CN106626535B - 一种高纤维体积含量phbv单聚合物复合材料及其制备方法 - Google Patents
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Abstract
本发明公开了一种高纤维体积含量聚(3‑羟基丁酸酯‑co‑3‑羟基戊酸酯)(PHBV)单聚合物复合材料及其制备方法,复合材料中增强相为3‑羟基戊酸酯(HV)含量为0~20mol%的PHBV纤维,基体是HV含量为10~100mol%的PHBV,增强相纤维的体积含量为5%~90%。复合材料的制备方法为:(1)将皮芯结构的PHBV纤维加工成纤维集合体;(2)将1~1000层皮芯结构PHBV纤维集合体叠加在一起;(3)在热压机上,在1~20MPa的压力和100~160℃的温度下,将皮芯结构PHBV纤维集合体热压成PHBV单聚合物复合材料。所得的PHBV单聚合物复合材料可用于包装、汽车等领域。
Description
技术领域
本发明涉及高分子材料领域,具体涉及高纤维体积含量聚(3-羟基丁酸酯-co-3-羟基戊酸酯)(PHBV)单聚合物复合材料及其制备方法。
背景技术
纤维增强聚合物基复合材料由于高的比强度、不腐蚀和高的断裂韧性已广泛应用于航空航天、休闲娱乐、汽车、建筑和体育工业等领域,另外,其作为轻质高强新材料,正在对低碳、环保的经济发展模式作出越来越大的贡献,因此,纤维增强复合材料的市场份额正在不断增加。然而,传统的纤维增强复合材料存在两个问题:第一,增强相和基体不同质,界面相容性差,且无法回收。第二,增强相为无机纤维或基于石油的聚合物纤维,基体为石油基聚合物,存在资源短缺和环境污染等问题。以资源可再生、生物可降解的聚合物为原料,开发单聚合物复合材料可解决上述两个问题。聚(3-羟基丁酸酯-co-3-羟基戊酸酯)(PHBV)资源可再生、生物可降解,PHBV单聚合物复合材料的制备将能解决纤维增强热塑性聚合物复合材料存在的瓶颈问题。
目前,PHBV单聚合物复合材料及其制备方法存在以下问题:(1)基体和增强相均为PHBV,以致加工窗口窄;(2)PHBV为热塑性高分子材料,粘度大,PHBV基体难以对增强相PHBV纤维充分浸润,增强相PHBV纤维难以均匀地分散在PHBV基体中,以致PHBV纤维的体积含量低。PHBV单聚合物复合材料的制备过程中若能解决上述问题,将会降低其加工难度,进一步改善复合材料的力学性能。
发明内容
本发明的目的是针对PHBV单聚合物复合材料的开发过程中存在的问题,开发出一种高纤维体积含量PHBV单聚合物复合材料,并提供了其制备方法。
高纤维体积含量聚(3-羟基丁酸酯-co-3-羟基戊酸酯)(PHBV)单聚合物复合材料,其组分包括:
(1)增强相为3-羟基戊酸酯(HV)含量为0~20mol%的PHBV纤维,当HV的含量为0时,PHBV即为聚(3-羟基丁酸酯)(PHB),增强相PHBV的粘均分子量为5.0×104~1.0×106;
(2)基体是HV含量为10~100mol%的PHBV,当HV的含量为100%时,PHBV即为聚(3-羟基戊酸酯)(PHV),皮层的粘均分子量为5.0×104~1.0×106;
(3)增强相纤维的体积含量为5%~90%。
所述的高纤维体积含量聚(3-羟基丁酸酯-co-3-羟基戊酸酯)(PHBV)单聚合物复合材料,其制备方法包括以下步骤:
(1)将皮芯结构的PHBV纤维加工成纤维集合体;
(2)将1~1000层皮芯结构PHBV纤维集合体叠加在一起;
