CN116080112B - Antibacterial composite film for medical instrument and preparation method thereof - Google Patents
Antibacterial composite film for medical instrument and preparation method thereof Download PDFInfo
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- CN116080112B CN116080112B CN202211233524.6A CN202211233524A CN116080112B CN 116080112 B CN116080112 B CN 116080112B CN 202211233524 A CN202211233524 A CN 202211233524A CN 116080112 B CN116080112 B CN 116080112B
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 83
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000004698 Polyethylene Substances 0.000 claims abstract description 57
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims abstract description 38
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000004715 ethylene vinyl alcohol Substances 0.000 claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 63
- 229920001223 polyethylene glycol Polymers 0.000 claims description 63
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 52
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 47
- 238000002156 mixing Methods 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 238000002791 soaking Methods 0.000 claims description 30
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 26
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 25
- 238000012545 processing Methods 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 23
- 229920001661 Chitosan Polymers 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 13
- DZAUWHJDUNRCTF-UHFFFAOYSA-N 3-(3,4-dihydroxyphenyl)propanoic acid Chemical compound OC(=O)CCC1=CC=C(O)C(O)=C1 DZAUWHJDUNRCTF-UHFFFAOYSA-N 0.000 claims description 13
- 229920002873 Polyethylenimine Polymers 0.000 claims description 13
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 11
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 11
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 238000005266 casting Methods 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 230000004888 barrier function Effects 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- 238000013461 design Methods 0.000 abstract description 3
- 238000004806 packaging method and process Methods 0.000 abstract description 3
- 238000004321 preservation Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 12
- 230000007704 transition Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000007654 immersion Methods 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 239000012785 packaging film Substances 0.000 description 4
- 229920006280 packaging film Polymers 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001795 light effect Effects 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/048—Forming gas barrier coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/056—Forming hydrophilic coatings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
- B29K2105/0011—Biocides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use 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 alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use 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; Derivatives of such polymers
- C08J2433/04—Characterised by the use 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; Derivatives of such polymers esters
- C08J2433/14—Characterised by the use 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; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
- C08J2433/16—Homopolymers or copolymers of esters containing halogen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/02—Polyamines
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Abstract
The application relates to the technical field of antibacterial composite films, in particular to an antibacterial composite film for medical instruments and a preparation method thereof; according to the scheme, PE, EVOH, PE is taken as a film material, three layers are co-extruded to prepare a base film which is a PE layer, an EVOH layer and a PE layer from top to bottom, and hydrophilic treatment is carried out on the surface of the base film; the technical design of the scheme is reasonable, the component proportion is proper, the prepared antibacterial composite film not only has excellent antibacterial performance, but also has excellent surface hydrophilicity, the adhesion between the hydrophilic coating and the base film is excellent, the overall barrier performance of the antibacterial composite film is improved, and the antibacterial composite film can be widely applied to the packaging and the preservation of medical instruments and has higher practicability.
Description
Technical Field
The application relates to the technical field of antibacterial composite films, in particular to an antibacterial composite film for medical instruments and a preparation method thereof.
Background
When the existing medical apparatus is transported and stored, the existing medical apparatus is generally required to be stored or transported after being packaged by a packaging film, and a polyethylene film is a common packaging film, but the barrier property of the pure polyethylene film can not meet the actual requirements, so that enterprises often select to use a multi-layer composite film as the packaging film in the research and development process.
Based on the application environment, the packaging film needs to have certain antibacterial performance, excellent barrier performance and waterproof performance, so the application discloses an antibacterial composite film for medical equipment and a preparation method thereof, and the technical problem is solved.
Disclosure of Invention
The application aims to provide an antibacterial composite film for medical equipment and a preparation method thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the application provides the following technical scheme:
a method for preparing an antibacterial composite film for medical equipment, comprising the following steps:
(1) Adding PE, EVOH, PE into an extruder in sequence, carrying out three-layer coextrusion after melting, casting into a sheet, and processing to obtain a base film, wherein the base film comprises a PE layer, an EVOH layer and a PE layer from top to bottom in sequence;
(2) Mixing polyethylenimine and Tris-HCl, adding catechol chitosan and multi-arm polyethylene glycol containing catechol groups, and stirring for 20-30 min to obtain antibacterial impregnating solution;
soaking the base film in the antibacterial soaking liquid for 6-8 h, taking out deionized water for washing, and airing to obtain a pretreated base film;
(3) Mixing methacryloxyethyl trimethyl ammonium chloride, trimethylolpropane triacrylate, a photoinitiator and ethanol, and uniformly stirring to obtain hydrophilic impregnation liquid;
and (3) soaking the pretreated base film in hydrophilic impregnating solution, curing for 6-8 min under ultraviolet light, taking out, washing with deionized water, and vacuum drying to obtain the antibacterial composite film.
