Vulcanization preparation process of medical puncture-resistant rubber gasket

Abstract

The invention belongs to the field of medical rubber materials, and particularly relates to a vulcanization preparation process of a medical puncture-resistant rubber gasket. A vulcanization preparation process of a medical puncture-resistant rubber gasket comprises the following steps: S1, raw rubber raw material preparation: crushing and mixing raw rubber raw materials to be vulcanized into raw rubber powder, removing impurities, and sieving; the raw rubber raw materials comprise halogenated butyl rubber, polyisoprene rubber and epichlorohydrin rubber; s2, preparing a rubber compound; the preparation method comprises the following steps: preheating an internal mixer to 80-100 DEG C, adding 80-90 parts by weight of raw rubber powder into the internal mixer, and refining at 115-125 DEG C for 5-9 minutes; adding 12-22 parts by weight of a modified composite filler, 2-6 parts by weight of zinc oxide, 1-3 parts by weight of stearic acid, 3-8 parts by weight of a crosslinking auxiliary agent and 0.5-1.2 parts by weight of an anti-aging agent, and mixing for 18-22 min; s3, calendaring and sheet discharging: calendaring and molding the rubber compound obtained in the step (2) to obtain a rubber compound sheet; s4, prevulcanization: putting the rubber compound sheet calendered in the step (3) into a mold cavity of a press vulcanizer, and carrying out under-vulcanization production to obtain a preformed sheet; the preformed rubber sheet in the step (4) and an organic solvent are subjected to cleaning treatment and drying and then put into a vulcanization mold to be subjected to vulcanization forming, the rubber gasket is obtained, the vulcanization temperature ranges from 140 DEG C to 150 DEG C, and the vulcanization time ranges from 3 min to 7 min. In order to solve the problem that the use performance of a medical rubber gasket is affected due to the fact that the medical rubber gasket is needled to fall scraps and is poor in rebound resilience, the invention provides the vulcanization preparation process of the medical needling-resistant rubber gasket.

Description

Technical Field

[0001] The present application belongs to the field of medical rubber materials, and specifically relates to a vulcanization preparation process for a medical needle-resistant rubber gasket. Background Art

[0002] In recent years, the rubber industry has developed rapidly, and the development of rubber in the field of medical materials has become more and more extensive. Therefore, the requirements for rubber performance are also high. As components such as septa and gaskets of medical packaging materials, they are not only required to have good chemical resistance and sealing properties, but also to be able to seal and preserve reagents well after repeated use without affecting the test results or changing the properties of the reagents.

[0003] At present, more than 90% of medical rubber gaskets are produced with butyl rubber as the base material. However, there are still some problems in the application of butyl rubber plugs, the most prominent of which is the problem of puncture and chipping. After multiple punctures, the cavity at the puncture site of the gasket will become larger and larger, and leakage often occurs at the puncture site. This situation poses a great risk to the quality of drugs and the safety of patient medication. In order to ensure the safety of clinical medication, it is very necessary to improve and enhance the puncture and chipping performance of butyl rubber plugs; in addition, during the use of rubber gaskets, due to the influence of multiple external force punctures or insufficient strength and resilience, they will be more prone to wear, burrs or cracks. Surface cracks may cause leakage and rupture, while internal cracks may lead to reduced gasket performance and easily produce defects of thermal oxidation aging, affecting the sealing effect. Therefore, crack failure and aging failure will seriously shorten the service life of the sealing gasket. Now there is an urgent need for a reliable solution that can effectively solve this problem. Summary of the invention

[0004] In order to solve the problem of medical rubber gaskets shedding and poor rebound performance upon needle puncture, which affects the performance of the rubber gasket, the present application provides a vulcanization preparation process for medical needle puncture-resistant rubber gaskets.

[0005] The present application provides a vulcanization preparation process for a medical needle-resistant rubber gasket, which adopts the following technical solution: S1: Preparation of raw rubber materials: crushing and mixing the raw rubber materials to be vulcanized into raw rubber powder, removing impurities and sieving; the raw rubber materials include halogenated butyl rubber, polyisoprene rubber and chloroether rubber; S2: preparing a rubber mixture; preheating an internal mixer to 80-100°C, adding 80-90 parts by weight of raw rubber powder into the internal mixer, and refining at 115-125°C for 5-9 minutes; adding 12-22 parts by weight of a modified composite filler, 2-6 parts by weight of zinc oxide, 1-3 parts by weight of stearic acid, 3-8 parts by weight of a crosslinking aid and 0.5-1.2 parts by weight of an antioxidant for mixing, and mixing for 18-22 minutes; S3: calendering to form a sheet: calendering the mixed rubber obtained in step (2) to obtain a mixed rubber sheet; S4: pre-vulcanization: placing the mixed rubber sheet calendered in step (3) into the mold cavity of a flat vulcanizer, and vulcanizing it to obtain a preformed film; S5: Vulcanization molding: The preformed rubber sheet in step (4) is cleaned with an organic solvent, dried, and then placed in a vulcanization mold for vulcanization molding to obtain a rubber gasket. The vulcanization temperature is 140-150° C. and the vulcanization time is 3-7 minutes.

[0006] By adopting the above technical scheme, the powdered raw rubber raw material, halogenated butyl rubber, polyisoprene rubber and chloroether rubber are mainly used as raw materials, and the halogenated butyl rubber and polyisoprene rubber are mixed. On the one hand, the double bonds of polyisoprene rubber and halogenated substituted butyl rubber are more active and have better cross-linking properties, so the air tightness of the rubber gasket material can be enhanced, and the rubber gasket material has the properties of heat resistance, ozone resistance, aging resistance and chemical resistance. On the other hand, the high elasticity and oxidation resistance of polyisoprene rubber can also be enhanced, so that the rubber gasket material has good stretching and rebound capabilities. On this basis, chloroether rubber is added, so that the rich active chlorine in the chloroether rubber further triggers the system. The polymerization reaction of unsaturated double bonds increases the attraction between molecules, and the gaps between molecular chains are smaller, so that a large number of carbon-carbon cross-linked bonds are formed more quickly in the system, further increasing the probability of polymerization reaction, which can greatly accelerate the vulcanization speed of the system, improve the vulcanization efficiency, further cross-link the molecular chains, restrict the movement of the molecular chains, increase the cross-linking density of the system, prevent liquid diffusion and penetration, and further improve the air tightness; in addition, a certain amount of ether bonds are introduced into the rubber system, which not only supplements the problem of insufficient adhesion of halogenated butyl rubber, but also enhances the adhesion of rubber gaskets, and also increases the self-lubricating properties of the rubber gasket surface, making the cross-linked structure of the rubber gasket not easy to crack, and avoiding the generation of needle puncture chips. In addition, the addition of modified composite fillers and cross-linking aids can further improve the anti-leakage, puncture resistance, and cracking resistance of the rubber gasket material, so as to enhance the reinforcement of the rubber, and improve the tensile strength, elasticity, and wear resistance.

[0007] By preparing the raw materials and performing two vulcanization processes, the crosslinking degree and strength of the rubber gasket can be enhanced. Under-sulfur vulcanization can initially shape the rubber gasket and make it have greater strength. The tensile strength, elasticity and tensile stress are still not ideal, and the elongation at break is also relatively high. However, the tear resistance and abrasion resistance of the vulcanized rubber are better than those of the ortho-vulcanized rubber. Therefore, the rubber gasket can be slightly under-sulfurized and the temperature can be adjusted for secondary vulcanization, which can further improve the mechanical properties of the rubber gasket, increase the tensile strength and enhance the stability. It can also help eliminate residual low-molecular substances, reduce the shrinkage and deformation that may occur during the use of the product, and improve the heat resistance and aging resistance of the rubber gasket, thereby extending the service life of the product.

