CN113429691A - Butyl rubber polypropylene thermoplastic elastomer capable of being sterilized by irradiation and preparation method thereof - Google Patents
Butyl rubber polypropylene thermoplastic elastomer capable of being sterilized by irradiation and preparation method thereof Download PDFInfo
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- CN113429691A CN113429691A CN202110898925.2A CN202110898925A CN113429691A CN 113429691 A CN113429691 A CN 113429691A CN 202110898925 A CN202110898925 A CN 202110898925A CN 113429691 A CN113429691 A CN 113429691A
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- thermoplastic elastomer
- butyl rubber
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- radiation
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 64
- -1 polypropylene Polymers 0.000 title claims abstract description 59
- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 52
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 50
- 229920005549 butyl rubber Polymers 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 229920001971 elastomer Polymers 0.000 claims abstract description 41
- 239000005060 rubber Substances 0.000 claims abstract description 37
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000004659 sterilization and disinfection Methods 0.000 claims abstract description 21
- 229920005557 bromobutyl Polymers 0.000 claims abstract description 17
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 16
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 16
- 230000001954 sterilising effect Effects 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 14
- 238000004132 cross linking Methods 0.000 claims abstract description 10
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- 230000005855 radiation Effects 0.000 claims description 29
- 238000004073 vulcanization Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 14
- 238000005469 granulation Methods 0.000 claims description 12
- 230000003179 granulation Effects 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 239000000806 elastomer Substances 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 5
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 4
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229920001169 thermoplastic Polymers 0.000 claims description 3
- 239000004416 thermosoftening plastic Substances 0.000 claims description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- 229920002367 Polyisobutene Polymers 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- 229920006132 styrene block copolymer Polymers 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 229920006465 Styrenic thermoplastic elastomer Polymers 0.000 claims 1
- MCPSMQGVSYDFLC-UHFFFAOYSA-N formaldehyde;2-octylphenol Chemical group O=C.CCCCCCCCC1=CC=CC=C1O MCPSMQGVSYDFLC-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 3
- 239000005022 packaging material Substances 0.000 abstract description 2
- GUTLYIVDDKVIGB-OUBTZVSYSA-N Cobalt-60 Chemical compound [60Co] GUTLYIVDDKVIGB-OUBTZVSYSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 10
- 230000008569 process Effects 0.000 description 6
- 239000004033 plastic Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000002285 radioactive effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 229920005555 halobutyl Polymers 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229940127554 medical product Drugs 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 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 description 1
- 238000009512 pharmaceutical packaging Methods 0.000 description 1
- 239000011129 pharmaceutical packaging material Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010074 rubber mixing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
- C08L23/283—Halogenated homo- or copolymers of iso-olefins
-
- 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
- C08L2205/03—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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Apparatus For Disinfection Or Sterilisation (AREA)
- Medical Preparation Storing Or Oral Administration Devices (AREA)
Abstract
The invention discloses a butyl rubber polypropylene thermoplastic elastomer capable of being sterilized by irradiation and a preparation method thereof, wherein the butyl rubber polypropylene thermoplastic elastomer comprises the following components in parts by mass: 100 parts of brominated butyl rubber, 20-40 parts of irradiation-resistant polypropylene resin, 40-70 parts of medical-grade rubber softening oil, 5-20 parts of styrene thermoplastic elastomer, 0.2-2 parts of cross-linking agent and cross-linking assistant, 0.1-1 part of antioxidant and 0.1-1 part of processing assistant. The butyl rubber polypropylene thermoplastic elastomer capable of being sterilized by irradiation has the characteristics of low hardness, excellent elasticity and air tightness, can meet the use requirement of a medical rubber plug material, can be sterilized by irradiation, has basically no reduction in mechanical property after being sterilized by irradiation of cobalt-60, and can meet the use requirement of a medical packaging material. The medical rubber plug sterilization device is applied to the field of medical rubber plugs, not only can simplify the production process flow of the medical rubber plugs, but also can shorten the sterilization flow of the medical rubber plugs and improve the efficiency.
Description
Technical Field
The invention relates to a butyl rubber polypropylene thermoplastic elastomer capable of being sterilized by irradiation and a preparation method thereof, belonging to the field of processing of high polymer materials.
