CN108164935A - 一种高gwit高cti薄壁阻燃玻纤增强低翘曲pet复合材料及其制备方法 - Google Patents
一种高gwit高cti薄壁阻燃玻纤增强低翘曲pet复合材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种高GWIT高CTI薄壁阻燃玻纤增强低翘曲PET复合材料及其制备方法。高GWIT高CTI薄壁阻燃玻纤增强低翘曲PET材料的原料组分包括：PET40‑60份，相容剂3‑8份，阻燃协效剂3‑8份，有卤阻燃剂10‑20份，灼热丝增强剂3‑8份，CTI增强剂3‑8份，抗氧剂0.1‑0.3份，成核剂0.1‑0.3份，矿物填充5‑10份，玻璃纤维10‑30份。本发明高GWIT高CTI阻燃玻纤增强低翘曲PET复合材料，在不影响材料力学性能、满足阻燃的前提下，显著提高了材料的灼热丝可燃性温度(GWIT)以及漏电起痕指数(CTI)，通过添加成核剂和矿物填充，解决产品的翘曲问题，降低产品的成型周期的同时也降低配方成本。
Description
技术领域
本发明涉及一种高GWIT高CTI薄壁阻燃玻纤增强低翘曲PET复合材料及其制备方法，属于PET复合材料领域。
背景技术
PET材料为聚对苯二甲酸乙二醇酯，为线性热塑性聚合物，最早是1953年由杜邦公司实现工业生产，是一种具有较高的熔融温度和高玻璃转化温度的结晶性高聚物。能够在较宽的温度范围内保持良好的物理性能，它的耐疲劳性、耐摩擦性、耐老化性、耐绝缘性突出，同时耐溶剂和耐酸性稳定，因而得到广泛的应用。改性制成的产品可以应用于电容器外壳、低压电器外壳、连接器和变压器骨架等等。随着PET产品在电子电器行业的广泛应用，环保概念已满足基本需求，人们对产品的电学性能也提出更高的要求，另外随着产品设计的多样性，越来越薄的产品相继问世，对产品阻燃厚度也提出更高的要求。
传统环保阻燃玻纤增强的PET复合材料只能满足大于等于1.6mm厚度的阻燃性能，灼热丝可燃性温度(GWIT)一般只能达到700℃左右，漏电起痕指数只能达到200-225V左右。材料应用于电子电器中，会存在很大的电性能安全隐患。目前市场上也出现高GWIT高CTI玻纤增强阻燃PET产品，但PET产品本身的结晶速度较慢，需要更高的成型温度和成型周期，生产出的产品会出现翘曲现象，使其在工程塑料应用领域中受到很大的限制。
发明内容
为了解决现有技术中阻燃玻纤增强PET的GWIT和CTI不能同时兼顾和产品出现翘曲现象等缺陷，本发明提供一种高GWIT高CTI薄壁阻燃玻纤增强低翘曲PET复合材料及其制备方法。
为解决上述技术问题，本发明所采用的技术方案如下：
一种高GWIT高CTI薄壁阻燃玻纤增强低翘曲PET材料，其原料组分包括：
所述PET粘度为中高等粘度树脂，特性粘度为0.83-0.92分升/克；灼热丝增强剂为三聚氰胺和磷酸酯的混合物；CTI增强剂为复合磷酸盐；玻璃纤维为无碱长纤，单丝直径为12μm；前述份数为质量份数。
GWIT为灼热丝起燃性温度,CTI为漏电起痕指数。
本申请通过对灼热丝增强剂、CTI增强剂的选择，使组合物产生了非常显著的协同效应，在不影响力学性能的基础上，可满足阻燃、高GWIT和高CTI的要求；成核剂和矿物填充按照配比搭配使用，降低了产品的成型周期，满足产品低翘曲要求；另外灼热丝增强剂为氮磷结构助剂，与溴系阻燃剂复配使用不仅可以提高产品的GWIT性能，同时提高产品的阻燃性能。
本申请对PET特性粘度的具体选择，进一步保证了产品的机械性能和阻燃性能。
