CN116606511B - High-temperature-resistant steam sterilization medical PVC material and preparation method thereof - Google Patents
High-temperature-resistant steam sterilization medical PVC material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 129
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 230000001954 sterilising effect Effects 0.000 title claims abstract description 19
- 238000004659 sterilization and disinfection Methods 0.000 title claims abstract description 19
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 60
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 41
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 22
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 20
- 229920005989 resin Polymers 0.000 claims abstract description 20
- 239000000314 lubricant Substances 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 15
- 239000004014 plasticizer Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims description 47
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 22
- 238000011282 treatment Methods 0.000 claims description 19
- 229910021529 ammonia Inorganic materials 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 17
- 239000002202 Polyethylene glycol Substances 0.000 claims description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 13
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000000084 colloidal system Substances 0.000 claims description 12
- 238000013329 compounding Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 238000005469 granulation Methods 0.000 claims description 12
- 230000003179 granulation Effects 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 12
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 12
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 12
- 235000011151 potassium sulphates Nutrition 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- -1 polyethylene Polymers 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- HORIEOQXBKUKGQ-UHFFFAOYSA-N bis(7-methyloctyl) cyclohexane-1,2-dicarboxylate Chemical compound CC(C)CCCCCCOC(=O)C1CCCCC1C(=O)OCCCCCCC(C)C HORIEOQXBKUKGQ-UHFFFAOYSA-N 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 6
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 6
- 235000013539 calcium stearate Nutrition 0.000 claims description 6
- 239000008116 calcium stearate Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000004806 diisononylester Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 229920002545 silicone oil Polymers 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 235000012424 soybean oil Nutrition 0.000 claims description 6
- 239000003549 soybean oil Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229940098697 zinc laurate Drugs 0.000 claims description 6
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- 238000009825 accumulation Methods 0.000 abstract description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
- 230000006641 stabilisation Effects 0.000 abstract description 2
- 238000011105 stabilization Methods 0.000 abstract description 2
- 238000004383 yellowing Methods 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 16
- 235000012239 silicon dioxide Nutrition 0.000 description 11
- 239000000654 additive Substances 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 9
- 239000005543 nano-size silicon particle Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 229920002413 Polyhexanide Polymers 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- VPPHKHDARGZSFK-UHFFFAOYSA-N 5,5-bis(hydroxymethyl)imidazolidine-2,4-dione Chemical compound OCC1(CO)NC(=O)NC1=O VPPHKHDARGZSFK-UHFFFAOYSA-N 0.000 description 1
- 206010002198 Anaphylactic reaction Diseases 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 201000004624 Dermatitis Diseases 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 206010070835 Skin sensitisation Diseases 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 208000003455 anaphylaxis Diseases 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 229940127554 medical product Drugs 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 231100000370 skin sensitisation Toxicity 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a high-temperature steam-resistant sterilization medical PVC material and a preparation method thereof, wherein the PVC material is prepared from the following raw materials in parts by weight: 80-150 parts of PVC resin powder, 30-50 parts of plasticizer, 5-10 parts of PVC modified auxiliary agent, 1-2 parts of heat stabilizer, 8-12 parts of auxiliary heat stabilizer, 1-6 parts of modified antibacterial agent and 1-2 parts of lubricant. According to the invention, the modified auxiliary agent is added into the PVC resin material, styrene is grafted into the modified auxiliary agent, the steric hindrance is increased by the benzene ring on the styrene, the friction resistance between molecular chains is increased during PVC processing, heat accumulation is easier, and the time required for plasticizing is shortened; meanwhile, the composite heat stabilizer (heat stabilizer and auxiliary heat stabilizer) used in the invention can improve the heat stabilization effect of the PVC material in steam sterilization and prevent the yellowing of the material to a certain extent. The PVC material prepared by the invention has better plasticizing performance, biological performance and antibacterial property, and has a certain application prospect.
Description
Technical Field
The invention belongs to the technical field of PVC material preparation, and particularly relates to a high-temperature steam sterilization-resistant medical PVC material and a preparation method thereof.
Background
By virtue of the advantages of good comprehensive performance (high strength, softness, transparency, rebound resilience) and high cost performance, the medical PVC material is one of the raw materials widely used in the field of medical appliances at present, such as medical products of oxygen masks, atomizing masks, nasal oxygen tubes and the like. PVC is used as a medical material, not only meets the material performance, but also meets the requirements of good biological performance, no carcinogenesis and no anaphylactic reaction; meanwhile, the antibacterial property is also a necessary performance requirement of the PVC material, and has important significance for the long-acting property of the service life of the PVC.
