CN114875574B - 高强高模聚乙烯醇纤维增强聚乳酸复合材料及制备方法 - Google Patents

高强高模聚乙烯醇纤维增强聚乳酸复合材料及制备方法 Download PDF

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CN114875574B
CN114875574B CN202210561330.2A CN202210561330A CN114875574B CN 114875574 B CN114875574 B CN 114875574B CN 202210561330 A CN202210561330 A CN 202210561330A CN 114875574 B CN114875574 B CN 114875574B
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pva
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刘庆生
刘潇宇
张航
赵薇
顾从可
石雪莹
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Jiangnan University
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Abstract

本发明公开了高强高模聚乙烯醇(PVA)纤维增强聚乳酸(PLA)复合材料及其制备方法，属于高分子材料领域。本发明的制备方法，包括如下步骤：(1)将不同比例的高强高模PVA纤维和PLA纤维加工成纤维网；(2)对纤维网进行加固，制得非织造材料；(3)以非织造材料为预制体，将其进行热压，制得高强高模PVA纤维增强PLA复合材料复合材料。在热压过程中，PLA纤维熔融成基体，高强高模PVA纤维保持原有的结构形态作为增强相。本发明所得的高强高模PVA纤维增强PLA复合材料具有绿色环保，力学性能优异的特点，可应用于汽车、建筑和体育工业等领域。

