CN110819083B - 一种高力学性能阻燃增强pet及其制备方法 - Google Patents

一种高力学性能阻燃增强pet及其制备方法 Download PDF

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CN110819083B
CN110819083B CN201910965434.8A CN201910965434A CN110819083B CN 110819083 B CN110819083 B CN 110819083B CN 201910965434 A CN201910965434 A CN 201910965434A CN 110819083 B CN110819083 B CN 110819083B
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万锋
杨杰
戴李宗
全敦华
王伟
陈明进
陈国荣
孙玉璞
吴腾达
刁雪峰
申应军
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Jinyoung Xiamen Advanced Materials Technology Co Ltd
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Abstract

本发明公开了一种高力学性能阻燃增强PET及其制备方法，由如下质量百分比的组分制成：PET树脂45‑70％、无碱短切玻璃纤维20‑40％、阻燃剂10‑15％、成核剂0.2‑0.8％、结晶促进剂0.2‑0.5％、偶联剂0.2‑1％、抗氧剂0.2‑0.5％和润滑剂0.2‑1％。本发明加入复式成核剂NA‑95和钠离子型E/MMA共聚物8920作为成核剂，综合两者的优点，既避免了单一成核剂的不足之处，又兼顾了PET各个结晶温度段的结晶效果，使得所制备的PET在各个性能方面都有所提高。

Description

一种高力学性能阻燃增强PET及其制备方法
技术领域
本发明属于PET制备技术领域，具体涉及一种高力学性能阻燃增强PET及其制备方法。
背景技术
聚对苯二甲酸乙二醇酯(PET)是一种韧性高、耐蠕变、抗疲劳、耐摩擦性能好、介电常数高的高分子塑料，其特性受环境中温度和湿度的影响小，因此PET材料可以应用在薄膜片材、包装瓶、电子电器、汽车配件、机械设备等很多领域。PET在电子电器领域应用时需对其进行阻燃增强改性，但PET为半结晶性聚合物，其玻璃化转变温度Tg较高(约78℃)，结晶速度缓慢，模塑周期长，导致其收缩率大，尺寸稳定性差，热变形温度低，很难满足设计要求。
目前，很多学者从注塑工艺上解决PET结晶问题，即在90℃以上模温注塑制件，该方法虽然有利于PET结晶，但对设备要求高，能耗大。也有学者通过添加苯甲酸钠来增加PET的成核能力或者添加增塑剂降低PET的玻璃化转变温度Tg，以达到提高PET结晶度的效果。苯甲酸钠和聚乙二醇虽然降低了PET的玻璃化转变温度Tg，一定程度上提高了PET的结晶度，但它们对PET本身存在分解作用，对PET结构有所破坏，降低了其力学性能，且在注塑过程中存在流延问题。
发明内容
本发明的目的在于克服现有技术缺陷，提供一种高力学性能阻燃增强PET及其制备方法。
本发明的技术方案如下：
一种高力学性能阻燃增强PET，由如下质量百分比的组分制成：
Figure BDA0002229778270000011
Figure BDA0002229778270000021
上述PET树脂(东莞市创锦塑胶原料有限公司)的特征粘度为0.8～1.0d1/g，上述阻燃剂由锑酸钠与溴系阻燃剂以1∶3-4的质量比复配而成，上述成核剂由改性复式成核剂NA-95(上海梁典化学品有限公司)和钠离子型E/MMA共聚物8920(美国杜邦)以1∶1的质量比组成，上述结晶促进剂为三苄基叉丙醚双酯己醇PX-520(东莞三合化工有限公司)。
在本发明的一个优选实施方案中，所述溴系阻燃剂为十溴二苯乙烷RDT-3(山东寿光卫东化工有限公司)、溴化聚苯乙烯XZ-6700(山东兄弟科技股份有限公司)或溴化环氧树脂KBE-2025K(开美化学科技(南通)有限公司)。
在本发明的一个优选实施方案中，所述偶联剂为Y-氨丙基三乙氧基硅烷KH-550(南京曙光化工集团有限公司)或Y-(2，3-环氧丙氧)丙基三甲氧基硅烷KH-560(南京曙光化工集团有限公司)。
在本发明的一个优选实施方案中，所述抗氧剂包括主抗氧剂和辅助抗氧剂，其中，主抗氧剂为四[β-(3，5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯1010(BASF)或四(2，4-二叔丁基苯基-4，4’联苯基)双亚膦酸酯HostanoxP-EPQ，辅助抗氧剂为抗氧剂9228(美国Dover chemical)，主抗氧剂和辅助抗氧剂的质量比为1-3∶1。
在本发明的一个优选实施方案中，所述润滑剂为季戊四醇四硬脂酸酯GLYCOLUBEPETS(美国龙沙)、乙撑双硬脂酰胺EBS(马来西亚南韩)、聚二甲基硅氧烷(玛雅试剂有限公司)或硬脂酸锌(广州亿峰化工科技有限公司)。
在本发明的一个优选实施方案中，所述无碱短切玻璃纤维的直径为7-14μm。
上述高力学性能阻燃增强PET的制备方法，包括如下步骤：
(1)按质量百分比称取各组分；
(2)将PET树脂和无碱短切玻璃纤维在100℃的鼓风干燥箱中干燥，检测水分含量小于500PPM；
(3)将步骤(2)处理后的PET树脂、阻燃剂、成核剂、结晶促进剂、偶联剂、抗氧剂和润滑剂置于低速混合机中混合均匀，得预混物；
(4)将步骤(3)所得的预混物加到双螺杆挤出机的主喂料斗，步骤(2)处理后的无碱短切玻璃纤维加到侧喂料斗，通过双螺杆挤出机熔融共混挤出，该挤出的温度为240-250℃，螺杆转速300-400r/min，即成。
本发明的有益效果是：本发明加入复式成核剂NA-95和钠离子型E/MMA共聚物8920作为成核剂，综合两者的优点，既避免了单一成核剂的不足之处，又兼顾了PET各个结晶温度段的结晶效果，使得所制备的PET在各个性能方面都有所提高。
具体实施方式
以下通过具体实施方式对本发明的技术方案进行进一步的说明和描述。
下述对比例和实施例包括如下步骤：
(1)按质量百分比称取各组分；
(2)将PET树脂和直径为7-14μm的无碱短切玻璃纤维在100℃的鼓风干燥箱中干燥，检测水分含量小于500PPM；
(3)将步骤(2)处理后的PET树脂、阻燃剂、成核剂、结晶促进剂、偶联剂、抗氧剂和润滑剂置于低速混合机中混合均匀，得预混物；
(4)将步骤(3)所得的预混物加到双螺杆挤出机的主喂料斗，步骤(2)处理后的无碱短切玻璃纤维加到侧喂料斗，通过双螺杆挤出机熔融共混挤出，该挤出的温度为240-250℃，螺杆转速300-400r/min，即成。
上述PET树脂的特征粘度为0.8～1.0dl/g，上述阻燃剂由锑酸钠与溴系阻燃剂以1∶3-4的质量比复配而成，上述成核剂由改性复式成核剂NA-95和钠离子型E/MMA共聚物8920以1∶1的质量比组成，上述结晶促进剂为三苄基叉丙醚双酯己醇PX-520。
溴系阻燃剂为十溴二苯乙烷RDT-3、溴化聚苯乙烯XZ-6700或溴化环氧树脂KBE-2025K。
各对比例和实施例中的各组分的添加量如下表1所示：
表1
Figure BDA0002229778270000031
Figure BDA0002229778270000041
各对比例所获得的技术效果如下表2所示：
表2
Figure BDA0002229778270000042
通过表2表明：
通过对比对比例1、对比例2、实施例1及对比例3的数据可得，加入成核剂可明显提高PET的拉伸强度、弯曲强度和负荷变形温度，这说明成核剂的加入会使PET的结晶度增加，从而提高PET的力学性能。将对比例1、对比例2及对比例3的测试数据对比可知，成核剂NA-95的加入对PET的热变形温度提升很大，能使PET结晶更为完全；而成核剂8920的加入对PET的热变形温度提升较小，结晶度相对更小。将实施例1与对比例1及对比例2的数据对比可知，将8920和NA-95混合加入对PET的整体性能都有很大提升，比单一加入一种成核剂效果好。
以上所述，仅为本发明的较佳实施例而已，故不能依此限定本发明实施的范围，即依本发明专利范围及说明书内容所作的等效变化与修饰，皆应仍属本发明涵盖的范围内。

