CN103554626B - 一种微发泡聚乙烯基木塑复合材料及其制备方法 - Google Patents
一种微发泡聚乙烯基木塑复合材料及其制备方法 Download PDFInfo
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Abstract
本发明公开一种微发泡聚乙烯基木塑复合材料及其制备方法。该微发泡聚乙烯基木塑复合材料将基体聚乙烯树脂、改性硅灰石粉和滑石粉、交联剂、润滑剂、热平衡型发泡剂、抗氧化剂、抗紫外线剂、颜料、改性植物纤维搅拌升温、混合均匀后冷却卸料,制得预混料,改性植物纤维选自木粉、竹粉、稻壳粉中的一种或两种以上以任意比例构成的混合物;将预混料放入挤出机中造粒、挤出发泡、冷却定型。本发明生产制造方便,原料价廉环保,微发泡聚乙烯基木塑复合材料的泡孔平均直径低至10μm、植物纤维含量高至45%,且复合材料的密度低、弯曲强度和冲击韧性高,应用领域广,本发明可应用于装饰、建筑、市政、包装、汽车内饰件等领域。
Description
技术领域
本发明涉及一种微发泡聚乙烯基木塑复合材料及其制备方法,属于复合材料领域,也属于林业工程领域。
背景技术
与传统木塑复合材料相比,木塑发泡复合材料由于泡孔的存在不仅可以降低材料的密度,而且这些气泡能够有效阻止材料中原有裂纹的扩展,使裂纹尖端变钝,从而赋予材料更为优良的热稳定性和耐疲劳性,在建筑装饰、室内装潢、工艺品市场、包装运输、汽车内饰件等领域都具有广阔的市场前景。聚乙烯(PE)作为通用塑料,与聚丙烯(PP)相比,价格低廉,具有较好的耐低温性能;与聚氯乙烯(PVC)相比,从制备到使用乃至废弃处理都更为环保;因此,采用PE为基体制备微发泡木塑复合材料具有资源、成本和环保优势。
但是聚乙烯基木塑复合材料的弯曲强度低、蠕变变形大,且当植物纤维含量增加至20%时,复合材料的冲击韧性即明显下降,且植物纤维的大量存在会增大复合材料的发泡难度,影响材料的发泡性能,进而削弱材料的力学性能,影响材料的使用。
发明内容
针对上述微发泡聚乙烯基木塑复合材料存在的弯曲强度低、冲击韧性差及发泡难度大等不足,本发明的目的是提供一种泡孔形态好、植物纤维含量高、密度低、弯曲强度和冲击韧性高的微发泡聚乙烯基木塑复合材料及其制备方法。该法采用化学交联和共混改性高密度聚乙烯和低密度聚乙烯,制备微发泡聚乙烯基木塑复合材料,并采用偶联剂改性的滑石粉和硅灰石粉作为改性填料增强增韧发泡复合材料,改善微发泡聚乙烯木塑复合材料发泡性能的同时,提高材料的弯曲强度和冲击韧性。该法简单易操作、原料价廉环保、材料质量轻、强度高、韧性好。
为实现上述目的,本发明采用如下技术方案:
所述微发泡聚乙烯基木塑复合材料,由包括以下质量份数的原料制备而成:
聚乙烯树脂100份,植物纤维 20~80份;滑石粉5~25份;硅灰石5~20份;偶联剂0.1~1.5份;润滑剂0.5~3份;发泡剂0.5~3份;交联剂0.1~3份;抗氧化剂0.5~2份;抗紫外线剂0.5~2份;界面相容剂1~7份;颜料1~3份。
所述的聚乙烯树脂由低密度聚乙烯和高密度聚乙烯组成,所述低密度聚乙烯为重均分子量Mw为40000~200000、结晶度为20%~40%、在230℃,2.16 KN测试条件下的熔体指数为1-15 g/10min的低密度聚乙烯粒料或粉料90份;以及重均分子量Mw为50000~300000、结晶度为70%~90%、在230℃,2.16 KN测试条件下的熔体指数为2-10 g/10min的高密度聚乙烯粒料或粉料10份。
所述的植物纤维为为木粉、竹粉、稻壳粉中的一种或两种以上以任意比例构成的混合物,含水率为1%-3%,平均粒径为40目~120目;所述的任意比例为本领域常规的比例,为一般技术人员能实现的技术。
所述的滑石粉平均粒径为1000~1500目。
所述的硅灰石粉为针状,长径比为10:1~20: 1,平均粒径为1000目~1500目。