Background
The halogenated butyl rubber not only has the advantages of high gas barrier property, aging resistance, high heat resistance, high damping property and the like of butyl rubber, but also has the characteristics of high vulcanization speed, high vulcanization efficiency, high vulcanization degree, small vulcanizing agent consumption, no zinc vulcanization and the like, and becomes an indispensable material in the field of medical rubber plugs. However, the traditional thermosetting butyl medical rubber plug product is generally produced by compression molding, and the production process comprises the working procedures of batching, raw rubber mixing, molding, vulcanizing, trimming, washing, drying and the like. The process flow is long, the equipment investment is large, the manual production cost is high, and impurities are easy to introduce.
Novel pharmaceutical packaging materials published by State Federal for development and improvement in 2013, 2 months, "Industrial Structure adjustment guide catalog" (2011), technical development and production thereof are listed in the sub-industry encouraging development in the pharmaceutical industry, and ultra-clean materials, high-barrier functional materials and novel administration mode packaging in the pharmaceutical packaging industry are particularly mentioned. In technical guidance principles (trial) for research on compatibility of chemicals and elastomer sealing elements published in 2018 in China, thermoplastic elastomers are listed as materials allowed by medical rubber sealing elements, and the guidance principles require that the thermoplastic elastomer sealing elements meet the requirements of a packaging system on sealing performance on one hand and have good compatibility with medicines on the other hand.
The BIIR/PP TPV dynamic vulcanization thermoplastic elastomer is a special TPV prepared by a large amount of BIIR and a small amount of PP through a full dynamic vulcanization technology, not only has the processability and the characteristic that leftover bits and pieces of TPV can be recycled, but also has the excellent elasticity and high barrier property of thermosetting butyl rubber, and the BIIR/PP TPV material has simple composition, complete vulcanization, no auxiliary agent prohibited to be added in a compatibility guiding principle, cleaner production process, simple process, energy conservation and synergy.
All medical products require sterilization prior to use. The traditional ethylene oxide disinfection method has the problem of air pollution, and the common medical rubber plug alkali liquor damp-heat method has the possibility of residues on medical instruments or medicine packaging materials and can cause harm to human bodies. Compared with the two disinfection methods, the irradiation disinfection method has the advantages of thorough disinfection, no residue and the like. In recent years, the radiation sterilization method is gradually replacing the ethylene oxide sterilization method and the wet heat sterilization method. However, the general medical grade PP has poor radiation stability, the mechanical property of the PP after radiation sterilization is seriously deteriorated, the color of the PP turns yellow, and the aging phenomenon is aggravated along with the increase of time, so that the using function is lost. With the irradiation disinfection becoming the main mode of medical supplies disinfection, the medical irradiation-resistant PP material has become a hot spot of competitive development in various countries.
If the medical rubber plug of the butyl rubber polypropylene thermoplastic elastomer which can be subjected to thermoplastic processing and can be sterilized by irradiation can be developed, the production process flow of the medical rubber plug can be greatly simplified, the sterilization process flow of the medical rubber plug can be shortened, and the efficiency is improved.
Disclosure of Invention
The invention aims to solve the technical problem of providing a butyl rubber polypropylene thermoplastic elastomer capable of being sterilized by irradiation and a preparation method thereof.
In order to solve the technical problem, the invention provides the following scheme: a butyl rubber polypropylene thermoplastic elastomer capable of being sterilized by radiation comprises the following components in parts by mass:
wherein:
further, the Mooney viscosity of the brominated butyl rubber is 32-46 (ML (1+8)125 ℃), and the halogen content is 1.25-1.8 mol%.
Furthermore, the melt index of the radiation-resistant polypropylene resin is 10-28 g/10 min. (test conditions 230 ℃ C., 2.16kg)
Further, the medical rubber softener is white oil, naphthenic oil orA polyisobutene having a kinematic viscosity at 40 ℃ of 40mm2/s～200mm2/s。
Further, the styrene thermoplastic elastomer is styrene-ethylene-propylene-styrene block copolymer thermoplastic elastomer
4044、
4055 or Yuanization YH-503T.