In the more optimized scheme, in the step (1), the thickness of the EVOH layer is 6-8 mu m, and the thickness of the PE layer is 30-32 mu m; the processing temperature of the PE layer was 180℃and the processing temperature of the EVOH layer was 210 ℃.
In a more optimized scheme, in the step (2), the preparation steps of the multi-arm polyethylene glycol containing catechol groups are as follows: mixing 3, 4-dihydroxybenzene propionic acid, acrylic acid, N-hydroxysuccinimide and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, and stirring in a water bath at 0-5 ℃ until the mixture is dissolved to obtain a solution A;
mixing terminal amino multi-arm polyethylene glycol with dichloromethane, stirring to uniformity, adding the solution A, continuing to react for 10-12 h at 25-30 ℃, and collecting the product after the reaction is finished to obtain the multi-arm polyethylene glycol containing catechol groups.
In an optimized scheme, the molar ratio of the amino-terminated multi-arm polyethylene glycol to the 3, 4-dihydroxybenzene propionic acid to the acrylic acid is 1:2.2:2.2.
the preparation method of the amino-terminated multi-arm polyethylene glycol comprises the following steps of:
s1: mixing p-toluenesulfonyl chloride and pyridine to obtain a p-toluenesulfonyl chloride mixed solution; mixing multi-arm polyethylene glycol and methylene dichloride, stirring until the multi-arm polyethylene glycol and methylene dichloride are dissolved, dripping p-toluenesulfonyl chloride mixed solution, stirring and reacting for 20-24 hours at 25-30 ℃, washing an organic phase with hydrochloric acid, purifying, washing, and vacuum drying to obtain a material B;
s2: mixing the material B with ammonia water, performing airtight reaction in an autoclave for 6-7 h at the reaction temperature of 140-145 ℃, cooling to room temperature, extracting with dichloromethane, purifying and washing, and drying with anhydrous sodium sulfate to obtain the amino-terminated multi-arm polyethylene glycol.
More optimized scheme, the multi-arm polyethylene glycol is any one of three-arm polyethylene glycol and four-arm polyethylene glycol; the mol ratio of the p-toluenesulfonyl chloride to the multi-arm polyethylene glycol is (4-5): 1.
in the more optimized scheme, in the step (2), the mass ratio of the polyethyleneimine, the catechol chitosan and the multi-arm polyethylene glycol containing catechol groups in the antibacterial impregnating solution is 3:1:2.
in the more optimized scheme, in the step (3), the mass ratio of the methacryloyloxyethyl trimethyl ammonium chloride to the trimethylolpropane triacrylate is 9:1, the dosage of the photoinitiator is 3-4wt% of the methacryloyloxyethyl trimethyl ammonium chloride.
According to a more optimized scheme, the antibacterial composite membrane is prepared by the preparation method of the antibacterial composite membrane for the medical instrument.
Compared with the prior art, the application has the following beneficial effects:
the application discloses an antibacterial composite film for medical instruments and a preparation method thereof, wherein PE, EVOH, PE is taken as a film material, three layers are co-extruded to prepare a base film which is a PE layer, an EVOH layer and a PE layer from top to bottom.
Based on the scheme, in order to further improve the comprehensive performance of the base film, the scheme firstly utilizes polyethyleneimine, catechol chitosan and multi-arm polyethylene glycol containing catechol groups to prepare antibacterial impregnating solution, and impregnates a transition layer on the surface of the base film, and the aim is that: on one hand, the antibacterial component chitosan is introduced into the antibacterial impregnating solution, so that the antibacterial performance of the surface of the base film can be improved; on the other hand, according to the scheme, catechol modification is carried out on chitosan, multi-arm polyethylene glycol containing catechol is prepared, and is blended with polyethyleneimine, so that a dopamine-like transition layer can be formed on the surface of a base membrane, and the transition layer can improve the combination property between the base membrane and a subsequent membrane layer; meanwhile, the dopamine transition layer is immersed on the surface of the base film, so that a hole sealing effect can be achieved, and the barrier property of the antibacterial composite film can be further improved.
