CN111961342A - 一种制备阻燃高韧pa66/ppo塑料合金的方法 - Google Patents
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Abstract
本发明属高分子材料领域,公开了一种制备阻燃高韧尼龙66/聚苯醚(PA66/PPO)塑料合金的方法。该方法如下:将马来酸酐(MAH)、高抗冲聚苯乙烯(HIPS)熔融混合在一起,挤出造粒;然后将粒料置于伽马射线辐射场中进行辐照,吸收剂量1kGy~100kGy。将辐照后的粒料与PA66、PPO、阻燃剂及其他助剂混合在一起;最后将上述混合物在挤出机上挤出造粒,得到阻燃高韧PA66/PPO塑料合金。
Description
技术领域
本发明涉及一种塑料合金,具体涉及一种制备阻燃高韧尼龙66/聚苯醚合金的方法,属高分子材料领域。
背景技术
尼龙66(PA66)和聚苯醚(PPO)都属于用途非常广泛的工程塑料。PA66具有许多优良的性能,如熔体流动性好、尺寸稳定性好、强度大、耐溶剂性好等特点,被广泛应用于汽车、机械制造、电子电器等领域。但其吸水率高,限制了应用。PPO刚性大、耐热性高、难燃,强度较高、电性能优良等。另外,聚苯醚还具有耐磨、无毒、耐污染等优点。PPO的介电常数和介电损耗在工程塑料中是最小的品种之一,几乎不受温度、湿度的影响。但是其熔体流动性不好,难以加工。鉴于PA66和PPO具有的上述性能优点和缺陷,可以将两者进行共混制备塑料合金,使两种塑料在性能方面实现优势互补,扬长避短,拓宽应用范围。
随着科学技术进步和经济发展,对塑料性能的要求越来越严苛,在许多工业应用领域及日常制品中都要求塑料具有阻燃性。纯的PA66的极限氧指数为22-23,属于可燃材料;PPO为28-29,属于难燃材料。PA66/PPO合金的极限氧指数介于两者之间,通常低于27,属于可燃材料。为了提高PA66/PPO合金的耐燃性,通常向合金中加入阻燃剂。
阻燃型的PA66/PPO合金需要首先解决PA66和PPO相容性不好的问题。PA66与PPO相容性不好,微观处于相分离状态,界面处结合能力差,导致合金的力学性能不好,强度、刚性低,尤其是韧性差。目前需要寻找更好的方法提高合金的综合性能。
发明内容
为提高PA66/PPO塑料合金的相容性,本发明提供了一种制备阻燃高韧PA66/PPO塑料合金的方法。
具体技术方案如下:该方法包括四个步骤:
步骤一,将马来酸酐(MAH)、聚苯乙烯(HIPS)熔融混合在一起,挤出造粒,其中MAH和HIPS的重量比是1:2~20;
步骤二,将步骤一中制备的粒料置于伽马射线辐射场中进行辐照处理,其中吸收剂量1kGy~100kGy;
步骤三,将辐照后的粒料与PA66、PPO、阻燃剂及其他助剂混合在一起,其中PA66、PPO、粒料、阻燃剂及其他助剂的重量比是100:50~900:10~200:2~100:2~50。所述其他助剂是防老剂、润滑剂中的一种或两种。
步骤四,将上述混合物在挤出机上挤出造粒,得到高抗冲PA66/PPO塑料合金。
本发明原理:步骤二中,在伽马射线作用下被辐照的物料产生自由基等活性点,活性点会引发MAH聚合。活性点位于HIPS分子链上,形成聚马来酸酐接枝链,接枝物标记为HIPS-g-MAH;活性点位于马来酸酐等其他成分时,形成非接枝的聚马来酸酐。HIPS-g-MAH中的PS与聚苯醚的相容性好,而聚马来酸酐接枝链与尼龙66的相容性好,由此,HIPS-g-MAH在界面处可以把尼龙66和聚苯醚两者连接起来,提高两者的相容性,使得合金的力学性能更好。
本发明技术优点与现有技术相比主要体现在如下方面:
HIPS-g-MAH有很多制备方法,大体可以归为化学法和辐射法。化学法使用有机溶剂,对环境不友好,而且MAH接枝率低。辐射法是一种物理方法,通常采用高能射线照射,在聚合物分子链上形成活性点。辐射法大致有两种途径,一是预辐射法,另一种是共辐射法。预辐射法先单独辐照聚合物,然后再与单体接触。其特点在于MAH的均聚物链很少,绝大多数都是接枝链,但缺点也很明显,就是大部分单体没有聚合,MAH转化率低。相对来说,共辐射法可以一步完成,操作简单、易行。实现共辐射接枝可以有三种形式,一是聚合物和单体在溶液中混合均匀后,除去溶剂,再进行射线辐照;二是聚合物粉体和单体粉体简单掺混在一起,再进行射线辐照;三是聚合物和单体熔融共混在一起,再进行射线辐照。这三种形式比较起来,第一种形式的缺点是使用了有机溶剂,不环保;第二种形式聚合物和单体的接触不紧密,接枝率很低。第三种形式则克服了其他两种形式的缺点,不使用有机溶剂,聚合物与单体的接触比较紧密。本发明采用第三种形式,即先将MAH与HIPS进行熔融共混,然后进行伽马射线辐照,得到HIPS-g-MAH接枝物。HIPS-g-MAH既起到对尼龙66进行增韧的目的,又能作为相容剂增进尼龙66和聚苯醚的相容性,充分发挥聚苯醚刚性大的优点,在显著提高尼龙66韧性的同时不降低其强度,由此制备方法得到的尼龙66/聚苯醚塑料合金,提高了物料的相容性,使得到的合金的力学性能更好。
