CN111153815B - 一种抗菌多酚材料和应用 - Google Patents

一种抗菌多酚材料和应用 Download PDF

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CN111153815B
CN111153815B CN202010160603.3A CN202010160603A CN111153815B CN 111153815 B CN111153815 B CN 111153815B CN 202010160603 A CN202010160603 A CN 202010160603A CN 111153815 B CN111153815 B CN 111153815B
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polyphenol
quaternary ammonium
antibacterial
ammonium salt
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徐福建
胡杨
龙立
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Beijing University of Chemical Technology
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Abstract

本发明公开了一种抗菌多酚材料，由多酚类化合物接枝单官能团季铵盐制备得到，分子式A为
Figure DDA0002405642430000011
其中a＝2～10，b＝6～20，X为F、Cl、Br、I；分子式B为
Figure DDA0002405642430000012
其中a＝2～10，b＝6～20，c＝5～11，X为F、Cl、Br、I；分子式C为
Figure DDA0002405642430000013
其中n＝6～20，X为F、Cl、Br、I；分子式D为
Figure DDA0002405642430000014
其中n＝6～20，d＝3～11，X为F、Cl、Br、I；本发明的制备方法操作简单，易于实施，且制备得到的抗菌多酚有优异的抗菌性能和生物相容性，有望应用于大规模生产。

Description

一种抗菌多酚材料和应用
技术领域
本发明属于抗菌凝血材料领域，涉及一种抗菌多酚材料和应用。
背景技术
多酚类化合物是分子中具有多个羟基的酚类总称,是植物体内最重要的次生代谢产物,主要存在于植物体的皮、根、叶和果肉中，含量仅次于纤维素、半纤维素和木质素，其多元酚结构具有独特的理化性质,如能与蛋白质、生物碱、多糖等结合，能与金属离子络合，具有还原性、捕捉自由基的活性和诸多衍生化反应活性等，从而广泛应用于农业、生态环境、食品、医药等领域。常见的多酚类化合物有单宁酸、花青素、儿茶素、栎精、没食子酸、鞣花酸、熊果苷、表没食子儿茶素没食子酸酯等。多酚类化合物可在材料及制品表面形成涂层，起到抗菌、抗氧化等作用。但其涂层稳定性较差,不能很好地粘附于底物上而且抗菌性能有限。
人们在日常生活中不可避免地接触到各种各样的微生物，由于纺织品等材料表面具有一定的粗糙度，细菌更易附着在上面，知识病菌传递至皮肤表面，对人体造成伤害。材料的抗菌处理是有效防止各种细菌生长繁殖的重要手段。季铵盐类抗菌剂由于成本低而成为主导产品。
针对以上问题，需要提供一种可以很好的具有良好抗菌性能和生物相容性良好的多酚类化合物涂层或抗菌多酚材料，将单官能团季铵盐(一端溴代季铵盐和一端环氧季铵盐)，卤代烷基试剂和环氧烷基试剂与多酚类化合物结合，可以提高其抗菌性能，对血液和体细胞的不良影响小，生物相容性优良。
发明内容
有鉴于此，本发明提供一种抗菌多酚材料和应用。本发明具体提供了如下的技术方案：1、一种抗菌多酚材料，由多酚类化合物接枝单官能团季铵盐制备得到，
