CN113417148A - 一种环保型聚氯乙烯人造革及其制备方法 - Google Patents

一种环保型聚氯乙烯人造革及其制备方法 Download PDF

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CN113417148A
CN113417148A CN202110578955.5A CN202110578955A CN113417148A CN 113417148 A CN113417148 A CN 113417148A CN 202110578955 A CN202110578955 A CN 202110578955A CN 113417148 A CN113417148 A CN 113417148A
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林斌生
黄仕明
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Guangdong Fion Leather Product Co ltd
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Abstract

本发明公开了一种环保型聚氯乙烯人造革,包括布基以及涂覆于所述布基上的涂层,所述涂层按重量份数计包括以下组分:聚氯乙烯树脂50‑80份、纳米氧化钙10‑15份、乙烯‑丙烯酸乙酯共聚物5‑10份、二月桂酸二丁基锡2‑5份、硬脂酸钡15‑20份、聚异丁烯多丁二酰亚胺8‑12份、氧化硼4‑6份、柠檬酸三丁酯增塑剂3‑8份。本发明采用的柠檬酸三丁酯增塑剂具有同PVC相容性好,塑料低温挠曲性能好,热稳定性高,环保无毒的优点;通过对聚氯乙烯面层和发泡层配方进行优化,在微观程度上改进PVC人造革的内部结构,其具有优异的力学性能。

