CN114085337B - 一种阻燃剂及其制备方法 - Google Patents
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Abstract
本发明提供一种阻燃剂及其制备方法。本发明的阻燃剂，通过包含8‑18质量份烯基磷酸酯、1‑10质量份乙烯基硅油、1‑8质量份烯基磺酸盐、1‑10质量份烯基羧酸的单体经共聚反应而制得，其重均分子量为5000‑200000g/mol。按本发明制备的阻燃剂其阻燃性能好，耐水洗，经其整理后的织物不含甲醛，非常环保，且手感好。尤其在环保型棉用耐久阻燃剂领域有非常出色的表现。
Description
技术领域
本发明涉及功能助剂领域，尤其涉及环保型耐久阻燃剂及其制备方法。
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。经过阻燃整理的织物按是否耐水洗可以分为暂时性阻燃织物和耐久阻燃织物，前者在水洗后会失去阻燃性能，应用受限；耐久阻燃织物能够在30-50次及以上水洗后，仍然具有优异的阻燃性能，应用范围更广。
例如用于棉纺织品的阻燃后整理法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–(二甲氧基磷酰基)丙酰胺(缩写为MDPPA)，以上阻燃剂对棉等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，使整理后棉等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等纺织品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，开发一种不含甲醛、安全环保的棉等纺织品用耐久阻燃剂，具有非常重要的现实意义。
发明内容
本发明的目的在于提供一种不含甲醛、安全环保的棉等纺织品用耐久阻燃剂。
根据本发明的一个方面，提供一种阻燃剂，通过包含8-18质量份烯基磷酸酯、1-10质量份乙烯基硅油、1-8质量份烯基磺酸盐、1-10质量份烯基羧酸的单体经共聚反应而制得，其重均分子量为5000-200000g/mol。
根据本发明的另一方面，提供阻燃剂的制备方法，包括如下步骤：
a)将烯基磷酸酯、烯基磺酸盐、乙烯基硅油、烯基羧酸和乳化剂投入反应釜，搅拌乳化；
b)进行乳液聚合。
本发明的技术方案的独创性表现在如下几个方面：
(1)本发明采用烯基磷酸酯，能有效地提升阻燃效果；
(2)加入烯基磺酸盐，进一步提升了阻燃性能；
(3)加入乙烯基硅油，与烯基磷酸酯、烯基磺酸盐具有协同增效的作用，使阻燃性能非常优异，并且能够改善整理织物的手感，提升整理织物的综合服用性能；
(4)烯基羧酸单体参与聚合，在分子中引入羧酸基团，尤其在处理棉等织物时，与织物分子中的羟基等基团发生反应，使阻燃剂和织物发生共价键结合，使得耐水洗性好；
(5)不同于常规棉等织物用耐久阻燃剂含甲醛或释放甲醛，本发明不含甲醛、不释放甲醛。
按本发明制备的阻燃剂其阻燃性能好，耐水洗，经其整理后的织物不含甲醛，非常环保，且手感好。尤其在环保型棉用耐久阻燃剂领域有非常出色的表现。
具体实施方式
在一个优选的实施方式中，本发明提供一种阻燃剂，通过包含8-18质量份烯基磷酸酯、1-8质量份乙烯基硅油、1-10质量份烯基磺酸盐、1-10质量份烯基羧酸的单体经共聚反应而制得，其重均分子量为5000-200000g/mol。
优选地，通过包含10-14质量份烯基磷酸酯、2-6质量份乙烯基硅油、3-9质量份烯基磺酸盐、5-8质量份烯基羧酸的单体经共聚反应而制得，其重均分子量更优选为10000-100000g/mol。
所述的烯基磷酸酯是2-甲基-2-丙烯酸-2-羟乙基酯磷酸酯、2-羟乙基甲基丙烯酸酯磷酸酯、乙烯基磷酸酯、乙烯基磷酸二甲酯、乙烯基膦酸二乙酯或其混合物。本发明中，通过采用烯基磷酸酯，能有效地提升阻燃效果。
所述的烯基磺酸盐是甲基丙烯磺酸钠、烯丙基磺酸钠或其组合物。本发明中，通过加入烯基磺酸盐，可以进一步提升阻燃性能。
所述的乙烯基硅油是单乙烯基封端，且粘度为100-1500cst、乙烯基含量为0.1-0.4mol％的单端乙烯基硅油。本发明中，通过加入乙烯基硅油，与烯基磷酸酯、烯基磺酸盐具有协同增效的作用，使阻燃性能非常优异，并且能够改善整理织物的手感，提升整理织物的综合服用性能。
所述的烯基羧酸是十二烯基丁二酸、巴豆酸、肉桂酸或其组合物。烯基羧酸单体通过参与聚合，在分子中引入羧酸基团，尤其在处理棉等织物时，与织物分子中的羟基等基团发生反应，使阻燃剂和织物发生共价键结合，使得耐水洗性好。
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的制备方法，包括如下步骤：
a)将烯基磷酸酯、烯基磺酸盐、乙烯基硅油、烯基羧酸和乳化剂投入反应釜，搅拌乳化；
b)进行乳液聚合。
在a)步骤中，例如在50-60℃搅拌乳化30-60分钟；
在b)步骤中，例如在60-80℃加入自由基引发剂进行乳液聚合。
所述的乳化剂是脂肪醇聚氧乙烯醚，例如可以采用异构十醇聚氧乙烯醚、异构十三醇聚氧乙烯醚等异构醇聚氧乙烯醚。
所述的自由基引发剂是过硫酸盐，例如可以采用过硫酸铵。
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。
所制得产品性能及其在纺织品上的应用与性能测定：
