CN103589060A - 玻纤增强聚丙烯/聚苯乙烯合金复合材料及其制备与应用 - Google Patents
玻纤增强聚丙烯/聚苯乙烯合金复合材料及其制备与应用 Download PDFInfo
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Abstract
本发明属于改性塑料技术领域,公开了一种易喷涂、浅缩痕玻纤增强聚丙烯/聚苯乙烯合金复合材料及其制备方法与应用。该合金复合材料包含以下质量分数的组分:聚丙烯40~69%;聚苯乙烯10~30%;短切玻璃纤维15~30%;矿物填充物1~20%;接枝聚丙烯2~5%;喷涂改进剂1~2%。本发明采用高结晶聚丙烯,可有效提高注塑过程中冷却固化速度,使成品表面具有浅缩痕、低翘曲、表面光泽度高的特性,且达因指数高,对油墨浸润性好。本发明加入了短切玻璃纤维与矿物填充物复合增强,使复合具有更好的力学性能,应用于家用电器和汽车工业,可以替代工程塑料使用,亦符合对尺寸稳定性、翘曲、力学性能要求高的制件的要求。
Description
技术领域
本发明属于改性塑料技术领域,特别涉及一种易喷涂、浅缩痕玻纤增强聚丙烯/聚苯乙烯合金复合材料及其制备方法与应用。
背景技术
玻璃纤维增强聚丙烯具有机械强度高、耐热性好、耐化学腐蚀、尺寸稳定等优点,广泛应用于家用电器、汽车、机械等领域。玻璃纤维增强聚丙烯的强度和模量能够媲美工程塑料,这进一步扩展了增强聚丙烯的应用前景。但由于聚丙烯材料本身极性很低,表面达因指数很低,导致在喷涂过程中,必须加入氯化聚丙烯进行预处理以提高其表面极性,增加了喷涂的工序和成本。另外,由于聚丙烯收缩率大、并且属结晶性材料,注塑成型后冷却固化速度慢,易出现缩痕现象,这种表面缺陷严重影响制品的外观美观程度,并且在喷涂后仍然可见,极大限制了聚丙烯材料在外观部件中的使用。
缩痕一般是由于塑料制品壁厚增加引起制品收缩率局部增加而产生的,它可能出现在外部尖角附近或者壁厚突变处,如凸起、加强筋或者支座的背后,有时也会出现在一些不常见的部位。产生凹痕的根本原因是材料的热胀冷缩,因为热塑性塑料的热膨胀系数相当高。膨胀和收缩的程度取决于许多因素,其中塑料的性能、型腔保压压力是最重要的因素,还有注塑件的尺寸和形状以及冷却速度和均匀性等也是影响因素。
中国专利CN1315465A公开了一种低翘曲玻璃纤维增强聚丙烯的材料,但由于基体树脂选择聚丙烯与聚苯乙烯合金,两者相容性差,制得材料物理性能较差,冲击强度降低,材料偏脆。
因此,开发一种易喷涂、浅缩痕的高性能的聚丙烯/聚苯乙烯合金复合材料是市场迫切的需求。
发明内容
为了克服上述现有技术中玻纤增强聚丙烯不易喷涂的缺点与缩痕现象严重等不足,本发明的首要目的在于提供一种易喷涂、浅缩痕玻纤增强聚丙烯/聚苯乙烯合金复合材料。
本发明另一目的在于提供上述易喷涂、浅缩痕玻纤增强聚丙烯/聚苯乙烯合金复合材料的制备方法。
本发明再一目的在于提供上述易喷涂、浅缩痕玻纤增强聚丙烯/聚苯乙烯合金复合材料在家电及汽车工业中的应用。
本发明的目的通过下述方案实现:
一种易喷涂、浅缩痕玻纤增强聚丙烯/聚苯乙烯合金复合材料,包含以下质量分数的组分:
所述的聚丙烯包括高结晶聚丙烯、均聚聚丙烯和共聚聚丙烯中的至少一种。
优选地,所述的聚丙烯的熔体流动速率为5~50g/10min(230℃,2.16kg)。
优选地,所述的聚丙烯指高结晶聚丙烯。
所述的聚苯乙烯为通用聚苯乙烯。
优选地,所述聚苯乙烯的牌号优选为GPPS-123P。
所述短切玻璃纤维的长度为0.2~10mm,直径为8~20μm。
所述的矿物填充物指硫酸钡、碳酸钙和云母中的至少一种。
所述的接枝聚丙烯为聚丙烯与不饱和酸或不饱和酸酐的接枝低聚物。
