CN112876636A - 一种水性抑菌抗病毒阴离子聚氨酯树脂及其制备方法 - Google Patents
一种水性抑菌抗病毒阴离子聚氨酯树脂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种水性抑菌抗病毒阴离子聚氨酯树脂及其制备方法,由以下原料及质量份组成:大分子多元醇30‑35份、多异氰酸酯5‑10份、亲水扩链剂2‑6份、氢氧化锌1‑2份、小分子醇类扩链剂0.5‑2份、胺类扩链剂1‑2份、催化剂0.01‑0.5份、有机溶剂5‑12份和去离子水45‑55份,所述亲水扩链剂为咖啡酸。咖啡酸作为亲水扩链剂使用,其易溶于有机溶剂,能更充分地与多异氰酸酯进行反应,提高聚合反应稳定性,咖啡酸具有较广泛的抑菌和抗病毒活性,能吸收紫外线,并且能够提高水性聚氨酯树脂的着色能力,Zn离子拥有长效的抗菌活性,Zn离子拥有长效的抗菌活性,将咖啡酸与氢氧化锌通过中和反应的方式获得带有Zn离子的咖啡酸锌溶液改性水性聚氨酯使得水性聚氨酯不需要添加抗菌助剂就可以获得优秀的抑菌抗病毒能力且表现出更好的储存稳定性。
Description
技术领域
本发明属于高分子材料领域,具体涉及一种水性抑菌抗病毒阴离子聚氨酯树脂及其制备方法。
背景技术
聚氨酯以其软硬度可调范围广、耐低温、柔韧性好、附着力强等优点被广泛应用于皮革涂饰、涂料、胶黏剂等领域。然而随着各国环境安全法律法规的出台,许多国家已限制了溶剂型聚氨酯的应用。
水性聚氨酯由于其连续相为水,安全易于保存和储存,且使用方便成本低,较完整的保留了溶剂型聚氨酯的特性,另外由于水性聚氨酯分子链中存在库仑力和氢键的作用,使其在某些性能上优于溶剂型聚氨酯,因此水性聚氨酯的研制与生产受到世界各国的重视,而且都取得了长足的发展。在水性聚氨酯的制备中,为了获得稳定的聚氨酯乳液,需在聚氨酯的预聚体分子中引入亲水基团,使其在水中乳化。根据其引入基团所带电性不同,将水性聚氨酯分为阳离子型、阴离子型、非离子型以及混合型水性聚氨酯。
阴离子型水性聚氨酯包括磺酸型和羧酸型,羧酸型水性聚氨酯的制备方法主要依靠二羟甲基丙酸(DMPA)和二羟甲基丁酸(DMBA)等亲水性扩链剂来制备,但是这两种亲水性扩链剂生产过程中均产生较重的污染,DMPA目前使用最广泛,但是由于其很难溶于丙酮中,所以在水性聚氨酯合成过程中较难反应;DMBA在丙酮中溶解度较大,合成过程中粘度也较小,但是生产污染严重,合成技术复杂,难度高,目前国内很少有规模生产的厂商。
目前很多阴离子型水性聚氨酯并不具有杀菌作用,所以亟待解决这个问题。
发明内容
本发明的主要目的在于提供一种水性抑菌抗病毒阴离子聚氨酯树脂及其制备方法,可以有效解决背景技术中提出的问题。
本发明的技术方案如下:
一种水性抑菌抗病毒阴离子聚氨酯树脂,由以下原料及质量份组成:大分子多元醇30-35份、多异氰酸酯5-10份、亲水扩链剂2-6份、氢氧化锌1-3 份、小分子醇类扩链剂0.5-2份、胺类扩链剂1-2份、催化剂0.01-0.5份、有机溶剂5-12份和去离子水45-55份,所述亲水扩链剂为咖啡酸。
进一步地,所述大分子多元醇包括聚四氢呋喃醚多元醇、聚碳酸酯多元醇、聚酯多元醇、聚己内酯多元醇、聚己二酸多元醇、聚环氧乙烷多元醇、聚环氧丙烷多元醇、聚硅氧烷多元醇中的任意一种或几种。
