CN116199928A - 一种表面改性抗菌聚氨酯材料、制备方法及应用 - Google Patents
一种表面改性抗菌聚氨酯材料、制备方法及应用 Download PDFInfo
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- CN116199928A CN116199928A CN202310037697.9A CN202310037697A CN116199928A CN 116199928 A CN116199928 A CN 116199928A CN 202310037697 A CN202310037697 A CN 202310037697A CN 116199928 A CN116199928 A CN 116199928A
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
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- C07F9/54—Quaternary phosphonium compounds
- C07F9/5407—Acyclic saturated phosphonium compounds
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/34—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-halogen bonds; Phosphonium salts
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- A—HUMAN NECESSITIES
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Abstract
本发明公开了一种表面改性抗菌聚氨酯材料、制备方法及应用,属于抗菌材料的制备技术领域。首先制备抗菌改性单体,再制备表面富羟基化聚氨酯薄膜,通过硅醇与羟基之间的偶联反应将抗菌改性单体接枝至富羟基化聚氨酯薄膜表面,即得表面改性抗菌聚氨酯材料。所述抗菌改性单体由硅烷偶联剂和季鏻盐不饱和化合物通过烯硫点击反应制备得到。其中硅烷偶联剂和季鏻盐不饱和化合物摩尔计量比为1~3。本发明的聚氨酯材料安全环保,抗菌性能高效持久,同时所述表面改性抗菌聚氨酯材料可于环保材料、建筑材料、医疗器械材料等领域都会有很大的应用前景。
Description
技术领域
本发明涉及一种表面改性抗菌聚氨酯材料、制备方法及应用,属于抗菌材料的制备技术领域。
背景技术
微生物的大量存在以及对材料表面的黏附限制了医疗植入、食品包装和水净化系统等领域的发展,也威胁着人们自身的健康。另一方面,频繁使用抗生素治疗细菌传染病,已使得多重药物耐受性菌株大量产生,耐药机制复杂多变,难以从根本上解决这一问题,这极大地增加了病人的痛苦和治疗费用。随着科学技术的不断进步和人们的生活水平日益提高,人们的自我健康意识正在不断加强,抗菌材料的应用也逐渐引起人们的重视。在日常生活中人们首先接触到都是形形色色的各种材料,比如日用品、食品包装、卫生用品、家用电器、公用设施等,乘坐公交车时所碰到的扶手,乘坐电梯时碰到的按钮,都成为了细菌繁殖、传播的场所。为了防止细菌传播,减少交叉感染,应倡导在社会公共场所推行使用抗菌产品,即指那些具有抑菌和杀菌性能的功能材料,以提高人们健康水平,造福人类。
