CN106977814A - 一种具有稳定抗菌性能的复合材料及其用途 - Google Patents

一种具有稳定抗菌性能的复合材料及其用途 Download PDF

Info

Publication number
CN106977814A
CN106977814A CN201710265051.0A CN201710265051A CN106977814A CN 106977814 A CN106977814 A CN 106977814A CN 201710265051 A CN201710265051 A CN 201710265051A CN 106977814 A CN106977814 A CN 106977814A
Authority
CN
China
Prior art keywords
composite
microbial property
property
plastics
raw material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201710265051.0A
Other languages
English (en)
Other versions
CN106977814B (zh
Inventor
王娟
贾鹏飞
张星辰
张伟亮
秘军民
秘占林
马丽娟
董旭彤
周丹袆
井栋宇
王思
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shijiazhuang University
Original Assignee
Hebei Huida Pingshan Plastic Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hebei Huida Pingshan Plastic Co Ltd filed Critical Hebei Huida Pingshan Plastic Co Ltd
Priority to CN201710265051.0A priority Critical patent/CN106977814B/zh
Publication of CN106977814A publication Critical patent/CN106977814A/zh
Application granted granted Critical
Publication of CN106977814B publication Critical patent/CN106977814B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10Homopolymers or copolymers of propene
    • C08L23/12Polypropene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00Compositions of unspecified macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00Compositions of unspecified rubbers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/06Polyethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02Homopolymers or copolymers of hydrocarbons
    • C08L25/04Homopolymers or copolymers of styrene
    • C08L25/06Polystyrene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06Homopolymers or copolymers of vinyl chloride
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18Homopolymers or copolymers or tetrafluoroethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04Homopolymers or copolymers of esters
    • C08L33/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12Homopolymers or copolymers of methyl methacrylate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00Properties characterising the ingredient of the composition
    • C08L2207/06Properties of polyethylene
    • C08L2207/066LDPE (radical process)

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

本发明公开了一种具有稳定抗菌性能的复合材料,该复合材料以高分子聚合塑料、纤维、橡胶为主体,在高分子聚合塑料、纤维、橡胶制备的初始阶段,在原料母粒中添加能够耐受原料母粒熔融温度而不丧失抗菌性能的改性添加剂,同时所述改性添加剂随着原料母粒的熔融而广泛、均匀的分散到复合材料的各处,并随着复合材料的冷却成型而均匀的固定到复合材料中,使所得复合材料本身具有永久性的、稳定的抗菌性能。