With the gradual improvement of the living standard of people, antibacterial plastics (containing medical PVC materials) with antibacterial performance are developed and used successively. From the method classification, the preparation method of the antibacterial plastic comprises the following steps: direct addition, antibacterial masterbatch, surface mount, lamination, post-processing, etc., wherein the direct addition is simple in process and relatively more in use; from the category of antibacterial agents, organic antibacterial agents and inorganic antibacterial agents can be classified, wherein the organic antibacterial agents mainly comprise acid, ester, alkali and alcohol raw materials; inorganic antibacterial agents are used in many cases, and Ag-based and Zn-based antibacterial agents are used, but the use of metal ions presents a certain safety and health risk.
In the prior art, the patent document CN109504001a uses zeolite, nano zinc oxide, calcium phosphate, polyhexamethylene biguanide hydrochloride, a combination of silane coupling agents or 30-50 parts of zeolite, nano zinc oxide, zirconium phosphate and organosilicon quaternary ammonium salt antibacterial agent, wherein the combination of silane coupling agents uses zirconium ions and zinc ions, and the polyhexamethylene biguanide hydrochloride is a long-acting antibacterial agent, and may have skin allergy problem; patent document CN109796701a provides a medical PVC plastic whose antibacterial is a combination of lithium carbonate and dimethylol hydantoin, which contains lithium ions.
In addition, the medical PVC material, such as the infusion apparatus catheter, has the defects of poor plasticizing effect and the like in the extrusion process, and is particularly characterized in that the surface of the catheter is provided with pits and crystal points, and the pits and crystal points are formed on the surface of the catheter, so that the thermal decomposition can be caused due to the short processing window period of the PVC material, and the too long retention time of the catheter; meanwhile, part of instruments are sterilized by high-temperature steam due to special requirements, the process parameters are 121 ℃ and 30min, and the internal plasticizer is separated out to cause the problems of product adhesion and the like, so that the thermal stability is poor.
Therefore, how to ensure the plasticization, the antibacterial property and other properties of the medical PVC material deserves intensive research.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a high-temperature steam-resistant sterilization medical PVC material and a preparation method thereof, and the obtained medical PVC material has good plasticization, good biological performance and good antibacterial performance.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
in a first aspect, the invention provides a high-temperature steam-resistant sterilization medical PVC material, which is prepared from the following raw materials in parts by weight: 80-150 parts of PVC resin powder, 30-50 parts of plasticizer, 5-10 parts of PVC modified auxiliary agent, 1-2 parts of heat stabilizer, 8-12 parts of auxiliary heat stabilizer, 1-6 parts of modified antibacterial agent and 1-2 parts of lubricant;
wherein, the preparation of the modified antibacterial agent comprises the following steps:
s1, dissolving tetraethoxysilane in an ammonia water-absolute ethyl alcohol solution, stirring for 1-5 hours, filtering, and drying in vacuum to obtain a precipitate; then adding the obtained precipitate into water, then adding polyethylene glycol, stirring and drying to obtain a material a;
s2, calcining the material a obtained in the step S1 at 790-820 ℃ for 3-8 hours, and obtaining a material b after calcining;
s3, adding the material b obtained in the step S2 into a hydrochloric acid solution with the mass concentration of 23-28% for treatment for 1-4 hours, and cleaning and drying the treatment to obtain a material c;
s4, ball milling the nano titanium dioxide on a high-energy ball mill for 0.5-2 h; obtaining a material d after the treatment is completed;
and S5, mixing the material c obtained in the step S3 and the material d obtained in the step S4, then adding KH550, and uniformly stirring to obtain the modified antibacterial property.
Preferably, the polymerization degree of the PVC resin powder is 1300-1500.
Preferably, the preparation of the PVC modifying aid comprises the following steps:
a1, adding 0.54g of potassium persulfate into 25mL of deionized water, and uniformly mixing to obtain a potassium persulfate solution for later use;
a2, uniformly blending 10g of butyl acrylate, 25g of methyl methacrylate and 15g of styrene to obtain a mixed material for later use;
a3, adding 3g of sodium dodecyl sulfate into 500g of deionized water, then placing the mixture in a water bath at 68 ℃, and introducing nitrogen to deoxidize; then adding 10g of the mixed material obtained in the step A2, uniformly stirring, and then adding 5mL of the potassium sulfate solution obtained in the step A1; after the reaction system turns blue, reacting for 20min, and then adding 10g of the mixed material obtained in the step A2 and 5mL of the potassium sulfate solution obtained in the step A1 every 15min until all the materials are added; then reacting for 2.5h, and ending the reaction; and demulsifying, washing, filtering and drying to obtain the PVC modified additive.
