CN111471242A - 一种耐划伤聚丙烯复合材料及其制备方法 - Google Patents
一种耐划伤聚丙烯复合材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种耐划伤聚丙烯复合材料及其制备方法,包括组分:聚丙烯22‑89份;短切无碱玻璃纤维5‑40份;极性单体接枝聚合物类相容剂0‑8份;增韧剂5‑20份;耐划伤剂0.5‑4份。本发明通过短切无碱玻璃纤维与耐划伤剂并用的方式,制备得到的复合材料具有优异的耐划伤性能,特别是针对皮纹纹理深度大于100μm的几何皮纹,也可以起到很好的耐划伤效果,既达到节约成本的目的,又保持了较高的力学性能和良好的气味。
Description
技术领域
本发明属于高分子材料领域,具体涉及一种耐划伤聚丙烯复合材料及其制备方法。
背景技术
聚丙烯是五大通用塑料之一,具有成本低、易加工成型、环保无毒等特点,被广泛的应用于汽车、家电等领域。但是同时纯的聚丙烯材料存在刚性差、收缩率大、尺寸稳定性差等缺点,为改善这些特性通常是加入滑石粉进行改性,而这会导致聚丙烯复合材料的耐划伤性能变差。对于该类材料注塑的汽车制件来说,在生产、运输及使用过程中,不可避免会受到硬物的碰擦,如乘客手指甲和鞋子等划伤,从而影响耐用性和美观。因此通常需要对滑石粉填充聚丙烯复合材料进行划伤性能的改性,常用的手段是添加耐划伤剂。
伴随着汽车行业的发展,消费者对汽车内外饰件的精细化和个性化关注程度越来越高。塑料件的皮纹作为影响汽车内外饰风格的重要因素之一,涉及到美学、触感、以及安全性,也在不断的发展变化,其中一个趋势是从普通的粗皮纹和细皮纹(通常皮纹纹理深度≤100μm),朝着几何皮纹的方向进行发展(通常皮纹纹理深度>100μm)。而皮纹的纹理深度是影响耐划伤性能的重要因素,对于相同的材料,皮纹越深则耐划伤效果越差。传统的经过正常含量(1%-3%)的耐划伤剂改性的滑石粉填充聚丙烯复合材料,已经不足以应付高纹理深度几何皮纹的耐划伤要求。
对于纹理深度较大的几何皮纹,虽然通过大量提高耐划伤剂的含量(≥5%)的方式,也可以起到改善划伤性能的作用,但是存在很多方面的问题:a.成本显著提高:耐划伤剂成本昂贵,提高划伤剂含量意味着成本会明显增加;b.力学性能受到显著的影响:耐划伤剂在聚丙烯复合材料中起到应力集中点的作用,提高划伤剂含量也伴随着力学性能的恶化;c.气味等级的显著提升:耐划伤剂相对聚丙烯基体气味更大,提高划伤剂含量气味也会随之升高。
发明内容
为了克服上述现有技术存在的不足,本发明的首要目的在于提供一种耐划伤聚丙烯复合材料,该复合材料具有优异的耐划伤性能,特别是针对皮纹纹理深度大于100μm的几何皮纹,也可以起到很好的耐划伤效果,既达到节约成本的目的,又保持了较高的力学性能和良好的气味。
本发明的另一目的在于提供上述耐划伤聚丙烯复合材料的制备方法。
本发明是通过以下技术方案实现的:
一种耐划伤聚丙烯复合材料,按重量份数计,包括以下组分:
聚丙烯 22-89份;
短切无碱玻璃纤维 5-40份;
极性单体接枝聚合物类相容剂 0-8份;
增韧剂 5-20份;
耐划伤剂 0.5-4份。
优选的,所述聚丙烯为均聚聚丙烯或共聚聚丙烯中的一种或两种的混合,所述聚丙烯在230℃、2.16kg的测试条件下,熔体流动速率为0.1-100g/10min。
优选的,所述短切无碱玻璃纤维的直径≤15μm,长度为3~5mm。