为了能增强混合物的相容性，同时提高产品的冲击性能，相容剂为乙烯-醋酸乙烯共聚物和乙烯丙烯酸丁酯质量比2:1的混合物。
为了进一步同时兼顾GWIT和CTI，优选，阻燃协效剂为硬脂酸锌、三氧化二锑和碳酸锌质量比为(2±1)：1:1的混合物。在卤素阻燃产品中，三氧化二锑的存在会严重降低CTI指数，本申请发明利用硬脂酸锌和碳酸锌部门代替三氧化二锑，在不影响阻燃效果的前提下，同时降低对CTI指数的影响。通过添加灼热丝和CTI增强剂，与卤素体系复配，进而提升产品的GWIT和CTI。
为了在保证产品阻燃性能的同时，提高产品的GWIT和CTI，优选，有卤阻燃剂为十溴二苯乙烷或溴化聚苯乙烯中的至少一种。
为了进一步增强各组分之间的协同效应，灼热丝增强剂为氮磷混合物RHPP-085-3A-3h。
为了进一步增强各组分之间的协同效应，CTI增强剂为辰东化学的磷酸盐PK-5001。
为了进一步增强各组分之间的协同效应，使产品GWIT和CTI得到进一步的提高，优选，抗氧剂为酚类抗氧剂或亚磷酸酯抗氧剂中的任意一种。进一步优选，抗氧剂为抗氧剂1010和抗氧剂168质量比为1:1d的混合物。
为了进一步保证产品低翘曲性能，成核剂为布吕格曼的聚酯成核剂P250。
进一步优选，矿物填充为1500目的滑石粒。
上述高GWIT高CTI薄壁阻燃玻纤增强低翘曲PET材料的制备方法，采用一步法在高速混合机中将原料混合均匀，通过双螺杆挤出机挤出造粒、干燥，得到的粒料，粒料再经注塑机注塑，即得。
本发明未提及的技术均参照现有技术。
本发明高GWIT高CTI阻燃玻纤增强低翘曲PET复合材料，在不影响材料力学性能、满足阻燃的前提下，显著提高了材料的灼热丝可燃性温度(GWIT)以及漏电起痕指数(CTI)，通过添加成核剂和矿物填充，解决产品的翘曲问题，降低产品的成型周期的同时也降低配方成本。
具体实施方式
为了更好地理解本发明，下面结合实施例进一步阐明本发明的内容，但本发明的内容不仅仅局限于下面的实施例。
实施例1:
取PET树脂(规格牌号：新疆屯河TH105)45.7kg，相容剂乙烯-醋酸乙烯共聚物(厂家：法国阿科玛)2kg和乙烯丙烯酸丁酯(厂家：杜邦)1kg，阻燃协效剂三氧化二锑(厂家：湖南安华)1kg，硬脂酸锌(厂家：深圳立托)2kg，碳酸锌1kg，有卤阻燃剂十溴二苯乙烷(厂家：泰州百力)15kg,灼热丝增强剂(厂家：深圳瑞鸿，氮磷混合物RHPP-085-3A-3h)6kg，CTI增强剂(厂家：广东辰东化学，磷酸盐PK-5001)6kg，成核剂P250(布吕格曼)100g，1500目滑石粒5kg，抗氧剂1010(雅宝)100g和抗氧剂168(雅宝)100g，玻璃纤维(无碱长纤，单丝直径为12μm，厂家：巨石化纤)15kg，加入高速混合机中搅拌分散均匀，出料，将其加入双螺杆挤出机中熔融共混挤出造粒，干燥，得到阻燃粒料，经注塑机注塑样条，检测力学性能、垂直燃烧性能，灼热丝可燃性温度和漏电起痕性能，结果见表1。
实施例2:
取PET树脂(规格牌号：新疆屯河TH105)40.7kg，相容剂乙烯-醋酸乙烯共聚物(厂家：法国阿科玛)2kg和乙烯丙烯酸丁酯(厂家：杜邦)1kg，阻燃协效剂三氧化二锑(厂家：湖南安华)1kg，硬脂酸锌(厂家：深圳立托)2kg，碳酸锌1kg，有卤阻燃剂十溴二苯乙烷(厂家：泰州百力)15kg,灼热丝增强剂(厂家：深圳瑞鸿，氮磷混合物RHPP-085-3A-3h)6kg，CTI增强剂(厂家：广东辰东化学，磷酸盐PK-5001)6kg，成核剂P250(布吕格曼)100g，1500目滑石粒5kg，抗氧剂1010(雅宝)100g和抗氧剂168(雅宝)100g，玻璃纤维(无碱长纤，单丝直径为12μm，厂家：巨石化纤)20kg，加入高速混合机中搅拌分散均匀，出料，将其加入双螺杆挤出机中熔融共混挤出造粒，干燥，得到阻燃粒料，经注塑机注塑样条，检测力学性能、垂直燃烧性能，灼热丝可燃性温度和漏电起痕性能，结果见表1。