所述的接枝聚丙烯的接枝率为0.3~1.2%,融指为50~120g/10min(230℃,2.16kg)。
优选地,所述的接枝聚丙烯指聚丙烯接枝马来酸、聚丙烯接枝衣康酸、聚丙烯接枝丙烯酸、聚丙烯接枝马来酸酐和聚丙烯接枝丙烯酸缩水甘油酯中的至少一种。
更优选地,所述的接枝聚丙烯指聚丙烯接枝马来酸酐。
所述的喷涂改进剂指固态双酚A环氧树脂。
优选地,所述的喷涂改进剂指CYD-011、CYD-012和E-31环氧树脂中的至少一种。
上述易喷涂、浅缩痕玻纤增强聚丙烯/聚苯乙烯合金复合材料中还可以包括0.1~2wt%的加工助剂。
所述的加工助剂指抗氧剂、成核剂、偶联剂、润滑剂和耐霉菌剂中的至少一种。
上述加工助剂为本领域常用试剂。
上述易喷涂、浅缩痕玻纤增强聚丙烯/聚苯乙烯合金复合材料的制备方法,包括以下具体步骤:
将聚丙烯、聚苯乙烯、矿物填充物、接枝聚丙烯和喷涂改进剂混合,然后从挤出机的主喂料口喂入;短切玻璃纤维从挤出机的侧喂料口喂入;熔融挤出、造粒后,得到易喷涂、浅缩痕玻纤增强聚丙烯/聚苯乙烯合金复合材料。
所述的挤出机优选双螺杆挤出机,所述的熔融指在220~250℃下熔融。
上述易喷涂、浅缩痕玻纤增强聚丙烯/聚苯乙烯合金复合材料在家电及汽车工业中的应用。
本发明的机理为:
本发明采用高结晶聚丙烯/聚苯乙烯与玻纤、填充物复合增强,因材料收缩率低,并且加入非结晶的聚苯乙烯组分,可有效提高材料在注塑过程中冷却固化速度,另外通过加入极性组分提高材料表面极性,提高材料达因指数,改善材料与油墨的附着力,制得的成品表面具有易喷涂、浅缩痕、低翘曲、表面光泽度高的特性,并且具有很高的弯曲强度和弯曲模量,加工性能好,成本低。
本发明相对于现有技术,具有如下的优点及有益效果:
(1)本发明的玻纤增强聚丙烯/聚苯乙烯合金复合材料,加入了短切玻璃纤维与矿物填充物复合增强,两者在聚丙烯中分布均匀。相比于单纯玻纤增强聚丙烯材料,本发明的玻纤增强聚丙烯材料具有更好的力学性能,应用于家用电器和汽车工业,可以替代工程塑料使用,亦符合对尺寸稳定性、翘曲、力学性能要求高的制件的要求。
(2)本发明采用高结晶聚丙烯,可有效提高材料在注塑过程中冷却固化速度,制得的成品表面具有浅缩痕、低翘曲、表面光泽度高的特性,并且具有很高的弯曲强度和弯曲模量,加工性能好,成本低,且达因指数高,材料对油墨浸润性好。
(3)本发明的聚丙烯/聚苯乙烯合金材料相容性好,表面无流痕、光泽度高。
具体实施方式
下面结合实施例对本发明作进一步详细的描述,但本发明的实施方式不限于此。
以下实施例中,挤出机熔融挤出的加工条件如下:一区温度210~230℃,二区温度220~240℃,三区温度220~240℃,四区温度220~240℃,五区温度230~250℃,六区温度240~260℃,七区温度230~250℃,八区温度220~240℃,九区温度200~220℃,主机转速250~360转/分钟。
实施例1~6
一种易喷涂、浅缩痕玻纤增强聚丙烯/聚苯乙烯合金复合材料,其原料配方如表1所示,其制备方法包括以下步骤:
将短切玻璃纤维以外的其他原料混合,然后从双螺杆挤出机的主喂料口喂入;短切玻璃纤维从双螺杆挤出机的侧喂料口喂入;原料在挤出机中熔融、挤出、造粒后得到易喷涂、浅缩痕玻纤增强聚丙烯/聚苯乙烯合金复合材料。
表1中,均聚聚丙烯的熔融指数为5g/min(230℃,2.16kg),共聚聚丙烯树的熔融指数为50g/min(230℃,2.16kg),高结晶聚丙烯的熔融指数为15g/min(230℃,2.06kg),聚苯乙烯为GPPS-123P(上海赛科),聚丙烯接枝马来酸酐的熔融指数为80g/min(230℃,2.16kg),接枝率为0.8%,所采用的短切玻璃纤维,其长度为0.2~10mm,直径为8~20μm。环氧树脂为CYD-011。
对比例1~2
