CN109135489A - 一种含有天然抗菌吸附因子的水性聚氨酯-丙烯酸酯皮革涂饰剂 - Google Patents

一种含有天然抗菌吸附因子的水性聚氨酯-丙烯酸酯皮革涂饰剂 Download PDF

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CN109135489A
CN109135489A CN201810763360.5A CN201810763360A CN109135489A CN 109135489 A CN109135489 A CN 109135489A CN 201810763360 A CN201810763360 A CN 201810763360A CN 109135489 A CN109135489 A CN 109135489A
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王春华
穆畅道
林炜
庄馥先
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Abstract

本发明公开了一种含有天然抗菌吸附因子的水性聚氨酯‑丙烯酸酯皮革涂饰剂,其特征在于先通过多元醇与二异氰酸酯和双羟甲基丙烯酸反应得到聚氨酯,然后加入甲基丙烯酸‑β‑羟丙酯得到C=C封端的聚氨酯,进一步通过自由基聚合反应引入天然抗菌吸附因子、丙烯酸酯类共聚单体,最后加入中和剂中和后在水中乳化制得。本方法可在分子水平上将天然抗菌吸附因子被引入到丙烯酸酯‑聚氨酯基体中,结合了丙烯酸酯和聚氨酯各自优异涂性能,并可赋予涂层持久的抗菌吸附性能。