优选地,所述大分子多元醇分子量在1000-3000之间。
优选地,所述小分子醇类扩链剂包括乙二醇、2-甲基-1,3-丙二醇、一缩二乙二醇、1,4-丁二醇、2,3-丁二醇、1,6-己二醇、新戊二醇、二甘醇、甘油、三羟甲基丙烷、山梨醇、三羟甲基环己烷中的一种或几种。
进一步地,所述二异氰酸酯是脂肪族二异氰酸酯、芳香族二异氰酸酯或它们的混合物。
优选地,所述脂肪族二异氰酸酯选自六亚甲基二异氰酸酯、环己基二异氰酸酯、4,4’-二环己基甲烷二异氰酸酯和异佛尔酮二异氰酸酯中的一种或几种;所述芳香族二异氰酸酯选自甲苯-2,4-二异氰酸酯、4,6-二甲苯二异氰酸酯、4,4’- 二苯基甲烷二异氰酸酯、1,5-萘二异氰酸酯、乙苯二异氰酸酯、3,3’-二甲基联苯 -4,4’-二异氰酸酯和3,3’-二甲基-4,4’-二苯基甲烷二异氰酸酯中的一种或几种。
进一步地,所述胺类扩链剂包括乙二胺、1,6-己二胺、异佛尔酮二胺和聚醚胺的一种或多种;所述的催化剂为有机铋;所述有机溶剂为丙酮。
一种水性抑菌抗病毒阴离子聚氨酯树脂的制备方法,按照以下步骤制备
S1:将亲水扩链剂咖啡酸和过量的氢氧化锌加入盛有50-60℃水的烧杯中混合,搅拌均匀获得咖啡酸锌溶液。
S2:将大分子多元醇、咖啡酸锌溶液、多异氰酸酯在80~95℃下反应2~4h;再加入小分子扩链剂在70~80℃下反应1~3h;然后加入催化剂、丙酮在75~ 85℃下反应2~4h;然后降温至30℃,加入丙酮,搅拌10-60min,获得预聚体;
S3:对预聚体进行乳化,其乳化过程为:转速调至1200r/min,将去离子水加入预聚体中,分散开后继续搅拌5-10min,然后将转速调整至1800r/min,加入后扩链剂,继续搅1-2h,获得预聚体乳液;
S4、对预聚体乳液进行脱溶,其脱溶过程为:将预聚体乳液升温至55℃, -0.08MPa条件下脱去乳液中的丙酮,便可得到水性抑菌抗病毒阴离子聚氨酯树脂。
一种抗菌型阳离子水性聚氨酯树脂在合成革领域的应用。
以上涉及到的化学反应式如下:
有益效果:
本发明提供一种抗菌型阴离子水性聚氨酯树脂及其制备方法,该水性聚氨酯包括以下原料组分:大分子多元醇,多异氰酸酯,亲水扩链剂,氢氧化锌,小分子醇类扩链剂,胺类扩链剂,催化剂,去离子水。其中,所述亲水扩链剂为咖啡酸。咖啡酸具有双羟基结构,并且带有一个羧基,与传统亲水扩链剂DMPA 与DMBA相仿,完全能够代替传统亲水扩链剂。本发明将咖啡酸与Zn离子通过离子键结合,并通过化学键合引入到阳离子水性聚氨酯分子链上,并且未与咖啡酸反应的氢氧化锌可以与异氰酸根反应形成脲基,从而避免功能添加剂对水性聚氨酯力学性能的影响,又可以实现良好的抗菌效果,同时增加了水性聚氨酯的机械强度。咖啡酸能够从菊科植物一枝黄花提取,来源安全环保无污染,并且已经广泛运用于医药、化妆品等方面,具有天然的抗菌抗病毒能力。但是,天然抗菌基团存在局限性,拥有抑菌持久力不足,容易降解失效等缺点。因此本发明在咖啡酸的羧基上以离子键键合的Zn离子,作为重金属离子,有着持久的抑菌抗病毒作用。经改性的咖啡酸通过羟基与异氰酸酯反应,双羟基结构能够让咖啡酸极易聚合在水性聚氨酯分子链上。本发明采用带有Zn离子的咖啡酸锌和一部分氢氧化锌与异氰酸根反应使得水性阳离子型聚氨酯树脂不需要添加杀菌助剂即可达到长效的抑菌抗病毒效果和优异的机械强度。
