Medical rubber sealing element with self-lubricating function and preparation method thereof

Abstract

The invention discloses a medical rubber sealing element with a self-lubricating function and a preparation method of the medical rubber sealing element, and relates to the field of manufacturing of medical rubber sealing elements. The medical rubber sealing element with the self-lubricating function prepared by the invention comprises a rubber compound, a vulcanizing agent and a self-lubricating agent, the rubber compound comprises cross-linked butyl rubber, chlorinated butyl rubber and chlorinated polyethylene rubber; the self-lubricating agent is modified fluorine-containing silicone oil, the cross-linked butyl rubber is prepared from acrylic hyperbranched siloxane and butyl rubber through a reaction, and acrylic hyperbranched siloxane is prepared from o-cresol epoxy acrylic acid, carboxyl-terminated poly (diethylene glycol adipate) and amino-terminated hyperbranched siloxane through a reaction; the modified fluorine-containing silicone oil is prepared by reacting fluorine-containing silane with dimethyl silicone oil and then crosslinking with triallyl isocyanurate, and the fluorine-containing silane is prepared by copolymerizing tetrafluoroethylene and perfluorovinyl ether and then reacting with a silane coupling agent, so that the lubricating property, high temperature resistance and lubricity of the medical rubber sealing element are improved.

Description

Technical Field

[0001] The invention relates to the field of manufacturing medical rubber sealing components, in particular to a medical rubber sealing component with a self-lubricating function and a preparation method thereof. Background Art

[0002] The medical industry uses rubber seals, such as rubber stoppers for disposable syringes, rubber stoppers and protective caps for prefilled syringes, bottle stoppers, etc. These are medical devices or pharmaceutical packaging materials. They need to come into contact with drugs during use and have high requirements for their physical, chemical and biological properties.

[0003] At present, the seals used in the domestic pharmaceutical industry need to be lubricated with silicone oil after production and manufacturing. The purpose is to increase the sliding and sealing properties of the rubber seal and its substrate, comply with regulatory requirements, and reduce the loss of lubricity and increase in resistance during long-term storage, which affects customer use. The production process of the currently used silicone oil lubrication method is to spray silicone oil onto the already formed rubber seal, and then add silicone oil to the rubber seal to make it lubricated. Through research on rubber composition, physical, chemical and biological properties of rubber, it was found that lubricants can be added to the vulcanization process in a certain way, so that the manufactured rubber seal products can have self-lubricating properties. The addition of lubricants during the production process reduces the subsequent production operations of rubber products, greatly reduces production costs and improves production efficiency.

[0004] Dimethicone oil is tasteless and nontoxic, has physiological inertness, good chemical stability, electrical insulation and weather resistance, and has a wide viscosity range, low freezing point, high flash point, good hydrophobicity, and has very high shearing resistance, can be used for a long time in 50~180 ℃ of temperature, is widely used as insulation, lubrication, shockproof, dustproof oil, dielectric fluid and heat carrier, has the additive etc. of as defoaming, demoulding, paint and daily cosmetics.Due to the non-stickiness of dimethicone oil and rubber, plastics, metal etc., be widely used in the lubrication of rubber seals, therefore select dimethicone oil for use as lubricant, by cross-linking catalytic performance, dimethicone oil is cross-linked into the rubber matrix, the rubber seal product formed that makes not only has the sealing performance of rubber, also has certain lubricity, and this lubricity does not decay with the increase over time.Therefore the present invention has studied and prepared a kind of medical rubber seal with self-lubricating function with lubricity. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to provide a medical rubber sealing element with self-lubricating function and a preparation method thereof.

[0006] The present invention proposes a technical solution to solve the above technical problems: a medical rubber seal with self-lubricating function, comprising a rubber compound and a compound; the rubber compound comprises cross-linked butyl rubber, chlorinated butyl rubber and chlorinated polyethylene rubber; the compound comprises a vulcanizing agent and a self-lubricant; the self-lubricant is a modified fluorine-containing silicone oil.

[0007] Preferably, the cross-linked butyl rubber is prepared by reacting acrylic hyperbranched siloxane with butyl rubber; and the acrylic hyperbranched siloxane is prepared by reacting o-cresol epoxy acrylate, carboxyl-terminated polyethylene glycol adipate and amino-terminated hyperbranched siloxane.

[0008] Preferably, the modified fluorinated silicone oil is prepared by reacting fluorinated silane with dimethyl silicone oil and then crosslinking with triallyl isocyanurate; the fluorinated silane is prepared by copolymerizing tetrafluoroethylene with perfluorovinyl ether and then reacting with a silane coupling agent; the silane coupling agent is KH-550.

[0009] Preferably, the vulcanizing agent is one or a mixture of ECHO-A vulcanizing agent, TDDS vulcanizing agent, 2,4,6-trimercapto-1,3,5-triazine, dicumyl peroxide, and sulfur.

[0010] Preferably, the method for preparing the medical rubber seal with self-lubricating function comprises the following specific steps:

[0011] S1. Under a nitrogen atmosphere, o-cresol epoxy acrylate, carboxyl-terminated polyethylene glycol adipate, and acetone were mixed in a mass ratio of 2:1:2-3, heated to 60-70°C, stirred and dissolved, and triethylamine (0.03-0.05 times the mass of o-cresol epoxy acrylate) was added. The temperature was raised to 80-82°C, and the reaction was carried out for 2-3 hours. The temperature was lowered to 60-62°C, and amino-terminated hyperbranched siloxane (0.2-0.4 times the mass of o-cresol epoxy acrylate) was added. The reaction was carried out for 3-4 hours, and the mixture was evaporated under reduced pressure and washed with deionized water for 3-5 times. The mixture was vacuum dried at 40-50°C for 24 hours to obtain acrylic hyperbranched siloxane.

