Layered rubber material as well as preparation method and application thereof

Abstract

The invention relates to the technical field of medical rubber materials, in particular to a layered rubber material and a preparation method and application thereof. The layered rubber material sequentially comprises a puncture rubber layer, an antibacterial rubber layer and a contact rubber layer from top to bottom; wherein the puncture rubber layer mainly comprises the following raw materials: ethylene propylene diene monomer, hydrogenated styrene-butadiene block copolymer and inorganic filler; the antibacterial rubber layer mainly comprises the following raw materials: aramid fiber modified butadiene styrene rubber and paeonol microcapsule modified isoprene rubber; the contact rubber layer is mainly prepared from butyl rubber and chitosan. According to the invention, the synergistic effect of the raw material components is utilized, so that the layered rubber material has good puncture resistance and air tightness and good compatibility with drugs, and the drug quality can be effectively guaranteed. According to the invention, the problems of poor air tightness, low drug compatibility and poor puncture resistance of the traditional Chinese medicine rubber plug in the prior art are effectively solved, and a new idea is provided for preparation of a medical rubber material.

Description

Technical Field

[0001] The invention relates to the technical field of preparing medical rubber materials, and in particular to a layered rubber material and a preparation method and application thereof. Background Art

[0002] Medical rubber stoppers play a vital role in the field of pharmaceutical packaging. They can be used to seal medicine bottles, infusion bottles and other containers to prevent leakage or contamination of drugs, while ensuring the stability of drug quality during storage and transportation. With the rapid development of the pharmaceutical industry, the requirements for drug quality and safety are increasing, which has also prompted the continuous research and development and innovation of medical rubber stopper materials. Ideal medical rubber stopper materials should have good sealing, chemical stability and biocompatibility to meet the packaging needs of different drugs.

[0003] Existing medical rubber plug materials mainly include butyl rubber, which has long been the main material for medical rubber plugs due to its excellent air tightness, chemical corrosion resistance and low air permeability. However, butyl rubber has a slow vulcanization speed, low production efficiency, and poor compatibility with certain specific drugs, which may cause visible foreign matter or chemical reactions in the drugs, affecting the quality of the drugs. In response to this, researchers have provided materials such as silicone rubber, halogenated butyl rubber or thermoplastic elastomers to replace butyl rubber. However, the air tightness of silicone rubber is relatively poor and cannot meet the packaging needs of drugs with high air tightness requirements; halogenated butyl rubber has problems with extractables and leachates when encountering oxidizing drugs, and has poor puncture resistance; thermoplastic elastomers still have a certain gap in sealing performance and long-term stability compared to traditional butyl rubber.

[0004] Based on this, the development of a rubber material with good air tightness and high drug compatibility has important practical significance for the development and innovation of medical rubber stoppers. Summary of the invention

[0005] In view of the problems of poor air tightness, low drug compatibility and poor puncture resistance of the existing medical rubber stoppers, the present invention provides a layered rubber material and its preparation method and application. The layered rubber material includes a puncture rubber layer, an antibacterial rubber layer and a contact rubber layer. By utilizing the synergistic effect of each raw material component, the layered rubber material has good puncture resistance and air tightness, good compatibility with drugs, and can effectively ensure the quality and stability of drugs, providing a new idea for the preparation of medical rubber materials.

[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions: The first aspect of the present invention provides a layered rubber material, which comprises a puncture rubber layer, an antibacterial rubber layer and a contact rubber layer in order from top to bottom; wherein the puncture rubber layer comprises the following raw material components in parts by weight: 40-50 parts of ethylene propylene rubber, 10-15 parts of hydrogenated styrene-butadiene block copolymer, 10-20 parts of inorganic filler, 1-5 parts of antioxidant, 1-3 parts of activator and 1-3 parts of vulcanization aid; wherein the inorganic filler comprises titanium powder and phlogopite powder; The antibacterial rubber layer comprises the following raw material components in parts by weight: 30-50 parts of aramid fiber modified styrene-butadiene rubber, 15-20 parts of paeonol microcapsule modified isoprene rubber, 1-5 parts of antioxidant, 1-3 parts of activator and 1-3 parts of vulcanization aid; The contact rubber layer comprises the following raw material components in parts by mass: 40-60 parts of butyl rubber, 1-5 parts of chitosan, 1-5 parts of antioxidant, 1-3 parts of activator and 1-3 parts of vulcanization aid.