Description

一种含有天然抗菌吸附因子的水性聚氨酯-丙烯酸酯皮革涂 饰剂
技术领域
本发明涉及抗菌防霉材料研究领域和皮革用涂饰材料开发领域,具体涉及一种含有天然抗菌吸附因子的水性聚氨酯-丙烯酸酯皮革涂饰剂。
背景技术
天然皮胶原独特的纤维编织结构和皮革产品天然手感的保持共同决定了其制造工艺尤其是涂饰过程的复杂性,单一品种的树脂往往很难满足其应用性能的需求。因而目前大多数皮革涂饰工艺都是将丙烯酸酯和聚氨酯这两大最为常用的树脂结合以实现优势互补,这促进了第三代水性PU——丙烯酸/聚氨酯(WPUA)的发展。
另一方面,天然皮革在适宜的温度和湿度条件下极易导致细菌及霉菌等微生物的生长和繁殖,因此皮革制品表面容易发生霉变并形成微生物污染。皮革制品不适合洗涤操作。因此开发具有抗菌性能的皮革涂饰剂是解决皮革制品表面微生物污染的最为有效的途径。目前,防止微生物污染最常用的方法是向涂层中引入具有杀菌功能的化合物或官能团。目前,常用的抗菌剂主要包括无机类、有机合成类和天然抗菌产物。目前关于抗菌聚氨酯涂料更多是是以添加无机抗菌剂为主,但添加无机抗菌剂会影响聚氨酯的力学性能。但大多数有机抗菌剂如三丁基锡(TBT)、酚类、双胍类、吡啶类、卤代胺类、季铵盐类和季鏻盐类等抗菌剂,在杀死微生物的同时,往往对细胞也会有毒害作用,对环境和人体健康都存在安全风险,且杀菌剂大多会诱导微生物产生耐药性。而皮革制品与人们日常生活密切相关,因此皮革的安全性也是越来越受到重视。因此需要寻找新的安全性高的抗菌因子和抗菌方法对皮革行业的可持续发展具有非常重要的意义。
近年来,新出现的抗菌吸附策略受到广泛关注,其原理从源头控制微生物在材料表面的吸附,即减少产品或材料表面与微生物分子之间的相互作用,从而有效防止了微生物在表面的进一步生长和繁殖。抗菌吸附涂层主要是通过改善涂层表面的结构以阻止微生物的吸附及进一步的繁殖,并无杀菌功效。过去20年,研究者对抗蛋白吸附材料的制备及其防污机理开展了广泛的研究,如目前研究较多的含PEG、两性离子基团的亲水性涂层;但是亲水性抗吸附单体的引入会使得涂层的疏水性降低,因而不适合应用于皮革涂层。目前有文献冰片类化合物因其结构中的三个手性碳原子的空间作用使其具有优异抗菌黏附性受到学术界的较多关注。其属于无毒的天然化合物,且其疏水性结构的存在,有利于提高皮革涂层的耐湿擦性,非常符合皮革行业对抗菌材料的要求。然而,目前关于如何将抗菌吸附性能的冰片类化合物通过化学键合引入丙烯酸酯-聚氨酯皮革涂饰剂的研究报道还未见文献和专利报道。
基于此,本发明公开了一种含有天然抗菌吸附因子的水性聚氨酯-丙烯酸酯皮革涂饰剂,将水性聚氨酯-丙烯酸酯优异的涂层性能与冰片类化合物的抗菌吸附性能相结合,开发新型的具有抗菌吸附性能的皮革涂饰剂。
发明内容
本发明目的在于提供一种含有天然抗菌吸附因子的水性聚氨酯-丙烯酸酯皮革涂饰剂,其特征在于先通过二异氰酸酯与多元醇以及双羟甲基丙烯酸反应得到聚氨酯,然后加入甲基丙烯酸-β-羟丙酯得到C=C封端的聚氨酯,进一步通过自由基聚合反应引入天然抗菌吸附因子、丙烯酸酯类共聚单体,最后加入中和剂中和后在水中高速乳化制得,其具体步骤如下:
1. 一种含有天然抗菌吸附因子的水性聚氨酯-丙烯酸酯皮革涂饰剂,其特征在于包括如下步骤:
1)将二异氰酸酯与聚合物二元醇按照摩尔比(3~5):1加入到反应器中,加入溶剂四氢呋喃,温度为50~80℃,搅拌反应0.5~1 h;然后升温至60~90℃,加入双羟甲基丙酸,反应1h, 双羟甲基丙酸与聚合物二元醇的摩尔比为(1~2):1
(2)接着向其中加入甲基丙烯酸-β-羟丙酯,温度为70~90℃,搅拌速度100~2000rpm,反应1~3 h,蒸发去除四氢呋喃,得到C=C封端的聚氨酯;
(3)然后天然抗菌吸附因子、丙烯酸酯类共聚单体包括甲基丙烯酸甲酯、甲基丙烯酸缩水甘油酯加入到反应器中,同时加入引发剂和乙酸乙酯,温度控制在75~100℃,搅拌速度为200~1000 rpm,搅拌反应2~4 h,得到含有天然抗菌吸附因子的丙烯酸酯-聚氨酯聚合物;
(4) 向上述聚合物在水中高速乳化分散10~30 min,乳化速度为4000~10000 rpm;得到含有天然抗菌吸附因子的水性聚氨酯-丙烯酸酯皮革涂饰乳液。
所述的一种含有天然抗菌吸附因子的水性聚氨酯-丙烯酸酯皮革涂饰剂,其特征在于所述的聚合物二元醇为分子量1000~8000的聚氧化丙烯二醇、聚四氢呋喃醚二醇、聚碳酸酯二醇中的一种或几种的混合物;所述的二异氰酸酯为异佛尔酮二异氰酸酯(IPDI)、二苯甲烷二异氰酸酯(MDI)、六亚甲基二异氰酸酯(HDI)的一种。