Description

高强高模聚乙烯醇纤维增强聚乳酸复合材料及制备方法
技术领域
本发明涉及高分子材料领域，具体涉及高强高模聚乙烯醇(PVA)纤维增强聚乳酸(PLA)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比强度高、耐腐蚀性强和断裂韧性高等特点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做出越来越大的贡献，因此，纤维增强聚合物基复合材料的市场占有率不断增加。然而，传统热塑性纤维增强复合材料存在两个问题：第一，增强相为苎麻、剑麻等天然植物纤维，植物纤维的长度和直径差异较大，复合材料的性能可控性差；第二，基体为石油基聚合物，存在资源短缺和环境污染等问题。以化学纤维增强资源可再生、生物可降解热塑性聚合物能够解决传统纤维增强热塑性聚合物复合材料存在的问题。
传统的热塑性纤维增强复合材料的增强相还存在与基体物质浸润性差、材料相容性差等问题，这导致复合材料产品强度较低，限制其应用范围。
聚乳酸(PLA)材料资源可再生、生物可降解，是所有已产业化的资源可再生、生物可降解热塑性聚合物中价格最低的聚合物；高强高模聚乙烯醇(PVA)纤维强度和模量高，价格较低。因此，开发高强高模PVA纤维增强PLA复合材料有望解决上述问题。但是，由于PLA的分子量高、粘度大，存在增强相纤维在基体中分散困难，分散度差，体积含量低等问题，亟需解决。
发明内容
本发明的目的是针对传统纤维增强热塑性聚合物复合材料开发过程中存在的问题，通过探索发现，一定条件下的高强高模PVA纤维作为增强相，一定条件下的PLA作为基体，在本发明所述的制备方法条件下，可获得一种强度高、增强相纤维体积含量高、纤维分散度好、环境友好、生物相容性好的复合材料。
本发明的第一个目的是提供一种高强高模PVA纤维增强PLA复合材料。
一种高强高模PVA纤维增强PLA复合材料，其组分包括：增强相高强高模聚PVA纤维、基体PLA。
在本发明的一种实施方式中，所述高强高模PVA纤维的线密度为1～9dtex，长度为6～80mm，所述基体PLA的分子量为3.0×104～1.0×106。
在本发明的一种实施方式中，所述高强高模PVA纤维与基体PLA的体积比为9:1～1:9。
在本发明的一种实施方式中，所述高强高模PVA纤维与基体PLA的体积比为4:6～2:8。
在本发明的一种实施方式中，所述高强高模PVA纤维与基体PLA的体积比为3:7。
本发明的第二个目的是提供所述高强高模PVA纤维增强PLA复合材料的制备方法，包括如下步骤：
(1)将高强高模PVA纤维和PLA纤维加工成纤维网；
(2)对纤维网进行加固，制得非织造材料；
(3)以非织造材料为预制体，将其进行热压制得高强高模PVA纤维增强PLA复合材料复合材料。
在热压过程中，PLA纤维熔融成基体，高强高模PVA纤维保持原有的结构形态作为增强相。
在本发明的一种实施方式中，所述高强高模PVA纤维与PLA纤维的体积比例为9:1～1:9。
在本发明的一种实施方式中，所述高强高模PVA纤维与基体PLA的体积比为4:6～2:8。
在本发明的一种实施方式中，所述高强高模PVA纤维与基体PLA的体积比为3:7。
PVA纤维和PLA在复合材料中起到相互协同配合的作用，二者的含量比例，是影响复合材料产品效果的一个关键因素。
在本发明的一种实施方式中，所述的加工成纤维网的方法为机械成网或气流成网中的一种。其中，梳理成网又称机械成网，将开松混合后的纤维通过梳理机梳理成由单纤维组成的纤网，供铺叠成网，梳理成网由于纤维按机器输出方向排列，因此纤网的纵横向强度差异较大；气流成网，纤维经开送混合后，喂入高速回转的锡林或刺棍，进一步梳理成单纤维。在锡林或刺棍的离心力和气流联合作用下，纤维从锯齿上脱落，靠气流输送，凝聚在成网帘(或尘笼)上，形成纤网。气流成网能使纤维在纤网中呈三维随机分布，因此纤网的纵横向强度差异较小。
在本发明的一种实施方式中，所述的高强高模PVA纤维增强PLA复合材料的制备方法，其特征在于加固方法为针刺、水刺和热粘合中的一种。
其中，针刺加固方法是用刺针对纤网进行反复穿刺加固纤网，刺针向下穿刺时，带有钩刺的刺针带住表层和里层的一些纤维穿过纤维层，在摩擦力的作用下纤维相互缠结，纤维的上下位移使纤网受到压缩，刺针回升时，纤网脱离钩刺停留在纤网中，纤维束组成的“销钉”钉入纤网，从而使已经产生压缩的纤网不再恢复，形成具有一定厚度、强度的针刺非织造材料；水刺加固工艺是依靠高压水，经过水刺头中的喷水板，形成微细的高压水针射流，对托网帘或转鼓上运动的纤网进行连续喷射，在水针直接冲击力和反射水流作用力的双重作用下,纤网中的纤维发生位移穿插、相互缠结抱合，形成无数的机械结合，从而使纤网得到加固；高分子聚合物材料大都具有热塑性，即加热到一定温度后会软化熔融，变成具有一定流动性的粘流体，冷却后又重新固化，变成固体。热粘合非织造工艺就是利用热塑性高分子聚合物材料这一特性，使纤网受热后部分纤维或热熔粉末软化熔融，纤维间产生粘连，冷却后纤网得到加固。
在本发明的一种实施方式中，所述的高强高模PVA纤维增强PLA复合材料的制备方法，其特征在于所述的热压压力为1～20MPa。
在本发明的一种实施方式中，所述的热压压力为8MPa。
在本发明的一种实施方式中，所述的热压温度为130～240℃。
在本发明的一种实施方式中，所述的热压温度为180～200℃。