Description

一种具有稳定抗菌性能的复合材料及其用途
技术领域
本发明涉及材料科学领域,尤其涉及一种自身具有抑菌杀菌性能的高分子聚合复合材料。
背景技术
细菌感染和传播引起疾病,甚至导致死亡,是威胁人类健康和生存的一个重要问题。为应对细菌的威胁,可以采用消毒剂对环境进行消毒。然而,大量消毒剂的使用会污染环境。因此,采用具有抑菌功能的制品阻止细菌传播受到广泛关注。
目前抑菌功能的制品主要是通过有机抗菌剂、无机抗菌剂、有机-无机复合抗菌剂或季铵盐高分子抗菌剂与制品材料共混而制备;也可以通过表面接枝的方式,使制品材料表面含各种抗菌基团,如季铵盐、金属离子、碘、壳聚糖等,获得抗菌性能;还可以通过制品材料基体改性的方式,使制品材料基体本身含有抗菌功能团,赋予其抗菌功能。
聚六亚甲基胍具有杀菌广谱,有效浓度低,作用速度快,性质稳定,易溶于水等优良性能,可在常温下使用,长期抑菌、无副作用;无腐蚀性;无色、无嗅;无毒;不燃、不爆、使用安全安全;价格适中;运输方便。聚六亚甲基胍在工业、农业、医用和日常生活中有着极其广泛的用途。聚六亚甲基胍盐酸盐可以破坏细胞膜完整性,其活性随着聚合度的增加而增加。在漂白或丝光等预处理过程中,会氧化棉纺织的葡萄糖单元而产生一些阴离子羧基,聚六亚甲基胍盐酸盐可以与这些棉纺织上的羧基通过离子相互作用而固定于纺织品上,从而提高了其抗菌活性的持久性。
然而,为了使得高分聚合材料自身具备抗菌性能,从而应用于食品、医用领域,聚六亚甲基胍却不具备实用性。一方面是因为聚六亚甲基胍还达不到医用产品级别的抗菌标准,需要对其抗菌性能进行进一步提高,更重要的问题在于,为了实现塑料的长期抗菌性必须将抗菌剂添加到塑料内部(表面涂覆只能起到临时杀菌的效果),为此需要在塑料的原料母粒中添加抗菌剂并随之一并熔融混匀,但是现有(改性前)的聚六亚甲基胍不一旦经历塑料母粒的高温熔融过程,其抑菌性能尤其是长期抑菌性能表现出大幅下降的趋势。
发明内容
本发明要解决的技术问题是提供一种具有稳定抗菌性能的复合材料。
为解决上述技术问题,本发明所采取的技术方案如下。
一种具有稳定抗菌性能的复合材料,该复合材料以高分子聚合塑料、纤维、橡胶为主体,在高分子聚合塑料、纤维、橡胶制备的初始阶段,在原料母粒中添加能够耐受原料母粒熔融温度而不丧失抗菌性能的改性添加剂,同时所述改性添加剂随着原料母粒的熔融而广泛、均匀的分散到复合材料的各处,并随着复合材料的冷却成型而均匀的固定到复合材料中,使所得复合材料本身具有永久性的、稳定的抗菌性能。
作为本发明的一种优选技术方案,所述改性添加剂采用经过设计修饰的改性聚六亚甲基胍,按重量份数计算此改性聚六亚甲基胍的用量为复合材料总重量的0.01%-0.5%。
作为本发明的一种优选技术方案,按重量份数计算所述改性聚六亚甲基胍的用量为复合材料总重量的0.05%。
作为本发明的一种优选技术方案,所改性聚六亚甲基胍的结构式为:
其中:R1选自H,COOH;R2选自H,NH2;聚合度n=5-50。
作为本发明的一种优选技术方案,所改性聚六亚甲基胍的聚合度n=15-25。
作为本发明的一种优选技术方案,所述R1为H;所述R2为H或NH2
作为本发明的一种优选技术方案,所述R1为COOH;所述R2为H或NH2
作为本发明的一种优选技术方案,聚合材料的主体选自聚丙烯塑料、聚乙烯塑料、聚苯乙烯塑料、低密度聚乙烯塑料、丙烯腈-丁二烯-苯乙烯共聚物塑料、聚碳酸酯塑料、聚氯乙烯塑料、聚四氟乙烯塑料、聚甲基丙烯酸甲酯塑料、聚酰胺塑料、聚对苯二甲酸丁二醇酯塑料、人造纤维、人造橡胶。
上述复合材料在食品、饮品、医疗行业中作为抗菌材料的用途。
采用上述技术方案所产生的有益效果在于:本发明的复合材料在原料母粒的高温熔融过程中,所添加的改性聚六亚甲基胍不仅能够耐受高温不丧失抗菌性能,同时还能随着原料母粒的熔融而广泛、均匀的分散到复合材料的各处,并随着复合材料的冷却成型而均匀的固定到复合材料中,使所得复合材料本身表现出永久性的、稳定的、优良的抗菌性能。具体可参见下文的试验例,本发明的复合材料不但24小时抑菌实验表现良好,尤其是长期抑菌实验也保持恒定而高效的抑菌抗菌属性,使得本发明在食品饮品包装、医用材料制备等行业领域具备广泛的应用前景。