所述的甲基丙烯酸-β-羟丙酯与聚合物二元醇的摩尔比为(2~4):1;
所述的含有天然抗菌吸附因子的化合物为丙烯酸异冰片酯,其与甲基丙烯酸-β-羟丙酯的摩尔比为2:1。
所述的甲基丙烯酸甲酯、甲基丙烯酸缩水甘油酯与甲基丙烯酸-β-羟丙酯的摩尔比为0.5: 0.5 :1;引发剂为过氧化苯甲酰,用量为丙烯酸酯类共聚单体质量的1~2%。
具体实施方式
下面给出本发明的四个实施例,以具体说明一种含有天然抗菌吸附因子的水性聚氨酯-丙烯酸酯皮革涂饰剂的制备方法。
实施例 1
称取20.00 g聚碳酸酯二醇(M n=2000)于反应器中,向反应器中加入11.1g异佛尔酮二异氰酸酯(IPDI), 300ml四氢呋喃溶剂,在氮气保护下机械搅拌,70℃下反应 1h。加入12.68g二羟甲基丙酸,80℃搅拌反应1h。加入5.76 g甲基丙烯酸-β-羟丙酯80℃下反应 1h,蒸发去除四氢呋喃,得到C=C封端的聚氨酯;
将8.32g天然抗菌吸附因子、2g甲基丙烯酸甲酯、2.84g甲基丙烯酸缩水甘油酯加入到C=C封端的聚氨酯中,同时加入0.27g过氧化苯甲酰引发剂和200 ml乙酸乙酯,温度控制在75℃,搅拌速度为500 rpm,反应 4 h,得到含有天然抗菌吸附因子的丙烯酸酯-聚氨酯聚合物;加入中和剂,温度为40℃,搅拌速度为500 rpm,中和30 min。将反应物加入去离子水中,高速搅拌乳化0.5 h,搅拌速度为6000 rpm,得到含有天然抗菌吸附因子的水性聚氨酯-丙烯酸酯皮革涂饰乳液。
实施例 2
称取20.00 g聚四氢呋喃醚二醇(M n=2000)于反应器中,向反应器中加入12.5g二苯甲烷二异氰酸酯(MDI), 300ml四氢呋喃溶剂,在氮气保护下机械搅拌,60℃下反应 1h。加入12.68g二羟甲基丙酸,70℃搅拌反应1h。加入5.76 g甲基丙烯酸-β-羟丙酯70℃下反应 1h,蒸发去除四氢呋喃,得到C=C封端的聚氨酯;
将8.32 g天然抗菌吸附因子、2 g甲基丙烯酸甲酯、2.84 g甲基丙烯酸缩水甘油酯加入到C=C封端的聚氨酯中,同时加入引发剂和乙酸乙酯,温度控制在75℃,搅拌速度为500rpm,反应 4 h,得到含有天然抗菌吸附因子的丙烯酸酯-聚氨酯聚合物;加入中和剂,温度为40℃,搅拌速度为500 rpm,中和30 min。将反应物加入去离子水中,高速搅拌乳化0.5 h,搅拌速度为6000 rpm,得到含有天然抗菌吸附因子的水性聚氨酯-丙烯酸酯皮革涂饰乳液。
实施例 3
称取10.00 g聚氧化丙烯二醇(M n=1000)于反应器中,向反应器中加入12.5g二苯甲烷二异氰酸酯(MDI),300ml四氢呋喃溶剂,在氮气保护下机械搅拌,60℃下反应 1h。加入12.68g二羟甲基丙酸,70℃搅拌反应1h。加入5.76 g甲基丙烯酸-β-羟丙酯70℃下反应 1h,蒸发去除四氢呋喃,得到C=C封端的聚氨酯;
将8.32 g天然抗菌吸附因子、2 g甲基丙烯酸甲酯、2.84 g甲基丙烯酸缩水甘油酯加入到C=C封端的聚氨酯中,,同时加入0.27g过氧化苯甲酰引发剂和200 ml乙酸乙酯,温度控制在75℃,搅拌速度为500 rpm,反应 4 h,得到含有天然抗菌吸附因子的丙烯酸酯-聚氨酯聚合物;加入中和剂,温度为40℃,搅拌速度为500 rpm,中和30 min。将反应物加入去离子水中,高速搅拌乳化0.5 h,搅拌速度为6000 rpm,得到含有天然抗菌吸附因子的水性聚氨酯-丙烯酸酯皮革涂饰乳液。
实施例 4
称取10.00 g聚氧化丙烯二醇(M n=1000)于反应器中,向反应器中加入8.4g六亚甲基二异氰酸酯(HDI),300ml四氢呋喃溶剂,在氮气保护下机械搅拌,75℃下反应 1h。加入12.68g二羟甲基丙酸,85℃搅拌反应1h。加入5.76 g甲基丙烯酸-β-羟丙酯85℃下反应 1h,蒸发去除四氢呋喃,得到C=C封端的聚氨酯;
将8.32g天然抗菌吸附因子、2g甲基丙烯酸甲酯、2.84g甲基丙烯酸缩水甘油酯加入到C=C封端的聚氨酯中,,同时加入0.27g过氧化苯甲酰引发剂和200 ml乙酸乙酯,温度控制在75℃,搅拌速度为500 rpm,反应 4 h,得到含有天然抗菌吸附因子的丙烯酸酯-聚氨酯聚合物;加入中和剂,温度为40℃,搅拌速度为500 rpm,中和30 min。将反应物加入去离子水中,高速搅拌乳化0.5 h,搅拌速度为6000 rpm,得到含有天然抗菌吸附因子的水性聚氨酯-丙烯酸酯皮革涂饰乳液。

