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CN103756310A - 一种聚酰胺/聚芳酯合金及其制备方法 - Google Patents

一种聚酰胺/聚芳酯合金及其制备方法 Download PDF

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CN103756310A
CN103756310A CN201410008249.7A CN201410008249A CN103756310A CN 103756310 A CN103756310 A CN 103756310A CN 201410008249 A CN201410008249 A CN 201410008249A CN 103756310 A CN103756310 A CN 103756310A
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alloy
polymeric amide
polyarylester
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杨桂生
储卫国
孙利明
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Hefei Genius New Materials Co Ltd
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Abstract

本发明公开了一种聚酰胺/聚芳酯合金，其由如下组分按照质量份制备而成：聚酰胺40-60份，双酚A聚芳酯20-40份，相容剂5-20份，抗氧剂0.2-2份，润滑剂0.2-2份。本发明还公开了该聚酰胺/聚芳酯合金的制备方法：按配比将聚酰胺、聚芳酯、相容剂、润滑剂和抗氧化剂一同混合，再将混合物料从双螺杆挤出机的主喂料口加入，经熔融挤出、冷却、切粒即可得聚酰胺/聚芳酯合金。本发明的聚酰胺/聚芳酯合金耐热性优异，热变形温度＞100℃（1.82MPa），热稳定好，其结构和共混物形态很少变化，重复加工性良好；合金成型收缩率小，制品不易变形翘曲；合金吸水率比聚酰胺树脂明显降低，缩短了材料成型前干燥时间。

Description

一种聚酰胺/聚芳酯合金及其制备方法
技术领域
本发明涉及高分子复合材料领域，尤其涉及一种聚酰胺/聚芳酯合金及其制备方法。
 
背景技术
聚酰胺纤维俗称尼龙，聚酰胺不仅具有优良的力学性能，易加工且其自润滑性及耐药品腐蚀性也很好，因而是一种使用较广泛的工程塑料。然尼龙的耐热性、平衡吸水率及干热尺寸稳定性的不足是扩大其应用的瓶颈难题。目前采取的改进措施是利用玻纤填充来改善耐热性和尺寸稳定性的不足，加入玻纤能够得到强度很高的材料，然其对材料加工要求很高，如果加工不良玻纤取向明显会使制件翘曲。另外玻纤加入使材料吸收更甚，同时还降低了制品表面光泽，使表面变差。也有通过添加填料来改善耐热和尺寸稳定性的方案，此方案得到的材料密度都很高，也限制了其在某些领域的应用。
 
发明内容
本发明的目的是克服现有技术的不足，提供一种聚酰胺/聚芳酯合金及其制备方法。
本发明通过如下技术方案实现上述目标：
一种聚酰胺/聚芳酯合金，其特征在于，由如下组分按照质量份制备而成：
聚酰胺          40-60份
双酚A聚芳酯     20-40份
相容剂          5-20份
抗氧剂          0.2-2份
润滑剂          0.2-2份
其中所述的聚酰胺为相对粘度2.4-3.0的聚酰胺66和/或聚酰胺6。
所述的双酚A聚芳酯为3,3’-偶氮苯二甲酰氯、双酚A为原料，十六烷基三甲基溴化铵为相转移剂，通过界面缩聚合成的含偶氮基团的聚芳酯，所述的双酚A聚芳酯合成方法出自武汉理工大学材料科学与工程学院牛永生、周伟在2006年2月第1期安阳工学院学报中发表的文献《界面缩聚合成含偶氮基团的双酚A聚芳酯》，其分子结构为                                               
Figure 2014100082497100002DEST_PATH_IMAGE002
。
此种结构的聚芳酯因其在主链中引入偶氮基团，使得主链刚性变得更加强，所以此种结构的聚芳酯玻璃化温度比通用聚芳酯高几十度，所以在加工和耐热性平衡中表现尤为突出。
所述的相容剂的重量组成为双酚A型环氧树脂2-8份、马来酸酐2-8份、甲基丙烯酸缩水甘油酯1-4份。
所述的抗氧剂为N,N’-1,6-亚已基-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰胺]（1098）或者为N,N’-1,6-亚已基-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰胺]（1098）和亚磷酸三(2，4-二叔丁基苯基)酯（168）组合物。
所述润滑剂为乙撑双硬脂酸酰胺（EBS）、聚乙烯蜡、硅酮母粒中的至少一种。
所述的一种聚酰胺/聚芳酯合金的制备方法如下：
按配比将聚酰胺、聚芳酯、相容剂、润滑剂和抗氧化剂一同混合，再将混合物料从双螺杆挤出机的主喂料口加入，经熔融挤出、冷却、切粒即可得聚酰胺/聚芳酯合金；其中双螺杆挤出机从进料段到机头的温度分别为：220-240℃、260-280℃、260-280℃、265-285℃、260-280℃、255-275℃、260-280℃ 和260-280℃，模头温度265-280℃。
与现有技术相比，本发明具有以下有益效果： 
1、聚酰胺/聚芳酯合金耐热性优异，热变形温度＞100℃（1.82MPa），热稳定好，其结构和共混物形态很少变化，重复加工性良好；
2、聚酰胺/聚芳酯合金成型收缩率小，制品不易变形翘曲；
3、聚酰胺/聚芳酯合金吸水率比聚酰胺树脂明显降低，缩短材料成型前干燥时间；
4、聚芳酯的密度不大，所以制取的合金密度也没有大幅提高。
 
