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WO2020073784A1 - 一种抗菌聚合物及其制备方法 - Google Patents

一种抗菌聚合物及其制备方法 Download PDF

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Publication number
WO2020073784A1
WO2020073784A1 PCT/CN2019/106766 CN2019106766W WO2020073784A1 WO 2020073784 A1 WO2020073784 A1 WO 2020073784A1 CN 2019106766 W CN2019106766 W CN 2019106766W WO 2020073784 A1 WO2020073784 A1 WO 2020073784A1
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Prior art keywords
antibacterial
add
reaction
guanidine
antibacterial polymer
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PCT/CN2019/106766
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English (en)
French (fr)
Inventor
刘及响
赵云瑞
李郁聪
Original Assignee
桂林新先立抗菌材料有限公司
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Application filed by 桂林新先立抗菌材料有限公司 filed Critical 桂林新先立抗菌材料有限公司
Priority to US17/281,527 priority Critical patent/US11773220B2/en
Priority to JP2021518925A priority patent/JP7107534B2/ja
Priority to EP19870521.2A priority patent/EP3865530A4/en
Publication of WO2020073784A1 publication Critical patent/WO2020073784A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0206—Polyalkylene(poly)amines
    • C08G73/0213—Preparatory process
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G85/00—General processes for preparing compounds provided for in this subclass
    • C08G85/004—Modification of polymers by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers

Definitions

  • the present application relates to the field of organic synthesis and the field of environmental protection. Specifically, the present application provides an antibacterial polymer formed by polymerizing a non-toxic / non-irritating polyol and a guanidine salt and a preparation method thereof.
  • chemical materials such as plastics and chemical fibers have the advantages of long life, stable properties, simple manufacturing, light weight, and no moisture absorption. Therefore, they have become a common raw material for manufacturing various daily necessities and clothing.
  • moisture, heat, and organic matter are relatively abundant, and the environment in which the form is prone to breed microorganisms. Therefore, it is often necessary to add antibacterial agents to these materials to form antibacterial materials.
  • inorganic antibacterial agents are mainly metal ions such as silver ions and zinc ions carried on zeolites. Due to their complicated preparation process, products often have unstable performance , And its antifungal properties are often defective.
  • Organic antibacterial agents mainly include quaternary ammonium salts, ethers, phenols, thiazoles, diphenyl ether compounds, etc., which have a fast sterilization speed and a wide antibacterial spectrum, but its heat and water resistance and chemical resistance are poor, and the product's antibacterial validity period Short, the above problems are particularly noticeable when used in materials that are frequently exposed to water washing, detergent, hot water, clothing, daily use containers and pipes.
  • the inventors previously polymerized polyamines and guanidine salts to obtain an antibacterial masterbatch and obtained the Chinese patent CN1111556C.
  • the masterbatch was actually used in plastics, fibers, coatings, etc., and achieved good practice. effect.
  • the masterbatch has a good anti-fungal effect, it has the same problem of insufficient water and washing resistance as most organic antibacterial agents (the water solubility of the guanidine structure makes this problem more pronounced), and existing such as CN1111556C
  • Antimicrobial masterbatches mostly use toxic / irritating raw materials such as polyamines. The waste water generated is not environmentally friendly and the possible residues on the products can irritate human skin. There is a need for further improvement of polymer antibacterial agents containing a guanidine structure.
  • the inventors further improved the polymer antibacterial agent containing a guanidine structure of CN1111556C, and prepared a new type of antibacterial polymer by polymerizing a polyhydric alcohol and a guanidine salt.
  • the polymer maintained the antibacterial performance similar to that of CN1111556C It has achieved a significant increase in heat, water and detergent resistance, making it more suitable for the preparation of plastic and fiber materials that are often exposed to water and washing; and uses non-toxic / non-irritating polyols as raw materials for environmental and The human body is more friendly than polyamines.
  • the present application provides an antibacterial polymer, which is formed by polymerizing a polyhydric alcohol or polyamine and a guanidine salt.
  • the antibacterial polymer is formed by polymerizing a polyhydric alcohol and a guanidine salt, and has the following structure:
  • X is selected from acrylate group, methacrylate group, crotonate group, undecylenate group, ethyl acrylate group, propyl acrylate group or hydroxypropyl methacrylate group Ester group.