Based on a dopamine-like transition layer, the scheme is that a pretreatment base film is placed in hydrophilic impregnating solution, methacrylic oxyethyl trimethyl ammonium chloride is used as a hydrophilic monomer, trimethylolpropane triacrylate is used as a cross-linking agent, and ultraviolet curing is carried out under the action of a photoinitiator, so that a hydrophilic film surface is formed on the surface of the pretreatment base film, and the hydrophilic performance and the antifouling performance of the antibacterial composite film are improved. Due to the existence of the dopamine-like transition layer, the surface of the dopamine-like transition layer contains a large amount of C=C, and is crosslinked under the subsequent ultraviolet light effect, so that the adhesion performance between the hydrophilic film layer and the base film is more excellent.
When the multi-arm polyethylene glycol containing catechol groups is prepared, firstly, carrying out end amination treatment on the multi-arm polyethylene glycol, and then utilizing the carboxyl reaction of amino groups and acrylic acid to introduce C=C; reacts with carboxyl in 3, 4-dihydroxybenzene propionic acid to introduce catechol bond, so as to ensure deposition of dopamine-like transition layer and subsequent application of hydrophilic coating. Here, it is emphasized that: compared with the conventional polyethylene glycol, the multi-arm polyethylene glycol has more active sites, is more compact in crosslinking during crosslinking, has more excellent hole sealing effect on a base film and has higher barrier property; meanwhile, the waterproof performance of the antibacterial composite film can be improved.
The scheme discloses an antibacterial composite film for medical instruments and a preparation method thereof, the process design is reasonable, the component ratio is proper, the prepared antibacterial composite film not only has excellent antibacterial performance, but also has excellent surface hydrophilicity, the adhesiveness between a hydrophilic coating and a base film is excellent, the overall barrier performance of the antibacterial composite film is improved, and the antibacterial composite film can be widely used for packaging and preserving medical instruments and has higher practicability.
Detailed Description
The following description of the technical solutions in the embodiments of the present application will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
In this example, p-toluenesulfonyl chloride, pyridine, dichloromethane, ammonia (a 834475), tetra-arm polyethylene glycol (a 875173, mw=5000) were all purchased from microphone agents; chitosan (C850346), acrylic acid, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, N-hydroxysuccinimide were all purchased from microphone agents; 3, 4-dihydroxybenzene propionic acid was purchased from Alfa Aesar company; polyethyleneimine (mw=10000), trimethylolpropane triacrylate, all purchased from Shanghai Ala Biochemical technologies Co., ltd; methacryloxyethyl trimethylammonium chloride was purchased from the scientific company of belkyo belgium; the photoinitiator was 2-hydroxy-2-methylpropionacetone, available from Shanghai Ala Biochemical technologies Co., ltd. EVOH is an ethylene-vinyl alcohol copolymer with an ethylene content of 32% available from Kunshan Huayi plastics Co., ltd; PE is high density polyethylene (5000S), available from Beijing bird' S petrochemical Co., ltd.
In the following examples, the preparation steps of the amino-terminated quadrifilar polyethylene glycol were:
s1: mixing p-toluenesulfonyl chloride (100 mmol) with pyridine to obtain a p-toluenesulfonyl chloride mixed solution; the concentration of the p-toluenesulfonyl chloride mixture was 0.6mmol/mL. Mixing four-arm polyethylene glycol (20 mmol) and 200mL of dichloromethane, stirring until the mixture is dissolved, dropwise adding p-toluenesulfonyl chloride mixed solution, stirring at 25 ℃ for reaction for 24 hours, washing an organic phase with hydrochloric acid, purifying, washing, and vacuum drying to obtain a material B.
S2: mixing the material B (10 mmol) with 120mL of ammonia water, performing airtight reaction in an autoclave for 6 hours, cooling to room temperature at 140 ℃, extracting with dichloromethane, purifying and washing, and drying with anhydrous sodium sulfate to obtain amino-terminated quadrifilar polyethylene glycol.