[0008] In a specific embodiment, the mass ratio of the halogenated butyl rubber, the polyisoprene rubber and the chloroether rubber is (35-44):23:(13-21).

[0009] By adopting the above technical solution, the halogenated butyl rubber, polyisoprene rubber and chloroether rubber are mixed to enhance the air tightness of the rubber gasket material. The rubber gasket material has the characteristics of high elasticity and oxidation resistance, which makes the rubber gasket material have good tensile and rebound capabilities, which can greatly accelerate the vulcanization speed of the system, improve the vulcanization efficiency, and avoid the generation of needle puncture chips. If the halogenated butyl rubber content is too low, the air tightness and sealing of the rubber gasket material will be reduced, and it is easy to leak; if the polyisoprene rubber content is too low, the gasket material may have insufficient needle puncture resistance and low mechanical properties; if the chloroether rubber content is too low, it is easy to cause the internal cross-linking performance and surface adhesion performance of the rubber gasket material to be insufficient, and it is easy to produce cracks, which reduces the anti-aging performance and reduces the service life of the gasket.

[0010] In a specific embodiment, the modified composite filler includes maleic anhydride grafted polypropylene fiber, modified mica powder, and polytetrafluoroethylene ultrafine powder.

[0011] Preferably, the mass ratio of the maleic anhydride grafted polypropylene fiber, the modified mica powder and the polytetrafluoroethylene ultrafine powder is (3-5):(1-3):1.

[0012] By adopting the above technical scheme, polypropylene fiber has the characteristics of high strength, wear resistance, corrosion resistance, etc., and enhances crack resistance and durability. By adding maleic anhydride grafted polypropylene fiber, on the one hand, it has high strength, wear resistance, corrosion resistance, etc., and enhances crack resistance and durability. On the other hand, maleic anhydride grafting can improve the compatibility of the modified composite filler with the polar rubber system, and enhance the sealing and long-term stability of the cross-linking process; the modified mica powder enhances the interaction with the rubber system. Mica powder is an inorganic powder with high modulus and high rigidity, which can effectively improve its tensile strength, flexural strength and flexural modulus. Then, polytetrafluoroethylene ultrafine powder with micron-level microporous structure is added. After needle puncture, it has self-lubrication and self-repairing properties, and the puncture hole is easier to close. Therefore, if the content of modified mica powder is too low, it may lead to insufficient long-term stability of the gasket material, which is easy to crack and oxidative deformation; if the content of maleic anhydride grafted polypropylene fiber is too low, the puncture resistance will be weakened and the long-term stability will be poor.

[0013] In a specific embodiment, the cross-linking auxiliary agent includes N,N'-m-phenylene bismaleimide and pentaerythritol stearate.

[0014] The mass ratio of the N,N'-m-phenylene bismaleimide to pentaerythritol stearate is (2-4):1.

[0015] By adopting the above technical scheme, N,N'-m-phenylene bismaleimide participates in the vulcanization process, the benzene ring vibrates, the CN stretches and vibrates, the cis double bonds in the five-membered heterocyclic ring are opened, and chemical cross-linking occurs between the rubber compound molecules. Because of the steric hindrance of the benzene ring, the disulfide groups are not easy to approach, forming a network structure with high cross-linking density, which has good heat-oxidative aging resistance and resistance to vulcanization reversion. Pentaerythritol stearate can enhance the dispersibility of N,N'-m-phenylene bismaleimide and modified composite fillers in the vulcanization process, enhance the compactness of the rubber network, the self-repairing ability after acupuncture, and the lubricity of the outer surface, prevent cracking, and have stronger heat resistance and resistance to vulcanization reversion.

[0016] In a specific embodiment, the vulcanization temperature of the pre-vulcanization is set to 152-158° C., and the vulcanization time is set to 70-80% of the positive vulcanization time of the mixed rubber measured at the corresponding temperature.

[0017] By adopting the above technical scheme, at a certain temperature, the rubber gasket material is changed from plastic to elastic, and the cross-linking density is maximized. At a certain temperature, the vulcanization time required for positive vulcanization is achieved. There is a certain positive vulcanization time and the vulcanization degree is controlled, thereby further inducing the rubber molecular chain to produce cross-linkable rubber macromolecular free radicals and generate cross-linking bonds. By controlling the temperature and vulcanization time to further induce the generation of free radicals, various side reactions are generated, a network structure is formed, and the vulcanization speed is increased to improve production efficiency.

[0018] The antioxidants are antioxidant RD and antioxidant 124 in a mass ratio of 3:1.

[0019] The particle size screened in S1 is 60-120 mesh.

[0020] Controlling the particle size of raw rubber powder within a specific range makes the raw materials easier to vulcanize and cross-link, thereby improving the vulcanization rate and quality.

[0021] In summary, this application has the following beneficial effects: 1. Through the raw rubber powder, halogenated butyl rubber, polyisoprene rubber and chloroether rubber as the main materials, halogenated butyl rubber and polyisoprene rubber are mixed. On the one hand, the double bonds of polyisoprene rubber and halogenated substituted butyl rubber are more active and cross-linked, so the air tightness of rubber gasket materials can be enhanced, and the performance of heat resistance, ozone resistance, aging resistance and chemical resistance can be enhanced. On the other hand, the high elasticity and oxidation resistance of polyisoprene rubber can be enhanced, so that the rubber gasket material has good stretching and rebound capabilities. On this basis, chloroether rubber is added, so that the rich active chlorine in chloroether rubber further triggers the unsaturated double bonds in the system. The polymerization reaction increases the attraction between molecules, makes the gaps between molecular chains smaller, forms a large number of carbon-carbon cross-links in the system more quickly, further increases the probability of polymerization, greatly accelerates the vulcanization speed of the system, improves the vulcanization efficiency, further cross-links the molecular chains, restricts the movement of the molecular chains, increases the cross-linking density of the system, prevents liquid diffusion and penetration, and further improves the air tightness; in addition, a certain amount of ether bonds are introduced into the rubber system, which not only supplements the problem of insufficient adhesion of halogenated butyl rubber, but also enhances the adhesion of rubber gaskets, and also increases the self-lubricating properties of the rubber gasket surface, making the cross-linked structure of the rubber gasket not easy to crack, and avoiding the generation of needle puncture chips. In addition, the addition of modified composite fillers and cross-linking aids can further improve the anti-leakage, puncture resistance, and cracking resistance of the rubber gasket material, so as to enhance the reinforcement of the rubber and improve the tensile strength, elasticity, and wear resistance.

[0022] By preparing the raw materials and performing two vulcanization processes, the crosslinking degree and strength of the rubber gasket can be enhanced. Under-sulfur vulcanization can initially shape the rubber gasket and make it have greater strength. The tensile strength, elasticity and tensile stress are still not ideal, and the elongation at break is also relatively high. However, the tear resistance and abrasion resistance of the vulcanized rubber are better than those of the ortho-vulcanized rubber. Therefore, the rubber gasket can be slightly under-sulfurized and the temperature can be adjusted for secondary vulcanization, which can further improve the mechanical properties of the rubber gasket, increase the tensile strength and enhance the stability. It can also help eliminate residual low-molecular substances, reduce the shrinkage and deformation that may occur during the use of the product, and improve the heat resistance and aging resistance of the rubber gasket, thereby extending the service life of the product.