Preferably, the heat stabilizer is prepared by compounding 30-50 parts of calcium stearate and 50-70 parts of zinc laurate; the auxiliary heat stabilizer is epoxidized soybean oil.
Preferably, the lubricant is prepared by compounding 40-50 parts of silicone oil and 50-60 parts of polyethylene wax; the plasticizer is selected from one or more of DEHP, DINCH, DOP.
Preferably, in step S1, the volume ratio of tetraethoxysilane to aqueous ammonia-absolute ethanol solution is 1:5, ammonia water-absolute ethanol solution is prepared from the following components in volume ratio of 2:3, mixing the concentrated ammonia water and absolute ethyl alcohol; precipitate: water: the mass ratio of polyethylene glycol is 1:2 to 8:0.006 to 0.015.
Preferably, in step S3, the ratio of the amount of the material b to the hydrochloric acid solution is 1g: 10-25 mL.
Preferably, in step S5, the mass ratio of the material c, the material d, and the KH550 is 1:0.5 to 2:2 to 5.
In a second aspect, the invention also provides a preparation method of the high-temperature steam-resistant sterilization medical PVC material, which comprises the following steps:
mixing the heat stabilizer and the auxiliary heat stabilizer, heating to 140 ℃, stirring until the heat stabilizer and the auxiliary heat stabilizer are fully dissolved, and then transferring the mixture into a colloid grinder for circular grinding until the diameter of solid particles in the colloid is smaller than 5 mu m, thus obtaining the composite heat stabilizer;
then, mixing PVC resin powder and PVC modified auxiliary agent under the conditions of 500r/min and heating rate of 8 ℃/min, adding plasticizer, composite heat stabilizer and modified antibacterial agent when the temperature reaches 68 ℃, then stirring under the stirring condition of 1000r/min, adding lubricant when the temperature reaches 112 ℃, keeping stirring to 148 ℃, then placing into a cold pot, and cooling to 40 ℃;
finally, screw granulation is performed.
Preferably, the process conditions for screw granulation are: the first stage temperature is 165 ℃, the second stage temperature is 170 ℃, the third stage temperature is 178 ℃, the fourth stage temperature is 178 ℃, the die temperature is 162 ℃ and the main screw rotating speed is 50r/min.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the modified auxiliary agent is added into the PVC resin material, styrene is grafted into the modified auxiliary agent, the steric hindrance is increased by the benzene ring on the styrene, the friction resistance between molecular chains is increased during PVC processing, heat accumulation is easier, and the time required for plasticizing is shortened.
2. The composite heat stabilizer and the modification auxiliary agent (heat stabilizer and auxiliary heat stabilizer) used in the invention can improve the heat stabilization effect of the PVC material in steam sterilization, have good plasticization and prevent the material from yellowing to a certain extent.
3. Aiming at the antibacterial property of PVC materials, the invention provides an inorganic modified antibacterial agent which does not contain metal ions; the modified antibacterial agent takes nano silicon dioxide and nano titanium dioxide as a composite main body, and fully combines the antibacterial advantages of the nano silicon dioxide and the nano titanium dioxide, but the nano silicon dioxide and the nano titanium dioxide have the defect of poor compatibility and are easy to agglomerate when being directly added into PVC resin, so the modified antibacterial agent is modified, and specifically: aiming at nano silicon dioxide, ethyl orthosilicate is used as a silicon source, a precipitate is obtained by preliminary treatment in an ammonia water-absolute ethyl alcohol system, then polyethylene glycol is used for treatment, silicon dioxide is generated after calcination, and polyethylene glycol carbonization is performed, so that the treatment can further enrich the pore canal structure of the silicon dioxide and improve the specific surface area (as the nano silicon dioxide has certain adsorption performance on bacteria or microorganisms and the like, the large specific surface area is also beneficial to more adsorption of the bacteria or microorganisms, the antibacterial effect is enhanced), and the agglomeration tendency of the silicon dioxide is reduced; then acid treatment is carried out to enrich the groups (hydroxyl, carboxyl and the like) on the surface of the silicon dioxide material, thereby being beneficial to the uniform adsorption and action of the subsequent silane coupling agent, further ensuring the dispersibility of the silane coupling agent modified antibacterial agent in PVC resin and reducing the agglomeration tendency; the nano titanium dioxide is subjected to high-energy ball milling before being compounded with the nano silicon dioxide, so that active groups on the surface of the nano titanium dioxide are enriched, the antibacterial property is improved, and the nano titanium dioxide and the nano silicon dioxide cooperate to have a good antibacterial effect.
Detailed Description
The following detailed description of embodiments of the invention is provided to emphasize that all embodiments are shown for the purpose of explaining the invention and are not to be construed as limiting the invention.
