CN117364487A - 一种持久阻燃涂层涤/棉混纺织物的制备方法 - Google Patents
一种持久阻燃涂层涤/棉混纺织物的制备方法 Download PDFInfo
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Abstract
本发明涉及一种持久阻燃涂层涤/棉混纺织物的制备方法,将聚乙烯醇、N‑(膦酰基甲基)亚氨基二乙酸、羟甲基膦酸二乙酯、次亚磷酸钠和三乙醇胺溶于蒸馏水中配置阻燃整理液后,通过浸轧‑焙烘的方法对涤/棉混纺织物进行处理,制得持久阻燃涂层涤/棉混纺织物;N‑(膦酰基甲基)亚氨基二乙酸的摩尔量大于羟甲基膦酸二乙酯和三乙醇胺的摩尔量之和。本发明的制备方法中,N‑(膦酰基甲基)亚氨基二乙酸可与棉纤维的羟基、聚乙烯醇的羟基发生酯化反应,在涤/棉混纺织物和聚乙烯醇膜之间形成网络状共价键桥接;网络状共价键接枝使得聚乙烯醇膜在织物上的耐久性提高,聚乙烯醇与织物之间形成的作用也有助于提高阻燃剂在织物上的耐久性。
Description
技术领域
本发明属于阻燃织物技术领域,涉及一种持久阻燃涂层涤/棉混纺织物的制备方法。
背景技术
涤/棉混纺织物具有优良的性能,广泛应用于床上用品、窗帘等室内装饰用品,但由于涤/棉混纺织物存在“烛芯效应”,进行阻燃整理的难度远远大于纯棉和纯涤纶织物。开发高效耐久的阻燃涤/棉混纺织物仍存在较大挑战。
文献1(新型阻燃剂在涤棉混纺织物中的应用[J]. 染整技术,2021,43(10):25-28)采用涤纶用阻燃剂、棉用阻燃剂/交联剂体系对涤/棉混纺织物进行阻燃改性;其中,该技术方案中棉用阻燃剂与棉纤维产生交联,而涤纶用阻燃剂与涤纶织物通过相似相溶原理结合,因此改性涤/棉混纺织物可耐20次水洗,然而两种阻燃剂之间单独作用,阻燃效率低,且接枝程度有限,其耐水洗性能有待进一步提高。
文献2(基于磷酸酯的阻燃涤纶织物的研发[J]. 现代丝绸科学与技术,2020,35(3):4-6,40.)采用植酸和聚乙烯醇通过酯化反应合成直链型的磷酸酯阻燃剂(即植酸作为阻燃剂接枝在聚乙烯醇上),但是磷酸酯阻燃剂涂覆在织物表面上,其中的聚乙烯醇成膜,与织物物理黏附,耐水洗性能差,仍需进一步提高。
文献3(接枝改性聚乙烯醇的纯棉织物阻燃整理[J]. 印染,2001,27(6):27-28)通过酯交换反应将磷酸酯阻燃剂溴代磷酸酯酰氯接枝到聚乙烯醇上,然后对纯棉织物进行阻燃整理,提高了磷酸酯阻燃剂在棉织物的耐水洗性能,然而该技术方案合成工艺繁杂,阻燃剂仅靠聚乙烯醇在棉织物上的成膜性能吸附在织物表面,聚乙烯醇在洗涤液的作用下容易发生溶胀,从而从织物上脱落,导致耐水洗性能有限,仍需进一步提高。
中国发明专利CN115652642A公开了一种阻燃耐久涤/棉混纺织物的制备方法,将植酸和尿素合成的大分子磷/氮阻燃剂、氨水和双氰胺加入蒸馏水中配置阻燃整理液,然后将涤/棉混纺织物浸入阻燃整理液中,通过浸轧-烘-焙的方法对涤/棉混纺织物进行处理,大分子磷/氮阻燃剂自身具有成膜性能,且可与棉纤维形成共价键结合,因此改性织物具有一定的耐久性;然而,大分子磷/氮阻燃剂形成的膜稳定性差,对织物的黏附性差(除了共价键结合区点位,膜的其他区域与织物物理黏附),因此经过水洗后会慢慢水解重新溶于洗涤液中,导致阻燃性能下降,阻燃涤/棉混纺织物可耐20次水洗,但仍需进一步提高。