[0023] 2. Polypropylene fiber has the characteristics of high strength, wear resistance, corrosion resistance, etc., which enhances crack resistance and durability. The addition of maleic anhydride grafted mica powder, on the one hand, mica is an inorganic powder with high modulus and high rigidity, which can effectively improve its tensile strength, flexural strength and flexural modulus. On the other hand, maleic anhydride grafting can improve the compatibility of modified composite fillers with polar rubber systems, enhance the sealing and long-term stability of the cross-linking process; and then add polytetrafluoroethylene ultrafine powder with micron-level microporous structure, which has self-lubrication and self-repairing properties after needle puncture, and the puncture hole is easier to close. Therefore, if the content of polypropylene fiber is too low, it may lead to insufficient long-term stability of the gasket material, which is easy to crack and oxidize and deform; if the content of maleic anhydride grafted mica powder is too low, the puncture resistance will be weakened and the long-term stability will be poor. DETAILED DESCRIPTION

[0024] The present application is further described in detail below with reference to the embodiments.

[0025] raw material Some of the raw materials used in the preparation examples and embodiments: The halogenated butyl rubber is chlorinated butyl rubber, model: 1066; the polyisoprene rubber model: XH-036; the chloroether rubber model CO / ECO, purchased from Shenyang Aviation Rubber and Plastic Products Factory; the polypropylene fiber model: HY-444; the mica powder (80 mesh) was purchased from Shijiazhuang Tuoju Mineral Products Co., Ltd.; the polytetrafluoroethylene ultrafine powder brand: TPD-505; the zinc oxide (30nm) product number: XH-ZnO.

[0026] The raw materials used in the examples and comparative examples that are not otherwise specified are all conventional products that can be purchased from the market.

[0027] Preparation example of modified composite filler Preparation Example 1 S1: 0.09 g of dicumyl peroxide was added to 1.8 g of tripropylene trimellitate to dissolve, 21 g of polypropylene fiber and 1.6 g of maleic anhydride mixed powder were evenly added, mixed and reacted at 160°C at a speed of 30 r / min for 10 min, and then collected to prepare maleic anhydride grafted polypropylene fiber.

[0028] S2: Weigh 6g of mica powder and add 2g of KH-792; after uniform ultrasonic dispersion, raise the temperature to 70°C, keep the reaction for 5h, filter, wash and dry at a constant temperature of 60°C for 8h to obtain modified mica powder.

[0029] S3: Maleic anhydride grafted polypropylene fiber, modified mica powder and polytetrafluoroethylene ultrafine powder are mixed evenly in a mass ratio of 5:3:1 to obtain a modified composite filler.

[0030] Preparation Example 2 S1: 0.09 g of dicumyl peroxide was added to 1.8 g of tripropylene trimellitate to dissolve, 21 g of polypropylene fiber and 1.6 g of maleic anhydride mixed powder were evenly added, mixed and reacted at 160°C at a speed of 30 r / min for 10 min, and then collected to prepare maleic anhydride grafted polypropylene fiber.

[0031] S2: Weigh 6g of mica powder and add 2g of KH-792; after uniform ultrasonic dispersion, raise the temperature to 70°C, keep the reaction for 5h, filter, wash and dry at a constant temperature of 60°C for 8h to obtain modified mica powder.

[0032] S3: Maleic anhydride grafted polypropylene fiber and modified mica powder are mixed evenly in a mass ratio of 6:3 to obtain a modified composite filler.

[0033] Preparation Example 3 S1: 0.09 g of dicumyl peroxide was added to 1.8 g of tripropylene trimellitate to dissolve, 21 g of polypropylene fiber and 1.6 g of maleic anhydride mixed powder were evenly added, mixed and reacted at 160°C at a speed of 30 r / min for 10 min, and then collected to prepare maleic anhydride grafted polypropylene fiber.

[0034] S2: Maleic anhydride grafted polypropylene fiber and polytetrafluoroethylene ultrafine powder are mixed evenly in a mass ratio of 8:1 to obtain a modified composite filler.

[0035] Preparation Example 4 S1: 0.09 g of dicumyl peroxide was added to 1.8 g of tripropylene trimellitate to dissolve, 21 g of polypropylene fiber and 1.6 g of maleic anhydride mixed powder were evenly added, mixed and reacted at 160°C at a speed of 30 r / min for 10 min, and then collected to prepare maleic anhydride grafted polypropylene fiber.

[0036] S2: Weigh 6g of mica powder and add 2g of KH-792; after uniform ultrasonic dispersion, raise the temperature to 70°C, keep the reaction for 5h, filter, wash and dry at a constant temperature of 60°C for 8h to obtain modified mica powder.

[0037] S3: Evenly mix the modified mica powder and the polytetrafluoroethylene ultrafine powder in a mass ratio of 8:1 to obtain a modified composite filler.

[0038] Preparation Example 5 S1: 0.09 g of dicumyl peroxide was added to 1.8 g of tripropylene trimellitate to dissolve, 21 g of polypropylene fiber and 1.6 g of maleic anhydride mixed powder were evenly added, mixed and reacted at 160°C at a speed of 30 r / min for 10 min, and then collected to prepare maleic anhydride grafted polypropylene fiber.

[0039] S2: Maleic anhydride grafted polypropylene fiber, mica powder and polytetrafluoroethylene ultrafine powder are mixed evenly in a mass ratio of 5:3:1 to obtain a modified composite filler.

[0040] Example 6 S1: Weigh 6g of mica powder and add 2g of KH-792; after uniform ultrasonic dispersion, raise the temperature to 70°C, keep the reaction for 5h, filter, wash and dry at a constant temperature of 60°C for 8h to obtain modified mica powder.

[0041] S2: Polypropylene fiber, modified mica powder and polytetrafluoroethylene ultrafine powder are mixed evenly in a mass ratio of 5:3:1 to obtain a modified composite filler. Example

[0042] Example 1 A vulcanization preparation process for a medical needle-resistant rubber gasket comprises the following steps: S1: preparing raw rubber materials: crushing and mixing raw rubber materials to be vulcanized into raw rubber powder, removing impurities and passing through a 120-mesh sieve; the raw rubber materials comprise: halogenated butyl rubber, polyisoprene rubber and chloroether rubber, wherein the ratio of halogenated butyl rubber, polyisoprene rubber and chloroether rubber is 35:23:21; S2: preparing a rubber mixture; preheating an internal mixer to 80°C, then adding 160g of raw rubber powder by weight into the mixer, and refining at 115°C for 9 minutes; adding 44g of the modified composite filler of Preparation Example 1, 12g of zinc oxide, 2g of stearic acid, 16g of N,N'-m-phenylene bismaleimide and pentaerythritol stearate in a mass ratio of 3:1, and 1g of antioxidant RD and antioxidant 124 in a mass ratio of 3:1, and mixing for 22 minutes; S3: calendering to form a sheet: calendering the mixed rubber obtained in step (2) to obtain a mixed rubber sheet; S4: Pre-vulcanization: The mixed rubber sheet calendered in step (3) is placed in the mold cavity of a flat vulcanizer for pre-vulcanization. The vulcanization temperature is set to 152°C. The positive vulcanization time (TC) of the rubber gasket formula measured at this temperature is 90 ) is 325s, and the vulcanization time is set to 80% of the positive vulcanization time, i.e. 260s; a preformed film is obtained; S5: Vulcanization molding: The preformed rubber sheet in step (4) is cleaned with an organic solvent, dried, and placed in a vulcanization mold for vulcanization molding to obtain a rubber gasket. The vulcanization temperature is 140° C. and the vulcanization time is 7 minutes.