Description

一种环保型聚氯乙烯人造革及其制备方法
技术领域
本发明涉及皮革加工技术领域,尤其涉及一种绿色环保的聚氯乙烯人造革及其制备方法。
背景技术
目前,聚氯乙烯人造革加工多采用邻苯二甲酸酯类增塑剂,在使用过程中增塑剂会逐渐迁移到制品表面而与人体接触。邻苯二甲酸酯主要用于聚氯乙烯材料,令聚氯乙烯由硬塑胶变为有弹性的塑胶,起到增塑剂的作用。它被普遍应用于玩具、食品包装材料、医用血袋和胶管、乙烯地板和壁纸、清洁剂、润滑油、个人护理用品(如指甲油、头发喷雾剂、香皂和洗发液)等数百种产品中,但对人体的健康有严重的危害。邻苯二甲酸酯类具有生殖毒性,还具有致突变和致癌作用同,对消费者个人安全造成重大威胁,因而欧盟已开始禁用此类物质;然而,增塑剂作为PVC人造革生产加工中的必要成分,不可或缺。因此,研发一种新的环保型增塑剂,用以制造环境友好型和消费者友好型PVC人造革产品,就显得很有必要。
发明内容
本发明的目的在于提供一种绿色环保的聚氯乙烯人造革及其制备方法
为实现上述的目的,本发明采用如下的技术方案:
一种环保型聚氯乙烯人造革,包括布基以及涂覆于所述布基上的涂层,所述涂层按重量份数计包括以下组分:聚氯乙烯树脂50-80份、纳米氧化钙10-15份、乙烯-丙烯酸乙酯共聚物5-10份、二月桂酸二丁基锡2-5份、硬脂酸钡15-20份、聚异丁烯多丁二酰亚胺8-12份、氧化硼4-6份、柠檬酸三丁酯增塑剂3-8份。
优选的,所述柠檬酸三丁酯由柠檬酸和丁醇按一定配比制得;所述柠檬酸三丁酯由柠檬酸和丁醇按一定配比1:1制得。
优选的,所述涂层按重量份数计包括以下组分:聚氯乙烯树脂60-70份、纳米氧化钙10-12份、乙烯-丙烯酸乙酯共聚物6-8份、二月桂酸二丁基锡3-4份、硬脂酸钡15-17份、聚异丁烯多丁二酰亚胺8-10份、氧化硼4-5份、柠檬酸三丁酯增塑剂3-6份。
本发明还提供了上述环保型聚氯乙烯人造革的制备方法,包括将聚氯乙烯树脂、纳米氧化钙、乙烯-丙烯酸乙酯共聚物、二月桂酸二丁基锡、硬脂酸钡、聚异丁烯多丁二酰亚胺、氧化硼、柠檬酸三丁酯增塑剂按一定配比发泡后,粘合到布基上,在一定温度烘干后制得。
优选的,烘干温度为40-80℃;烘干时间为16-32h。
乙烯-丙烯酸乙酯共聚物中丙烯酸乙酯含量15%~30%;其具有很好的柔韧性、热稳定性和加工性;耐环境应力开裂性、抗冲击性、耐弯曲疲劳性、低温性均优于低密度聚乙烯,与聚氯乙烯树脂有好的相容性,并可与大量填料混合而不变脆。
本发明制备了一种新型的环保型聚氯乙烯人造革,首先通过柠檬酸和正丁醇制备了一种环保型增塑剂柠檬酸三丁酯。柠檬酸作为一种三羧酸类化合物,与其他羧酸类具有相同的化学和物理性质。柠檬酸是一种较强的有机酸,在溶液的状态下有三个H+可以电离。
正丁醇为一种制造油漆,人造纤维,洗涤剂的常用醇类化合物,正丁醇与柠檬酸在浓硫酸、催化剂的作用下发生酯化反应,而后经过活性炭脱色、过滤、中和、水洗、减压蒸馏得到柠檬酸三丁酯(TBC)。
TBC作为一种新型“绿色”的环保增塑剂,具有相容性好,增塑效率高、挥发性小、耐寒、耐光、耐水等优良特性,将其加入到聚氯乙烯(PVC)中后,增塑效果与邻苯二甲酸二辛酯(DOP)和邻苯二甲酸二丁酯(DBP)等增塑剂相当。TBC应用十分广泛,在食品、药物及仪器包装方面,由于TBC具有同聚氯乙烯(PVC)相容性好和增塑效率高的优点,采用TBC增塑的PVC薄膜具有很好的透气性和透水性,可使肉类保鲜,延长蔬菜保鲜期;在医药行业,将TBC作为载体加入到药物中,可使药剂外表面弹性强,不易破碎,而且它的存在可使药物在一定时间内按照一定的速率在体内缓慢释放,保持药物在血液中的有效浓度,达到有效治疗的目的;在生物降解方面,在降解高分子材料中加入适当的TBC可使聚合物由刚性链变为柔性链,并且赋予其可加工性。
纳米氧化钙作为一种常用的填料,在加入到PVC体系中后,填充到PVC链段之间,起到补助增强的作用,提高了PVC材料的耐磨性的同时还能降低生产成本。硬脂酸钡在PVC产品中做产品的热稳定剂,耐老化,耐热性好。同时兼具有润滑剂的作用,减少分子链之间的摩擦,温度高时会起到外润滑剂的作用,在涂饰时起到脱模的效果。
聚异丁烯多丁二酰亚胺作为分散剂,是一种分子内同时具有亲油性和亲水性两种相反性质的界面活性剂。可均一分散那些难于溶解于液体的无机,有机的固体及液体颗粒,同时也能防止颗粒的沉降和凝聚,形成安定混合液所需的两亲性试剂。分散剂的作用是使用润湿分散剂减少完成分散过程所需要的时间和能量,稳定所分散的分散体,改性粒子表面性质,调整粒子的运动性。氧化硼作为添加的阻燃剂,对PVC材料起到阻燃的效果,高温状态下熔化封闭燃烧物表面,形成玻璃体遮盖层,起到隔绝的作用。同时由于熔化带走大量热量,可以改变某些可燃性链段的热分解途径,抑制可燃性气体的产生,进而达到阻燃的目的。
综上,本发明通过制备环保型增塑剂柠檬酸三丁酯,将其添加到聚氯乙烯体系中,在增加聚氯乙烯高聚物物理机械性能的同时,还能有效抑制增塑剂在使用过程中的迁移,兼具绿色环保的理念。
本发明通过对聚氯乙烯面层和发泡层配方进行优化,在微观程度上改进PVC人造革的内部结构,其具有优异的力学性能。
具体实施方式
下面将结合本发明实施例对本发明实施例中的技术方案进行清楚、完整地描述,但不构成对本发明保护范围的限制。
实施例1
一种环保型聚氯乙烯人造革,包括布基以及涂覆于布基上的涂层,其中,涂层按重量份数计包括以下组分:聚氯乙烯树脂50份、纳米氧化钙10份、乙烯-丙烯酸乙酯共聚物5份、二月桂酸二丁基锡2份、硬脂酸钡15份、聚异丁烯多丁二酰亚胺8份、氧化硼4份、柠檬酸三丁酯增塑剂3份。
制备方法,将聚氯乙烯树脂、纳米氧化钙、乙烯-丙烯酸乙酯共聚物、二月桂酸二丁基锡、硬脂酸钡、聚异丁烯多丁二酰亚胺、氧化硼、柠檬酸三丁酯增塑剂按上述配比发泡后,粘合到布基上,在60℃烘干,时间为24h。
实施例2
一种环保型聚氯乙烯人造革,包括布基以及涂覆于布基上的涂层,其中,涂层按重量份数计包括以下组分:聚氯乙烯树脂80份、纳米氧化钙15份、乙烯-丙烯酸乙酯共聚物10份、二月桂酸二丁基锡5份、硬脂酸钡20份、聚异丁烯多丁二酰亚胺12份、氧化硼6份、柠檬酸三丁酯增塑剂8份。
制备方法同实施例1
实施例3
一种环保型聚氯乙烯人造革,包括布基以及涂覆于布基上的涂层,其中,涂层按重量份数计包括以下组分:聚氯乙烯树脂60份、纳米氧化钙12份、乙烯-丙烯酸乙酯共聚物12份、二月桂酸二丁基锡3份、硬脂酸钡18份、聚异丁烯多丁二酰亚胺10份、氧化硼5份、柠檬酸三丁酯增塑剂5份。
制备方法同实施例1
实施例4
一种环保型聚氯乙烯人造革,包括布基以及涂覆于布基上的涂层,其中,涂层按重量份数计包括以下组分:聚氯乙烯树脂70份、纳米氧化钙10份、乙烯-丙烯酸乙酯共聚物7份、二月桂酸二丁基锡4份、硬脂酸钡16份、聚异丁烯多丁二酰亚胺10份、氧化硼5份、柠檬酸三丁酯增塑剂5份。
制备方法同实施例1
对实施例1-4所得的人造革进行测试,见下表1
表1
测试项目 实施例1 实施例2 实施例3 实施例4
撕裂强度/径向N 90 92 88 90
撕裂强度/纬向N 85 86 85 87
剥离强度/径向N 89 90 88 89
剥离强度/纬向N 86 85 87 86
本发明采用的柠檬酸三丁酯增塑剂具有同PVC相容性好,塑料低温挠曲性能好,热稳定性高,环保无毒的优点;通过对聚氯乙烯面层和发泡层配方进行优化,在微观程度上改进PVC人造革的内部结构,其具有优异的力学性能。
以上所述是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也视为本发明的保护范围。