具体实施方式
为使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解,下面结合具体实施方式,进一步阐述本发明。
反应原料:
聚碳酸酯多元醇:陶氏,上海和铄化工有限公司
聚四氢呋喃醚多元醇:陶氏,上海和铄化工有限公司
聚己内酯多元醇:陶氏,上海和铄化工有限公司
异佛尔酮二异氰酸酯:陶氏,上海和铄化工有限公司
六亚甲基二异氰酸酯:陶氏,上海和铄化工有限公司
甲苯二异氰酸酯:陶氏,上海和铄化工有限公司
1,4-丁二醇:上海顺雅化工进出口有限公司
乙二醇:苏州康硕化工有限公司
1,6-己二醇:山东开普勒生物科技有限公司
二羟甲基丁酸:山东开普勒生物科技有限公司
咖啡酸:阿拉丁试剂(上海)有限公司
氢氧化锌:阿拉丁试剂(上海)有限公司
丙酮:阿拉丁试剂(上海)有限公司
乙二胺:阿拉丁试剂(上海)有限公司
有机铋:上海惠今化工贸易有限公司
实施例1
一种水性抑菌抗病毒阴离子聚氨酯树脂制备方法
S1.将3g咖啡酸和1.5g氢氧化锌加入盛有10g50-60℃水的烧杯中混合,搅拌均匀获得ph=9的14.5g咖啡酸锌溶液。
S2.将聚碳酸酯多元醇300g投入装有温度计、搅拌器、回流冷凝管的1000mL四口烧瓶中,升温至110℃,于>-0.09MPa的真空度下脱水1h,降温至60℃,加入14.5g咖啡酸锌溶液,搅拌均匀后投入异佛尔酮二异氰酸酯70g,于90℃反应2h。降温至70℃,投入小分子扩链剂乙二醇5g,于70℃继续反应1小时。降温至<50℃,加入催化剂有机铋0.5g和丙酮40ml,搅拌升温至75℃反应4h。然后降温至20℃,加入丙酮80ml,搅拌30min,获得预聚体;
S3.对预聚体进行乳化,其乳化过程为:将去离子水500g加入分散缸中,打开搅拌,把转速调整到1200r/min,将预聚体加入至分散缸中,分散开后继续搅拌5-10 min,然后将转速调整至1800r/min,加入后扩链剂乙二胺10g水溶液,继续搅拌1-2h,获得预聚体乳液;
S4.对预聚体乳液进行脱溶,其脱溶过程为:将预聚体乳液升温至55℃,-0.08MPa条件下脱去乳液中的丙酮,便可得到水性抑菌抗病毒阴离子聚氨酯树脂。
实施例2
一种水性抑菌抗病毒阴离子聚氨酯树脂制备方法
S1.将4g咖啡酸和1.75g氢氧化锌加入盛有10g50-60℃水的烧杯中混合,搅拌均匀获得ph=8.7的15.75g咖啡酸锌溶液。
S2.将聚四氢呋喃醚多元醇310g投入装有温度计、搅拌器、回流冷凝管的1000mL四口烧瓶中,升温至110℃,于>-0.09MPa的真空度下脱水1h,降温至60℃,加入15.75g的咖啡酸锌溶液,搅拌均匀后投入异佛尔酮二异氰酸酯72g,于90℃反应2h。降温至70℃,投入小分子扩链剂乙二醇6g,于70℃继续反应1小时。降温至<50℃,加入催化剂有机铋0.7g和丙酮40ml,搅拌升温至75℃反应4h。然后降温至20℃,加入丙酮80ml,搅拌30min,获得预聚体;
S3.对预聚体进行乳化,其乳化过程为:将去离子水550g加入分散缸中,打开搅拌,把转速调整到1200r/min,将预聚体加入至分散缸中,分散开后继续搅拌5-10 min,然后将转速调整至1800r/min,加入后扩链剂乙二胺11g水溶液,继续搅拌1-2h,获得预聚体乳液;
