CN117164922A - Polytetrafluoroethylene-butyl rubber composite rubber plug for injector and preparation method thereof - Google Patents
Polytetrafluoroethylene-butyl rubber composite rubber plug for injector and preparation method thereof Download PDFInfo
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- CN117164922A CN117164922A CN202311214579.7A CN202311214579A CN117164922A CN 117164922 A CN117164922 A CN 117164922A CN 202311214579 A CN202311214579 A CN 202311214579A CN 117164922 A CN117164922 A CN 117164922A
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- polytetrafluoroethylene
- butyl rubber
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- rubber plug
- coating
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- 229920005549 butyl rubber Polymers 0.000 title claims abstract description 115
- 229920001971 elastomer Polymers 0.000 title claims abstract description 72
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 51
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 95
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 95
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 95
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000000576 coating method Methods 0.000 claims abstract description 47
- 239000004962 Polyamide-imide Substances 0.000 claims abstract description 46
- 239000011248 coating agent Substances 0.000 claims abstract description 46
- 229920002312 polyamide-imide Polymers 0.000 claims abstract description 46
- 239000003822 epoxy resin Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 14
- 238000010008 shearing Methods 0.000 claims abstract description 10
- 229910021389 graphene Inorganic materials 0.000 claims description 31
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- 239000004094 surface-active agent Substances 0.000 claims description 16
- 229920000459 Nitrile rubber Polymers 0.000 claims description 14
- 229920005557 bromobutyl Polymers 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 239000005995 Aluminium silicate Substances 0.000 claims description 10
- 239000004147 Sorbitan trioleate Substances 0.000 claims description 10
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 claims description 10
- 235000012211 aluminium silicate Nutrition 0.000 claims description 10
- 239000006229 carbon black Substances 0.000 claims description 10
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 10
- 229960000391 sorbitan trioleate Drugs 0.000 claims description 10
- 235000019337 sorbitan trioleate Nutrition 0.000 claims description 10
- 235000021355 Stearic acid Nutrition 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 9
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 9
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 9
- 239000008117 stearic acid Substances 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 239000011787 zinc oxide Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 150000003505 terpenes Chemical class 0.000 claims description 5
- 235000007586 terpenes Nutrition 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 239000007849 furan resin Substances 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 238000004073 vulcanization Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 10
- 238000007789 sealing Methods 0.000 abstract description 10
- 230000000052 comparative effect Effects 0.000 description 19
- 239000003814 drug Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 8
- 229940079593 drug Drugs 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920005555 halobutyl Polymers 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- QYQDKDWGWDOFFU-IUODEOHRSA-N Cefotiam Chemical compound CN(C)CCN1N=NN=C1SCC1=C(C(O)=O)N2C(=O)[C@@H](NC(=O)CC=3N=C(N)SC=3)[C@H]2SC1 QYQDKDWGWDOFFU-IUODEOHRSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229960001242 cefotiam Drugs 0.000 description 1
- 229960000479 ceftriaxone sodium Drugs 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- FDRNWTJTHBSPMW-GNXCPKRQSA-L disodium;(6r,7r)-7-[[(2e)-2-(2-amino-1,3-thiazol-4-yl)-2-methoxyiminoacetyl]amino]-3-[(2-methyl-6-oxido-5-oxo-1,2,4-triazin-3-yl)sulfanylmethyl]-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylate Chemical compound [Na+].[Na+].S([C@@H]1[C@@H](C(N1C=1C([O-])=O)=O)NC(=O)/C(=N/OC)C=2N=C(N)SC=2)CC=1CSC1=NC(=O)C([O-])=NN1C FDRNWTJTHBSPMW-GNXCPKRQSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
Abstract
The application relates to the field of butyl rubber plugs, and particularly discloses a polytetrafluoroethylene-butyl rubber composite rubber plug for an injector and a preparation method thereof. The polytetrafluoroethylene-butyl rubber composite rubber plug for the injector comprises a butyl rubber plug and a polytetrafluoroethylene film wrapped on the surface of the butyl rubber plug, wherein the polytetrafluoroethylene film is coated by a coating comprising the following components in parts by mass: 60-80 parts of polytetrafluoroethylene, 5-15 parts of epoxy resin, 3-8 parts of polyamide-imide modified graphene, 0.5-2 parts of auxiliary agent and 80-100 parts of solvent; the preparation method comprises the following steps: mixing the raw materials according to the proportion, and shearing and uniformly mixing to obtain polytetrafluoroethylene coating; and (3) coating polytetrafluoroethylene coating on the surface of the butyl rubber plug, and curing at 180-250 ℃ to obtain the composite rubber plug. The polytetrafluoroethylene-butyl rubber composite rubber plug has the advantages of good sealing performance, difficult peeling of polytetrafluoroethylene films and strong use stability.