细菌的繁殖严重影响人类的健康,无机金属如Ag+虽然具有抗菌性,但将其分散在材料中会发生迁移,使得材料的抗菌效果不持久,并且会造成环境污染。抗菌剂分为无机和有机抗菌剂[CN 107163280 B]。无机抗菌剂有Ag+、Cu2+、Zn2+,将其分散在材料中可制备抗菌材料。但是时间过长就会引起抗菌剂迁移,不仅会造成环境污染,而且抗菌效果不能持久。将其添加入塑料制品中,时间过长制品颜色会发生变化,影响使用。有机抗菌剂有酸、酯、醇、酚、季铵盐等小分子,这类小分子添加入材料中也会发生迁移,并且毒性大,在很大程度上限制了其使用。
抗菌材料在日常生活中应用广泛,尤其是薄膜材料中的应用。目前一般通过给材料涂覆涂层的方法来赋予特定功能。利用静电吸附、疏水作用力等物理作用直接将功能性物质固定在材料表面。Mohan等人(Bracic M,Fras-Zemljic L,Perez L,et al.Protein-Repellent and antimicrobial nanoparticle coatings from hyaluronic acid and aLysine-derived biocompatible surfactant[J].Journal of Materials Chemistry B,2017,5:3888-3897.)报道一种改性聚硅氧烷材料的方法,通过静电吸附上一层阳离子聚合物聚乙烯亚胺,最后涂覆上不同的功能性多糖,对金黄色葡萄球菌具有抗菌效果,但存在抗菌效果不持久等问题。较于物理方法,由于底物和改性材料之间存在化学键,化学改性方法能更持久稳定地发挥其抗菌功能。现有技术中主要是将高分子季铵盐化学键接到材料中,不迁移,抗菌效果持久,属于接触型抗菌,然而季铵盐单体带有正电荷,相互排斥,不易通过直接均聚得到高分子量的聚合物[CN 103232587 A]。同时季铵盐抗菌剂的研究早已相当成熟,应用也是相当广泛,然而它的过度使用已造成很多微生物对其产生了耐药性。季鏻盐抗菌剂是继季铵盐抗菌剂之后的又一类抗菌剂。从它们的结构来看,氮原子被磷原子所替代,这一差别造成同类型季鏻盐的抗菌活性比季铵盐的抗菌活性要好。因此本专利提出一种制备方法简单且同时具备抗菌性能材料制备方法。
发明内容
本发明的目的是克服上述不足之处,提供一种表面改性抗菌聚氨酯材料、制备方法及应用,本发明引入带烷基链季鏻盐改性单体,共价改性材料表面,有效提高材料的抗菌性能,达到接触抗菌的目的。
本发明的技术方案:
一种表面改性抗菌聚氨酯材料的制备方法,所述表面改性抗菌聚氨酯材料是通过抗菌改性单体与表面富羟基化聚氨酯薄膜之间硅醇与羟基发生的偶联反应,将抗菌改性单体接枝至富羟基化聚氨酯薄膜表面,即得表面改性抗菌聚氨酯材料;
所述抗菌改性单体结构通式为:
其中R1为烷基(-CmH2m+1)、环己烷基、苯基中的一种;R2为-OCH3或-OCH2CH3;X为Br、Cl、I卤素原子;
所述的表面富羟基化聚氨酯薄膜由以下方法制备得到:将聚氨酯薄膜洗涤并干燥后,置于氧等子离子机进行处理,浸泡、干燥后得表面富羟基化聚氨酯薄膜。
