CN113863019B - 一种抗老化pvc篷布及其制备工艺 - Google Patents
一种抗老化pvc篷布及其制备工艺 Download PDFInfo
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Abstract
本发明公开了一种抗老化PVC篷布及其制备工艺。抗老化PVC篷布包括基布层和涂覆在基布层上的PVC面料层,按重量份计,所述PVC面料层的制备原料包括PVC糊树脂70‑90份、增塑剂20‑30份、防老化剂5‑10份、氯化石蜡3‑5份、水滑石3‑5份、纳米二氧化钛15‑25份和有机溶剂60‑80份。抗老化PVC篷布的制备工艺包括如下步骤:将PVC糊树脂、增塑剂、氯化石蜡和有机溶剂混合,再加入防老化剂、水滑石和纳米二氧化钛,搅拌均匀,得PVC面料混合物;将PVC面料混合物涂覆在基布层的上表面,烘干,得抗老化PVC篷布。本申请提供的抗老化PVC篷布,耐高温老化效果和耐迁移性好。
Description
技术领域
本发明涉及篷布领域,尤其是涉及一种抗老化PVC篷布及其制备工艺。
背景技术
PVC篷布是以高强度帆布为基布,涂敷聚氯乙烯(PVC)糊状树脂配加增塑剂、防霉剂、抗静电剂等多种化学助剂,经高温塑化而成。具有高强度、防水、防霉、耐磨、耐用、耐寒等性能。PVC篷布是日常生活中常见的产品,广泛用于汽车遮盖防水帆布、汽车盖货防水篷布、火车盖货防水帆布、船用防水帆布、农业种植园搭棚防水篷布、建筑工地钢材遮盖防水篷布、各种温室保温篷布、国际贸易搭棚篷布、各种畜牧养殖业篷布卷帘、露天货场盖货防水帆布、车站搭棚防水帆布、码头盖货防水帆布等。PVC篷布不仅耐使用性能强,而且有着很好的时尚效果。
但PVC篷布在长时间使用过程中,PVC篷布接触化学物质(尤其是一些酸碱性太大,或者是盐度过高的物质),或者PVC篷布在太阳底下暴晒或接触到110℃以上高温,PVC均容易发生分解,PVC篷布出现极为严重的老化现象,导致PVC篷布的拉伸强度和断裂伸长率下降,从而缩短了PVC篷布的使用寿命。
发明内容
为了改善PVC篷布容易老化的问题,本申请提供一种抗老化PVC篷布及其制备工艺。
第一方面,本申请提供一种抗老化PVC篷布,采用如下技术方案实现:
一种抗老化PVC篷布,包括基布层和涂覆在基布层上的PVC面料层,按重量份计,所述PVC面料层的制备原料包括PVC糊树脂70-90份、增塑剂20-30份、防老化剂5-10份、氯化石蜡3-5份、水滑石3-5份、纳米二氧化钛15-25份和有机溶剂60-80份。
通过采用上述技术方案,由于水滑石的层板由镁八面体和铝氧八面体组成,具有较强的碱性,且水滑石的热稳定性好,水滑石在空气中低于200℃时仅失去层间水分,使得水滑石可以作为PVC糊树脂的稳定剂。纳米二氧化钛是白色疏松粉末,屏蔽紫外线作用强,有良好的分散性和耐候性,且纳米二氧化钛对PVC糊树脂具有填补缺口、润滑的作用,可以提高PVC篷布的强度。水滑石和纳米二氧化钛共同作用,不仅可以使PVC篷布在高温、紫外线照射下不易变色分解,从而提高了PVC篷布老化后拉伸强度保持率和老化后断裂伸长率保持率;同时,水滑石的层状结构和纳米二氧化钛的疏松结构还有利于减少增塑剂从PVC篷布中发生迁移,提高了PVC篷布的耐迁移性。
优选的,所述PVC糊树脂的聚合度为1500。
当PVC糊树脂的聚合度为1500时,PVC糊树脂的表观密度较低,有利于提高增塑剂与PVC糊树脂的分子间作用力,从而降低了PVC篷布的迁移率;且聚合度为1500的PVC糊树脂,具有更好的热稳定性和耐候性,有利于提高PVC篷布高温老化后的拉伸强度和断裂伸长率。
优选的,所述防老化剂由硬脂酸钡、季戊四醇二亚磷酸双十八酯和4,4’-硫代双(6-叔丁基间甲酚)按质量比1:(0.4-0.6):(0.2-0.3)混合而成。