因此,研究一种持久阻燃涂层涤棉混纺织物的制备方法,以解决现有技术中涤棉混纺织物耐久性低的问题,具有十分重要的意义。
发明内容
本发明的目的是解决现有技术中存在的问题,提供一种持久阻燃涂层涤/棉混纺织物的制备方法。
为达到上述目的,本发明采用的技术方案如下:
一种持久阻燃涂层涤/棉混纺织物的制备方法,将聚乙烯醇、N-(膦酰基甲基)亚氨基二乙酸、羟甲基膦酸二乙酯、次亚磷酸钠和三乙醇胺溶于蒸馏水中(将蒸馏水加热至80~90℃后再加入上述试剂,有助于聚乙烯醇等试剂的溶解)配置阻燃整理液后,通过浸轧-焙烘的方法对涤/棉混纺织物进行处理,制得持久阻燃涂层涤/棉混纺织物;
N-(膦酰基甲基)亚氨基二乙酸的摩尔量大于羟甲基膦酸二乙酯和三乙醇胺的摩尔量之和;
N-(膦酰基甲基)亚氨基二乙酸含有两个羧基基团,可与棉纤维的羟基、聚乙烯醇的羟基以及羟甲基膦酸二乙酯和三乙醇胺的羟基发生酯化反应,从而将聚乙烯醇和含磷阻燃基接枝在涤/棉混纺织物上;理论上,羟甲基膦酸二乙酯和三乙醇胺均采用N-(膦酰基甲基)亚氨基二乙酸进行接枝,按照摩尔比1:1进行,同时N-(膦酰基甲基)亚氨基二乙酸也可以在聚乙烯醇和棉纤维之间充当交联剂,上述反应在催化剂存在和焙烘的条件下同时进行,因此保证N-(膦酰基甲基)亚氨基二乙酸的摩尔量大于羟甲基膦酸二乙酯和三乙醇胺的摩尔量之和,有助于促进N-(膦酰基甲基)亚氨基二乙酸与羟甲基膦酸二乙酯和三乙醇胺的反应,以及与聚乙烯醇和棉纤维之间的交联反应;
次亚磷酸钠可催化N-(膦酰基甲基)亚氨基二乙酸的羧基和羟基之间的酯化反应;三乙醇胺首先可作为富含羟基和氮元素组份,与含磷阻燃基团结合构建膨胀阻燃体系,提高阻燃效率;另外还可以作为碱剂改善改性涤/棉混纺织物的手感。
作为优选的技术方案:
如上所述的一种持久阻燃涂层涤/棉混纺织物的制备方法,涤/棉混纺织物为65/35、50/50或35/65的涤/棉混纺织物。
如上所述的一种持久阻燃涂层涤/棉混纺织物的制备方法,持久阻燃涂层涤/棉混纺织物的极限氧指数不低于30.5%,损毁长度不高于11.7cm,经45次水洗后的损毁长度不高于14.0cm(处理前的涤/棉混纺织物的损毁长度为30cm,极限氧指数为18.5%)。
如上所述的一种持久阻燃涂层涤/棉混纺织物的制备方法,阻燃整理液中,聚乙烯醇的含量为60~80g/L,N-(膦酰基甲基)亚氨基二乙酸的含量为150~200g/L,羟甲基膦酸二乙酯的含量为50~70g/L,次亚磷酸钠的含量为50~70g/L,三乙醇胺的含量为30~40g/L;
如上所述的一种持久阻燃涂层涤/棉混纺织物的制备方法,聚乙烯醇为1788型或1799型。
如上所述的一种持久阻燃涂层涤/棉混纺织物的制备方法,浸轧的轧余率为90~110%。
如上所述的一种持久阻燃涂层涤/棉混纺织物的制备方法,烘焙的工艺参数为:预烘温度75~85℃,预烘时间4~7min;焙烘温度140~150℃,焙烘时间3~5min;聚乙烯醇在焙烘条件下具有良好的成膜性,与涤/棉混纺织物的黏附性较高;另外聚乙烯醇直链上富含活性羟基,为阻燃剂的接枝和形成网络状交联提供基础,N-(膦酰基甲基)亚氨基二乙酸用量高,有利于形成共价键交联,但过高则浪费。