The preparation method of catechol chitosan comprises the following steps: taking chitosan (3.25 mmol) and 5mL hydrochloric acid (the concentration is 1 mol/L), uniformly mixing, adding 45mL deionized water, and adjusting the pH to 5 by sodium hydroxide to obtain a chitosan solution; 3, 4-dihydroxybenzene propionic acid (3.25 mmol) is dissolved in 5mL of deionized water, mixed and added into chitosan solution, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, N-hydroxysuccinimide, 25mL of deionized water and 25mL of ethanol mixed solution are added, stirring reaction is carried out for 10h at 25 ℃, and catechol chitosan is obtained after dialysis and freeze drying. The molar ratio of the chitosan to the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride to the N-hydroxysuccinimide is 2:1:1.
example 1:
a method for preparing an antibacterial composite film for medical equipment, comprising the following steps:
(1) Sequentially adding 100 parts by mass of PE, 100 parts by mass of EVOH and 100 parts by mass of PE into an extruder, carrying out three-layer coextrusion after melting, casting into a sheet, and processing to obtain a base film, wherein the base film sequentially comprises a PE layer, an EVOH layer and a PE layer from top to bottom; the thickness of the EVOH layer is 8 mu m, and the thickness of the PE layer is 30 mu m; the processing temperature of the PE layer was 180℃and the processing temperature of the EVOH layer was 210 ℃.
(2) Mixing 3, 4-dihydroxybenzene propionic acid (2.2 mmol), acrylic acid (2.2 mmol), N-hydroxysuccinimide (5 mmol) and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (5 mmol), and stirring in a water bath at 0 ℃ until the mixture is dissolved to obtain a solution A;
mixing amino-terminated quadrifilar polyethylene glycol (1 mmol) and 50mL of dichloromethane, stirring to uniformity, adding the solution A, continuing to react for 12h at 25 ℃, and collecting the product after the reaction is finished to obtain the multi-arm polyethylene glycol containing catechol groups.
(3) Mixing 30mg of polyethyleneimine and 30mL of Tris-HCl, adding 10mg of catechol chitosan and 20mg of multi-arm polyethylene glycol containing catechol groups, and stirring for 20min to obtain an antibacterial impregnating solution.
Soaking the base film in antibacterial soaking liquid for 6 hours, taking out deionized water for washing, and airing to obtain a pretreated base film; when the base film is immersed in the antibacterial immersion liquid, the bath ratio is 1:10.
(4) Mixing methacryloyloxyethyl trimethyl ammonium chloride, trimethylolpropane triacrylate, 0.16g of photoinitiator and 20g of ethanol, and stirring uniformly to obtain hydrophilic impregnating solution; the mass ratio of the methacryloyloxyethyl trimethyl ammonium chloride to the trimethylolpropane triacrylate is 9:1, wherein the dosage of the photoinitiator is 4wt% of that of the methacryloyloxyethyl trimethyl ammonium chloride.
Soaking the pretreated base film in hydrophilic soaking liquid, wherein the bath ratio is 1:8, 8; curing for 6min under ultraviolet light (365 nm), taking out, washing with deionized water, and vacuum drying to obtain the antibacterial composite film.
Example 2:
a method for preparing an antibacterial composite film for medical equipment, comprising the following steps:
(1) Sequentially adding 100 parts by mass of PE, 100 parts by mass of EVOH and 100 parts by mass of PE into an extruder, carrying out three-layer coextrusion after melting, casting into a sheet, and processing to obtain a base film, wherein the base film sequentially comprises a PE layer, an EVOH layer and a PE layer from top to bottom; the thickness of the EVOH layer is 8 mu m, and the thickness of the PE layer is 30 mu m; the processing temperature of the PE layer was 180℃and the processing temperature of the EVOH layer was 210 ℃.
(2) Mixing 3, 4-dihydroxybenzene propionic acid (2.2 mmol), acrylic acid (2.2 mmol), N-hydroxysuccinimide (5 mmol) and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (5 mmol), and stirring in a water bath at 0 ℃ until the mixture is dissolved to obtain a solution A;
mixing amino-terminated quadrifilar polyethylene glycol (1 mmol) and 50mL of dichloromethane, stirring to uniformity, adding the solution A, continuing to react for 11h at 30 ℃, and collecting the product after the reaction is finished to obtain the multi-arm polyethylene glycol containing catechol groups.
(3) Mixing 30mg of polyethyleneimine and 30mL of Tris-HCl, adding 10mg of catechol chitosan and 20mg of multi-arm polyethylene glycol containing catechol groups, and stirring for 25min to obtain an antibacterial impregnating solution.
Soaking the base film in antibacterial soaking liquid for 7 hours, taking out deionized water for washing, and airing to obtain a pretreated base film; when the base film is immersed in the antibacterial immersion liquid, the bath ratio is 1:10.