All raw materials in the invention are purchased through market approaches unless otherwise specified. Wherein the polymerization degree of the PVC resin powder is 1300; the grain diameter of the nano titanium dioxide is about 40 nm; the polyethylene glycol is PEG200.
Meanwhile, unless otherwise specified, parts in the present invention refer to parts by weight.
Example 1
A preparation method of a modified antibacterial agent comprises the following steps:
s1, dissolving tetraethoxysilane in an ammonia water-absolute ethyl alcohol solution, stirring for 1.5 hours, filtering, and drying in vacuum to obtain a precipitate; then adding the obtained precipitate into water, then adding polyethylene glycol, stirring and drying to obtain a material a;
s2, calcining the material a obtained in the step S1 at 810 ℃ for 5 hours, and obtaining a material b after calcining;
s3, adding the material b obtained in the step S2 into a hydrochloric acid solution with the mass concentration of 25% for treatment for 2 hours, and cleaning and drying the material c;
s4, ball milling the nano titanium dioxide on a high-energy ball mill for 1h; obtaining a material d after the treatment is completed;
and S5, mixing the material c obtained in the step S3 and the material d obtained in the step S4, then adding KH550, and uniformly stirring to obtain the modified antibacterial property.
In the step S1, the volume ratio of the tetraethoxysilane to the ammonia water-absolute ethanol solution is 1:5, ammonia water-absolute ethanol solution is prepared from the following components in volume ratio of 2:3, mixing the concentrated ammonia water and absolute ethyl alcohol; precipitate: water: the mass ratio of polyethylene glycol is 1:5:0.008.
in the step S3, the dosage ratio of the material b to the hydrochloric acid solution is 1g:12mL.
In the step S5, the mass ratio of the material c to the material d to the KH550 is 1:1:2.5.
example 2
A preparation method of a modified antibacterial agent comprises the following steps:
s1, dissolving tetraethoxysilane in an ammonia water-absolute ethyl alcohol solution, stirring for 2 hours, filtering, and drying in vacuum to obtain a precipitate; then adding the obtained precipitate into water, then adding polyethylene glycol, stirring and drying to obtain a material a;
s2, calcining the material a obtained in the step S1 at 800 ℃ for 5.5 hours, and obtaining a material b after calcining;
s3, adding the material b obtained in the step S2 into hydrochloric acid solution with the mass concentration of 28% for treatment for 2 hours, and cleaning and drying the material c;
s4, ball milling the nano titanium dioxide on a high-energy ball mill for 1h; obtaining a material d after the treatment is completed;
and S5, mixing the material c obtained in the step S3 and the material d obtained in the step S4, then adding KH550, and uniformly stirring to obtain the modified antibacterial property.
In the step S1, the volume ratio of the tetraethoxysilane to the ammonia water-absolute ethanol solution is 1:5, ammonia water-absolute ethanol solution is prepared from the following components in volume ratio of 2:3, mixing the concentrated ammonia water and absolute ethyl alcohol; precipitate: water: the mass ratio of polyethylene glycol is 1:5:0.01.
in the step S3, the dosage ratio of the material b to the hydrochloric acid solution is 1g:15mL.
In the step S5, the mass ratio of the material c to the material d to the KH550 is 1:1:2.8.
example 3
The high-temperature steam-resistant sterilization medical PVC material is prepared from the following raw materials in mass: 100g of PVC resin powder, 45g of DINCH, 6g of PVC modifying additive, 1.5g of heat stabilizer, 9g of epoxidized soybean oil, 2.5g of modified antibacterial agent and 1.5g of lubricant.
The heat stabilizer is prepared by compounding 40 parts of calcium stearate and 60 parts of zinc laurate.
Wherein the lubricant is prepared by compounding 40 parts of silicone oil and 50 parts of polyethylene wax.
Wherein the modified antibacterial agent is the antibacterial agent prepared in example 1.
Wherein, the preparation of the PVC modified auxiliary agent comprises the following steps:
a1, adding 0.54g of potassium persulfate into 25mL of deionized water, and uniformly mixing to obtain a potassium persulfate solution for later use;
a2, uniformly blending 10g of butyl acrylate, 25g of methyl methacrylate and 15g of styrene to obtain a mixed material for later use;
a3, adding 3g of sodium dodecyl sulfate into 500g of deionized water, then placing the mixture in a water bath at 68 ℃, and introducing nitrogen to deoxidize; then adding 10g of the mixed material obtained in the step A2, uniformly stirring, and then adding 5mL of the potassium sulfate solution obtained in the step A1; after the reaction system turns blue, reacting for 20min, and then adding 10g of the mixed material obtained in the step A2 and 5mL of the potassium sulfate solution obtained in the step A1 every 15min until all the materials are added; then reacting for 2.5h, and ending the reaction; and demulsifying, washing, filtering and drying to obtain the PVC modified additive.
