CN114656674A - Medical film material containing environment-friendly stabilizer, preparation method and application - Google Patents
Medical film material containing environment-friendly stabilizer, preparation method and application Download PDFInfo
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- CN114656674A CN114656674A CN202210444382.1A CN202210444382A CN114656674A CN 114656674 A CN114656674 A CN 114656674A CN 202210444382 A CN202210444382 A CN 202210444382A CN 114656674 A CN114656674 A CN 114656674A
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- 239000000463 material Substances 0.000 title claims abstract description 83
- 239000003381 stabilizer Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 81
- 239000011347 resin Substances 0.000 claims abstract description 81
- 239000004801 Chlorinated PVC Substances 0.000 claims abstract description 59
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 claims abstract description 59
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 17
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000004806 packaging method and process Methods 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 239000002270 dispersing agent Substances 0.000 claims description 15
- 238000005187 foaming Methods 0.000 claims description 15
- 229920000098 polyolefin Polymers 0.000 claims description 15
- 239000002667 nucleating agent Substances 0.000 claims description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000012530 fluid Substances 0.000 claims description 12
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 claims description 10
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims description 10
- RZRNAYUHWVFMIP-HXUWFJFHSA-N glycerol monolinoleate Natural products CCCCCCCCC=CCCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-HXUWFJFHSA-N 0.000 claims description 10
- 239000005995 Aluminium silicate Substances 0.000 claims description 8
- 235000012211 aluminium silicate Nutrition 0.000 claims description 8
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 8
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 7
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 7
- 229920001169 thermoplastic Polymers 0.000 claims description 7
- 239000004416 thermosoftening plastic Substances 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 229960000892 attapulgite Drugs 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 229910052625 palygorskite Inorganic materials 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 14
- 238000013012 foaming technology Methods 0.000 abstract description 5
- 239000012567 medical material Substances 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 238000004134 energy conservation Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000010096 film blowing Methods 0.000 abstract description 3
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- 229920001610 polycaprolactone Polymers 0.000 description 26
- 239000004800 polyvinyl chloride Substances 0.000 description 9
- 229920000915 polyvinyl chloride Polymers 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 239000005543 nano-size silicon particle Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005034 decoration Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- YAHBZWSDRFSFOO-UHFFFAOYSA-L dimethyltin(2+);2-(2-ethylhexoxy)-2-oxoethanethiolate Chemical compound CCCCC(CC)COC(=O)CS[Sn](C)(C)SCC(=O)OCC(CC)CCCC YAHBZWSDRFSFOO-UHFFFAOYSA-L 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
Classifications
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/26—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
-
- 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
- C08J2207/00—Foams characterised by their intended use
- C08J2207/10—Medical applications, e.g. biocompatible scaffolds
-
- 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
- C08J2327/00—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 a halogen; Derivatives of such polymers
- C08J2327/22—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 a halogen; Derivatives of such polymers modified by chemical after-treatment
- C08J2327/24—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 a halogen; Derivatives of such polymers modified by chemical after-treatment halogenated
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- 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
- C08J2427/00—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 a halogen; Derivatives of such polymers
- C08J2427/22—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 a halogen; Derivatives of such polymers modified by chemical after-treatment
- C08J2427/24—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 a halogen; Derivatives of such polymers modified by chemical after-treatment halogenated
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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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- Chemical Kinetics & Catalysis (AREA)
- Hematology (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Materials For Medical Uses (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a medical film material containing an environment-friendly stabilizer, a preparation method and application thereof, the medical film material containing the environment-friendly stabilizer is prepared by blending modified CPVC resin and PCL resin and processing the blend by a carbon dioxide physical foaming technology, the mechanical property and the flexibility of the medical film material are excellent, and compared with a film blowing processing technology in the prior art, the processing cost is obviously reduced; the medical film material containing the environment-friendly stabilizer can be used for manufacturing medical instruments, medical instrument packaging bags or wound dressings, and the selection range of the medical materials is widened. The preparation method of the medical film material containing the environment-friendly stabilizer, disclosed by the invention, has the advantages of simple operation steps, low requirement on operators, no generation of toxic and harmful substances in the preparation process, and accordance with the requirements of green processing process and energy conservation and emission reduction.
Description
Technical Field
The invention relates to the technical field of medical materials, in particular to a medical film material containing an environment-friendly stabilizer, a preparation method and application.
Background
Polyvinyl chloride (PVC) is one of the most widely used materials, and is widely used for preparing medical films, such as wound dressings, gloves, blood storage bags and other medical devices, and packaging bags for medical devices are mostly prepared from PVC.