Furthermore, the filler is selected from one of talcum powder, calcined kaolin, montmorillonite and calcium carbonate or a composition of at least two of the talcum powder, the calcined kaolin, the montmorillonite and the calcium carbonate according to any proportion.
Further, the cross-linking agent is octyl phenolic resin, and one or a combination of at least two of HY-2055, SP-1045 and SP-1055 in any proportion.
Further, the crosslinking assistant is zinc oxide or stannous chloride.
Further, the antioxidant is: one of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (hereinafter, referred to as an antioxidant 1010), dodecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (hereinafter, referred to as an antioxidant 1076), poly { [6- [ (1,1,3, 3-tetramethylbutyl) amino ] ] -1,3, 5-triazine-2, 4-bis [ (2,2,6,6, -tetramethyl-piperidyl) imino ] -1, 6-hexadiene [ (2,2,6, 6-tetramethyl-4-piperidyl) imino ] } (hereinafter, referred to as an antioxidant 944) or a combination of at least two of them at an arbitrary ratio.
Further, the processing aid is one of PE wax, PP wax and silicone master batch or a composition of at least two of the PE wax, the PP wax and the silicone master batch according to any proportion.
The second purpose of the invention is to provide a preparation method of the butyl rubber polypropylene thermoplastic elastomer capable of being sterilized by radiation, which comprises the following steps:
s1, weighing the brominated butyl rubber, the radiation-resistant PP, the medical-grade rubber softening oil, the styrene elastomer, the antioxidant and the processing aid according to parts by weight, mixing in an internal mixer to obtain a premix,
s2, adding the premix into a main feed of a double-screw extruder, adding the cross-linking agent and the cross-linking auxiliary agent into a side feed of the double-screw extruder, and carrying out dynamic vulcanization extrusion granulation to obtain the butyl rubber polypropylene thermoplastic elastomer particles capable of being subjected to irradiation sterilization.
Further, the melt extrusion temperature of the double-screw extruder is 170-210 ℃, and the screw rotating speed is 300-500 rpm/min.
The invention has the beneficial effects that:
the butyl rubber polypropylene thermoplastic elastomer capable of being sterilized by irradiation has certain irradiation resistance by adding the irradiation-resistant polypropylene resin and the styrene thermoplastic elastomer. The molecular chain of the styrene thermoplastic elastomer contains benzene rings, and the sponge effect of the benzene rings can reduce the damage of irradiation on the molecular chain of the polymer, so that the butyl rubber polypropylene thermoplastic elastomer has certain irradiation resistance. The hindered amine antioxidant can eliminate peroxy radicals and decompose hydroperoxides, thereby effectively inhibiting the breakage of polypropylene molecular chains in the irradiation process, and further improving the irradiation resistance of the butyl rubber polypropylene thermoplastic elastomer.
The butyl rubber polypropylene thermoplastic elastomer capable of being sterilized by irradiation can not only keep the excellent elasticity and sealing property of the low-hardness butyl rubber polypropylene thermoplastic elastomer, but also be sterilized by irradiation, so that the application range of the butyl rubber polypropylene thermoplastic elastomer is expanded, and the safety of the elastomer material in the application of medical packaging is improved.
By comparing the comparative examples to which no radiation-resistant polypropylene was added, it was found that not only there was no radiation sterilizability but also the mechanical properties decreased rapidly after irradiation. The rubber plug can be applied to the field of medical rubber plugs, medical packaging products such as medical rubber plugs, pre-encapsulated rubber plugs, combined covers, oral liquid gaskets and the like can be directly formed by injection molding, the sterilization process can be simplified, energy is saved, efficiency is improved, and the cost is reduced.
Detailed Description
The present invention will be further described with reference to the following specific examples, but the present invention is not limited to the examples set forth below.
The method for evaluating the tensile property of the butyl rubber polypropylene thermoplastic elastomer capable of being sterilized by irradiation adopts GB/T528-2009; the evaluation method of the hardness adopts GB/T2411-2008; GB/T7759.1-2015 was used for compression set.
The irradiation process is completed in air at normal temperature and the irradiation source is 1.5X 1015The Co-60 plate-shaped gamma-ray radioactive source with Bq radioactive intensity has the irradiation dose rate of 4kGy/h and the irradiation dose of 25kGy or 50 kGy.