  • the present application provides a preparation method of the antibacterial polymer, which includes: mixing a polyol and a guanidine salt in a molar ratio of 1: 0.8-1.8. Add to the reactor, adjust the pH to acidic under the protection of nitrogen, heat to 120-180 °C, react for 1-4 hours, and then add 5% -25% by weight of polyol and guanidine salt containing active unsaturated double bond C3- The C20 compound undergoes esterification or ring-opening condensation reaction, and the reaction is terminated after 10 to 120 minutes.
  • the molar ratio of polyol to guanidine salt is 1: 1 to 1.5.
  • the polyhydric alcohol is selected from ethylene glycol, propylene glycol, butylene glycol, pentanediol, 1,6-hexanediol, 1,10-decanediol
  • the guanidine salt is selected from guanidine carbonate, guanidine hydrochloride, guanidine nitrate, Guanidine sulfate, guanidine phosphate, guanidine acetate
  • C3-C20 compounds containing active unsaturated double bonds are selected from acrylic acid, methacrylic acid, epoxyethyl acrylate, glycidyl acrylate, epoxybutyl acrylate, methacrylic acid ring Oxypropyl ester, epoxy ethyl methacrylate, epoxy butyl methacrylate, methyl methacrylate, ethyl methacrylate, butyl acrylate, ethyl acrylate, 2-hydroxyethyl acrylate, acrylic acid- 2-hydroxy
  • preparation method specifically includes:
  • preparation method specifically includes:
  • preparation method specifically includes:
  • the molecular weight of the product is about 8300, the thermal decomposition temperature is about 340 °C, and the infrared spectrum shows the characteristic absorption peak.
  • the molecular weight of the product is about 11500, the thermal decomposition temperature is about 360 °C, and the infrared spectrum shows the characteristic absorption peak.
  • the molecular weight of the product is about 10600, the thermal decomposition temperature is about 300 °C, and the infrared spectrum shows the characteristic absorption peak.
  • injection molding materials are completed by the cooperative enterprise; the antibacterial masterbatch of CN1111556C is prepared according to Example 1 in this publication; the antibacterial masterbatch of this application is prepared according to the method of Example 1; PP-R resin raw material particles, methyl phenyl Silicone oil, polypropylene wax (molecular weight 12000), talc powder (3000 mesh) are all conventional types purchased from Ningbo Zhenhai Better Plastic Co., Ltd. and Shanghai Yuxi Industrial Co., Ltd .; the injection molding machine is Yujiang YJ88 horizontal injection machine.
  • Material 1 For every 100 parts by weight of PPR particles, add 3 parts by weight (1.1) of the antibacterial masterbatch of this application, 0.2 parts by weight of methylphenyl silicone oil, 0.3 parts by weight of polypropylene wax, and 1 part by weight of talc
  • Material 2 For every 100 parts by weight of PPR particles, add 5 parts by weight (1.1) of the antibacterial masterbatch of this application, 0.2 parts by weight of methylphenyl silicone oil, 0.3 parts by weight of polypropylene wax, and 0.7 parts by weight of talc;
  • Material 3 For every 100 parts by weight of PPR particles, add 1 part by weight (1.2) of the antibacterial masterbatch of this application, 0.3 parts by weight of methylphenyl silicone oil, 0.5 parts by weight of polypropylene wax, and 1 part by weight of talc;
  • Material 4 For every 100 parts by weight of PPR particles, add 3 parts by weight of CN1111556C antibacterial masterbatch, 0.2 parts by weight of methylphenyl silicone oil, 0.3 parts by weight of polypropylene wax, and 1 part by weight of talc;
  • the specific preparation process is as follows: PPR resin raw material particles are added to the mixer, methylphenyl silicone oil is added under 200rmp, and after continuous mixing for 5 minutes, talc powder, polypropylene wax and optional antibacterial masterbatch of this application / CN1111556C antibacterial are added sequentially The masterbatch is mixed for 5 minutes and then loaded into the injection molding machine to prepare antibacterial injection molding materials (the working temperature of the four areas of the injection molding machine is about 200 ° C, 210 ° C, 220 ° C, and 210 ° C in order).
