CN112625373A - Medical hard PVC material with high heat resistance and electron beam resistance and preparation method thereof - Google Patents
Medical hard PVC material with high heat resistance and electron beam resistance and preparation method thereof Download PDFInfo
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- CN112625373A CN112625373A CN202011109429.6A CN202011109429A CN112625373A CN 112625373 A CN112625373 A CN 112625373A CN 202011109429 A CN202011109429 A CN 202011109429A CN 112625373 A CN112625373 A CN 112625373A
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- 239000000463 material Substances 0.000 title claims abstract description 62
- 238000010894 electron beam technology Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000011347 resin Substances 0.000 claims abstract description 40
- 229920005989 resin Polymers 0.000 claims abstract description 40
- 239000003381 stabilizer Substances 0.000 claims abstract description 31
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 23
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 23
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 23
- 230000001954 sterilising effect Effects 0.000 claims abstract description 23
- 239000004609 Impact Modifier Substances 0.000 claims abstract description 22
- 238000004659 sterilization and disinfection Methods 0.000 claims abstract description 22
- 239000000314 lubricant Substances 0.000 claims abstract description 17
- 150000003254 radicals Chemical class 0.000 claims abstract description 17
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 13
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 6
- -1 rare earth metal stearate Chemical class 0.000 claims description 30
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 16
- 235000021355 Stearic acid Nutrition 0.000 claims description 14
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 14
- 239000008117 stearic acid Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 8
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 8
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 7
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims description 7
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 7
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 7
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 claims description 7
- 235000021388 linseed oil Nutrition 0.000 claims description 7
- 239000000944 linseed oil Substances 0.000 claims description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 claims description 7
- 229920000638 styrene acrylonitrile Polymers 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- YAHBZWSDRFSFOO-UHFFFAOYSA-L dimethyltin(2+);2-(2-ethylhexoxy)-2-oxoethanethiolate Chemical group CCCCC(CC)COC(=O)CS[Sn](C)(C)SCC(=O)OCC(CC)CCCC YAHBZWSDRFSFOO-UHFFFAOYSA-L 0.000 claims description 6
- JKBYAWVSVVSRIX-UHFFFAOYSA-N octadecyl 2-(1-octadecoxy-1-oxopropan-2-yl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)SC(C)C(=O)OCCCCCCCCCCCCCCCCCC JKBYAWVSVVSRIX-UHFFFAOYSA-N 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- 230000001276 controlling effect Effects 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000004643 material aging Methods 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000004383 yellowing Methods 0.000 abstract description 6
- 230000009467 reduction Effects 0.000 abstract description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 49
- 239000004800 polyvinyl chloride Substances 0.000 description 49
- 150000001875 compounds Chemical class 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000010791 quenching Methods 0.000 description 7
- 230000000171 quenching effect Effects 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 6
- 230000005855 radiation Effects 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 238000005844 autocatalytic reaction Methods 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 238000012925 biological evaluation Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000036512 infertility Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Apparatus For Disinfection Or Sterilisation (AREA)
- Materials For Medical Uses (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a medical hard PVC material with high heat resistance and electron beam irradiation resistance for sterilization and a preparation method thereof. The invention comprises the following components in parts by weight: 100.0 parts of medical PVC resin powder; 2.0-3.0 parts of organic tin stabilizer; 15.0-30.0 parts of heat-resistant modified resin, 5.0-10.0 parts of impact modifier and 1.0-2.0 parts of processing aid; 2.0-5.0 parts of an auxiliary heat stabilizer; antioxidant: 0.5-1.0 part; 1.0-2.0 parts of a composite free radical quencher; 0.5-1.0 part of lubricant. The invention mainly solves the problems of serious yellowing and sharp reduction of mechanical properties of the existing medical hard PVC material after electron beam irradiation sterilization, and simultaneously improves the use temperature of the material.
Description
Technical Field
The invention relates to a medical hard PVC material with high heat resistance and ray resistance and sterilization and a preparation method thereof.