具体实施方式
以下实施例详细说明了本发明。本发明所使用的各种原料及各项设备均为常规市售产品,均能够通过市场购买直接获得。
实施例1:
以聚六亚甲基单胍为原料,加入苯甲酸,苯甲酸与聚六亚甲基单胍的质量比为0.01:1,在氮气保护下进行接枝反应,反应温度为120℃,常压下搅拌,反应3h,然后降温至80℃,出料即得,接枝后聚六亚甲基单胍增重1%。制备得到的化合物的熔点为:熔点达到130-150℃。本实施例制备的产品结构式为:
;R1=H;R2=H;n=5。
所得聚六亚甲基单胍按重量比0.05%的用量作为原料之一添加到复合材料的制备母粒中,采用常规方法制备得出具有永久稳定抗菌性能的复合材料。
实施例2
以聚六亚甲基单胍为原料 ,加入邻苯二甲酸酐,邻苯二甲酸酐与聚六亚甲基单胍的质量比为0.001:1,在氮气保护下进行接枝反应,反应温度为180℃,常压下搅拌,反应1h,然后降温至100℃,出料即得,接枝后聚六亚甲基单胍增重3%。制备得到的化合物的熔点为:熔点达到150-180℃。本实施例制备的产品结构式为:
;R1= COOH;R2= NH2;n=50。
所得聚六亚甲基单胍按重量比0.05%的用量作为原料之一添加到复合材料的制备母粒中,采用常规方法制备得出具有永久稳定抗菌性能的复合材料。
实施例3
以聚六亚甲基单胍为原料 ,加入对氨基苯甲酸,氨基苯甲酸与聚六亚甲基单胍的质量比为0.0025:1,在氮气保护下进行接枝反应,反应温度为150℃,常压下搅拌,反应3h,然后降温至90℃,出料即得,接枝后聚六亚甲基单胍增重2%。制备得到的化合物的熔点为:熔点达到130-230℃。本实施例制备的产品结构式为:
;R1=H;R2= NH2;n=20。
所得聚六亚甲基单胍按重量比0.05%的用量作为原料之一添加到复合材料的制备母粒中,采用常规方法制备得出具有永久稳定抗菌性能的复合材料。
实施例4
以聚六亚甲基单胍为原料 ,加入苯甲酰氯,苯甲酰氯与聚六亚甲基单胍的质量比为0.0025:1,在氮气保护下进行接枝反应,反应温度为140℃,常压下搅拌,反应4h,然后降温至85℃,出料即得,接枝后聚六亚甲基单胍增重5%。制备得到的化合物的熔点为:熔点达到200-230℃。本实施例制备的产品结构式为:
;R1= COOH;R2=H;n=20。
所得聚六亚甲基单胍按重量比0.05%的用量作为原料之一添加到复合材料的制备母粒中,采用常规方法制备得出具有永久稳定抗菌性能的复合材料。
实施例5
以聚六亚甲基单胍为原料 ,加入苯甲酸甲酯,苯甲酸甲酯与聚六亚甲基单胍的质量比为0.0017:1,在氮气保护下进行接枝反应,反应温度为160℃,常压下搅拌,反应5h,然后降温至95℃,出料即得,接枝后聚六亚甲基单胍增重4%。制备得到的化合物的熔点为:熔点(或称为玻璃化温度)达到180-210℃。本实施例制备的产品结构式为:
;R1=H;R2=H;n=30。
所得聚六亚甲基单胍按重量比0.05%的用量作为原料之一添加到复合材料的制备母粒中,采用常规方法制备得出具有永久稳定抗菌性能的复合材料。
实施例6
以聚六亚甲基单胍为原料 ,加入苯甲酸,苯甲酸与聚六亚甲基单胍的质量比为0.0013:1,在氮气保护下进行接枝反应,反应温度为180℃,常压下搅拌,反应5h,然后降温至100℃,出料即得,接枝后聚六亚甲基单胍增重1%。制备得到的化合物的熔点为:熔点达到130-140℃。本实施例制备的产品结构式为:
;R1= COOH;R2= NH2;n=40。
所得聚六亚甲基单胍按重量比0.05%的用量作为原料之一添加到复合材料的制备母粒中,采用常规方法制备得出具有永久稳定抗菌性能的复合材料。
实施例7
以聚六亚甲基单胍为原料 ,加入邻苯二甲酸酐,邻苯二甲酸酐与聚六亚甲基单胍的质量比为0.005:1,在氮气保护下进行接枝反应,反应温度为120℃,常压下搅拌,反应3h,然后降温至80℃,出料即得,接枝后聚六亚甲基单胍增重4%。制备得到的化合物的熔点为:熔点达到180-190℃。本实施例制备的产品结构式为:
;R1=H;R2=H;n=10。
所得聚六亚甲基单胍按重量比0.05%的用量作为原料之一添加到复合材料的制备母粒中,采用常规方法制备得出具有永久稳定抗菌性能的复合材料。
实施例8
以聚六亚甲基单胍为原料 ,加入对氨基苯甲酸,对氨基苯甲酸与聚六亚甲基单胍的质量比为0.0025:1,在氮气保护下进行接枝反应,反应温度为150℃,常压下搅拌,反应4h,然后降温至90℃,出料即得,接枝后聚六亚甲基单胍增重3%。制备得到的化合物的熔点为:熔点达到160-230℃。本实施例制备的产品结构式为:
;R1= COOH;R2=H;n=20。
所得聚六亚甲基单胍按重量比0.05%的用量作为原料之一添加到复合材料的制备母粒中,采用常规方法制备得出具有永久稳定抗菌性能的复合材料。
实施例9
以聚六亚甲基单胍为原料 ,加入苯甲酸甲酯,苯甲酸甲酯与聚六亚甲基单胍的质量比为0.0025:1,在氮气保护下进行接枝反应,反应温度为160℃,常压下搅拌,反应3h,然后降温至90℃,出料即得,接枝后聚六亚甲基单胍增重4%。制备得到的化合物的熔点为:熔点达到160-230℃。本实施例制备的产品结构式为:
;R1= COOH;R2= NH2;n=20。
所得聚六亚甲基单胍按重量比0.05%的用量作为原料之一添加到复合材料的制备母粒中,采用常规方法制备得出具有永久稳定抗菌性能的复合材料。
实施例10
以聚六亚甲基单胍为原料 ,加入苯甲酰氯,苯甲酰氯与聚六亚甲基单胍的质量比为0.0017:1,在氮气保护下进行接枝反应,反应温度为150℃,常压下搅拌,反应2h,然后降温至90℃,出料即得,接枝后聚六亚甲基单胍增重5%。制备得到的化合物的熔点为:熔点达到130-180℃。本实施例制备的产品结构式为:
;R1=H;R2=H;n=30。
所得聚六亚甲基单胍按重量比0.05%的用量作为原料之一添加到复合材料的制备母粒中,采用常规方法制备得出具有永久稳定抗菌性能的复合材料。
实施例11
高分子材料的短期抑菌效果测试。贴膜法(定量法):按卫生部抗菌塑料抗菌性能试验方法和抗菌效果QB/T 2591-2003测试。在5cm×5cm片材样品上,用无菌棉将0.4mL大肠杆菌菌液(106CFU/mL)平铺在样品表面同时贴上无菌保鲜膜,37℃恒温箱中培养24小时后用20mL的PBS缓冲液冲洗贴膜,得到菌液(104 CFU/mL),进行活菌平板计数。同时做空白实验和对照试验。每个试样平行测定5次,抑菌率(Y)按下式计算:Y=(A-B)/A×100%,结果见下表。
表1高分子材料的抑菌效果测试
从表1的24小时抑菌试验结果来看,本发明的改性聚六亚甲基胍化合物加入到制备的医用高分子材料中与普通高分子材料和加入聚六亚甲基胍盐酸盐的高分子材料的抑菌效果对比后,加入本发明的改性聚六亚甲基胍化合物的高分子材料经过24小时后抑菌率达到100%,明显高于加入聚六亚甲基胍盐酸盐的PE,具有显著性差异。
实施例12
高分子材料的长期抑菌效果测试。贴膜法(定量法):按卫生部抗菌塑料抗菌性能试验方法和抗菌效果QB/T 2591-2003测试。在5cm×5cm片材样品上,用无菌棉将0.4mL大肠杆菌菌液(106CFU/mL)平铺在样品表面同时贴上无菌保鲜膜,37℃恒温箱中加速培养3个月后用20 mL的PBS缓冲液冲洗贴膜,得到菌液(104 CFU/mL),进行活菌平板计数。同时做空白实验和对照试验。每个试样平行测定5次,抑菌率(Y)按下式计算:Y=(A-B)/A×100%,结果见下表。
表2高分子材料的抑菌效果测试
从表2的三个月加速抑菌试验结果来看,本发明的改性聚六亚甲基胍化合物加入到制备的医用高分子材料中与普通高分子材料和加入聚六亚甲基胍盐酸盐的高分子材料的抑菌效果对比后,加入本发明的改性聚六亚甲基胍化合物的高分子材料经过3个月加速试验后抑菌率几乎达到100%,明显高于加入聚六亚甲基胍盐酸盐的PE,具有非常显著性差异。
上述描述仅作为本发明可实施的技术方案提出,不作为对其技术方案本身的单一限制条件。

