CN115536942B - 一种植物纤维增强聚丙烯复合材料及其制备方法 - Google Patents

一种植物纤维增强聚丙烯复合材料及其制备方法 Download PDF

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CN115536942B
CN115536942B CN202211313214.5A CN202211313214A CN115536942B CN 115536942 B CN115536942 B CN 115536942B CN 202211313214 A CN202211313214 A CN 202211313214A CN 115536942 B CN115536942 B CN 115536942B
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temperature resistant
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polypropylene composite
fiber
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CN115536942A (zh
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余林华
周素蓉
苏中淮
王彬
王海利
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Suzhou Sunway Polymer Co ltd
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Abstract

本申请涉及聚丙烯复合材料技术领域,具体公开了一种植物纤维增强聚丙烯复合材料及其制备方法,植物纤维增强聚丙烯复合材料,由包含以下重量份数的原料制成:均聚聚丙烯68‑99份;马来酸酐接枝聚丙烯5‑10份;耐高温改性稻草纤维15‑20份;竹纤维10‑15份;中空玻璃微珠1‑3份;抗氧剂0.1‑1份;润滑剂0.1‑1份;炭黑0.1‑1份。本申请具有提高聚丙烯复合材料拉伸强度、弯曲强度和冲击强度的效果。

Description

一种植物纤维增强聚丙烯复合材料及其制备方法
技术领域
本发明涉及聚丙烯复合材料技术领域,尤其是涉及一种植物纤维增强聚丙烯复合材料及其制备方法。
背景技术
聚丙烯,简称PP,是一种半结晶的热塑性塑料。具有较高的耐冲击性,机械性质强韧,在80℃以下能耐酸、碱、盐液及多种有机溶剂的腐蚀,能在高温和氧化作用下分解。聚丙烯广泛应用于服装、毛毯等纤维制品、医疗器械、汽车、自行车、零件、输送管道、化工容器等生产,也用于食品、药品包装。
随着社会的快速发展,汽车保有量越来越多,给人们出行带来方便快捷。目前,节能、环保、安全和智能都成为汽车发展的新动向。与此同时,能源和环境是当今世界面临的两大问题,两者都与汽车产业发展息息相关,制造出“低能耗”、“低排放”甚至“零排放”的汽车是汽车行业需要思考的问题。相较于汽车的动力***和传动***的技术改革,轻量化是降低能耗、减少排放的最为有效的措施之一。以天然环保新材料的植物纤维为增强材料,制备的植物纤维复合材料具有密度小、模量与强度高特点,非常适合汽车部件的轻量化。
相关技术中公开了一种含有植物纤维的聚丙烯复合材料,所述复合材料以植物纤维为增强纤维,以聚丙烯为基体;所述植物纤维由***纤维与椰壳纤维混杂得到;所述植物纤维和聚丙烯的质量比为3:7;所述***纤维与椰壳纤维的混杂质量比为0:1-7:3。