Examples 1 to 3: butyl rubber polypropylene thermoplastic elastomer material capable of being sterilized by irradiation and preparation method thereof
The preparation method of the butyl rubber polypropylene thermoplastic elastomer material capable of being sterilized by irradiation specifically comprises the following steps:
the following examples 1-3 and comparative examples 1-2 all adopt the preparation method of the butyl rubber polypropylene thermoplastic elastomer material capable of being sterilized by irradiation, and the difference is that the mixture ratio fractions of the raw materials are different.
Example 1:
the formula of the butyl rubber polypropylene thermoplastic elastomer capable of being sterilized by irradiation comprises the following components in parts by weight.
The preparation process comprises the following steps:
(1) rubber and plastic pre-mixing: the brominated butyl rubber, the radiation-resistant polypropylene resin, the medical-grade rubber softening oil, the styrene thermoplastic elastomer, the antioxidant and other auxiliaries are mixed according to respective parts by weight, then the mixture is put into an internal mixer, the temperature of the internal mixer is 165 ℃, the internal mixing is carried out for 30min, the rubber and the resin are fully and uniformly mixed, and the mixture is sent into a single-screw extruder for granulation, so that a pre-mixed intermediate is obtained.
(2) Dynamic vulcanization: and (3) putting the premixed intermediate, the cross-linking agent and the cross-linking auxiliary agent into a double-screw extruder according to a certain proportion for dynamic vulcanization and granulation, wherein the rotating speed of a screw is 350r/min, and the length-diameter ratio of the screw is 48.
Example 2:
the formula of the butyl rubber polypropylene thermoplastic elastomer capable of being sterilized by irradiation comprises the following components in parts by weight.
The preparation process comprises the following steps:
(1) rubber and plastic pre-mixing: the brominated butyl rubber, the radiation-resistant polypropylene resin, the medical-grade rubber softening oil, the styrene thermoplastic elastomer, the antioxidant and other auxiliaries are mixed according to respective parts by weight, then the mixture is put into an internal mixer, the temperature of the internal mixer is 165 ℃, the internal mixing is carried out for 30min, the rubber and the resin are fully and uniformly mixed, and the mixture is sent into a single-screw extruder for granulation, so that a pre-mixed intermediate is obtained.
(2) Dynamic vulcanization: and (3) putting the premixed intermediate, the cross-linking agent and the cross-linking auxiliary agent into a double-screw extruder according to a certain proportion for dynamic vulcanization and granulation, wherein the rotating speed of a screw is 350r/min, and the length-diameter ratio of the screw is 48.
Example 3:
the formula of the butyl rubber polypropylene thermoplastic elastomer capable of being sterilized by irradiation comprises the following components in parts by weight.
The preparation process comprises the following steps:
(1) rubber and plastic pre-mixing: the brominated butyl rubber, the radiation-resistant polypropylene resin, the medical-grade rubber softening oil, the styrene thermoplastic elastomer, the antioxidant and other auxiliaries are mixed according to respective parts by weight, then the mixture is put into an internal mixer, the temperature of the internal mixer is 165 ℃, the internal mixing is carried out for 30min, the rubber and the resin are fully and uniformly mixed, and the mixture is sent into a single-screw extruder for granulation, so that a pre-mixed intermediate is obtained.
(2) Dynamic vulcanization: and (3) putting the premixed intermediate, the cross-linking agent and the cross-linking auxiliary agent into a double-screw extruder according to a certain proportion for dynamic vulcanization and granulation, wherein the rotating speed of a screw is 350r/min, and the length-diameter ratio of the screw is 48.
Comparative example 1:
the butyl rubber polypropylene thermoplastic elastomer comprises the following components in parts by weight.
The preparation process comprises the following steps:
(1) rubber and plastic pre-mixing: the brominated butyl rubber, the polypropylene resin, the medical-grade rubber softening oil, the styrene thermoplastic elastomer, the antioxidant and other auxiliaries are mixed according to respective parts by weight, then the mixture is put into an internal mixer, the temperature of the internal mixer is 165 ℃, the internal mixing is carried out for 30min, the rubber and the resin are fully and uniformly mixed, and the mixture is sent into a single-screw extruder for granulation, so that a pre-mixing intermediate is obtained.