进一步地,抗菌改性单体与表面富羟基化聚氨酯薄膜组成比例为:
抗菌改性单体 0.1-10重量份;
表面富羟基化聚氨酯薄膜 100重量份。
进一步地,所述抗菌改性单体的制备方法:将硅烷偶联剂和季鏻盐不饱和单体以摩尔计量比进行混合加入溶剂中,加入催化剂,UV紫外光下通过烯硫点击反应,经旋蒸洗涤干燥后得到抗菌改性单体。
进一步地,所述抗菌改性单体制备中,硅烷偶联剂和季鏻盐不饱和化合物摩尔计量比为1~3:1。
进一步地,所述抗菌改性单体制备中:所述硅烷偶联剂为巯丙基三甲氧基硅烷或巯丙基三乙氧基硅烷;所述季鏻盐不饱和单体为烯丙基三乙基溴化鏻、烯丙基三丁基碘化鏻、烯丙基三环己基溴化鏻或烯丙基三苯基溴化鏻中的一种或两种以上混合;所述催化剂为2,2-二甲氧基-2-苯基苯乙酮、1-羟基环己基苯基甲酮或苯甲酰甲酸甲酯中的一种;所述溶剂为二氯甲烷或三氯甲烷;所用洗涤液为无水乙醚;
所述表面富羟基化聚氨酯薄膜过程中:所述聚氨酯薄膜为高透明的TPU薄膜;洗涤聚氨酯薄膜的洗涤液为甲醇、乙醇或水中的一种或两种以上混合使用;浸泡液为水。
抗菌改性单体与表面富羟基化聚氨酯薄膜之间硅醇与羟基发生的偶联反应过程中:将抗菌改性单体与表面富羟基化聚氨酯薄膜置于盛有接枝溶液的反应容器中,高温反应,洗涤、干燥得到表面改性抗菌聚氨酯材料;所述接枝溶液为无水乙醇、水或甲苯中的一种或两种以上混合;所用洗涤液为无水乙醇、水或甲苯中的一种或两种以上先后使用。
进一步地,加入催化剂质量为硅烷偶联剂和季鏻盐不饱和单体总质量的1‰~5‰,在功率200W波长365nm的UV紫外光灯下反应4-10h。
进一步地,聚氨酯薄膜在超声环境下洗涤(20~80mL洗涤液2)数次后,氧等离子体机处理条件为:40~80W下处理2~10min,取出聚氨酯薄膜浸入水中处理2~10min。
进一步地,先将抗菌改性单体溶于接枝溶剂,混合0.5h-4h;再将表面富羟基化聚氨酯薄膜置于接枝溶液中,40~80℃下反应6~24h。
本发明还旨在提供上述方法制得的表面改性抗菌聚氨酯材料的应用,所述表面改性抗菌聚氨酯材料可应用于环保材料、建筑材料、医疗器械材料。
为了测定材料的抗菌性能,将聚氨酯材料置于紫外灯下预先灭菌,再对薄膜进行抗菌率检测。根据本发明提供的制备方法所获得的季鏻盐抗菌聚氨酯具有抗菌率高、抗菌时效性长、抗菌物质不迁移等特点。
本发明的有益效果:
1、本发明使用硅烷偶联剂和季鏻盐不饱和化合物通过烯硫点击反应制备得到抗菌改性单体,并通过一步法接入聚氨酯薄膜,以简单的工艺得到表面带有亲水性的季鏻正离子,同时引入了长碳链的薄膜材料,赋予其抗细菌粘附性能及提高抗菌性能。
2、本发明制备以共价键合的方式引入季鏻盐长烷基链的抗菌聚氨酯材料,磷原子比氮原子的半径大,对应的离子半径也大,极化作用强,更容易失去电子,使季鏻盐正电性增加,导致季鏻盐更容易与带负电荷的菌体发生静电吸附而杀死细菌,最终使得材料具有优异的抗菌性能。
3、本发明所制备的抗菌聚氨酯材料,步骤简单,具有高抗菌率并且不会发生迁移,使用安全,可应用在食品包装等各个领域。
附图说明
图1为QPS4(抗菌改性单体)的红外谱图。
图2为QPS4(抗菌改性单体)的核磁共振氢谱。
图3为TPU-QPS4(实施例4)与TPU-QPS5(对比例1)的抗菌测试结果。
具体实施方式
下面结合实施例,进一步说明本发明。
实施例1