Background
At present, three modes of high-temperature steam sterilization, ethylene oxide sterilization and radiation sterilization are commonly adopted for disposable polyvinyl chloride medical consumables all over the world, along with the stricter and stricter environmental protection, the traditional ethylene oxide sterilization is eliminated at higher speed in the developed international areas and countries in recent years, the steam sterilization has high material requirements and is difficult to popularize, and the adoption of the electron beam radiation sterilization mode for sterilizing medical instruments has a series of advantages of strong penetrating power, high sterilization speed, high efficiency, normal temperature sterilization and the like. However, as no plasticizer is added to the medical hard PVC material, when the medical hard PVC material is sterilized by electron beam irradiation, the electron beam directly destroys the PVC material, the PVC is rapidly degraded and subjected to intermolecular dehydrochlorination reaction to rapidly form a chromophoric group, which causes the hard PVC material to be severely yellowed (dark brown) and the mechanical properties to be sharply reduced. Meanwhile, various processing aids are added into the hard PVC material, but the use temperature of the material is not increased, and the hard PVC material is often deformed when used under a higher temperature condition.
Therefore, the problem that the cracking risk of the hard joint prepared from the hard PVC material in the using process is caused by severe yellowing (dark brown) of the existing medical hard PVC material after electron beam sterilization and sharp reduction of mechanical properties is urgently needed to be solved. Meanwhile, the medical instruments are transported across regions for a long time at high temperature, the thermal deformation temperature of the existing medical hard PVC material is usually not high, and the medical instruments are easy to lose effectiveness due to thermal deformation in the transportation process, so that the problem of increasing the thermal deformation temperature of the hard PVC material is also a problem which needs to be solved urgently.
Disclosure of Invention
The invention aims to provide a high-heat-resistance electron beam-resistant sterilization medical hard PVC material and a preparation method thereof, and mainly solves two problems that the existing medical hard PVC material is seriously yellowed (dark brown) after being subjected to ray sterilization, the mechanical property is sharply reduced, and the thermal deformation temperature of the existing medical hard PVC material is improved.
In order to solve the technical problems, the invention adopts the technical scheme that:
the medical hard PVC material with high heat resistance and ray resistance for sterilization is characterized by comprising the following raw materials in parts by weight:
medical PVC resin powder: 100.0 parts;
organic tin stabilizers: 2.0-3.0 parts;
heat-resistant modified resin: 15.0 to 30.0 portions
Impact modifier: 5.0-10.0 parts;
processing aid: 1.0-2.0 parts;
auxiliary heat stabilizer: 2.0-5.0 parts;
antioxidant: 0.5-1.0 part;
complex radical quencher: 1.0-2.0 parts;
lubricant: 0.5 to 1.0 portion.
As a limitation of the present invention: the invention
The medical PVC resin powder is suspension PVC resin, the polymerization degree is 500-800, and the dosage is 100 parts by weight.
The organic tin stabilizer is methyl tin mercaptide stabilizer, and the dosage of the organic tin stabilizer is 2.0 to 3.0 weight parts.
The heat-resistant modified resin is a mixture consisting of 30-50% of alpha-methyl styrene polymer, 30-40% of styrene-maleic anhydride copolymer and 10-30% of styrene acrylonitrile, and the dosage of the heat-resistant modified resin is 15.0-30.0 parts by weight.
The impact modifier is styrene impact modifier and is used in 5.0-10.0 weight portions.
The processing aid is methacrylate processing aid and is used in an amount of 1.0-2.0 parts by weight.
The auxiliary heat stabilizer is epoxy linseed oil, and the dosage of the auxiliary heat stabilizer is 2.0 to 5.0 parts by weight.
The antioxidant consists of 30-40% of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate (antioxidant 1076), 30-40% of dioctadecyl thiodipropionate (antioxidant DSTP) and 20-30% of tridecyl phosphite (TTDP), and the dosage of the antioxidant is 0.5-1.0 part by weight.
The composite free radical quenching agent is stearic acid rare earth metal organic complex 50-70% and 2-mercaptobenzimidazole 30-50%, and the dosage is 1.0-2.0 weight parts.
The lubricant consists of 40-60% of stearic acid and 40-60% of polyethylene wax, and the dosage of the lubricant is 0.5-1.0 part by weight.
As a further limitation to the invention, the preparation method of the medical hard PVC material with low yellowing after electron beam sterilization, provided by the invention, comprises the following specific preparation steps:
1) putting PVC resin into a high-speed mixer, regulating the rotating speed to 400rpm, adding a certain amount of organic tin stabilizer, heat-resistant modified resin, impact modifier, processing aid, auxiliary stabilizer, antioxidant, composite free radical quencher and lubricant, increasing the rotating speed to 1000-1200rpm, putting into a cooling mixer after the temperature of the high-speed mixed material reaches 110-120 ℃, controlling the rotating speed to 15rpm, and discharging when the temperature of the material reaches 40-50 ℃;
2) adding the cooled materials into a double-screw extrusion granulator, wherein the temperatures of the four regions of a machine barrel are respectively as follows: the temperature of the first zone is 90-100 ℃, the temperature of the second zone is 100-;
3) and extruding, plasticizing and granulating the materials, cooling to 35-45 ℃ to obtain the medical hard PVC material, and packaging for later use.