(2) Dynamic vulcanization: and (3) putting the premixed intermediate, the cross-linking agent and the cross-linking auxiliary agent into a double-screw extruder according to a certain proportion for dynamic vulcanization and granulation, wherein the rotating speed of a screw is 350r/min, and the length-diameter ratio of the screw is 48.
Comparative example 2:
the butyl rubber polypropylene thermoplastic elastomer comprises the following components in parts by weight.
The preparation process comprises the following steps:
(1) rubber and plastic pre-mixing: the brominated butyl rubber, the polypropylene resin, the medical-grade rubber softening oil, the styrene thermoplastic elastomer, the antioxidant and other auxiliaries are mixed according to respective parts by weight, then the mixture is put into an internal mixer, the temperature of the internal mixer is 165 ℃, the internal mixing is carried out for 30min, the rubber and the resin are fully and uniformly mixed, and the mixture is sent into a single-screw extruder for granulation, so that a pre-mixing intermediate is obtained.
(2) Dynamic vulcanization: and (3) putting the premixed intermediate, the cross-linking agent and the cross-linking auxiliary agent into a double-screw extruder according to a certain proportion for dynamic vulcanization and granulation, wherein the rotating speed of a screw is 350r/min, and the length-diameter ratio of the screw is 48.
The raw materials used in the above examples and comparative examples are illustrated below:
1. brominated butyl rubber used was either brominated butyl rubber 2211 manufactured by Exxon Mobil, USA, BBK-232 manufactured by Nizhnekamsk, Russia, or brominated butyl rubber 2040 manufactured by Arrhenikogaceae, Germany. The brominated butyl rubber has a halogen content of 1.25 to 1.8 mol% and a Mooney viscosity of 32 to 46(ML (1+8)125 ℃).
2. The radiation-resistant polypropylene adopts K2328 (medical grade) produced by Yanshan petrochemical industry, PP J-560M (medical grade) produced by Letian chemical industry or K1P38 (medical grade) produced by Taiwan chemical industry, and the radiation-resistant dose is 50 kGy. The melt index was around 28g/10 min.
3. The medical grade rubber softening oil adopts medical grade naphthenic oil, and the kinematic viscosity of the medical grade naphthenic oil at 40 ℃ is between 40 and 200 square millimeters per second.
4. As the styrene-based thermoplastic elastomer, YH-503T produced by Yuanization or SEEPS-4055 produced by SEPTON 4033 of Coly corporation is used.
5. The antioxidant is antioxidant 1010 or antioxidant 944.
Table 1: comparison of Performance between examples 1 to 3 and comparative examples 1 to 2
The tensile strength of the above-described butyl rubber polypropylene thermoplastic elastomer as a function of time is shown in Table 2.
TABLE 2 tensile Strength of butyl rubber Polypropylene thermoplastic elastomer as a function of time
| Day of radiation sterilization | After 1 week of irradiation sterilization | Sterilizing by irradiation for 1 month | After irradiation sterilization for half a year | |
| Example 1 | 4.2 | 4.1 | 4.2 | 4.2 |
| Example 2 | 4.4 | 4.3 | 4.4 | 4.4 |
| Example 3 | 4.5 | 4.4 | 4.6 | 4.4 |
| Comparative example 1 | 3.0 | 2.8 | 2.6 | 2.6 |
| Comparative example 2 | 3.0 | 2.9 | 2.6 | 2.5 |
Through comparison between the examples 1-3 and the comparative examples 1-2, the thermoplastic elastomer of the composition disclosed by the invention is added with the radiation-resistant polypropylene and the styrene thermoplastic elastomer, and the hindered phenol antioxidant and the hindered amine antioxidant to be compounded, so that the composition can obtain radiation sterilization performance, and the comparative example without the radiation-resistant polypropylene is not added, and after radiation, the mechanical property is reduced quickly, so that the composition cannot be used for a long time.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (10)
1. A butyl rubber polypropylene thermoplastic elastomer capable of being sterilized by irradiation is characterized by comprising the following components in parts by mass:
2. the radiation sterilizable butyl rubber polypropylene thermoplastic elastomer according to claim 1, wherein the brominated butyl rubber has a Mooney viscosity of 32 to 46 and a halogen content of 1.25 to 1.8 mol%.