S4.对预聚体乳液进行脱溶,其脱溶过程为:将预聚体乳液升温至55℃,-0.08MPa条件下脱去乳液中的丙酮,便可得到水性抑菌抗病毒阴离子聚氨酯树脂。
实施例3
一种水性抑菌抗病毒阴离子聚氨酯树脂制备方法
S1.将4.5g咖啡酸和1.9g氢氧化锌加入盛有10g50-60℃水的烧杯中混合,搅拌均匀获得ph=8.8的16.4g咖啡酸锌溶液。
S2.将聚四氢呋喃醚多元醇315g投入装有温度计、搅拌器、回流冷凝管的1000mL四口烧瓶中,升温至110℃,于>-0.09MPa的真空度下脱水1h,降温至60℃,加入16.4g的咖啡酸锌溶液,搅拌均匀后投入六亚甲基二异氰酸酯56g,于90℃反应2h。降温至70℃,投入小分子扩链剂1,4-丁二醇7.8g,于70℃继续反应1 小时。降温至<50℃,加入催化剂有机铋0.8g和丙酮40ml,搅拌升温至75℃反应4h。然后降温至20℃,加入丙酮80ml,搅拌30min,获得预聚体;
S3.对预聚体进行乳化,其乳化过程为:将去离子水540g加入分散缸中,打开搅拌,把转速调整到1200r/min,将预聚体加入至分散缸中,分散开后继续搅拌5-10 min,然后将转速调整至1800r/min,加入后扩链剂乙二胺10.3g水溶液,继续搅拌1-2h,获得预聚体乳液;
S4.对预聚体乳液进行脱溶,其脱溶过程为:将预聚体乳液升温至55℃,-0.08MPa条件下脱去乳液中的丙酮,便可得到水性抑菌抗病毒阴离子聚氨酯树脂。
对比例1
S1.将聚碳酸酯多元醇300g投入装有温度计、搅拌器、回流冷凝管的1000mL四口烧瓶中,升温至110℃,于>-0.09MPa的真空度下脱水1h,降温至60℃,加入经烘干处理的阴离子扩链剂DMBA5g,搅拌均匀后投入异佛尔酮二异氰酸酯70g,于90℃反应2h。降温至70℃,投入小分子扩链剂乙二醇5g,于70℃继续反应1小时。降温至<50℃,加入催化剂有机铋0.5g和丙酮40ml,搅拌升温至75℃反应4h。然后降温至20℃,加入中和剂三乙胺7g和丙酮80ml,搅拌30min,获得预聚体;
S2.对预聚体进行乳化,其乳化过程为:将去离子水500g加入分散缸中,打开搅拌,把转速调整到1200r/min,将预聚体加入至分散缸中,分散开后继续搅拌5-10 min,然后将转速调整至1800r/min,加入后扩链剂乙二胺10g水溶液,继续搅拌1-2h,获得预聚体乳液;
S3.对预聚体乳液进行脱溶,其脱溶过程为:将预聚体乳液升温至55℃,-0.08MPa条件下脱去乳液中的丙酮,便可得到水性阴离子聚氨酯树脂。
对比例2
在对比例1的树脂内添加普通市售的抑菌抗病毒功能填料。
对比例3
S1.将聚己内酯多元醇323g投入装有温度计、搅拌器、回流冷凝管的1000mL四口烧瓶中,升温至110℃,于>-0.09MPa的真空度下脱水1h,降温至60℃,加入经烘干处理的阴离子扩链剂绿原酸5g,搅拌均匀后投入异佛尔酮二异氰酸酯30g和六亚甲基二异氰酸酯23g,于90℃反应2h。降温至70℃,投入小分子扩链剂1,6-己二醇8.2g,于70℃继续反应1小时。降温至<50℃,加入催化剂有机铋1.0g和丙酮40ml,搅拌升温至75℃反应4h。然后降温至20℃,加入中和剂三乙胺10.2g和丙酮70ml,搅拌30min,获得预聚体;