Description
Technical Field
The application relates to the field of butyl rubber plugs, in particular to a polytetrafluoroethylene-butyl rubber composite rubber plug for an injector.
Background
Halogenated butyl rubber is commonly used in the field of manufacturing medical rubber plugs, including rubber plugs for syringes, due to the characteristics of low air permeability, low moisture permeability, good heat aging resistance, high cleanliness and the like.
Since the rubber plug and the drug undergo cross reaction by adsorption, absorption or leaching, a coating film or a film coating treatment is usually carried out on the surface of the butyl rubber plug. In the related art, a polytetrafluoroethylene film is coated on the surface of a naked butyl rubber plug, so that the precipitation of vulcanizing agents and various other additives in the halogenated butyl rubber plug can be effectively blocked after the polytetrafluoroethylene film is formed, the pollution to the stored product is avoided, and the compatibility of the butyl rubber plug body and medicines is improved.
However, the polytetrafluoroethylene film has limited ductility and low mutual adhesion with the butyl rubber stopper body, and interlayer separation is liable to occur, so that the polytetrafluoroethylene film is likely to be broken and peeled off during the use of the rubber stopper for the syringe, and the butyl rubber body is likely to be exposed, and therefore, the improvement is required.
Disclosure of Invention
In order to ensure the use stability of the rubber plug for the injector, the application provides a polytetrafluoroethylene-butyl rubber composite rubber plug for the injector and a preparation method thereof.
In a first aspect, the application provides a polytetrafluoroethylene-butyl rubber composite rubber plug for an injector, which adopts the following technical scheme:
the polytetrafluoroethylene-butyl rubber composite rubber plug for the injector comprises a butyl rubber plug and a polytetrafluoroethylene film wrapped on the surface of the butyl rubber plug, wherein the polytetrafluoroethylene film is coated by a coating comprising the following components in parts by mass:
60-80 parts of polytetrafluoroethylene,
5-15 parts of epoxy resin,
3-8 parts of polyamide-imide modified graphene,
0.5-2 parts of auxiliary agent,
80-100 parts of solvent.
By adopting the technical scheme, the adhesive capacity of the polytetrafluoroethylene film to the butyl rubber plug body is improved by blending the epoxy resin and the polytetrafluoroethylene, and meanwhile, the toughness and the extensibility of the polytetrafluoroethylene film are improved, and the sealing performance of the polytetrafluoroethylene film is ensured; the graphene is beneficial to enhancing the toughness and ageing resistance of the polytetrafluoroethylene film, can adsorb alkane long-chain molecules, is beneficial to improving the compatibility of each component, can increase the specific surface area of the connecting interface of the polytetrafluoroethylene film and the butyl rubber plug, and is beneficial to improving the bonding strength of the polytetrafluoroethylene film to the butyl rubber; the polyamide imide has good adhesiveness and flexibility, can generate crosslinking reaction with the epoxy resin, and improves the adhesive strength of the polytetrafluoroethylene film; the polyamide imide is used for grafting modification of the graphene, so that the dispersion performance of the graphene is improved, the uniform dispersion of the graphene is promoted, and meanwhile, the adhesive performance and the flexibility of the polytetrafluoroethylene film are further improved;
according to the application, the polytetrafluoroethylene film is improved, so that the toughness and extensibility of the polytetrafluoroethylene film are improved, the bonding strength of the polytetrafluoroethylene film to the butyl rubber plug body is improved, the possibility that the polytetrafluoroethylene film is broken and peeled off from the butyl rubber plug body in the use process of the polytetrafluoroethylene-butyl rubber composite rubber plug is reduced, and the use stability and durability of the polytetrafluoroethylene-butyl rubber composite rubber plug are improved.
Preferably, the preparation method of the polyamideimide-modified graphene comprises the following steps:
dissolving aqueous polyamide-imide and a surfactant into an alcohol-water solution, adding graphene powder, carrying out ultrasonic treatment for 30-60min, separating, and drying to obtain polyamide-imide modified graphene.
Preferably, the mass ratio of the aqueous polyamide imide to the surfactant to the graphene powder is 1 (0.01-0.05) to 5-8.
Preferably, the surfactant is a fluoro surfactant.
By adopting the technical scheme, the polyamide imide is grafted to the graphene, so that the compatibility of the graphene, polytetrafluoroethylene and epoxy resin is improved, and the uniform dispersion of the graphene is promoted; the surfactant treatment is beneficial to further improving the dispersion performance of the graphene and improving the grafting efficiency of the polyamide imide.
Preferably, the auxiliary agent is selected from one or a combination of more of self-crosslinking agent, defoamer, emulsifier and coupling agent.