所述的偶联剂为本领域常规技术,本发明优选硅烷类或钛酸酯类或铝酸酯类偶联剂。
所述的润滑剂为本领域常规技术,本发明优选聚乙烯蜡或硬脂酸或硬脂酸盐中的一种或两种的混合物。
所述的发泡剂为本领域常规技术,本发明优选热平衡型发泡剂,型号为Hydrocell 232的偶氮二甲酰胺复合物。
所述的交联剂为本领域常规技术,本发明优选过氧化二异丙苯(DCP),粉状,工业级。
所述的抗氧化剂为本领域常规技术,本发明优选受阻酚类抗氧化剂1010和亚磷酸酯类抗氧化剂168,以1:1比例复配的复合物。
所述的抗紫外线剂为本领域常规技术,本发明优选2-羟基-4-正辛氧基二苯甲酮UV531。
所述的颜料为本领域常规技术,本发明优选氧化铁等无机颜料粉或塑料专用有机颜料。
所述的界面相容剂为本领域常规技术,本发明优选丙烯酸化合物类接枝的聚乙烯或丙烯酸化合物类接枝的聚丙烯或丙烯酸化合物类接枝的茂金属乙烯-1-辛烯共聚物。
丙烯酸化合物类接枝的聚乙烯优选马来酸酐接枝聚乙烯(MAPE);丙烯酸化合物类接枝的聚丙烯优选马来酸酐接枝聚丙烯(MAPP);丙烯酸化合物类接枝的茂金属乙烯-1-辛烯共聚物优选马来酸酐接枝茂金属乙烯-1-辛烯共聚物(MAPOE)。
本发明所述的微发泡聚乙烯基木塑复合材料及其制备方法,其制备步骤为:
1)滑石粉和硅灰石粉改性,将干燥的滑石粉和硅灰石粉放入高速混合机中,搅拌升温至80~100℃,采用与体积浓度为99%的乙醇以1:1~1:8比例稀释的偶联剂计量喷雾,搅拌10~30min后,冷却卸料,制成改性填料;
2)按配方比称取各原料;将低密度聚乙烯(LDPE)、高密度聚乙烯(HDPE)、改性填料、交联剂、润滑剂、发泡剂、抗氧化剂、抗紫外线剂、颜料、界面相容剂、干燥的植物纤维放入高速混合机中,搅拌升温至110~120℃,搅拌15~50 min后,冷却卸料,制成预混料;
3)将上述造粒的木塑粒子,放入双螺杆挤出机中,挤出发泡法制备微发泡聚乙烯基木塑复合材料;挤出机料筒温度为165~180℃、机头温度为155~175℃、模具温度为155~165℃。
本发明的特点是:采用交联改性和共混改性的方式,改善聚乙烯基木塑复合材料的发泡性能,采用低密度聚乙烯为重均分子量Mw为40000~200000、结晶度为20%~40%、熔体指数(230℃,2.16 KN) 为1-15 g/10min的LDPE粒料或粉料;所述的高密度聚乙烯为重均分子量Mw为50000~300000、结晶度为70%~90%、熔体指数(230℃,2.16KN)为 2-10 g/10min的HDPE粒料或粉料,使得与木粉、竹粉等植物纤维交联改性和共混改性更容易,操作过程简单且环保,制备的微发泡聚乙烯基木塑复合材料的植物纤维含量高达至45%、密度低、泡孔形态良好、泡孔的平均直径低至10 μm;而且通过添加改性填料,增强增韧复合材料,制备的微发泡聚乙烯基木塑复合材料弯曲强度高、冲击韧性大,可应用到室内装饰装潢、建筑材料、包装运输、工艺品市场,制成家具、踢脚线、吊顶线条、地板、相框、镜框、画框、缓冲包装材料等,也可应用到汽车内饰件等高档材料领域,具有广阔的市场空间和发展前景。
具体实施方式
本发明下面结合实施例来予以阐明,所述的份为质量份。下述实施例中的低密度聚乙烯为重均分子量Mw为40000~200000、结晶度为20%~40%、熔体指数(230℃,2.16 KN) 为1-15 g/10min的LDPE粒料或粉料;所述的高密度聚乙烯为重均分子量Mw为50000~300000、结晶度为70%~90%、熔体指数(230℃,2.16KN)为 2-10 g/10min的HDPE粒料或粉料;木粉、竹粉均购自浙江临安市明珠竹木粉有限公司;稻壳粉购自无锡润绿复合制品有限公司;滑石粉和硅灰石粉均购自江西盛泰化工有限公司;硅烷KH550偶联剂购自南京道宁化工有限公司;交联剂过氧化二异丙苯(DCP)购自上海高桥石化精细化工公司;润滑剂聚乙烯蜡或硬脂酸或硬脂酸盐均为市售;发泡剂偶氮二甲酰胺复合物购自广州辉科化工有限公司;抗氧化剂为受阻酚类抗氧化剂1010/亚磷酸酯类抗氧化剂168复配物(B225)购自瑞士汽巴公司,抗紫外线剂UV531购自瑞士汽巴公司;氧化铁颜料粉购自湖南三环颜料有限公司;界面相容剂马来酸酐接枝茂金属乙烯-1-辛烯共聚物(MAPOE)购自南京德巴化工有限公司。