Chlorinated polyvinyl chloride (CPVC) resin is a nontoxic and environment-friendly resin material, which is obtained by further chlorinating PVC resin, and compared with a PVC material, the CPVC material has the advantages that the mechanical property and the heat resistance are further improved. At present, CPVC (chlorinated polyvinyl chloride) materials are widely applied to the fields of industrial pipelines, fire-fighting pipelines, household drinking water pipelines and the like. CPVC resins have higher processing temperature and viscosity than PVC resins, and therefore, it is necessary to modify the processing to obtain excellent processability and plasticizing performance, and finally obtain CPVC products with excellent properties. CPVC materials have sufficient hardness and strength for applications, but have insufficient toughness and are generally used as a hard engineering plastic.
The thermoplastic polycaprolactone resin (PCL) is a thermoplastic polyester obtained by ring-opening polymerization of caprolactone, has 5 nonpolar methylene groups and 1 polar ester group on the structural unit, has good flexibility and processability, but is too flexible to be used alone, lacks strength and hardness, and further limits the application range because the melting point is only about 60 ℃. Although the PCL material has biocompatibility and nontoxicity and can be used for medical materials and drug sustained-release systems, the PCL material has the defects of mechanical property and heat resistance, and the application can be further widened only by modifying other materials.
The CPVC material has the softening temperature of over 110 ℃, simultaneously has good hardness and mechanical property, and is completely complementary with the PCL material in performance. In terms of material structure, the polar ester group of the PCL can interact with the C-Cl bond of the CPVC, and the PCL and the CPVC have certain compatibility, so that the PCL and the CPVC are blended and modified to obtain a novel material with more potential in the medical and medical fields.
The carbon dioxide gas foaming technology is a green physical foaming processing method, does not generate any chemical foaming agent residue, has various advantages compared with the traditional chemical foaming method, and is widely accepted by the scientific and industrial circles at home and abroad. However, the literature of preparing the medical film material containing the environmental-friendly stabilizer by adopting the carbon dioxide foaming technology has not been reported.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a medical film material containing an environment-friendly stabilizer, a preparation method and application thereof, the medical film material containing the environment-friendly stabilizer disclosed by the invention is prepared by blending modified CPVC resin and PCL resin and processing the blended resin by a carbon dioxide physical foaming technology, the mechanical property and the flexibility of the medical film material are excellent, and compared with a film blowing processing technology in the prior art, the processing cost is obviously reduced; the medical film material containing the environment-friendly stabilizer can be used for manufacturing medical instruments, medical instrument packaging bags or wound dressings, and the selection range of medical materials is widened. The preparation method of the medical film material containing the environment-friendly stabilizer, disclosed by the invention, has the advantages of simple operation steps, low requirement on operators, no generation of toxic and harmful substances in the preparation process, and accordance with the requirements of green processing process and energy conservation and emission reduction.
In order to achieve the purpose, the technical scheme of the invention is to design a medical film material containing an environment-friendly stabilizer, which comprises the following components in parts by weight: 40-60 parts of modified CPVC resin, 40-60 parts of PCL resin and 0.1-0.5 part of foaming nucleating agent;
based on 100 parts of CPVC resin, the modified CPVC resin is prepared by plasticizing, extruding and granulating 100 parts of CPVC resin, 2.0-3.0 parts of tin methyl mercaptide, 0.5-1.0 part of environment-friendly calcium-zinc stabilizer, 0.5-1.0 part of glycerol monooleate, 0.5-1.0 part of low molecular weight polyolefin and 1-5 parts of dispersant.
The preferable technical scheme is that the modified CPVC resin is prepared by plasticizing, extruding and granulating 100 parts of CPVC resin, 2.5 parts of tin methyl mercaptide, 0.5 part of environment-friendly calcium-zinc stabilizer, 0.5 part of glycerol monooleate, 0.5 part of low-molecular-weight polyolefin and 5 parts of dispersant by 100 parts of CPVC resin.
Further preferably, the polymerization degree of the CPVC resin is 700-800, and the molecular weight of the low molecular weight polyolefin is 1500-5000.
Further preferably, the dispersant is one or more of calcium carbonate, talcum powder, montmorillonite, white carbon black and kaolin.
Further preferably, the foaming nucleating agent is one or more of nano calcium carbonate, nano silicon dioxide, nano montmorillonite, nano zinc oxide, nano alumina, nano titanium dioxide, talcum powder, kaolin and attapulgite.
