CN115011048A - Preparation method and application of polyvinyl chloride antibacterial composite material - Google Patents

Preparation method and application of polyvinyl chloride antibacterial composite material Download PDF

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Publication number
CN115011048A
CN115011048A CN202210861666.0A CN202210861666A CN115011048A CN 115011048 A CN115011048 A CN 115011048A CN 202210861666 A CN202210861666 A CN 202210861666A CN 115011048 A CN115011048 A CN 115011048A
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polyvinyl chloride
preparation
composite material
benzoic acid
antibacterial composite
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谢友亮
谢小纯
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Guangdong Liangfengda Industrial Co ltd
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Guangdong Liangfengda Industrial Co ltd
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    • 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
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

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

Abstract

The invention relates to the technical field of high polymer materials and discloses a polyvinyl chloride antibacterial composite material.an alkyl pyridinium antibacterial group and a carboxyl functional group are introduced into a side chain of polyvinyl chloride, and are blended and modified with polyvinyl chloride resin and carboxyl nitrile rubber; meanwhile, carboxyl introduced by the polyvinyl chloride side chain has good intermolecular interaction with the carboxyl nitrile rubber, and chemical bonding occurs in melting and mixing, so that the carboxyl nitrile rubber and the polyvinyl chloride resin have good compatibility and interface bonding force, the nitrile rubber has good toughening and modifying effects on the strength of the polyvinyl chloride resin, and the mechanical strength and toughness of the material are improved.