[0007] The present invention designs a rubber material with a layered structure, which includes a puncture rubber layer, an antibacterial rubber layer and a contact rubber layer from top to bottom. The puncture rubber layer has excellent puncture resistance and wear resistance, and can be used as a surface material of a medical rubber plug that contacts the outside world; the antibacterial rubber layer also serves as a supporting connection layer, which not only connects the surface material and the contact drug layer material, but also prevents external bacteria from contaminating the drug, thereby improving the quality and stability of the drug; the contact rubber layer material will not chemically react with the drug, has good drug compatibility, and can ensure the stable performance of the drug.

[0008] Among them, hydrogenated styrene-butadiene block copolymer has a unique block structure, and the middle ethylene-butylene block provides good flexibility and elasticity. After blending with EPDM rubber, it can make the rubber molecular chain more flexible. When subjected to puncture force, the molecular chain can slip and rearrange better, thereby absorbing and dispersing the energy of puncture. At the same time, a strong entanglement can be formed between the hydrogenated styrene-butadiene block copolymer molecular chain and the rubber molecular chain, making the overall structure of the blending system more stable and improving the puncture resistance of the rubber material. Titanium powder can significantly enhance the reinforcement of rubber, make rubber products more tough and wear-resistant, and greatly extend the service life of rubber materials. Adding phlogopite powder to rubber can significantly improve the mechanical strength, toughness and other properties of rubber materials. Working synergistically with titanium powder, it can achieve the purpose of improving the puncture resistance of rubber.

[0009] Aramid fiber has high tensile strength and modulus, excellent heat resistance and chemical corrosion resistance, which can enhance the mechanical properties of styrene-butadiene rubber, improve its tear resistance, wear resistance and puncture resistance, and enhance the ability of styrene-butadiene rubber to resist chemical erosion. In an environment where it is exposed to oils, acids and alkalis, the performance is better maintained. The addition of paeonol microcapsules to modify isoprene rubber can improve the antibacterial properties and thermal stability of layered rubber materials. Paeonol has antibacterial and anti-inflammatory effects. Paeonol is made into microcapsules and added to isoprene rubber. During the use of rubber, the microcapsules can slowly release paeonol by diffusion, penetration and other methods, and continue to exert its characteristics. There is an interaction between the microcapsule wall material and the rubber molecular chain, which can enhance the cohesion of isoprene rubber and improve the mechanical properties and thermal stability of rubber materials.

[0010] Since the contact rubber layer will directly contact the medicine, chitosan is added to the contact rubber layer in the present invention. Chitosan has certain barrier properties, which can improve the barrier properties of rubber to gases and liquids, enhance the sealing effect, and extend the service life of rubber products. Chitosan has good antibacterial properties. When used together with butyl rubber, it can give the rubber antibacterial function, effectively inhibit the growth and reproduction of bacteria, and improve the safety performance of medicines.

[0011] In summary, the layered rubber material of the present invention has good air tightness, puncture resistance and biocompatibility, and can effectively solve the problems of poor air tightness, low drug compatibility and poor puncture resistance of medical rubber stoppers in the prior art, providing a new idea for the preparation of medical rubber stopper materials.

[0012] Preferably, the preparation method of the paeonol microcapsule modified isoprene rubber comprises the following steps: S1, dissolving the wall material in deionized water to obtain a wall material solution; adding an alcohol solution of paeonol to the wall material solution, mixing evenly, to obtain a core-wall mixed solution; spray drying the core-wall mixed solution to obtain paeonol microcapsules; S2, kneading the isoprene rubber at 50° C.-60° C. to obtain kneaded rubber; adding the paeonol microcapsules to the kneaded rubber, and kneading to obtain a mixed rubber; S3, adding a vulcanizing agent, an accelerator and a reinforcing agent to the mixed rubber, mixing them evenly, and vulcanizing them at 100° C.-110° C. to obtain paeonol microcapsule modified isoprene rubber.

[0013] Further preferably, in S1, the wall material is gum arabic or gelatin.

[0014] Further preferably, in S1, the mass ratio of the wall material to the deionized water is 1:20-1:30.

[0015] Further preferably, in S1, the mass ratio of the alcohol solution of paeonol to the wall material solution is 1:10-1:20.

[0016] Further preferably, in S1, the mass percentage of paeonol in the alcohol solution of paeonol is 60%-70%.

[0017] Further preferably, in S1, the inlet air temperature of the spray drying is 90°C-100°C, the outlet air temperature is 80°C-90°C, the feed rate is 2mL / min-5mL / min; and the atomization pressure is 0.2MPa-0.4MPa.

[0018] Further preferably, in S2, the banburying time is 5 min-10 min.

[0019] Further preferably, in S2, the mass ratio of the paeonol microcapsules to the isoprene rubber is 3:100-8:100.