实施例一
将滑石粉15份和硅灰石粉10份放置在100℃的烘箱中干燥8小时后,放入高速混合机中,搅拌升温至90℃,采用与体积浓度为99%的乙醇以1:2比例稀释的硅烷偶联剂KH550(硅烷偶联剂KH550占滑石粉和硅灰石粉总质量的2%)喷雾,混合15min后,冷却卸料,制成改性填料;将木粉放置在105℃的烘箱中干燥10小时。按质量比将低密度聚乙烯90份、高密度聚乙烯10份、改性填料、交联剂1.5份、润滑剂1份、发泡剂2份、抗氧化剂1份、抗紫外线剂1份、界面相容剂1.5份、木粉20份、颜料2份放入高速混合机中,混合25 min后,冷却卸料,制成预混料后挤出造粒,造粒温度为165℃、造粒时间为20 min,得到木塑粒子;采用挤出机进行熔融、共混、挤出、经发泡模具发泡、冷却定型,成型微发泡聚乙烯基木塑复合材料板材,挤出机料筒温度175℃、机头温度165℃、模具温度160℃。
实施例二
将滑石粉10份和硅灰石粉10份放置在100℃的烘箱中干燥8小时后,放入高速混合机中,搅拌升温至90℃,采用与体积浓度为99%的乙醇以1:2比例稀释的硅烷偶联剂KH550(硅烷偶联剂KH550占滑石粉和硅灰石粉总质量的2%)计量喷雾,混合15min后,冷却卸料,制成改性填料;将竹粉放置在105℃的烘箱中干燥10小时。按质量比将低密度聚乙烯90份、高密度聚乙烯10份、改性填料、交联剂1.5份、润滑剂1.5份、抗氧化剂1份、抗紫外线剂1份、竹粉40份、界面相容剂3份、颜料2份放入高速混合机中,混合25 min后,冷却卸料,制成预混料后挤出造粒,造粒温度为165℃、造粒时间为20 min,得到木塑粒子;采用挤出机进行熔融共混、挤出、经发泡模具发泡、冷却定型,成型微发泡聚乙烯基木塑复合材料板材,挤出机料筒温度175℃、机头温度165℃、模具温度160℃。
实施例三
将滑石粉10份和硅灰石粉10份放置在100℃的烘箱中干燥8小时后,放入高速混合机中,搅拌升温至90℃,采用与体积浓度为99%的乙醇以1:2比例稀释的硅烷偶联剂KH550(硅烷偶联剂KH550占滑石粉和硅灰石粉总质量的2%)计量喷雾,混合12min后,冷却卸料,制成改性填料;将稻壳粉放置在105℃的烘箱中干燥10小时。按重量比将低密度聚乙烯90份、高密度聚乙烯10份、改性填料、交联剂1份、润滑剂2份、抗氧化剂1份、抗紫外线剂1份、稻壳粉60份、界面相容剂4份、颜料2份放入高速混合机中,混合30 min后,冷却卸料,制成预混料后挤出造粒,造粒温度为165℃、造粒时间为20 min,得到木塑粒子;采用挤出机进行熔融、共混、挤出、经发泡模具发泡、冷却定型,成型微发泡聚乙烯基木塑复合材料板材,挤出机料筒温度180℃、机头温度165℃、模具温度160℃。
以下通过检测材料的物理力学性能,证明本发明实施例1、实施例2和实施例3的效果,其检测结果如下:
实施例1、实施例2和实施例3中微发泡聚乙烯基木塑发泡复合材料,其密度分别为0.81 g·cm-3、0.86 g·cm-3和0.91 g·cm-3,而相应的普通未发泡聚乙烯基木塑复合材料的密度分别为0.96 g·cm-3、0.99 g·cm-3和1.04 g·cm-3,密度降低了近15%;弯曲强度分别为16.56 MPa、17.19 MPa和17.54 MPa,而相应的普通未发泡聚乙烯基木塑复合材料的弯曲强度分别为15.12 MPa、15.73 MPa和15.82 MPa,弯曲强度提高了约10%;缺口冲击强度分别为16.78 KJ·m-2、13.57 KJ·m-2和12.31 KJ·m-2,而相应的普通未发泡聚乙烯基木塑复合材料的缺口冲击强度分别为14.98 KJ·m-2、12.04 KJ·m-2和10.97 KJ·m-2,缺口冲击强度提高了约13%。