分子式A为
Figure BDA0002405642410000021
其中a＝2～10，b＝6～20，X为F、Cl、Br、I；
分子式B为
Figure BDA0002405642410000022
其中a＝2～10，b＝6～20，c＝5～11，X为F、Cl、Br、I；
分子式C为
Figure BDA0002405642410000023
其中n＝6～20，X为F、Cl、Br、I；
分子式D为
Figure BDA0002405642410000024
其中n＝6～20，d＝3～11，X为F、Cl、Br、I。
进一步，所述的单官能团季铵盐为一端卤代季铵盐
Figure BDA0002405642410000025
一端卤代季铵盐
Figure BDA0002405642410000026
与
Figure BDA0002405642410000027
的混合物、一端环氧季铵盐
Figure BDA0002405642410000028
或一端环氧季铵盐
Figure BDA0002405642410000031
与
Figure BDA0002405642410000032
的混合物，其中a＝2～10，b＝6～20，c＝5～11，d＝3～9，n＝6～20，X为Cl或Br。
进一步，分子式A的制备包括以下步骤：
1)将两端卤代烷烃
Figure BDA0002405642410000033
与叔胺烷基试剂
Figure BDA0002405642410000034
进行反应，经过沉淀干燥，得到一端卤代季铵盐
Figure BDA0002405642410000035
其中a＝2～10，b＝6～20，X为Cl或Br；
2)将多酚类化合物与步骤1)的一端卤代季铵盐进行反应，所述的一端卤代季铵盐与多酚类化合物的摩尔比为(50～0.1):1；经沉淀干燥，得到改性多酚QTA-A。
进一步，分子式B的制备包括以下步骤：
1)将两端卤代烷烃
Figure BDA0002405642410000036
与叔胺烷基试剂
Figure BDA0002405642410000037
进行反应，经过沉淀干燥，得到一端卤代季铵盐
Figure BDA0002405642410000038
其中a＝2～10，b＝6～20，X为Cl或Br；
2)将多酚类化合物与步骤1)的一端卤代季铵盐和
Figure BDA0002405642410000039
进行反应，其中c＝5～11，经沉淀干燥，得到具有抗菌性能的改性多酚AQTA-A，所述的
Figure BDA00024056424100000310
为溴己烷、溴辛烷、溴癸烷或溴十二烷，所述的一端卤代季铵盐和
Figure BDA00024056424100000311
与多酚类化合物的摩尔比为(50～0.1):(50～0.1):1。
进一步，步骤1)所述的两端卤代烷烃为1,2-二溴乙烷，1，3-二溴丙烷，1，4-二溴丁烷，1，5-二溴丁烷或1，6-二溴己烷，步骤1)所述的叔胺烷基试剂为N,N-二甲基己胺、N,N-二甲基辛胺、N,N-二甲基壬基胺、N,N-二甲基癸胺、十四烷基二甲基叔胺或十六烷基二甲基叔胺。
进一步，分子式C的制备包括以下步骤包括以下步骤：
1)将环氧氯丙烷与叔胺烷基试剂
Figure BDA00024056424100000312
进行反应，其中n＝6～20，经过沉淀干燥，得到一端环氧季铵盐
Figure BDA00024056424100000313
其中n＝6～20，X为Cl；
2)将多酚类化合物与步骤1)的一端环氧季铵盐进行反应，经沉淀干燥，得到改性多酚QTA-B。
进一步，分子式D的制备包括以下步骤包括以下步骤：
1)将环氧氯丙烷与叔胺烷基试剂
Figure BDA0002405642410000041
进行反应，其中n＝6～20，经过沉淀干燥，得到一端环氧季铵盐
Figure BDA0002405642410000042
