CN111635629B - 一种低吸水率玻纤增强无卤阻燃聚酰胺材料及其制备方法 - Google Patents
一种低吸水率玻纤增强无卤阻燃聚酰胺材料及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种低吸水率玻纤增强无卤阻燃聚酰胺材料及其制备方法,属于高分子材料技术领域。该材料包括如下组分:聚酰胺树脂、接枝物、烷基酚醛硫化树脂、玻璃纤维、阻燃剂、热稳定助剂、加工润滑剂、硅油。在聚酰胺树脂中加入一定量的玻璃纤维和阻燃剂,对其进行阻燃、增强改性,使最终的材料具有环保阻燃、强度高、耐温好等优点。更重要的是,同时在聚酰胺树脂中加入一定量的烷基酚醛硫化树脂和接枝物,能够有效减少最终制备的玻纤增强无卤阻燃聚酰胺材料的吸水率,解决了其因吸湿性导致尺寸稳定性、力学性能、电性能变差等问题,同时具有添加量少、效率高、成本低、对材料性能无影响等优点。该材料制备方法简单,易操作,对设备要求不高,适合扩大化生产。
Description
技术领域
本发明属于高分子材料技术领域,具体涉及一种低吸水率玻纤增强无卤阻燃聚酰胺材料及其制备方法。
背景技术
聚酰胺6(PA6)、聚酰胺66(PA66)因其优异的综合性能,已成为了使用最为广泛的工程塑料之一,被广泛用于汽车、航天航空、通用机械、电子电气、仪器仪表、家用电器及办公仪器等领域。玻纤加入PA6、PA66有利于提高材料的强度、耐温性能、耐腐蚀性以及降低成本,同时对其进行阻燃改性以提高PA6、PA66材料的耐燃性,从而增大聚酰胺材料的使用领域,但PA6、PA66产品在后期的使用过程中,因其分子链中-NHCO-基团具有较强的极性,容易与环境中的水分子形成氢键,使产品具有较大的吸水率增,导致PA6、PA66产品的尺寸稳定性、力学性能、电性能变差,从而影响产品的使用。
为了降低PA6、PA66的吸水率,研究者提出多种解决方案,主要有以下三种方法:1、添加填料(玻纤、滑石粉、蒙脱土、硅灰石等),通过降低PA6、PA66在复合材料中的含量来降低吸水率;2、添加低吸水率材料(聚烯烃、聚酮、芳香尼龙、PPS、PPO等),通过添加低吸水率材料与PA6、PA66合金的形式来降低吸水率;3、添加低吸水助剂(与酰胺基团反应的单体,与酰胺基团作用的酸酐基、羧酸基、接枝物,起屏蔽作用的蜡、硅酮等),通过降低酰胺与水形成氢键和屏蔽水与酰胺基团接触的方法来降低吸水率。以上方法虽然能降低PA6、PA66的吸水率,但面临填料和低吸水率材料添加量多、效率有限、对整个材料性能有影响、成本昂贵、有颜色等问题,限制了PA6、PA66的使用范围。
发明内容
有鉴于此,本发明的目的之一在于提供一种低吸水率玻纤增强无卤阻燃聚酰胺材料;目的之二在于提供一种低吸水率玻纤增强无卤阻燃聚酰胺材料的制备方法。
为达到上述目的,本发明提供如下技术方案:
1、一种低吸水率玻纤增强无卤阻燃聚酰胺材料,按重量份计,所述低吸水率玻纤增强无卤阻燃聚酰胺材料包括如下组分:聚酰胺树脂30-60份、接枝物1-2份、烷基酚醛硫化树脂1-2份、玻璃纤维10-50份、阻燃剂15-25份、热稳定助剂0.5-0.8份、加工润滑剂0.3-0.8份、硅油0.03-0.05份。
优选的,所述聚酰胺树脂为脂肪族聚酰胺树脂。
优选的,所述聚酰胺树脂为聚酰胺6(PA6)或聚酰胺66(PA66)中的一种或多种。