S2.对预聚体进行乳化,其乳化过程为:将去离子水538g加入分散缸中,打开搅拌,把转速调整到1200r/min,将预聚体加入至分散缸中,分散开后继续搅拌5-10 min,然后将转速调整至1800r/min,加入后扩链剂乙二胺12.2g水溶液,继续搅拌1-2h,获得预聚体乳液;
S3.对预聚体乳液进行脱溶,其脱溶过程为:将预聚体乳液升温至55℃,-0.08MPa条件下脱去乳液中的丙酮,便可得到水性抑菌抗病毒阴离子聚氨酯树脂。
对比例4
S1.将聚己内酯多元醇320g投入装有温度计、搅拌器、回流冷凝管的1000mL四口烧瓶中,升温至110℃,于>-0.09MPa的真空度下脱水1h,降温至60℃,加入经烘干处理的阴离子扩链剂咖啡酸5g,搅拌均匀后投入异佛尔酮二异氰酸酯25g和六亚甲基二异氰酸酯25g,于90℃反应2h。降温至70℃,投入小分子扩链剂1,6-己二醇7.5g,于70℃继续反应1小时。降温至<50℃,加入催化剂有机铋1.0g和丙酮40ml,搅拌升温至75℃反应4h。然后降温至20℃,加入中和剂三乙胺9.1g和丙酮70ml,搅拌30min,获得预聚体;
S2.对预聚体进行乳化,其乳化过程为:将去离子水538g加入分散缸中,打开搅拌,把转速调整到1200r/min,将预聚体加入至分散缸中,分散开后继续搅拌5-10 min,然后将转速调整至1800r/min,加入后扩链剂乙二胺12.2g水溶液,继续搅拌1-2h,获得预聚体乳液;
S3.对预聚体乳液进行脱溶,其脱溶过程为:将预聚体乳液升温至55℃,-0.08MPa条件下脱去乳液中的丙酮,便可得到水性抑菌抗病毒阴离子聚氨酯树脂。
质量鉴定
对实施例1-3以及对比例1-3制得水性聚氨酯进行性能测试
抑菌性测试:按照GB/T 21866-2008规定进行测试。
合成革物性测试:采用0.80mm作为标准厚度,按照QB/T 4197-2011规定进行测试。
抑菌性测试:按照GB/T 21866-2008规定进行测试。
合成革物性测试:采用0.80mm作为标准厚度,按照QB/T 5143-2017规定进行测试。
表1抗菌性能测试结果
表2拉伸性能、抗撕裂性以及耐折性测试结果
表3对制得的抗菌性阴离子水性聚氨酯树脂性能进行监测
从表1可以看出,本发明各实例的带有Zn离子的咖啡酸锌和氢氧化锌改性的水性抑菌抗病毒阴离子型水性聚氨酯树脂具有优秀的抑菌抗病毒能力,抑菌活性与杀灭率均强于添加抑菌功能助剂的普通树脂和利用绿原酸或咖啡酸改性的水性聚氨酯,并且抑菌速率明显强于对比例的树脂。。
从表2可以看出,本发明各实例相比于普通树脂作为合成革用湿法树脂,所制成的产品在物性上略有提升,具有优秀的耐折牢度、剥离强度、撕裂强度、拉伸强度等物性。完全符合水性湿法合成革的物性要求。
从表3可以看出,本发明使用咖啡酸锌作为抗菌性水性聚氨酯扩链剂对比已有发明专利中将绿原酸作为抗菌性扩链剂有多项优点。绿原酸拥有五个羟基基团,且羟基基团不对称,以绿原酸作为扩链剂,易导致水性聚氨酯分子量不可控,分子粒径分布不均匀,极大地影响了水性聚氨酯乳液的成膜性和储存稳定性。
以上显示和描述了本发明的基本原理和主要特征和本发明的优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明精神和范围的前提下,本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (9)