在本发明的一种实施方式中，所述的热压温度为190℃。
热压压力和热压温度影响PLA纤维熔融状态的流动性，流动性较差会导致PLA纤维对PVA纤维的包裹浸润效果，流动性较强会改变已固定形态PVA纤维网形态发生不可预料的变化，都会影响最终复合材料产品的强度。由于不同材料的特性不同，过高的温度还会导致材料的分解，无法从现有技术中直接获得适合本发明的压力和温度条件。
因此，通过探究，确定合适的热压压力和热压温度条件，是制备本发明复合材料的关键条件之一。
本发明第三个目的是提供获得的高强高模PVA纤维增强PLA复合材料在航空航天、休闲娱乐、汽车、建筑或体育工业领域的应用。
本发明的有益效果：
(1)高强高模PVA纤维增强PLA复合材料中基体PLA是一种可生物降解、可资源再生、生物相容性好的高分子材料，是一种环境友好型材料；
(2)高强高模PVA纤维增强PLA复合材料的预制体，为PLA纤维和高强高模PVA纤维经梳理成网加固后制得的非织造材料，非织造材料中PLA纤维和PVA纤维的混合比例可控，混合均匀，以致复合材料中PVA纤维在PLA基体中分散均匀，基体对增强相的浸润性好，纤维体积含量可高达90％；
(3)增强相PVA纤维和基体PLA的熔点相差大，复合材料的加工窗口宽。
(4)本发明请求保护的高强高模PVA纤维增强PLA复合材料，以及通过本发明请求保护方法所制备的复合材料，除兼具上述优势以外，还具有相对于现有技术更突出的强度，其拉伸强度可达200.8MPa。
(5)本发明制备的高强高模PVA纤维增强PLA复合材料可以用在航空航天、休闲娱乐、汽车、建筑或体育工业领域。
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力要求书所限定的范围。
实施例中，拉伸强度和断裂伸长率测试条件为：在Instron 3385H(美国Instron公司)万能材料试验机上，采用尺寸为100mm×20mm×1mm的矩形试件，在室温下测定拉伸性能。十字头加载速度5mm/min，加持距离65mm，每个样品重复测试5次。
实施例1
(1)以长度均为38mm、线密度均为2.2dtex的PLA纤维与高强高模PVA纤维为原料，按照7:3的比例，进行开松、混合——梳理成网，制得PVA/PLA纤维网；
(2)将PVA/PLA纤维网喂入针刺机，对其针刺加固，制得PVA/PLA复合针刺非织造材料；
(3)将PVA/PLA针刺非织造材料进行热压，热压压力为8MPa、热压时间为10min、热压温度为190℃，制得高强高模PVA纤维增强PLA复合材料，所得复合材料的拉伸强度为180.3MPa，断裂伸长率为15.9％。
实施例2
(1)以长度均为6mm、线密度均为2.2dtex的PLA纤维与高强高模PVA纤维为原料，按照8:2的比例，进行开松、混合并通过气流成网的方式成网，制得PVA/PLA纤维网；
(2)将PVA/PLA纤维网进行热风粘合，制得PVA/PLA热粘合非织造材料；
(3)将PVA/PLA热粘合非织造材料进行热压，热压压力为8MPa、热压时间为10min、热压温度为180℃，制得高强高模PVA纤维增强PLA复合材料，所得复合材料的拉伸强度为105.72MPa，断裂伸长率为6.16％。
实施例3
(1)以长度均为51mm、线密度均为4.4dtex的PLA纤维与高强高模PVA纤维为原料，按照6:4的比例，进行开松、混合——梳理成网，制得PVA/PLA纤维网；
(2)将PVA/PLA纤维网喂入水刺设备，对其水刺加固，制得PVA/PLA水刺非织造材料；
(3)将PVA/PLA水刺非织造材料进行热压，热压压力为8MPa、热压时间为10min、热压温度为200℃，制得高强高模PVA纤维增强PLA复合材料，所得复合材料的拉伸强度为162.5MPa，断裂伸长率为12.7％。
实施例4
(1)以长度均为51mm、线密度均为4.4dtex的PLA纤维与高强高模PVA纤维为原料，按照7：3的比例，进行开松、混合——梳理成网，制得PVA/PLA纤维网；
(2)将高强高模PVA/PLA纤维网喂入热轧设备，对其加固，制得PVA/PLA复合针刺非织造材料；
(3)将PVA/PLA针刺非织造材料进行热压，热压压力为8MPa、热压时间为10min、热压温度为190℃，制得高强高模PVA纤维增强PLA复合材料，所得复合材料的拉伸强度为200.8MPa，断裂伸长率为17.7％。

Claims (3)

1.一种高强高模PVA纤维增强PLA复合材料的制备方法，其特征在于，包括如下步骤：
（1）以长度均为51mm、线密度均为4.4dtex的PLA纤维与高强高模PVA纤维为原料，按照7：3的比例，进行开松、混合——梳理成网，制得PVA/PLA纤维网；
（2）将高强高模PVA/PLA纤维网喂入热轧设备，对其加固，制得PVA/PLA复合非织造材料；
（3）将PVA/PLA复合非织造材料进行热压，热压压力为8MPa、热压时间为10min、热压温度为190℃，制得高强高模PVA纤维增强PLA复合材料。
2.权利要求1所述的方法制备得到的高强高模PVA纤维增强PLA复合材料。
3.权利要求2所述的高强高模PVA纤维增强PLA复合材料在航空航天、休闲娱乐、汽车、建筑或体育工业领域的应用。
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