  • the materials 1-5 are further processed:
  • Material 1-1 The plastic sheet of material 1 is added to the drum-type washing machine with the recommended amount of washing liquid (blue moon, unscented type), and washed 50 times (approximately 1 hour each time) in a normal program at 40 ° C. dry;
  • Material 2-1 The plastic sheet of material 2 is added to the drum-type washing machine with the recommended amount of washing liquid (blue moon, unscented type), and washed 50 times (approximately 1 hour each time) in a normal program at 40 ° C. dry;
  • Material 3-1 The plastic sheet of material 3 is added to the drum-type washing machine with the recommended amount of washing liquid (blue moon, unscented type), and washed 50 times (approximately 1 hour each time) at 40 ° C in a normal program. dry;
  • Material 4-1 The plastic sheet of material 4 is added to the drum-type washing machine with the recommended amount of washing liquid (blue moon, unscented type), and washed 50 times (approximately 1 hour each time) at 40 ° C in a normal program, and rinsed clean. dry.
  • washing liquid blue moon, unscented type
  • the antibacterial performance test was carried out by the Antibacterial Material Testing Center of the Institute of Physics and Chemistry of the Chinese Academy of Sciences. The experiment basically followed the People ’s Republic of China National Light Industry Standard QB / T2591-2003.
  • Detection of bacteria and Candida albicans the sterilized polyethylene film was covered with The plastic samples were eluted after 24 hours of incubation. After 48 hours of incubation (72 hours of Candida albicans), live bacteria were counted according to the method of GB4789.2 to calculate the antibacterial rate.
  • Detection of mold Spread the plastic sheet on the plate medium and spray the mold spore suspension evenly. After 28 days of cultivation, the area covered by mold growth is detected.
  • Bacterial test objects include: Staphylococcus aureus ATCC 6538, Escherichia coli ATCC 2592, 2 and the fungus Candida albicans (ATCC) 10231, fungal test objects include: Aspergillus niger ( Aspergillusniger) ATCC 6275, ballet shell (Chaetoomium globsum) ATCC 6205,