In the technical scheme, the compound free radical quenching agent used by the invention has the advantages of high-efficiency inhibition and combination with free radicals generated after PVC electron beam irradiation sterilization, wherein the compound free radical quenching agent is a stearic acid rare earth organic complex and 2-mercaptobenzimidazole. The stearic acid rare earth organic complex is formed by reacting nitric acid rare earth with stearic acid dissolved in ethanol under alkaline conditions. The rare earth metal elements comprise lanthanum (La), cerium (Ce), neodymium (Nd) and the like, and rare earth metal ions in the rare earth organic complex and organic ligands form ionic bonds mainly through electrostatic attraction and easily form a stable complex with chlorine. Therefore, the rare earth cation can effectively inhibit the removal reaction of active chlorine on the PVC chain, thereby efficiently inhibiting the generation of free radicals on the PVC molecular chain. The 2-mercaptobenzimidazole compound can quickly form free radicals after being irradiated by high-energy rays, and the free radicals react with PVC degradation free radicals to quickly terminate the degradation process.
The antioxidant 1076 and DSTP used in the invention can further inhibit the decomposition of PVC molecular chains after being sterilized by electron beam irradiation, and meanwhile, the phosphite ester is added to have the functions of efficiently chelating PVC and absorbing hydrogen chloride; the auxiliary stabilizer of the epoxy linseed oil can absorb hydrogen chloride to prevent the autocatalysis of PVC.
The heat-resistant modified resin used in the invention is a mixture consisting of 30-50% of alpha-methyl styrene polymer, 30-40% of styrene-maleic anhydride copolymer and 10-30% of styrene acrylonitrile. The resin contains a large amount of benzene rings on a molecular chain, has high rigidity, and thus has good heat resistance; meanwhile, the benzene ring structure can absorb a large amount of radiation energy and homogenize in molecules, so that molecular chains are not easy to break and degrade during irradiation sterilization, and the yellowing resistance of the PVC material is further enhanced.
The invention can obviously inhibit the problems of serious yellowing and reduced mechanical property of medical hard PVC materials after radiation sterilization by matching the above materials, thereby achieving the purpose of radiation-resistant sterility, and simultaneously adding the heat-resistant modifier can improve the use temperature of the hard PVC materials on one hand and improve the yellowing resistance of the materials on the other hand.
Drawings
FIG. 1 is a complex of a rare earth metal ion in a rare earth organic complex and chlorine in an organic ligand, where RE is a rare earth metal.
Detailed Description
The present invention will now be described in detail with reference to specific examples.
Example 1
The material provided by the invention is prepared from the following raw materials in parts by weight:
medical PVC resin powder: 100.0 parts;
organic tin stabilizers: 2.0 parts of (B);
heat-resistant modified resin: 15.0 parts of (B);
impact modifier: 5.0 parts of (B);
processing aid: 2.0 parts of (B);
auxiliary heat stabilizer: 5.0 parts of (B);
antioxidant: 0.5 part;
complex radical quencher: 2.0 parts of (B);
lubricant: 0.6 part.
The medical PVC resin powder is suspension PVC resin, and the polymerization degree is 500-800; the organic tin stabilizer is methyl tin mercaptide stabilizer; the heat-resistant modified resin is a mixture consisting of 30-50% of alpha-methyl styrene polymer, 30-40% of styrene-maleic anhydride copolymer and 10-30% of styrene acrylonitrile; the impact modifier is a styrene impact modifier; the processing aid is a methacrylate processing aid; the auxiliary stabilizer is epoxy linseed oil; the antioxidant is a compound consisting of 30-40% of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate (antioxidant 1076), 30-40% of dioctadecyl thiodipropionate (antioxidant DSTP) and 20-30% of tridecyl phosphite (TTDP); the compound free radical quenching agent is a compound consisting of 50-70% of stearic acid rare earth metal organic complex and 30-50% of 2-mercaptobenzimidazole; the lubricant is a compound consisting of 40-60% of stearic acid and 40-60% of polyethylene wax.