将0.02mol巯丙基三甲氧基硅烷,0.01mol烯丙基三乙基溴化鏻在20mL二氯甲烷中进行混合,加入催化剂2,2-二甲氧基-2-苯基苯乙酮质量比为1‰(占巯丙基三甲氧基硅烷加烯丙基三乙基溴化鏻总量的质量比),在200W的UV紫外光灯(365nm)下反应6h,经旋蒸除去溶剂,通过无水乙醚洗涤除去未反应物,干燥得到抗菌改性单体(QPS1)。
将TPU聚氨酯薄膜(鸿达塑胶,0.2mm)在超声环境下洗涤(20mL甲醇)3次,干燥后放置于氧等离子体机中,40W下处理4min,取出聚氨酯薄膜浸入5mL水中处理4min,惰性气体吹拂下干燥得到表面富羟基化聚氨酯薄膜(TPU1)。
将0.9g QPS1溶于5mL接枝溶液无水乙醇,混合0.5h;将20g TPU1置于接枝溶液中,50℃下反应6h,20mL无水乙醇洗涤3次,干燥得到表面改性抗菌聚氨酯材料TPU-QPS1。并根据相关标准进行抗菌测试,抗菌率结果列入表1中。
实施例2
将0.03mol巯丙基三乙氧基硅烷,0.02mol烯丙基三丁基碘化鏻在40mL二氯甲烷中进行混合,加入催化剂苯甲酰甲酸甲酯质量比为3‰(占巯丙基三甲氧基硅烷加烯丙基三乙基溴化鏻总量的质量比),在200W的UV紫外光灯(365nm)下反应7h,经旋蒸除去溶剂,通过无水乙醚洗涤除去未反应物,干燥得到抗菌改性单体(QPS2)。
将TPU聚氨酯薄膜(鸿达塑胶,0.2mm)在超声环境下洗涤(40mL乙醇)3次,干燥后放置于氧等离子体机中,50W下处理4min,取出聚氨酯薄膜浸入5mL水中处理4min,惰性气体吹拂下干燥得到表面富羟基化聚氨酯薄膜(TPU2)。
将1.2g QPS2溶于10mL接枝溶液水,混合0.6h;25g TPU2置于接枝溶液中,60℃下反应7h,20mL无水乙醇洗涤3次,干燥得到表面改性抗菌聚氨酯材料TPU-QPS2。并根据相关标准进行抗菌测试,抗菌率结果列入表1中。
实施例3
将0.025mol巯丙基三乙氧基硅烷,0.02mol烯丙基三环己基溴化鏻在40mL二氯甲烷中进行混合,加入催化剂1-羟基环己基苯基甲酮质量比为3‰(占巯丙基三甲氧基硅烷加烯丙基三乙基溴化鏻总量的质量比),在200W的UV紫外光灯(365nm)下反应8h,经旋蒸除去溶剂,通过无水乙醚洗涤除去未反应物,干燥得到抗菌改性单体(QPS3)。
将TPU聚氨酯薄膜(鸿达塑胶,0.2mm)在超声环境下洗涤(40mL水)3次,干燥后放置于氧等离子体机中,60W下处理5min,取出聚氨酯薄膜浸入10mL水中处理4min,惰性气体吹拂下干燥得到表面富羟基化聚氨酯薄膜(TPU3)。
将1.4g QPS3溶于10mL接枝溶液无水乙醇,混合0.5h;将23g TPU3置于接枝溶液中,70℃下反应7h,20mL无水乙醇与20mL水分别洗涤3次,干燥得到表面改性抗菌聚氨酯材料TPU-QPS4。并根据相关标准进行抗菌测试,抗菌率结果列入表1中。
实施例4
将0.04mol巯丙基三甲氧基硅烷,0.02mol烯丙基三苯基溴化鏻在40mL二氯甲烷中进行混合,加入催化剂2,2-二甲氧基-2-苯基苯乙酮质量比为4‰(占巯丙基三甲氧基硅烷加烯丙基三乙基溴化鏻总量的质量比),在200W的UV紫外光灯(365nm)下反应7h,经旋蒸除去溶剂,通过无水乙醚洗涤除去未反应物,干燥得到抗菌改性单体(QPS4)。