优选的,所述极性单体接枝聚合物类相容剂的聚合物部分为聚烯烃共聚物,具体为聚乙烯、聚丙烯、乙烯-α-乙烯-辛烯共聚物、苯乙烯与丁二烯的共聚物、聚乙烯-聚苯乙烯-聚丙烯三元共聚物、乙烯-丙烯-丁二烯三元共聚物、乙烯-丙烯酸酯共聚物、乙烯-丙烯酸酯-甲基丙烯酸缩水甘油酯聚合物的至少一种;其接枝的极性单体部分为可双键聚合的酸酐类单体、丙烯酸类单体和丙烯酸酯类单体中的至少一种。其中:可双键聚合的酸酐类单体为马来酸、富马酸、衣康酸、柠康酸、柠康酸酐或乙烯基丁二酸酐中的至少一种,丙烯酸类单体为丙烯酸或甲基丙烯酸中的至少一种,丙烯酸酯类单体为丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸甲酯或甲基丙烯酸环氧丙酯中的至少一种。
优选的,所述增韧剂为高密度聚乙烯、低密度聚乙烯、线性低密度聚乙烯、乙烯-醋酸乙烯共聚物、氢化的乙烯-丁二烯-苯乙烯共聚物、苯乙烯-丁二烯-苯乙烯三元嵌段共聚物、氢化的苯乙烯-丁二烯-苯乙烯三元嵌段共聚物、乙烯-α-乙烯-辛烯共聚物、三元乙丙胶或聚氨酯中的一种或几种的混合。
优选的,所述的耐划伤剂为脂肪酸酰胺类耐划伤剂或硅酮类耐划伤剂中的至少一种,其中所述脂肪酸酰胺类耐划伤剂选自油酸酰胺、芥酸酰胺、乙撑双硬脂酸酰胺中的至少一种,所述硅酮类耐划伤剂为聚硅氧烷。
根据实际性能需要,本发明所述的耐划伤聚丙烯复合材料,按重量份数计,还包括0-5份的其它功能助剂,所述其它功能助剂为抗氧剂、润滑剂、着色剂、发泡剂、表面活性剂、增塑剂、偶联剂、阻燃剂、光稳定剂、抗静电助剂、抗微生物助剂、成核剂或气味吸附剂中的一种或几种的混合。其中,合适的抗氧剂为主抗氧剂和辅抗氧剂的复配,其中主抗氧剂为受阻酚类化合物如四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯(抗氧剂1010),辅抗氧剂为亚磷酸酯类化合物如三(2,4-二叔丁基苯基)亚磷酸酯(抗氧剂168);合适的着色剂为炭黑。
本发明还提供了上述耐划伤聚丙烯复合材料的制备方法,包括如下步骤:
(1)按配比称取各组分,将各组分加入高混机内高速混合1-3min,混合均匀后得到预混料;
(2)将预混料置于双螺杆挤出机的主喂料口进行熔融挤出,造粒干燥即得成品。
作为本发明进一步优选的技术方案,本发明上述耐划伤聚丙烯复合材料的制备方法,包括如下步骤:
(1)按配比称取各组分,将除短切无碱玻璃纤维外的其他组分加入高混机内干混1-3min,制得混合物A;
(2)将混合物A从螺杆主喂料口加入双螺杆挤出机,短切无碱玻璃纤维从螺杆中部侧向喂料口加入双螺杆挤出机,经熔融挤出后造粒干燥即得成品。
优选的,步骤(2)中,所述双螺杆挤出机中熔融挤出的条件为:一区温度80-120℃,二区温度190-210℃,三区温度210-230℃,四区温度210-230℃,五区温度210-230℃,六区温度210-230℃,七区温度210-230℃,八区温度210-230℃,九区温度210-230℃,主机转速200-800转/分钟;所述双螺杆挤出机的长径比为36:1~56:1。
与现有技术相比,本发明具有如下有益效果:
(1)本发明通过短切无碱玻璃纤维与耐划伤剂并用的方式,制备得到的复合材料具有优异的耐划伤性能,特别是针对皮纹纹理深度大于100μm的几何皮纹,也可以起到很好的耐划伤效果;
(2)本发明一方面无需增加耐划伤剂的含量,另一方面由于短切无碱玻璃纤维特殊的高长径比的结构,制备得到的复合材料在保证优异耐划伤性能的同时,既达到节约成本的目的,又保持了较高的力学性能和良好的气味。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明,单不以任何形式限制本发明。应当指出的是,对本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进。这些都属于本发明的保护范围。