The specific manufacturing steps are as follows:
1) putting PVC resin into a high-speed mixer, regulating the rotating speed to 400rpm, then adding an organic tin stabilizer, an impact modifier, a processing aid, an auxiliary stabilizer, an antioxidant, a composite free radical quencher and a lubricant in proportion, increasing the rotating speed to 1000-1200rpm, putting into a cooling mixer after the temperature of the high-speed mixed material reaches 110-120 ℃, controlling the rotating speed to 15rpm, and discharging when the temperature of the material reaches 40-50 ℃;
2) adding the cooled materials into a double-screw extrusion granulator, wherein the temperatures of the four regions of a machine barrel are respectively as follows: the temperature of the first zone is 90-100 ℃, the temperature of the second zone is 100-;
3) and extruding, plasticizing and granulating the materials, cooling to 35-45 ℃ to obtain the medical hard PVC material, and packaging for later use.
Example 2
The material provided by the invention is prepared from the following raw materials in parts by weight:
medical PVC resin powder: 100.0 parts;
organic tin stabilizers: 3.0 parts of (B);
heat-resistant modified resin: 20.0 portion
Impact modifier: 8.0 parts of (B);
processing aid: 1.5 parts;
auxiliary heat stabilizer: 3.0 parts of (B);
antioxidant: 1.0 part;
complex radical quencher: 1.0 part;
lubricant: 0.8 part.
The medical PVC resin powder is suspension PVC resin, and the polymerization degree is 500-800; the organic tin stabilizer is methyl tin mercaptide stabilizer; the heat-resistant modified resin is a mixture consisting of 30-50% of alpha-methyl styrene polymer, 30-40% of styrene-maleic anhydride copolymer and 10-30% of styrene acrylonitrile; the impact modifier is a styrene impact modifier; the processing aid is a methacrylate processing aid; the auxiliary stabilizer is epoxy linseed oil; the antioxidant is a compound consisting of 30-40% of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate (antioxidant 1076), 30-40% of dioctadecyl thiodipropionate (antioxidant DSTP) and 20-30% of tridecyl phosphite (TTDP); the compound free radical quenching agent is a compound consisting of 50-70% of stearic acid rare earth metal organic complex and 30-50% of 2-mercaptobenzimidazole; the lubricant is a compound consisting of 40-60% of stearic acid and 40-60% of polyethylene wax.
The preparation method is the same as that of example 1.
Example 3
The material provided by the invention is prepared from the following raw materials in parts by weight:
medical PVC resin powder: 100 parts of (A);
organic tin stabilizers: 3.0 parts of (B);
heat-resistant modified resin: 20.0 parts of (B);
impact modifier: 7.0 parts;
processing aid: 1.0 part;
auxiliary heat stabilizer: 2.0 parts of (B);
antioxidant: 0.5 part;
complex radical quencher: 1.5 parts;
lubricant: 1.0 part.
The medical PVC resin powder is suspension PVC resin, and the polymerization degree is 500-800; the organic tin stabilizer is methyl tin mercaptide stabilizer; the heat-resistant modified resin is a mixture consisting of 30-50% of alpha-methyl styrene polymer, 30-40% of styrene-maleic anhydride copolymer and 10-30% of styrene acrylonitrile; the impact modifier is a styrene impact modifier; the processing aid is a methacrylate processing aid; the auxiliary stabilizer is epoxy linseed oil; the antioxidant is a compound consisting of 30-40% of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate (antioxidant 1076), 30-40% of dioctadecyl thiodipropionate (antioxidant DSTP) and 20-30% of tridecyl phosphite (TTDP); the compound free radical quenching agent is a compound consisting of 50-70% of stearic acid rare earth metal organic complex and 30-50% of 2-mercaptobenzimidazole; the lubricant is a compound consisting of 40-60% of stearic acid and 40-60% of polyethylene wax.
The preparation method is the same as that of example 1.
Example 4
The material provided by the invention is prepared from the following raw materials in parts by weight:
medical PVC resin powder: 100 parts of (A);
organic tin stabilizers: 2.5 parts;
heat-resistant modified resin: 30 parts of (1);
impact modifier: 10.0 parts;
processing aid: 1.0 part;
auxiliary heat stabilizer: 2.0 parts of (B);
antioxidant: 0.5 part;
complex radical quencher: 1.2 parts;
lubricant: 1.0 part.