将TPU聚氨酯薄膜(鸿达塑胶,0.2mm)在超声环境下洗涤(20mL乙醇20mL水)3次,干燥后放置于氧等离子体机中,50W下处理5min,取出聚氨酯薄膜浸入10mL水中处理5min,惰性气体吹拂下干燥得到表面富羟基化聚氨酯薄膜(TPU4)。
将1.4g QPS4溶于20mL接枝溶液无水乙醇,混合0.5h;将30g TPU4置于接枝溶液中,65℃下反应7h,20mL无水乙醇与20mL水分别洗涤3次,干燥得到表面改性抗菌聚氨酯材料TPU-QPS4。并根据相关标准进行抗菌测试,抗菌率结果列入表1中。
对比例1
将TPU聚氨酯薄膜(鸿达塑胶,0.2mm)在超声环境下洗涤(20mL乙醇20mL水)3次,干燥后放置于氧等离子体机中,40W下处理6min,取出聚氨酯薄膜浸入10mL水中处理6min,惰性气体吹拂下干燥得到表面富羟基化聚氨酯薄膜(TPU5)。
将0.8g巯丙基三甲氧基硅烷溶于20mL接枝溶液无水乙醇,混合0.5h;将30g TPU5置于接枝溶液中,65℃下反应7h,20mL无水乙醇与20mL水分别洗涤3次,干燥得到表面改性抗菌聚氨酯材料TPU-QPS5。并根据相关标准进行抗菌测试,抗菌率结果列入表1中。
对比例2
将TPU聚氨酯薄膜(鸿达塑胶,0.2mm)在超声环境下洗涤(20mL乙醇10mL水)3次,干燥后放置于氧等离子体机中,50W下处理4min,取出聚氨酯薄膜浸入10mL水中处理4min,惰性气体吹拂下干燥得到表面富羟基化聚氨酯薄膜(TPU6)。
将0.8g巯丙基三乙氧基硅烷溶于25mL接枝溶液无水乙醇,混合0.7h;将40g TPU6置于接枝溶液中,70℃下反应8h,20mL无水乙醇与10mL水分别洗涤3次,干燥得到表面改性抗菌聚氨酯材料TPU-QPS6。并根据相关标准进行抗菌测试,抗菌率结果列入表1中。
表1实施例与对比例的性能
抗菌率(%) | |
实施例1 | 44 |
实施例2 | 65 |
实施例3 | 94 |
实施例4 | 100 |
对比例1 | 0 |
对比例2 | 0 |
从上述实施例1-4和对比例1-2的性能测试数据中,可以分析得出:未对其进行抗菌改性单体改性的聚氨酯薄膜的抗菌率为零;当季鏻盐中烷基链的碳原子个数为5-6时,聚氨酯薄膜抗菌性能优异;当引入芳香环结构时,聚氨酯薄膜抗菌性能最为优异。
实施例5
将0.035mol巯丙基三甲氧基硅烷,0.025mol烯丙基三苯基溴化鏻在30mL二氯甲烷中进行混合,加入催化剂烯2,2-二甲氧基-2-苯基苯乙酮质量比为2‰(占巯丙基三甲氧基硅烷加烯丙基三乙基溴化鏻总量的质量比),在200W的UV紫外光灯(365nm)下反应6h,经旋蒸除去溶剂,通过无水乙醚洗涤除去未反应物,干燥得到抗菌改性单体(QPS5)。
将TPU聚氨酯薄膜(鸿达塑胶,0.2mm)在超声环境下洗涤(20mL乙醇)3次,干燥后放置于氧等离子体机中,50W下处理6min,取出聚氨酯薄膜浸入10mL水中处理6min,惰性气体吹拂下干燥得到表面富羟基化聚氨酯薄膜(TPU7)。
将0.2g QPS5溶于20mL接枝溶液无水乙醇,混合0.5h;将50g TPU7置于接枝溶液中,60℃下反应6h,20mL无水乙醇洗涤3次,干燥得到表面改性抗菌聚氨酯材料TPU-QPS7。并根据相关标准进行抗菌测试,抗菌率结果列入表2中。
实施例6