具体实施方式
下面结合具体实施例，进一步阐述本发明。应该理解，这些实施例仅用于说明本发明，而不用于限定本发明的保护范围。在实际应用中技术人员根据本发明做出的不背离本发明原则的改进和调整，仍属于本发明的保护范围。
 
实施例1
称取聚酰胺PA66为60份、双酚A聚芳酯20份、双酚A型环氧树脂8份、马来酸酐8份、甲基丙烯酸缩水甘油酯4份、润滑剂乙撑双硬脂酸酰胺EBS为0.2份、抗氧化剂N,N’-1,6-亚已基-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰胺]（1098）为0.5份一同混合均匀，再将混合物料从双螺杆挤出机的主喂料口加入，经熔融挤出、冷却、切粒即可得聚酰胺/聚芳酯合金；其中双螺杆挤出机从进料段到机头的温度分别为： 240℃、280℃、280℃、285℃、280℃、275℃、280℃ 和280℃，模头温度280℃。
 
实施例2
称取聚酰胺PA6为40份、双酚A聚芳酯40份、双酚A型环氧树脂2份、马来酸酐8份、甲基丙烯酸缩水甘油酯1份、润滑剂聚乙烯蜡为2份、抗氧化剂N,N’-1,6-亚已基-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰胺]（1098）为1份和亚磷酸三(2，4-二叔丁基苯基)酯（168）为1份一同混合均匀，再将混合物料从双螺杆挤出机的主喂料口加入，经熔融挤出、冷却、切粒即可得聚酰胺/聚芳酯合金；其中双螺杆挤出机从进料段到机头的温度分别为： 230℃、270℃、270℃、275℃、270℃、265℃、270℃ 和270℃，模头温度270℃。
 
实施例3
称取聚酰胺PA6为55份、双酚A聚芳酯35份、双酚A型环氧树脂6份、马来酸酐2份、甲基丙烯酸缩水甘油酯2份、润滑剂聚乙烯蜡为0.3份和硅酮母粒0.3份、抗氧化剂N,N’-1,6-亚已基-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰胺]（1098）为0.2份和亚磷酸三(2，4-二叔丁基苯基)酯（168）为0.3份一同混合均匀，再将混合物料从双螺杆挤出机的主喂料口加入，经熔融挤出、冷却、切粒即可得聚酰胺/聚芳酯合金；其中双螺杆挤出机从进料段到机头的温度分别为：220℃、260℃、260℃、265℃、260℃、255℃、260℃ 和260℃，模头温度265℃。
 
实施例4
称取聚酰胺PA66为50份、双酚A聚芳酯30份、双酚A型环氧树脂8份、马来酸酐5份、甲基丙烯酸缩水甘油酯3份、润滑剂乙撑双硬脂酸酰胺EBS为0.2份、聚乙烯蜡为0.2份和硅酮母粒0.4份、抗氧化剂N,N’-1,6-亚已基-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰胺]（1098）为0.3份和亚磷酸三(2，4-二叔丁基苯基)酯（168）为0.5份一同混合均匀，再将混合物料从双螺杆挤出机的主喂料口加入，经熔融挤出、冷却、切粒即可得聚酰胺/聚芳酯合金；其中双螺杆挤出机从进料段到机头的温度分别为：240℃、280℃、280℃、285℃、280℃、275℃、280℃ 和280℃，模头温度280℃。
 
实施例5
称取聚酰胺PA66为30份、聚酰胺6为30份、双酚A聚芳酯30份、双酚A型环氧树脂3份、马来酸酐2份、甲基丙烯酸缩水甘油酯4份、润滑剂乙撑双硬脂酸酰胺EBS为0.3份、聚乙烯蜡为0.2份和硅酮母粒0.2份、抗氧化剂N,N’-1,6-亚已基-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰胺]（1098）为0.1份和亚磷酸三(2，4-二叔丁基苯基)酯（168）为0.1份一同混合均匀，再将混合物料从双螺杆挤出机的主喂料口加入，经熔融挤出、冷却、切粒即可得聚酰胺/聚芳酯合金；其中双螺杆挤出机从进料段到机头的温度分别为：230℃、270℃、270℃、275℃、270℃、265℃、270℃ 和270℃，模头温度270℃。
 
