol),以180转/分钟左右的转速在室温下继续搅拌10分钟,得所述环保阻燃剂组合物3。应用效果见表1。
各实施例的应用效果如表1所示。
表1应用效果
由表1可以看出,阻燃剂用量350g/L时,经本发明制备的改进的环保阻燃剂组合物整理棉织物的阻燃效果明显优于四羟甲基氯化磷和Pyrovatex CP。降低本发明制备的改进的环保阻燃剂组合物的用量为280g/L时,其阻燃效果与四羟甲基氯化磷和Pyrovatex CP用量350g/L时相当,且本发明制备的改进的环保阻燃剂组合物整理棉织物布面甲醛含量低,经水洗12次后阻燃性能基本不下降。
Claims (7)
3.如权利要求1或2所述的环保阻燃剂组合物,其特征在于,所述磷系阻燃剂包含N–羟甲基–3–(二甲氧基磷羧基)丙酰胺、四羟甲基氯化磷或其组合。
4.如权利要求1或2所述的环保阻燃剂组合物,其特征在于,所述的水是去离子水。
5.如权利要求1或2所述的环保阻燃剂组合物的制备方法,其特征在于:它包括以下几个步骤:
1)将水、磷系阻燃剂加入反应釜,室温搅拌20-30分钟;
2)加入杂多酸,室温搅拌10-20分钟;
3)加入端羟基超支化聚酰胺,室温搅拌10分钟,制得所述改进的环保阻燃剂组合物。
6.如权利要求5所述的制备方法,其特征在于,所述的室温为15-30℃。
7.如权利要求5所述的制备方法,其特征在于,所述的搅拌在100-400转/分钟下进行。
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