将0.03mol巯丙基三甲氧基硅烷,0.02mol烯丙基三苯基溴化鏻在30mL二氯甲烷中进行混合,加入催化剂烯2,2-二甲氧基-2-苯基苯乙酮质量比为2‰(占巯丙基三甲氧基硅烷加烯丙基三乙基溴化鏻总量的质量比),在200W的UV紫外光灯(365nm)下反应6h,经旋蒸除去溶剂,通过无水乙醚洗涤除去未反应物,干燥得到抗菌改性单体(QPS6)。
将TPU聚氨酯薄膜(鸿达塑胶,0.2mm)在超声环境下洗涤(20mL水)3次,干燥后放置于氧等离子体机中,40W下处理6min,取出聚氨酯薄膜浸入10mL水中处理6min,惰性气体吹拂下干燥得到表面富羟基化聚氨酯薄膜(TPU8)。
将0.4g QPS6溶于20mL接枝溶液无水乙醇,混合0.6h;将45g TPU8置于接枝溶液中,65℃下反应7h,20mL无水乙醇洗涤3次,干燥得到表面改性抗菌聚氨酯材料TPU-QPS8。并根据相关标准进行抗菌测试,抗菌率结果列入表2中。
实施例7
将0.04mol巯丙基三乙氧基硅烷,0.02mol烯丙基三苯基溴化鏻在40mL二氯甲烷中进行混合,加入催化剂烯1-羟基环己基苯基甲酮质量比为4‰(占巯丙基三甲氧基硅烷加烯丙基三乙基溴化鏻总量的质量比),在200W的UV紫外光灯(365nm)下反应8h,经旋蒸除去溶剂,通过无水乙醚洗涤除去未反应物,干燥得到抗菌改性单体(QPS7)。
将TPU聚氨酯薄膜(鸿达塑胶,0.2mm)在超声环境下洗涤(20mL水20mL乙醇)3次,干燥后放置于氧等离子体机中,60W下处理6min,取出聚氨酯薄膜浸入10mL水中处理5min,惰性气体吹拂下干燥得到表面富羟基化聚氨酯薄膜(TPU9)。
将1.2g QPS7溶于20mL接枝溶液无水乙醇与水(体积比1:1),混合0.5h;将45gTPU9置于接枝溶液中,75℃下反应8h,20mL无水乙醇洗涤3次,干燥得到表面改性抗菌聚氨酯材料TPU-QPS9。并根据相关标准进行抗菌测试,抗菌率结果列入表2中。
对比例3
将TPU聚氨酯薄膜(鸿达塑胶,0.2mm)在超声环境下洗涤(10mL水)3次,干燥后放置于氧等离子体机中,45W下处理6min,取出聚氨酯薄膜浸入10mL水中处理4min,惰性气体吹拂下干燥得到表面富羟基化聚氨酯薄膜(TPU10)。
将1.2g巯丙基三甲氧基硅烷溶于25mL接枝溶液无水乙醇,混合0.7h;将40g TPU10置于接枝溶液中,75℃下反应8h,20mL无水乙醇与10mL水分别洗涤3次,干燥得到聚氨酯材料TPU-QPS10。并根据相关标准进行抗菌测试,抗菌率结果列入表2中。
对比例4
将TPU聚氨酯薄膜(鸿达塑胶,0.2mm)在超声环境下洗涤(10mL水10mL无水乙醇)3次,干燥后放置于氧等离子体机中,55W下处理6min,取出聚氨酯薄膜浸入15mL水中处理5min,惰性气体吹拂下干燥得到表面富羟基化聚氨酯薄膜(TPU11)。
将1.2g巯丙基三乙氧基硅烷溶于25mL接枝溶液无水乙醇,混合0.7h;将38g TPU11置于接枝溶液中,75℃下反应8h,20mL无水乙醇与10mL水分别洗涤3次,干燥得到聚氨酯材料TPU-QPS11。并根据相关标准进行抗菌测试,抗菌率结果列入表2中。
表2实施例与对比例的性能
抗菌率(%) | |
实施例5 | 48 |
实施例6 | 71 |
实施例7 | 100 |
对比例3 | 0 |
对比例4 | 0 |