The medical PVC resin powder is suspension PVC resin, and the polymerization degree is 500-800; the organic tin stabilizer is methyl tin mercaptide stabilizer; the heat-resistant modified resin is a mixture consisting of 30-50% of alpha-methyl styrene polymer, 30-40% of styrene-maleic anhydride copolymer and 10-30% of styrene acrylonitrile; the impact modifier is a styrene impact modifier; the processing aid is a methacrylate processing aid; the auxiliary stabilizer is epoxy linseed oil; the antioxidant is a compound consisting of 30-40% of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate (antioxidant 1076), 30-40% of dioctadecyl thiodipropionate (antioxidant DSTP) and 20-30% of tridecyl phosphite (TTDP); the compound free radical quenching agent is a compound consisting of 50-70% of stearic acid rare earth metal organic complex and 30-50% of 2-mercaptobenzimidazole; the lubricant is a compound consisting of 40-60% of stearic acid and 40-60% of polyethylene wax.
The preparation method is the same as that of example 1.
4 examples were selected from the basic formulation of the present invention for verification and testing of various properties, as shown in tables 1 and 2.
Table 1: table for comparing properties of three examples
Table 2: performance detection according to GB 16886 plus 2011 biological evaluation of medical instruments
And (3) testing conditions are as follows: the material prepared according to the invention is sterilized by 40KGY radiation.
As shown by various performance tests of 3 embodiments, the medical hard PVC material prepared by the method greatly improves the thermal deformation temperature, and meanwhile, the mechanical property of the material after 40KGY electron beam irradiation sterilization meets the requirement, and the biological property meets the standard requirement of GB 16886-.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. That is, all equivalent changes and modifications made according to the content of the claims of the present invention should be within the technical scope of the present invention.
Claims (11)
1. A medical hard PVC material with high heat resistance and electron beam irradiation sterilization is characterized in that the medical hard PVC material comprises the following raw material components in parts by weight:
medical PVC resin powder: 100.0 parts;
organic tin stabilizers: 2.0-3.0 parts;
heat-resistant modified resin: 15.0-30.0 parts;
impact modifier: 5.0-10.0 parts;
processing aid: 1.0-2.0 parts;
auxiliary heat stabilizer: 2.0-5.0 parts;
antioxidant: 0.5-1.0 part;
complex radical quencher: 1.0-2.0 parts;
lubricant: 0.5 to 1.0 portion.
2. The material as claimed in claim 1, wherein the medical PVC resin powder is suspension PVC resin with a degree of polymerization of 500-800.
3. The material according to claim 1, characterized in that said organotin stabilizer is a methyltin mercaptide stabilizer.
4. The material of claim 1, wherein the heat-resistant modified resin is a mixture of 30-50% of an α -methylstyrene polymer, 30-40% of a styrene-maleic anhydride copolymer, and 10-30% of styrene acrylonitrile.
5. The material of claim 1, wherein the impact modifier is a styrenic impact modifier.
6. The material of claim 1, wherein said processing aid is a methacrylate processing aid.
7. The material of claim 1 wherein said secondary heat stabilizer is epoxidized linseed oil.
8. The material according to claim 1, characterized in that said antioxidant consists of 30-40% of n-octadecyl- β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1076), 30-40% of dioctadecyl thiodipropionate (antioxidant DSTP) and 20-30% of tridecyl phosphite (TTDP).
9. The material of claim 1, wherein the complex radical quencher comprises 50-70% of organic complex of rare earth metal stearate and 30-50% of 2-mercaptobenzimidazole.