发明原理:
现有技术中,单独将阻燃剂接枝在涤/棉混纺织物表面,无法为阻燃涂层提供优异的阻燃耐久性,因为在水洗过程中阻燃剂与织物形成的酯键会逐渐水解,经水洗去除;聚乙烯醇可在涤/棉混纺织物表面成膜,对涤/棉混纺织物具有一定的黏附性;然而仅靠聚乙烯醇对织物的黏附性能对阻燃涂层的耐水洗性能提升程度有限;单独将阻燃剂接枝在聚乙烯醇膜上,聚乙烯醇膜与涤/棉混纺织物物理黏附,无法为阻燃涂层提供优异的阻燃耐久性,因为在水洗过程中阻燃剂与聚乙烯醇形成的酯键会逐渐水解,经水洗去除,且聚乙烯醇膜在水洗过程中会溶胀脱落,导致阻燃效果变差。
本发明中N-(膦酰基甲基)亚氨基二乙酸含有两个羧基基团,可与棉纤维的羟基、聚乙烯醇的羟基发生酯化反应,从而在涤/棉混纺织物和聚乙烯醇膜之间形成网络状共价键桥接;另外,羟甲基膦酸二乙酯、三乙醇胺的羟基也可以与N-(膦酰基甲基)亚氨基二乙酸的羧基产生酯化反应,因此,羟甲基膦酸二乙酯、三乙醇胺与N-(膦酰基甲基)亚氨基二乙酸产生酯键时,也会与聚乙烯醇产生酯化交联反应,从而将聚乙烯醇膜交联在织物表面,从而使得聚乙烯醇膜难以在水洗过程中脱落。此外,聚乙烯醇膜自身对织物具有较高的粘附性,并通过共价键接枝在织物表面,因此可以提高阻燃耐久性。另外,只有同时将与聚乙烯醇膜和棉纤维产生共价键结合阻燃剂的酯键水解,才能将阻燃剂溶于洗涤液中,失去阻燃效果。因此,本发明制得的一种持久阻燃涂层涤/棉混纺织物更加耐水洗。
此外,N-(膦酰基甲基)亚氨基二乙酸不仅可以作为网络交联剂,而且富含磷元素和氮元素,具有较高的阻燃效率;然而N-(膦酰基甲基)亚氨基二乙酸作为网络交联剂用量过高导致涂层涤/棉混纺织物手感较硬,阻燃性能仍需进一步提高,采用羟甲基膦酸二乙酯和三乙醇胺与N-(膦酰基甲基)亚氨基二乙酸结合,构建膨胀型阻燃体系,进一步提高阻燃效率和涂层耐久性。
有益效果:
(1)本发明一种持久阻燃涂层涤/棉混纺织物的制备方法,N-(膦酰基甲基)亚氨基二乙酸含有两个羧基基团,可与棉纤维的羟基、聚乙烯醇的羟基发生酯化反应,从而在涤/棉混纺织物和聚乙烯醇膜之间形成网络状共价键桥接;网络状共价键接枝使得聚乙烯醇膜在织物上的耐久性提高,聚乙烯醇与织物之间形成的作用也有助于提高阻燃剂在织物上的耐久性;
(2)本发明一种持久阻燃涂层涤/棉混纺织物的制备方法,采用羟甲基膦酸二乙酯和三乙醇胺与N-(膦酰基甲基)亚氨基二乙酸结合,构建膨胀型阻燃体系,进一步提高阻燃效率和涂层耐久性。
附图说明
图1为本发明聚乙烯醇阻燃涂层与涤/棉混纺织物的交联机理示意图;
图2为本发明实施例1的未涂层涤/棉混纺织物(即实施例中的涤/棉混纺织物)和涂层涤/棉混纺织物(即持久阻燃涂层涤/棉混纺织物)的表面形貌图;
图3为本发明实施例1的涤/棉混纺织物和阻燃涂层涤/棉混纺织物的红外光谱图。
具体实施方式
下面结合具体实施方式,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。