[0012] S2. The butyl rubber was masticated on an open mill for 5 to 8 minutes at a temperature of 60 to 80°C, and a plasticizer, polyisobutylene, a tackifier, a C5 petroleum resin, and an antioxidant, SK1010, were added. The temperature was raised to 115 to 125°C and mixing continued for 5 to 8 minutes. Acrylic hyperbranched siloxane was added and mixing continued for 5 to 8 minutes. The temperature was raised to 160 to 180°C, and dicumyl peroxide was added. The reaction was allowed to proceed for 30 to 60 minutes under a nitrogen atmosphere and the material was discharged to obtain a cross-linked butyl rubber.

[0013] S3. The tetrafluoroethylene and perfluorovinyl ether copolymer was mixed with a mass fraction of 5 to 8% sodium hydroxide solution, heated to 60 to 62 ° C, reacted for 40 to 60 min, and then a silane coupling agent KH-550 mixture was added. The mass ratio of the silane coupling agent KH-550, ethanol and acetic acid in the silane coupling agent KH-550 mixture was 3:5 to 10:0.1, and the mass ratio of the silane coupling agent KH-550 to the tetrafluoroethylene and perfluorovinyl ether copolymer was 3 to 5:100. The mixture was heated to 80 to 90 ° C, refluxed for 6 to 8 h, filtered and washed with ethanol 3 to 5 times, and dried at 80 to 90 ° C to obtain a fluorinated silane;

[0014] S4. Under a nitrogen atmosphere, dimethyl silicone oil and ethanol are mixed in a mass ratio of 2:1 to 1.2, heated to 60 to 62°C, stirred evenly, and then 0.1 to 0.2 times the mass of dimethyl silicone oil and 0.01 to 0.02 times the mass of dimethyl silicone oil are added as catalyst triethylamine, heated to 80 to 82°C, refluxed for 4 to 6 hours, and triallyl isocyanurate is added at a mass of 0.05 to 0.07 times the mass of dimethyl silicone oil. The temperature is raised to 120 to 130°C, reacted for 50 to 80 minutes, and then heated to 150 to 160°C and reacted for 2 to 4 hours to obtain a modified fluorinated silicone oil, which is a self-lubricant;

[0015] S5. Mix cross-linked butyl rubber, chlorinated butyl rubber and chlorinated polyethylene rubber in a mass ratio of 5-7:1-4:3-4.5 to prepare a rubber compound; mix a vulcanizing agent and a self-lubricating agent in a mass ratio of 1-5:15-20 to prepare a complex; mix the rubber compound and the complex in a mass ratio of 100:3.3-4.2 and vulcanize the mixture in a vulcanization mold at 155-195°C, at a vulcanization pressure of 160-210 kg / cm2 and a vulcanization time of 300-600 s. After cutting, cleaning, sterilizing and drying, a medical rubber seal with self-lubricating function is obtained.

[0016] Preferably, in the above step S1, the preparation method of o-cresol epoxy acrylate is as follows: under a nitrogen atmosphere, JF-220 epoxy resin and p-hydroxyanisole are mixed in a mass ratio of 10:0.02-0.05, the temperature is raised to 80-82°C, and an acrylic acid mixture with a mass ratio of 0.4-0.6 times that of the JF-220 epoxy resin is added dropwise at a rate of 1-3 ml / min, wherein the mass ratio of acrylic acid to catalyst triphenylphosphine in the acrylic acid mixture is 10:0.02-0.04, the temperature is raised to 90-110°C, the reaction is carried out for 4-5 hours, the temperature is lowered and the distillation is carried out under reduced pressure to obtain o-cresol epoxy acrylate.

[0017] Preferably, in the above step S1, the preparation method of the carboxyl-terminated poly(ethylene adipate glycol) is as follows: adipic acid, diethylene glycol, stannous chloride and phosphorous acid are mixed in a mass ratio of 10:7-8:0.06-0.1:0.05, heated to 160-200°C, reacted for 4-5 hours, reduced pressure to 0.01-0.03 MPa, continued to react for 6-8 hours, extracted with ethyl acetate and washed with deionized water for 3-5 times, added sodium chloride to precipitate, dried with anhydrous sodium sulfate, and rotary evaporated to obtain the carboxyl-terminated poly(ethylene adipate glycol) .

[0018] Preferably, the degree of polymerization of the carboxyl-terminated polyethylene glycol adipate is 13-16, and the molecular weight range is 3700-4500.

[0019] Preferably, in the above step S1, the preparation method of the amino-terminated hyperbranched siloxane is as follows: under a nitrogen atmosphere, allyl glycidyl ether is heated to 90-95° C., 0.12-0.14 times the mass of chloroplatinic acid isopropanol solution is added, and a mass fraction of 1% catalyst chloroplatinic acid isopropanol solution is added dropwise at a rate of 1-3 ml / min. 10-20 times the mass of allyl glycidyl ether 1,1,3,3-tetramethyldisiloxane is added dropwise at a rate of 1-3 ml / min, reacting for 6-8 hours, distilling under reduced pressure, and then adding diethylenetriamine at a rate of 1-3 ml / min. 0.1-0.2 times the mass of allyl glycidyl ether is added dropwise at a rate of 1-3 ml / min, and the reaction is continued for 2-4 hours to obtain the amino-terminated hyperbranched siloxane.

[0020] Preferably, in the above step S2, the mass ratio of butyl rubber, plasticizer polyisobutylene, tackifier C5 petroleum resin, antioxidant SK1010, acrylic hyperbranched siloxane and dicumyl peroxide is 100:10-20:15-25:0.2-0.5:6-12:1.5-3.