具体实施方式
为对本发明进行更好地说明,举实施例如下:
实施例1
称取1000gHIPS和100gMAH,用密炼机进行熔融共混。取出共混物,装入聚乙烯袋中,密封,放入伽马射线辐射场中进行辐照。吸收剂量30kGy,剂量率1kGy/小时。取出,粉碎,得到粉状的HIPS-g-MAH。
分别称取2000gPA66、2000gPPO、1000g HIPS-g-MAH、500g磷硅阻燃剂、100g尼龙加工润滑剂,然后掺混在一起。用双螺杆挤出机挤出造粒,得到阻燃高韧尼龙66/聚苯醚塑料合金。
对其做力学性能测定:拉伸强度75.0MPa,弯曲强度98.6MPa,弹性模量5.68GPa,断裂伸长率6.24%,断裂强度76.08,冲击强度(缺口)8.68KJ/mm2,极限氧指数31.8。
实施例2
称取2000gHIPS和400gMAH,用密炼机进行熔融共混。取出共混物,装入聚乙烯袋中,密封,放入伽马射线辐射场中进行辐照。吸收剂量10kGy,剂量率1kGy/小时。取出,粉碎,得到粉状的HIPS-g-MAH。
分别称取1000gPA66、2000gPPO、2000g HIPS-g-MAH、500g磷硅阻燃剂、100g尼龙加工润滑剂,然后掺混在一起。用双螺杆挤出机挤出造粒,得到阻燃高韧尼龙66/聚苯醚塑料合金。
对其做力学性能测定:拉伸强度78.6MPa,弯曲强度102.4MPa,弹性模量5.25GPa,断裂伸长率7.84%,断裂强度85.7,冲击强度(缺口)11.4KJ/mm2,极限氧指数30.2。
对比例1
称取1000gHIPS,进行粉碎;称取100gMAH,用50g丙酮溶解均匀。将粉状的HIPS加入到MAH的丙酮溶液中,掺混均匀。放置12小时后,室温抽真空除去残余丙酮。取出,装入聚乙烯袋中,密封,放入伽马射线辐射场中进行辐照。吸收剂量30kGy,剂量率1kGy/小时。取出,粉碎,得到粉状的HIPS-g-MAH。
分别称取2000gPA66、2000gPPO、1000g HIPS-g-MAH、500g磷硅阻燃剂、100g尼龙加工润滑剂,然后掺混在一起。用双螺杆挤出机挤出造粒,得到PA66/PPO塑料合金。
对其做力学性能测定:拉伸强度60.1MPa,弯曲强度68.11MPa,弹性模量4.25GPa,断裂伸长率4.43%,断裂强度60.45,冲击强度5.94KJ/mm2,极限氧指数28.2。
在实施例1中,HIPS与MAH熔融混合,然后再辐照,得到HIPS-g-MAH。与实施例1相比,对比例1中HIPS与MAH简单混合在一起后进行辐照,得到HIPS-g-MAH。制备工艺不一样,增容效果也就不一样,实施例1中PA66/PPO合金的韧性和阻燃性好。
对比例2
称取2000gHIPS和80gMAH,用密炼机进行熔融共混。取出共混物,装入聚乙烯袋中,密封,放入伽马射线辐射场中进行辐照。吸收剂量10kGy,剂量率1kGy/小时。取出,粉碎,得到粉状的HIPS-g-MAH。
分别称取1000gPA66、2000gPPO、2000g HIPS-g-MAH、500g磷硅阻燃剂、100g尼龙加工润滑剂,然后掺混在一起。用双螺杆挤出机挤出造粒,得到阻燃高韧PA66/PPO合金。
对其做力学性能测定:拉伸强度75.3MPa,弯曲强度82.6MPa,弹性模量4.78GPa,断裂伸长率4.84%,断裂强度65.7,冲击强度(缺口)6.14KJ/mm2。极限氧指数29.2.
在实施例2中,MAH与HIPS的比例为1:5。而在对比例2中,MAH与HIPS的比例为1:25。实施例2中合金的力学性能及阻燃性都比对比例2中要高,说明HIPS-g-MAH中MAH的量对合金的性能有影响,其含量低时增容效果不好。
Claims (2)
1.一种制备阻燃PA66/PPO塑料合金的方法,其特征在于:通过如下步骤实现:
(1)将马来酸酐、聚苯乙烯熔融混合在一起,挤出造粒,其中马来酸酐和聚苯乙烯的重量比是1:2~20;
(2)将步骤(1)中制备的粒料置于伽马射线辐射场中进行辐照处理;
(3)将辐照后的粒料与PA66、PPO、阻燃剂、其他助剂混合在一起,其中PA66、PPO、粒料、阻燃剂及其他助剂的重量比是100:50~900:10~200:2~100:2~50;
(4)将上述混合物在挤出机上挤出造粒,得到阻燃PA66/PPO塑料合金;
所述其他助剂是防老剂、润滑剂中的一种或两种。
2.如权利要求1所述的制备阻燃PA66/PPO塑料合金的方法,其特征在于,步骤(2)辐照吸收剂量1kGy~100kGy。
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CN114085522B (zh) * | 2021-12-31 | 2024-03-08 | 焦作同辐科技有限责任公司 | 一种高cti值无卤阻燃玻纤增强pa66/ppo复合材料及其制备方法 |
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