Claims (5)

1.一种高力学性能阻燃增强PET，其特征在于：由如下质量百分比的组分制成：
PET树脂 45-70%
无碱短切玻璃纤维 20-40%
阻燃剂 10-15%
成核剂 0.2-0.8%
结晶促进剂 0.2-0.5%
偶联剂 0.2-1%
抗氧剂 0.2-0.5%
润滑剂 0.2-1%；
上述PET树脂的特征粘度为0.8~1.0 dl/g，上述阻燃剂由锑酸钠与溴系阻燃剂以1:3-4的质量比复配而成，上述成核剂由改性复式成核剂NA-95和钠离子型E/MMA共聚物8920以1:1的质量比组成，上述结晶促进剂为三苄基叉丙醚双酯己醇PX-520，上述抗氧剂包括主抗氧剂和辅助抗氧剂，其中，主抗氧剂为四[β-（3，5-二叔丁基-4-羟基苯基）丙酸]季戊四醇酯1010或四（2,4-二叔丁基苯基-4,4’联苯基）双亚膦酸酯HostanoxP-EPQ，辅助抗氧剂为抗氧剂9228，主抗氧剂和辅助抗氧剂的质量比为1-3:1，上述润滑剂为季戊四醇四硬脂酸酯GLYCOLUBE PETS、乙撑双硬脂酰胺EBS、聚二甲基硅氧烷或硬脂酸锌。
2.如权利要求1所述的一种高力学性能阻燃增强PET，其特征在于：所述溴系阻燃剂为十溴二苯乙烷RDT-3、溴化聚苯乙烯XZ-6700或溴化环氧树脂KBE-2025K。
3.如权利要求1所述的一种高力学性能阻燃增强PET，其特征在于：所述偶联剂为Y-氨丙基三乙氧基硅烷KH-550或Y-（2,3-环氧丙氧）丙基三甲氧基硅烷KH-560。
4.如权利要求1所述的一种高力学性能阻燃增强PET，其特征在于：所述无碱短切玻璃纤维的直径为7-14μm。
5.权利要求1至4中任一权利要求所述的一种高力学性能阻燃增强PET的制备方法，其特征在于：包括如下步骤：
（1）按质量百分比称取各组分；
（2）将PET树脂和无碱短切玻璃纤维在100 ℃的鼓风干燥箱中干燥，检测水分含量小于500PPM；
（3）将步骤（2）处理后的PET树脂、阻燃剂、成核剂、结晶促进剂、偶联剂、抗氧剂和润滑剂置于低速混合机中混合均匀，得预混物；
（4）将步骤（3）所得的预混物加到双螺杆挤出机的主喂料斗，步骤（2）处理后的无碱短切玻璃纤维加到侧喂料斗，通过双螺杆挤出机熔融共混挤出，该挤出的温度为240 -250℃，螺杆转速300-400 r /min，即成。
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