本发明涉及的测试方法如下:
极限氧指数:采用GB/T 5454-1997《纺织品 燃烧性能实验 氧指数法》测试持久阻燃涂层涤/棉混纺织物的极限氧指数;
损毁长度:采用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》测试持久阻燃涂层涤/棉混纺织物的损毁长度。
经50次水洗后的损毁长度:本发明中对持久阻燃涂层涤/棉混纺织物按照AATCC61-2013《家用和商用耐洗涤色牢度的加速试验》进行水洗,采用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》测试持久阻燃涂层涤/棉混纺织物的损毁长度。
实施例1
一种持久阻燃涂层涤/棉混纺织物的制备方法,如图1所示,具体步骤如下:
(1)将1788型聚乙烯醇、N-(膦酰基甲基)亚氨基二乙酸、羟甲基膦酸二乙酯、次亚磷酸钠和三乙醇胺溶于预先加热至80℃的蒸馏水中配置阻燃整理液;
阻燃整理液中,聚乙烯醇的含量为60g/L,N-(膦酰基甲基)亚氨基二乙酸的含量为150g/L,羟甲基膦酸二乙酯的含量为50g/L,次亚磷酸钠的含量为50g/L,三乙醇胺的含量为30g/L;
(2)通过浸轧-焙烘的方法对65/35的涤/棉混纺织物进行处理,制得持久阻燃涂层涤/棉混纺织物;
浸轧-烘焙的工艺参数为:轧余率90%;预烘温度75℃,预烘时间7min;焙烘温度140℃,焙烘时间5min。
最终制得的持久阻燃涂层涤/棉混纺织物的极限氧指数为30.5%,损毁长度为11.7cm,经45次水洗后的损毁长度为14cm。
如图2所示,未涂层涤/棉混纺织物表面较为光滑,而涂层涤/棉混纺织物表面沉积了大量的阻燃剂。
如图3所示,与未涂层涤/棉混纺织物相比,阻燃涂层涤/棉混纺织物的红外光谱中1208cm-1和1065cm-1处的吸收峰发生明显变化,这是由阻燃涂层中含磷基团P=O和P-O结构引起的;另外,经阻燃涂层后,涤/棉混纺织物红外光谱中1704cm-1处的吸收峰偏移至1720cm-1处,这是因为阻燃涂层中形成了新的羧酸酯结构,上述结果表明阻燃涂层成功地沉积在涤/棉混纺织物上。
对比例1
一种涂层涤/棉混纺织物的制备方法,基本同实施例1,不同之处仅在于用等体积的水替代次亚磷酸钠。
制得的涂层涤/棉混纺织物极限氧指数为30.1%,损毁长度为12.0cm,仅可耐10次水洗。
将实施例1和对比例1进行对比,可以发现对比例1可以发现对比例1的阻燃性能好,但其耐水洗性能较差,这是因为在该条件下,聚乙烯醇可以较好的成膜,但阻燃剂与聚乙烯醇、棉纤维无法发生共价键交联反应,而仅靠聚乙烯醇对织物的黏附性能对阻燃涂层的耐水洗性能提升程度有限。
对比例2
一种涂层涤/棉混纺织物的制备方法,基本同实施例1,不同之处仅在于步骤(1)中用等体积的水替代聚乙烯醇。
制得的涂层涤/棉混纺织物极限氧指数为30.7%,损毁长度为11.5cm,仅可耐10次水洗。
将实施例1和对比例2进行对比,可以发现对比例2的涂层涤/棉混纺织物的阻燃性能较好,但其耐水洗性能较差,这是因为单独将阻燃剂接枝在涤/棉混纺织物表面,无法为阻燃涂层提供优异的阻燃耐久性,另外涤/棉混纺织中棉纤维组分较少,可以产生接枝的阻燃剂量少,且在水洗过程中阻燃剂与织物形成的酯键会逐渐水解,经水洗去除。