(4) Mixing methacryloyloxyethyl trimethyl ammonium chloride, trimethylolpropane triacrylate, 0.16g of photoinitiator and 20g of ethanol, and stirring uniformly to obtain hydrophilic impregnating solution; the mass ratio of the methacryloyloxyethyl trimethyl ammonium chloride to the trimethylolpropane triacrylate is 9:1, wherein the dosage of the photoinitiator is 4wt% of that of the methacryloyloxyethyl trimethyl ammonium chloride.
Soaking the pretreated base film in hydrophilic soaking liquid, wherein the bath ratio is 1:8, 8; curing for 7min under ultraviolet light (365 nm), taking out, washing with deionized water, and vacuum drying to obtain the antibacterial composite film.
Example 3:
a method for preparing an antibacterial composite film for medical equipment, comprising the following steps:
(1) Sequentially adding 100 parts by mass of PE, 100 parts by mass of EVOH and 100 parts by mass of PE into an extruder, carrying out three-layer coextrusion after melting, casting into a sheet, and processing to obtain a base film, wherein the base film sequentially comprises a PE layer, an EVOH layer and a PE layer from top to bottom; the thickness of the EVOH layer is 8 mu m, and the thickness of the PE layer is 30 mu m; the processing temperature of the PE layer was 180℃and the processing temperature of the EVOH layer was 210 ℃.
(2) Mixing 3, 4-dihydroxybenzene propionic acid (2.2 mmol), acrylic acid (2.2 mmol), N-hydroxysuccinimide (5 mmol) and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (5 mmol), and stirring in a water bath at 0 ℃ until the mixture is dissolved to obtain a solution A;
mixing amino-terminated quadrifilar polyethylene glycol (1 mmol) and 50mL of dichloromethane, stirring to uniformity, adding the solution A, continuously reacting for 12h at 30 ℃, and collecting the product after the reaction is finished to obtain the multi-arm polyethylene glycol containing catechol groups.
(3) Mixing 30mg of polyethyleneimine and 30mL of Tris-HCl, adding 10mg of catechol chitosan and 20mg of multi-arm polyethylene glycol containing catechol groups, and stirring for 30min to obtain an antibacterial impregnating solution.
Soaking the base film in antibacterial soaking liquid for 8 hours, taking out deionized water for washing, and airing to obtain a pretreated base film; when the base film is immersed in the antibacterial immersion liquid, the bath ratio is 1:10.
(4) Mixing methacryloyloxyethyl trimethyl ammonium chloride, trimethylolpropane triacrylate, 0.16g of photoinitiator and 20g of ethanol, and stirring uniformly to obtain hydrophilic impregnating solution; the mass ratio of the methacryloyloxyethyl trimethyl ammonium chloride to the trimethylolpropane triacrylate is 9:1, wherein the dosage of the photoinitiator is 4wt% of that of the methacryloyloxyethyl trimethyl ammonium chloride.
Soaking the pretreated base film in hydrophilic soaking liquid, wherein the bath ratio is 1:8, 8; curing for 8min under ultraviolet light (365 nm), taking out, washing with deionized water, and vacuum drying to obtain the antibacterial composite film.
Comparative example 1:
a method for preparing an antibacterial composite film for medical equipment, comprising the following steps:
(1) Sequentially adding 100 parts by mass of PE, 100 parts by mass of EVOH and 100 parts by mass of PE into an extruder, carrying out three-layer coextrusion after melting, casting into a sheet, and processing to obtain a base film, wherein the base film sequentially comprises a PE layer, an EVOH layer and a PE layer from top to bottom; the thickness of the EVOH layer is 8 mu m, and the thickness of the PE layer is 30 mu m; the processing temperature of the PE layer was 180℃and the processing temperature of the EVOH layer was 210 ℃.
(2) Mixing 3, 4-dihydroxybenzene propionic acid (2.2 mmol), acrylic acid (2.2 mmol), N-hydroxysuccinimide (5 mmol) and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (5 mmol), and stirring in a water bath at 0 ℃ until the mixture is dissolved to obtain a solution A;
mixing amino-terminated quadrifilar polyethylene glycol (1 mmol) and 50mL of dichloromethane, stirring to uniformity, adding the solution A, continuously reacting for 12h at 30 ℃, and collecting the product after the reaction is finished to obtain the multi-arm polyethylene glycol containing catechol groups.