  • the above experimental data shows that the antibacterial performance of the antibacterial masterbatch of this application is basically the same as that of CN1111556C antibacterial masterbatch (the performance of anti-E. Coli is slightly worse under individual conditions), but the ability to withstand hot water and detergent is significantly stronger than that of CN1111556C antibacterial masterbatch.
  • the anti-bacterial and fungal properties After hot water treatment and washing treatment, the anti-bacterial and fungal properties have little change, but CN1111556C has reduced anti-bacterial and fungal properties after hot water treatment, and lost most of the anti-bacterial and anti-fungal properties.
  • the above-mentioned properties of the antibacterial masterbatch of this application make it suitable for the preparation of injection molding materials, polymer materials, fabrics, non-woven fabrics, films, etc., and can maintain the antibacterial ability better after long-term use / after washing.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

本发明提供了一种抗菌聚合物及其制备方法，其由多元醇与胍盐聚合而成，具有以下结构： (I) 制备方法中使用无毒无刺激的多元醇为原料对环境和人体友好。

Description

一种抗菌聚合物及其制备方法 一技术领域
本申请涉及有机合成领域以及环保领域，具体地，本申请提供了一种使用无毒/无刺激的多元醇与胍盐聚合形成的抗菌聚合物及其制备方法。
二背景技术
塑料、化纤等化学材料相比天然材料具有寿命长、性质稳定、制造简单、质量轻、不吸湿等优点，因而成为制造各种日常用品和衣物的常用原材料。上述化学材料常用的浴室、厨房、包袋、衣物等情形中，湿、热、有机质均较为丰富，形式容易滋生微生物的环境。因此，经常需要向这些材料中加入抗菌剂形成抗菌材料。
常用的塑料抗菌剂中，天然抗菌剂由于价格和稳定性的原因无法广泛应用；无机抗菌剂主要为载于沸石上的银离子和锌离子等金属离子，由于其制备工艺复杂产品往往性能不稳定，而且其抗真菌性能往往有缺陷。有机抗菌剂主要有季铵盐类、醚类、苯酚类、噻唑类、联苯醚类化合物等，其杀菌速度快、抗菌谱广，但其耐热耐水耐化学品性能差，产品的抗菌有效期短，上述问题在用于频繁接触水洗、洗涤剂、热水的衣物、日用容器和管道等材料时特别显著。
发明人先前将多元胺与胍盐聚合，获得了一种抗菌母料并取得了中国专利CN1111556C，随后的应用中，该母料被实际用于塑料、纤维、涂料等方面，取得了良好的实际效果。但该母料虽然抗霉菌效果良好，但与大多数有机抗菌剂一样存在耐水耐洗涤性能不足的问题(胍结构的水溶性使这一问题更为显著)，而且包括CN1111556C在内的现有此类抗菌母料多采用有毒/刺激性的原料如多元胺，产生的污水废料对环保不利且产品上可能的残留会对人体皮肤有刺激。含胍结构的聚合物抗菌剂存在进一步改进的需求。
三发明内容
针对上述问题，发明人进一步改进了CN1111556C的含胍结构的聚合物抗菌剂，使用多元醇与胍盐聚合制备了新型抗菌聚合物，该聚合物在保持类似CN1111556C抗菌聚合物抗菌性能的前提下，实现了耐热、耐水、耐洗涤剂能力的显著提高，使得其更适合用于经常接触水和洗涤的塑料、纤维材料的制备；而且采用无毒/无刺激的多元醇作为原料，对环境和人体比多元胺更为友好。
基本反应原理如下：
Figure PCTCN2019106766-appb-000001
一方面，本申请提供了一种抗菌聚合物，其由多元醇或多元胺与胍盐聚合而成。
进一步地，该抗菌聚合物由多元醇与胍盐聚合而成，具有以下结构：
Figure PCTCN2019106766-appb-000002