实施例3:
取PET树脂(规格牌号：新疆屯河TH105)43.7kg，相容剂乙烯-醋酸乙烯共聚物(厂家：法国阿科玛)2kg和乙烯丙烯酸丁酯(厂家：杜邦)1kg，阻燃协效剂三氧化二锑(厂家：湖南安华)1kg，硬脂酸锌(厂家：深圳立托)2kg，碳酸锌1kg，有卤阻燃剂十溴二苯乙烷(厂家：泰州百力)15kg,灼热丝增强剂(厂家：深圳瑞鸿，氮磷混合物RHPP-085-3A-3h)8kg，CTI增强剂(厂家：广东辰东化学，磷酸盐PK-5001)6kg，成核剂P250(布吕格曼)100g，1500目滑石粒5kg，抗氧剂1010(雅宝)100g和抗氧剂168(雅宝)100g，玻璃纤维(无碱长纤，单丝直径为12μm，厂家：巨石化纤)15kg，加入高速混合机中搅拌分散均匀，出料，将其加入双螺杆挤出机中熔融共混挤出造粒，干燥，得到阻燃粒料，经注塑机注塑样条，检测力学性能、垂直燃烧性能，灼热丝可燃性温度和漏电起痕性能，结果见表1。
实施例4：
取PET树脂(规格牌号：新疆屯河TH105)43.7kg，相容剂乙烯-醋酸乙烯共聚物(厂家：法国阿科玛)2kg和乙烯丙烯酸丁酯(厂家：杜邦)1kg，阻燃协效剂三氧化二锑(厂家：湖南安华)1kg，硬脂酸锌(厂家：深圳立托)2kg，碳酸锌1kg，有卤阻燃剂十溴二苯乙烷(厂家：泰州百力)15kg,灼热丝增强剂(厂家：深圳瑞鸿，氮磷混合物RHPP-085-3A-3h)6kg，CTI增强剂(厂家：广东辰东化学，磷酸盐PK-5001):8kg，成核剂P250(布吕格曼)100g，1500目滑石粒5kg，抗氧剂1010(雅宝)100g和抗氧剂168(雅宝)100g，玻璃纤维(无碱长纤，单丝直径为12μm，厂家：巨石化纤)15kg，加入高速混合机中搅拌分散均匀，出料，将其加入双螺杆挤出机中熔融共混挤出造粒，干燥，得到阻燃粒料，经注塑机注塑样条，检测力学性能、垂直燃烧性能，灼热丝可燃性温度和漏电起痕性能，结果见表1。
力学性能测试依据ASTM标准，阻燃性能测试依据UL94标准。灼热丝可燃性温度测试依据IEC60695-2-11:2000标准，漏电起痕指数测试依据IEC60112：2003标准,翘曲采用目测，参照GB841-2006标准，好代表无翘曲。
表1实施例材料性能
Claims (10)
1.一种高GWIT高CTI薄壁阻燃玻纤增强低翘曲PET材料，其特征在于：其原料组分包括：
PET的特性粘度为0.83-0.92分升/克；灼热丝增强剂为三聚氰胺和磷酸酯的混合物；CTI增强剂为复合磷酸盐；玻璃纤维为无碱长纤，单丝直径为12μm；前述份数为质量份数。
2.如权利要求1所述的高GWIT高CTI薄壁阻燃玻纤增强低翘曲PET材料，其特征在于：相容剂为乙烯-醋酸乙烯共聚物和乙烯丙烯酸丁酯质量比2:1的混合物。
3.如权利要求1或2所述的高GWIT高CTI薄壁阻燃玻纤增强低翘曲PET材料，其特征在于：阻燃协效剂为硬脂酸锌、三氧化二锑和碳酸锌质量比为(2±1)：1:1的混合物。
4.如权利要求1或2所述的高GWIT高CTI薄壁阻燃玻纤增强低翘曲PET材料，其特征在于：有卤阻燃剂为十溴二苯乙烷或溴化聚苯乙烯中的至少一种。
5.如权利要求1或2所述的高GWIT高CTI薄壁阻燃玻纤增强低翘曲PET材料，其特征在于：灼热丝增强剂为氮磷混合物RHPP-085-3A-3h。