其中n＝6～20，X为Cl；
2)将多酚类化合物与步骤1)的一端环氧季铵盐和
Figure BDA0002405642410000043
进行反应，其中d＝3～9，经沉淀干燥，得到具有抗菌性能的改性多酚AQTA-B，所述的
Figure BDA0002405642410000044
为1,2-环氧己烷、1,2-环氧辛烷、1,2-环氧癸烷或1,2-环氧十二烷，所述的一端环氧季铵盐和
Figure BDA0002405642410000045
与多酚类化合物的摩尔比为(50～0.1):(50～0.1):1。
进一步，步骤1)所述的叔胺烷基试剂为N,N-二甲基己胺、N,N-二甲基辛胺、N,N-二甲基壬基胺、N,N-二甲基癸胺、十四烷基二甲基叔胺或十六烷基二甲基叔胺。
进一步，所述的多酚类化合物为原花青素、栎精、单宁酸、没食子酸、鞣花酸或熊果苷。
2、上述一种抗菌多酚材料在制备抗菌产品上的应用，应用方法为：
1)将抗菌多酚材料通过浸泡、喷涂、滴注、涂刷等方式，结合到塑料、玻璃、金属、陶瓷等材料表面，制备相应抗菌塑料、玻璃、金属等产品；
2)在塑料、橡胶、聚氨酯等产品生产过程中，将抗菌多酚材料作为添加剂，加工到塑料、橡胶、聚氨酯等材料本体中，制备相应抗菌塑料、玻璃、金属等产品；
3)将多酚类化合物与壳聚糖、淀粉等混合，通过成膜或冻干等方式制备抗菌膜、抗菌海绵、抗菌粉等产品。
本发明的有益效果在于：本发明构建了由一端溴代季铵盐和一端环氧季铵盐改性的抗菌多酚(QTA-A、QTA-B)，两者均可以利用季铵盐正电荷提高多酚类化合物的抗菌性，实现对纱布、聚氨酯等材料的抗菌改性，从而制备得到具有优异抗菌性能的涂层或材料。进一步构建了由一端溴代季铵盐和一端环氧季铵盐分别与卤代烷基试剂和环氧烷基试剂同时改性的抗菌多酚(AQTA-A、AQTA-B)，两者均可以利用季铵盐正电荷提高多酚类化合物的抗菌性能，通过长烷基链的烷基化可进一步实现对纱布、聚氨酯等材料的抗菌改性，从而制备得到具有优异抗菌性能和生物相容性较好的涂层或材料。本发明的制备方法操作简单，易于实施，且制备得到的抗菌多酚有优异的抗菌性能和生物相容性，有望应用于大规模生产。
附图说明
为了使本发明的目的、技术方案和有益效果更加清楚，本发明提供如下附图：
图1为QTA-A2在d6-DMSO中的核磁谱图。
图2为AQTA-A1在d6-DMSO中的核磁谱图。
具体实施方式
下面结合附图，对本发明的优选实施例进行详细的描述。
实施例1
1)1moL 1,6-二溴己烷与0.2moL N,N-二甲基癸胺在65℃反应24小时，异丙醚沉淀，真空干燥，得到一端溴代季铵盐A，分子式为
Figure BDA0002405642410000051
2)将0.1mol没食子酸，2mol Na2CO3和2mol一端溴代季铵盐A，50℃反应12h，，经沉淀干燥，到改性多酚QTA-A1。
实施例2
1)1moL 1,6-二溴己烷与0.2moL N,N-二甲基辛胺
Figure BDA0002405642410000052
室温反应24小时，异丙醚沉淀，真空干燥，得到一端溴代季铵盐B，分子式为
Figure BDA0002405642410000053
2)将0.1mol单宁酸，2mol Na2CO3和2mol一端溴代季铵盐B，50℃反应12h，，经沉淀干燥，得到改性多酚QTA-A2。
实施例3
1)如实施例1步骤1)，制备一端溴代季铵盐A，分子式为
Figure BDA0002405642410000054
2)将0.1mol单宁酸，2mol Na2CO3和1mol一端溴代季铵盐A，1mol溴癸烷，50℃反应12h，经沉淀干燥，得到改性多酚AQTA-A1。
实施例4
1)1moL 1,3-二溴丙烷与0.2moL N,N-二甲基己胺室温反应24小时，异丙醚沉淀，真空干燥，得到一端溴代季铵盐C，分子式为
Figure BDA0002405642410000061