Further preferably, the PCL resin is thermoplastic crystal polyester obtained by ring-opening polymerization of caprolactone, and the melting point of the PCL resin is within the range of 59-64 ℃.
A preparation method of the medical film material containing the environment-friendly stabilizer comprises the following steps:
s1: according to the weight ratio, placing the CPVC resin, the tin methyl mercaptide, the environment-friendly calcium-zinc stabilizer, the glycerol monooleate, the low-molecular-weight polyolefin and the dispersing agent into a high-speed stirrer, mixing for 10min at 120 ℃ and 5min at 60 ℃, then transferring into a double-screw extruder, and carrying out extrusion granulation at 185 ℃ and at the rotating speed of 35r/min to obtain the modified CPVC resin;
s2: placing the modified CPVC resin, the PCL resin and the foaming nucleating agent into a high-speed stirrer according to the weight part ratio, and mixing for 30min at 50 ℃ to obtain a primary mixed material;
s3: placing the primary mixed material prepared in the step S2 in an internal mixer, and mixing for 5min at 185 ℃ and the rotating speed of 35r/min to obtain a secondary mixed material;
s4: placing the secondary mixed material prepared in the step S3 into a flat vulcanizing machine, and pressing into a film blank of 10mm multiplied by 0.5mm at 185 ℃;
s5: placing the film blank prepared in the step S4 in a pressure container, and treating for 24 hours under the condition of the saturated carbon dioxide gas pressure of 3.5Mpa to obtain a film containing carbon dioxide fluid;
s6: and (5) taking out the film containing the carbon dioxide fluid prepared in the step (S5), immediately placing the film in a water bath at 70 ℃ for treatment for 30S, taking out the film and naturally airing the film to obtain a finished product of the medical film material containing the environment-friendly stabilizer.
The application of the medical film material containing the environment-friendly stabilizer is used for manufacturing medical instruments, medical instrument packaging bags or wound dressings.
The invention has the advantages and beneficial effects that:
1. the medical film material containing the environment-friendly stabilizer is prepared by blending the modified CPVC resin and the PCL resin and processing the mixture by a carbon dioxide physical foaming technology, has excellent mechanical property and flexibility, and obviously reduces the processing cost compared with a film blowing processing technology in the prior art.
2. The medical film material containing the environment-friendly stabilizer disclosed by the invention can be used for manufacturing medical instruments, medical instrument packaging bags or wound dressings, and the selection range of medical materials is widened.
3. The preparation method of the medical film material containing the environment-friendly stabilizer, disclosed by the invention, has the advantages of simple operation steps, low requirement on operators, no generation of toxic and harmful substances in the preparation process, and accordance with the requirements of green processing process and energy conservation and emission reduction.
Detailed Description
The following further describes embodiments of the present invention with reference to examples. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1
A medical film material containing an environment-friendly stabilizer comprises the following components in parts by weight: 50 parts of modified CPVC resin, 50 parts of PCL resin and 0.3 part of foaming nucleating agent;
based on 100 parts of CPVC resin, the modified CPVC resin is prepared by plasticizing, extruding and granulating 100 parts of CPVC resin, 2.5 parts of tin methyl mercaptide, 0.5 part of environment-friendly calcium-zinc stabilizer, 0.5 part of glycerol monooleate, 0.5 part of low molecular weight polyolefin and 5 parts of dispersing agent.
Preferably, the degree of polymerization of the CPVC resin is 700-800, and the molecular weight of the low molecular weight polyolefin is 1500-5000; the dispersant is calcium carbonate; the foaming nucleating agent is nano calcium carbonate; the PCL resin is thermoplastic crystalline polyester obtained by ring-opening polymerization of caprolactone, and the melting point range of the PCL resin is 59-64 ℃.