In this embodiment, a method for preparing the PVC material is also provided, including the following steps:
mixing the heat stabilizer and the auxiliary heat stabilizer, heating to 140 ℃, stirring until the heat stabilizer and the auxiliary heat stabilizer are fully dissolved, and then transferring the mixture into a colloid grinder for circular grinding until the diameter of solid particles in the colloid is smaller than 5 mu m, thus obtaining the composite heat stabilizer;
then, mixing PVC resin powder and PVC modified auxiliary agent under the conditions of 500r/min and heating rate of 8 ℃/min, adding plasticizer, composite heat stabilizer and modified antibacterial agent when the temperature reaches 68 ℃, then stirring under the stirring condition of 1000r/min, adding lubricant when the temperature reaches 112 ℃, keeping stirring to 148 ℃, then placing into a cold pot, and cooling to 40 ℃;
finally, screw granulation is carried out; wherein, the technological conditions of screw granulation are as follows: the first stage temperature is 165 ℃, the second stage temperature is 170 ℃, the third stage temperature is 178 ℃, the fourth stage temperature is 178 ℃, the die temperature is 162 ℃ and the main screw rotating speed is 50r/min.
Example 4
The high-temperature steam-resistant sterilization medical PVC material is prepared from the following raw materials in mass: 100g of PVC resin powder, 50g of DINCH, 7g of PVC modifying additive, 1.3g of heat stabilizer, 9g of epoxidized soybean oil, 2.8g of modified antibacterial agent and 1.5g of lubricant.
Wherein the heat stabilizer is prepared by compounding 45 parts of calcium stearate and 55 parts of zinc laurate.
Wherein the lubricant is prepared by compounding 45 parts of silicone oil and 55 parts of polyethylene wax.
Wherein the modified antibacterial agent is the antibacterial agent prepared in example 1.
Wherein, the preparation of the PVC modified auxiliary agent comprises the following steps:
a1, adding 0.54g of potassium persulfate into 25mL of deionized water, and uniformly mixing to obtain a potassium persulfate solution for later use;
a2, uniformly blending 10g of butyl acrylate, 25g of methyl methacrylate and 15g of styrene to obtain a mixed material for later use;
a3, adding 3g of sodium dodecyl sulfate into 500g of deionized water, then placing the mixture in a water bath at 68 ℃, and introducing nitrogen to deoxidize; then adding 10g of the mixed material obtained in the step A2, uniformly stirring, and then adding 5mL of the potassium sulfate solution obtained in the step A1; after the reaction system turns blue, reacting for 20min, and then adding 10g of the mixed material obtained in the step A2 and 5mL of the potassium sulfate solution obtained in the step A1 every 15min until all the materials are added; then reacting for 2.5h, and ending the reaction; and demulsifying, washing, filtering and drying to obtain the PVC modified additive.
In this embodiment, a method for preparing the PVC material is also provided, including the following steps:
mixing the heat stabilizer and the auxiliary heat stabilizer, heating to 140 ℃, stirring until the heat stabilizer and the auxiliary heat stabilizer are fully dissolved, and then transferring the mixture into a colloid grinder for circular grinding until the diameter of solid particles in the colloid is smaller than 5 mu m, thus obtaining the composite heat stabilizer;
then, mixing PVC resin powder and PVC modified auxiliary agent under the conditions of 500r/min and heating rate of 8 ℃/min, adding plasticizer, composite heat stabilizer and modified antibacterial agent when the temperature reaches 68 ℃, then stirring under the stirring condition of 1000r/min, adding lubricant when the temperature reaches 112 ℃, keeping stirring to 148 ℃, then placing into a cold pot, and cooling to 40 ℃;
finally, screw granulation is carried out; wherein, the technological conditions of screw granulation are as follows: the first stage temperature is 165 ℃, the second stage temperature is 170 ℃, the third stage temperature is 178 ℃, the fourth stage temperature is 178 ℃, the die temperature is 162 ℃ and the main screw rotating speed is 50r/min.
Comparative example 1
In comparison with example 1, the treatment in comparative example 1, which does not contain polyethylene glycol, was the same as the rest. Specifically, the preparation method of the modified antibacterial agent comprises the following steps:
s1, dissolving tetraethoxysilane in an ammonia water-absolute ethanol solution, stirring for 1.5 hours, filtering, and drying in vacuum to obtain a precipitate, namely a material a;
s2, calcining the material a obtained in the step S1 at 810 ℃ for 5 hours, and obtaining a material b after calcining;
s3, adding the material b obtained in the step S2 into a hydrochloric acid solution with the mass concentration of 25% for treatment for 2 hours, and cleaning and drying the material c;
s4, ball milling the nano titanium dioxide on a high-energy ball mill for 1h; obtaining a material d after the treatment is completed;
and S5, mixing the material c obtained in the step S3 and the material d obtained in the step S4, then adding KH550, and uniformly stirring to obtain the modified antibacterial property.