上述实施例所得的合金材料在270-300℃注塑成各种样条，依据表1所列测试方法测试各项性能，实施例1-5各材料性能如表2和表3所示，同时表3还列出了PA6及PA66的各项参数。
表1 测试方法
拉伸强度 ISO 527
弯曲强度 ISO 178
弯曲模量 ISO 178
简支梁缺口冲击强度 ISO 179-1
热变形温度（1.82MPa） ISO 75-1、2
收缩率 ISO 294-4
吸水率 ISO 62
密度 ISO 1183
表2 合金材料性能测试
性能 实施例1 实施例2 实施例3
拉伸强度MPa 75.6 79.7 78.2
弯曲强度MPa 114 132 124
弯曲模量MPa 2686 2961 2320
简支梁缺口冲击强度Kj/m2 9.1 8.3 7.1
热变形温度（1.82MPa）℃ 107 127 119
收缩率% 0.8 0.5 0.7
吸水率% 1.1 0.6 0.7
密度g/cm3 1.18 1.22 1.21
表3 合金材料性能测试
性能 实施例4 实施例5 PA6 PA66
拉伸强度MPa 77.8 72.2 62.7 72.6
弯曲强度MPa 120 119 88.8 110
弯曲模量MPa 2530 2411 2010 2603
简支梁缺口冲击强度Kj/m2 7.6 8.4 8.8 7.6
热变形温度（1.82MPa）℃ 112 112 61 70
收缩率% 0.8 0.7 1.5 1.9
吸水率% 0.9 1.0 2.1 1.7
密度g/cm3 1.20 1.20 1.14 1.14
由表2、表3可以看出聚酰胺/聚芳酯合金由于较好地相容性，所以力学性能并未降低，而热变形温度得到明显提高普遍都＞100℃（1.82MPa），表现出良好的热稳定，聚酰胺/聚芳酯合金成型收缩率也比聚酰胺树脂小，制品不易变形翘曲；聚酰胺/聚芳酯合金吸水率比聚酰胺树脂明显降低，缩短材料成型前干燥时间；另外，聚酰胺/聚芳酯合金的密度并没有大幅提高。

Claims (7)

1.一种聚酰胺/聚芳酯合金，其特征在于，由如下组分按照质量份制备而成：
聚酰胺          40-60份
双酚A聚芳酯     20-40份
相容剂          5-20份
抗氧剂          0.2-2份
润滑剂          0.2-2份。
2.如权利要求1的所述的一种聚酰胺/聚芳酯合金，其特征在于，所述聚酰胺为相对粘度2.4-3.0的聚酰胺66和/或聚酰胺6。
3.如权利要求1的所述的一种聚酰胺/聚芳酯合金，其特征在于，所述的双酚A聚芳酯分子结构为
Figure 2014100082497100001DEST_PATH_IMAGE002
。
4.如权利要求1的所述的一种聚酰胺/聚芳酯合金，其特征在于，所述的相容剂的重量组成为双酚A型环氧树脂2-8份、马来酸酐2-8份、甲基丙烯酸缩水甘油酯1-4份。
5.如权利要求1的所述的一种聚酰胺/聚芳酯合金，其特征在于，所述的抗氧剂为N,N’-1,6-亚已基-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰胺]或者为N,N’-1,6-亚已基-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰胺]和亚磷酸三(2，4-二叔丁基苯基)酯组合物。
6.如权利要求1的所述的一种聚酰胺/聚芳酯合金，其特征在于，所述润滑剂为乙撑双硬脂酸酰胺、聚乙烯蜡、硅酮母粒中的至少一种。
7.一种权利要求1-6任一项所述聚酰胺/聚芳酯合金的制备方法，步骤如下：
按配比将聚酰胺、双酚A聚芳酯、相容剂、润滑剂和抗氧剂一同混合，再将混合物料从双螺杆挤出机的主喂料口加入，经熔融挤出、冷却、切粒即可得聚酰胺/聚芳酯合金；其中双螺杆挤出机从进料段到机头的温度分别为：220-240℃、260-280℃、260-280℃、265-285℃、260-280℃、255-275℃、260-280℃ 和260-280℃，模头温度265-280℃。
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CN111961341A (zh) * 2020-08-25 2020-11-20 宁波公牛电器有限公司 一种复合材料及其制备方法、固定架及墙壁开关

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