1.一种水性抑菌抗病毒阴离子聚氨酯树脂,其特征在于:由以下原料及质量份组成:大分子多元醇30-35份、多异氰酸酯5-10 份、亲水扩链剂2-6份、氢氧化锌1-3份、小分子醇类扩链剂0.5-2 份、胺类扩链剂1-2 份、催化剂0.01-0. 5 份、有机溶剂5-12份和去离子水45-55 份,所述亲水扩链剂为咖啡酸。
2.根据权利要求1所述的一种水性抑菌抗病毒阴离子聚氨酯树脂,其特征在于:所述大分子多元醇包括聚四氢呋喃醚多元醇、聚碳酸酯多元醇、聚酯多元醇、聚己内酯多元醇、聚己二酸多元醇、聚环氧乙烷多元醇、聚环氧丙烷多元醇、聚硅氧烷多元醇中的任意一种或几种。
3.根据权利要求2所述的一种水性抑菌抗病毒阴离子聚氨酯树脂,其特征在于:所述大分子多元醇分子量在1000-3000之间。
4.根据权利要求1所述的一种水性抑菌抗病毒阴离子聚氨酯树脂,其特征在于:所述小分子醇类扩链剂包括乙二醇、2-甲基-1,3-丙二醇、一缩二乙二醇、1,4-丁二醇、2,3-丁二醇、1,6-己二醇、新戊二醇、二甘醇、甘油、三羟甲基丙烷、山梨醇、三羟甲基环己烷中的一种或几种。
5.根据权利要求1所述的一种水性抑菌抗病毒阴离子聚氨酯树脂,其特征在于:所述二异氰酸酯是脂肪族二异氰酸酯、芳香族二异氰酸酯或它们的混合物。
6.根据权利要求5所述的一种水性抑菌抗病毒阴离子聚氨酯树脂,其特征在于:所述脂肪族二异氰酸酯选自六亚甲基二异氰酸酯、环己基二异氰酸酯、4,4’-二环己基甲烷二异氰酸酯和异佛尔酮二异氰酸酯中的一种或几种;所述芳香族二异氰酸酯选自甲苯-2,4-二异氰酸酯、4,6-二甲苯二异氰酸酯、4,4’-二苯基甲烷二异氰酸酯、1,5-萘二异氰酸酯、乙苯二异氰酸酯、3,3’ -二甲基联苯-4,4’-二异氰酸酯和3,3’-二甲基-4,4’-二苯基甲烷二异氰酸酯中的一种或几种。
7.根据权利要求1所述的一种水性抑菌抗病毒阴离子聚氨酯树脂及其制备方法,其特征在于:所述胺类扩链剂包括乙二胺、1,6-己二胺、异佛尔酮二胺和聚醚胺的一种或多种;所述的催化剂为有机铋;所述有机溶剂为丙酮。
8.一种如权利要求1-7任一项所述的水性抑菌抗病毒阴离子聚氨酯树脂的制备方法,其特征在于:按照以下步骤制备
S1:将亲水扩链剂咖啡酸和过量的氢氧化锌加入盛有50-60°C水的烧杯中混合,搅拌均匀获得咖啡酸锌溶液;
S2:将大分子多元醇、咖啡酸锌溶液、多异氰酸酯在80~95℃下反应2~4h;再加入小分子扩链剂在70~80℃下反应1~3h;然后加入催化剂、丙酮在75~85℃下反应2~4h;然后降温至30 ℃,加入丙酮,搅拌 10-60min,获得预聚体;
S3:对预聚体进行乳化,其乳化过程为:转速调至1200r/min,将去离子水加入预聚体中,分散开后继续搅拌5-10 min,然后将转速调整至1800r/min,加入后扩链剂,继续搅1-2h,获得预聚体乳液;
S4、对预聚体乳液进行脱溶,其脱溶过程为:将预聚体乳液升温至55℃,-0.08MPa条件下脱去乳液中的丙酮,便可得到水性抑菌抗病毒阴离子聚氨酯树脂。
9.一种如权利要求8所述水性抑菌抗病毒阴离子聚氨酯树脂在合成革领域的应用。
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