In the step S1, the volume ratio of the tetraethoxysilane to the ammonia water-absolute ethanol solution is 1:5, ammonia water-absolute ethanol solution is prepared from the following components in volume ratio of 2:3, mixing the concentrated ammonia water and absolute ethyl alcohol.
In the step S3, the dosage ratio of the material b to the hydrochloric acid solution is 1g:12mL.
In the step S5, the mass ratio of the material c to the material d to the KH550 is 1:1:2.5.
comparative example 2
In comparison with example 1, comparative example 2 does not contain a hydrochloric acid solution treatment, and the rest of the treatments are the same. Specifically, the preparation method of the modified antibacterial agent comprises the following steps:
s1, dissolving tetraethoxysilane in an ammonia water-absolute ethyl alcohol solution, stirring for 1.5 hours, filtering, and drying in vacuum to obtain a precipitate; then adding the obtained precipitate into water, then adding polyethylene glycol, stirring and drying to obtain a material a;
s2, calcining the material a obtained in the step S1 at 810 ℃ for 5 hours, and obtaining a material b after calcining;
s3, ball milling the nano titanium dioxide on a high-energy ball mill for 1h; obtaining a material d after the treatment is completed;
and S4, mixing the material b obtained in the step S2 and the material d obtained in the step S3, then adding KH550, and uniformly stirring to obtain the modified antibacterial property.
In the step S1, the volume ratio of the tetraethoxysilane to the ammonia water-absolute ethanol solution is 1:5, ammonia water-absolute ethanol solution is prepared from the following components in volume ratio of 2:3, mixing the concentrated ammonia water and absolute ethyl alcohol; precipitate: water: the mass ratio of polyethylene glycol is 1:5:0.008.
in the step S4, the mass ratio of the material c to the material d to the KH550 is 1:1:2.5.
comparative example 3
Comparative example 3 is different from example 3 in that the modified antibacterial agent prepared in comparative example 1 is used in comparative example 3, as compared with example 3. In particular to a high-temperature steam-resistant sterilization medical PVC material which is prepared from the following raw materials in mass: 100g of PVC resin powder, 45g of DINCH, 6g of PVC modifying additive, 1.5g of heat stabilizer, 9g of epoxidized soybean oil, 2.5g of modified antibacterial agent and 1.5g of lubricant.
The heat stabilizer is prepared by compounding 40 parts of calcium stearate and 60 parts of zinc laurate.
Wherein the lubricant is prepared by compounding 40 parts of silicone oil and 50 parts of polyethylene wax.
Wherein, the modified antibacterial agent is the antibacterial agent prepared in comparative example 1.
Wherein, the preparation of the PVC modified auxiliary agent comprises the following steps:
a1, adding 0.54g of potassium persulfate into 25mL of deionized water, and uniformly mixing to obtain a potassium persulfate solution for later use;
a2, uniformly blending 10g of butyl acrylate, 25g of methyl methacrylate and 15g of styrene to obtain a mixed material for later use;
a3, adding 3g of sodium dodecyl sulfate into 500g of deionized water, then placing the mixture in a water bath at 68 ℃, and introducing nitrogen to deoxidize; then adding 10g of the mixed material obtained in the step A2, uniformly stirring, and then adding 5mL of the potassium sulfate solution obtained in the step A1; after the reaction system turns blue, reacting for 20min, and then adding 10g of the mixed material obtained in the step A2 and 5mL of the potassium sulfate solution obtained in the step A1 every 15min until all the materials are added; then reacting for 2.5h, and ending the reaction; and demulsifying, washing, filtering and drying to obtain the PVC modified additive.
In this comparative example, there is also provided a method for preparing the above PVC material, comprising the steps of:
mixing the heat stabilizer and the auxiliary heat stabilizer, heating to 140 ℃, stirring until the heat stabilizer and the auxiliary heat stabilizer are fully dissolved, and then transferring the mixture into a colloid grinder for circular grinding until the diameter of solid particles in the colloid is smaller than 5 mu m, thus obtaining the composite heat stabilizer;
then, mixing PVC resin powder and PVC modified auxiliary agent under the conditions of 500r/min and heating rate of 8 ℃/min, adding plasticizer, composite heat stabilizer and modified antibacterial agent when the temperature reaches 68 ℃, then stirring under the stirring condition of 1000r/min, adding lubricant when the temperature reaches 112 ℃, keeping stirring to 148 ℃, then placing into a cold pot, and cooling to 40 ℃;
finally, screw granulation is carried out; wherein, the technological conditions of screw granulation are as follows: the first stage temperature is 165 ℃, the second stage temperature is 170 ℃, the third stage temperature is 178 ℃, the fourth stage temperature is 178 ℃, the die temperature is 162 ℃ and the main screw rotating speed is 50r/min.