Description

Preparation method and application of polyvinyl chloride antibacterial composite material
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a preparation method and application of a polyvinyl chloride antibacterial composite material.
Background
Polyvinyl chloride is one of general plastics with the largest yield in the world, the modification of polyvinyl chloride is a research hotspot in recent years, and the influence of acrylic acid on the performance of waste carboxyl nitrile rubber/polyvinyl chloride and blends reports that the acrylic acid is used for grafting modified polyvinyl chloride and waste carboxyl nitrile rubber to carry out blending modification, a small amount of acrylic acid is added to generate chemical bonds between the two surfaces, so that the adhesive force between the two phase interfaces is increased, and the mechanical property of the polyvinyl chloride blend is improved.
In order to expand the practical application of polyvinyl chloride, the antibacterial modification of polyvinyl chloride materials has important significance, and the antibacterial property of polyvinyl chloride plastics is improved by utilizing methacryloyloxyethyl trimethyl ammonium chloride antibacterial agent to graft copolymerize with polyvinyl chloride and then to blend and modify with polyvinyl chloride.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a polyvinyl chloride antibacterial composite material.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a polyvinyl chloride antibacterial composite material is prepared according to the following method:
(1) adding 4-isocyanate benzoic acid and 2-amino-5- (aminomethyl) pyridine into tetrahydrofuran, and reacting at room temperature to obtain 2-aminopyridine urea benzoic acid; and then adding maleic anhydride grafted polyvinyl chloride and 2-aminopyridine urea benzoic acid into the solvent, stirring the mixture in a nitrogen atmosphere for grafting reaction, drying the mixture in vacuum after the reaction, and washing the product by distilled water and ethanol to obtain the pyridylbenzoic acid grafted polyvinyl chloride.
(2) Adding pyridine benzoic acid grafted polyvinyl chloride into N, N-dimethylformamide, stirring for dissolving, and adding alkyl chloride (C) n H 2n+1 Cl and n are 10-18), heating to 80-110 ℃, reacting for 12-36h, cooling after reaction, drying in vacuum, washing the product with distilled water and ethanol to obtain pyridinium benzoic acid grafted polyvinyl chloride;
Figure RE-GDA0003788858600000021
(3) adding polyvinyl chloride resin, pyridine salt benzoic acid grafted polyvinyl chloride and an auxiliary agent into a double-roller mixing roll for mixing, then adding carboxyl nitrile rubber, and performing hot pressing-cold pressing on the materials after uniform melting and mixing to obtain the polyvinyl chloride antibacterial composite material.
Preferably, the solvent in (1) comprises N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and xylene.
Preferably, the maleic anhydride grafted polyvinyl chloride in the step (1) is used in an amount of 100 parts by weight, and the 2-aminopyridine urea benzoic acid is used in an amount of 3-15 parts by weight.
Preferably, the grafting reaction in (1) is carried out at 20-35 ℃ for 3-5h, and then at 110-140 ℃ for 6-12 h.
Preferably, the pyridine benzoic acid grafted polyvinyl chloride in the step (2) is used in an amount of 100 parts by weight and the alkyl chloride is 5-30 parts by weight.
Preferably, the auxiliary agent in (3) comprises 2-4% of stabilizer, 1-2% of lubricant and 20-30% of plasticizer.
Preferably, the usage amount of the pyridinium benzoic acid grafted polyvinyl chloride in the step (3) is 6-30%, and the usage amount of the carboxylated nitrile rubber is 5-20%.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
according to the polyvinyl chloride antibacterial composite material, the acylidene cyclization reaction is carried out on 2-aminopyridine urea benzoic acid and maleic anhydride grafted polyvinyl chloride, and alkyl chloride pyridinium is used for quaternization to synthesize pyridinium benzoic acid grafted polyvinyl chloride, so that an alkyl pyridinium antibacterial group and a carboxyl functional group are introduced into a side chain of the polyvinyl chloride and are used as functional auxiliaries to be blended and modified with polyvinyl chloride resin and carboxyl nitrile rubber, the introduced pyridinium antibacterial group has the advantages of high grafting rate and low migration loss tendency, and the polyvinyl chloride material is endowed with long-acting and different antibacterial performance; meanwhile, carboxyl introduced by the polyvinyl chloride side chain has good intermolecular interaction with the carboxyl nitrile rubber, and chemical bonding occurs in melting and mixing, so that the carboxyl nitrile rubber and the polyvinyl chloride resin have good compatibility and interface bonding force, the nitrile rubber has good toughening and modifying effects on the strength of the polyvinyl chloride resin, and the mechanical strength and toughness of the material are improved.
Detailed Description
Example 1
(1) Adding 4-isocyanate benzoic acid and 2-amino-5- (aminomethyl) pyridine into tetrahydrofuran, and reacting at room temperature to obtain 2-aminopyridine urea benzoic acid; then adding 2g of maleic anhydride grafted polyvinyl chloride and 0.06g of 2-aminopyridine urea benzoic acid into N-methylpyrrolidone, stirring and grafting reaction at 20 ℃ for 4h in nitrogen atmosphere, then reacting at 120 ℃ for 12h, drying in vacuum after reaction, washing products with distilled water and ethanol, and obtaining the pyridylbenzoic acid grafted polyvinyl chloride.
(2) Adding 5g of pyridine benzoic acid grafted polyvinyl chloride into N, N-dimethylformamide, stirring to dissolve, adding 0.25g of 1-chlorododecane, heating to 110 ℃, reacting for 36 hours, cooling and vacuum drying after reaction, and washing a product by using distilled water and ethanol to obtain the pyridine benzoic acid grafted polyvinyl chloride.