本发明实施例及对比例所用的原材料均来源于市购,但不限于这些材料:
聚丙烯:共聚聚丙烯,在230℃、2.16kg的条件下熔体流动速率为30g/min;
短切无碱玻璃纤维1:直径8μm,长度4mm;
短切无碱玻璃纤维2:直径12μm,长度3mm;
短切无碱玻璃纤维3:直径20μm,长度4mm;
极性单体接枝聚合物类相容剂1:马来酸酐接枝聚丙烯;
极性单体接枝聚合物类相容剂2:丙烯酸接枝聚乙烯;
增韧剂:乙烯-α-乙烯-辛烯共聚物;
耐划伤剂:聚硅氧烷、芥酸酰胺;
滑石粉:平均粒径为5μm;
主抗氧剂:四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯(抗氧剂1010);
辅抗氧剂:三(2,4-二叔丁基苯基)亚磷酸酯(抗氧剂168);
着色剂:炭黑。
实施例1-9和对比例1-4:
(1)按表1配比称取各组分,将除短切无碱玻璃纤维外的其他组分加入高混机内干混1~3min,得到混合物A;
(2)将混合物A从螺杆主喂料口加入双螺杆挤出机,短切无碱玻璃纤维从螺杆中部侧向喂料口加入双螺杆挤出机,经熔融挤出后造粒干燥即得成品。双螺杆挤出机的熔融挤出的条件为:一区温度90℃,二区温度200℃,三区温度200℃,四区温度220℃,五区温度220℃,六区温度220℃,七区温度220℃,八区温度220℃,九区温度220℃,主机转速500r/min;双螺杆挤出机的长径比为40:1。
实施例10:
制备工艺:按表1配比称取各组分,将各组分加入高混机内高速混合1-3min,混合均匀后得到预混料;将预混料置于双螺杆挤出机的主喂料口进行熔融挤出,造粒干燥即得成品。
双螺杆挤出机的熔融挤出的条件同实施例3。
性能测试方法:
耐划伤性能:实施例和对比例中聚丙烯复合材料制备成不同皮纹纹理深度的样板进行测试(40μm的细皮纹,80μm的粗皮纹,120μm的几何皮纹,160μm的几何皮纹),按照PV3952进行耐划伤性能测试,测试划伤用力为10N。采用划伤前后色差△L值变化大小来评估,材料耐划伤性能越好,△L值越小,通常主机厂判定合格的标准为各类型皮纹均需达到△L≤1.5。
拉伸性能:按ISO527执行;
弯曲性能:按ISO178执行;
冲击性能:按ISO180执行;
密度:按ISO1183执行;
气味:按PV3900执行。
表1实施例1-10及对比例1-4中各组分的用量
续表1:
从表1可以看出:将对比例2与对比例1相比,通过将耐划伤剂含量从2份增加到6份,耐划伤性能△L虽然降低后可以符合要求,但是力学性能有非常明显的衰减,且该方案成本非常高,因此对比例2中的方案并不具有实用性。将实施例1与对比例1相比,通过将滑石粉替换为短切无碱玻璃纤维,耐划伤剂在保持2份的基础上,也达到了和对比例2基本一样的耐划伤效果,且力学性能不仅没有衰减,反而还有上升。将实施例2-4与对比例3进行比较,随着耐划伤剂含量的增加,△L值明显降低,特别是对于120μm和160μm皮纹深度的几何皮纹,更有明显的效果,其中当未添加有耐划伤剂时(对比例3),皮纹深度大的皮纹无法满足△L≤1.5的要求。将实施例3与实施例1进行比较,极性单体接枝聚合物类相容剂的存在可以进一步降低△L值,因为其可以起到加强短切无碱玻璃纤维和基体相互的作用,进一步改善耐划伤性能。综合实施例1、实施例3和对比例1,可以发现极性单体接枝聚合物类相容剂与耐划伤剂对于改善耐划伤性能有一定的协同作用。
Claims (10)
1.一种耐划伤聚丙烯复合材料,其特征在于,按重量份数计,包括以下组分:
聚丙烯 22-89份;
短切无碱玻璃纤维 5-40份;