Preferably, the solvent is selected from one or more of an ester solvent, an alcohol solvent, and an alcohol ether solvent.
By adopting the technical scheme, the full dissolution and mixing of the components are promoted.
Preferably, the butyl rubber plug comprises the following components in parts by weight:
80-100 parts of brominated butyl rubber,
10-20 parts of hydrogenated nitrile rubber,
5-15 parts of terpene resin,
2-5 parts of sorbitan trioleate,
1-10 parts of calcined kaolin,
1-10 parts of carbon black,
1-5 parts of zinc oxide,
2-3 parts of promoter,
1-3 parts of stearic acid,
5-8 parts of aromatic hydrocarbon oil,
1.5-2 parts of sulfur.
By adopting the technical scheme, the hydrogenated nitrile rubber has good sealing property, corrosion resistance, heat resistance and cohesiveness, and the processability of a butyl rubber system is improved by adding the hydrogenated nitrile rubber and the brominated butyl rubber, so that the mutual viscosity and the self-adhesion of the butyl rubber plug are improved, and the cohesive strength of the polytetrafluoroethylene film to the butyl rubber plug is improved; by adding tackifying resin, the components are bonded together, and the mutual adhesiveness of the butyl rubber plug body and the polytetrafluoroethylene film is improved; the sorbitan trioleate as a nonionic surfactant can improve the dispersion effect of calcined kaolin, carbon black and alumina inorganic matters, is beneficial to improving the compatibility of all components, enhances the acting force among all components and improves the blending effect;
according to the application, through optimizing the raw material formula of the butyl rubber plug, the self-adhesion and mutual adhesion of the butyl rubber plug are improved while the sealing performance of the butyl rubber plug is ensured, the adhesion of the polytetrafluoroethylene film to the butyl rubber plug is promoted, the possibility of stripping between the polytetrafluoroethylene film and the butyl rubber plug body is further reduced, and the use stability of the polytetrafluoroethylene-butyl rubber composite rubber plug is improved.
Preferably, the tackifying resin is one or a combination of more of terpene resin, phenolic resin and furan resin.
Preferably, the accelerator is selected from one or more of accelerator TMTD, accelerator CZ, accelerator M and accelerator DM.
Preferably, the polytetrafluoroethylene film is coated to a thickness of 4-10 μm.
By adopting the technical scheme, the possibility of insufficient wear resistance and protection effect caused by excessively thin polytetrafluoroethylene film is reduced, and the possibility of elasticity reduction of the butyl rubber plug caused by the excessively thin polytetrafluoroethylene film is reduced.
In a second aspect, the application provides a preparation method of a polytetrafluoroethylene-butyl rubber composite rubber plug for an injector, which adopts the following technical scheme:
a preparation method of a polytetrafluoroethylene-butyl rubber composite rubber plug for an injector comprises the following steps:
according to the proportion, polytetrafluoroethylene, epoxy resin, polyamide-imide modified graphene, an auxiliary agent and a solvent are mixed. Mixing, shearing and uniformly mixing at 70-90 ℃ to obtain polytetrafluoroethylene coating;
and (3) coating polytetrafluoroethylene coating on the surface of the butyl rubber plug, and curing at 180-250 ℃ to obtain the composite rubber plug.
By adopting the technical scheme, the adhesion between the polytetrafluoroethylene coating and the butyl rubber plug is good, and the toughness and ductility of the cured polytetrafluoroethylene film are good, so that the polytetrafluoroethylene-butyl rubber composite rubber plug has excellent use effect and application stability.
Preferably, the brominated butyl rubber, the hydrogenated nitrile rubber, the tackifying resin, the sorbitan trioleate, the calcined kaolin, the carbon black, the zinc oxide, the accelerator, the stearic acid, the aromatic hydrocarbon oil and the sulfur are mixed according to the proportion, are mixed, are put into a mold for vulcanization after the rubber is discharged, and are obtained.
By adopting the technical scheme, the butyl rubber plug with good sealing performance, mutual adhesion and better self-adhesion can be prepared.