(3) Adding polyvinyl chloride resin, 6% of pyridinium benzoic acid grafted polyvinyl chloride, 3% of calcium-zinc stabilizer, 2% of lubricant stearic acid and 25% of plasticizer DOP into a double-roller mixing roll for mixing, then adding 5% of carboxyl nitrile rubber, and performing hot pressing-cold pressing process on the materials after uniform melting and mixing to obtain the polyvinyl chloride antibacterial composite material.
Example 2
(1) Adding 2g of maleic anhydride grafted polyvinyl chloride and 0.12g of 2-aminopyridine urea benzoic acid into dimethylbenzene, stirring and grafting at 35 ℃ for 5h in a nitrogen atmosphere, then reacting at 130 ℃ for 12h, drying in vacuum after reaction, washing the product with distilled water and ethanol, and obtaining the pyridylbenzoic acid grafted polyvinyl chloride.
(2) Adding 5g of pyridine benzoic acid grafted polyvinyl chloride into N, N-dimethylformamide, stirring to dissolve, adding 0.6g of 1-chlorotetradecane, heating to 110 ℃, reacting for 24 hours, cooling and vacuum drying after reaction, and washing a product by using distilled water and ethanol to obtain the pyridine benzoic acid grafted polyvinyl chloride.
(3) Adding polyvinyl chloride resin, 15% of pyridinium benzoic acid grafted polyvinyl chloride, 2-4% of calcium zinc stabilizer, 1% of lubricant calcium stearate and 20% of plasticizer DOP into a double-roller mixing roll to mix, then adding 10% of carboxyl nitrile rubber, and performing hot pressing-cold pressing on the materials after uniformly melting and mixing to obtain the polyvinyl chloride antibacterial composite material.
Example 3
(1) Adding 2g of maleic anhydride grafted polyvinyl chloride and 0.22g of 2-aminopyridine urea benzoic acid into N, N-dimethylformamide, stirring and grafting reaction at 35 ℃ for 5h in a nitrogen atmosphere, then reacting at 140 ℃ for 10h, drying in vacuum after reaction, washing the product with distilled water and ethanol, and obtaining the pyridylbenzoic acid grafted polyvinyl chloride.
(2) Adding 5g of pyridine benzoic acid grafted polyvinyl chloride into N, N-dimethylformamide, stirring for dissolving, adding 1g of 1-chlorohexadecane, heating to 110 ℃, reacting for 12 hours, cooling and vacuum drying after reaction, and washing a product by using distilled water and ethanol to obtain the pyridine benzoic acid grafted polyvinyl chloride.
(3) Adding polyvinyl chloride resin, 20% of pyridinium benzoic acid grafted polyvinyl chloride, 4% of calcium-zinc stabilizer, 1% of lubricant stearic acid and 25% of plasticizer DOP into a double-roller mixing roll for mixing, then adding 15% of carboxylic nitrile rubber, and performing hot pressing-cold pressing on the materials after uniform melting and mixing to obtain the polyvinyl chloride antibacterial composite material.
Example 4
(1) Adding 2g of maleic anhydride grafted polyvinyl chloride and 0.3g of 2-aminopyridine urea benzoic acid into N, N-dimethylacetamide, stirring and grafting reaction at 25 ℃ for 4h in a nitrogen atmosphere, then reacting at 120 ℃ for 6h, drying in vacuum after reaction, washing the product with distilled water and ethanol, and obtaining the pyridylbenzoic acid grafted polyvinyl chloride.
(2) Adding 5g of pyridine benzoic acid grafted polyvinyl chloride into N, N-dimethylformamide, stirring to dissolve, adding 1.5g of 1-chlorooctadecane, heating to 110 ℃, reacting for 36 hours, cooling and vacuum drying after reaction, and washing a product by using distilled water and ethanol to obtain the pyridine benzoic acid grafted polyvinyl chloride.
(3) Adding polyvinyl chloride resin, 30% of pyridinium benzoic acid grafted polyvinyl chloride, 4% of stabilizer, 1% of lubricant and 20% of plasticizer into a double-roller mixing roll for mixing, then adding 20% of carboxyl nitrile rubber, and performing hot pressing-cold pressing on the materials after uniform melting and mixing to obtain the polyvinyl chloride antibacterial composite material.
Comparative example 1
(1) Adding 2g of maleic anhydride grafted polyvinyl chloride and 0.2g of 2-aminopyridine urea benzoic acid into N-methylpyrrolidone, stirring and grafting reaction at 35 ℃ for 5h in a nitrogen atmosphere, then reacting at 110 ℃ for 12h, drying in vacuum after reaction, washing the product with distilled water and ethanol, and obtaining the pyridylbenzoic acid grafted polyvinyl chloride.
(2) Adding polyvinyl chloride resin, 15% of pyridine benzoic acid grafted polyvinyl chloride, 3% of calcium-zinc stabilizer, 1% of lubricant stearic acid and 25% of plasticizer DOP into a double-roller mixing roll for mixing, then adding 10% of carboxyl nitrile rubber, and carrying out hot pressing-cold pressing on the materials after uniform melting and mixing to obtain the polyvinyl chloride composite material.
Taking Escherichia coli as a test strain, and preparing activated Escherichia coli liquid and phosphate buffer solution to have a concentration of 10 6 CFU/mL bacterial suspension, then 0.5mL bacterial suspension is transferred and dripped into a film containing agar culture medium and polyvinyl chloride antibacterial composite material, the film is cultured in a constant temperature incubator at 37 ℃ for 24h, and the diameter of the inhibition zone is measured after the culture.
Figure RE-GDA0003788858600000061
The polyvinyl chloride antibacterial composite material is prepared into a strip sample of 12cm multiplied by 4cm multiplied by 0.5cm, the tensile property is tested by a tensile testing machine, and the tensile rate is 5 mm/min.
The polyvinyl chloride antibacterial composite material is prepared into a strip sample of 10cm multiplied by 5cm multiplied by 0.5cm, and the impact resistance is tested by a simple beam impact tester.
Figure RE-GDA0003788858600000062
The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be regarded as equivalent replacements within the protection scope of the present invention.