优选的,所述接枝物为乙烯-辛烯共聚物接枝马来酸酐(POE-g-MAH)、乙烯-辛烯共聚物接枝甲基丙烯酸缩水甘油酯(POE-g-GMA)、三元乙丙橡胶接枝马来酸酐(EPDM-g-MAH)、三元乙丙橡胶接枝甲基丙烯酸缩水甘油酯(EPDM-g-GMA)、聚乙烯接枝马来酸酐(PE-g-MAH)、聚乙烯接枝甲基丙烯酸缩水甘油酯(PE-g-GMA)、聚丙烯接枝马来酸酐(PP-g-MAH)或聚丙烯接枝甲基丙烯酸缩水甘油酯(PP-g-GMA)中的一种或多种。
优选的,所述烷基酚醛硫化树脂中羟甲基含量为4-15%。
优选的,所述烷基酚醛硫化树脂为辛基酚醛硫化树脂或叔丁酚醛硫化树脂中的一种。
优选的,所述玻璃纤维为无碱玻璃连续纤维或无碱玻璃纤维短切纱中的一种或多种。
优选的,所述阻燃剂为二烷基次膦酸盐、三聚氰胺聚磷酸盐或三聚氰胺氰尿酸盐中的一种或多种;所述热稳定助剂为抗氧剂1010、抗氧剂168、抗氧剂1098、抗氧剂1076、抗氧剂H10或抗氧剂H161中的一种或多种;所述加工润滑剂为聚乙烯蜡、硅酮、硬锌或硬钙中的一种或多种。
2、所述的一种低吸水率玻纤增强无卤阻燃聚酰胺材料的制备方法,所述方法如下:将聚酰胺树脂、接枝物、烷基酚醛硫化树脂、阻燃剂、热稳定助剂、加工润滑剂和硅油混匀后由主加料口加入挤出机中,将玻璃纤维由侧加料口加入所述挤出机,经熔融、共混、挤出、牵条、切粒、烘干,即可。
优选的,所述挤出机为同向双螺杆挤出机,长径比为40。
优选的,所述同向双螺杆挤出机的螺纹组合为:48×3、32、22×2、K48×30°、22、K32×45°、K22×60°、K22×60°、22、K32×45°、K22×60°、32、K32×90°、11L、48×3、32×2、22×3、K32×45°、K22×60°、22、K32×45°L、22、K32×45°、K22×60°、22、K32×90°、11L、48×4、32×4、22×3、螺杆头。
优选的,所述挤出机从主加料口到机头各段温度为:50℃、90-150℃、220-270℃、220-270℃、220-270℃、230-270℃、230-270℃、230-270℃、230-270℃、220-260℃。
优选的,所述挤出机的转速为250-300r/min。
本发明的有益效果在于:本发明提供了一种低吸水率玻纤增强无卤阻燃聚酰胺材料及其制备方法,在聚酰胺树脂中加入一定量的玻璃纤维和阻燃剂,对其进行阻燃、增强改性,使最终的材料具有环保阻燃、强度高、耐温好等优点。更重要的是,同时在聚酰胺树脂中加入一定量的烷基酚醛硫化树脂和接枝物,能够有效减少最终制备的玻纤增强无卤阻燃聚酰胺材料的吸水率,解决了其因吸湿性导致尺寸稳定性、力学性能、电性能变差等问题,同时具有添加量少、效率高、成本低、对材料性能无影响等优点。其中,烷基酚醛硫化树脂中的羟甲基和酚基均能优先于水与聚酰胺树脂的中酰胺基团作用,有效减少酰胺基团与水分子形成氢键,从而减少最终制备的玻纤增强无卤阻燃聚酰胺材料的吸水率。另外,接枝物的加入,能够增加烷基酚醛硫化树脂与聚酰胺树脂的相容性,从而一方面增加烷基酚醛硫化树脂中的羟甲基和酚基与聚酰胺树脂的中酰胺基团的接触,保证了烷基酚醛硫化树脂中的羟甲基和酚基能够最大程度与聚酰胺树脂的中酰胺基团发生作用,进一步保证了最终制备的玻纤增强无卤阻燃聚酰胺材料的低吸水率;另一方面,烷基酚醛硫化树脂均匀分散于聚酰胺树脂中,可以保证最终制备的玻纤增强无卤阻燃聚酰胺材料的力学性能。该材料制备方法简单,易操作,对设备要求不高,适合扩大化生产。