In summary, the application has the following beneficial effects:
1. according to the application, the polytetrafluoroethylene film is improved, so that the toughness and extensibility of the polytetrafluoroethylene film are improved, the adhesive strength of the polytetrafluoroethylene film to the butyl rubber plug body is improved, the possibility that the polytetrafluoroethylene film is broken and peeled off from the butyl rubber plug body in the use process of the polytetrafluoroethylene-butyl rubber composite rubber plug is reduced, and the use stability and durability of the polytetrafluoroethylene-butyl rubber composite rubber plug are improved;
2. according to the application, through blending of the epoxy resin and the polytetrafluoroethylene, the bonding capacity of the polytetrafluoroethylene film to the butyl rubber plug body is improved, and meanwhile, the toughness and the extensibility of the polytetrafluoroethylene film are improved; by adding the polyamide-imide grafted graphene, the uniform dispersion of the graphene is ensured, the specific surface area of the joint interface of the polytetrafluoroethylene film and the butyl rubber plug body is increased, the bonding strength of the polytetrafluoroethylene film to the butyl rubber is improved, the characteristics of good adhesiveness and flexibility of the polyamide-imide are fully exerted, and the bonding performance and flexibility of the polytetrafluoroethylene film are further improved;
3. according to the application, the hydrogenated nitrile rubber and the brominated butyl rubber are added for compatibility by optimizing the raw material formula of the butyl rubber plug, so that the self-adhesion and mutual adhesion of the butyl rubber plug are improved while the sealing performance of the butyl rubber plug is ensured, the adhesion of a polytetrafluoroethylene film to the butyl rubber plug is promoted, the possibility of stripping between the polytetrafluoroethylene film and the butyl rubber plug body is further reduced, and the use stability of the polytetrafluoroethylene-butyl rubber composite rubber plug is improved.
Detailed Description
The present application will be described in further detail with reference to examples.
Preparation example
Preparation example 1
The preparation example discloses polyamide imide modified graphene, which is prepared by the following steps:
100g of aqueous polyamide-imide and 3g of surfactant are dissolved into 50wt% of 2L ethanol aqueous solution, and are uniformly stirred, 500g of graphene powder is added into the solution, and after uniform stirring, ultrasonic treatment is carried out for 40min, filtration and drying are carried out at 60 ℃ to obtain polyamide-imide modified graphene.
In the preparation example, the model of the aqueous polyamide imide is BOAMID PRD30NC, and the surfactant is fluorine surfactant FC-4430; the average particle diameter of the graphene powder was 20nm.
Preparation example 2
The present preparation example differs from preparation example 1 only in that the preparation method of polyamideimide-modified graphene is as follows:
100g of aqueous polyamide-imide and 3g of surfactant are dissolved into 50wt% of 2L ethanol aqueous solution, uniformly stirred, 660g of graphene powder is added into the solution, after uniform stirring, ultrasonic treatment is carried out for 40min, filtration and drying are carried out at 60 ℃ to obtain polyamide-imide modified graphene.
Preparation example 3
The present preparation example differs from preparation example 1 only in that the preparation method of polyamideimide-modified graphene is as follows:
100g of aqueous polyamide-imide and 3g of surfactant are dissolved into 50wt% of 2L ethanol aqueous solution, uniformly stirred, 800g of graphene powder is added into the solution, after uniform stirring, ultrasonic treatment is carried out for 40min, filtration and drying are carried out at 60 ℃ to obtain polyamide-imide modified graphene.
Preparation example 4
The present preparation example differs from preparation example 1 only in that the preparation method of polyamideimide-modified graphene is as follows:
100g of aqueous polyamide-imide and 3g of surfactant are dissolved into 50wt% of 2L ethanol aqueous solution, uniformly stirred, 400g of graphene powder is added into the solution, after uniform stirring, ultrasonic treatment is carried out for 40min, filtration and drying are carried out at 60 ℃ to obtain polyamide-imide modified graphene.
Preparation example 5
The present preparation example differs from preparation example 1 only in that the preparation method of polyamideimide-modified graphene is as follows:
100g of aqueous polyamide-imide and 3g of surfactant are dissolved into 50wt% of 2L ethanol aqueous solution, and are stirred uniformly, 900g of graphene powder is added into the solution, and after uniform stirring, ultrasonic treatment is carried out for 40min, filtration and drying are carried out at 60 ℃ to obtain polyamide-imide modified graphene.
Preparation example 6
The present preparation example differs from preparation example 1 only in that the preparation method of polyamideimide-modified graphene is as follows:
100g of aqueous polyamide-imide is dissolved into 50wt% of 2L ethanol aqueous solution, and is stirred uniformly, then 500g of graphene powder is added into the aqueous solution, and after stirring uniformly, ultrasonic treatment is carried out for 40min, filtration and drying are carried out at 60 ℃ to obtain polyamide-imide modified graphene.
Examples
Example 1
The embodiment discloses a polytetrafluoroethylene-butyl rubber composite rubber plug for an injector, which comprises a butyl rubber plug body and a polytetrafluoroethylene film wrapped on the surface of the butyl rubber plug body.