综上所述可见,本发明的微发泡聚乙烯基木塑复合材料与普通未发泡聚乙烯基木塑复合材料相比,具有更低的密度、更高的弯曲强度和冲击韧性,材料的比强度提高了30%左右。
Claims (7)
1.一种微发泡聚乙烯基木塑复合材料,由下述质量份数的组分制成:聚乙烯树脂100份,植物纤维 20~80份;滑石粉5~25份;硅灰石5~20份;偶联剂0.1~1.5份;润滑剂0.5~3份;发泡剂0.5~3份;交联剂0.1~3份;抗氧化剂0.5~2份;抗紫外线剂0.5~2份;界面相容剂1~7份;颜料1~3份;
所述的聚乙烯树脂由低密度聚乙烯和高密度聚乙烯组成,所述低密度聚乙烯为重均分子量Mw为40000~200000、结晶度为20%~40%、在230℃,2.16 KN测试条件下的熔体指数为1-15 g/10min的低密度聚乙烯粒料或粉料90份;以及重均分子量Mw为50000~300000、结晶度为70%~90%、在230℃,2.16 KN测试条件下的熔体指数为2-10 g/10min的高密度聚乙烯粒料或粉料10份;
所述的植物纤维为木粉、竹粉、稻壳粉中的一种或两种以上的混合物,含水率为1%~3%,平均粒径为40目~120目;
所述的发泡剂为热平衡型发泡剂,型号为Hydrocell 232的偶氮二甲酰胺复合物,热分解温度为165-200℃、发气量为180 ml/g。
2.根据权利要求1所述的微发泡聚乙烯基木塑复合材料,其特征在于:
所述的滑石粉,其平均粒径为1000目~1500目;所述的硅灰石粉为针状,长径比为10:1~20: 1,平均粒径为1000目~1500目。
3.根据权利要求1或2所述的微发泡聚乙烯基木塑复合材料,其特征在于:
所述的偶联剂为硅烷类或钛酸酯类或铝酸酯类偶联剂;所述的交联剂为过氧化二异丙苯,粉状,工业级;所述的润滑剂为:聚乙烯蜡或硬脂酸或硬脂酸盐的一种或两种的混合物。
4.根据权利要求1或2所述的微发泡聚乙烯基木塑复合材料,其特征在于:
所述的抗氧化剂为受阻酚类抗氧化剂1010和亚磷酸酯类抗氧化剂168以1:1比例复配的混合物;所述的抗紫外线剂为2-羟基-4-正辛氧基二苯甲酮UV531。
5.根据权利要求1或2所述的微发泡聚乙烯基木塑复合材料,其特征在于:
所述的界面相容剂为丙烯酸化合物类接枝的聚乙烯或丙烯酸化合物类接枝的聚丙烯或丙烯酸化合物类接枝的茂金属乙烯-1-辛烯共聚物;所述的颜料为无机颜料粉或塑料专用有机颜料粉。
6.根据权利要求5所述的微发泡聚乙烯基木塑复合材料,其特征在于: 所述的无机颜料粉为氧化铁颜料粉。
7.权利要求1-6任一所述的微发泡聚乙烯基木塑复合材料及其制备方法,其特征在于,其制备步骤为:
1)改性滑石粉和硅灰石粉:将干燥的滑石粉和硅灰石粉放在高速混合机中,搅拌升温至80~100℃,采用与体积浓度为99%的乙醇以1:1~1:8比例稀释的偶联剂计量喷雾,搅拌10~30min后,冷却卸料,制成改性填料;
2)将按配方称量的低密度聚乙烯、高密度聚乙烯、交联剂、润滑剂、发泡剂、抗氧化剂、抗紫外线剂、颜料、界面相容剂、干燥的植物纤维以及步骤1)制得的改性填料放入高速混合机中,搅拌升温至110~120℃,搅拌15~50 min后,冷却卸料,制成预混料;
3)将步骤2)混合的预混料放入挤出机中,造粒成木塑粒子,造粒温度为:145~160℃、造粒时间为20~40 min;
4)将步骤3)造粒的木塑粒子,放入双螺杆挤出机中,挤出发泡法制备微发泡聚乙烯基木塑复合材料;挤出机的料筒温度为165~185℃、机头温度为155~175℃、模具温度为155~165℃。
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