针对上述相关技术,发明人认为植物纤维表面的亲水性较好,与聚丙烯之间的界面相容性较差,且植物纤维的耐高温性能较差,在聚丙烯复合材料高温熔融挤出后,会造成聚丙烯复合材料力学性能下降。
发明内容
为了提高聚丙烯复合材料的力学性能,本申请提供一种植物纤维增强聚丙烯复合材料及其制备方法。
第一方面,本申请提供一种植物纤维增强聚丙烯复合材料,采用如下的技术方案:一种植物纤维增强聚丙烯复合材料,由包含以下重量份数的原料制成:
均聚聚丙烯68-99份;
马来酸酐接枝聚丙烯5-10份;
耐高温改性稻草纤维15-20份;
竹纤维10-15份;
中空玻璃微珠1-3份;
抗氧剂0.1-1份;
润滑剂0.1-1份;
炭黑0.1-1份;
所述耐高温改性稻草纤维的制备方法包括以下步骤:
碱处理,将稻草纤维与10-12wt%NaOH溶液混合,浸泡24-36h,取出,洗涤至中性,干燥,得到碱处理稻草纤维;
改性处理,将碱处理稻草纤维用3-4wt%乙烯基三(β-甲氧基乙氧基)硅烷的甲醇溶液浸泡24-48h,固液分离,干燥,得到改性稻草纤维;
耐高温处理,配置含有泡沫炭颗粒的耐高温涂料,将耐高温涂料喷涂至改性稻草纤维的表面,加热固化,得到耐高温改性稻草纤维。
通过采用上述技术方案,本申请通过加入耐高温改性稻草纤维,一方面,泡沫炭内部疏松多孔,密度小,强度高,耐高温,比表面积大,导热系数低,具有隔热的作用,耐高温涂料能够提高稻草纤维的耐高温性能,使其在挤出成型过程中不会碳化受损,耐高温改性稻草纤维在材料内部乱向交错分布,形成立体网络结构,提高了材料韧性,从而提高了聚丙烯的力学性能;另一方面,耐高温涂料改善了稻草纤维的表面性质,涂料表面与聚丙烯相容性更好,界面粘接力较强,从而进一步提高了聚丙烯的力学性能;乙烯基三(β-甲氧基乙氧基)硅烷作为耐高温偶联剂,能够使改性稻草纤维与耐高温涂料结合更加牢固,在高温挤出成型时,改性稻草纤维与耐高温涂料不易分离,进而提高了聚丙烯复合材料的力学性能。
聚丙烯是非极性聚合物,与竹纤维、耐高温改性稻草纤维难以形成有效的界面黏接,而马来酸酐接枝聚丙烯含有极性基团,既可以与聚丙烯相容,马来酸酐还可以与竹纤维、耐高温改性稻草纤维和中空玻璃微珠表面的羟基反应,增强了聚丙烯与竹纤维、耐高温改性稻草纤维和中空玻璃微珠之间的键合力,提高聚丙烯复合材料的拉伸强度、弯曲强度和冲击强度。
竹纤维虽然耐温性比稻草纤维好,但是价格较高;稻草纤维虽然耐温性比竹纤维差,但是来源广泛,容易加工,成本较低;本申请采用耐高温改性稻草纤维代替一部分竹纤维,成本基本不变甚至降低,材料力学性能更好。
可选的,所述耐高温涂料由包括如下重量份的组分制成:
双酚A型环氧树脂100份;
聚酰胺树脂10-20份;
3-(2,3-环氧丙氧)丙基三甲氧基硅烷1.5-3份;
多孔二氧化硅8-15份;
稀释剂7-8份;
2-乙基-4-甲基咪唑2-4份;
均苯四甲酸酐10-12份;
丙酮35-40份。
通过采用上述技术方案,聚酰胺树脂和双酚A型环氧树脂复配,能够得到耐高温且力学性能较好的涂料;2-乙基-4-甲基咪唑是中温固化剂,主要是为了使涂料附着在稻草纤维表面,而且2-乙基-4-甲基咪唑能够与马来酸酐接枝聚丙烯反应,提高了耐高温涂料与聚丙烯之间的结合力;均苯四甲酸酐是高温固化剂,加工耐高温改性稻草纤维时不参与固化反应,在进行熔融挤出时,能够进一步促进剩余的双酚A型环氧树脂固化,提高了耐高温涂料与稻草纤维、聚丙烯之间的结合力,3-(2,3-环氧丙氧)丙基三甲氧基硅烷是耐高温的偶联剂,改善了多孔二氧化硅与树脂基体的相容性,多孔二氧化硅疏松多孔,作为隔热填料,提高了耐高温涂料的耐温性。