极性单体接枝聚合物类相容剂 0-8份;
增韧剂 5-20份;
耐划伤剂 0.5-4份。
2.根据权利要求1所述的耐划伤聚丙烯复合材料,其特征在于,所述聚丙烯为均聚聚丙烯
或共聚聚丙烯中的一种或两种的混合,所述聚丙烯在230℃、2.16kg的测试条件下,熔体流动速率为0.1-100 g/10min。
3.根据权利要求1所述的耐划伤聚丙烯复合材料,其特征在于,所述短切无碱玻璃纤维的直径≤15μm,长度为3~5mm。
4.根据权利要求1所述的耐划伤聚丙烯复合材料,其特征在于,所述极性单体接枝聚合物类相容剂的聚合物部分为聚烯烃共聚物,具体为聚乙烯、聚丙烯、乙烯-α-乙烯-辛烯共聚物、苯乙烯与丁二烯的共聚物、聚乙烯-聚苯乙烯-聚丙烯三元共聚物、乙烯-丙烯-丁二烯三元共聚物、乙烯-丙烯酸酯共聚物、乙烯-丙烯酸酯-甲基丙烯酸缩水甘油酯聚合物的至少一种;所述极性单体部分为可双键聚合的酸酐类单体、丙烯酸类单体和丙烯酸酯类单体中的至少一种;其中,所述可双键聚合的酸酐类单体为马来酸、富马酸、衣康酸、柠康酸、柠康酸酐或乙烯基丁二酸酐中的至少一种,所述丙烯酸类单体为丙烯酸或甲基丙烯酸中的至少一种,所述丙烯酸酯类单体为丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸甲酯或甲基丙烯酸环氧丙酯中的至少一种。
5.根据权利要求1所述的耐划伤聚丙烯复合材料,其特征在于,所述增韧剂为高密度聚乙烯、低密度聚乙烯、线性低密度聚乙烯、乙烯-醋酸乙烯共聚物、氢化的乙烯-丁二烯-苯乙烯共聚物、苯乙烯-丁二烯-苯乙烯三元嵌段共聚物、氢化的苯乙烯-丁二烯-苯乙烯三元嵌段共聚物、乙烯-α-乙烯-辛烯共聚物、三元乙丙胶或聚氨酯中的一种或几种的混合。
6.根据权利要求1所述的耐划伤聚丙烯复合材料,其特征在于, 所述的耐划伤剂为脂肪酸酰胺类耐划伤剂或硅酮类耐划伤剂中的至少一种,其中所述脂肪酸酰胺类耐划伤剂选自油酸酰胺、芥酸酰胺、乙撑双硬脂酸酰胺中的至少一种,所述硅酮类耐划伤剂为聚硅氧烷。
7.根据权利要求6所述的耐划伤聚丙烯复合材料,其特征在于,按重量份数计,还包括0-5份的其它功能助剂,所述其它功能助剂为抗氧剂、润滑剂、着色剂、发泡剂、表面活性剂、增塑剂、偶联剂、阻燃剂、光稳定剂、抗静电助剂、抗微生物助剂、成核剂或气味吸附剂中的一种或几种的混合。
8.根据权利要求1-7任一项所述的耐划伤聚丙烯复合材料的制备方法,其特征在于,包括如下步骤:
(1)按配比称取各组分,将各组分加入高混机内高速混合1-3min,混合均匀后得到预混料;
(2)将预混料置于双螺杆挤出机的主喂料口进行熔融挤出,造粒干燥即得成品。
9.根据权利要求1-7任一项所述的耐划伤聚丙烯复合材料的制备方法,其特征在于,包括如下步骤:
(1)按配比称取各组分,将除短切无碱玻璃纤维外的其他组分加入高混机内干混1-3min,制得混合物A;
(2)将混合物A从螺杆主喂料口加入双螺杆挤出机,短切无碱玻璃纤维从螺杆中部侧向喂料口加入双螺杆挤出机,经熔融挤出后造粒干燥即得成品。
10.根据权利要求8或9所述的耐划伤聚丙烯复合材料的制备方法,其特征在于,步骤(2)中,所述双螺杆挤出机中熔融挤出的条件为:一区温度80-120℃,二区温度190-210℃,三区温度210-230℃,四区温度210-230℃,五区温度210-230℃,六区温度210-230℃,七区温度210-230℃,八区温度210-230℃,九区温度210-230℃,主机转速200-800转/分钟;所述双螺杆挤出机的长径比为36:1~56:1。
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