实施例2
一种持久阻燃涂层涤/棉混纺织物的制备方法,具体步骤如下:
(1)将1788型聚乙烯醇、N-(膦酰基甲基)亚氨基二乙酸、羟甲基膦酸二乙酯、次亚磷酸钠和三乙醇胺溶于预先加热至82℃的蒸馏水中配置阻燃整理液;
阻燃整理液中,聚乙烯醇的含量为65g/L,N-(膦酰基甲基)亚氨基二乙酸的含量为160g/L,羟甲基膦酸二乙酯的含量为55g/L,次亚磷酸钠的含量为55g/L,三乙醇胺的含量为32g/L;
(2)通过浸轧-焙烘的方法对50/50的涤/棉混纺织物进行处理,制得持久阻燃涂层涤/棉混纺织物;
浸轧-烘焙的工艺参数为:轧余率95%;预烘温度77℃,预烘时间6.5min;焙烘温度142℃,焙烘时间4.5min。
最终制得的持久阻燃涂层涤/棉混纺织物的极限氧指数为31.2%,损毁长度为11.3cm,经45次水洗后的损毁长度为13.7cm。
实施例3
一种持久阻燃涂层涤/棉混纺织物的制备方法,具体步骤如下:
(1)将1788型聚乙烯醇、N-(膦酰基甲基)亚氨基二乙酸、羟甲基膦酸二乙酯、次亚磷酸钠和三乙醇胺溶于预先加热至84℃的蒸馏水中配置阻燃整理液;
阻燃整理液中,聚乙烯醇的含量为70g/L,N-(膦酰基甲基)亚氨基二乙酸的含量为170g/L,羟甲基膦酸二乙酯的含量为60g/L,次亚磷酸钠的含量为60g/L,三乙醇胺的含量为34g/L;
(2)通过浸轧-焙烘的方法对35/65的涤/棉混纺织物进行处理,制得持久阻燃涂层涤/棉混纺织物;
浸轧-烘焙的工艺参数为:轧余率100%;预烘温度79℃,预烘时间6min;焙烘温度144℃,焙烘时间4.2min。
最终制得的持久阻燃涂层涤/棉混纺织物的极限氧指数为31.8%,损毁长度为10.9cm,经45次水洗后的损毁长度为13.2cm。
实施例4
一种持久阻燃涂层涤/棉混纺织物的制备方法,具体步骤如下:
(1)将1799型聚乙烯醇、N-(膦酰基甲基)亚氨基二乙酸、羟甲基膦酸二乙酯、次亚磷酸钠和三乙醇胺溶于预先加热至86℃的蒸馏水中配置阻燃整理液;
阻燃整理液中,聚乙烯醇的含量为75g/L,N-(膦酰基甲基)亚氨基二乙酸的含量为180g/L,羟甲基膦酸二乙酯的含量为65g/L,次亚磷酸钠的含量为65g/L,三乙醇胺的含量为36g/L;
(2)通过浸轧-焙烘的方法对65/35的涤/棉混纺织物进行处理,制得持久阻燃涂层涤/棉混纺织物;
浸轧-烘焙的工艺参数为:轧余率105%;预烘温度81℃,预烘时间5.5min;焙烘温度146℃,焙烘时间4min。
最终制得的持久阻燃涂层涤/棉混纺织物的极限氧指数为32.1%,损毁长度为10.5cm,经45次水洗后的损毁长度为12.6cm。
实施例5
一种持久阻燃涂层涤/棉混纺织物的制备方法,具体步骤如下:
(1)将1799型聚乙烯醇、N-(膦酰基甲基)亚氨基二乙酸、羟甲基膦酸二乙酯、次亚磷酸钠和三乙醇胺溶于预先加热至88℃的蒸馏水中配置阻燃整理液;
阻燃整理液中,聚乙烯醇的含量为75g/L,N-(膦酰基甲基)亚氨基二乙酸的含量为190g/L,羟甲基膦酸二乙酯的含量为65g/L,次亚磷酸钠的含量为65g/L,三乙醇胺的含量为38g/L;