可选的,所述稻草纤维的长度为1-2mm,直径为45-55μm。
可选的,所述耐高温涂料固化后的厚度为15-30μm。
通过采用上述技术方案,耐高温涂料的厚度太薄,隔热性能较差,厚度太厚,隔热性能没有显著提升,但是会增加材料成本。
可选的,所述泡沫炭颗粒的制备方法包括以下步骤:将酚醛树脂、椰壳纤维、正戊烷、碳酸丙烯酯、十二烷基磺酸钠混合均匀,注入成型模具内,加热至82-84℃,发泡固化25-30min,得到炭化前驱体,将炭化前驱体置于氮气气氛下,高温炭化,冷却,粉碎,筛分,得到泡沫炭颗粒。
可选的,所述酚醛树脂、椰壳纤维、正戊烷、碳酸丙烯酯和十二烷基磺酸钠的质量比为100:(6-8):(8-11):(1-2):(3-5)。
通过采用上述技术方案,如果仅仅采用酚醛树脂制作泡沫炭颗粒,泡沫炭颗粒的隔热性能较好,但是抗压强度较低,本申请通过加入椰壳纤维,椰壳纤维与酚醛树脂一起被炭化,可以提高泡沫炭颗粒的抗压强度;正戊烷作为发泡剂,起到发泡的作用,碳酸丙烯酯可以降低酚醛树脂的固化温度,降低能耗和加工成本,同时提高材料的粘接强度;十二烷基磺酸钠作为分散剂,起到促进各组分分散均匀的作用。
可选的,所述高温炭化步骤具体为:先升温至460-470℃,炭化2.5-3h,再升温至960-980℃,炭化2-3h。
通过采用上述技术方案,两步进行炭化,能够固定泡沫炭颗粒的孔隙结构,提高泡沫炭颗粒的比表面积,提高泡沫炭颗粒与耐高温涂料之间的粘合力。
可选的,所述中空玻璃微珠经过偶联剂改性处理:将中空玻璃微珠和乙烯基三(β-甲氧基乙氧基)硅烷按质量比为100:(2-4)溶解于乙醇水溶液中,超声分散后,加入盐酸调节pH为3.5-4,加热至85-90℃,搅拌均匀,固液分离,用无水乙醇洗涤,干燥,得到改性后的中空玻璃微珠。
通过采用上述技术方案,中空玻璃微珠经过偶联剂改性处理后,乙烯基三(β-甲氧基乙氧基)硅烷与中空玻璃微珠表面的羟基通过氢键或化学反应脱水形成C-O-Si基团联接在一起,从而提高了中空玻璃微珠与聚丙烯的相容性,进而提高了聚丙烯复合材料的力学性能;中空玻璃微珠还能够降低聚丙烯复合材料的导热系数,从而使得制备的聚丙烯复合材料的隔热性能优良,以达到所需的隔热性能要求。
第二方面,本申请提供一种植物纤维增强聚丙烯复合材料的制备方法,采用如下的技术方案:
一种植物纤维增强聚丙烯复合材料的制备方法,包括以下步骤:
步骤一,将均聚聚丙烯、马来酸酐接枝聚丙烯、中空玻璃微珠、抗氧剂、润滑剂、炭黑混合搅拌均匀,得到混合料;
步骤二,将混合料加入双螺杆挤出机的主喂料口,在190-260℃熔融共混,得到熔融共混物;
步骤三,将竹纤维和耐高温改性稻草纤维从双螺杆挤出机的侧喂料口加入,与熔融共混物在190-260℃熔融共混后挤出,冷却,造粒,干燥,得到植物纤维增强聚丙烯复合材料。
通过采用上述技术方案,通过加入马来酸酐接枝聚丙烯、竹纤维和耐高温改性稻草纤维,提高了聚丙烯复合材料的力学性能;通过加入改性后的中空玻璃微珠,提高了聚丙烯复合材料的拉伸强度;中空玻璃微珠还能够降低聚丙烯复合材料的导热系数,从而使得制备的聚丙烯复合材料的隔热性能优良,以达到所需的隔热性能要求。
综上所述,本申请具有以下有益效果:
1、由于本申请通过加入耐高温改性稻草纤维,一方面,耐高温涂料能够提高稻草纤维的耐高温性能,使其在挤出成型过程中不会碳化受损,耐高温改性稻草纤维在材料内部乱向交错分布,形成立体网络结构,提高了材料韧性,从而提高了聚丙烯的力学性能;另一方面,耐高温涂料改善了稻草纤维的表面性质,涂料表面与聚丙烯相容性更好,界面粘接力较强,从而进一步提高了聚丙烯的力学性能。