The preparation method of the medical film material containing the environment-friendly stabilizer comprises the following steps:
s1: according to the weight ratio, placing the CPVC resin, the tin methyl mercaptide, the environment-friendly calcium-zinc stabilizer, the glycerol monooleate, the low-molecular-weight polyolefin and the dispersing agent into a high-speed stirrer, mixing for 10min at 120 ℃ and 5min at 60 ℃, then transferring into a double-screw extruder, and carrying out extrusion granulation at 185 ℃ and at the rotating speed of 35r/min to obtain the modified CPVC resin;
s2: placing the modified CPVC resin, the PCL resin and the foaming nucleating agent into a high-speed stirrer according to the weight part ratio, and mixing for 30min at 50 ℃ to obtain a primary mixed material;
s3: placing the primary mixed material prepared in the step S2 in an internal mixer, and mixing for 5min at 185 ℃ and the rotating speed of 35r/min to obtain a secondary mixed material;
s4: placing the secondary mixed material prepared in the step S3 into a flat vulcanizing machine, and pressing into a film blank of 10mm multiplied by 0.5mm at 185 ℃;
s5: placing the film blank prepared in the step S4 in a pressure container, and treating for 24 hours under the condition of the saturated carbon dioxide gas pressure of 3.5Mpa to obtain a film containing carbon dioxide fluid;
s6: and (5) taking out the film containing the carbon dioxide fluid prepared in the step (S5), immediately placing the film in a water bath at 70 ℃ for treatment for 30S, taking out the film and naturally airing the film to obtain a finished product of the medical film material containing the environment-friendly stabilizer.
Example 2
A medical film material containing an environment-friendly stabilizer comprises the following components in parts by weight: 40 parts of modified CPVC resin, 60 parts of PCL resin and 0.1 part of foaming nucleating agent;
based on 100 parts of CPVC resin, the modified CPVC resin is prepared by plasticizing, extruding and granulating 100 parts of CPVC resin, 2.0 parts of tin methyl mercaptide, 0.8 part of environment-friendly calcium-zinc stabilizer, 0.8 part of glycerol monooleate, 0.8 part of low molecular weight polyolefin and 1 part of dispersant.
Preferably, the degree of polymerization of the CPVC resin is 700-800, and the molecular weight of the low molecular weight polyolefin is 1500-5000; the dispersing agent is talcum powder and montmorillonite with the mass ratio of 1: 1; the foaming nucleating agent is nano silicon dioxide and nano montmorillonite, and the mass ratio of the nano silicon dioxide to the nano montmorillonite is 1: 1; the PCL resin is thermoplastic crystalline polyester obtained by ring-opening polymerization of caprolactone, and the melting point range of the PCL resin is 59-64 ℃.
The preparation method of the medical film material containing the environmental protection stabilizer is the same as the preparation method of the medical film material containing the environmental protection stabilizer in the example 1.
Example 3
A medical film material containing an environment-friendly stabilizer comprises the following components in parts by weight: 60 parts of modified CPVC resin, 40 parts of PCL resin and 0.5 part of foaming nucleating agent;
based on 100 parts of CPVC resin, the modified CPVC resin is prepared by plasticizing, extruding and granulating 100 parts of CPVC resin, 3.0 parts of tin methyl mercaptide, 0.1 part of environment-friendly calcium-zinc stabilizer, 1.0 part of glycerol monooleate, 1.0 part of low molecular weight polyolefin and 3 parts of dispersing agent.
Preferably, the degree of polymerization of the CPVC resin is 700-800, and the molecular weight of the low molecular weight polyolefin is 1500-5000; the dispersant is white carbon black and kaolin, and the mass ratio of the white carbon black to the kaolin is 1: 1; the foaming nucleating agent is talcum powder, kaolin and attapulgite, and the mass ratio of the talcum powder to the kaolin to the attapulgite is 1: 1; the PCL resin is thermoplastic crystalline polyester obtained by ring-opening polymerization of caprolactone, and the melting point range of the PCL resin is 59-64 ℃.
The preparation method of the medical film material containing the environmental protection stabilizer is the same as the preparation method of the medical film material containing the environmental protection stabilizer in the example 1.
Comparative example 1
A film material comprises the following components in parts by weight: CPVC resin 100 parts and methyl tin mercaptide 2.5 parts.
The preparation method of the medical film material containing the environment-friendly stabilizer comprises the following steps:
step 1: according to the weight ratio, placing the CPVC resin and the tin methyl mercaptide in a high-speed stirrer, mixing for 10min at 120 ℃ and 5min at 60 ℃, then transferring the mixture to a double-screw extruder, and carrying out extrusion granulation at 185 ℃ and 35r/min to obtain modified CPVC resin;
step 2: placing the modified CPVC resin prepared in the step 1 into an internal mixer, mixing for 5min at 185 ℃ and at the rotating speed of 35r/min, then placing into a flat vulcanizing machine, and pressing into a film blank with the thickness of 10mm multiplied by 0.5mm at 185 ℃;
and step 3: placing the film blank prepared in the step 2 in a pressure container, and treating for 24 hours under the condition of saturated carbon dioxide pressure of 3.5Mpa to obtain a film containing carbon dioxide fluid;
and 4, step 4: and (4) taking out the film containing the carbon dioxide fluid prepared in the step (3), immediately placing the film in a water bath at 70 ℃ for treatment for 30s, taking out the film and naturally airing the film to obtain a finished film material.