Claims (5)

1.一种含有天然抗菌吸附因子的水性聚氨酯-丙烯酸酯皮革涂饰剂,其特征在于包括如下步骤:
(1)将二异氰酸酯与聚合物二元醇按照摩尔比(3.0~5.0):1加入到反应器中,加入溶剂四氢呋喃,温度为50~80℃,搅拌反应0.5~1 h;然后升温至60~90℃,加入双羟甲基丙酸,反应1h, 双羟甲基丙酸与聚合物二元醇的摩尔比为(1~2):1
(2)向反应器中加入甲基丙烯酸-β-羟丙酯,温度为70~90℃,搅拌速度100~2000rpm,反应1~3 h,蒸发去除四氢呋喃,得到C=C封端的聚氨酯;
(3)将含有天然抗菌吸附因子的化合物、丙烯酸酯类共聚单体包括甲基丙烯酸甲酯、甲基丙烯酸缩水甘油酯加入到反应器中,同时加入引发剂和乙酸乙酯,温度控制在75~100℃,搅拌速度为200~1000 rpm,搅拌反应2~4 h,得到含有天然抗菌吸附因子的丙烯酸酯-聚氨酯聚合物;
(4) 向上述聚合物在水中高速乳化分散10~30 min,乳化速度为4000~10000 rpm;得到含有天然抗菌吸附因子的水性丙烯酸酯-聚氨酯皮革涂饰乳液。
2.根据权利要求1所述的一种含有天然抗菌吸附因子的水性丙烯酸酯-聚氨酯皮革涂饰剂,其特征在于所述的聚合物二元醇为分子量1000~8000的聚氧化丙烯二醇、聚四氢呋喃醚二醇、聚碳酸酯二醇中的一种或几种的混合物;所述的二异氰酸酯为异佛尔酮二异氰酸酯(IPDI)、二苯甲烷二异氰酸酯(MDI)、六亚甲基二异氰酸酯(HDI)的一种。
3.根据权利要求1所述的一种含有天然抗菌吸附因子的水性丙烯酸酯-聚氨酯皮革涂饰剂,其特征在于所述的甲基丙烯酸-β-羟丙酯与聚合物二元醇的摩尔比为(2~4):1。
4.根据权利要求1所述的一种含有天然抗菌吸附因子的水性聚氨酯-丙烯酸酯皮革涂饰剂,其特征在于所述的含有天然抗菌吸附因子的化合物为丙烯酸异冰片酯,其与甲基丙烯酸-β-羟丙酯的摩尔比为2:1。
5.根据权利要求1所述的一种含有天然抗菌吸附因子的水性丙烯酸酯-聚氨酯皮革涂饰剂,所述的甲基丙烯酸甲酯、甲基丙烯酸缩水甘油酯与甲基丙烯酸-β-羟丙酯的摩尔比为0.5: 0.5 :1;引发剂为过氧化苯甲酰,用量为丙烯酸酯类共聚单体质量的1~2%。
CN201810763360.5A 2018-07-12 2018-07-12 一种含有天然抗菌吸附因子的水性聚氨酯-丙烯酸酯皮革涂饰剂 Active CN109135489B (zh)

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CN115286947B (zh) * 2022-08-19 2023-04-25 华容县恒兴建材有限公司 一种高固体份、高耐水性抗菌水性聚氨酯涂料及其制备方法

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