[0021] Preferably, in the above step S3, the preparation method of the tetrafluoroethylene and perfluorovinyl ether copolymer is as follows: under a nitrogen atmosphere, tetrafluoroethylene, perfluorovinyl ether, and octafluorocyclobutane are mixed in a mass ratio of 4 to 5:1 to 2:10, stirred evenly, and then 0.01 to 0.02 times the mass of tetrafluoroethylene as an initiator perfluorobutyl peroxide is added, the temperature is raised to 40 to 50° C., the pressure is maintained at 1.2 to 1.5 MPa, and the reaction is carried out for 3 to 6 hours. During the reaction, 2 to 3 times the mass of perfluorovinyl ether of tetrafluoroethylene is added, and after cooling to room temperature, the mixture is condensed and washed 5 to 8 times with ultrapure water at a temperature of 94 to 98° C., filtered, and vacuum dried at 220 to 280° C. to obtain a tetrafluoroethylene and perfluorovinyl ether copolymer.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] The medical rubber seal with self-lubricating function prepared by the present invention comprises a rubber compound, a vulcanizing agent and a self-lubricating agent; the rubber compound comprises cross-linked butyl rubber, chlorinated butyl rubber and chlorinated polyethylene rubber; the self-lubricating agent is a modified fluorine-containing silicone oil;

[0024] Cross-linked butyl rubber is produced by the reaction of acrylic hyperbranched siloxane with butyl rubber. The acrylic hyperbranched siloxane is produced by the reaction of o-cresol epoxy acrylate, carboxyl-terminated poly(ethylene glycol adipate) and amino-terminated hyperbranched siloxane. The epoxy groups on the o-cresol epoxy acrylate undergo a ring-opening reaction with the carboxyl-terminated poly(ethylene glycol adipate) and amino-terminated hyperbranched siloxane to form acrylic hyperbranched siloxane with active hydroxyl groups and acrylic acid. This increases the cross-linking density and forms a three-dimensional network with the butyl rubber. The introduction of siloxane and poly(ethylene glycol adipate) not only blocks the diffusion of oil molecules but also synergistically enhances lubrication performance and high-temperature resistance.

[0025] Modified fluorinated silicone oil is made by reacting fluorinated silane with dimethyl silicone oil and then cross-linking with triallyl isocyanurate. Fluorinated silane is made by copolymerizing tetrafluoroethylene and perfluorovinyl ether and then reacting with a silane coupling agent. The copolymer of tetrafluoroethylene and perfluorovinyl ether can effectively improve the lubrication and anti-aging properties of silicone oil. The silane coupling agent is then introduced into the dimethyl silicone oil through the copolymer, which further enhances the interfacial bonding strength and lubricity. Further cross-linking with triallyl isocyanurate forms a stable lubricating layer in the rubber matrix, thereby improving the lubricity of medical rubber seals and preventing them from swelling during long-term use. DETAILED DESCRIPTION

[0026] The present invention is described in detail below through examples. It should be noted that the following examples are intended only to further illustrate the present invention and are not to be construed as limiting the scope of protection of the present invention. Those skilled in the art may make non-essential improvements and adjustments to the present invention based on the above disclosure. Unless otherwise defined, all professional and scientific terms used herein have the same meanings as those familiar to those skilled in the art.

[0027] In order to more clearly illustrate the method provided by the present invention, the following examples are used to describe in detail the various index test methods of the self-lubricating medical rubber seals prepared in the examples and comparative examples as follows:

[0028] Lubrication performance: A self-lubricating medical rubber seal was tested using a YYB-03 tensile testing machine to simulate the movement of a plunger. The starting force and sustained force of the piston moving within the syringe barrel were recorded.

[0029] High temperature resistance: After aging the self-lubricating medical rubber seal at 70°C for 48 hours, the lubrication performance was tested again.

[0030] Cytotoxicity: Medical rubber seals with self-lubricating function are subjected to cytotoxicity test with reference to ISO 10993-5.

[0031] Example 1

[0032] The preparation method of the medical rubber seal with self-lubricating function in this embodiment is as follows:

[0033] S1. Under a nitrogen atmosphere, JF-220 epoxy resin and p-hydroxyanisole were mixed in a mass ratio of 10:0.02, heated to 80 ° C, and a mixture of acrylic acid 0.4 times the mass of JF-220 epoxy resin was added dropwise at a rate of 1 ml / min. The mass ratio of acrylic acid to catalyst triphenylphosphine in the acrylic acid mixture was 10:0.02. The mixture was heated to 90-110 ° C, reacted for 4-5 hours, cooled and distilled under reduced pressure to obtain o-cresol epoxy acrylic acid; hexanediol was added dropwise to obtain 1% hydroxyanisole. Acid, diethylene glycol, stannous chloride and phosphorous acid were mixed in a mass ratio of 10:7:0.06:0.05, heated to 160 ° C, reacted for 4 hours, reduced to 0.01 MPa, continued to react for 6 hours, extracted with ethyl acetate and washed with deionized water 3 times, added with sodium chloride to precipitate, dried with anhydrous sodium sulfate, and rotary evaporated to obtain terminal carboxyl poly (ethylene glycol adipate); under a nitrogen atmosphere, allyl glycidyl ether was heated to 90 ° C, chloroplatinic acid isopropanol solution was added, and the mixture was stirred for 2 hours. To a 1% catalyst solution of chloroplatinic acid isopropanol with a mass fraction of 0.12 times, 1,1,3,3-tetramethyldisiloxane with a mass fraction of 10 times that of allyl glycidyl ether was added dropwise at a rate of 1 ml / min, and the reaction was continued for 6 hours. The mixture was then distilled under reduced pressure, and then diethylenetriamine with a mass fraction of 0.1 times that of allyl glycidyl ether was added dropwise at a rate of 1 ml / min. The temperature was raised to 70°C and the reaction was continued for 2 hours to obtain amino-terminated hyperbranched siloxane. Under a nitrogen atmosphere, o-cresol epoxypropene was added. Acrylic acid, carboxyl-terminated polyethylene glycol adipate, and acetone were mixed in a mass ratio of 2:1:2, heated to 60°C, stirred and dissolved, and then triethylamine (0.03 times the mass of o-cresol epoxy acrylic acid) was added. The mixture was heated to 80°C and reacted for 2 hours. The mixture was cooled to 60°C and amino-terminated hyperbranched siloxane (0.2 times the mass of o-cresol epoxy acrylic acid) was added. The mixture was reacted for 3 hours, and the mixture was distilled under reduced pressure and washed with deionized water three times. The mixture was vacuum dried at 40°C for 24 hours to obtain acrylic hyperbranched siloxane.