Comparative example 4
Comparative example 4 is different from example 3 in that the modified antibacterial agent prepared in comparative example 2 is used in comparative example 4, compared with example 3. In particular to a high-temperature steam-resistant sterilization medical PVC material which is prepared from the following raw materials in mass: 100g of PVC resin powder, 45g of DINCH, 6g of PVC modifying additive, 1.5g of heat stabilizer, 9g of epoxidized soybean oil, 2.5g of modified antibacterial agent and 1.5g of lubricant.
The heat stabilizer is prepared by compounding 40 parts of calcium stearate and 60 parts of zinc laurate.
Wherein the lubricant is prepared by compounding 40 parts of silicone oil and 50 parts of polyethylene wax.
Wherein, the modified antibacterial agent is the antibacterial agent prepared in comparative example 2.
Wherein, the preparation of the PVC modified auxiliary agent comprises the following steps:
a1, adding 0.54g of potassium persulfate into 25mL of deionized water, and uniformly mixing to obtain a potassium persulfate solution for later use;
a2, uniformly blending 10g of butyl acrylate, 25g of methyl methacrylate and 15g of styrene to obtain a mixed material for later use;
a3, adding 3g of sodium dodecyl sulfate into 500g of deionized water, then placing the mixture in a water bath at 68 ℃, and introducing nitrogen to deoxidize; then adding 10g of the mixed material obtained in the step A2, uniformly stirring, and then adding 5mL of the potassium sulfate solution obtained in the step A1; after the reaction system turns blue, reacting for 20min, and then adding 10g of the mixed material obtained in the step A2 and 5mL of the potassium sulfate solution obtained in the step A1 every 15min until all the materials are added; then reacting for 2.5h, and ending the reaction; and demulsifying, washing, filtering and drying to obtain the PVC modified additive.
In this embodiment, a method for preparing the PVC material is also provided, including the following steps:
mixing the heat stabilizer and the auxiliary heat stabilizer, heating to 140 ℃, stirring until the heat stabilizer and the auxiliary heat stabilizer are fully dissolved, and then transferring the mixture into a colloid grinder for circular grinding until the diameter of solid particles in the colloid is smaller than 5 mu m, thus obtaining the composite heat stabilizer;
then, mixing PVC resin powder and PVC modified auxiliary agent under the conditions of 500r/min and heating rate of 8 ℃/min, adding plasticizer, composite heat stabilizer and modified antibacterial agent when the temperature reaches 68 ℃, then stirring under the stirring condition of 1000r/min, adding lubricant when the temperature reaches 112 ℃, keeping stirring to 148 ℃, then placing into a cold pot, and cooling to 40 ℃;
finally, screw granulation is carried out; wherein, the technological conditions of screw granulation are as follows: the first stage temperature is 165 ℃, the second stage temperature is 170 ℃, the third stage temperature is 178 ℃, the fourth stage temperature is 178 ℃, the die temperature is 162 ℃ and the main screw rotating speed is 50r/min.
The PVC materials prepared in examples 3 to 4 and comparative examples 3 to 4 were subjected to performance test, specifically as follows:
(1) Plasticizing Performance test
The test is carried out by a Hark plasticizing rheometer, the test temperature is 180 ℃, the rotating speed is 60rpm, and the feeding amount is 57g.
(2) Thermal stability Performance test
The thermal stability test was performed with reference to GB/T15595-2008, at 180 ℃.
(3) Biological Performance test
Intradermal stimulation and skin sensitization biological performance testing was performed according to GB/T16886.10-2017.
(4) Antibacterial property test
The detection is carried out with reference to GB15979-2002 appendix C5.
The test results are shown in Table 1.