本发明的其他优点、目标和特征在某种程度上将在随后的说明书中进行阐述,并且在某种程度上,基于对下文的考察研究对本领域技术人员而言将是显而易见的,或者可以从本发明的实践中得到教导。本发明的目标和其他优点可以通过下面的说明书来实现和获得。
具体实施方式
以下通过特定的具体实例说明本发明的实施方式,本领域技术人员可由本说明书所揭露的内容轻易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方式加以实施或应用,本说明书中的各项细节也可以基于不同观点与应用,在没有背离本发明的精神下进行各种修饰或改变。
实施例1
一种低吸水率玻纤增强无卤阻燃聚酰胺材料,按重量份计,该低吸水率玻纤增强无卤阻燃聚酰胺材料包括如下组分:PA6 46份、POE-g-MAH 2份、羟甲基含量为10%的辛基酚醛硫化树脂2份、无碱玻璃连续纤维30份、二乙基次磷酸铝12份、三聚氰胺氰尿酸盐8份、抗氧剂H10 0.5份、硅酮0.5份、硅油0.03份。
实施例2
一种低吸水率玻纤增强无卤阻燃聚酰胺材料,按重量份计,该低吸水率玻纤增强无卤阻燃聚酰胺材料包括如下组分:PA6 30份、EPDM-g-MAH 1份、羟甲基含量为10%的辛基酚醛硫化树脂2份、无碱玻璃连续纤维42份、二乙基次磷酸铝15份、三聚氰胺氰尿酸盐10份、抗氧剂H10 0.7份、硅酮0.8份、硅油0.04份。
实施例3
一种低吸水率玻纤增强无卤阻燃聚酰胺材料,按重量份计,该低吸水率玻纤增强无卤阻燃聚酰胺材料包括如下组分:PA6 60份、PE-g-MAH 2份、羟甲基含量为10%的辛基酚醛硫化树脂1份、无碱玻璃连续纤维22份、二乙基次磷酸铝8份、三聚氰胺氰尿酸盐7份、抗氧剂H10 0.8份、硅酮0.3份、硅油0.05份。
实施例4至实施例6
将实施例1至实施例3中PA6均替换为PA66。
对比例1
与实施例1的区别在于,将辛基酚醛硫化树脂替换为线性酚醛树脂。
对比例2
与实施例1的区别在于,PA6 48份、羟甲基含量为10%的辛基酚醛硫化树脂0份。
对比例3
与实施例4的区别在于,将辛基酚醛硫化树脂替换为线性酚醛树脂。
对比例4
与实施例4的区别在于,PA66 48份、羟甲基含量为10%的辛基酚醛硫化树脂0份。
实施例1至实施例3中低吸水率玻纤增强无卤阻燃聚酰胺材料及对比例1至对比例2中聚酰胺材料均按如下方法制备:将聚酰胺树脂、接枝物、烷基酚醛硫化树脂、阻燃剂、热稳定助剂、加工润滑剂和硅油混匀后由主加料口加入长径比(L/D)为40的同向双螺杆挤出机中,将玻璃纤维由侧加料口加入该挤出机,经熔融、共混、挤出、牵条、切粒、烘干,即可,其中,该挤出机的螺纹组合为:48×3、32、22×2、K48×30°、22、K32×45°、K22×60°、K22×60°、22、K32×45°、K22×60°、32、K32×90°、11L、48×3、32×2、22×3、K32×45°、K22×60°、22、K32×45°L、22、K32×45°、K22×60°、22、K32×90°、11L、48×4、32×4、22×3、螺杆头;挤出机从主加料口到机头各段温度为:50℃、150℃、230℃、230℃、240℃、240℃、240℃、240℃、240℃、230℃,挤出机的转速为300r/min。