Comparative example 2
A film material comprises the following components in parts by weight: 100 parts of PVC resin and 2.5 parts of tin methyl mercaptide.
The preparation method of the medical film material containing the environment-friendly stabilizer comprises the following steps:
step 1: according to the weight portion ratio, putting the PVC resin and the tin methyl mercaptide into a high-speed stirrer, mixing for 10min at 120 ℃ and for 5min at 60 ℃, then transferring the mixture into a double-screw extruder, and extruding and granulating at 185 ℃ and 35r/min to obtain modified PVC resin;
step 2: placing the modified PVC resin prepared in the step 1 into an internal mixer, mixing for 5min at 185 ℃ and at the rotating speed of 35r/min, then placing into a flat vulcanizing machine, and pressing into a film blank of 10mm multiplied by 0.5mm at 185 ℃;
and 3, step 3: placing the film blank prepared in the step 2 in a pressure container, and treating for 24 hours under the condition of the saturated carbon dioxide pressure of 3.5Mpa to obtain a film containing carbon dioxide fluid;
and 4, step 4: and (4) taking out the film containing the carbon dioxide fluid prepared in the step (3), immediately placing the film in a water bath at 70 ℃ for treatment for 30s, taking out the film and naturally airing the film to obtain a finished film material.
Comparative example 3
A film material comprises the following components in parts by weight: 100 parts of PCL resin.
The preparation method of the medical film material containing the environment-friendly stabilizer comprises the following steps:
step 1: placing the PCL resin into an internal mixer, mixing for 5min at 185 ℃ and at the rotating speed of 35r/min, then placing the mixture into a flat vulcanizing machine, and pressing into a film blank with the thickness of 10mm multiplied by 0.5mm at 185 ℃;
step 2: placing the film blank prepared in the step 1 in a pressure container, and treating for 24 hours under the condition of the saturated carbon dioxide pressure of 3.5Mpa to obtain a film containing carbon dioxide fluid;
and step 3: and (3) taking out the film containing the carbon dioxide fluid prepared in the step (2), immediately placing the film in a water bath at 70 ℃ for treatment for 30s, taking out the film and naturally airing the film to obtain a finished film material.
The medical film materials containing the environmental-friendly stabilizer prepared in the examples 1 to 3 and the film materials prepared in the comparative examples 1 to 3 are respectively subjected to tensile strength and elongation at break tests by using an electronic universal tester, wherein the tensile rate is 50mm/min, and the test results are shown in table 1:
TABLE 1 tensile Strength and elongation at Break test results for the medical film materials containing environmental protection stabilizers prepared in examples 1-3 and the film materials prepared in comparative examples 1-3
The experimental data of table 1 show that: compared with the film materials prepared in comparative examples 1 to 3, the medical film materials containing the environment-friendly stabilizer prepared in examples 1 to 3 have higher tensile strength and elongation at break; wherein the film material prepared in comparative example 1 has a poor elongation at break although it has a high tensile strength; the medical film material containing the environment-friendly stabilizer prepared by the method has excellent mechanical property, and the aim of the invention is achieved.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the technical principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A medical film material containing an environment-friendly stabilizer is characterized by comprising the following components in parts by weight: 40-60 parts of modified CPVC resin, 40-60 parts of PCL resin and 0.1-0.5 part of foaming nucleating agent;
based on 100 parts of CPVC resin, the modified CPVC resin is prepared by plasticizing, extruding and granulating 100 parts of CPVC resin, 2.0-3.0 parts of tin methyl mercaptide, 0.5-1.0 part of environment-friendly calcium-zinc stabilizer, 0.5-1.0 part of glycerol monooleate, 0.5-1.0 part of low molecular weight polyolefin and 1-5 parts of dispersant.
2. The medical film material containing an environmentally friendly stabilizer as claimed in claim 1, wherein the modified CPVC resin is prepared by plasticizing, extruding and granulating 100 parts of CPVC resin, 2.5 parts of tin methyl mercaptide, 0.5 part of environmentally friendly calcium zinc stabilizer, 0.5 part of glycerol monooleate, 0.5 part of low molecular weight polyolefin, and 5 parts of dispersant, based on 100 parts of CPVC resin.