[0043] Example 2 A vulcanization preparation process for a medical needle-resistant rubber gasket comprises the following steps: S1: preparing raw rubber materials: crushing and mixing the raw rubber materials to be vulcanized into raw rubber powder, removing impurities and passing through a 120-mesh sieve; the raw rubber materials comprise: halogenated butyl rubber, polyisoprene rubber and chloroether rubber, wherein the ratio of halogenated butyl rubber, polyisoprene rubber and chloroether rubber is 44:23:13; S2: preparing a rubber mixture; preheating an internal mixer to 100°C, then adding 180g of raw rubber powder by weight into the mixer, and refining at 125°C for 5min; adding 24g of the modified composite filler of Preparation Example 1, 4g of zinc oxide, 2g of stearic acid, 6g of N,N'-m-phenylene bismaleimide and pentaerythritol stearate in a mass ratio of 3:1, and 2g of antioxidant RD and antioxidant 124 in a mass ratio of 3:1, and mixing for 18min; S3: calendering to form a sheet: calendering the mixed rubber obtained in step (2) to obtain a mixed rubber sheet; S4: Pre-vulcanization: The mixed rubber sheet calendered in step (3) is placed in the mold cavity of a flat vulcanizer for pre-vulcanization. The vulcanization temperature is set to 152°C. The positive vulcanization time (TC) of the rubber gasket formula measured at this temperature is 90 ) is 325s, and the vulcanization time is set to 80% of the positive vulcanization time, i.e. 260s; a preformed film is obtained; S5: Vulcanization molding: The preformed rubber sheet in step (4) is cleaned with an organic solvent, dried, and then placed in a vulcanization mold for vulcanization molding to obtain a rubber gasket. The vulcanization temperature is 150° C. and the vulcanization time is 3 minutes.

[0044] Example 3 A vulcanization preparation process for a medical needle-puncture-resistant rubber gasket comprises the following steps: S1: preparing raw rubber materials: crushing and mixing raw rubber materials to be vulcanized into raw rubber powder, removing impurities and passing through a 120-mesh sieve; the raw rubber materials comprise: halogenated butyl rubber, polyisoprene rubber and chloroether rubber, wherein the halogenated butyl rubber, polyisoprene rubber and chloroether rubber are in a ratio of 30:23:30; S2: preparing a rubber mixture; preheating an internal mixer to 100°C, then adding 180g of raw rubber powder by weight into the mixer, and refining at 125°C for 5min; adding 24g of the modified composite filler of Preparation Example 1, 4g of zinc oxide, 2g of stearic acid, 6g of N,N'-m-phenylene bismaleimide and pentaerythritol stearate in a mass ratio of 3:1, and 2g of antioxidant RD and antioxidant 124 in a mass ratio of 3:1, and mixing for 18min; S3: calendering to form a sheet: calendering the mixed rubber obtained in step (2) to obtain a mixed rubber sheet; S4: Pre-vulcanization: The mixed rubber sheet calendered in step (3) is placed in the mold cavity of a flat vulcanizer for pre-vulcanization. The vulcanization temperature is set to 152°C. The positive vulcanization time (TC) of the rubber gasket formula measured at this temperature is 90 ) is 325s, and the vulcanization time is set to 80% of the positive vulcanization time, i.e. 260s; a preformed film is obtained; S5: Vulcanization molding: The preformed rubber sheet in step (4) is cleaned with an organic solvent, dried, and then placed in a vulcanization mold for vulcanization molding to obtain a rubber gasket. The vulcanization temperature is 150° C. and the vulcanization time is 3 minutes.

[0045] Example 4 A vulcanization preparation process for a medical needle-resistant rubber gasket comprises the following steps: S1: preparing raw rubber materials: crushing and mixing raw rubber materials to be vulcanized into raw rubber powder, removing impurities and passing through a 120-mesh sieve; the raw rubber materials comprise: halogenated butyl rubber, polyisoprene rubber and chloroether rubber, wherein the ratio of halogenated butyl rubber, polyisoprene rubber and chloroether rubber is 47:23:10; S2: preparing a rubber mixture; preheating an internal mixer to 100°C, then adding 180g of raw rubber powder by weight into the mixer, and refining at 125°C for 5min; adding 24g of the modified composite filler of Preparation Example 1, 4g of zinc oxide, 2g of stearic acid, 6g of N,N'-m-phenylene bismaleimide and pentaerythritol stearate in a mass ratio of 3:1, and 2g of antioxidant RD and antioxidant 124 in a mass ratio of 3:1, and mixing for 18min; S3: calendering to form a sheet: calendering the mixed rubber obtained in step (2) to obtain a mixed rubber sheet; S4: Pre-vulcanization: The mixed rubber sheet calendered in step (3) is placed in the mold cavity of a flat vulcanizer for pre-vulcanization. The vulcanization temperature is set to 152°C. The positive vulcanization time (TC) of the rubber gasket formula measured at this temperature is 90 ) is 325s, and the vulcanization time is set to 80% of the positive vulcanization time, i.e. 260s; a preformed film is obtained; S5: Vulcanization molding: The preformed rubber sheet in step (4) is cleaned with an organic solvent, dried, and then placed in a vulcanization mold for vulcanization molding to obtain a rubber gasket. The vulcanization temperature is 150° C. and the vulcanization time is 3 minutes.

[0046] Example 5 A vulcanization preparation process for a medical needle-resistant rubber gasket comprises the following steps: S1: preparing raw rubber materials: crushing and mixing the raw rubber materials to be vulcanized into raw rubber powder, removing impurities and passing through a 120-mesh sieve; the raw rubber materials comprise: halogenated butyl rubber, polyisoprene rubber and chloroether rubber, wherein the ratio of halogenated butyl rubber, polyisoprene rubber and chloroether rubber is 44:23:13; S2: preparing a rubber mixture; preheating an internal mixer to 100°C, then adding 180g of raw rubber powder by weight into the mixer, and refining at 125°C for 5min; adding 24g of the modified composite filler of Preparation Example 2, 4g of zinc oxide, 2g of stearic acid, 6g of N,N'-m-phenylene bismaleimide and pentaerythritol stearate in a mass ratio of 3:1, and 2g of antioxidant RD and antioxidant 124 in a mass ratio of 3:1, and mixing for 18min; S3: calendering to form a sheet: calendering the mixed rubber obtained in step (2) to obtain a mixed rubber sheet; S4: Pre-vulcanization: The mixed rubber sheet calendered in step (3) is placed in the mold cavity of a flat vulcanizer for pre-vulcanization. The vulcanization temperature is set to 152°C. The positive vulcanization time (TC) of the rubber gasket formula measured at this temperature is 90 ) is 325s, and the vulcanization time is set to 80% of the positive vulcanization time, i.e. 260s; a preformed film is obtained; S5: Vulcanization molding: The preformed rubber sheet in step (4) is cleaned with an organic solvent, dried, and then placed in a vulcanization mold for vulcanization molding to obtain a rubber gasket. The vulcanization temperature is 150° C. and the vulcanization time is 3 minutes.