(3)在热压机上,在一定压力和温度下,将皮芯结构PHBV纤维集合体热压成PHBV单聚合物复合材料。
所述的高纤维体积含量聚(3-羟基丁酸酯-co-3-羟基戊酸酯)(PHBV)单聚合物复合材料的制备方法,其特征在于所述的纤维集合体包括机织物、针织物和非织造布。
所述的高纤维体积含量聚(3-羟基丁酸酯-co-3-羟基戊酸酯)(PHBV)单聚合物复合材料的制备方法,其特征在于所述的热压压力为1~20MPa。
所述的高纤维体积含量聚(3-羟基丁酸酯-co-3-羟基戊酸酯)(PHBV)单聚合物复合材料的制备方法,其特征在于所述的热压温度为100~160℃。
有益效果:
(1)该PHBV单聚合物复合材料的增强相和基体均为PHBV,资源可再生、生物可降解,界面相容型好,材料的力学性能好。
(2)PHBV单聚合物复合材料由皮芯结构聚乳酸纤维制得,基体和增强相结合在直径为几微米到几十微米的纤维中,纤维的分散性好,基体对增强相的浸润性好,纤维的体积含量可高达90%。
(3)皮芯结构PHBV纤维中皮层和芯层间的熔点差异大,复合材料的加工窗口宽。
具体实施方式
下面结合具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不限制本发明的范围。此外应理解,在阅读了本发明讲授的内容之后,本领域技术人员可以对本发明各种改动或修改,这些等价形式同样落入本申请所附权利要求书所限定的范围。
实施例1
以皮芯结构PHBV短纤维为原料,其中芯层为3-羟基戊酸酯(HV)含量为0的PHBV纤维,即PHB,粘均分子量为3.9×105;皮层为HV含量为20mol%的PHBV,粘均分子量为4.5×105,皮和芯的体积比为30:70,通过梳理成网,热风粘合加固制得皮芯结构PHBV非织造布(面密度为22g/m2),将100层PHBV非织造布叠加在一起,在热压机上,在5MPa的压力下,130℃的温度下,热压成单聚合物PHBV复合材料。所得PHBV单聚合物复合材料的拉伸断裂强度为50.8MPa,断裂伸长率为45.2%。
实施例2
以皮芯结构PHBV短纤维为原料,其中芯层为3-羟基戊酸酯(HV)含量为2.5mol%的PHBV纤维,粘均分子量为5.6×105;皮层为HV含量为29mol%的PHBV,粘均分子量为2.6×105,皮和芯的体积比为20:80,通过梳理成网,热风粘合加固制得皮芯结构PHBV非织造布(面密度为18g/m2),将50层PHBV非织造布叠加在一起,在热压机上,在4MPa的压力下,100℃的温度下,热压成单聚合物PHBV复合材料。所得PHBV单聚合物复合材料的拉伸断裂强度为55.7MPa,断裂伸长率为30.2%。
实施例3
以皮芯结构PHBV短纤维为原料,其中芯层为3-羟基戊酸酯(HV)含量为0的PHBV纤维,即PHB,粘均分子量为3.9×105;皮层为HV含量为12mol%的PHBV,粘均分子量为4.8×105,皮和芯的体积比为30:70,通过梳理成网,热风粘合加固制得皮芯结构PHBV非织造布(面密度为20g/m2),将100层PHBV非织造布叠加在一起,在热压机上,在8MPa的压力下,155℃的温度下,热压成单聚合物PHBV复合材料。所得PHBV单聚合物复合材料的拉伸断裂强度为48.2MPa,断裂伸长率为37.5%。
实施例4