2、本申请通过加入马来酸酐接枝聚丙烯,马来酸酐接枝聚丙烯含有极性基团,既可以与聚丙烯相容,马来酸酐还可以与竹纤维、耐高温改性稻草纤维表面的羟基反应,增强了聚丙烯与竹纤维、耐高温改性稻草纤维之间的键合力,提高聚丙烯复合材料的拉伸强度、弯曲强度和冲击强度。
3、本申请对中空玻璃微珠进行偶联剂改性处理,乙烯基三(β-甲氧基乙氧基)硅烷与中空玻璃微珠表面的羟基通过氢键或化学反应脱水形成C-O-Si基团联接在一起,从而提高了中空玻璃微珠与聚丙烯的相容性,进而提高了聚丙烯复合材料的拉伸强度;中空玻璃微珠还能够降低聚丙烯复合材料的导热系数,从而使得制备的聚丙烯复合材料的隔热性能优良,以达到所需的隔热性能要求。
具体实施方式
以下结合实施例对本申请作进一步详细说明。
耐高温改性稻草纤维的制备例
制备例1
耐高温改性稻草纤维,其制备方法包括以下步骤:
碱处理,将长度为1mm、直径为45μm稻草纤维与10wt%NaOH溶液混合,搅拌均匀,浸泡36h,取出,用水洗涤至中性,干燥,得到碱处理稻草纤维;
改性处理,将碱处理稻草纤维用3wt%乙烯基三(β-甲氧基乙氧基)硅烷的甲醇溶液浸泡48h,过滤,干燥,得到改性稻草纤维;
耐高温处理,配置含有泡沫炭颗粒的耐高温涂料:耐高温涂料由包括如下重量的组分制成:双酚A型环氧树脂E44 100kg;
聚酰胺树脂10kg,聚酰胺树脂是聚酰胺-66;
3-(2,3-环氧丙氧)丙基三甲氧基硅烷1.5kg;
多孔二氧化硅8kg;
稀释剂7kg,稀释剂是丁基缩水甘油醚;
2-乙基-4-甲基咪唑2kg;
均苯四甲酸酐10kg;
丙酮35kg;
泡沫炭颗粒与耐高温涂料的质量比为1:100;
泡沫炭颗粒,其制备方法包括以下步骤:将酚醛树脂、椰壳纤维、正戊烷、碳酸丙烯酯、十二烷基磺酸钠混合均匀,酚醛树脂、椰壳纤维、正戊烷、碳酸丙烯酯和十二烷基磺酸钠的质量比为100:6:8:1:3,注入成型模具内,加热至82℃,发泡固化30min,得到炭化前驱体,将炭化前驱体置于氮气气氛下,升温至960℃炭化2.5h,冷却至常温,粉碎,筛分,得到粒径为5μm的泡沫炭颗粒;
含有泡沫炭颗粒的耐高温涂料的制备方法为:将耐高温涂料的组分与泡沫炭颗粒混合,搅拌均匀,即得;
将耐高温涂料喷涂至改性稻草纤维的表面,采用喷雾干燥工艺加热固化,耐高温涂料固化后的厚度为15μm,得到耐高温改性稻草纤维。
制备例2
耐高温改性稻草纤维,其制备方法包括以下步骤:
碱处理,将长度为1.5mm、直径为50μm稻草纤维与11wt%NaOH溶液混合,搅拌均匀,浸泡30h,取出,用水洗涤至中性,干燥,得到碱处理稻草纤维;
改性处理,将碱处理稻草纤维用3.5wt%乙烯基三(β-甲氧基乙氧基)硅烷的甲醇溶液浸泡36h,过滤,干燥,得到改性稻草纤维;
耐高温处理,配置含有泡沫炭颗粒的耐高温涂料:耐高温涂料的配比与制备例1相同,泡沫炭颗粒与耐高温涂料的质量比为1.5:100;
泡沫炭颗粒,其制备方法包括以下步骤:将酚醛树脂、椰壳纤维、正戊烷、碳酸丙烯酯、十二烷基磺酸钠混合均匀,酚醛树脂、椰壳纤维、正戊烷、碳酸丙烯酯和十二烷基磺酸钠的质量比为100:7:10:1.5:4,注入成型模具内,加热至83℃,发泡固化28min,得到炭化前驱体,将炭化前驱体置于氮气气氛下,升温至965℃炭化2h,冷却至常温,粉碎,筛分,得到粒径为8μm的泡沫炭颗粒;
含有泡沫炭颗粒的耐高温涂料的制备方法为:将耐高温涂料的组分与泡沫炭颗粒混合,搅拌均匀,即得;