Claims (7)

1. A preparation method of a polyvinyl chloride antibacterial composite material is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) adding 4-isocyanate benzoic acid and 2-amino-5- (aminomethyl) pyridine into tetrahydrofuran, and reacting at room temperature to obtain 2-aminopyridine carbamido benzoic acid; then adding maleic anhydride grafted polyvinyl chloride and 2-aminopyridine urea benzoic acid into the solvent, stirring the mixture in a nitrogen atmosphere for grafting reaction, drying the mixture in vacuum after the reaction, and washing the product by distilled water and ethanol to obtain the pyridylbenzoic acid grafted polyvinyl chloride;
(2) adding pyridine benzoic acid grafted polyvinyl chloride into N, N-dimethylformamide, stirring for dissolving, and adding alkyl chloride (C) n H 2n+1 Cl and n are 10-18), heating to 80-110 ℃, reacting for 12-36h, cooling after reaction, drying in vacuum, washing the product with distilled water and ethanol to obtain pyridinium benzoic acid grafted polyvinyl chloride;
(3) adding polyvinyl chloride resin, pyridine salt benzoic acid grafted polyvinyl chloride and an auxiliary agent into a double-roller mixing roll for mixing, then adding carboxyl nitrile rubber, and performing hot pressing-cold pressing on the materials after uniform melting and mixing to obtain the polyvinyl chloride antibacterial composite material.
2. The preparation method of the polyvinyl chloride antibacterial composite material according to claim 1, wherein the preparation method comprises the following steps: the solvent in the step (1) comprises N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and xylene.
3. The preparation method of the polyvinyl chloride antibacterial composite material according to claim 1, wherein the preparation method comprises the following steps: the dosage of the maleic anhydride grafted polyvinyl chloride in the step (1) is 100 parts by weight, and the dosage of the 2-aminopyridine urea benzoic acid is 3-15 parts by weight.
4. The preparation method of the polyvinyl chloride antibacterial composite material according to claim 1, wherein the preparation method comprises the following steps: the grafting reaction in the step (1) is carried out at 20-35 ℃ for 3-5h and then at 110-140 ℃ for 6-12 h.
5. The preparation method of the polyvinyl chloride antibacterial composite material according to claim 1, wherein the preparation method comprises the following steps: the usage amount of the pyridylbenzoic acid grafted polyvinyl chloride in the step (2) is 100 parts by weight, and the alkyl chloride is 5-30 parts by weight.
6. The preparation method of the polyvinyl chloride antibacterial composite material according to claim 1, wherein the preparation method comprises the following steps: the auxiliary agent in the step (3) comprises 2-4% of stabilizer, 1-2% of lubricant and 20-30% of plasticizer.
7. The preparation method of the polyvinyl chloride antibacterial composite material according to claim 1, wherein the preparation method comprises the following steps: in the step (3), the dosage of the pyridinium benzoic acid grafted polyvinyl chloride is 6-30% and the dosage of the carboxylated nitrile rubber is 5-20%.
CN202210861666.0A 2022-07-20 2022-07-20 Preparation method and application of polyvinyl chloride antibacterial composite material Pending CN115011048A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115850884A (en) * 2022-12-27 2023-03-28 义乌市希福防护用品有限公司 Preparation method of isolation and protection mask material with antibacterial function
CN116813998A (en) * 2023-07-05 2023-09-29 湖南盛业土工材料制造有限公司 Conductive composite geomembrane
CN117089105A (en) * 2023-07-25 2023-11-21 江苏隆科明泰新材料科技有限公司 Manufacturing process and application of polyvinyl chloride coiled material floor based on closed cell foaming technology
CN117586702A (en) * 2024-01-19 2024-02-23 海阳市凌晖包装有限公司 Self-adhesive protective film for PP decorative plate and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103073907A (en) * 2011-10-26 2013-05-01 中国石油化工股份有限公司 Antibacterial thermoplastic plastic composition and preparation method thereof
JP2020158759A (en) * 2019-03-25 2020-10-01 積水化学工業株式会社 Method for producing maleic anhydride modified polyvinyl chloride resin composition
CN111944232A (en) * 2019-05-17 2020-11-17 中国石油化工股份有限公司 Antibacterial plastic composition and preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103073907A (en) * 2011-10-26 2013-05-01 中国石油化工股份有限公司 Antibacterial thermoplastic plastic composition and preparation method thereof
JP2020158759A (en) * 2019-03-25 2020-10-01 積水化学工業株式会社 Method for producing maleic anhydride modified polyvinyl chloride resin composition
CN111944232A (en) * 2019-05-17 2020-11-17 中国石油化工股份有限公司 Antibacterial plastic composition and preparation method and application thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115850884A (en) * 2022-12-27 2023-03-28 义乌市希福防护用品有限公司 Preparation method of isolation and protection mask material with antibacterial function
CN115850884B (en) * 2022-12-27 2024-03-19 义乌市希福防护用品有限公司 Preparation method of isolation protective mask material with antibacterial function
CN116813998A (en) * 2023-07-05 2023-09-29 湖南盛业土工材料制造有限公司 Conductive composite geomembrane
CN116813998B (en) * 2023-07-05 2024-03-22 湖南盛业土工材料制造有限公司 Conductive composite geomembrane
CN117089105A (en) * 2023-07-25 2023-11-21 江苏隆科明泰新材料科技有限公司 Manufacturing process and application of polyvinyl chloride coiled material floor based on closed cell foaming technology
CN117586702A (en) * 2024-01-19 2024-02-23 海阳市凌晖包装有限公司 Self-adhesive protective film for PP decorative plate and preparation method thereof
CN117586702B (en) * 2024-01-19 2024-03-22 海阳市凌晖包装有限公司 Self-adhesive protective film for PP decorative plate and preparation method thereof

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