1)重均分子量测定：
采用HLC-8320GPC型凝胶渗透色谱仪(日本东曹株式会社)测定，25℃时流动相为DMF，以聚甲基丙烯酸甲酯(PMMA)作为参比。
2)在纺织品的应用工艺：
试样：棉府绸
配方：阻燃剂350g/L；次亚磷酸钠30g/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
3)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。检出限为20mg/kg，低于检出限的结果报告为“未检出”；
手感：由经过训练的五人分别对织物进行评价，取平均值：1-5分，1分最差，5分最好。
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53g、2-甲基-2-丙烯酸-2-羟乙基酯磷酸酯(购自武汉拉那白医药化工有限公司)8g、乙烯基磷酸酯4g、甲基丙烯磺酸钠4g、单端乙烯基硅油SiVans MV 1000(粘度1000cst，乙烯基含量0.17mol％，购自矽万斯材料科技南通有限公司)5g、十二烯基丁二酸6g、异构十三醇聚氧乙烯醚(Lutensol TO-5，购自巴斯夫股份公司)3g、异构十三醇聚氧乙烯醚(Lutensol TO-7，购自巴斯夫股份公司)7g，55℃搅拌乳化30分钟，然后升温至75℃，滴加过硫酸铵水溶液(质量分数5％)10g，滴加结束后，80℃保温2小时，得所述环保型棉用耐久阻燃剂1，测得重均分子量为30000g/mol。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51g、2-羟乙基甲基丙烯酸酯磷酸酯(购自精德化学，牌号：PM1000)7g、乙烯基磷酸二甲酯2g、乙烯基膦酸二乙酯2g、甲基丙烯磺酸钠4g、烯丙基磺酸钠3g、单端乙烯基硅油SiVans MV 500(粘度500cst，乙烯基含量0.32mol％，购自矽万斯材料科技南通有限公司)4g、十二烯基丁二酸3g、巴豆酸3g、异构十三醇聚氧乙烯醚(Lutensol TO-5，购自巴斯夫股份公司)5g、异构十醇聚氧乙烯醚(Lutensol XL-50，购自巴斯夫股份公司)6g，55℃搅拌乳化30分钟，然后升温至75℃，滴加过硫酸铵水溶液(质量分数5％)10g，滴加结束后，80℃保温2小时，得所述环保型棉用耐久阻燃剂2，测得重均分子量为50000g/mol。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50g、2-羟乙基甲基丙烯酸酯磷酸酯(购自精德化学，牌号：PM1000)10g、乙烯基膦酸二乙酯3g、烯丙基磺酸钠8g、单端乙烯基硅油SiVans MV 500(粘度500cst，乙烯基含量0.32mol％，购自矽万斯材料科技南通有限公司)3g、十二烯基丁二酸3g、肉桂酸4g、异构十醇聚氧乙烯醚(Lutensol XL-70，购自巴斯夫股份公司)5g、异构十醇聚氧乙烯醚(Lutensol XP-50，购自巴斯夫股份公司)4g，55℃搅拌乳化30分钟，然后升温至75℃，滴加过硫酸铵水溶液(质量分数5％)10g，滴加结束后，80℃保温2小时，得所述环保型棉用耐久阻燃剂3，测得重均分子量为80000g/mol。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，经本发明制备的改进的环保阻燃剂整理棉织物的阻燃效果与四羟甲基氯化磷和Pyrovatex CP相当，不同于四羟甲基氯化磷和Pyrovatex CP，本发明制备的环保型棉用耐久阻燃剂整理棉织物未检出甲醛，且手感好。
产业上应用的可能性
根据本发明，可以容易地制备出不含甲醛且耐水洗的阻燃剂，尤其在环保型棉用耐久阻燃剂领域有非常重要的现实意义。
Claims (6)
1.一种阻燃剂，通过包含8-18质量份烯基磷酸酯、1-8质量份乙烯基硅油、1-10质量份烯基磺酸盐、1-10质量份烯基羧酸的单体经共聚反应而制得，其重均分子量为5000-200000g/mol，
所述的烯基磷酸酯是2-甲基-2-丙烯酸-2-羟乙基酯磷酸酯、乙烯基磷酸酯、乙烯基磷酸二甲酯、乙烯基膦酸二乙酯或其混合物，
所述的烯基磺酸盐是甲基丙烯磺酸钠、烯丙基磺酸钠或其组合物，
所述的乙烯基硅油是单乙烯基封端，且粘度为100-1500cst、乙烯基含量为0.1-0.4mol%的单端乙烯基硅油，
所述的烯基羧酸是十二烯基丁二酸、巴豆酸、肉桂酸或其组合物。
2.如权利要求1所述的阻燃剂，其特征在于，通过包含10-14质量份烯基磷酸酯、2-6质量份乙烯基硅油、3-9质量份烯基磺酸盐、5-8质量份烯基羧酸的单体经共聚反应而制得，其重均分子量为10000-100000 g/mol。
3.如权利要求1或2所述的阻燃剂的制备方法，包括如下步骤：
a) 将烯基磷酸酯、烯基磺酸盐、乙烯基硅油、烯基羧酸和乳化剂投入反应釜，搅拌乳化；
b) 进行乳液聚合。
4.如权利要求3所述的阻燃剂的制备方法，其特征在于，所述的乳化剂是脂肪醇聚氧乙烯醚。
5.如权利要求3所述的阻燃剂的制备方法，其特征在于，
a) 在50-60℃搅拌乳化30-60分钟；
b) 在60-80℃加入自由基引发剂进行乳液聚合。
6.如权利要求5所述的阻燃剂的制备方法，其特征在于，所述的自由基引发剂是过硫酸盐。
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