将耐高温涂料喷涂至改性稻草纤维的表面,采用喷雾干燥工艺加热固化,耐高温涂料固化后的厚度为20μm,得到耐高温改性稻草纤维。
制备例3
耐高温改性稻草纤维,其制备方法包括以下步骤:
碱处理,将长度为2mm、直径为55μm稻草纤维与12wt%NaOH溶液混合,搅拌均匀,浸泡24h,取出,用水洗涤至中性,干燥,得到碱处理稻草纤维;
改性处理,将碱处理稻草纤维用4wt%乙烯基三(β-甲氧基乙氧基)硅烷的甲醇溶液浸泡24h,过滤,干燥,得到改性稻草纤维;
耐高温处理,配置含有泡沫炭颗粒的耐高温涂料:耐高温涂料的配比与制备例1相同,泡沫炭颗粒与耐高温涂料的质量比为2:100;
泡沫炭颗粒,其制备方法包括以下步骤:将酚醛树脂、椰壳纤维、正戊烷、碳酸丙烯酯、十二烷基磺酸钠混合均匀,酚醛树脂、椰壳纤维、正戊烷、碳酸丙烯酯和十二烷基磺酸钠的质量比为100:8:11:2:5,注入成型模具内,加热至84℃,发泡固化25min,得到炭化前驱体,将炭化前驱体置于氮气气氛下,升温至970℃炭化2h,冷却至常温,粉碎,筛分,得到粒径为8μm的泡沫炭颗粒;
含有泡沫炭颗粒的耐高温涂料的制备方法为:将耐高温涂料的组分与泡沫炭颗粒混合,搅拌均匀,即得;
将耐高温涂料喷涂至改性稻草纤维的表面,采用喷雾干燥工艺加热固化,耐高温涂料固化后的厚度为30μm,得到耐高温改性稻草纤维。
制备例4
与制备例2的不同之处在于,泡沫炭颗粒的制备方法包括以下步骤:将酚醛树脂、椰壳纤维、正戊烷、碳酸丙烯酯、十二烷基磺酸钠混合均匀,酚醛树脂、椰壳纤维、正戊烷、碳酸丙烯酯和十二烷基磺酸钠的质量比为100:7:10:1.5:4,注入成型模具内,加热至83℃,发泡固化28min,得到炭化前驱体,将炭化前驱体置于氮气气氛下,先升温至460℃,炭化3h,再升温至960℃,炭化3h,冷却至常温,粉碎,筛分,得到粒径为8μm的泡沫炭颗粒。
制备例5
与制备例2的不同之处在于,泡沫炭颗粒的制备方法包括以下步骤:将酚醛树脂、椰壳纤维、正戊烷、碳酸丙烯酯、十二烷基磺酸钠混合均匀,酚醛树脂、椰壳纤维、正戊烷、碳酸丙烯酯和十二烷基磺酸钠的质量比为100:7:10:1.5:4,注入成型模具内,加热至83℃,发泡固化28min,得到炭化前驱体,将炭化前驱体置于氮气气氛下,先升温至470℃,炭化2.5h,再升温至980℃,炭化2h,冷却至常温,粉碎,筛分,得到粒径为8μm的泡沫炭颗粒。
制备例6
与制备例4的不同之处在于,泡沫炭颗粒的制备方法包括以下步骤:将酚醛树脂、正戊烷、碳酸丙烯酯、十二烷基磺酸钠混合均匀,酚醛树脂、正戊烷、碳酸丙烯酯和十二烷基磺酸钠的质量比为100:10:1.5:4,注入成型模具内,加热至83℃,发泡固化28min,得到炭化前驱体,将炭化前驱体置于氮气气氛下,先升温至470℃,炭化2.5h,再升温至980℃,炭化2h,冷却至常温,粉碎,筛分,得到粒径为8μm的泡沫炭颗粒。
中空玻璃微珠的制备例7
中空玻璃微珠经过偶联剂改性处理:将中空玻璃微珠和乙烯基三(β-甲氧基乙氧基)硅烷按质量比为100:2溶解于80%乙醇水溶液中,超声分散后,加入盐酸调节pH为3.5,加热至85℃,搅拌均匀,过滤,用无水乙醇洗涤固体,干燥,得到改性后的中空玻璃微珠。
中空玻璃微珠的制备例8
中空玻璃微珠经过偶联剂改性处理:将中空玻璃微珠和乙烯基三(β-甲氧基乙氧基)硅烷按质量比为100:4溶解于75%乙醇水溶液中,超声分散后,加入盐酸调节pH为4,加热至90℃,搅拌均匀,过滤,用无水乙醇洗涤固体,干燥,得到改性后的中空玻璃微珠。
制备例9
与制备例5的不同之处在于,耐高温涂料由包括如下重量的组分制成:
双酚A型环氧树脂E44 100kg;