(3) Mixing 30mg of polyethyleneimine and 30mL of Tris-HCl, adding 10mg of chitosan and 20mg of multi-arm polyethylene glycol containing catechol groups, and stirring for 30min to obtain an antibacterial impregnating solution.
Soaking the base film in antibacterial soaking liquid for 8 hours, taking out deionized water for washing, and airing to obtain a pretreated base film; when the base film is immersed in the antibacterial immersion liquid, the bath ratio is 1:10.
(4) Mixing methacryloyloxyethyl trimethyl ammonium chloride, trimethylolpropane triacrylate, 0.16g of photoinitiator and 20g of ethanol, and stirring uniformly to obtain hydrophilic impregnating solution; the mass ratio of the methacryloyloxyethyl trimethyl ammonium chloride to the trimethylolpropane triacrylate is 9:1, wherein the dosage of the photoinitiator is 4wt% of that of the methacryloyloxyethyl trimethyl ammonium chloride.
Soaking the pretreated base film in hydrophilic soaking liquid, wherein the bath ratio is 1:8, 8; curing for 8min under ultraviolet light (365 nm), taking out, washing with deionized water, and vacuum drying to obtain the antibacterial composite film.
With example 3 as a control, no catechol chitosan was introduced in comparative example 1, only chitosan was added, and the rest of the procedure was unchanged.
Comparative example 2:
a method for preparing an antibacterial composite film for medical equipment, comprising the following steps:
(1) Sequentially adding 100 parts by mass of PE, 100 parts by mass of EVOH and 100 parts by mass of PE into an extruder, carrying out three-layer coextrusion after melting, casting into a sheet, and processing to obtain a base film, wherein the base film sequentially comprises a PE layer, an EVOH layer and a PE layer from top to bottom; the thickness of the EVOH layer is 8 mu m, and the thickness of the PE layer is 30 mu m; the processing temperature of the PE layer was 180℃and the processing temperature of the EVOH layer was 210 ℃.
(2) Mixing 3, 4-dihydroxybenzene propionic acid (1.2 mmol), acrylic acid (1.2 mmol), N-hydroxysuccinimide (3 mmol) and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (3 mmol), and stirring in a water bath at 0 ℃ until the mixture is dissolved to obtain a solution A;
mixing amino-terminated polyethylene glycol (1 mmol) and 50mL of dichloromethane, stirring to uniformity, adding the solution A, continuing to react for 12h at 30 ℃, and collecting the product after the reaction is finished to obtain the multi-arm polyethylene glycol containing catechol groups. The molar ratio of the amino-terminated polyethylene glycol to the 3, 4-dihydroxybenzene propionic acid to the acrylic acid is 1:1.2:1.2.
(3) Mixing 30mg of polyethyleneimine and 30mL of Tris-HCl, adding 10mg of catechol chitosan and 20mg of multi-arm polyethylene glycol containing catechol groups, and stirring for 30min to obtain an antibacterial impregnating solution.
Soaking the base film in antibacterial soaking liquid for 8 hours, taking out deionized water for washing, and airing to obtain a pretreated base film; when the base film is immersed in the antibacterial immersion liquid, the bath ratio is 1:10.
(4) Mixing methacryloyloxyethyl trimethyl ammonium chloride, trimethylolpropane triacrylate, 0.16g of photoinitiator and 20g of ethanol, and stirring uniformly to obtain hydrophilic impregnating solution; the mass ratio of the methacryloyloxyethyl trimethyl ammonium chloride to the trimethylolpropane triacrylate is 9:1, wherein the dosage of the photoinitiator is 4wt% of that of the methacryloyloxyethyl trimethyl ammonium chloride.
Soaking the pretreated base film in hydrophilic soaking liquid, wherein the bath ratio is 1:8, 8; curing for 8min under ultraviolet light (365 nm), taking out, washing with deionized water, and vacuum drying to obtain the antibacterial composite film.
With example 3 as a control, the four-arm polyethylene glycol was replaced with polyethylene glycol in comparative example 2, and amino-terminated polyethylene glycol was prepared as described above, with the molar ratio of p-toluenesulfonyl chloride to four-arm polyethylene glycol replaced with 3:1, preparing a composite membrane by utilizing amino-terminated polyethylene glycol, and keeping the rest steps unchanged.