更优选的,所述硬脂酸钡、季戊四醇二亚磷酸双十八酯和4,4’-硫代双(6-叔丁基间甲酚)的质量比为1:0.55:0.22。
季戊四醇二亚磷酸双十八酯含有双亚磷酸酯结构,且烷基三价磷含量较高,使得抗氧效果更突出与高效;4,4’-硫代双(6-叔丁基间甲酚)具有硫代双酚结构,具有游离基终止剂和氢过氧化物分解剂的双重功能,抗老化效果好,且能很好的保持PVC糊树脂的力学性能。本申请人在研究过程中意外的发现硬脂酸钡、季戊四醇二亚磷酸双十八酯和4,4’-硫代双(6-叔丁基间甲酚)复合使用,尤其是当硬脂酸钡、季戊四醇二亚磷酸双十八酯和4,4’-硫代双(6-叔丁基间甲酚)的质量比为1:0.55:0.22时,与单独作用或两者作用相比,三者复合使用显著提高了PVC篷布的耐老化性,还能提高PVC篷布的耐迁移性。这可能是由于季戊四醇二亚磷酸双十八酯和4,4’-硫代双(6-叔丁基间甲酚)的结构有利于提高增塑剂与PVC糊树脂的分子间作用力,进而抑制增塑剂分子从PVC篷布中迁移或扩散。
优选的,所述增塑剂由合成植物酯、邻苯二甲酸二异壬酯和环氧脂肪酸甲酯按质量比1:(0.5-0.7):(0.1-0.2)混合而成。
更优选的,所述合成植物酯、邻苯二甲酸二异壬酯和环氧脂肪酸甲酯的质量比为1:0.62:0.16。
合成植物酯、邻苯二甲酸二异壬酯和环氧脂肪酸甲酯三者复合使用显著提高了PVC篷布的耐迁移性,还能提高PVC篷布的耐老化性能。这可能是由于合成植物酯以植物油为原料、环氧脂肪酸甲酯以天然植物油为原料,使得合成植物酯和环氧脂肪酸甲酯与PVC糊树脂相溶性好,且均对光和热有良好的稳定作用,可以提高PVC篷布的物理性能并延长老化时间;加上邻苯二甲酸二异壬酯的碳链较长,可以与防老化剂中的季戊四醇二亚磷酸双十八酯相互作用,提高了PVC篷布的耐老化性能,同时还能增大增塑剂与PVC糊树脂的分子间作用力,从而提高PVC篷布的抗迁移性能。尤其是当合成植物酯、邻苯二甲酸二异壬酯和环氧脂肪酸甲酯的质量比为1:0.62:0.16时,PVC篷布的耐迁移性和耐老化性能更优。
优选的,所述PVC面料层的制备原料还包括1.5-2.5重量份的聚乙烯醇。
聚乙烯醇是一种带有仲羟基的线性高分子聚合物,分子中的羟基具有较高的活性,聚乙烯醇的羟基与水滑石表面分布的大量羟基之间的氢键作用较强,从而有利于提高增塑剂与PVC糊树脂的分子间作用力,且聚乙烯醇具有高粘着性、易成膜,从而提高PVC篷布的耐迁移性。
优选的,所述基布层为EP帆布。
第二方面,本申请提供一种抗老化PVC篷布的制备工艺,采用如下的技术方案:一种抗老化PVC篷布的制备工艺,包括如下步骤:
将PVC糊树脂、增塑剂、氯化石蜡和有机溶剂混合,再加入防老化剂、水滑石和纳米二氧化钛,搅拌均匀,得PVC面料混合物;
将PVC面料混合物涂覆在基布层的上表面,烘干,得抗老化PVC篷布。
通过采用上述技术方案,本申请抗老化PVC篷布的制备工艺操作简单,耐老化效果好,且PVC面料层不易脱落。
优选的,所述烘干的温度为60-80℃。
综上所述,本申请具有以下有益效果:
1、水滑石和纳米二氧化钛共同作用,不仅可以使PVC篷布在高温、紫外线照射下不易变色分解,从而提高了PVC篷布老化后拉伸强度保持率和老化后断裂伸长率保持率;同时,水滑石的层状结构和纳米二氧化钛的疏松结构还有利于减少增塑剂从PVC篷布中发生迁移,提高了PVC篷布的耐迁移性。
2、硬脂酸钡、季戊四醇二亚磷酸双十八酯和4,4’-硫代双(6-叔丁基间甲酚)复合使用,显著提高了PVC篷布的耐老化性,还能提高PVC篷布的耐迁移性。
3、合成植物酯、邻苯二甲酸二异壬酯和环氧脂肪酸甲酯三者复合使用显著提高了PVC篷布的耐迁移性,还能提高PVC篷布的耐老化性能。