一种玻纤增强聚丙烯材料,其原料配方如表1所示,其制备方法包括以下步骤:
将短切玻璃纤维(长度为0.2~10mm,直径为8~20μm)以外的其它组分预混,将混合均匀的物料置于双螺杆挤出机主喂料口中,玻璃纤维单独从侧喂料口进入,双螺杆机熔融挤出,造粒后干燥。
将实施例1~6、对比例1~2制备得到的粒料注塑成力学样条进行测试,测试标准:拉伸强度ASTM D638;断裂伸长率ASTM D638;弯曲强度ASTMD790;弯曲模量ASTM D790;悬臂梁缺口冲击强度ASTM D256;达因指数EnerDyne达因笔。测试结果见表2。
表1玻纤增强聚丙烯/聚苯乙烯合金复合材料配方表(单位:重量份)
表2玻纤增强聚丙烯/聚苯乙烯合金复合材料性能指标
由表2可见,对比例的材料为目前市场上通用的玻纤增强PP/PS产品,采用普遍的配方及加工工艺,其表面缩痕均远深于本实施例所述聚丙烯/聚苯乙烯合金复合材料,而其达因指数较低,并且说明采用现有技术制备的产品表面缩痕较为严重,材料表面达因指数低,不利于油墨的浸润。
本发明的实施例采用高结晶聚丙烯/聚苯乙烯合金与玻纤、填充物复合增强的方式,可有效降低制品外观缩痕,并且达因指数高,材料对油墨浸润性好,力学性能优异,加工性能良好,成本低。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (10)
2.根据权利要求1所述的玻纤增强聚丙烯/聚苯乙烯合金复合材料,其特征在于:所述的聚丙烯指高结晶聚丙烯、均聚聚丙烯和共聚聚丙烯中的至少一种;所述的聚丙烯的熔体流动速率为5~50g/10min(230℃,2.16kg)。
3.根据权利要求1所述的玻纤增强聚丙烯/聚苯乙烯合金复合材料,其特征在于:所述短切玻璃纤维的长度为0.2~10mm,直径为8~20μm;所述的矿物填充物指硫酸钡、碳酸钙和云母中的至少一种;所述的接枝聚丙烯为聚丙烯与不饱和酸或不饱和酸酐的接枝低聚物。
4.根据权利要求1所述的玻纤增强聚丙烯/聚苯乙烯合金复合材料,其特征在于:所述的接枝聚丙烯的接枝率为0.3~1.2%,融指为50~120g/10min(230℃,2.16kg);所述的喷涂改进剂指固态双酚A环氧树脂。
5.根据权利要求1所述的玻纤增强聚丙烯/聚苯乙烯合金复合材料,其特征在于:所述的接枝聚丙烯指聚丙烯接枝马来酸、聚丙烯接枝衣康酸、聚丙烯接枝丙烯酸、聚丙烯接枝马来酸酐和聚丙烯接枝丙烯酸缩水甘油酯中的至少一种。
6.根据权利要求1所述的玻纤增强聚丙烯/聚苯乙烯合金复合材料,其特征在于:所述的聚丙烯指高结晶聚丙烯;所述的接枝聚丙烯指聚丙烯接枝马来酸酐;所述的喷涂改进剂指CYD-011、CYD-012和E-31环氧树脂中的至少一种。
7.根据权利要求1所述的玻纤增强聚丙烯/聚苯乙烯合金复合材料,其特征在于:所述玻纤增强聚丙烯/聚苯乙烯合金复合材料中含有0.1~2wt%的加工助剂。
8.根据权利要求7所述的玻纤增强聚丙烯/聚苯乙烯合金复合材料,其特征在于:所述的加工助剂指抗氧剂、成核剂、偶联剂、润滑剂和耐霉菌剂中的至少一种。
9.一种根据权利要求1~8任一项所述的玻纤增强聚丙烯/聚苯乙烯合金复合材料的制备方法,其特征在于包括以下具体步骤:
将聚丙烯、聚苯乙烯、矿物填充物、接枝聚丙烯和喷涂改进剂混合,然后从挤出机的主喂料口喂入;短切玻璃纤维从挤出机的侧喂料口喂入;熔融挤出、造粒后,得到易喷涂、浅缩痕玻纤增强聚丙烯/聚苯乙烯合金复合材料;
所述的挤出机优选双螺杆挤出机;所述的熔融指在220~250℃下熔融。
10.根据权利要求1~8任一项所述的玻纤增强聚丙烯/聚苯乙烯合金复合材料在家电及汽车工业中的应用。
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