Claims (9)

1.一种具有稳定抗菌性能的复合材料,该复合材料以高分子聚合塑料、纤维、橡胶为主体,其特征在于:在高分子聚合塑料、纤维、橡胶制备的初始阶段,在原料母粒中添加能够耐受原料母粒熔融温度而不丧失抗菌性能的改性添加剂,同时所述改性添加剂随着原料母粒的熔融而广泛、均匀的分散到复合材料的各处,并随着复合材料的冷却成型而均匀的固定到复合材料中,使所得复合材料本身具有永久性的、稳定的抗菌性能。
2.根据权利要求1所述的具有稳定抗菌性能的复合材料,其特征在于:所述改性添加剂采用经过设计修饰的改性聚六亚甲基胍,按重量份数计算此改性聚六亚甲基胍的用量为复合材料总重量的0.01%-0.5%。
3.根据权利要求2所述的具有稳定抗菌性能的复合材料,其特征在于:按重量份数计算所述改性聚六亚甲基胍的用量为复合材料总重量的0.05%。
4.根据权利要求2所述的具有稳定抗菌性能的复合材料,其特征在于:所改性聚六亚甲基胍的结构式为:
其中:R1选自H,COOH;R2选自H,NH2;聚合度n=5-50。
5.根据权利要求4所述的具有稳定抗菌性能的复合材料,其特征在于:所改性聚六亚甲基胍的聚合度n=15-25。
6.根据权利要求4所述的具有稳定抗菌性能的复合材料,其特征在于:所述R1为H;所述R2为H或NH2
7.根据权利要求4所述的具有稳定抗菌性能的复合材料,其特征在于:所述R1为COOH;所述R2为H或NH2
8.根据权利要求1所述的具有稳定抗菌性能的复合材料,其特征在于:聚合材料的主体选自聚丙烯塑料、聚乙烯塑料、聚苯乙烯塑料、低密度聚乙烯塑料、丙烯腈-丁二烯-苯乙烯共聚物塑料、聚碳酸酯塑料、聚氯乙烯塑料、聚四氟乙烯塑料、聚甲基丙烯酸甲酯塑料、聚酰胺塑料、聚对苯二甲酸丁二醇酯塑料、人造纤维、人造橡胶。
9.权利要求1所述的复合材料在食品、饮品、医疗行业中作为抗菌材料的用途。
CN201710265051.0A 2017-04-21 2017-04-21 一种具有稳定抗菌性能的复合材料及其用途 Active CN106977814B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710265051.0A CN106977814B (zh) 2017-04-21 2017-04-21 一种具有稳定抗菌性能的复合材料及其用途

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710265051.0A CN106977814B (zh) 2017-04-21 2017-04-21 一种具有稳定抗菌性能的复合材料及其用途

Publications (2)

Publication Number Publication Date
CN106977814A true CN106977814A (zh) 2017-07-25
CN106977814B CN106977814B (zh) 2020-03-06

Family

ID=59345592

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710265051.0A Active CN106977814B (zh) 2017-04-21 2017-04-21 一种具有稳定抗菌性能的复合材料及其用途

Country Status (1)

Country Link
CN (1) CN106977814B (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111393637A (zh) * 2020-04-02 2020-07-10 安阳崇高纳米材料科技有限公司 一种改性聚胍盐抗菌防霉剂及其制备方法和在硅酮结构密封胶中的应用

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6097908A (ja) * 1983-11-02 1985-05-31 Kurita Water Ind Ltd 用水系の抗菌剤
RU2034789C1 (ru) * 1993-07-20 1995-05-10 Дмитрий Александрович Топчиев Способ стерилизации питьевой воды
JP2003267808A (ja) * 2002-03-14 2003-09-25 Daiwa Kagaku Kogyo Kk レジオネラ対応薬湯用除菌剤
CN102234392A (zh) * 2010-04-22 2011-11-09 中国石油化工股份有限公司 一种抗菌聚丙烯双向拉伸薄膜及其制备方法
CN102464821A (zh) * 2010-11-18 2012-05-23 上海杰事杰新材料(集团)股份有限公司 一种抗菌耐老化抗静电塑料母料及其制备方法
CN102838809A (zh) * 2012-09-26 2012-12-26 上海瀚氏模具成型有限公司 抗菌聚丙烯塑料及其制备方法
CN103059405A (zh) * 2013-01-06 2013-04-24 上海秋橙新材料科技有限公司 抗菌聚丙烯塑料

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6097908A (ja) * 1983-11-02 1985-05-31 Kurita Water Ind Ltd 用水系の抗菌剤
RU2034789C1 (ru) * 1993-07-20 1995-05-10 Дмитрий Александрович Топчиев Способ стерилизации питьевой воды
JP2003267808A (ja) * 2002-03-14 2003-09-25 Daiwa Kagaku Kogyo Kk レジオネラ対応薬湯用除菌剤
CN102234392A (zh) * 2010-04-22 2011-11-09 中国石油化工股份有限公司 一种抗菌聚丙烯双向拉伸薄膜及其制备方法
CN102464821A (zh) * 2010-11-18 2012-05-23 上海杰事杰新材料(集团)股份有限公司 一种抗菌耐老化抗静电塑料母料及其制备方法
CN102838809A (zh) * 2012-09-26 2012-12-26 上海瀚氏模具成型有限公司 抗菌聚丙烯塑料及其制备方法
CN103059405A (zh) * 2013-01-06 2013-04-24 上海秋橙新材料科技有限公司 抗菌聚丙烯塑料