The preparation of the butyl rubber plug body comprises the following raw materials by mass: 900g of brominated butyl rubber, 200g of hydrogenated nitrile rubber, 110g of tackifying resin, 30g of sorbitan trioleate, 60g of calcined kaolin, 60g of carbon black, 30g of zinc oxide, 10g of accelerator TMTD, 10g of accelerator M, 20g of stearic acid, 60g of aromatic hydrocarbon oil and 15g of sulfur.
In this example, the type of brominated butyl rubber is ExxonMobil 2255x21; the model of the hydrogenated nitrile rubber is a Rayleigh 2011L; the tackifying resin may be selected from one or more of terpene resin, phenolic resin, and furan resin, in this example, a terpene resin of model kpl-22565.
The preparation method of the butyl rubber body comprises the following steps:
respectively plasticating the brominated butyl rubber and the hydrogenated nitrile rubber in the formula amount for 5min at 40 ℃;
adding plasticated brominated butyl rubber, hydrogenated nitrile rubber, tackifying resin, sorbitan trioleate, calcined kaolin, carbon black, zinc oxide, an accelerator, stearic acid, aromatic hydrocarbon oil and sulfur into a mixer, controlling the feeding temperature to be 70 ℃, the discharging temperature to be 80 ℃ and the rubber discharging temperature to be not higher than 110 ℃;
and (3) adding the mixture after the rubber is discharged into a die, and vulcanizing for 30min at 150 ℃ to obtain the butyl rubber plug.
The preparation method of the polytetrafluoroethylene-butyl rubber composite rubber plug for the injector comprises the following steps:
680g of polytetrafluoroethylene, 90g of epoxy resin, 60g of polyamide-imide modified graphene, 10g of auxiliary agent and 880g of solvent are mixed, and shearing and mixing are carried out uniformly at 75 ℃ to obtain polytetrafluoroethylene coating;
and (3) coating polytetrafluoroethylene coating on the surface of the butyl rubber plug, and curing at 230 ℃ to obtain the composite rubber plug.
The polytetrafluoroethylene coating may have a coating thickness of 4-10 μm, in this example a coating thickness of 6 μm. In this embodiment, the epoxy resin is bisphenol a type epoxy resin E44; polyamide imide-modified graphene was prepared from preparation example 1; the auxiliary agent is a crosslinking assistant, in particular to potassium persulfate; the solvent is ethyl acetate.
Example 2
The present example differs from example 1 only in that the preparation method of the polytetrafluoroethylene-butyl rubber composite rubber plug for the syringe is as follows:
600g of polytetrafluoroethylene, 150g of epoxy resin, 80g of polyamide-imide modified graphene prepared in preparation example 1, 20g of auxiliary agent and 1000g of solvent are mixed, and shearing and mixing are carried out uniformly at 75 ℃ to obtain polytetrafluoroethylene coating;
and (3) coating polytetrafluoroethylene coating on the surface of the butyl rubber plug, wherein the coating thickness is 6 mu m, and curing at 230 ℃ to obtain the composite rubber plug.
Example 3
The present example differs from example 1 only in that the preparation method of the polytetrafluoroethylene-butyl rubber composite rubber plug for the syringe is as follows:
mixing 800g of polytetrafluoroethylene, 50g of epoxy resin, 30g of polyamide-imide modified graphene prepared in preparation example 1, 5g of auxiliary agent and 800g of solvent, and shearing and uniformly mixing at 75 ℃ to obtain polytetrafluoroethylene coating;
and (3) coating polytetrafluoroethylene coating on the surface of the butyl rubber plug, wherein the coating thickness is 6 mu m, and curing at 230 ℃ to obtain the composite rubber plug.
Example 4
This example differs from example 1 only in that polyamideimide-modified graphene was produced from production example 2.
Example 5
This example differs from example 1 only in that polyamideimide-modified graphene was produced from production example 3.
Example 6
This example differs from example 1 only in that polyamideimide-modified graphene was produced from preparation example 4.
Example 7
This example differs from example 1 only in that polyamideimide-modified graphene was produced from preparation example 5.
Example 8
This example differs from example 1 only in that the preparation of the butyl rubber stopper body comprises the following raw materials by mass: 1000g of brominated butyl rubber, 100g of hydrogenated nitrile rubber, 150g of tackifying resin, 20g of sorbitan trioleate, 10g of calcined kaolin, 10g of carbon black, 10g of zinc oxide, 15g of accelerator TMTD, 15g of accelerator M, 30g of stearic acid, 80g of aromatic hydrocarbon oil and 15g of sulfur.
Example 9
This example differs from example 1 only in that the preparation of the butyl rubber stopper body comprises the following raw materials by mass: 800g of brominated butyl rubber, 300g of hydrogenated nitrile rubber, 50g of tackifying resin, 50g of sorbitan trioleate, 100g of calcined kaolin, 100g of carbon black, 50g of zinc oxide, 10g of accelerator TMTD, 10g of accelerator M, 10g of stearic acid, 50g of aromatic hydrocarbon oil and 20g of sulfur.