从上述实施例5-7和对比例3-4的性能测试数据中,可以分析得出:未对其进行季鏻盐改性的聚氨酯薄膜的抗菌率为零;当烷基链的碳原子个数为5-6时,聚氨酯薄膜抗菌性能优异;当引入芳香环结构时,聚氨酯薄膜抗菌性能优异;随着抗菌改性单体含量的增加,相应的聚氨酯链中季鏻化程度的增加,聚氨酯薄膜抗菌得到增强。
所属领域的普通技术人员应当理解:以上所述仅为本发明的具体实施例而已,并不用于限制本发明,凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
2.根据权利要求1所述的一种表面改性抗菌聚氨酯材料的制备方法,其特征在于,抗菌改性单体与表面富羟基化聚氨酯薄膜组成比例为:
抗菌改性单体 0.1-10重量份;
表面富羟基化聚氨酯薄膜 100重量份。
3.根据权利要求1所述的一种表面改性抗菌聚氨酯材料的制备方法,其特征在于,所述抗菌改性单体的制备方法:将硅烷偶联剂和季鏻盐不饱和单体以摩尔计量比进行混合加入溶剂中,加入催化剂,UV紫外光下通过烯硫点击反应,经旋蒸洗涤干燥后得到抗菌改性单体。
4.根据权利要求3所述的一种表面改性抗菌聚氨酯材料的制备方法,其特征在于,所述抗菌改性单体制备中,硅烷偶联剂和季鏻盐不饱和化合物摩尔计量比为1~3:1。
5.根据权利要求1-4任一所述一种表面改性抗菌聚氨酯材料的制备方法,其特征在于,
所述抗菌改性单体制备中:所述硅烷偶联剂为巯丙基三甲氧基硅烷或巯丙基三乙氧基硅烷;所述季鏻盐不饱和单体为烯丙基三乙基溴化鏻、烯丙基三丁基碘化鏻、烯丙基三环己基溴化鏻或烯丙基三苯基溴化鏻中的一种或两种以上混合;所述催化剂为2,2-二甲氧基-2-苯基苯乙酮、1-羟基环己基苯基甲酮或苯甲酰甲酸甲酯中的一种;所述溶剂为二氯甲烷或三氯甲烷;所用洗涤液为无水乙醚;
所述表面富羟基化聚氨酯薄膜过程中:所述聚氨酯薄膜为TPU薄膜;洗涤聚氨酯薄膜的洗涤液为甲醇、乙醇或水中的一种或两种以上混合使用;浸泡液为水;
抗菌改性单体与表面富羟基化聚氨酯薄膜之间硅醇与羟基发生的偶联反应过程中:将抗菌改性单体与表面富羟基化聚氨酯薄膜置于盛有接枝溶液的反应容器中,高温反应,洗涤、干燥得到表面改性抗菌聚氨酯材料;所述接枝溶液为无水乙醇、水或甲苯中的一种或两种以上混合;所用洗涤液为无水乙醇、水或甲苯中的一种或两种以上先后使用。
6.根据权利要求1-4任一所述一种表面改性抗菌聚氨酯材料的制备方法,其特征在于:加入催化剂质量为硅烷偶联剂和季鏻盐不饱和单体总质量的1‰~5‰,在功率200W波长365nm的UV紫外光灯下反应4-10h。
7.根据权利要求1-4所述一种表面改性抗菌聚氨酯材料的制备方法,其特征在于:聚氨酯薄膜在超声环境下洗涤后,氧等离子体机处理条件为:40~80W下处理2~10min,取出聚氨酯薄膜浸入水中处理2~10min。
8.根据权利要求1-4任一所述一种表面改性抗菌聚氨酯材料的制备方法,其特征在于:先将抗菌改性单体溶于接枝溶剂,混合0.5h-4h;再将表面富羟基化聚氨酯薄膜置于接枝溶液中,40~80℃下反应6~24h。
9.权利要求1-8任一方法制得的表面改性抗菌聚氨酯材料。
10.权利要求1-8任一方法制得的表面改性抗菌聚氨酯材料的应用,其特征在于:所述表面改性抗菌聚氨酯材料可应用于环保材料、建筑材料、医疗器械材料。
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