2)将0.1mol鞣花酸，2mol Na2CO3和0.01mol一端溴代季铵盐C，50℃反应12h，，经沉淀干燥，得到改性多酚QTA-A3。
实施例5
1)1moL 1,5-二溴丁烷与0.2moL N,N-二甲基辛胺
Figure BDA0002405642410000062
室温反应24小时，异丙醚沉淀，真空干燥，得到一端溴代季铵盐D，分子式为
Figure BDA0002405642410000063
2)将0.1mol栎精，2mol Na2CO3和5mol一端溴代季铵盐D，50℃反应12h，，经沉淀干燥，得到改性多酚QTA-A4。
实施例6
1)1moL 1,5-二溴乙烷与0.2moL十四烷基二甲基叔胺
Figure BDA0002405642410000064
室温反应24小时，异丙醚沉淀，真空干燥，得到一端溴代季铵盐E，分子式为
Figure BDA0002405642410000065
2)将0.1mol熊果苷，2mol Na2CO3和5mol一端溴代季铵盐E，50℃反应12h，，经沉淀干燥，得到改性多酚QTA-A5。
实施例7
1)3mol环氧氯丙烷
Figure BDA0002405642410000066
与1mol十六烷基二甲基叔胺
Figure BDA0002405642410000067
进行反应，经过沉淀干燥，得到一端环氧季铵盐F，分子式为
Figure BDA0002405642410000068
2)0.1mol栎精溶于50mL去离子水中，加入NaOH调节pH至8，加入0.01mol一端环氧季铵盐F进行反应，经沉淀干燥，得到改性多酚QTA-B1。
实施例8
1)3mol环氧氯丙烷
Figure BDA0002405642410000069
与1mol十四烷基二甲基叔胺
Figure BDA00024056424100000610
进行反应，经过沉淀干燥，得到一端环氧季铵盐G，分子式为
Figure BDA0002405642410000071
2)0.1mol原花青素溶于50mL去离子水，加入NaOH调节pH至8，加入0.5mol一端环氧季铵盐G进行反应，经沉淀干燥，得到改性多酚QTA-B2。
实施例9
1)3mol环氧氯丙烷
Figure BDA0002405642410000072
与1mol N,N-二甲基己胺
Figure BDA0002405642410000073
进行反应，经过沉淀干燥，得到一端环氧季铵盐H，分子式为
Figure BDA0002405642410000074
2)将0.1mol单宁酸溶于50mL去离子水中，加入NaOH调节pH至8，加入5mol一端环氧季铵盐H进行反应，经沉淀干燥，得到改性多酚QTA-B3。
实施例10
1)如实施例9，制备得到一端环氧季铵盐H，分子式为
Figure BDA0002405642410000075
2)将0.1mol单宁酸溶于50mL去离子水中，加入NaOH调节pH至8，加入5mol一端环氧季铵盐H和1mol 1,2-环氧癸烷反应，经沉淀干燥，得到改性多酚AQTA-B1。
实施例11
1)3mol环氧氯丙烷
Figure BDA0002405642410000076
与1mol N,N-二甲基辛胺
Figure BDA0002405642410000077
进行反应，经过沉淀干燥，得到一端环氧季铵盐I，分子式为
Figure BDA0002405642410000078
2)将0.1mol鞣花酸溶于50mL去离子水中，加入NaOH调节pH至8，加入2mol一端环氧季铵盐I进行反应，经沉淀干燥，得到改性多酚QTA-B4。
实施例12
1)3mol环氧氯丙烷
Figure BDA0002405642410000079
与1mol N,N-二甲基癸胺
Figure BDA00024056424100000710
进行反应，经过沉淀干燥，得到一端环氧季铵盐J，分子式为
Figure BDA00024056424100000711