实施例4至实施例6中低吸水率玻纤增强无卤阻燃聚酰胺材料及对比例3至对比例4中聚酰胺材料均按如下方法制备:将聚酰胺树脂、接枝物、烷基酚醛硫化树脂、阻燃剂、热稳定助剂、加工润滑剂和硅油混匀后由主加料口加入长径比(L/D)为40的同向双螺杆挤出机中,将玻璃纤维由侧加料口加入该挤出机,经熔融、共混、挤出、牵条、切粒、烘干,即可,其中,该挤出机的螺纹组合为:48×3、32、22×2、K48×30°、22、K32×45°、K22×60°、K22×60°、22、K32×45°、K22×60°、32、K32×90°、11L、48×3、32×2、22×3、K32×45°、K22×60°、22、K32×45°L、22、K32×45°、K22×60°、22、K32×90°、11L、48×4、32×4、22×3、螺杆头;挤出机从主加料口到机头各段温度为:50℃、150℃、260℃、260℃、270℃、270℃、270℃、270℃、270℃、260℃,挤出机的转速为300r/min。
测试实施例1至实施例6中低吸水率玻纤增强无卤阻燃聚酰胺材料及对比例1至对比例4中聚酰胺材料的拉伸强度、冲击强度、缺口冲击强度、弯曲模量、热变形温度、密度和吸水率,测试结果见表1。
表1
性能 | 拉伸强度 | 冲击强度 | 缺口冲击强度 | 弯曲模量 | 热变形温度 | 密度 | 阻燃性 | 吸水率 |
测试标准 | ISO 527 | ISO 180 | ISO 180 | ISO 178 | ISO 75 | ISO1183 | UL94 | ISO 62 |
测试条件 | 50mm/min | 23℃ | 23℃ | 2mm/min | 0.45Mpa | 方法A | 3.2 | 方法1 |
单位 | MPa | Kj/m<sup>2</sup> | Kj/m<sup>2</sup> | MPa | ℃ | g/cm<sup>3</sup> | - | % |
实施例1 | 128.5 | 45.4 | 12.1 | 6479 | 193.4 | 1.43 | V-0 | 1.15 |
对比例1 | 129.4 | 44.9 | 11.9 | 6543 | 194.1 | 1.43 | V-0 | 1.61 |
对比例2 | 127.4 | 44.9 | 11.9 | 6475 | 194.2 | 1.43 | V-0 | 1.78 |
实施例2 | 143.2 | 46.4 | 13.7 | 6832 | 197.3 | 1.56 | V-0 | 0.98 |
实施例3 | 120.6 | 43.1 | 10.8 | 5934 | 187.5 | 1.36 | V-0 | 1.36 |
实施例4 | 130.7 | 43.8 | 11.5 | 6598 | 235.4 | 1.44 | V-0 | 0.84 |
对比例3 | 130.2 | 44.7 | 10.7 | 6549 | 238.1 | 1.44 | V-0 | 1.24 |
对比例4 | 129.1 | 44.1 | 10.8 | 6612 | 237.1 | 1.44 | V-0 | 1.39 |
实施例5 | 145.7 | 46.7 | 13.5 | 7002 | 241.8 | 1.57 | V-0 | 0.75 |
实施例6 | 124.9 | 40.4 | 10.3 | 6154 | 230.7 | 1.36 | V-0 | 1.17 |