Example 10
This example differs from example 1 only in that the preparation of the butyl rubber stopper body comprises the following raw materials by mass: 1100g of brominated butyl rubber, 110g of tackifying resin, 30g of sorbitan trioleate, 60g of calcined kaolin, 60g of carbon black, 30g of zinc oxide, 10g of accelerator TMTD, 10g of accelerator M, 20g of stearic acid, 60g of aromatic hydrocarbon oil and 15g of sulfur.
Comparative example
Comparative example 1
The comparative example differs from comparative example 1 only in that the preparation method of the polytetrafluoroethylene-butyl rubber composite rubber plug for the syringe is as follows:
mixing 740g of polytetrafluoroethylene, 90g of epoxy resin, 10g of auxiliary agent and 880g of solvent, and shearing and uniformly mixing at 75 ℃ to obtain polytetrafluoroethylene coating;
and (3) coating polytetrafluoroethylene coating on the surface of the butyl rubber plug, wherein the coating thickness is 6 mu m, and curing at 230 ℃ to obtain the composite rubber plug.
Comparative example 2
The comparative example differs from example 1 only in that the preparation method of the polytetrafluoroethylene-butyl rubber composite rubber plug for the syringe is as follows:
680g of polytetrafluoroethylene, 90g of epoxy resin, 10g of aqueous polyamide imide, 50g of graphene, 10g of auxiliary agent and 880g of solvent are mixed, and shearing and mixing are carried out uniformly at 75 ℃ to obtain polytetrafluoroethylene coating;
and (3) coating polytetrafluoroethylene coating on the surface of the butyl rubber plug, wherein the coating thickness is 6 mu m, and curing at 230 ℃ to obtain the composite rubber plug.
Comparative example 3
The comparative example differs from example 1 only in that the preparation method of the polytetrafluoroethylene-butyl rubber composite rubber plug for the syringe is as follows:
680g of polytetrafluoroethylene, 90g of epoxy resin, 60g of aqueous polyamide-imide, 10g of auxiliary agent and 880g of solvent are mixed, and shearing and mixing are carried out uniformly at 75 ℃ to obtain polytetrafluoroethylene coating;
and (3) coating polytetrafluoroethylene coating on the surface of the butyl rubber plug, wherein the coating thickness is 6 mu m, and curing at 230 ℃ to obtain the composite rubber plug.
Comparative example 4
The comparative example differs from example 1 only in that the preparation method of the polytetrafluoroethylene-butyl rubber composite rubber plug for the syringe is as follows:
680g of polytetrafluoroethylene, 90g of epoxy resin, 60g of graphene, 10g of auxiliary agent and 880g of solvent are mixed, and shearing and mixing are carried out uniformly at 75 ℃ to obtain polytetrafluoroethylene coating;
and (3) coating polytetrafluoroethylene coating on the surface of the butyl rubber plug, wherein the coating thickness is 6 mu m, and curing at 230 ℃ to obtain the composite rubber plug.
Performance test one: the sealing performance of the polytetrafluoroethylene-butyl rubber composite rubber plug for the injector prepared in each example and each comparative example is detected by referring to one of the sealing performance of the rubber plug and the container in the standard YBB00052005-2015 of halogenated butyl rubber plug for sterile powder for injection, and if the methylene blue solution does not permeate into the bottle, the sealing performance is qualified; the results are shown in Table 1;
and II, testing: the raw material formulas for producing the butyl rubber plug in each example and each comparative example are respectively prepared into rubber sheets for detection, polytetrafluoroethylene coating prepared in each example and each comparative example is sprayed onto the corresponding rubber sheets for detection according to a spraying process, the rubber sheets are heated and cured, the rubber sheets are placed in an autoclave, a sterilization method of the medical rubber plug is simulated, the temperature is kept at 121+/-2 ℃ for 30 minutes, pressure is relieved, after the rubber sheets are placed at room temperature for 24 hours, the peeling strength is detected by referring to the standard YBB00102003-2015 peeling strength measuring method, and if peeling is possible, the peeling strength is recorded; if the paper cannot be peeled, recording as non-peelable; the results are shown in Table 1; and (3) testing: the raw material formulas for producing butyl rubber plugs in each example and each comparative example are respectively prepared into rubber sheets for detection, polytetrafluoroethylene coatings prepared in each example and each comparative example are sprayed onto the corresponding rubber sheets for detection according to a spraying process, the rubber sheets are heated and cured, the rubber sheets are placed in 0.5mol/L hydrochloric acid solution for 12 hours, washed with water, placed in 0.5mol/L sodium hydroxide solution for 12 hours, washed with water, and subjected to peel strength detection by referring to the standard YBB00102003-2015 peel strength measurement method, and if the rubber sheets can be peeled, the peel strength is recorded; if the paper cannot be peeled, recording as non-peelable; the results are shown in Table 1;
and (4) testing: referring to YBB00142002-2015, the pharmaceutical compatibility of the polytetrafluoroethylene-butyl rubber composite rubber plug for the injector prepared in each example and each comparative example is detected, wherein the experimental medicines are (1) cefotiam for injection with the specification of 1.0g and (2) ceftriaxone sodium for injection with the specification of 1.0g. The above drugs were put into bottles covered with each example and each comparative example and inverted, and subjected to an acceleration test to observe clarity for various periods of time, and the results are shown in table 2.