Comparative example 3:
a method for preparing an antibacterial composite film for medical equipment, comprising the following steps:
(1) Sequentially adding 100 parts by mass of PE, 100 parts by mass of EVOH and 100 parts by mass of PE into an extruder, carrying out three-layer coextrusion after melting, casting into a sheet, and processing to obtain a base film, wherein the base film sequentially comprises a PE layer, an EVOH layer and a PE layer from top to bottom; the thickness of the EVOH layer is 8 mu m, and the thickness of the PE layer is 30 mu m; the processing temperature of the PE layer was 180℃and the processing temperature of the EVOH layer was 210 ℃.
(2) Mixing acrylic acid (2.2 mmol), N-hydroxysuccinimide (3 mmol) and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (3 mmol), and stirring in a water bath at 0 ℃ until the mixture is dissolved to obtain a solution A;
mixing amino-terminated four-arm polyethylene glycol (1 mmol) and 50mL of dichloromethane, stirring to uniformity, adding the solution A, continuing to react for 12h at 30 ℃, and collecting the product after the reaction is finished to obtain the multi-arm polyethylene glycol.
(3) Mixing 30mg of polyethylenimine and 30mL of Tris-HCl, adding 10mg of catechol chitosan and 20mg of multi-arm polyethylene glycol, and stirring for 30min to obtain an antibacterial impregnation liquid.
Soaking the base film in antibacterial soaking liquid for 8 hours, taking out deionized water for washing, and airing to obtain a pretreated base film; when the base film is immersed in the antibacterial immersion liquid, the bath ratio is 1:10.
(4) Mixing methacryloyloxyethyl trimethyl ammonium chloride, trimethylolpropane triacrylate, 0.16g of photoinitiator and 20g of ethanol, and stirring uniformly to obtain hydrophilic impregnating solution; the mass ratio of the methacryloyloxyethyl trimethyl ammonium chloride to the trimethylolpropane triacrylate is 9:1, wherein the dosage of the photoinitiator is 4wt% of that of the methacryloyloxyethyl trimethyl ammonium chloride.
Soaking the pretreated base film in hydrophilic soaking liquid, wherein the bath ratio is 1:8, 8; curing for 8min under ultraviolet light (365 nm), taking out, washing with deionized water, and vacuum drying to obtain the antibacterial composite film.
With example 3 as a control, the catechol group was not grafted to the multi-arm polyethylene glycol in comparative example 3, and the rest of the procedure was unchanged.
Detection experiment:
1. a base film was prepared according to the method disclosed in examples 1-3, dumbbell-shaped samples were prepared according to the method disclosed in GB/T13022-1991, the yield strength was tested, the stretching was performed at a stretching speed of 5mm/min at the time of the test, and 10 samples were tested to average.
| Project | Example 1 | Example 2 | Example 3 |
| Yield strength (MPa) | 12.6 | 12.7 | 12.6 |
2. Taking the antibacterial composite films prepared in the examples 1-3 and the comparative examples 1-3, and performing performance detection;
static water contact angle: the surface water contact angle of the antibacterial composite film was tested, 5 different position points were taken during the test, 3 μl of water was dropped, and the test results were recorded and averaged.
Antibacterial properties: the antibacterial property is tested according to the method disclosed in GB/T2591-2003, and the test strain is Escherichia coli.
Oxygen permeability: the test was carried out according to the method common to GB/T19789-2005, the test sample size being 50cm 2 After testing, the oxygen transmission coefficient was calculated for each group of 5 sample films tested and the average value was recorded for the discs having a test temperature of 25 ℃ and a humidity of 60%.
Water vapor permeability: the test was carried out according to the method common to GB/T2653-2010, the test sample size being 10cm 2 After testing, the water vapor transmission coefficient was calculated, 5 sample films were tested for each group and the average value was recorded. The test temperature was 25℃and the humidity was 60%.
Adhesion rating: the adhesion between the base film surface coating and the base film was tested according to GB/T9286-2021, the dicing method was deeply diced through to the base film, tested and rated.