Table 1 test results
As can be seen from Table 1, the PVC material prepared by each embodiment of the application has excellent plasticizing performance, thermal stability, biological performance and antibacterial property.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (5)
1. A preparation method of a high-temperature steam-resistant sterilization medical PVC material is characterized in that,
the high-temperature-resistant steam sterilization medical PVC material is prepared from the following raw materials in parts by weight: 80-150 parts of PVC resin powder, 30-50 parts of plasticizer, 5-10 parts of PVC modified auxiliary agent, 1-2 parts of heat stabilizer, 8-12 parts of auxiliary heat stabilizer, 1-6 parts of modified antibacterial agent and 1-2 parts of lubricant;
the preparation method comprises the following steps: mixing the heat stabilizer and the auxiliary heat stabilizer, heating to 140 ℃, stirring until the heat stabilizer and the auxiliary heat stabilizer are fully dissolved, and then transferring the mixture into a colloid grinder for circular grinding until the diameter of solid particles in the colloid is smaller than 5 mu m, thus obtaining the composite heat stabilizer; then, mixing PVC resin powder and PVC modified auxiliary agent under the conditions of 500r/min and heating rate of 8 ℃/min, adding plasticizer, composite heat stabilizer and modified antibacterial agent when the temperature reaches 68 ℃, then stirring under the stirring condition of 1000r/min, adding lubricant when the temperature reaches 112 ℃, keeping stirring to 148 ℃, then placing into a cold pot, and cooling to 40 ℃; finally, screw granulation is carried out;
wherein, the preparation of the modified antibacterial agent comprises the following steps:
s1, dissolving tetraethoxysilane in an ammonia water-absolute ethyl alcohol solution, stirring for 1-5 hours, filtering, and drying in vacuum to obtain a precipitate; then adding the obtained precipitate into water, then adding polyethylene glycol, stirring and drying to obtain a material a;
s2, calcining the material a obtained in the step S1 at 790-820 ℃ for 3-8 hours, and obtaining a material b after calcining;
s3, adding the material b obtained in the step S2 into a hydrochloric acid solution with the mass concentration of 23-28% for treatment for 1-4 hours, and cleaning and drying the treatment to obtain a material c;
s4, ball milling the nano titanium dioxide on a high-energy ball mill for 0.5-2 h; obtaining a material d after the treatment is completed;
s5, mixing the material c obtained in the step S3 and the material d obtained in the step S4, then adding KH550, and uniformly stirring to obtain modified antibacterial property;
wherein, the preparation of the PVC modified auxiliary agent comprises the following steps:
a1, adding 0.54g of potassium persulfate into 25mL of deionized water, and uniformly mixing to obtain a potassium persulfate solution for later use;
a2, uniformly blending 10g of butyl acrylate, 25g of methyl methacrylate and 15g of styrene to obtain a mixed material for later use;
a3, adding 3g of sodium dodecyl sulfate into 500g of deionized water, then placing the mixture in a water bath at 68 ℃, and introducing nitrogen to deoxidize; then adding 10g of the mixed material obtained in the step A2, uniformly stirring, and then adding 5mL of the potassium sulfate solution obtained in the step A1; after the reaction system turns blue, reacting for 20min, and then adding 10g of the mixed material obtained in the step A2 and 5mL of the potassium sulfate solution obtained in the step A1 every 15min until all the materials are added; then reacting for 2.5h, and ending the reaction; demulsification, washing, filtering and drying are carried out, thus obtaining the PVC modified auxiliary agent;
in the step S1, the volume ratio of the tetraethoxysilane to the ammonia water-absolute ethanol solution is 1:5, ammonia water-absolute ethanol solution is prepared from the following components in volume ratio of 2:3, mixing the concentrated ammonia water and absolute ethyl alcohol; precipitate: water: the mass ratio of polyethylene glycol is 1:2 to 8:0.006 to 0.015;
in the step S5, the mass ratio of the material c to the material d to the KH550 is 1:0.5 to 2:2 to 5;
in the step S3, the dosage ratio of the material b to the hydrochloric acid solution is 1g: 10-25 mL.
2. The method for preparing a high-temperature steam sterilization medical PVC material according to claim 1, wherein the polymerization degree of the PVC resin powder is 1300-1500.
3. The method for preparing the high-temperature steam-resistant sterilization medical PVC material according to claim 1, wherein the heat stabilizer is prepared by compounding 30-50 parts of calcium stearate and 50-70 parts of zinc laurate; the auxiliary heat stabilizer is epoxidized soybean oil.
4. The preparation method of the high-temperature steam-resistant sterilization medical PVC material according to claim 1, wherein the lubricant is prepared by compounding 40-50 parts of silicone oil and 50-60 parts of polyethylene wax; the plasticizer is selected from one or more of DEHP, DINCH, DOP.
5. The method for preparing the high-temperature steam-resistant sterilization medical PVC material according to claim 1, wherein the technological conditions of screw granulation are as follows: the first stage temperature is 165 ℃, the second stage temperature is 170 ℃, the third stage temperature is 178 ℃, the fourth stage temperature is 178 ℃, the die temperature is 162 ℃ and the main screw rotating speed is 50r/min.
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