[0047] Example 6 A vulcanization preparation process for a medical needle-resistant rubber gasket comprises the following steps: S1: preparing raw rubber materials: crushing and mixing the raw rubber materials to be vulcanized into raw rubber powder, removing impurities and passing through a 120-mesh sieve; the raw rubber materials comprise: halogenated butyl rubber, polyisoprene rubber and chloroether rubber, wherein the ratio of halogenated butyl rubber, polyisoprene rubber and chloroether rubber is 44:23:13; S2: preparing a rubber mixture; preheating an internal mixer to 100°C, then adding 180g of raw rubber powder by weight into the mixer, and refining at 125°C for 5min; adding 24g of the modified composite filler of Preparation Example 3, 4g of zinc oxide, 2g of stearic acid, 6g of N,N'-m-phenylene bismaleimide and pentaerythritol stearate in a mass ratio of 3:1, and 2g of antioxidant RD and antioxidant 124 in a mass ratio of 3:1, and mixing for 18min; S3: calendering to form a sheet: calendering the mixed rubber obtained in step (2) to obtain a mixed rubber sheet; S4: Pre-vulcanization: The mixed rubber sheet calendered in step (3) is placed in the mold cavity of a flat vulcanizer for pre-vulcanization. The vulcanization temperature is set to 152°C. The positive vulcanization time (TC) of the rubber gasket formula measured at this temperature is 90 ) is 325s, and the vulcanization time is set to 80% of the positive vulcanization time, i.e. 260s; a preformed film is obtained; S5: Vulcanization molding: The preformed rubber sheet in step (4) is cleaned with an organic solvent, dried, and then placed in a vulcanization mold for vulcanization molding to obtain a rubber gasket. The vulcanization temperature is 150° C. and the vulcanization time is 3 minutes.

[0048] Example 7 A vulcanization preparation process for a medical needle-resistant rubber gasket comprises the following steps: S1: preparing raw rubber materials: crushing and mixing the raw rubber materials to be vulcanized into raw rubber powder, removing impurities and passing through a 120-mesh sieve; the raw rubber materials comprise: halogenated butyl rubber, polyisoprene rubber and chloroether rubber, wherein the ratio of halogenated butyl rubber, polyisoprene rubber and chloroether rubber is 44:23:13; S2: preparing a rubber mixture; preheating an internal mixer to 100°C, then adding 180g of raw rubber powder by weight into the mixer, and refining at 125°C for 5min; adding 24g of the modified composite filler of Preparation Example 4, 4g of zinc oxide, 2g of stearic acid, 6g of N,N'-m-phenylene bismaleimide and pentaerythritol stearate in a mass ratio of 3:1, and 2g of antioxidant RD and antioxidant 124 in a mass ratio of 3:1, and mixing for 18min; S3: calendering to form a sheet: calendering the mixed rubber obtained in step (2) to obtain a mixed rubber sheet; S4: Pre-vulcanization: The mixed rubber sheet calendered in step (3) is placed in the mold cavity of a flat vulcanizer for pre-vulcanization. The vulcanization temperature is set to 152°C. The positive vulcanization time (TC) of the rubber gasket formula measured at this temperature is 90 ) is 325s, and the vulcanization time is set to 80% of the positive vulcanization time, i.e. 260s; a preformed film is obtained; S5: Vulcanization molding: The preformed rubber sheet in step (4) is cleaned with an organic solvent, dried, and then placed in a vulcanization mold for vulcanization molding to obtain a rubber gasket. The vulcanization temperature is 150° C. and the vulcanization time is 3 minutes.

[0049] Example 8 A vulcanization preparation process for a medical needle-resistant rubber gasket comprises the following steps: S1: preparing raw rubber materials: crushing and mixing the raw rubber materials to be vulcanized into raw rubber powder, removing impurities and passing through a 120-mesh sieve; the raw rubber materials comprise: halogenated butyl rubber, polyisoprene rubber and chloroether rubber, wherein the ratio of halogenated butyl rubber, polyisoprene rubber and chloroether rubber is 44:23:13; S2: preparing a rubber mixture; preheating an internal mixer to 100°C, then adding 180g of raw rubber powder by weight, and refining at 125°C for 5min; adding 24g of the modified composite filler of Preparation Example 5, 4g of zinc oxide, 2g of stearic acid, 6g of N,N'-m-phenylene bismaleimide and pentaerythritol stearate in a mass ratio of 3:1, and 2g of antioxidant RD and antioxidant 124 in a mass ratio of 3:1, and mixing for 18min; S3: calendering to form a sheet: calendering the mixed rubber obtained in step (2) to obtain a mixed rubber sheet; S4: Pre-vulcanization: The mixed rubber sheet calendered in step (3) is placed in the mold cavity of a flat vulcanizer for pre-vulcanization. The vulcanization temperature is set to 152°C. The positive vulcanization time (TC) of the rubber gasket formula measured at this temperature is 90 ) is 325s, and the vulcanization time is set to 80% of the positive vulcanization time, i.e. 260s; a preformed film is obtained; S5: Vulcanization molding: The preformed rubber sheet in step (4) is cleaned with an organic solvent, dried, and then placed in a vulcanization mold for vulcanization molding to obtain a rubber gasket. The vulcanization temperature is 150° C. and the vulcanization time is 3 minutes.

[0050] Example 9 A vulcanization preparation process for a medical needle-resistant rubber gasket comprises the following steps: S1: preparing raw rubber materials: crushing and mixing the raw rubber materials to be vulcanized into raw rubber powder, removing impurities and passing through a 120-mesh sieve; the raw rubber materials comprise: halogenated butyl rubber, polyisoprene rubber and chloroether rubber, wherein the ratio of halogenated butyl rubber, polyisoprene rubber and chloroether rubber is 44:23:13; S2: prepare the mixed rubber; preheat the internal mixer to 100°C, then add 180g of raw rubber powder, and mix at 125°C for 5 minutes; add 24g of the modified composite filler of Preparation Example 6, 4g of zinc oxide, 2g of stearic acid, 6g of N,N'-m-phenylene bismaleimide and pentaerythritol stearate in a mass ratio of 3:1. Mix with 2g of antioxidant RD and antioxidant 124 in a mass ratio of 3:1, and mix for 18 minutes; S3: calendering to form a sheet: calendering the mixed rubber obtained in step (2) to obtain a mixed rubber sheet; S4: Pre-vulcanization: The mixed rubber sheet calendered in step (3) is placed in the mold cavity of a flat vulcanizer for pre-vulcanization. The vulcanization temperature is set to 152°C. The positive vulcanization time (TC) of the rubber gasket formula measured at this temperature is 90 ) is 325s, and the vulcanization time is set to 80% of the positive vulcanization time, i.e. 260s; a preformed film is obtained; S5: Vulcanization molding: The preformed rubber sheet in step (4) is cleaned with an organic solvent, dried, and then placed in a vulcanization mold for vulcanization molding to obtain a rubber gasket. The vulcanization temperature is 150° C. and the vulcanization time is 3 minutes.

[0051] Example 10 A vulcanization preparation process for a medical needle-resistant rubber gasket comprises the following steps: S1: preparing raw rubber materials: crushing and mixing the raw rubber materials to be vulcanized into raw rubber powder, removing impurities and passing through a 120-mesh sieve; the raw rubber materials comprise: halogenated butyl rubber, polyisoprene rubber and chloroether rubber, wherein the ratio of halogenated butyl rubber, polyisoprene rubber and chloroether rubber is 44:23:13; S2: preparing a rubber mixture; preheating an internal mixer to 100°C, adding 180g of raw rubber powder by weight, and refining at 125°C for 5min; adding 24g of the modified composite filler of Preparation Example 1, 4g of zinc oxide, 2g of stearic acid, 6g of N,N'-m-phenylene bismaleimide and 2g of antioxidant RD and antioxidant 124 in a mass ratio of 3:1, and mixing for 18min; S3: calendering to form a sheet: calendering the mixed rubber obtained in step (2) to obtain a mixed rubber sheet; S4: Pre-vulcanization: The mixed rubber sheet calendered in step (3) is placed in the mold cavity of a flat vulcanizer for pre-vulcanization. The vulcanization temperature is set to 152°C. The positive vulcanization time (TC) of the rubber gasket formula measured at this temperature is 90 ) is 325s, and the vulcanization time is set to 80% of the positive vulcanization time, i.e. 260s; a preformed film is obtained; S5: Vulcanization molding: The preformed rubber sheet in step (4) is cleaned with an organic solvent, dried, and then placed in a vulcanization mold for vulcanization molding to obtain a rubber gasket. The vulcanization temperature is 150° C. and the vulcanization time is 3 minutes.