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
柳峰: "聚六亚甲胍盐酸盐的合成及其在织物抗菌整理上的应用", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111393637A (zh) * 2020-04-02 2020-07-10 安阳崇高纳米材料科技有限公司 一种改性聚胍盐抗菌防霉剂及其制备方法和在硅酮结构密封胶中的应用
CN111393637B (zh) * 2020-04-02 2023-03-31 安阳崇高纳米材料科技有限公司 一种改性聚胍盐抗菌防霉剂及其制备方法和在硅酮结构密封胶中的应用

Also Published As

Publication number Publication date
CN106977814B (zh) 2020-03-06

Similar Documents

Publication Publication Date Title
US8043632B2 (en) Process for making antimicrobial articles by reacting chitosan with amino-reactive polymer surfaces
US10226047B2 (en) Fibrous antimicrobial materials, structures, and barrier applications
US5658915A (en) Polyelectrolyte complex antibacterial agent and antibacterial material
ES2719590T3 (es) Producto antimicrobiano y antivírico
Chen et al. Biocidal efficacy, biofilm-controlling function, and controlled release effect of chloromelamine-based bioresponsive fibrous materials
US20170360040A1 (en) Modified polysaccharides for use as anti-microbial agents
KR101255528B1 (ko) 통상적이고 상업적으로 중요한 중합체를 내구성 및재충전성 항균 중합체성 물질로 전환시키는 방법
TW200904880A (en) Antimicrobial polyolefin and polyester compositions
US20070224161A1 (en) Compositions and methods for making and using acyclic N-halamine-based biocidal polymeric materials and articles
Ma et al. N-halamine polypropylene nonwoven fabrics with rechargeable antibacterial and antiviral functions for medical applications
Arora et al. Polymer based antimicrobial coatings as potential biomaterial: A review
CN107099031B (zh) 一种耐高温改性聚六亚甲基胍及其制备方法和用途
CN108276572A (zh) 一种支化聚氨基酸抑菌剂及应用
CN106977814A (zh) 一种具有稳定抗菌性能的复合材料及其用途
Gong et al. Polyhexamethylene biguanide hydrochloride anchored polymeric elastic fibers with robust antibacterial performance
EP0945064A1 (en) 2,2,6,6-Tetramethyl-4-piperidine derivatives as antimicrobial additives for polymer resins
Goldade et al. Antimicrobial fibers for textile clothing and medicine: current state
CN111217956B (zh) 阳离子型释迦果状丙烯酸酯共聚物抗菌微球的制备方法
CA2092289A1 (en) Antimicrobial hydrogels
CN102051020A (zh) 一种抗菌聚甲醛组合物及其制备方法和应用
WO2019213833A1 (zh) 一种具有抗菌作用的生物基材料及用途
WO2016121539A1 (ja) 耐水耐有機溶媒性組成物
CN107501876A (zh) 一种抗菌聚对苯二甲酸乙二醇酯塑料及其制备方法
CN105030819A (zh) 一种3-羟基-4-吡啶酮类高分子铁螯合剂的用途
JP3289055B2 (ja) 高分子電解質錯体抗菌剤及び抗菌性材料

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right
TA01 Transfer of patent application right

Effective date of registration: 20190329

Address after: 050000 No. 6 Changjiang Avenue, Shijiazhuang City, Hebei Province

Applicant after: Shijiazhuang College

Applicant after: Hebei Huida Pingshan Plastic Co. Ltd.

Address before: 050000 No. 168 Pingguang South Road, Pingshan County, Shijiazhuang City, Hebei Province

Applicant before: Hebei Huida Pingshan Plastic Co. Ltd.

GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20201207

Address after: 050000 No. 6 Changjiang Road, Hebei, Shijiazhuang

Patentee after: SHIJIAZHUANG University

Address before: 050000 No. 6 Changjiang Road, Hebei, Shijiazhuang

Patentee before: SHIJIAZHUANG University

Patentee before: HEBEI PROVINCE PINGSHAN COUNTY HUIDA PLASTIC Co.,Ltd.