[0034] S2. The butyl rubber was plasticized on an open mill for 5 min at a temperature of 60 ° C., a plasticizer polyisobutylene, a tackifier C5 petroleum resin and an antioxidant SK1010 were added, the temperature was raised to 115 ° C, mixing was continued for 5 min, an acrylic hyperbranched siloxane was added, mixing was continued for 5 min, the temperature was raised to 160 ° C, dicumyl peroxide was added, the mass ratio of butyl rubber, plasticizer polyisobutylene, tackifier C5 petroleum resin, antioxidant SK1010, acrylic hyperbranched siloxane and dicumyl peroxide was 100:10:15:0.2:6:1.5, under a nitrogen atmosphere, the reaction was allowed to proceed for 30 min, and the discharge was used to obtain a cross-linked butyl rubber;

[0035] S3. Under a nitrogen atmosphere, tetrafluoroethylene, perfluorovinyl ether, and octafluorocyclobutane were mixed in a mass ratio of 4:1:10, stirred evenly, and then 0.01 times the mass of tetrafluoroethylene as an initiator, perfluorobutyl peroxide, was added. The temperature was raised to 40°C, the pressure was maintained at 1.2 MPa, and the reaction was carried out for 3 hours. During the reaction, 2 times the mass of perfluorovinyl ether of tetrafluoroethylene was added. After cooling to room temperature, the mixture was condensed and washed 5 times with ultrapure water at a temperature of 94°C, filtered, and dried in a vacuum at 220°C to obtain a copolymer of tetrafluoroethylene and perfluorovinyl ether. The perfluorovinyl ether copolymer was mixed with a 5% sodium hydroxide solution by mass, heated to 60° C., reacted for 40 minutes, and then a silane coupling agent KH-550 mixed solution was added, wherein the mass ratio of the silane coupling agent KH-550, ethanol and acetic acid in the silane coupling agent KH-550 mixed solution was 3:5:0.1, and the mass ratio of the silane coupling agent KH-550 to tetrafluoroethylene and perfluorovinyl ether copolymer was 3:100. The mixture was heated to 80° C., refluxed for 6 hours, filtered, washed with ethanol three times, and dried at 80° C. to obtain a fluorinated silane.

[0036] S4. Under a nitrogen atmosphere, dimethyl silicone oil and ethanol were mixed in a mass ratio of 2:1, heated to 60°C, stirred evenly, and then 0.1-0.2 times the mass of dimethyl silicone oil in fluorosilane and 0.01 times the mass of dimethyl silicone oil in catalyst triethylamine were added. The temperature was raised to 80°C and refluxed for 4 hours. Triallyl isocyanurate was added at 0.05 times the mass of dimethyl silicone oil, and the temperature was raised to 120°C. After reacting for 50 minutes, the temperature was raised to 150°C and reacted for 2 hours to obtain a modified fluorinated silicone oil, which is a self-lubricant.

[0037] S5. Cross-linked butyl rubber, chlorinated butyl rubber, and chlorinated polyethylene rubber are mixed in a mass ratio of 5:1:3 to prepare a rubber compound; a vulcanizing agent and a self-lubricating agent are mixed in a mass ratio of 1:15 to prepare a compound; the rubber compound and the compound are mixed in a mass ratio of 100:3.3 and vulcanized in a vulcanization mold at 155°C and a vulcanization pressure of 160 kg / cm 2The vulcanization time is 300s. After cutting, cleaning, sterilization and drying, a medical rubber seal with self-lubricating function is obtained.

[0038] Example 2

[0039] The preparation method of the medical rubber seal with self-lubricating function in this embodiment is as follows:

[0040] S1. Under a nitrogen atmosphere, JF-220 epoxy resin and p-hydroxyanisole were mixed in a mass ratio of 10:0.04, heated to 81 ° C, and a mixture of acrylic acid 0.5 times the mass of JF-220 epoxy resin was added dropwise at a rate of 2 ml / min. The mass ratio of acrylic acid to catalyst triphenylphosphine in the acrylic acid mixture was 10:0.03. The mixture was heated to 100 ° C and reacted for 4.5 hours. The temperature was lowered and distilled under reduced pressure to obtain o-cresol epoxy acrylic acid; adipic acid and dimethyl ether were added dropwise at a rate of 2 ml / min. Ethylene glycol, stannous chloride and phosphorous acid were mixed in a mass ratio of 10:7.5:0.08:0.05, heated to 180°C, reacted for 4.5 hours, reduced to 0.02 MPa, and continued to react for 7 hours. The mixture was extracted with ethyl acetate and washed with deionized water four times. Sodium chloride was added to precipitate the mixture, dried over anhydrous sodium sulfate, and rotary evaporated to obtain carboxyl-terminated poly(ethylene adipate glycol); under a nitrogen atmosphere, allyl glycidyl ether was heated to 93°C, and chloroplatinic acid isopropanol was added to dissolve the mixture in a mass of 0. .13 times the mass fraction of 1% catalyst chloroplatinic acid isopropanol solution, add 15 times the mass of allyl glycidyl ether 1,1,3,3-tetramethyldisiloxane at a rate of 2 ml / min, react for 7 hours, distill under reduced pressure, then add 0.15 times the mass of allyl glycidyl ether diethylenetriamine at a rate of 2 ml / min, heat to 75 ° C and continue to react for 3 hours to obtain amino-terminated hyperbranched siloxane; under nitrogen atmosphere, add o-cresol epoxy acrylic acid, terminal Carboxyl poly(ethylene glycol adipate) and acetone were mixed in a mass ratio of 2:1:2.5, heated to 65°C, stirred and dissolved, and then triethylamine (0.04 times the mass of o-cresol epoxy acrylate) was added. The mixture was heated to 81°C and reacted for 2.5 hours. The mixture was cooled to 61°C and amino-terminated hyperbranched siloxane (0.3 times the mass of o-cresol epoxy acrylate) was added. The mixture was reacted for 3.5 hours. The mixture was distilled under reduced pressure and washed with deionized water four times. The mixture was vacuum dried at 45°C for 24 hours to obtain acrylic hyperbranched siloxane.