由表1可知,实施例1至实施例3、实施例4至实施例6中各材料在加入了烷基酚醛硫化树脂后,均具有较低的吸水率,在加入了玻璃纤维后,均展现出较高的拉伸强度和弯曲模量。
对比实施例1、对比例1和对比例2中材料的吸水率发现,实施例1中材料加入烷基酚醛硫化树脂后,吸水率均低于加入线性酚醛树脂和不加酚醛树脂材料的吸水率,同样,对比实施例4、对比例3和对比例4中材料的吸水率发现,实施例4中材料加入烷基酚醛硫化树脂后,吸水率均低于加入线性酚醛树脂和不加酚醛树脂材料的吸水率。
最后说明的是,以上实施例仅用以说明本发明的技术方案而非限制,尽管参照较佳实施例对本发明进行了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本技术方案的宗旨和范围,其均应涵盖在本发明的权利要求范围当中。
Claims (10)
1.一种低吸水率玻纤增强无卤阻燃聚酰胺材料,其特征在于,按重量份计,所述低吸水率玻纤增强无卤阻燃聚酰胺材料包括如下组分:聚酰胺树脂30-60份、接枝物1-2份、烷基酚醛硫化树脂1-2份、玻璃纤维10-50份、阻燃剂15-25份、热稳定助剂0.5-0.8份、加工润滑剂0.3-0.8份、硅油0.03-0.05份;
所述加工润滑剂为聚乙烯蜡、硅酮、硬锌或硬钙中的一种或多种。
2.如权利要求1所述的一种低吸水率玻纤增强无卤阻燃聚酰胺材料,其特征在于,所述聚酰胺树脂为脂肪族聚酰胺树脂。
3.如权利要求2所述的一种低吸水率玻纤增强无卤阻燃聚酰胺材料,其特征在于,所述聚酰胺树脂为聚酰胺6或聚酰胺66中的一种或多种。
4.如权利要求1所述的一种低吸水率玻纤增强无卤阻燃聚酰胺材料,其特征在于,所述接枝物为乙烯-辛烯共聚物接枝马来酸酐、乙烯-辛烯共聚物接枝甲基丙烯酸缩水甘油酯、三元乙丙橡胶接枝马来酸酐、三元乙丙橡胶接枝甲基丙烯酸缩水甘油酯、聚乙烯接枝马来酸酐、聚乙烯接枝甲基丙烯酸缩水甘油酯、聚丙烯接枝马来酸酐或聚丙烯接枝甲基丙烯酸缩水甘油酯中的一种或多种。
5.如权利要求1所述的一种低吸水率玻纤增强无卤阻燃聚酰胺材料,其特征在于,所述烷基酚醛硫化树脂中羟甲基含量为4-15%。
6.如权利要求1所述的一种低吸水率玻纤增强无卤阻燃聚酰胺材料,其特征在于,所述玻璃纤维为无碱玻璃连续纤维或无碱玻璃纤维短切纱中的一种或多种。
7.如权利要求1所述的一种低吸水率玻纤增强无卤阻燃聚酰胺材料,其特征在于,所述阻燃剂为二烷基次膦酸盐、三聚氰胺聚磷酸盐或三聚氰胺氰尿酸盐中的一种或多种;所述热稳定助剂为抗氧剂1010、抗氧剂168、抗氧剂1098、抗氧剂1076、抗氧剂H10或抗氧剂H161中的一种或多种。
8.权利要求1-7任一项所述的一种低吸水率玻纤增强无卤阻燃聚酰胺材料的制备方法,其特征在于,所述方法如下:将聚酰胺树脂、接枝物、烷基酚醛硫化树脂、阻燃剂、热稳定助剂、加工润滑剂和硅油混匀后由主加料口加入挤出机中,将玻璃纤维由侧加料口加入所述挤出机,经熔融、共混、挤出、牵条、切粒、烘干,即可。
9.如权利要求8所述的方法,其特征在于,所述挤出机从主加料口到机头各段温度为:50℃、90-150℃、220-270℃、220-270℃、220-270℃、230-270℃、230-270℃、230-270℃、230-270℃、220-260℃。
10.如权利要求8所述的方法,其特征在于,所述挤出机的转速为250-300r/min。
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