聚酰胺树脂15kg,聚酰胺树脂是聚酰胺-66;
3-(2,3-环氧丙氧)丙基三甲氧基硅烷2kg;
多孔二氧化硅10kg;
稀释剂7.5kg,稀释剂是丁基缩水甘油醚;
2-乙基-4-甲基咪唑3kg;
均苯四甲酸酐11kg;
丙酮38kg。
制备例10
与制备例5的不同之处在于,耐高温涂料由包括如下重量的组分制成:
双酚A型环氧树脂E44 100kg;
聚酰胺树脂20kg,聚酰胺树脂是聚酰胺-66;
3-(2,3-环氧丙氧)丙基三甲氧基硅烷3kg;
多孔二氧化硅15kg;
稀释剂8kg,稀释剂是丁基缩水甘油醚;
2-乙基-4-甲基咪唑4kg;
均苯四甲酸酐12kg;
丙酮40kg。
对比制备例1
与制备例1的不同之处在于,将耐高温涂料中的聚酰胺树脂替换为等质量的双酚A型环氧树脂E44。
对比制备例2
与制备例1的不同之处在于,将耐高温涂料中的均苯四甲酸酐替换为等质量的2-乙基-4-甲基咪唑。
对比制备例3
与制备例1的不同之处在于,将3wt%乙烯基三(β-甲氧基乙氧基)硅烷的甲醇溶液替换为3wt%KH550的甲醇溶液。
实施例
实施例1
一种植物纤维增强聚丙烯复合材料,由包含以下重量份数的原料制成:
均聚聚丙烯68kg;
马来酸酐接枝聚丙烯5kg,购自科艾斯化学有限公司,牌号为B2;
耐高温改性稻草纤维15kg;
竹纤维15kg,长度为3mm,直径为15um;
中空玻璃微珠1kg,型号为K85;
抗氧剂0.1kg,抗氧剂为硫代二丙酸双十八醇酯;
润滑剂0.1kg,润滑剂为聚乙烯蜡;
炭黑0.1份;
耐高温改性稻草纤维由制备例1制得;
植物纤维增强聚丙烯复合材料的制备方法,包括以下步骤:
步骤一,将均聚聚丙烯、马来酸酐接枝聚丙烯、中空玻璃微珠、抗氧剂、润滑剂、炭黑混合搅拌均匀,得到混合料;
步骤二,将混合料加入双螺杆挤出机的主喂料口,在190-260℃熔融共混,得到熔融共混物;
步骤三,将竹纤维和耐高温改性稻草纤维从双螺杆挤出机的侧喂料口加入,与熔融共混物在190-260℃熔融共混后挤出,冷却,造粒,干燥,得到植物纤维增强聚丙烯复合材料。
实施例2-6
与实施例1的不同之处在于,耐高温改性稻草纤维依次由制备例2-6制得。
实施例7-8
与实施例5的不同之处在于,中空玻璃微珠分别采用制备例7和制备例8制备的改性后的中空玻璃微珠。
实施例9-10
与实施例8的不同之处在于,耐高温改性稻草纤维依次由制备例9-10制得。
实施例11
与实施例9的不同之处在于,聚丙烯复合材料由包含以下重量份数的原料制成:
均聚聚丙烯85kg;
马来酸酐接枝聚丙烯8kg,购自科艾斯化学有限公司,牌号为B2;
耐高温改性稻草纤维18kg;
竹纤维12kg,长度为2mm,直径为10um;
中空玻璃微珠2kg;
抗氧剂0.5kg,抗氧剂为硫代二丙酸双十八醇酯;
润滑剂0.5kg,润滑剂为聚乙烯蜡;
炭黑0.5份;
耐高温改性稻草纤维由制备例9制得。
实施例12
与实施例9的不同之处在于,聚丙烯复合材料由包含以下重量份数的原料制成:
均聚聚丙烯99kg;
马来酸酐接枝聚丙烯10kg,购自科艾斯化学有限公司,牌号为B2;
耐高温改性稻草纤维20kg;
竹纤维10kg,长度为2mm,直径为10um;
中空玻璃微珠3kg;
抗氧剂1kg,抗氧剂为硫代二丙酸双十八醇酯;
润滑剂1kg,润滑剂为聚乙烯蜡;
炭黑1份;
耐高温改性稻草纤维由制备例9制得。
对比例
对比例1
一种植物纤维增强聚丙烯复合材料,与实施例1的不同之处在于,耐高温改性稻草纤维由对比制备例1制得。
对比例2-3
一种植物纤维增强聚丙烯复合材料,与实施例1的不同之处在于,耐高温改性稻草纤维依次由对比制备例2-3制得。