2)将0.1mol熊果苷溶于50mL去离子水中，加入NaOH调节pH至8，加入1mol一端环氧季铵盐I进行反应，经沉淀干燥，得到改性多酚QTA-B5。
实施例13
如实施例2，制备改性多酚QTA-A2，继续进行如下反应：将0.1g QTA-A2溶于10mL乙醇，将1cm×1cm纱布浸泡到其中，干燥烘干得改性抗菌纱布QTA-A2。
实施例14
如实施例3，制备改性多酚AQTA-A1，继续进行如下反应：将0.1g AQTA-A1溶于10mL乙醇，将1cm×1cm纱布浸泡到其中，干燥烘干得改性抗菌纱布AQTA-A1。
实施例15
如实施例9，制备改性多酚QTA-B3，继续进行如下反应：取100g干燥PU，再加入1g改性多酚QTA-B3，充分混合均匀；通过微型双螺杆挤出机中挤出，再通过注塑机注塑成型得到改性抗菌聚氨酯QTA-B3。
实施例16
如实施例10，制备改性多酚AQTA-B1，继续进行如下反应：取100g干燥PU，再加入1g改性多酚AQTA-B1，充分混合均匀；通过微型双螺杆挤出机中挤出，再通过注塑机注塑成型得到改性抗菌聚氨酯AQTA-B1。
实施例17
如实施例8，制备改性多酚QTA-B2，继续进行如下反应：将0.5g改性多酚QTA-B2溶解在二氯甲烷中，然后加入50g多孔淀粉，搅拌2小时后，离心水、乙醇洗涤然后真空干燥得到改性抗菌淀粉QTA-B2。
对比例1
如实施例8步骤1)制备一端环氧季铵盐G，分子式为
Figure BDA0002405642410000081
继续进行如下反应：将0.1g一端环氧季铵盐G溶于10mL乙醇，将1cm×1cm纱布浸泡到其中，真空干燥烘干得改性抗菌纱布G。
测试例1材料结构表征
检测条件：实施例2、3溶于氘代DMAO溶液中在1H核磁共振仪(1H NMR)进行结构检测。检测方法：将受试材料溶于氘代DMSO配制成8mg/mL的溶液检测，结果如图1和2所示。
图1为QTA-A2在d6-DMSO中的核磁谱图，从图1中可以看出，化学位移0.8ppm处峰归属于季铵盐端甲基质子(a)，化学位移1.0～2.0ppm处峰归属于季铵盐烷基链的亚甲基质子(b)，化学位移3.0ppm左右处峰归属于季铵盐季铵化N上的2个甲基上的质子(c)，化学位移3.2ppm左右处峰归属于季铵盐紧邻季铵化N上的2个亚甲基上的质子(d)，化学位移3.4～3.6ppm左右处峰归属于季铵盐与单宁酸酚羟基相连的亚甲基上的质子(e)化学位移4.0～4.5ppm归属于单宁酸环氧五元环上的质子(f)。由此可见QTA-A2的成功制备。
从图2中可以看出，化学位移0.8ppm处峰归属于季铵盐端甲基质子(a)和溴癸烷端甲基质子(a)，化学位移1.0～2.0ppm处峰归属于季铵盐烷基链的亚甲基质子(b)和溴癸烷的亚甲基质子(b)，化学位移3.0ppm左右处峰归属于季铵盐季铵化N上的2个甲基上的质子(c)，化学位移3.2ppm左右处峰归属于季铵盐紧邻季铵化N上的2个亚甲基上的质子(d)，化学位移4.0ppm处峰归属于季铵盐与单宁酸酚羟基相连的亚甲基上的质子(e)，化学位移4.0～4.5ppm归属于单宁酸环氧五元环上的质子(f)。由此可见AQTA-A1的成功制备。
测试例2抗菌效果对比
检测条件：实验例1-12、与实施例1、8对应的多酚类化合物原料(没食子酸、原花青素)和单官能团季铵盐(一端溴代季铵盐A，一端环氧季铵盐G)进行金黄色葡萄球菌的抑菌性能测试。检测用菌为金黄色葡萄球菌ATCC 25923。
检测方法：将受试材料配制成0.5mg/mL的水溶液或分散液(灭菌处理)，每管5mL，对照组为无菌水。将培养好的金黄色葡萄球菌用PBS稀释成浓度为1×106CFU/mL的细菌悬液。取上述悬菌液，在每管样液和对照样液中滴加100μL，混合均匀。此时开始计时，作用20min。分别从每管样液和对照样液中吸取0.5mL，加入5mL PBS中，充分混匀后，作适当稀释，取0.5mL置于平皿中，加入15mL冷却至40～45℃的营养琼脂培养基，转动平皿，使其充分混匀。37℃培养48h,做活菌落计数。实验重复三次并按下式计算抑菌率：