[0052] Embodiment 11 A vulcanization preparation process for a medical needle-resistant rubber gasket comprises the following steps: S1: preparing raw rubber materials: crushing and mixing the raw rubber materials to be vulcanized into raw rubber powder, removing impurities and passing through a 120-mesh sieve; the raw rubber materials comprise: halogenated butyl rubber, polyisoprene rubber and chloroether rubber, wherein the ratio of halogenated butyl rubber, polyisoprene rubber and chloroether rubber is 44:23:13; S2: preparing a rubber mixture; preheating an internal mixer to 100°C, then adding 180g of raw rubber powder by weight into the mixer, and refining at 125°C for 5min; adding 24g of the modified composite filler of Preparation Example 1, 4g of zinc oxide, 2g of stearic acid, 6g of N,N'-m-phenylene bismaleimide and pentaerythritol stearate in a mass ratio of 3:1, and 2g of antioxidant RD and antioxidant 124 in a mass ratio of 3:1, and mixing for 18min; S3: calendering to form a sheet: calendering the mixed rubber obtained in step (2) to obtain a mixed rubber sheet; S4: Pre-vulcanization: The mixed rubber sheet calendered in step (3) is placed in the mold cavity of a flat vulcanizer for pre-vulcanization. The vulcanization temperature is set to 152°C. The positive vulcanization time (TC) of the rubber gasket formula measured at this temperature is 90 ) is 325s, and the vulcanization time is set to 88% of the positive vulcanization time, i.e. 286s; a preformed film is obtained; S5: Vulcanization molding: The preformed rubber sheet in step (4) is cleaned with an organic solvent, dried, and then placed in a vulcanization mold for vulcanization molding to obtain a rubber gasket. The vulcanization temperature is 150° C. and the vulcanization time is 3 minutes.

[0053] Example 12 A vulcanization preparation process for a medical needle-resistant rubber gasket comprises the following steps: S1: preparing raw rubber materials: crushing and mixing the raw rubber materials to be vulcanized into raw rubber powder, removing impurities and passing through a 300-mesh sieve; the raw rubber materials comprise: halogenated butyl rubber, polyisoprene rubber and chloroether rubber, wherein the ratio of halogenated butyl rubber, polyisoprene rubber and chloroether rubber is 44:23:13; S2: preparing a rubber mixture; preheating an internal mixer to 100°C, then adding 180g of raw rubber powder by weight into the mixer, and refining at 125°C for 5min; adding 24g of the modified composite filler of Preparation Example 1, 4g of zinc oxide, 2g of stearic acid, 6g of N,N'-m-phenylene bismaleimide and pentaerythritol stearate in a mass ratio of 3:1, and 2g of antioxidant RD and antioxidant 124 in a mass ratio of 3:1, and mixing for 18min; S3: calendering to form a sheet: calendering the mixed rubber obtained in step (2) to obtain a mixed rubber sheet; S4: Pre-vulcanization: The mixed rubber sheet calendered in step (3) is placed in the mold cavity of a flat vulcanizer for pre-vulcanization. The vulcanization temperature is set to 152°C. The positive vulcanization time (TC) of the rubber gasket formula measured at this temperature is 90 ) is 325s, and the vulcanization time is set to 80% of the positive vulcanization time, i.e. 260s; a preformed film is obtained; S5: Vulcanization molding: The preformed rubber sheet in step (4) is cleaned with an organic solvent, dried, and then placed in a vulcanization mold for vulcanization molding to obtain a rubber gasket. The vulcanization temperature is 150° C. and the vulcanization time is 3 minutes.

[0054] Comparative Example Comparative Example 1 A vulcanization preparation process for a medical needle-resistant rubber gasket comprises the following steps: S1: preparing raw rubber materials: crushing and mixing raw rubber materials to be vulcanized into raw rubber powder, removing impurities and passing through a 120-mesh sieve; the raw rubber materials comprise: halogenated butyl rubber and polyisoprene rubber, wherein the ratio of halogenated butyl rubber, polyisoprene rubber and chloroether rubber is 57:13; S2: preparing a rubber mixture; preheating an internal mixer to 100°C, then adding 180g of raw rubber powder by weight into the mixer, and refining at 125°C for 5min; adding 24g of the modified composite filler of Preparation Example 1, 4g of zinc oxide, 2g of stearic acid, 6g of N,N'-m-phenylene bismaleimide and pentaerythritol stearate in a mass ratio of 3:1, and 2g of antioxidant RD and antioxidant 124 in a mass ratio of 3:1, and mixing for 18min; S3: calendering to form a sheet: calendering the mixed rubber obtained in step (2) to obtain a mixed rubber sheet; S4: Pre-vulcanization: The mixed rubber sheet calendered in step (3) is placed in the mold cavity of a flat vulcanizer for pre-vulcanization. The vulcanization temperature is set to 152°C. The positive vulcanization time (TC) of the rubber gasket formula measured at this temperature is 90 ) is 325s, and the vulcanization time is set to 80% of the positive vulcanization time, i.e. 260s; a preformed film is obtained; S5: Vulcanization molding: The preformed rubber sheet in step (4) is cleaned with an organic solvent, dried, and then placed in a vulcanization mold for vulcanization molding to obtain a rubber gasket. The vulcanization temperature is 150° C. and the vulcanization time is 3 minutes.

[0055] Comparative Example 2 A vulcanization preparation process for a medical needle-resistant rubber gasket comprises the following steps: S1: preparing raw rubber materials: crushing and mixing the raw rubber materials to be vulcanized into raw rubber powder, removing impurities and passing through a 120-mesh sieve; the raw rubber materials comprise: halogenated butyl rubber and chloroether rubber, wherein the ratio of halogenated butyl rubber to chloroether rubber is 44:36; S2: preparing a rubber mixture; preheating an internal mixer to 100°C, then adding 180g of raw rubber powder by weight into the mixer, and refining at 125°C for 5min; adding 24g of the modified composite filler of Preparation Example 1, 4g of zinc oxide, 2g of stearic acid, 6g of N,N'-m-phenylene bismaleimide and pentaerythritol stearate in a mass ratio of 3:1, and 2g of antioxidant RD and antioxidant 124 in a mass ratio of 3:1, and mixing for 18min; S3: calendering to form a sheet: calendering the mixed rubber obtained in step (2) to obtain a mixed rubber sheet; S4: Pre-vulcanization: The mixed rubber sheet calendered in step (3) is placed in the mold cavity of a flat vulcanizer for pre-vulcanization. The vulcanization temperature is set to 152°C. The positive vulcanization time (TC) of the rubber gasket formula measured at this temperature is 90 ) is 325s, and the vulcanization time is set to 80% of the positive vulcanization time, i.e. 260s; a preformed film is obtained; S5: Vulcanization molding: The preformed rubber sheet in step (4) is cleaned with an organic solvent, dried, and then placed in a vulcanization mold for vulcanization molding to obtain a rubber gasket. The vulcanization temperature is 150° C. and the vulcanization time is 3 minutes.