其中n＝5-10，m＝50-150；Y -为选自Cl -、NO 3 -、HCO 3 -、CH 3COO -、HSO 4 -或H 2PO 4 -阴离子；X为含1-5个活性不饱和双键的C5-C20酯基或醚基；Z为H或X。
进一步地，该抗菌聚合物中，X选自丙烯酸酯基、甲基丙烯酸酯基、丁烯酸酯基、十一碳烯酯基、丙烯酸乙酯基、丙烯酸丙酯基或甲基丙烯酸羟基丙酯基。
另一方面，本申请提供了该抗菌聚合物的制备方法，包括：将多元醇与胍盐以摩尔比1∶0.8-1.8的比例混合。加入反应器中，氮气保护下，调pH至酸性，加热至120-180℃，反应1-4小时，而后再加入多元醇和胍盐重量5％-25％的含活性不饱和双键的C3-C20化合物，进行酯化或开环缩合反应，10-120分钟后，结束反应。
进一步地，多元醇与胍盐的摩尔比为1∶1-1.5。
进一步地，多元醇选自乙二醇、丙二醇、丁二醇、戊二醇、1，6-己二醇、1，10-癸二醇；胍盐选自碳酸胍、盐酸胍、硝酸胍、硫酸胍、磷酸胍、乙酸胍；含活性不饱和双键的C3-C20化合物选自丙烯酸、甲基丙烯酸、丙烯酸环氧乙酯、丙烯酸环氧丙酯、丙烯酸环氧丁酯、甲基丙烯酸环氧丙酯、甲基丙烯酸环氧乙酯、甲基丙烯酸环氧丁酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸丁酯、丙烯酸乙酯、丙烯酸-2-羟基乙酯、丙烯酸-2-羟基丙酯、甲基丙烯酸环氧丙酯、甲基丙烯酸-2-羟基丙酯、马来酸酐、富马酸酯、衣康酸。
进一步地，制备方法具体包括：
取乙二醇124g，硝酸胍260g，加入反应釜中，混合均匀，氮气保护下，以盐酸调pH为5，加热至120℃，反应3h，再加入丙烯酸30g，进行酯化反应1h，结束反应。
进一步地，制备方法具体包括：
取丙二醇152g，碳酸胍254g，加入反应釜中，混合均匀，氮气保护下，以盐酸调pH为4，加热至130℃，反应2.5h，再加入甲基丙烯酸25g，进行酯化反应1.5h，结束反应。
进一步地，制备方法具体包括：
取1，6-己二醇118g，盐酸胍100g，加入反应釜中，混合均匀，氮气保护下，以盐酸调pH为3，加热至150℃，反应2h，再加入丙烯酸环氧丙烷20g，进行酯化反应2h，结束反应。
四具体实施方式
实施例1本申请抗菌母料的制备
1.1取乙二醇124g，硝酸胍260g，加入反应釜中，混合均匀，氮气保护下，以盐酸调pH为5，加热至120℃，反应3h，再加入丙烯酸30g，进行酯化反应1h，结束反应。造粒。
产品分子量约8300，热分解温度约340℃，红外图谱显示应有的特征吸收峰。
1.2取1，6-己二醇118g，盐酸胍100g，加入反应釜中，混合均匀，氮气保护下，以盐酸调pH为3，加热至150℃，反应2h，再加入丙烯酸环氧丙烷20g，进行酯化反应2h，结束反应。造粒。
产品分子量约11500，热分解温度约360℃，红外图谱显示应有的特征吸收峰。
1.3取丙二醇152g，碳酸胍254g，加入反应釜中，混合均匀，氮气保护下，以盐酸调pH为4，加热至130℃，反应2.5h，再加入甲基丙烯酸25g，进行酯化反应1.5h，结束反应。造粒。
产品分子量约10600，热分解温度约300℃，红外图谱显示应有的特征吸收峰。
实施例2使用本申请抗菌母料制备PPR注塑材料
注塑材料具体制备由合作企业完成；CN1111556C的抗菌母料按照该公开文本中的实施例1制备；本申请的抗菌母料按照实施例1的方法制备；PP-R树脂原料颗粒、甲基苯基硅油、聚丙烯蜡(分子量12000)、滑石粉(3000目)均为购自宁波市镇海百特思塑化有限公司和上海雨汐实业有限公司的常规种类；注塑机为煜江YJ88卧式注塑机。
材料1：每100重量份PPR颗粒，加入本申请抗菌母料3重量份(1.1)，甲基苯基硅油0.2重量份、聚丙烯蜡0.3重量份、滑石粉1重量份；
材料2：每100重量份PPR颗粒，加入本申请抗菌母料5重量份(1.1)，甲基苯基硅油0.2重量份、聚丙烯蜡0.3重量份、滑石粉0.7重量份；
材料3：每100重量份PPR颗粒，加入本申请抗菌母料1重量份(1.2)，甲基苯基硅油0.3重量份、聚丙烯蜡0.5重量份、滑石粉1重量份；
材料4：每100重量份PPR颗粒，加入CN1111556C抗菌母料3重量份，甲基苯基硅油0.2重量份、聚丙烯蜡0.3重量份、滑石粉1重量份；
材料5：不加入抗菌母料。
具体制备过程为：将PPR树脂原料颗粒加入到混合机中，200rmp下加入甲基苯基硅油，继续混合5分钟后依次加入滑石粉、聚丙烯蜡和可选的本申请抗菌母料/CN1111556C抗菌母料，继续混合5分钟后装入注塑机，制得抗菌注塑材料(注塑机四个区域工作温度依次为约200℃、210℃、220℃、210℃)。
表1所制备材料的主要性能
Figure PCTCN2019106766-appb-000003
为检测本申请抗菌注塑材料的耐热水和洗涤剂性能，对材料1-5进行进一步处理：
材料1-1：材料1的塑料片在滚筒式洗衣机中加入说明书推荐量的洗衣液(蓝月亮，无香型)，以普通程序40℃洗涤50次(每次约1小时)，漂洗干净，干燥；
材料2-1：材料2的塑料片在滚筒式洗衣机中加入说明书推荐量的洗衣液(蓝月亮，无香型)，以普通程序40℃洗涤50次(每次约1小时)，漂洗干净，干燥；