X＝(A-B)/A×100％，式中：X—抑菌率，％A—对照样品平均菌落数B—被试样品平均菌落数，得到各材料平均抑菌率结果如下表：
表2-1平均抑菌率测试
Figure DA00024056424137835390
Figure BDA0002405642410000101
从表2-1中可以看出，实施例1-12的抑菌率远高于多酚类化合物原料(原花青素、没食子酸)和单官能团季铵盐(一端溴代季铵盐A，一端环氧季铵盐G)。
由此可见，经单官能团季铵盐改性后的多酚(实施例1-12)的抑菌效果要明显优于未改性的多酚类化合物原料及单官能团季铵盐。
检测条件：实验例13-16与未改性本体(普通纱布、聚氨酯)进行金黄色葡萄球菌的抑菌性能测试。检测用菌为金黄色葡萄球菌ATCC 25923。
检测方法：对于实施例13-16，将利用改性多酚制得的抗菌纱布和聚氨酯及相同大小的未改性普通纱布、聚氨酯制成1cm2方形样片，与3mL浓度为3×105CFU/mL的LB细菌培养液于12孔板中共同培养，3mL纯LB培养基为阴性对照，3mL纯菌液为阳性对照，12小时后吸取共培养菌液100μL置于96孔板中读取DO600。实验重复三次，待测孔的吸光度减去空白对照(纯LB培养基)孔的吸光度，作为测试孔的吸光度A测；正常对照(纯菌液)孔减去空白对照(纯LB培养基)的吸光度，作为对照孔的吸光度A对照；(A对照-A测)/A对照为测试孔的抑菌率，百分数表示，得到各材料平均抑菌率结果如下表2-2；
表2-2平均抑菌率测试
Figure BDA0002405642410000102
从表2-2中可以看出，实施例13-16得到的抗菌产品的抑菌率远高于未改性本体(普通纱布、聚氨酯)。
由此可见，由改性多酚制备的抗菌产品(实施例13-16)的抑菌效果要明显优于未改性本体(普通纱布、聚氨酯)。
测试例3细胞毒性对比
检测条件：在L929细胞系中通过MTT(噻唑蓝)法评价实施例13-16的改性抗菌纱布QTA-A2，改性抗菌纱布AQTA-A1，改性抗菌聚氨酯QTA-B3，改性抗菌聚氨酯AQTA-B1，对比例1的改性抗菌纱布G及未改性本体(普通纱布、聚氨酯)的生物相容性。
检测方法：取1cm2抗菌产品的方形样片置于无血清DMEM培养液中，37℃下浸泡过夜；使用含有20％血清的DMEM培养液等体积稀释浸提液，得到浸提液；在96孔板中按104～105个细胞/孔接种，37℃，5％CO2条件下孵育24小时后每孔加入100μL不同材料的浸提液；培养24小时后，加入含MTT的无血清培养液(MTT浓度为0.5mg/mL)，在培养箱中染色4小时后移除培养液。加入100μL DMSO溶解。酶标仪测定490nm波长处的光吸收值，根据测得的吸光值来判断活细胞相对数量，表征细胞活性。待测孔的吸光度减去空白对照(细胞全死)孔的吸光度，作为测试孔的吸光度A测；正常对照(培养液未加聚合物)孔减去空白对照(细胞全死)的吸光度，作为对照孔的吸光度A对照；两者的比值A测/A对照为测试孔相对存活率的数值，百分数表示，测试孔和对照孔均以六个平行孔的平均值计算。不同抗菌多酚或抗菌产品的细胞毒性如表3中所示：
表3细胞毒性测试
Figure BDA0002405642410000111
从表3中可以看出，实施例13-16得到的抗菌产品的细胞毒性远低于对比1的改性抗菌纱布G(仅使用季铵盐单体进行改性纱布，季铵盐未接枝到多酚类化合物上)。
最后说明的是，以上优选实施例仅用以说明本发明的技术方案而非限制，尽管通过上述优选实施例已经对本发明进行了详细的描述，但本领域技术人员应当理解，可以在形式上和细节上对其作出各种各样的改变，而不偏离本发明权利要求书所限定的范围。

Claims (3)

1.一种抗菌多酚材料，其特征在于，由多酚类化合物接枝单官能团季铵盐制备得到，分子A的制备包括以下步骤：