[0056] Comparative Example 3 A vulcanization preparation process for a medical needle-resistant rubber gasket comprises the following steps: S1: preparing raw rubber materials: crushing and mixing the raw rubber materials to be vulcanized into raw rubber powder, removing impurities and passing through a 120-mesh sieve; the raw rubber materials comprise polyisoprene rubber and epichlorohydrin rubber, wherein the ratio of polyisoprene rubber to epichlorohydrin rubber is 67:13; S2: prepare the mixed rubber; preheat the internal mixer to 100°C, then add 180g of raw rubber powder, and mix at 125°C for 5 minutes; add 24g of the modified composite filler of Preparation Example 1, 4g of zinc oxide, 2g of stearic acid, 6g of N,N'-m-phenylene bismaleimide and pentaerythritol stearate in a mass ratio of 3:1. Mix with 2g of antioxidant RD and antioxidant 124 in a mass ratio of 3:1, and mix for 18 minutes; S3: calendering to form a sheet: calendering the mixed rubber obtained in step (2) to obtain a mixed rubber sheet; S4: Pre-vulcanization: The mixed rubber sheet calendered in step (3) is placed in the mold cavity of a flat vulcanizer for pre-vulcanization. The vulcanization temperature is set to 152°C. The positive vulcanization time (TC) of the rubber gasket formula measured at this temperature is 90 ) is 325s, and the vulcanization time is set to 80% of the positive vulcanization time, i.e. 260s; a preformed film is obtained; S5: Vulcanization molding: The preformed rubber sheet in step (4) is cleaned with an organic solvent, dried, and then placed in a vulcanization mold for vulcanization molding to obtain a rubber gasket. The vulcanization temperature is 150° C. and the vulcanization time is 3 minutes.

[0057] Comparative Example 4 A vulcanization preparation process for a medical needle-resistant rubber gasket comprises the following steps: S1: preparing raw rubber materials: crushing and mixing the raw rubber materials to be vulcanized into raw rubber powder, removing impurities and passing through a 120-mesh sieve; the raw rubber materials comprise: halogenated butyl rubber, polyisoprene rubber and chloroether rubber, wherein the ratio of halogenated butyl rubber, polyisoprene rubber and chloroether rubber is 44:23:13; S2: preparing a rubber mixture; preheating an internal mixer to 100°C, then adding 204g of raw rubber powder, and refining at 125°C for 5min; adding 4g of zinc oxide, 2g of stearic acid, 6g of N,N'-m-phenylene bismaleimide and pentaerythritol stearate in a mass ratio of 3:1, and 2g of antioxidant RD and antioxidant 124 in a mass ratio of 3:1, and mixing for 18min; S3: calendering to form a sheet: calendering the mixed rubber obtained in step (2) to obtain a mixed rubber sheet; S4: Pre-vulcanization: The mixed rubber sheet calendered in step (3) is placed in the mold cavity of a flat vulcanizer for pre-vulcanization. The vulcanization temperature is set to 152°C. The positive vulcanization time (TC) of the rubber gasket formula measured at this temperature is 90 ) is 325s, and the vulcanization time is set to 80% of the positive vulcanization time, i.e. 260s; a preformed film is obtained; S5: Vulcanization molding: The preformed rubber sheet in step (4) is cleaned with an organic solvent, dried, and then placed in a vulcanization mold for vulcanization molding to obtain a rubber gasket. The vulcanization temperature is 150° C. and the vulcanization time is 3 minutes.

[0058] Comparative Example 5 A vulcanization preparation process for a medical needle-resistant rubber gasket comprises the following steps: S1: preparing raw rubber materials: crushing and mixing the raw rubber materials to be vulcanized into raw rubber powder, removing impurities and passing through a 120-mesh sieve; the raw rubber materials comprise: halogenated butyl rubber, polyisoprene rubber and chloroether rubber, wherein the ratio of halogenated butyl rubber, polyisoprene rubber and chloroether rubber is 44:23:13; S2: preparing a rubber mixture; preheating an internal mixer to 100°C, adding 186g of raw rubber powder by weight, and refining at 125°C for 5min; adding 24g of the modified composite filler of Preparation Example 1, 4g of zinc oxide, 2g of stearic acid, and 2g of antioxidant RD and antioxidant 124 in a mass ratio of 3:1, and mixing for 18min; S3: calendering to form a sheet: calendering the mixed rubber obtained in step (2) to obtain a mixed rubber sheet; S4: Pre-vulcanization: The mixed rubber sheet calendered in step (3) is placed in the mold cavity of a flat vulcanizer for pre-vulcanization. The vulcanization temperature is set to 152°C. The positive vulcanization time (TC) of the rubber gasket formula measured at this temperature is 90 ) is 325s, and the vulcanization time is set to 80% of the positive vulcanization time, i.e. 260s; a preformed film is obtained; S5: Vulcanization molding: The preformed rubber sheet in step (4) is cleaned with an organic solvent, dried, and then placed in a vulcanization mold for vulcanization molding to obtain a rubber gasket. The vulcanization temperature is 150° C. and the vulcanization time is 3 minutes.

[0059] Comparative Example 6 A vulcanization preparation process for a medical needle-resistant rubber gasket comprises the following steps: S1: preparing raw rubber materials: crushing and mixing the raw rubber materials to be vulcanized into raw rubber powder, removing impurities and passing through a 120-mesh sieve; the raw rubber materials comprise: halogenated butyl rubber, polyisoprene rubber and chloroether rubber, wherein the ratio of halogenated butyl rubber, polyisoprene rubber and chloroether rubber is 44:23:13; S2: preparing a rubber mixture; preheating an internal mixer to 100°C, then adding 204g of raw rubber powder, and refining at 125°C for 5min; adding 24g of the modified composite filler of Preparation Example 1, 4g of zinc oxide, 2g of stearic acid, 6g of N,N'-m-phenylene bismaleimide and pentaerythritol stearate in a mass ratio of 3:1, and 2g of antioxidant RD and antioxidant 124 in a mass ratio of 3:1, and mixing for 18min; S3: calendering to form a sheet: calendering the mixed rubber obtained in step (2) to obtain a mixed rubber sheet; S4: Pre-vulcanization: The mixed rubber sheet calendered in step (3) is placed in the mold cavity of a flat vulcanizer. The vulcanization temperature is set to 152°C. The positive vulcanization time (TC) of the rubber gasket formula measured at this temperature is 90 ) is 325s, and the vulcanization time is set to 80% of the positive vulcanization time, i.e. 260s; a vulcanized molding film is obtained; Performance Testing The performance test of the medical needle-resistant rubber gasket prepared by the vulcanization preparation process of the medical needle-resistant rubber gasket prepared in Examples 1-12 and Comparative Examples 1-6 was conducted by the following method: a. Puncture resistance: Determine the chip removal and sealing performance after needle puncture according to the standards of YBB00052005-2015 and YBB00042005-2015 (methylene blue solution is not allowed to enter).

[0060] b. Tensile strength: tested according to the relevant methods in standard GB / T 528-2009.

[0061] c. Tensile strength retention rate: The sample is subjected to aging treatment, and the aging method is carried out according to the relevant method in standard GB / T3512-2001, the aging temperature is 175°C, and the aging time is 96h. After the aging treatment is completed, the tensile strength of the sample is tested using the method in 2.1 Tensile Strength, recorded as T1, and the calculation formula of the tensile strength retention rate S is as follows: S = T1 / T0*100%.