4、聚乙烯醇的加入可以提高增塑剂与PVC糊树脂的分子间作用力,且聚乙烯醇具有高粘着性、易成膜,从而提高PVC篷布的耐迁移性。
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。
本申请使用的原料均可通过市售获得,其中:
PVC糊树脂P440,聚合度1500,购买自常州市荣仁化工有限公司;
PVC糊树脂P450,聚合度1000,购买自常州市荣仁化工有限公司;
氯化石蜡,工业级CP-70,购买自济南汇锦川商贸有限公司;
水滑石,牌号为购买自日本协和化学;
合成植物酯,酯含量99%,购买自苏州伊格特化工有限公司;
聚乙烯醇,型号为26-99(L),醇解度99.0-100.0%,购买自皖维。
实施例
实施例1-19提供了一种抗老化PVC篷布,以下以实施例1为例进行说明。
实施例1提供的抗老化PVC篷布,包括EP帆布和涂覆在EP帆布上表面的PVC面料层,其制备工艺为:
将0.7kg PVC糊树脂P450、0.2kg合成植物酯、0.03kg氯化石蜡和0.6kg环己酮混合,再加入0.05kg硬脂酸钡、0.03kg水滑石和0.15kg纳米二氧化钛,搅拌均匀,得PVC面料混合物;将PVC面料混合物涂覆在EP帆布的上表面(涂覆量为2g/cm2),在70℃烘干,得抗老化PVC篷布。
实施例2-5,与实施例1不同之处在于:PVC面料混合物的组成不同,具体见表1。
表1实施例1-5PVC面料混合物的组成
其中,聚乙烯醇的型号为26-99(L)。
实施例4、5对应的PVC面料混合物的制备步骤为:PVC糊树脂P450、合成植物酯、氯化石蜡、聚乙烯醇和环己酮混合,再加入硬脂酸钡、水滑石和纳米二氧化钛,搅拌均匀,得PVC面料混合物。
实施例6,与实施例5不同之处在于:PVC糊树脂P450等质量替换为PVC糊树脂P440。
实施例7-12,与实施例6不同之处在于:防老化剂的组成不同,具体见表2。
表2实施例6-12防老化剂的组成
其中,季戊四醇二亚磷酸双十八酯的CAS号为3806-34-6;4,4'-硫代双(6-叔丁基间甲酚)的CAS号为96-69-5。
实施例13-19,与实施例12不同之处在于:增塑剂的组成不同,具体见表3。
表3实施例12-19增塑剂的组成
其中,邻苯二甲酸二异壬酯的CAS号为28553-12-0;环氧脂肪酸甲酯的CAS号为6084-76-0。
对比例
对比例1,与实施例1不同之处在于:水滑石等质量替换为纳米二氧化钛。
对比例2,与实施例1不同之处在于:纳米二氧化钛等质量替换为水滑石。
性能检测试验
针对本申请实施例1-19和对比例1-2提供的抗老化PVC篷布,进行如下的性能检测。
1、耐高温老化测试:将实施例1-19和对比例1-2所述抗老化PVC篷布在120℃下老化处理1000h后,参照GB/T 528-1998的标准在50mm/min下测试抗老化PVC篷布老化前后的拉伸强度、断裂伸长率,计算抗老化PVC篷布的老化后拉伸强度保持率和老化后断裂伸长率保持率,其中,老化后拉伸强度保持率=老化后的拉伸强度/老化前的拉伸强度×100%,老化后断裂伸长率保持率=老化后的断裂伸长率/老化前的断裂伸长率×100%,测试结果见表4。
2、耐迁移性:用重量损失法测试实施例1-19和对比例1-2所述抗老化PVC篷布的迁移率,测试温度为100℃、测试时间为10天,测试结果见表4。
表4耐高温老化和耐迁移性的测试结果
以下针对表4的测试数据,详细说明本申请。
对比实施例1和对比例1-2的实验数据,可以发现水滑石和纳米二氧化钛共同作用,可以明显提高PVC篷布老化后拉伸强度保持率和老化后断裂伸长率保持率,同时耐迁移性也有少许提高。
对比实施例3-5的实验数据,可以发现聚乙烯醇的加入可以显著提高PVC篷布的耐迁移性,同时PVC篷布老化后拉伸强度保持率和老化后断裂伸长率保持率也有少许提高。