6.如权利要求1或2所述的高GWIT高CTI薄壁阻燃玻纤增强低翘曲PET材料，其特征在于：CTI增强剂为磷酸盐PK-5001。
7.如权利要求1或2所述的高GWIT高CTI薄壁阻燃玻纤增强低翘曲PET材料，其特征在于：抗氧剂为酚类抗氧剂或亚磷酸酯抗氧剂中的任意一种。
8.如权利要求1或2所述的高GWIT高CTI薄壁阻燃玻纤增强低翘曲PET材料，其特征在于：成核剂为聚酯成核剂P250。
9.如权利要求1或2所述的高GWIT高CTI薄壁阻燃玻纤增强低翘曲PET材料，其特征在于：矿物填充为1500目的滑石粒。
10.权利要求1-9任意一项所述的高GWIT高CTI薄壁阻燃玻纤增强低翘曲PET材料的制备方法，其特征在于：在高速混合机中将原料混合均匀，通过双螺杆挤出机挤出造粒、干燥，得到的粒料，粒料再经注塑机注塑，即得。
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| CN110016209A (zh) * | 2019-04-16 | 2019-07-16 | 武汉顺威赛特工程塑料有限公司 | 一种gwit850℃增强阻燃pbt及其制备方法和应用 |
| US20240158631A1 (en) * | 2022-11-11 | 2024-05-16 | Nan Ya Plastics Corporation | High strength flame retardant polyester material |
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| WO2005121232A1 (en) * | 2004-06-10 | 2005-12-22 | Italmatch Chemicals S.P.A. | Polyester compositions flame retarded with halogen-free additives |
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| WO2005121232A1 (en) * | 2004-06-10 | 2005-12-22 | Italmatch Chemicals S.P.A. | Polyester compositions flame retarded with halogen-free additives |
| CN102952380A (zh) * | 2012-12-04 | 2013-03-06 | 上海日之升新技术发展有限公司 | 一种高cti值、高gwit值环保阻燃玻纤增强pet材料及其制备方法 |
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| CN110016209A (zh) * | 2019-04-16 | 2019-07-16 | 武汉顺威赛特工程塑料有限公司 | 一种gwit850℃增强阻燃pbt及其制备方法和应用 |
| US20240158631A1 (en) * | 2022-11-11 | 2024-05-16 | Nan Ya Plastics Corporation | High strength flame retardant polyester material |
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