材料3-1：材料3的塑料片在滚筒式洗衣机中加入说明书推荐量的洗衣液(蓝月亮，无香型)，以普通程序40℃洗涤50次(每次约1小时)，漂洗干净，干燥；
材料4-1：材料4的塑料片在滚筒式洗衣机中加入说明书推荐量的洗衣液(蓝月亮，无香型)，以普通程序40℃洗涤50次(每次约1小时)，漂洗干净，干燥。
实施例3注塑材料抗菌性能检测
抗菌性能检测由中国科学院理化所抗菌材料检测中心进行，实验基本遵循中华人民共和国国轻工行业标准QB/T2591-2003，检测细菌和白色念珠菌：将灭菌后的聚乙烯薄膜平铺覆盖于塑料样品上，培养24小时后洗脱，培养48小时后(白色念珠菌72小时)按照GB 4789.2的方法活菌计数，计算抗菌率。检测霉菌：将塑料片平铺于平板培养基上，均匀喷洒霉菌孢子悬液，培养28日后检测霉菌生长覆盖面积。
细菌测试对象包括：金黄色葡萄球菌(Staphylococcus aureus)ATCC 6538、大肠埃希氏菌(Escherichia coli)ATCC 2592，2并加入真菌白色念珠菌(Canidia Albicans)ATCC 10231，霉菌测试对象包括：黑曲霉(Aspergillus niger)ATCC 6275、球毛壳(Chaetoomium globsum)ATCC 6205、
表1注塑材料的抗细菌/白色念珠菌性能
Figure PCTCN2019106766-appb-000004
Figure PCTCN2019106766-appb-000005
*参照QB/T2591-2003标准，90％以下即不能称为有抗菌作用。
表2.注塑材料的抗霉菌性能
样品编号 黑曲霉长霉等级 球毛壳长霉等级
材料1 0级 0级
材料2 0级 0级
材料3 0级 0级
材料4 0级 0级
材料5 无抗菌作用 无抗菌作用
材料1-1 0级 0级
材料2-1 0级 0级
材料3-1 0级 0级
材料4-1 1级 无抗菌作用
*霉菌生长覆盖面积大于10％(2级)即不能称为有抗菌作用。
以上实验数据显示，本申请抗菌母料的抗菌性能与CN1111556C抗菌母料基本等同(个别条件下抗大肠杆菌性能略差)，但耐受热水和洗涤剂能力明显强于CN1111556C抗菌母料，高强度热水和洗涤处理后抗细菌霉菌性能几无变化，而CN1111556C在热水处理后抗细菌霉菌性能都有降低，丧失了大部分抗细菌性能和抗霉菌性能。
另外的实验表明，含实施例1(1.3)抗菌母料的塑料材料机械和抗菌性能与含实施例1(1.1和1.2)近似，同时制成的材料也具有类似的耐受热水浸泡和洗涤能力(为节约时间和费用未委托进行完整检测)。
本申请抗菌母料的上述性能使得其适合制备注塑材料，聚合物材料，织物，无纺布，薄膜等，能在长时间使用后/洗涤后较好的保持抗菌能力。
上述实施例中的注塑材料制品仅是为了举例列出，其余使用本申请抗菌母料的产品，如各种塑料薄膜，无纺布，织物等技术方案的抗菌效果可以从实施例2、3合理预期，并且这些技术方案也在本申请公开和要求保护的范围内。

Claims (3)

  1. 一种抗菌聚合物，其由多元醇与胍盐聚合而成，具有以下结构：
    Figure PCTCN2019106766-appb-100001
    其中n＝5-10，m＝50-150；Y -为选自Cl -、NO 3 -、HCO 3 -、CH 3COO -、HSO 4 -或H 2PO 4 -阴离子；X为含1-5个活性不饱和双键的C5-C20酯基或醚基；Z为H或X；所述抗菌聚合物按照以下方法制备而成：取乙二醇124g，硝酸胍260g，加入反应釜中，混合均匀，氮气保护下，调pH为5，加热至120℃，反应3h，再加入丙烯酸30g，进行酯化反应1h，结束反应。
  2. 一种抗菌聚合物，其由多元醇与胍盐聚合而成，具有以下结构：
    Figure PCTCN2019106766-appb-100002
    其中n＝5-10，m＝50-150；Y -为选自Cl -、NO 3 -、HCO 3 -、CH 3COO -、HSO 4 -或H 2PO 4 -阴离子；X为含1-5个活性不饱和双键的C5-C20酯基或醚基；Z为H或X；所述抗菌聚合物按照以下方法制备而成：取丙二醇152g，碳酸胍254g，加入反应釜中，混合均匀，氮气保护下，调pH为4，加热至130℃，反应2.5h，再加入甲基丙烯酸25g，进行酯化反应1.5h，结束反应。
  3. 一种抗菌聚合物，其由多元醇与胍盐聚合而成，具有以下结构：
    Figure PCTCN2019106766-appb-100003
    其中n＝5-10，m＝50-150；Y -为选自Cl -、NO 3 -、HCO 3 -、CH 3COO -、HSO 4 -或H 2PO 4 -阴离子；X为含1-5个活性不饱和双键的C5-C20酯基或醚基；Z为H或X；所述抗菌聚合物按照以下方法制备而成：取1，6-己二醇118g，盐酸胍100g，加入反应釜中，混合均匀，氮气保护下，调pH为3，加热至150℃，反应2h，再加入丙烯酸环氧丙烷20g，进行酯化反应2h，结束反应。
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