10. The material of claim 1 wherein said lubricant is a composite of 40-60% stearic acid and 40-60% polyethylene wax.
11. The preparation method of medical rigid PVC material with high heat resistance and electron beam irradiation sterilization according to claim 1, characterized in that the method comprises the following specific preparation steps:
1) putting PVC resin into a high-speed mixer, regulating the rotating speed to 400rpm, adding a certain amount of organic tin stabilizer, heat-resistant modified resin, impact modifier, processing aid, auxiliary stabilizer, antioxidant, composite free radical quencher and lubricant, increasing the rotating speed to 1000-1200rpm, putting into a cooling mixer after the temperature of the high-speed mixed material reaches 110-120 ℃, controlling the rotating speed to 15rpm, and discharging when the temperature of the material reaches 40-50 ℃;
2) adding the cooled materials into a double-screw extrusion granulator, wherein the temperatures of the four regions of a machine barrel are respectively as follows: the temperature of the first zone is 90-100 ℃, the temperature of the second zone is 100-;
3) and extruding, plasticizing and granulating the materials, cooling to 35-45 ℃ to obtain the hard PVC material, and packaging for later use.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1358727A (en) * | 2000-12-11 | 2002-07-17 | 周智育 | Distearic acid rareearth maleic acid diester base tin compound and preparation process and use |
| US20030176544A1 (en) * | 2002-03-15 | 2003-09-18 | Polyone Corporation | Rigid PVC compounding compositions exhibiting weather resistance and PVC degradation resistance in hot sunny climates |
| CN102863719A (en) * | 2012-10-29 | 2013-01-09 | 成都市新津事丰医疗器械有限公司 | High-Vicat softening temperature rigid polyvinyl chloride (PVC) medical modified material |
| CN103059470A (en) * | 2012-12-25 | 2013-04-24 | 东莞市祺龙电业有限公司 | A kind of high wear-resisting environment-friendly PVC modified material and preparation method thereof |
| CN104231468A (en) * | 2014-01-03 | 2014-12-24 | 江苏金材科技有限公司 | Anti-radiation medicinal polyvinyl chloride (PVC) hard sheet and preparation method thereof |
| CN105237902A (en) * | 2015-09-09 | 2016-01-13 | 深圳恒方大高分子材料科技有限公司 | Medical PVC material suitable for [beta]-electron beam sterilization and preparation method thereof |
| CN107200952A (en) * | 2017-05-18 | 2017-09-26 | 东莞市兄奕塑胶制品有限公司 | A kind of tasteless environment-friendly type PVC edge band and preparation method thereof |
| CN108148391A (en) * | 2017-12-30 | 2018-06-12 | 广东聚石化学股份有限公司 | A kind of uvioresistant halogen-free flame retardant PC/ABS alloy and preparation method thereof |
-
2020
- 2020-10-16 CN CN202011109429.6A patent/CN112625373B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1358727A (en) * | 2000-12-11 | 2002-07-17 | 周智育 | Distearic acid rareearth maleic acid diester base tin compound and preparation process and use |
| US20030176544A1 (en) * | 2002-03-15 | 2003-09-18 | Polyone Corporation | Rigid PVC compounding compositions exhibiting weather resistance and PVC degradation resistance in hot sunny climates |
| CN102863719A (en) * | 2012-10-29 | 2013-01-09 | 成都市新津事丰医疗器械有限公司 | High-Vicat softening temperature rigid polyvinyl chloride (PVC) medical modified material |
| CN103059470A (en) * | 2012-12-25 | 2013-04-24 | 东莞市祺龙电业有限公司 | A kind of high wear-resisting environment-friendly PVC modified material and preparation method thereof |
| CN104231468A (en) * | 2014-01-03 | 2014-12-24 | 江苏金材科技有限公司 | Anti-radiation medicinal polyvinyl chloride (PVC) hard sheet and preparation method thereof |
| CN105237902A (en) * | 2015-09-09 | 2016-01-13 | 深圳恒方大高分子材料科技有限公司 | Medical PVC material suitable for [beta]-electron beam sterilization and preparation method thereof |
| CN107200952A (en) * | 2017-05-18 | 2017-09-26 | 东莞市兄奕塑胶制品有限公司 | A kind of tasteless environment-friendly type PVC edge band and preparation method thereof |
| CN108148391A (en) * | 2017-12-30 | 2018-06-12 | 广东聚石化学股份有限公司 | A kind of uvioresistant halogen-free flame retardant PC/ABS alloy and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| YASUNORI NIHRO, ET AL: "3-0-Alkylascorbic Acids as Free Radical Quenchers. 3. Protective Effect on Coronary Occlusion-Raperfusion Induced Arrhythmias in Anesthetized Rats", 《J. MED. CHEM.》, vol. 35, no. 9, pages 1618 - 1623 * |
| 傅中华 等: "苯乙烯二乙烯基苯共聚物的辐射效应研究", pages 94 - 99 * |
| 张书华等: "《高性能电缆材料及其应用技术》", 31 December 2015, 上海交通大学出版社, pages: 193 - 194 * |
| 文国元等: "《多能的塑料》", 31 October 1978, 上海科学技术出版社, pages: 60 * |
| 李建军: "《塑料配方设计》", 31 May 2019, 中国轻工业出版社, pages: 279 * |
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