[0062] d. Rebound rate: Tested in accordance with GB / T20671 "Non-metallic gasket material classification system and test methods Gasket material compression rate rebound rate test method": Performance see Table 1: Table 1 Performance test results As can be seen from Table 1, by comparing Examples 1-4 and Comparative Examples 1-3, the puncture resistance, sealing, resilience and tensile aging resistance of the rubber gasket prepared in Example 2 are all better than those of Comparative Examples 1-3. The mixture of halogenated butyl rubber, polyisoprene rubber and chloroether rubber can enhance the air tightness of the rubber gasket material, and has the characteristics of high elasticity and oxidation resistance, so that the rubber gasket material has good tensile and rebound capabilities, which can greatly accelerate the vulcanization speed of the system, improve the vulcanization efficiency, and avoid the generation of needle puncture chips. If the content of halogenated butyl rubber is too low, the air tightness and sealing of the rubber gasket material will be reduced, and it is easy to leak; if the content of polyisoprene rubber is too low, the gasket material may have insufficient needle puncture resistance and low mechanical properties; if the content of chloroether rubber is too low, it is easy to cause the internal cross-linking performance and surface adhesion performance of the rubber gasket material to be insufficient, and it is easy to produce cracks, which reduces the anti-aging performance and reduces the service life of the gasket.

[0063] By comparing Example 2 with Examples 6-9 and Comparative Example 4, it can be seen that the puncture resistance, sealing, resilience and tensile aging resistance of the rubber gasket prepared in Example 2 are all better than those of Examples 6-9. Analysis shows that polypropylene fiber has the characteristics of high strength, wear resistance, corrosion resistance and the like, and enhances crack resistance and durability. By adding maleic anhydride grafted polypropylene fiber, on the one hand, it has the characteristics of high strength, wear resistance, corrosion resistance and the like, and enhances crack resistance and durability. On the other hand, maleic anhydride grafting can improve the compatibility of the modified composite filler with the polar rubber system, and enhance the sealing and long-term stability of the cross-linking process; the modified mica powder enhances the interaction with the rubber system. Mica powder is an inorganic powder with high modulus and high rigidity, which can effectively improve its tensile strength, flexural strength and flexural modulus. When polytetrafluoroethylene ultrafine powder with a micron-sized microporous structure is added, it has self-lubrication and self-repairing properties after needle puncture, and the puncture hole is easier to close. Therefore, if the content of modified mica powder is too low, the gasket material may have insufficient long-term stability, which may lead to cracking and oxidation deformation; if the content of maleic anhydride grafted polypropylene fiber is too low, the puncture resistance will be weakened and the long-term stability will be poor.

[0064] By comparing Example 2 with Example 10 and Comparative Example 5, it can be seen that the puncture resistance, sealing, resilience and tensile aging resistance of the rubber gasket prepared in Example 2 are all better than those in Example 10 and Comparative Example 5. It is analyzed that N, N'-phenylene bismaleimide participates in the vulcanization process, the benzene ring vibrates, the CN stretches and vibrates, the cis double bonds in the five-membered heterocyclic ring are opened, and chemical cross-linking occurs between the rubber compound molecules. Because of the steric hindrance of the benzene ring, the disulfide groups are not easy to approach, forming a network structure with high cross-linking density, which has good heat-oxidative aging resistance and resistance to vulcanization reversion. Pentaerythritol stearate can enhance the dispersibility of N, N'-phenylene bismaleimide and modified composite fillers during the vulcanization process, enhance the compactness of the rubber network, the self-repairing ability after acupuncture, and the lubricity of the outer surface, prevent cracking, and have stronger heat resistance and resistance to vulcanization reversion.

[0065] By comparing Example 2 with Example 11 and Comparative Example 6, it can be known that the crosslinking degree and strength of the rubber gasket are enhanced by preparing the raw materials and performing two vulcanization processes. Under-sulfurization can make the rubber gasket initially shaped and have greater strength. The tensile strength, elasticity and tensile stress are still not ideal, and the elongation at break is also relatively high, but the tear resistance and wear resistance of the vulcanized rubber are better than those of the positive vulcanized rubber; therefore, the rubber gasket can be slightly under-sulfurized, and the temperature can be adjusted for secondary vulcanization to further improve the mechanical properties of the rubber gasket, improve the tensile strength, and enhance the stability: and it is helpful to eliminate residual low-molecular substances, reduce the shrinkage and deformation that may occur during the use of the product, and improve the heat resistance and aging resistance of the rubber gasket. The vulcanization time required for positive vulcanization is reached at a certain temperature, and the rubber molecular chain is further induced to produce crosslinkable rubber macromolecular free radicals to generate crosslinking bonds. The temperature and vulcanization time are controlled to further induce the generation of free radicals, accompanied by various side reactions, to form a network structure, and to increase the vulcanization speed to improve production efficiency.

[0066] The above are all preferred embodiments of the present application, and the protection scope of the present application is not limited thereto. Therefore, any equivalent changes made according to the structure, shape, and principle of the present application should be included in the protection scope of the present application.

Claims

1. A vulcanization preparation process for a medical needle-resistant rubber gasket, characterized in that: Includes the following step: S1: Preparation of raw rubber materials: crushing and mixing the raw rubber materials to be vulcanized into raw rubber powder, removing impurities and sieving; the raw rubber materials include halogenated butyl rubber, polyisoprene rubber and chloroether rubber; S2: preparing a rubber mixture; preheating an internal mixer to 80-100°C, adding 80-90 parts by weight of raw rubber powder into the internal mixer, and refining at 115-125°C for 5-9 minutes; adding 12-22 parts by weight of a modified composite filler, 2-6 parts by weight of zinc oxide, 1-3 parts by weight of stearic acid, 3-8 parts by weight of a crosslinking aid and 0.5-1.2 parts by weight of an antioxidant for mixing, and mixing for 18-22 minutes; S3: calendering to form a sheet: calendering the mixed rubber obtained in step (2) to obtain a mixed rubber sheet; S4: pre-vulcanization: placing the mixed rubber sheet calendered in step (3) into the mold cavity of a flat vulcanizer, and vulcanizing it to obtain a preformed film; S5: Vulcanization molding: The preformed rubber sheet in step (4) is cleaned with an organic solvent, dried, and then placed in a vulcanization mold for vulcanization molding to obtain a rubber gasket. The vulcanization temperature is 140-150° C. and the vulcanization time is 3-7 minutes.

2. The vulcanization preparation process of the medical needle-resistant rubber gasket according to claim 1, characterized in that: The mass ratio of the halogenated butyl rubber, polyisoprene rubber and chloroether rubber is (35-44):23:(13-21).

3. The vulcanization preparation process of the medical needle-resistant rubber gasket according to claim 1, characterized in that: The modified composite filler comprises maleic anhydride grafted polypropylene fiber, modified mica powder and polytetrafluoroethylene ultrafine powder.

4. The vulcanization preparation process of the medical needle-resistant rubber gasket according to claim 3 is characterized in that: The mass ratio of the maleic anhydride grafted polypropylene fiber, the modified mica powder and the polytetrafluoroethylene ultrafine powder is (3-5): (1-3):

1.

5. The vulcanization preparation process of the medical needle-resistant rubber gasket according to claim 1, characterized in that: The cross-linking auxiliary agent includes N,N'-m-phenylene bismaleimide and pentaerythritol stearate.

6. The vulcanization preparation process of the medical needle-resistant rubber gasket according to claim 5, characterized in that: The mass ratio of the N,N'-m-phenylene bismaleimide to pentaerythritol stearate is (2-4):

1.

7. The vulcanization preparation process of the medical needle-resistant rubber gasket according to claim 1, characterized in that: The vulcanization temperature of the pre-vulcanization is set to 152-158° C., and the vulcanization time is set to 70-80% of the positive vulcanization time measured at the corresponding temperature of the mixed rubber.

8. The vulcanization preparation process of the medical needle-resistant rubber gasket according to claim 1, characterized in that: The particle size screened in S1 is 60-120 mesh.

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