对比实施例5-6的实验数据,可以发现聚合度为1500的PVC糊树脂P440对应PVC篷布的耐老化性优于聚合度为1000的PVC糊树脂P450对应PVC篷布的耐老化性,这是由于聚合度为1500的PVC糊树脂P440表观密度较低,有利于提高增塑剂与PVC糊树脂的分子间作用力。
对比实施例6-10的实验数据,可以发现实施例10采用硬脂酸钡、季戊四醇二亚磷酸双十八酯和4,4’-硫代双(6-叔丁基间甲酚)复合使用对应PVC篷布老化后拉伸强度保持率和老化后断裂伸长率保持率较高,迁移率较低。说明与单独作用或两者作用相比,硬脂酸钡、季戊四醇二亚磷酸双十八酯和4,4’-硫代双(6-叔丁基间甲酚)三者复合使用可显著提高PVC篷布的耐老化性,还能提高PVC篷布的耐迁移性。对比实施例10-12的实验数据,可以发现当硬脂酸钡、季戊四醇二亚磷酸双十八酯和4,4’-硫代双(6-叔丁基间甲酚)的质量比为1:0.55:0.22时,PVC篷布的耐高温老化效果和耐迁移性更优。
对比实施例12-17的实验数据,可以发现实施例17合成植物酯、邻苯二甲酸二异壬酯和环氧脂肪酸甲酯三者复合使用对应PVC篷布的迁移率较低,说明与合成植物酯、邻苯二甲酸二异壬酯、环氧脂肪酸甲酯中一种或两者作用相比,三者复合使用可显著提高PVC篷布的耐迁移性,同时三者复合使用的耐高温老化效果也较优。对比实施例17-19的实验数据,可以发现当合成植物酯、邻苯二甲酸二异壬酯和环氧脂肪酸甲酯的质量比为1:0.62:0.16时,PVC篷布的耐迁移性和耐高温老化效果更优。
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 (10)
1.一种抗老化PVC篷布,包括基布层和涂覆在基布层上的PVC面料层,其特征在于,按重量份计,所述PVC面料层的制备原料包括PVC糊树脂70-90份、增塑剂20-30份、防老化剂5-10份、氯化石蜡3-5份、水滑石3-5份、纳米二氧化钛15-25份和有机溶剂60-80份。
2.根据权利要求1所述的一种抗老化PVC篷布,其特征在于,所述PVC糊树脂的聚合度为1500。
3.根据权利要求1所述的一种抗老化PVC篷布,其特征在于,所述防老化剂由硬脂酸钡、季戊四醇二亚磷酸双十八酯和4,4’-硫代双(6-叔丁基间甲酚)按质量比1:(0.4-0.6):(0.2-0.3)混合而成。
4.根据权利要求3所述的一种抗老化PVC篷布,其特征在于,所述硬脂酸钡、季戊四醇二亚磷酸双十八酯和4,4’-硫代双(6-叔丁基间甲酚)的质量比为1:0.55:0.22。
5.根据权利要求1所述的一种抗老化PVC篷布,其特征在于,所述增塑剂由合成植物酯、邻苯二甲酸二异壬酯和环氧脂肪酸甲酯按质量比1:(0.5-0.7):(0.1-0.2)混合而成。
6.根据权利要求5所述的一种抗老化PVC篷布,其特征在于,所述合成植物酯、邻苯二甲酸二异壬酯和环氧脂肪酸甲酯的质量比为1:0.62:0.16。
7.根据权利要求1-6任一项所述的一种抗老化PVC篷布,其特征在于,所述PVC面料层的制备原料还包括1.5-2.5重量份的聚乙烯醇。
8.根据权利要求1所述的一种抗老化PVC篷布,其特征在于,所述基布层为EP帆布。
9.权利要求1-8任一项所述的一种抗老化PVC篷布的制备工艺,其特征在于,包括如下步骤:
将PVC糊树脂、增塑剂、氯化石蜡和有机溶剂混合,再加入防老化剂、水滑石和纳米二氧化钛,搅拌均匀,得PVC面料混合物;
将PVC面料混合物涂覆在基布层的上表面,烘干,得抗老化PVC篷布。
10.根据权利要求9所述的一种抗老化PVC篷布的制备工艺,其特征在于,所述烘干的温度为60-80℃。
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