[0020] Further preferably, in S2, the mixing temperature is 70-80°C, and the mixing time is 10 min-15 min.

[0021] Further preferably, in S3, the amount of the vulcanizing agent added is 2%-3% of the mass of the mixed rubber.

[0022] Further preferably, in S3, the amount of the accelerator added is 1%-2% of the mass of the mixed rubber.

[0023] Further preferably, in S3, the amount of the reinforcing agent added is 5%-10% of the mass of the mixed rubber.

[0024] Further preferably, in S3, the vulcanizing agent is tetramethylthiuram disulfide.

[0025] More preferably, in S3, the accelerator is zinc diethyldithiocarbamate.

[0026] More preferably, in S3, the reinforcing agent is carbon black.

[0027] Further preferably, in S3, the vulcanization time is 4 min-6 min, and the vulcanization pressure is 8 MPa-10 MPa.

[0028] Preferably, the preparation method of the aramid fiber modified styrene butadiene rubber comprises the following steps: Step a, crushing the aramid fiber to obtain short aramid fiber; dispersing the short aramid fiber in a low boiling point organic solvent, filtering, drying, and performing thermal oxidation treatment at 180° C. to 220° C. for 30 min to 50 min to obtain pretreated aramid fiber; Step b, kneading the styrene-butadiene rubber at 65° C.-75° C. for 10 min-15 min to obtain kneaded styrene-butadiene rubber; adding the pretreated aramid fiber to the kneaded styrene-butadiene rubber, kneading at 60° C.-85° C. for 20 min-25 min to obtain a mixed rubber; Step c, adding a vulcanizing agent, an accelerator and a reinforcing agent to the mixed rubber, mixing them evenly, and vulcanizing them at 150° C.-170° C. to obtain aramid fiber modified styrene butadiene rubber.

[0029] Further preferably, in step a, the length of the short aramid fiber is 0.5 mm-1.5 mm.

[0030] Further preferably, in step a, the low boiling point solvent is acetone.

[0031] Further preferably, in step a, the mass volume ratio of the short aramid fiber to the low boiling point organic solvent is 1 g:3 mL-1 g:5 mL.

[0032] Further preferably, in step b, the mass ratio of the pretreated aramid fiber to the styrene-butadiene rubber is 1:10-1:20.

[0033] Further preferably, in step c, the vulcanization pressure is 10 MPa-20 MPa, and the vulcanization time is 4 min-8 min.

[0034] Further preferably, in step c, the amount of the vulcanizing agent added is 2%-3% of the mass of the mixed rubber.

[0035] Further preferably, in step c, the amount of the accelerator added is 1%-2% of the mass of the mixed rubber.

[0036] Further preferably, in step c, the amount of the reinforcing agent added is 5%-8% of the mass of the mixed rubber.

[0037] Further preferably, in step c, the vulcanizing agent is sodium hexamethylenediamine carbamate.

[0038] Further preferably, in step c, the accelerator is sodium dimethyldithiocarbamate.

[0039] Further preferably, in step c, the reinforcing agent is carbon black.

[0040] Preferably, the inorganic filler comprises titanium dioxide powder and phlogopite powder in a mass ratio of 1:2-1:5.

[0041] Preferably, the thickness of the puncture rubber layer is 450 μm-800 μm.

[0042] Preferably, the antibacterial rubber layer has a thickness of 250 μm-500 μm.

[0043] Preferably, the thickness of the contact rubber layer is 450 μm-600 μm.

[0044] Preferably, the antioxidant is antioxidant MB.

[0045] Preferably, the activator is stearic acid.

[0046] Preferably, the vulcanization aid is sulfur and ethylene thiourea in a mass ratio of 1:2-1:3.

[0047] The second aspect of the present invention provides a method for preparing the layered rubber material, comprising the following steps: Step 1, weigh the raw materials of each component of the puncture rubber layer according to the designed ratio, mix them evenly, vulcanize them at 160° C.-180° C., and extrude them to obtain the puncture rubber layer material; Step 2: weigh the various components of the antibacterial rubber layer according to the designed ratio, mix them evenly, vulcanize them at 160° C.-180° C., and extrude them to obtain the antibacterial rubber layer material; Step 3, weigh the raw materials of the contact rubber layer according to the designed ratio, mix them evenly, vulcanize them at 160° C.-180° C., and extrude them to obtain the contact rubber layer material; Step 4: stack the puncture rubber layer material, the antibacterial rubber layer material and the contact rubber layer material in sequence, and extrude and shape them to obtain a layered rubber material.