Conclusion: the scheme discloses an antibacterial composite film for medical instruments and a preparation method thereof, the process design is reasonable, the component ratio is proper, the prepared antibacterial composite film not only has excellent antibacterial performance, but also has excellent surface hydrophilicity, the adhesiveness between a hydrophilic coating and a base film is excellent, the overall barrier performance of the antibacterial composite film is improved, and the antibacterial composite film can be widely used for packaging and preserving medical instruments and has higher practicability.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present application, and the present application is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present application has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (6)
1. The preparation method of the antibacterial composite film for the medical instrument is characterized by comprising the following steps of: the method comprises the following steps:
(1) Adding PE, EVOH, PE into an extruder in sequence, carrying out three-layer coextrusion after melting, casting into a sheet, and processing to obtain a base film, wherein the base film comprises a PE layer, an EVOH layer and a PE layer from top to bottom in sequence;
(2) Mixing polyethylenimine and Tris-HCl, adding catechol chitosan and multi-arm polyethylene glycol containing catechol groups, and stirring for 20-30 min to obtain antibacterial impregnating solution; the mass ratio of the polyethyleneimine to the catechol chitosan to the multi-arm polyethylene glycol containing catechol groups in the antibacterial impregnating solution is 3:1:2;
soaking the base film in the antibacterial soaking liquid for 6-8 h, taking out deionized water for washing, and airing to obtain a pretreated base film;
(3) Mixing methacryloxyethyl trimethyl ammonium chloride, trimethylolpropane triacrylate, a photoinitiator and ethanol, and uniformly stirring to obtain hydrophilic impregnation liquid; the mass ratio of the methacryloyloxyethyl trimethyl ammonium chloride to the trimethylolpropane triacrylate is 9:1, the dosage of the photoinitiator is 3-4wt% of methacryloyloxyethyl trimethyl ammonium chloride;
soaking the pretreated base film in hydrophilic impregnating solution, curing for 6-8 min under ultraviolet light, taking out, washing with deionized water, and vacuum drying to obtain an antibacterial composite film;
wherein the preparation steps of the multi-arm polyethylene glycol containing catechol groups are as follows: mixing 3, 4-dihydroxybenzene propionic acid, acrylic acid, N-hydroxysuccinimide and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, and stirring in a water bath at 0-5 ℃ until the mixture is dissolved to obtain a solution A;
mixing terminal amino multi-arm polyethylene glycol with dichloromethane, stirring to uniformity, adding the solution A, continuing to react for 10-12 h at 25-30 ℃, and collecting the product after the reaction is finished to obtain the multi-arm polyethylene glycol containing catechol groups.
2. The method for preparing an antibacterial composite film for medical equipment according to claim 1, wherein the method comprises the following steps: in the step (1), the thickness of the EVOH layer is 6-8 mu m, and the thickness of the PE layer is 30-32 mu m; the processing temperature of the PE layer was 180℃and the processing temperature of the EVOH layer was 210 ℃.
3. The method for preparing an antibacterial composite film for medical equipment according to claim 2, wherein: the molar ratio of the terminal amino multi-arm polyethylene glycol to the 3, 4-dihydroxybenzene propionic acid to the acrylic acid is 1:2.2:2.2.
4. the method for preparing an antibacterial composite film for medical equipment according to claim 2, wherein: the preparation method of the amino-terminated multi-arm polyethylene glycol comprises the following steps:
s1: mixing p-toluenesulfonyl chloride and pyridine to obtain a p-toluenesulfonyl chloride mixed solution; mixing multi-arm polyethylene glycol and methylene dichloride, stirring until the multi-arm polyethylene glycol and methylene dichloride are dissolved, dripping p-toluenesulfonyl chloride mixed solution, stirring and reacting for 20-24 hours at 25-30 ℃, washing an organic phase with hydrochloric acid, purifying, washing, and vacuum drying to obtain a material B;
s2: mixing the material B with ammonia water, performing airtight reaction in an autoclave for 6-7 h at the reaction temperature of 140-145 ℃, cooling to room temperature, extracting with dichloromethane, purifying and washing, and drying with anhydrous sodium sulfate to obtain the amino-terminated multi-arm polyethylene glycol.
5. The method for preparing an antibacterial composite film for medical equipment according to claim 4, wherein the method comprises the following steps: in the step S1, the multi-arm polyethylene glycol is any one of three-arm polyethylene glycol and four-arm polyethylene glycol; the mol ratio of the p-toluenesulfonyl chloride to the multi-arm polyethylene glycol is (4-5): 1.
6. an antibacterial composite film prepared by the method for preparing an antibacterial composite film for medical equipment according to any one of claims 1 to 5.
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Denomination of invention: An antibacterial composite film for medical devices and its preparation method Granted publication date: 20230929 Pledgee: Jiangyin branch of Bank of China Ltd. Pledgor: Jiangyin Shenmei packaging material Co.,Ltd. Registration number: Y2024980002440 |
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