1)将两端卤代烷烃
Figure FDA0002942198360000011
与叔胺烷基试剂
Figure FDA0002942198360000012
进行反应，经过沉淀干燥，得到一端卤代季铵盐
Figure FDA0002942198360000013
其中a＝2～10，b＝6～20，X为Cl或Br；
2)将多酚类化合物与步骤1)的一端卤代季铵盐进行反应，所述的一端卤代季铵盐与多酚类化合物的摩尔比为(50～0.1):1；经沉淀干燥，得到改性多酚QTA-A；
分子B的制备包括以下步骤：
1)将两端卤代烷烃
Figure FDA0002942198360000014
与叔胺烷基试剂
Figure FDA0002942198360000015
进行反应，经过沉淀干燥，得到一端卤代季铵盐
Figure FDA0002942198360000016
其中a＝2～10，b＝6～20，X为Cl或Br；
2)将多酚类化合物与步骤1)的一端卤代季铵盐和
Figure FDA0002942198360000017
进行反应，其中c＝5～11，经沉淀干燥，得到具有抗菌性能的改性多酚AQTA-A，所述的
Figure FDA0002942198360000018
为溴己烷、溴辛烷、溴癸烷或溴十二烷，所述的一端卤代季铵盐和
Figure FDA0002942198360000019
与多酚类化合物的摩尔比为(50～0.1):(50～0.1):1；
分子C的制备包括以下步骤包括以下步骤：
1)将环氧氯丙烷与叔胺烷基试剂
Figure FDA00029421983600000110
进行反应，其中n＝6～20，经过沉淀干燥，得到一端环氧季铵盐
Figure FDA00029421983600000111
其中n＝6～20，X为Cl；
2)将多酚类化合物与步骤1)的一端环氧季铵盐进行反应，经沉淀干燥，得到改性多酚QTA-B；
分子D的制备包括以下步骤包括以下步骤：
1)将环氧氯丙烷与叔胺烷基试剂
Figure FDA00029421983600000112
进行反应，其中n＝6～20，经过沉淀干燥，得到一端环氧季铵盐
Figure FDA0002942198360000021
其中n＝6～20，X为Cl；
2)将多酚类化合物与步骤1)的一端环氧季铵盐和
Figure FDA0002942198360000022
进行反应，其中d＝3～9，经沉淀干燥，得到具有抗菌性能的改性多酚AQTA-B，所述的
Figure FDA0002942198360000023
为1,2-环氧己烷、1,2-环氧辛烷、1,2-环氧癸烷或1,2-环氧十二烷，所述的一端环氧季铵盐和
Figure FDA0002942198360000024
与多酚类化合物的摩尔比为(50～0.1):(50～0.1):1；
所述的多酚类化合物为原花青素、栎精、单宁酸、没食子酸、鞣花酸或熊果苷。
2.根据权利要求1所述的一种抗菌多酚材料，其特征在于，步骤1)所述的两端卤代烷烃为1,2-二溴乙烷，1，3-二溴丙烷，1，4-二溴丁烷，1，5-二溴丁烷或1，6-二溴己烷，步骤1)所述的叔胺烷基试剂为N,N-二甲基己胺、N,N-二甲基辛胺、N,N-二甲基壬基胺、N,N-二甲基癸胺、十四烷基二甲基叔胺或十六烷基二甲基叔胺。
3.根据权利要求1所述的一种抗菌多酚材料在制备抗菌产品上的应用，其特征在于，应用方法为：
1)将抗菌多酚材料通过浸泡、喷涂、滴注、涂刷方式，结合到塑料、玻璃、金属、陶瓷材料表面，制备相应抗菌塑料、玻璃、金属产品；
2)在塑料、橡胶、聚氨酯产品生产过程中，将抗菌多酚材料作为添加剂，加工到塑料、橡胶、聚氨酯材料本体中，制备相应抗菌塑料、玻璃、金属产品；
3)将多酚类化合物与壳聚糖、淀粉混合，通过成膜或冻干方式制备抗菌膜、抗菌海绵、抗菌粉产品。
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