对比例4
一种植物纤维增强聚丙烯复合材料,与实施例1的不同之处在于,将耐高温改性稻草纤维替换为等质量的竹纤维。
对比例5
一种植物纤维增强聚丙烯复合材料,与实施例1的不同之处在于,将耐高温改性稻草纤维替换为等质量的未经过碱处理、改性处理和耐高温处理的稻草纤维。
对比例6
一种植物纤维增强聚丙烯复合材料,与实施例1的不同之处在于,将马来酸酐接枝聚丙烯替换为等质量的均聚聚丙烯。
性能检测试验检测方法:取实施例1-12和对比例1-6中的植物纤维增强聚丙烯复合材料,分别测试拉伸强度、弯曲强度和无缺口冲击强度,拉伸强度测试方法参照GB/T1040,弯曲强度测试方法参照GB/T9341,无缺口冲击强度测试方法参照GB/T1843,测试结果如表1所示。
表1测试结果
Figure BDA0003908493150000111
Figure BDA0003908493150000121
结合实施例1和对比例1-6并结合表1可以看出,对比例6仅采用均聚聚丙烯,实施例1在对比例6的基础上采用一部分的马来酸酐接枝聚丙烯替换部分均聚聚丙烯,拉伸强度、弯曲强度和无缺口冲击强度均有提升,说明采用马来酸酐接枝聚丙烯能够提高聚丙烯复合材料的力学性能;对比例5将耐高温改性稻草纤维替换为等质量的未经过碱处理、改性处理和耐高温处理的稻草纤维,拉伸强度、弯曲强度和无缺口冲击强度均下降,说明普通的稻草纤维与聚丙烯复合材料的相容性较差,对比例4将耐高温改性稻草纤维替换为等质量的竹纤维,拉伸强度、弯曲强度和无缺口冲击强度均下降,说明竹纤维与聚丙烯复合材料的相容性较差,而本申请的耐高温改性稻草纤维与聚丙烯复合材料的相容性好,提高了聚丙烯复合材料的力学性能;对比例3采用不耐高温的硅烷偶联剂改性碱处理稻草纤维,拉伸强度、弯曲强度和无缺口冲击强度均下降,可能是因为KH550耐高温性能较差,在挤出熔融时稻草纤维与耐高温涂料之间的粘接力降低,稻草纤维耐高温性能下降,容易碳化受损,导致聚丙烯复合材料力学性能降低;对比例2仅采用2-乙基-4-甲基咪唑作为中温固化剂,拉伸强度、弯曲强度和无缺口冲击强度均下降,可能是因为均苯四甲酸酐是高温固化剂,加工耐高温改性稻草纤维时不参与固化反应,在进行熔融挤出时,能够进一步促进剩余的双酚A型环氧树脂固化,提高了耐高温涂料与稻草纤维、聚丙烯之间的结合力,进而提高聚丙烯复合材料力学性能;对比例1的耐高温涂料中仅加入双酚A型环氧树脂,拉伸强度、弯曲强度和无缺口冲击强度均下降,说明聚酰胺树脂和双酚A型环氧树脂复配,能够得到耐高温且力学性能较好的涂料,对稻草纤维起到保护作用,从而提高聚丙烯复合材料的力学性能。
结合实施例1-12并结合表1可以看出,实施例1-3中,实施例2的综合力学性能较好,说明制备例2制备得到的耐高温改性稻草纤维综合性能较好;实施例4-5采用2步碳化加工泡沫炭颗粒,拉伸强度、弯曲强度和无缺口冲击强度均略有提升,说明2步碳化工艺能够提高泡沫炭颗粒与耐高温涂料之间的粘合力,进而提高聚丙烯复合材料力学性能,实施例5的综合力学性能较好;实施例6在实施例4的基础上去掉了椰壳纤维,拉伸强度、弯曲强度和无缺口冲击强度均下降,可能是因为去掉了椰壳纤维后,泡沫炭颗粒的强度下降,进而导致耐高温涂料的力学性能下降,降低了聚丙烯复合材料力学性能;实施例7-8将中空玻璃微珠进行偶联剂改性处理,拉伸强度、弯曲强度和无缺口冲击强度均有提升,说明中空玻璃微珠经过偶联剂改性处理后,提高了中空玻璃微珠与聚丙烯的相容性,进而提高了聚丙烯复合材料的力学性能,实施例8的综合力学性能较好;实施例9-10改变了耐高温涂料的配比后,拉伸强度、弯曲强度和无缺口冲击强度均有提升,且实施例9的综合力学性能较好,说明耐高温涂料的配比会影响耐高温改性稻草纤维的性能,进而影响聚丙烯复合材料的力学性能;实施例11-12改变了聚丙烯复合材料的配比后,拉伸强度、弯曲强度和无缺口冲击强度均有提升,且实施例11的综合力学性能较好,聚丙烯复合材料的配比会影响聚丙烯复合材料的力学性能。
