CN113308877B - 一种高性能的阻燃纤维的制备方法 - Google Patents
一种高性能的阻燃纤维的制备方法 Download PDFInfo
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Abstract
本发明涉及一种高性能的阻燃纤维的制备方法，包括将聚丙烯腈分散到水和乙醇的混合溶剂中得到溶胶，然后进行静电纺丝，低温下收集得到介孔纳米纤维，然后浸没于银掺杂的纳米二氧化钛水溶胶中进行改性处理，然后分散在乙醇和水的混合溶剂中加入硅酸乙酯、乙烯基三乙氧基硅烷和氨水进行反应，得到具有抗菌、环保和高阻燃性能的高性能的阻燃纤维材料。
Description
技术领域
本发明涉及隔热阻燃纤维的制备领域，具体涉及一种高性能的阻燃纤维的制备方法。
背景技术
阻燃纤维是制备具有阻燃效果纺织品的基础材料，常用的阻燃纺织品例如窗帘、床垫、汽车内饰等，家具以及汽车等领域，普遍存在由于高分子材料的应用，存在一定的甲醛，且长时间使用容易产生细菌，对材料的防火性能要求也更高；随着我国家具和汽车市场的迅速发展，安全、环保、卫生逐渐成为消费者考量的重要因素，因此研究出具有抗菌、环保以及高阻燃性能的纤维材料具有广大的应用市场。
现有技术中已经制备相关的纤维材料，很难同时满足高阻燃性、抗菌性以及环保性能，且即使存在相应的阻燃纤维，也存在相应性能不高的缺陷。
中国专利CN 110359106 A公开了一种高温隔热阻燃纤维，其采用聚酰胺酸盐水凝胶进行溶液纺丝，纺丝时进行定向冷冻，并收集冰冻纤维；冰冻纤维进行冷冻干燥去除冰晶，得到具有取向孔结构的多孔纤维，但是其孔径达到10-100μm，不能达到有效负载改性纳米材料的附着要求，而且由于孔径过大，孔径结构如果负载纳米材料负载量少，则不能有效负载（容易在使用过程中分离、脱落），附着量过大，则成本太高，因此需要保证纤维孔径结构与负载的纳米材料的粒径相匹配，而通常情况下，无机纳米材料粒径越小，其相应的催化性能和抗菌性能更好，因此上述技术方案得到多孔纤维无法有效对其改性处理，且得到纤维并非纳米纤维，不能满足高档纺织品的纺织要求。
中国专利为CN108977915A公开了一种阻燃型丙纶短纤维及其制备方法，介绍了一种阻燃型丙纶短纤维，由以下重量份组分制成，丙纶切片80～120份、聚丙烯腈基碳纤维40～60份、阻燃剂40～60份、分散剂20～40份、增塑剂10～20份和色母粒20～30份，该专利直接将纤维原料和其他改性组分机械混合，直接将原料机械混合很难保证组分充分均匀，不能达到很好的阻燃性能和抗菌性能。
中国专利CN108866668A公开了一种纳米阻燃材料，将丙烯单体、含乙烯基的硅烷偶联剂、乳化剂、引发剂、纳米氢氧化镁、多聚磷酸铵、纳米二氧化硅、溶剂，获得的纺丝溶液通过气体喷纺工艺制备得到，该工艺将改性组分与纤维原料组分直接混合喷纺得到，虽然阻燃性能好，力学性能强，但是其抗菌性差和环保性能不达标。
基于现有技术中公开的阻燃纤维存在的各种不足，我们公司历时3年研发了一种具有抗菌、高阻燃性能的纳米纤维材料，且具有十分好的环保效果。
发明内容
一种高性能的阻燃纤维的制备方法，包括如下步骤：
1）将一定去离子水和无水乙醇按照一定比例混合形成混合溶剂，其中去离子水和无水乙醇的体积比为1:9-15；
2）称取适量的聚丙烯腈溶于上述混合溶剂中，在50℃剧烈搅拌形成溶胶；