(2)通过浸轧-焙烘的方法对50/50的涤/棉混纺织物进行处理,制得持久阻燃涂层涤/棉混纺织物;
浸轧-烘焙的工艺参数为:轧余率108%;预烘温度83℃,预烘时间5min;焙烘温度148℃,焙烘时间3.5min。
最终制得的持久阻燃涂层涤/棉混纺织物的极限氧指数为32.3%,损毁长度为10.4cm,经45次水洗后的损毁长度为12.5cm。
实施例6
一种持久阻燃涂层涤/棉混纺织物的制备方法,具体步骤如下:
(1)将1799型聚乙烯醇、N-(膦酰基甲基)亚氨基二乙酸、羟甲基膦酸二乙酯、次亚磷酸钠和三乙醇胺溶于预先加热至90℃的蒸馏水中配置阻燃整理液;
阻燃整理液中,聚乙烯醇的含量为80g/L,N-(膦酰基甲基)亚氨基二乙酸的含量为200g/L,羟甲基膦酸二乙酯的含量为70g/L,次亚磷酸钠的含量为70g/L,三乙醇胺的含量为40g/L;
(2)通过浸轧-焙烘的方法对35/65的涤/棉混纺织物进行处理,制得持久阻燃涂层涤/棉混纺织物;
浸轧-烘焙的工艺参数为:轧余率110%;预烘温度85℃,预烘时间4min;焙烘温度150℃,焙烘时间3min。
最终制得的持久阻燃涂层涤/棉混纺织物的极限氧指数为32.5%,损毁长度为10.1cm,经45次水洗后的损毁长度为12.1cm。
Claims (7)
1.一种持久阻燃涂层涤/棉混纺织物的制备方法,其特征在于:将聚乙烯醇、N-(膦酰基甲基)亚氨基二乙酸、羟甲基膦酸二乙酯、次亚磷酸钠和三乙醇胺溶于蒸馏水中配置阻燃整理液后,通过浸轧-焙烘的方法对涤/棉混纺织物进行处理,制得持久阻燃涂层涤/棉混纺织物;
N-(膦酰基甲基)亚氨基二乙酸的摩尔量大于羟甲基膦酸二乙酯和三乙醇胺的摩尔量之和。
2.根据权利要求1所述的一种持久阻燃涂层涤/棉混纺织物的制备方法,其特征在于,涤/棉混纺织物为65/35、50/50或35/65的涤/棉混纺织物。
3.根据权利要求2所述的一种持久阻燃涂层涤/棉混纺织物的制备方法,其特征在于,持久阻燃涂层涤/棉混纺织物的极限氧指数不低于30.5%,损毁长度不高于11.7cm,经45次水洗后的损毁长度不高于14.0cm。
4.根据权利要求1所述的一种持久阻燃涂层涤/棉混纺织物的制备方法,其特征在于,阻燃整理液中,聚乙烯醇的含量为60~80g/L,N-(膦酰基甲基)亚氨基二乙酸的含量为150~200g/L,羟甲基膦酸二乙酯的含量为50~70g/L,次亚磷酸钠的含量为50~70g/L,三乙醇胺的含量为30~40g/L。
5.根据权利要求4所述的一种持久阻燃涂层涤/棉混纺织物的制备方法,其特征在于,聚乙烯醇为1788型或1799型。
6.根据权利要求1所述的一种持久阻燃涂层涤/棉混纺织物的制备方法,其特征在于,浸轧的轧余率为90~110%。
7.根据权利要求6所述的一种持久阻燃涂层涤/棉混纺织物的制备方法,其特征在于,烘焙的工艺参数为:预烘温度75~85℃,预烘时间4~7min;焙烘温度140~150℃,焙烘时间3~5min。
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