3. The environmentally friendly stabilizer-containing medical film material as claimed in claim 2, wherein the degree of polymerization of the CPVC resin is 700-800, and the molecular weight of the low molecular weight polyolefin is 1500-5000.
4. The medical film material containing the environmental-friendly stabilizer as claimed in claim 2, wherein the dispersant is one or more of calcium carbonate, talcum powder, montmorillonite, white carbon black and kaolin.
5. The medical film material containing the environmental-friendly stabilizer as claimed in claim 1, wherein the foaming nucleating agent is one or more of nano calcium carbonate, nano silica, nano montmorillonite, nano zinc oxide, nano alumina, nano titanium dioxide, talcum powder, kaolin and attapulgite.
6. The medical film material containing environment-friendly stabilizer according to claim 1, wherein the PCL resin is thermoplastic crystalline polyester obtained by ring-opening polymerization of caprolactone, and the melting point of the PCL resin is within a range of 59-64 ℃.
7. A preparation method of a medical film material containing an environment-friendly stabilizer is characterized in that the preparation method of the medical film material containing the environment-friendly stabilizer as claimed in any one of claims 1 to 6 comprises the following steps:
s1: according to the weight portion ratio of the CPVC resin, the tin methyl mercaptide, the environment-friendly calcium-zinc stabilizer, the glycerol monooleate, the low molecular weight polyolefin and the dispersing agent are placed in a high-speed stirrer, mixed for 10min at 120 ℃ and mixed for 5min at 60 ℃, then transferred to a double-screw extruder, and extruded and granulated at 185 ℃ and the rotating speed of 35r/min to obtain the modified CPVC resin;
s2: the modified CPVC resin, the PCL resin and the foaming nucleating agent are placed in a high-speed stirrer and mixed for 30min at the temperature of 50 ℃ according to the weight part ratio of claim 1 to obtain a primary mixed material;
s3: placing the primary mixed material prepared in the step S2 in an internal mixer, and mixing for 5min at 185 ℃ and the rotating speed of 35r/min to obtain a secondary mixed material;
s4: placing the secondary mixed material prepared in the step S3 into a flat vulcanizing machine, and pressing into a film blank of 10mm multiplied by 0.5mm at 185 ℃;
s5: placing the film blank prepared in the step S4 in a pressure container, and treating for 24 hours under the condition of the saturated carbon dioxide gas pressure of 3.5Mpa to obtain a film containing carbon dioxide fluid;
s6: and (5) taking out the film containing the carbon dioxide fluid prepared in the step (S5), immediately placing the film in a water bath at 70 ℃ for treatment for 30S, taking out the film and naturally airing the film to obtain a finished product of the medical film material containing the environment-friendly stabilizer.
8. The application of the medical film material containing the environment-friendly stabilizer is characterized in that the medical film material containing the environment-friendly stabilizer in any one of claims 1 to 6 is used for manufacturing medical instruments, medical instrument packaging bags or wound dressings.
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| CN101486821A (en) * | 2008-10-28 | 2009-07-22 | 广东联塑科技实业有限公司 | Nontoxic chlorinated polyvinyl chloride pipe and preparation thereof |
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| CN103102631A (en) * | 2012-02-09 | 2013-05-15 | 芜湖特贝特材料科技有限公司 | CPVC/PVC (Chlorinated Polyvinyl Chloride/Polyvinyl Chloride) heat-resistant composite extruded and foamed based on supercritical CO2 (Carbon Dioxide) and preparation method of CPVC/PVC heat-resistant composite |
| CN105348705A (en) * | 2015-10-30 | 2016-02-24 | 永高股份有限公司 | Preparation method of CPVC for nontoxic and high-processing stability cold and hot water |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4370286A (en) * | 1981-09-14 | 1983-01-25 | The B. F. Goodrich Company | Chlorinated polyvinyl chloride composition |
| CN101486821A (en) * | 2008-10-28 | 2009-07-22 | 广东联塑科技实业有限公司 | Nontoxic chlorinated polyvinyl chloride pipe and preparation thereof |
| CN103102631A (en) * | 2012-02-09 | 2013-05-15 | 芜湖特贝特材料科技有限公司 | CPVC/PVC (Chlorinated Polyvinyl Chloride/Polyvinyl Chloride) heat-resistant composite extruded and foamed based on supercritical CO2 (Carbon Dioxide) and preparation method of CPVC/PVC heat-resistant composite |
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Application publication date: 20220624 |