TABLE 1
TABLE 2
As can be seen by combining examples 1-3 and combining tables 1 and 2, the polytetrafluoroethylene-butyl rubber composite rubber plug for the injector, which is prepared by the method disclosed by the application, has excellent drug compatibility and sealing property, and the polytetrafluoroethylene film and the butyl rubber plug body have good adhesion and are not easy to peel, so that the polytetrafluoroethylene-butyl rubber composite rubber plug for the injector disclosed by the application has excellent use effect and application stability.
As can be seen from the combination of example 1 and comparative examples 3 to 4 and the combination of tables 1 and 2, when aqueous polyamideimide or unmodified graphene is added alone, the peel strength of the polytetrafluoroethylene film and the butyl rubber stopper body is low, and when unmodified graphene is added alone, the drug compatibility is low, which may be due to poor compatibility of unmodified graphene and polytetrafluoroethylene organic system, uneven dispersion and possibility of exposure at the connection interface, resulting in a decrease in adhesive strength and drug compatibility.
It can be seen from the combination of the example 1 and the comparative examples 1-2 and the combination of the tables 1 and 2 that the addition of the polyamide-imide grafted and modified graphene can remarkably improve the bonding performance of the polytetrafluoroethylene film and the butyl rubber plug body, and the polyamide-imide grafted and wrapped graphene has excellent drug compatibility, so that the compatibility of graphene powder in a polytetrafluoroethylene organic system is improved, the dispersion degree of the graphene powder is improved, the specific surface area of the polytetrafluoroethylene film connection interface is improved, the polyamide-imide and the epoxy resin crosslinked with the polyamide-imide can be bonded with the butyl rubber plug body, and the peel strength of the polytetrafluoroethylene film and the butyl rubber plug body is greatly improved while the direct contact between a medicine and the butyl rubber plug body is isolated.
As can be seen from the combination of examples 1, 4-7 and tables 1 and 2, when the ratio of aqueous polyamideimide to graphene powder is too small, the peel strength of the polytetrafluoroethylene film to the butyl rubber body is reduced, which may be due to the reduced grafting ratio of polyamideimide, resulting in reduced dispersibility of graphene, and the graphene is not fully encapsulated by the organic system, thus improving the possibility of exposure at the connection interface of the graphene to the polytetrafluoroethylene film; when the ratio of the aqueous polyamideimide to the graphene powder is too large, the change in peel strength of the polytetrafluoroethylene film to the butyl rubber body is not remarkable, probably because the grafting ratio of the aqueous polyamideimide reaches the upper limit.
As can be seen from the combination of example 1 and example 10 and the combination of table 1 and table 2, the raw material formulation of the butyl rubber plug body is optimized by referring to the method disclosed by the application, and the hydrogenated nitrile rubber and the brominated butyl rubber are selected for compatibility, so that the adhesive strength of the polytetrafluoroethylene film and the butyl rubber plug body is improved, and the use stability of the polytetrafluoroethylene film-butyl rubber composite rubber plug is improved.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (10)
1. The polytetrafluoroethylene-butyl rubber composite rubber plug for the injector is characterized by comprising a butyl rubber plug and a polytetrafluoroethylene film wrapped on the surface of the butyl rubber plug, wherein the polytetrafluoroethylene film is coated by a coating comprising the following components in parts by mass:
60-80 parts of polytetrafluoroethylene,
5-15 parts of epoxy resin,
3-8 parts of polyamide-imide modified graphene,
0.5-2 parts of auxiliary agent,
80-100 parts of solvent.
2. The polytetrafluoroethylene-butyl rubber composite rubber stopper for an injector according to claim 1, wherein: the preparation method of the polyamide imide modified graphene comprises the following steps:
dissolving aqueous polyamide-imide and a surfactant into an alcohol-water solution, adding graphene powder, carrying out ultrasonic treatment for 30-60min, separating, and drying to obtain polyamide-imide modified graphene.