[0041] S2. The butyl rubber was masticated on an open mill for 7 min at a temperature of 70 ° C., a plasticizer polyisobutylene, a tackifier C5 petroleum resin and an antioxidant SK1010 were added, the temperature was raised to 120 ° C, mixing was continued for 6 min, an acrylic hyperbranched siloxane was added, mixing was continued for 6 min, the temperature was raised to 170 ° C, dicumyl peroxide was added, the mass ratio of butyl rubber, plasticizer polyisobutylene, tackifier C5 petroleum resin, antioxidant SK1010, acrylic hyperbranched siloxane and dicumyl peroxide was 100:15:20:0.35:9:2.5, under a nitrogen atmosphere, the reaction was allowed to proceed for 45 min, and the material was discharged to obtain a cross-linked butyl rubber;

[0042] S3. Under a nitrogen atmosphere, tetrafluoroethylene, perfluorovinyl ether, and octafluorocyclobutane were mixed in a mass ratio of 4:1.5:10, stirred evenly, and then 0.015 times the mass of tetrafluoroethylene as an initiator, perfluorobutyl peroxide, was added. The temperature was raised to 45°C, the pressure was maintained at 1.4 MPa, and the reaction was carried out for 5 hours. During the reaction, 2.5 times the mass of perfluorovinyl ether of tetrafluoroethylene was added. After cooling to room temperature, the mixture was condensed and washed 7 times with ultrapure water at a temperature of 96°C, filtered, and dried in a vacuum at 240°C to obtain a copolymer of tetrafluoroethylene and perfluorovinyl ether. A copolymer of ethylene and perfluorovinyl ether was mixed with a 7% by mass sodium hydroxide solution, heated to 61° C., reacted for 50 minutes, and then a silane coupling agent KH-550 mixed solution was added, wherein the mass ratio of the silane coupling agent KH-550, ethanol, and acetic acid in the silane coupling agent KH-550 mixed solution was 3:8:0.1, and the mass ratio of the silane coupling agent KH-550 to the tetrafluoroethylene and perfluorovinyl ether copolymer was 4:100. The mixture was heated to 85° C., refluxed for 7 hours, filtered, washed with ethanol four times, and dried at 85° C. to obtain a fluorinated silane.

[0043] S4. Under a nitrogen atmosphere, dimethyl silicone oil and ethanol were mixed in a mass ratio of 2:1.1, heated to 61°C, stirred evenly, and then 0.15 times the mass of dimethyl silicone oil was added with fluorosilane and 0.015 times the mass of dimethyl silicone oil as catalyst triethylamine. The temperature was raised to 81°C and refluxed for 5 hours. Triallyl isocyanurate was added at a mass of 0.06 times the mass of dimethyl silicone oil, and the temperature was raised to 125°C. After reacting for 65 minutes, the temperature was raised to 155°C and reacted for 3 hours to obtain a modified fluorinated silicone oil, which is a self-lubricant.

[0044] S5. Cross-linked butyl rubber, chlorinated butyl rubber, and chlorinated polyethylene rubber were mixed in a mass ratio of 6:2.5:3.7 to prepare a rubber compound; a vulcanizing agent and a self-lubricating agent were mixed in a mass ratio of 3:18 to prepare a compound; the rubber compound and the compound were mixed in a mass ratio of 100:3.8 and vulcanized in a vulcanizing mold at 175°C at a vulcanizing pressure of 190 kg / cm 2The vulcanization time is 500s. After cutting, cleaning, sterilization and drying, a medical rubber seal with self-lubricating function is obtained.

[0045] Example 3

[0046] The preparation method of the medical rubber seal with self-lubricating function in this embodiment is as follows:

[0047] S1. Under a nitrogen atmosphere, JF-220 epoxy resin and p-hydroxyanisole were mixed in a mass ratio of 10:0.05, heated to 82 ° C, and an acrylic acid mixture 0.6 times the mass of JF-220 epoxy resin was added dropwise at a rate of 3 ml / min. The mass ratio of acrylic acid to catalyst triphenylphosphine in the acrylic acid mixture was 10:0.04. The mixture was heated to 110 ° C, reacted for 5h, cooled and distilled under reduced pressure to obtain o-cresol epoxy acrylic acid; adipic acid, a condensate Diethylene glycol, stannous chloride and phosphorous acid were mixed in a mass ratio of 10:8:0.1:0.05, heated to 200 ° C, reacted for 5 h, reduced to 0.03 MPa, continued to react for 8 h, extracted with ethyl acetate and washed with deionized water 5 times, added with sodium chloride to precipitate, dried with anhydrous sodium sulfate, and rotary evaporated to obtain carboxyl-terminated poly (ethylene glycol adipate); under a nitrogen atmosphere, allyl glycidyl ether was heated to 95 ° C, chloroplatinic acid isopropanol solution was added, and the mass of 0 .14 ​​times the mass fraction of 1% catalyst chloroplatinic acid isopropanol solution, add 20 times the mass of allyl glycidyl ether 1,1,3,3-tetramethyldisiloxane at a rate of 3 ml / min, react for 8 hours, distill under reduced pressure, then add 0.2 times the mass of allyl glycidyl ether diethylenetriamine at a rate of 3 ml / min, heat to 80 ° C and continue to react for 4 hours to obtain amino-terminated hyperbranched siloxane; under nitrogen atmosphere, add o-cresol epoxy acrylic acid , carboxyl-terminated polyethylene glycol adipate and acetone were mixed in a mass ratio of 2:1:3, heated to 70°C, stirred and dissolved, and then triethylamine (0.05 times the mass of o-cresol epoxy acrylic acid) was added. The mixture was heated to 82°C and reacted for 3 hours. The mixture was cooled to 62°C and amino-terminated hyperbranched siloxane (0.4 times the mass of o-cresol epoxy acrylic acid) was added. The mixture was reacted for 4 hours, and the mixture was distilled under reduced pressure and washed with deionized water for 5 times. The mixture was dried in vacuo at 50°C for 24 hours to obtain acrylic hyperbranched siloxane.

[0048] S2. The butyl rubber was plasticized on an open mill for 8 min at a temperature of 80 ° C., a plasticizer polyisobutylene, a tackifier C5 petroleum resin and an antioxidant SK1010 were added, the temperature was raised to 125 ° C, mixing was continued for 8 min, an acrylic hyperbranched siloxane was added, mixing was continued for 8 min, the temperature was raised to 180 ° C, dicumyl peroxide was added, the mass ratio of butyl rubber, plasticizer polyisobutylene, tackifier C5 petroleum resin, antioxidant SK1010, acrylic hyperbranched siloxane and dicumyl peroxide was 100:20:25:0.5:12:3, under a nitrogen atmosphere, the reaction was carried out for 60 min, and the material was discharged to obtain a cross-linked butyl rubber;

[0049] S3. Under a nitrogen atmosphere, tetrafluoroethylene, perfluorovinyl ether, and octafluorocyclobutane were mixed in a mass ratio of 5:2:10, stirred evenly, and then 0.02 times the mass of tetrafluoroethylene as an initiator, perfluorobutyl peroxide, was added. The temperature was raised to 50°C, the pressure was maintained at 1.5 MPa, and the reaction was carried out for 6 hours. During the reaction, 3 times the mass of perfluorovinyl ether of tetrafluoroethylene was added. After cooling to room temperature, the mixture was condensed and washed 8 times with ultrapure water at a temperature of 98°C, filtered, and vacuum dried at 280°C to obtain a copolymer of tetrafluoroethylene and perfluorovinyl ether. A perfluorovinyl ether copolymer was mixed with an 8% by mass sodium hydroxide solution, heated to 62° C., reacted for 60 minutes, and then a silane coupling agent KH-550 mixed solution was added, wherein the mass ratio of the silane coupling agent KH-550, ethanol, and acetic acid in the silane coupling agent KH-550 mixed solution was 3:10:0.1, and the mass ratio of the silane coupling agent KH-550, tetrafluoroethylene, and perfluorovinyl ether copolymer was 5:100. The mixture was heated to 90° C., refluxed for 8 hours, filtered, washed with ethanol 5 times, and dried at 90° C. to obtain a fluorinated silane.

[0050] S4. Under a nitrogen atmosphere, dimethyl silicone oil and ethanol were mixed in a mass ratio of 1.2, heated to 62°C, stirred evenly, and then 0.2 times the mass of dimethyl silicone oil in the amount of fluorosilane and 0.02 times the mass of dimethyl silicone oil in the amount of catalyst triethylamine were added. The mixture was heated to 82°C and refluxed for 6 hours. Triallyl isocyanurate was added at a mass of 0.07 times the mass of dimethyl silicone oil, and the mixture was heated to 130°C and reacted for 80 minutes. The mixture was then heated to 160°C and reacted for 4 hours to obtain a modified fluorosilicone oil, which is a self-lubricant.

[0051] S5. Cross-linked butyl rubber, chlorinated butyl rubber, and chlorinated polyethylene rubber are mixed in a mass ratio of 7:4:4.5 to prepare a rubber compound; a vulcanizing agent and a self-lubricating agent are mixed in a mass ratio of 5:20 to prepare a compound; the rubber compound and the compound are mixed in a mass ratio of 100:4.2 and vulcanized in a vulcanization mold at 195°C and a vulcanization pressure of 210 kg / cm 2 The vulcanization time is 600s. After cutting, cleaning, sterilization and drying, a medical rubber seal with self-lubricating function is obtained.

[0052] Comparative Example 1

[0053] The preparation method of Comparative Example 1 is the same as that of Example 2. The difference between the self-lubricating medical rubber seal and Example 2 is that the cross-linked butyl rubber is prepared by reacting amino hyperbranched siloxane with butyl rubber.

[0054] Comparative Example 2

[0055] The preparation method of Comparative Example 2 is the same as that of Example 2. The difference between the nanomaterial for heating element prepared by the hot air furnace and Example 2 is that the cross-linked butyl rubber is prepared by the reaction of o-cresol epoxy acrylic acid and butyl rubber.

[0056] Comparative Example 3

[0057] The preparation method of Comparative Example 3 is the same as that of Example 2. The difference between the self-lubricating medical rubber seal and Example 2 is that the modified fluorinated silicone oil is simply the reaction of fluorinated silane and dimethyl silicone oil.