本具体实施例仅仅是对本申请的解释,其并不是对本申请的限制,本领域技术人员在阅读完本说明书后可以根据需要对本实施例做出没有创造性贡献的修改,但只要在本申请的权利要求范围内都受到专利法的保护。

Claims (4)

1.一种植物纤维增强聚丙烯复合材料,其特征在于:由包含以下重量份数的原料制成:
均聚聚丙烯68-99份;
马来酸酐接枝聚丙烯5-10份;
耐高温改性稻草纤维15-20份;
竹纤维10-15份;
中空玻璃微珠1-3份;
抗氧剂0.1-1份;
润滑剂0.1-1份;
炭黑0.1-1份;
所述耐高温改性稻草纤维的制备方法包括以下步骤:
碱处理,将稻草纤维与10-12wt%NaOH溶液混合,浸泡24-36h,取出,洗涤至中性,干燥,得到碱处理稻草纤维;
改性处理,将碱处理稻草纤维用3-4wt%乙烯基三(β-甲氧基乙氧基) 硅烷的甲醇溶液浸泡24-48h,固液分离,干燥,得到改性稻草纤维;
耐高温处理,配置含有泡沫炭颗粒的耐高温涂料,将耐高温涂料喷涂至改性稻草纤维的表面,加热固化,得到耐高温改性稻草纤维;
所述耐高温涂料由包括如下重量份的组分制成:
双酚A型环氧树脂100份;
聚酰胺树脂10-20份;
3-(2,3-环氧丙氧)丙基三甲氧基硅烷1.5-3份;
多孔二氧化硅8-15份;
稀释剂7-8份;
2-乙基-4-甲基咪唑2-4份;
均苯四甲酸酐10-12份;
丙酮35-40份;
所述泡沫炭颗粒的制备方法包括以下步骤:将酚醛树脂、椰壳纤维、正戊烷、碳酸丙烯酯、十二烷基磺酸钠混合均匀,注入成型模具内,加热至82-84℃,发泡固化25-30min,得到炭化前驱体,将炭化前驱体置于氮气气氛下,高温炭化,冷却,粉碎,筛分,得到泡沫炭颗粒;
所述酚醛树脂、椰壳纤维、正戊烷、碳酸丙烯酯和十二烷基磺酸钠的质量比为100:(6-8):(8-11):(1-2):(3-5);
所述高温炭化步骤具体为:先升温至460-470℃,炭化2.5-3h,再升温至960-980℃,炭化2-3h;
所述中空玻璃微珠经过偶联剂改性处理:将中空玻璃微珠和乙烯基三(β-甲氧基乙氧基) 硅烷按质量比为100:(2-4)溶解于乙醇水溶液中,超声分散后,加入盐酸调节pH为3.5-4,加热至85-90℃,搅拌均匀,固液分离,用无水乙醇洗涤,干燥,得到改性后的中空玻璃微珠。
2.根据权利要求1所述的一种植物纤维增强聚丙烯复合材料,其特征在于:所述稻草纤维的长度为1-2mm,直径为45-55μm。
3.根据权利要求1所述的一种植物纤维增强聚丙烯复合材料,其特征在于:所述耐高温涂料固化后的厚度为15-30μm。
4.权利要求1-3任一项所述的植物纤维增强聚丙烯复合材料的制备方法,其特征在于:包括以下步骤:
步骤一,将均聚聚丙烯、马来酸酐接枝聚丙烯、中空玻璃微珠、抗氧剂、润滑剂、炭黑混合搅拌均匀,得到混合料;
步骤二,将混合料加入双螺杆挤出机的主喂料口,在190-260℃熔融共混,得到熔融共混物;
步骤三,将竹纤维和耐高温改性稻草纤维从双螺杆挤出机的侧喂料口加入,与熔融共混物在190-260℃熔融共混后挤出,冷却,造粒,干燥,得到植物纤维增强聚丙烯复合材料。
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