3）将上述溶胶通过静电纺丝机进行静电纺丝，调节静电纺丝机的纺丝电压为25-45 kV，使纺丝液喷射形成直径在100-500nm之间的纳米纤维，纳米纤维喷射到基材上，在基材形成冰冻的固纳米纤维；基材为圆形铜片，基材的接收距离为10-20cm；控制静电纺丝机中收集基材的温度为-50℃到-20℃，使溶胶体系中的水形成细微的冰晶，均匀分散在得到的固纳米纤维中；
4）将得到的冰冻的固纳米纤维置于真空低温下干燥，使冰晶气化，形成具有介孔结构的纳米多孔聚丙烯腈纤维；
5）制备银掺杂的二氧化钛纳米水溶胶：将钛酸四丁酯、冰醋酸和无水乙醇溶液混合形成溶液A；将表面活性剂、去离子水和无水乙醇形成溶液B，在搅拌条件下将溶液A滴加到溶液B中，搅拌1-2h后形成溶胶溶液；将一定量预先配制的摩尔浓度为0.1-0.2mol/L的硝酸银水溶液滴加到上述溶胶溶液中，再继续搅拌1-2h小时，得到银掺杂的二氧化钛纳米水溶胶；其中银掺杂的二氧化钛的粒径为10-20nm；
6）取一定量的步骤4）得到具有介孔结构的纳米多孔聚丙烯腈纤维分散到步骤5）获得的纳米银掺杂的二氧化钛纳米水溶胶，超声处理2-4小时，取出，真空干燥，得到负载银掺杂的纳米二氧化钛的纳米多孔聚丙烯腈纤维；
7）将负载银掺杂的纳米二氧化钛的纳米多孔聚丙烯腈纤维分散在水和乙醇的混合溶液中，加入硅酸乙酯、乙烯基三乙氧基硅烷和氨水，搅拌反应1-3h，过滤，干燥处理，得到高性能的阻燃纤维。
优选地，步骤5）的表面活性剂为甜菜碱型两性表面活性剂，加入量为银掺杂的二氧化钛纳米水溶胶质量的1-5%。
优选地，步骤3）中的真空低温干燥的真空度为1-50Pa、温度为-5到5℃。
优选地，步骤4）中所述的介孔结构的孔径为15-30nm。
优选地，步骤5）中的银掺杂的二氧化钛纳米水溶胶，银与二氧化钛的摩尔比为1-5:100.
优选地，步骤6）中真空干燥为60-80℃，干燥时间为12-24h。
优选地，步骤7）中，所述反应在25-45℃下进行.
优选地，步骤7）中，所述硅酸乙酯、所述乙烯基三乙氧基硅烷和所述氨水分别采用滴加的形式加入混合溶液。
优选地，步骤7）中，负载银掺杂的纳米二氧化钛的纳米多孔聚丙烯腈纤维、硅酸乙酯、乙烯基三乙氧基硅烷和氨水的质量比为1:0.5-0.8:1-1.1:1。
本发明的有益效果：
1、本发明利用乙醇低温不易凝固，而水在低温下容易凝固结冰的特性，且乙醇和水互溶的特性，通过控制水和乙醇的比例，保证配制的聚丙烯腈溶胶中，溶剂组分乙醇含量高，而水的含量低，从而使少量的水分分散在聚丙烯腈溶胶，在静电纺丝过程中，由于超低温环境，使少量的水分迅速形成细微的冰晶分散在得到冰冻聚丙烯腈纤维中，而大量的乙醇的挥发除去，再在真空低温下干燥，使细小的冰晶直接气化，在聚丙烯腈纤维中形成孔径为15-30nm的介孔，且孔径可以通过控制乙醇和水的比例进行控制，从而使纳米聚丙烯腈纤维有效负载常用的改性无机材料材料；
2、本发明制备银掺杂二氧化钛的纳米水溶胶，通过控制原料的浓度、搅拌速率和表面活性剂的加入量可以有效控制二氧化钛的粒径，将具有介孔结构的纳米多孔聚丙烯腈纤维浸没在银掺杂二氧化钛的纳米水溶胶，搅拌、取出、干燥使银掺杂的二氧化钛纳米颗粒有效负载在介孔结构中，利用银的杀菌性能和纳米二氧化钛的光催化性能，从而使得材料的具有杀菌性能和光催化降解甲醛的作用，能够满足家具、汽车内饰的环保和卫生需求；