[0058] Comparative Example 4

[0059] The preparation method of Comparative Example 4 is the same as that of Example 2. The difference between the self-lubricating medical rubber seal and Example 2 is that the self-lubricant is only dimethyl silicone oil.

[0060] Comparative Example 5

[0061] The preparation method of Comparative Example 5 is the same as that of Example 2. The difference between the self-lubricating medical rubber seal and Example 2 is that the modified fluorine-containing silicone oil is prepared by reacting silane coupling agent KH-550 with dimethyl silicone oil and then cross-linking with triallyl isocyanurate.

[0062] Effect Examples

[0063] Table 1 below shows the performance test results of the self-lubricating medical rubber seals prepared in Examples and Comparative Examples.

[0064] Table 1

[0065]

[0066] From the comparison of the performance data in Table 1, it can be seen that the medical rubber seal with self-lubricating function prepared by the present invention has excellent lubricity and high temperature resistance;

[0067] From the comparison of the experimental data of Examples 1, 2, and 3 and Comparative Examples 1 and 2, it can be found that the epoxy groups on the o-cresol epoxy acrylate react with the carboxyl-terminated polyethylene glycol adipate and the amino-terminated hyperbranched siloxane through a ring-opening reaction to form an acrylic hyperbranched siloxane having active hydroxyl groups and acrylic acid, thereby increasing the crosslinking density and forming a three-dimensional network with the butyl rubber. The introduction of siloxane and polyethylene glycol adipate not only blocks the diffusion of oil molecules but also synergistically enhances oil resistance and high temperature resistance.

[0068] From the comparison of the experimental data of Example 1, Example 2, Example 3 and Comparative Example 3, Comparative Example 4, Comparative Example 5, it can be found that the copolymer of tetrafluoroethylene and perfluorovinyl ether can effectively improve the lubrication and anti-aging properties of silicone oil. The silane coupling agent is introduced into the dimethyl silicone oil through the copolymer, which further enhances the interfacial bonding force and lubricity. Further cross-linking with triallyl isocyanurate forms a stable lubricating layer in the rubber matrix, thereby improving the lubricity of medical rubber seals, thereby preventing the medical rubber seals from swelling during long-term use.

[0069] Obviously, the above embodiments are merely examples for the purpose of clearly illustrating the embodiments of the present invention and are not intended to limit the embodiments of the present invention. Those skilled in the art will readily appreciate that other variations or modifications based on the above description are possible. It is not necessary and impossible to enumerate all embodiments here. However, such obvious variations or modifications arising from the spirit of the present invention remain within the scope of protection of the present invention.

Claims

1. A medical rubber seal with self-lubricating function, characterized in that: The invention comprises a rubber compound and a compound; the rubber compound comprises cross-linked butyl rubber, chlorinated butyl rubber and chlorinated polyethylene rubber; the compound comprises a vulcanizing agent and a self-lubricant; and the self-lubricant is modified fluorine-containing silicone oil.

2. The medical rubber seal with self-lubricating function according to claim 1, characterized in that: The cross-linked butyl rubber is prepared by the reaction of acrylic hyperbranched siloxane and butyl rubber; the acrylic hyperbranched siloxane is prepared by the reaction of o-cresol epoxy acrylate, carboxyl-terminated polyethylene glycol adipate and amino-terminated hyperbranched siloxane.

3. The medical rubber seal with self-lubricating function according to claim 1, characterized in that: The modified fluorine-containing silicone oil is prepared by reacting fluorine-containing silane with dimethyl silicone oil and then cross-linking with triallyl isocyanurate; the fluorine-containing silane is prepared by copolymerizing tetrafluoroethylene and perfluorovinyl ether and then reacting with a silane coupling agent; the silane coupling agent is KH-550.

4. The medical rubber seal with self-lubricating function according to claim 1, characterized in that: The vulcanizing agent is one of ECHO-A vulcanizing agent, TDDS vulcanizing agent, 2,4,6-trimercapto-1,3,5-triazine, dicumyl peroxide, and sulfur, or a mixture of several of them.

5. The method for preparing a medical rubber seal with self-lubricating function according to claim 1, characterized in that: The specific steps include: S1. Under a nitrogen atmosphere, o-cresol epoxy acrylate, carboxyl-terminated polyethylene glycol adipate, and acetone were mixed in a mass ratio of 2:1:2-3, heated to 60-70°C, stirred and dissolved, and triethylamine (0.03-0.05 times the mass of o-cresol epoxy acrylate) was added. The temperature was raised to 80-82°C, and the reaction was carried out for 2-3 hours. The temperature was lowered to 60-62°C, and amino-terminated hyperbranched siloxane (0.2-0.4 times the mass of o-cresol epoxy acrylate) was added. The reaction was carried out for 3-4 hours, and the mixture was evaporated under reduced pressure and washed with deionized water for 3-5 times. The mixture was vacuum dried at 40-50°C for 24 hours to obtain acrylic hyperbranched siloxane. S2. The butyl rubber was masticated on an open mill for 5 to 8 minutes at a temperature of 60 to 80°C, and a plasticizer, polyisobutylene, a tackifier, a C5 petroleum resin, and an antioxidant, SK1010, were added. The temperature was raised to 115 to 125°C and mixing continued for 5 to 8 minutes. Acrylic hyperbranched siloxane was added and mixing continued for 5 to 8 minutes. The temperature was raised to 160 to 180°C, and dicumyl peroxide was added. The reaction was allowed to proceed for 30 to 60 minutes under a nitrogen atmosphere and the material was discharged to obtain a cross-linked butyl rubber. S3. The tetrafluoroethylene and perfluorovinyl ether copolymer was mixed with a mass fraction of 5 to 8% sodium hydroxide solution, heated to 60 to 62 ° C, reacted for 40 to 60 min, and then a silane coupling agent KH-550 mixture was added. The mass ratio of the silane coupling agent KH-550, ethanol and acetic acid in the silane coupling agent KH-550 mixture was 3:5 to 10:0.1, and the mass ratio of the silane coupling agent KH-550 to the tetrafluoroethylene and perfluorovinyl ether copolymer was 3 to 5:

100. The mixture was heated to 80 to 90 ° C, refluxed for 6 to 8 h, filtered and washed with ethanol 3 to 5 times, and dried at 80 to 90 ° C to obtain a fluorinated silane; S4. Under a nitrogen atmosphere, dimethyl silicone oil and ethanol are mixed in a mass ratio of 2:1 to 1.2, heated to 60 to 62°C, stirred evenly, and then 0.1 to 0.2 times the mass of dimethyl silicone oil and 0.01 to 0.02 times the mass of dimethyl silicone oil are added as catalyst triethylamine, heated to 80 to 82°C, refluxed for 4 to 6 hours, and triallyl isocyanurate is added at a mass of 0.05 to 0.07 times the mass of dimethyl silicone oil. The temperature is raised to 120 to 130°C, reacted for 50 to 80 minutes, and then heated to 150 to 160°C and reacted for 2 to 4 hours to obtain a modified fluorinated silicone oil, which is a self-lubricant; S5. Mix cross-linked butyl rubber, chlorinated butyl rubber and chlorinated polyethylene rubber in a mass ratio of 5-7:1-4:3-4.5 to prepare a rubber compound; mix a vulcanizing agent and a self-lubricating agent in a mass ratio of 1-5:15-20 to prepare a complex; mix the rubber compound and the complex in a mass ratio of 100:3.3-4.2 and vulcanize the mixture in a vulcanization mold at 155-195°C, at a vulcanization pressure of 160-210 kg / cm2 and a vulcanization time of 300-600 s. After cutting, cleaning, sterilizing and drying, a medical rubber seal with self-lubricating function is obtained.

6. The method for preparing a medical rubber seal with self-lubricating function according to claim 5, characterized in that: In the above step S1, the preparation method of o-cresol epoxy acrylate is as follows: under a nitrogen atmosphere, JF-220 epoxy resin and p-hydroxyanisole are mixed in a mass ratio of 10:0.02-0.05, the temperature is raised to 80-82° C., and an acrylic acid mixture with a mass ratio of 0.4-0.6 times that of the JF-220 epoxy resin is added dropwise at a rate of 1-3 ml / min, wherein the mass ratio of acrylic acid to catalyst triphenylphosphine in the acrylic acid mixture is 10:0.02-0.04, the temperature is raised to 90-110° C., the reaction is carried out for 4-5 hours, the temperature is lowered and the distillation is carried out under reduced pressure to obtain o-cresol epoxy acrylate.

7. The method for preparing a medical rubber seal with self-lubricating function according to claim 5, characterized in that: In the above step S1, the preparation method of terminal carboxyl poly(ethylene adipate glycol) is as follows: adipic acid, diethylene glycol, stannous chloride and phosphorous acid are mixed in a mass ratio of 10:7-8:0.06-0.1:0.05, heated to 160-200°C, reacted for 4-5 hours, reduced pressure to 0.01-0.03 MPa, continued to react for 6-8 hours, extracted with ethyl acetate and washed with deionized water 3-5 times, added sodium chloride to precipitate, dried with anhydrous sodium sulfate, and rotary evaporated to obtain terminal carboxyl poly(ethylene adipate glycol) 8. The method for preparing a medical rubber seal with self-lubricating function according to claim 5, characterized in that: In the above step S1, the preparation method of the amino-terminated hyperbranched siloxane is as follows: under a nitrogen atmosphere, allyl glycidyl ether is heated to 90-95° C., a 1% catalyst chloroplatinic acid isopropanol solution with a mass fraction of 0.12-0.14 times the mass of chloroplatinic acid isopropanol is added, and 1,1,3,3-tetramethyldisiloxane with a mass fraction of 10-20 times the mass of allyl glycidyl ether is added dropwise at a rate of 1-3 ml / min, reacted for 6-8 hours, distilled under reduced pressure, and then 0.1-0.2 times the mass of allyl glycidyl ether diethylenetriamine is added dropwise at a rate of 1-3 ml / min, and the temperature is raised to 70-80° C. and the reaction is continued for 2-4 hours to obtain the amino-terminated hyperbranched siloxane.

9. The method for preparing a medical rubber seal with self-lubricating function according to claim 5, characterized in that: In the above step S2, the mass ratio of butyl rubber, plasticizer polyisobutylene, tackifier C5 petroleum resin, antioxidant SK1010, acrylic hyperbranched siloxane and dicumyl peroxide is 100:10-20:15-25:0.2-0.5:6-12:1.5-3.

10. The method for preparing a medical rubber seal with self-lubricating function according to claim 5, characterized in that: In the above step S3, the preparation method of the tetrafluoroethylene and perfluorovinyl ether copolymer is as follows: under a nitrogen atmosphere, tetrafluoroethylene, perfluorovinyl ether, and octafluorocyclobutane are mixed in a mass ratio of 4 to 5:1 to 2:10, stirred evenly, and then 0.01 to 0.02 times the mass of tetrafluoroethylene as an initiator perfluorobutyl peroxide is added, the temperature is raised to 40 to 50°C, the pressure is maintained at 1.2 to 1.5 MPa, and the reaction is carried out for 3 to 6 hours. During the reaction, 2 to 3 times the mass of perfluorovinyl ether is added to tetrafluoroethylene. After cooling to room temperature, the mixture is condensed and washed 5 to 8 times with ultrapure water at a temperature of 94 to 98°C, filtered, and vacuum dried at 220 to 280°C to obtain a tetrafluoroethylene and perfluorovinyl ether copolymer.

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