以皮芯结构PHBV短纤维为原料,其中芯层为3-羟基戊酸酯(HV)含量为2.5mol%的PHBV纤维,粘均分子量为3.9×105;皮层为HV含量为77mol%的PHBV,粘均分子量为2.8×105,皮和芯的体积比为35:65,通过梳理成网,热风粘合加固制得皮芯结构PHBV非织造布(面密度为20g/m2),将100层PHBV非织造布叠加在一起,在热压机上,在8MPa的压力下,120℃的温度下,热压成单聚合物PHBV复合材料。所得PHBV单聚合物复合材料的拉伸断裂强度为45.3MPa,断裂伸长率为40.8%。
Claims (5)
1.一种高纤维体积含量聚(3-羟基丁酸酯-co-3-羟基戊酸酯)单聚合物复合材料,其组分包括:
(1)增强相为3-羟基戊酸酯结构单元含量为0~20mol%的聚(3-羟基丁酸酯-co-3-羟基戊酸酯)纤维,当3-羟基戊酸酯结构单元含量为0时,聚(3-羟基丁酸酯-co-3-羟基戊酸酯)即为聚(3-羟基丁酸酯),增强相聚(3-羟基丁酸酯-co-3-羟基戊酸酯)的粘均分子量为5.0×104~1.0×106;
(2)基体是3-羟基戊酸酯结构单元含量为10~100mol%的聚(3-羟基丁酸酯-co-3-羟基戊酸酯),当3-羟基戊酸酯结构单元含量为100mol%时,聚(3-羟基丁酸酯-co-3-羟基戊酸酯)即为聚(3-羟基戊酸酯),基体的粘均分子量为5.0×104~1.0×106;
(3)增强相纤维的体积含量为5%~90%。
2.根据权利要求1所述的高纤维体积含量聚(3-羟基丁酸酯-co-3-羟基戊酸酯)单聚合物复合材料的制备方法,包括以下步骤:
(1)将皮芯结构的聚(3-羟基丁酸酯-co-3-羟基戊酸酯)纤维加工成纤维集合体,皮芯结构的聚(3-羟基丁酸酯-co-3-羟基戊酸酯)纤维中芯层为3-羟基戊酸酯结构单元含量为0~20mol%的聚(3-羟基丁酸酯-co-3-羟基戊酸酯),当3-羟基戊酸酯结构单元的含量为0时,聚(3-羟基丁酸酯-co-3-羟基戊酸酯)即为聚(3-羟基丁酸酯),芯层聚(3-羟基丁酸酯-co-3-羟基戊酸酯)的粘均分子量为5.0×104~1.0×106;皮层是3-羟基戊酸酯结构单元含量为10~100mol%的聚(3-羟基丁酸酯-co-3-羟基戊酸酯),当3-羟基戊酸酯结构单元含量为100mol%时,聚(3-羟基丁酸酯-co-3-羟基戊酸酯)即为聚(3-羟基戊酸酯),皮层的粘均分子量为5.0×104~1.0×106;芯层的体积含量为5%~90%;
(2)将1~1000层皮芯结构聚(3-羟基丁酸酯-co-3-羟基戊酸酯)纤维集合体叠加在一起;
(3)在热压机上,在一定压力和温度下,将皮芯结构聚(3-羟基丁酸酯-co-3-羟基戊酸酯)纤维集合体热压成单聚合物聚(3-羟基丁酸酯-co-3-羟基戊酸酯)复合材料,热压过程中皮芯结构聚(3-羟基丁酸酯-co-3-羟基戊酸酯)纤维中的皮层熔融成基体,芯层保持原有的结构形态作为增强相。
3.根据权利要求2所述的高纤维体积含量聚(3-羟基丁酸酯-co-3-羟基戊酸酯)单聚合物复合材料的制备方法,其特征在于所述的纤维集合体包括机织物、针织物和非织造布。
4.根据权利要求2所述的高纤维体积含量聚(3-羟基丁酸酯-co-3-羟基戊酸酯)单聚合物复合材料的制备方法,其特征在于所述的热压压力为1~20MPa。
5.根据权利要求2所述的高纤维体积含量聚(3-羟基丁酸酯-co-3-羟基戊酸酯)单聚合物复合材料的制备方法,其特征在于所述的热压温度为100~160℃。
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