Claims (6)

1.一种环保型聚氯乙烯人造革,其牲征在于,包括布基以及涂覆于所述布基上的涂层,所述涂层按重量份数计包括以下组分:聚氯乙烯树脂50-80份、纳米氧化钙10-15份、乙烯-丙烯酸乙酯共聚物5-10份、二月桂酸二丁基锡2-5份、硬脂酸钡15-20份、聚异丁烯多丁二酰亚胺8-12份、氧化硼4-6份、柠檬酸三丁酯增塑剂3-8份,所述柠檬酸三丁酯由柠檬酸和丁醇按一定配比制得。
2.如权利要求1所述的环保型聚氯乙烯人造革,其牲征在于:所述柠檬酸三丁酯由柠檬酸和丁醇按一定配比1:1制得。
3.如权利要求1所述的环保型聚氯乙烯人造革,其牲征在于:所述涂层按重量份数计包括以下组分:聚氯乙烯树脂60-70份、纳米氧化钙10-12份、乙烯-丙烯酸乙酯共聚物6-8份、二月桂酸二丁基锡3-4份、硬脂酸钡15-17份、聚异丁烯多丁二酰亚胺8-10份、氧化硼4-5份、柠檬酸三丁酯增塑剂3-6份。
4.一种制备如权利要求1-3任一项所述的环保型聚氯乙烯人造革的方法,其牲征在于:将聚氯乙烯树脂、纳米氧化钙、乙烯-丙烯酸乙酯共聚物、二月桂酸二丁基锡、硬脂酸钡、聚异丁烯多丁二酰亚胺、氧化硼、柠檬酸三丁酯增塑剂按一定配比发泡后,粘合到布基上,在一定温度烘干后制得。
5.如权利要求5所述环保型聚氯乙烯人造革的制备方法,其牲征在于:烘干温度为40-80℃。
6.如权利要求5所述环保型聚氯乙烯人造革的制备方法,其牲征在于:烘干时间为16-32h。
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