3. The radiation sterilizable butyl rubber polypropylene thermoplastic elastomer according to claim 1, wherein the melt index of the radiation resistant polypropylene resin is 10-28 g/10 min.
4. The radiation sterilizable butyl rubber polypropylene thermoplastic elastomer according to claim 1, wherein the medical-grade rubber softener is white oil, naphthenic oil or polyisobutylene having a kinematic viscosity of 40mm at 40 ℃ C2/s～200mm2/s。
5. The radiation sterilizable butyl rubber polypropylene thermoplastic elastomer of claim 1, wherein the styrenic thermoplastic elastomer is a styrene-ethylene-propylene-styrene block copolymer thermoplastic elastomer
4044、
4055 or YH-503T.
6. The radiation sterilizable butyl rubber polypropylene thermoplastic elastomer according to claim 1, wherein the crosslinking agent is octyl phenol-formaldehyde resin, one of HY-2055, SP-1045 and SP-1055 or a combination of at least two of the foregoing in any proportion; the crosslinking assistant is zinc oxide or stannous chloride.
7. The radiation sterilizable butyl rubber polypropylene thermoplastic elastomer of claim 1, wherein the antioxidant is: pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], dodecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, poly { [6- [ (1,1,3, 3-tetramethylbutyl) amino ] ] -1,3, 5-triazine-2, 4-bis [ (2,2,6,6, -tetramethyl-piperidyl) imino ] -1, 6-hexamethylene [ (2,2,6, 6-tetramethyl-4-piperidyl) imino ] } or a combination of at least two thereof in an arbitrary ratio.
8. The processing aid is one of PE wax, PP wax and silicone master batch or a composition of at least two of the PE wax, the PP wax and the silicone master batch according to any proportion.
9. A method for preparing the butyl rubber polypropylene thermoplastic elastomer capable of being sterilized by radiation according to any one of claims 1 to 8, which comprises the following steps:
s1, weighing the brominated butyl rubber, the radiation-resistant PP, the medical-grade rubber softening oil, the styrene elastomer, the antioxidant and the processing aid in parts by weight, and mixing in an internal mixer to obtain a premix;
s2, adding the premix into a main feed of a double-screw extruder, adding the cross-linking agent and the cross-linking auxiliary agent into a side feed of the double-screw extruder, and carrying out dynamic vulcanization extrusion granulation to obtain the radiation sterilization resistant butyl dynamic vulcanization thermoplastic elastomer particles.
10. The method according to claim 9, wherein the melt extrusion temperature of the twin-screw extruder is 170 to 210 ℃ and the screw rotation speed is 300 to 500 rpm/min.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101247838A (en) * | 2005-08-26 | 2008-08-20 | 贝克顿迪肯森公司 | Methods of sterilizing elastomeric sealing articles |
| CN103834099A (en) * | 2012-11-27 | 2014-06-04 | 中国石油天然气股份有限公司 | Special radiation-resistant medical polypropylene material |
| CN110776699A (en) * | 2019-10-28 | 2020-02-11 | 郑州大学 | Radiation-resistant sterilizing medicinal thermoplastic elastomer and preparation method thereof |
| CN110791031A (en) * | 2019-12-04 | 2020-02-14 | 北京橡胶工业研究设计院有限公司 | Low-hardness brominated butyl rubber polypropylene thermoplastic elastomer |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101247838A (en) * | 2005-08-26 | 2008-08-20 | 贝克顿迪肯森公司 | Methods of sterilizing elastomeric sealing articles |
| CN103834099A (en) * | 2012-11-27 | 2014-06-04 | 中国石油天然气股份有限公司 | Special radiation-resistant medical polypropylene material |
| CN110776699A (en) * | 2019-10-28 | 2020-02-11 | 郑州大学 | Radiation-resistant sterilizing medicinal thermoplastic elastomer and preparation method thereof |
| CN110791031A (en) * | 2019-12-04 | 2020-02-14 | 北京橡胶工业研究设计院有限公司 | Low-hardness brominated butyl rubber polypropylene thermoplastic elastomer |
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