3. The polytetrafluoroethylene-butyl rubber composite rubber stopper for an injector according to claim 2, wherein: the mass ratio of the aqueous polyamide imide to the surfactant to the graphene powder is 1 (0.01-0.05) to 5-8.
4. The polytetrafluoroethylene-butyl rubber composite rubber stopper for an injector according to claim 2, wherein: the surfactant is a fluorine surfactant.
5. The polytetrafluoroethylene-butyl rubber composite rubber stopper for an injector according to claim 1, wherein: the solvent is selected from one or more of an ester solvent, an alcohol solvent and an alcohol ether solvent.
6. The polytetrafluoroethylene-butyl rubber composite rubber stopper for an injector according to claim 1, wherein: the butyl rubber plug comprises the following components in parts by weight:
80-100 parts of brominated butyl rubber,
10-30 parts of hydrogenated nitrile rubber,
5-15 parts of tackifying resin,
2-5 parts of sorbitan trioleate,
1-10 parts of calcined kaolin,
1-10 parts of carbon black,
1-5 parts of zinc oxide,
2-3 parts of promoter,
1-3 parts of stearic acid,
5-8 parts of aromatic hydrocarbon oil,
1.5-2 parts of sulfur.
7. The polytetrafluoroethylene-butyl rubber composite rubber stopper for an injector according to claim 6, wherein: the tackifying resin is one or a combination of more of terpene resin, phenolic resin and furan resin.
8. The polytetrafluoroethylene-butyl rubber composite rubber stopper for an injector according to claim 1, wherein: the coating thickness of the polytetrafluoroethylene film is 4-10 mu m.
9. A method for preparing a polytetrafluoroethylene-butyl rubber composite rubber plug for an injector according to any one of claims 1-8, wherein: the method comprises the following steps:
mixing polytetrafluoroethylene, epoxy resin, polyamide-imide modified graphene, an auxiliary agent and a solvent according to a proportion, and shearing and uniformly mixing at 70-90 ℃ to obtain polytetrafluoroethylene coating;
and (3) coating polytetrafluoroethylene coating on the surface of the butyl rubber plug, and curing at 180-250 ℃ to obtain the composite rubber plug.
10. The method for preparing the polytetrafluoroethylene-butyl rubber composite rubber plug for the injector according to claim 9, wherein the method comprises the following steps: the preparation method of the butyl rubber plug comprises the following steps:
according to the proportion, the brominated butyl rubber, the hydrogenated nitrile rubber, the tackifying resin, the sorbitan trioleate, the calcined kaolin, the carbon black, the zinc oxide, the accelerator, the stearic acid, the aromatic hydrocarbon oil and the sulfur are mixed, and then put into a mold for vulcanization after rubber is discharged, so as to obtain the butyl rubber plug.
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Citations (5)
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|---|---|---|---|---|
| US6090081A (en) * | 1997-05-22 | 2000-07-18 | Daikyo Seiko, Ltd. | Sealing stopper for a syringe and a prefilled syringe |
| CN105482280A (en) * | 2016-01-14 | 2016-04-13 | 武夷学院 | Sulfur-free aldehyde-free rubber plug and preparation method thereof |
| CN109337347A (en) * | 2018-10-11 | 2019-02-15 | 安徽中马橡塑制品有限公司 | A kind of environmental protection Medical rubber plug composite material and preparation method |
| CN112898617A (en) * | 2021-01-22 | 2021-06-04 | 应城市恒天药业包装有限公司 | Halogenated butyl rubber plug and preparation method thereof |
| CN112898836A (en) * | 2021-02-22 | 2021-06-04 | 黄骅市津华制动部件有限公司 | Teflon coating and preparation process and application thereof |
-
2023
- 2023-09-20 CN CN202311214579.7A patent/CN117164922A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6090081A (en) * | 1997-05-22 | 2000-07-18 | Daikyo Seiko, Ltd. | Sealing stopper for a syringe and a prefilled syringe |
| CN105482280A (en) * | 2016-01-14 | 2016-04-13 | 武夷学院 | Sulfur-free aldehyde-free rubber plug and preparation method thereof |
| CN109337347A (en) * | 2018-10-11 | 2019-02-15 | 安徽中马橡塑制品有限公司 | A kind of environmental protection Medical rubber plug composite material and preparation method |
| CN112898617A (en) * | 2021-01-22 | 2021-06-04 | 应城市恒天药业包装有限公司 | Halogenated butyl rubber plug and preparation method thereof |
| CN112898836A (en) * | 2021-02-22 | 2021-06-04 | 黄骅市津华制动部件有限公司 | Teflon coating and preparation process and application thereof |
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