3、本发明利用负载银掺杂的纳米二氧化钛的纳米多孔聚丙烯腈纤维分散在水和乙醇的混合溶液中，加入硅酸乙酯、乙烯基三乙氧基硅烷和氨水中，反应可以在纤维表面包覆一层薄薄的二氧化硅结构，一方面使得进一步固化负载的银掺杂二氧化钛纳米颗粒；另一方面，可以提高纤维的阻燃性能；另外，由于加入乙烯基三乙氧基硅烷，在纤维材料表面具有乙烯基，使得纤维材料能在后续应用中与其他树脂类材料结合过程，乙烯基与参与其他不饱和树脂的交联网络中，使得制备的纺织品机械性能更强；
4、本发明中在制备银掺杂二氧化钛的纳米水溶胶时，选择表面活性剂为甜菜碱型两性表面活性剂不仅可以起到在纳米二氧化钛溶胶过程中调理二氧化钛粒径的作用，更重要是甜菜碱型两性表面活性剂是由季铵盐型盐离子部分和羧酸型阴离子部分构成，其存在的氨基团在纤维中可以与聚丙烯腈纤维表面的不饱和键结合，另一方面，其存在在羧基可以起到羧化纤维的作用，使纤维表面存在羧基，可以与二氧化硅包覆层结合，提高二氧化硅包覆层的附着力更强。
具体实施方式
实施例1：
包括如下步骤：
1）将一定去离子水和无水乙醇按照一定比例混合形成混合溶剂，其中去离子水和无水乙醇的体积比为1:9-15；
2）称取适量的聚丙烯腈溶于上述混合溶剂中，在50℃剧烈搅拌形成溶胶；
3）将上述溶胶通过静电纺丝机进行静电纺丝，调节静电纺丝机的纺丝电压为25-45 kV，使纺丝液喷射形成直径在100-500nm之间的纳米纤维，纳米纤维喷射到基材上，在基材形成冰冻的固纳米纤维；基材为圆形铜片，基材的接收距离为10-20cm；控制静电纺丝机中收集基材的温度为-50℃到-20℃，使溶胶体系中的水形成细微的冰晶，均匀分散在得到的固纳米纤维中；
4）将得到的冰冻的固纳米纤维置于真空低温下干燥，使冰晶气化，形成具有介孔结构的纳米多孔聚丙烯腈纤维；
5）制备银掺杂的二氧化钛纳米水溶胶：将钛酸四丁酯、冰醋酸和无水乙醇溶液混合形成溶液A；将甜菜碱型两性表面活性剂、去离子水和无水乙醇形成溶液B，在搅拌条件下将溶液A滴加到溶液B中，搅拌1-2h后形成溶胶溶液；将一定量预先配制的摩尔浓度为0.1-0.2mol/L的硝酸银水溶液滴加到上述溶胶溶液中，再继续搅拌1-2h小时，得到银掺杂的二氧化钛纳米水溶胶；其中银掺杂的二氧化钛的粒径为10-20nm；
6）取一定量的步骤4）得到具有介孔结构的纳米多孔聚丙烯腈纤维分散到步骤5）获得的纳米银掺杂的二氧化钛纳米水溶胶，超声处理2-4小时，取出，真空干燥，得到负载银掺杂的纳米二氧化钛的纳米多孔聚丙烯腈纤维；
7）将负载银掺杂的纳米二氧化钛的纳米多孔聚丙烯腈纤维分散在水和乙醇的混合溶液中，加入硅酸乙酯、乙烯基三乙氧基硅烷和氨水，搅拌反应1-3h，过滤，干燥处理，得到高性能的阻燃纤维。
对比例1：
与实施例1不同的是，加入的表面活性剂为十六烷基三甲基溴化铵或十二烷基硫酸钠。
对比例2：
与实施例1不同的是步骤1）的溶剂全部为水。
对比例3：
与实施例1不同的是，没有进行步骤5）和步骤6）处理。
对比例4：
与实施例1不同的是，没有进行步骤7）处理。
性能测试实验：
1、分别将实施例1和对比例1-4的纤维材料在进行机械摩擦处理，即将得到纤维材料平铺在钢板，再钢板上再加盖另一块钢板，施加40MPa的压力并进行相反方向运动，进行高压摩擦1h，过10000目筛。
2、分别将实施例1和对比例1-4的纤维材料进行采用具有代表性的抗菌性能测试方法GB15979-2002标准测试。
3、光催化降解甲醛测试
分别将称取相同量的实施例1和对比例1-4的纤维材料置于5个不同的容器中，向容器中插入甲醛浓度气敏传感器的传感棒，然后通入相同量的甲醛气体，保证五个不同容器中甲醛浓度为0.06mg/m3，在可见光照射下24h。
4、阻燃性能测试
分别将实施例1和对比例1-4的纤维材料置于空气条件下进行着火温度点测试检测结果分析如表1所示：
上述实施例只为说明本发明的技术构思及特点，并非对本发明作任何形式上的限制，虽然本发明已以较佳实施例揭露如上，然而并非用以限定本发明，凡根据本发明精神实质所作的等效变化，都应涵盖在本发明的保护范围之内。
Claims (8)
1.一种高性能的阻燃纤维的制备方法，包括如下步骤：
1）将一定去离子水和无水乙醇按照一定比例混合形成混合溶剂，其中去离子水和无水乙醇的体积比为1: 9-15；
2）称取适量的聚丙烯腈溶于上述混合溶剂中，在50℃剧烈搅拌形成溶胶；
3）将上述溶胶通过静电纺丝机进行静电纺丝，调节静电纺丝机的纺丝电压为25-45kV，使纺丝液喷射形成直径在100-500nm之间的纳米纤维，纳米纤维喷射到基材上，在基材形成冰冻的固纳米纤维；基材为圆形铜片，基材的接收距离为10-20cm；控制静电纺丝机中收集基材的温度为-50℃到-20℃，使溶胶体系中的水形成细微的冰晶，均匀分散在得到的固纳米纤维中；
4）将得到的冰冻的固纳米纤维置于真空低温下干燥，使冰晶气化，形成具有介孔结构的纳米多孔聚丙烯腈纤维；
5）制备银掺杂的二氧化钛纳米水溶胶：将钛酸四丁酯、冰醋酸和无水乙醇溶液混合形成溶液A；将表面活性剂、去离子水和无水乙醇形成溶液B，在搅拌条件下将溶液A滴加到溶液B中，搅拌1-2h后形成溶胶溶液；将一定量预先配制的摩尔浓度为0.1-0.2mol/L的硝酸银水溶液滴加到上述溶胶溶液中，再继续搅拌1-2h小时，得到银掺杂的二氧化钛纳米水溶胶；其中银掺杂的二氧化钛的粒径为10-20nm；
6）取一定量的步骤4）得到具有介孔结构的纳米多孔聚丙烯腈纤维分散到步骤5）获得的纳米银掺杂的二氧化钛纳米水溶胶，超声处理2-4小时，取出，真空干燥，得到负载银掺杂的纳米二氧化钛的纳米多孔聚丙烯腈纤维；
7）将负载银掺杂的纳米二氧化钛的纳米多孔聚丙烯腈纤维分散在水和乙醇的混合溶液中，加入硅酸乙酯、乙烯基三乙氧基硅烷和氨水，搅拌反应1-3h，过滤，干燥处理，得到高性能的阻燃纤维；
所述步骤5）的表面活性剂为甜菜碱型两性表面活性剂，加入量为银掺杂的二氧化钛纳米水溶胶质量的1-5%。
2.根据权利要求1所述的一种高性能的阻燃纤维的制备方法，步骤4）中的真空低温干燥的真空度为1-50Pa、温度为-5到5℃。
3.根据权利要求1所述的一种高性能的阻燃纤维的制备方法，步骤4）中所述的介孔结构的孔径为15-30nm。
4.根据权利要求1所述的一种高性能的阻燃纤维的制备方法，步骤5）中的银掺杂的二氧化钛纳米水溶胶，银与二氧化钛的摩尔比为1-5:100。
5.根据权利要求1所述的一种高性能的阻燃纤维的制备方法，步骤6）中真空干燥为60-80℃，干燥时间为12-24h。
6.根据权利要求1所述的一种高性能的阻燃纤维的制备方法，步骤7）中，所述反应在25-45℃下进行。
7.根据权利要求1所述的一种高性能的阻燃纤维的制备方法，步骤7）中，所述硅酸乙酯、所述乙烯基三乙氧基硅烷和所述氨水分别采用滴加的形式加入混合溶液。
8.根据权利要求1所述的一种高性能的阻燃纤维的制备方法，步骤7）中，负载银掺杂的纳米二氧化钛的纳米多孔聚丙烯腈纤维、硅酸乙酯、乙烯基三乙氧基硅烷和氨水的质量比为1:0.5-0.8:1-1.1:1。
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