[0048] Preferably, in step 1, the vulcanization pressure is 10 MPa-15 MPa, and the vulcanization time is 4 min-8 min.

[0049] Preferably, in step 2, the vulcanization pressure is 10 MPa-15 MPa, and the vulcanization time is 5 min-10 min.

[0050] Preferably, in step three, the vulcanization pressure is 10 MPa-15 MPa, and the vulcanization time is 5 min-8 min.

[0051] The third aspect of the present invention provides an application of the layered rubber material or the layered rubber material prepared by the method for preparing the layered rubber material in the field of preparing medical rubber plug materials.

[0052] In summary, the present invention provides a layered rubber material including a puncture rubber layer, an antibacterial rubber layer and a contact rubber layer. By utilizing the interaction of the raw materials of each rubber layer, the layered rubber material has good puncture resistance and air tightness, good compatibility with drugs, and can effectively ensure the quality and stability of drugs. The technical solution of the present invention effectively solves the problems of poor air tightness, low drug compatibility, and poor puncture resistance of medical rubber stoppers in the prior art, and provides a new idea for the preparation of medical rubber materials. DETAILED DESCRIPTION

[0053] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0054] Example 1 This embodiment provides a layered rubber material and a preparation method thereof, which specifically includes the following contents: The layered rubber material includes a puncture rubber layer, an antibacterial rubber layer and a contact rubber layer from top to bottom; wherein the puncture rubber layer includes the following raw material components in parts by weight: 50 parts of EPDM rubber, 12 parts of hydrogenated styrene-butadiene block copolymer, 15 parts of inorganic filler, 3 parts of antioxidant MB, 2 parts of stearic acid, and 2 parts of sulfur and ethylene sulfur in a mass ratio of 1:2.5; wherein the inorganic filler includes titanium powder and phlogopite powder in a mass ratio of 1:4; The antibacterial rubber layer comprises the following raw material components in parts by weight: 35 parts of aramid fiber modified styrene-butadiene rubber, 18 parts of paeonol microcapsule modified isoprene rubber, 3 parts of antioxidant MB, 2 parts of stearic acid, and 2 parts of sulfur and ethylene sulfide in a mass ratio of 1:2.5; The contact rubber layer comprises the following raw material components in parts by mass: 50 parts of butyl rubber, 3 parts of chitosan, 3 parts of antioxidant MB, 2 parts of stearic acid, and 2 parts of sulfur and ethylene thiourea in a mass ratio of 1:2.5.

[0055] The method for preparing the layered rubber material comprises the following steps: Step 1: weigh the raw materials of each component of the puncture rubber layer according to the designed ratio, mix them evenly, vulcanize them at 170° C. and 10 MPa for 6 min, and extrude them to obtain a puncture rubber layer material with a thickness of 680 μm; Step 2: weigh the raw materials of each component of the antibacterial rubber layer according to the designed ratio, mix them evenly, vulcanize them at 165° C. and 12 MPa for 6 min, and extrude them to obtain an antibacterial rubber layer material with a thickness of 370 μm; Step 3: Weigh the raw materials of the contact rubber layer according to the designed ratio, mix them evenly, vulcanize them at 175° C. and 13 MPa for 8 min, and extrude them to obtain a contact rubber layer material with a thickness of 500 μm; Step 4: stack the puncture rubber layer material, the antibacterial rubber layer material and the contact rubber layer material in sequence, and extrude and shape them to obtain a layered rubber material.

[0056] The preparation method of the paeonol microcapsule modified isoprene rubber comprises the following steps: S1. Dissolve 30 g of gum arabic in 800 g of deionized water, heat and dissolve to obtain a wall material solution; add 50 g of paeonol alcohol solution to the wall material solution, mix well, and obtain a core-wall mixed solution; spray dry the core-wall mixed solution, set the spray drying inlet air temperature to 95° C., the outlet air temperature to 85° C., the feed rate to 3 mL / min; the atomization pressure to 0.3 MPa, and obtain paeonol microcapsules; S2, kneading 1 kg of isoprene rubber at 55° C. for 8 min to obtain kneaded rubber; adding 50 g of the paeonol microcapsules to the kneaded rubber, and kneading at 75° C. for 12 min to obtain a mixed rubber; S3, adding 50g of tetramethylthiuram disulfide, 30g of zinc diethyldithiocarbamate and 100g of carbon black to the mixed rubber, mixing evenly, and vulcanizing at 105°C and 9MPa for 5min to obtain paeonol microcapsule modified isoprene rubber.

[0057] The preparation method of the aramid fiber modified styrene butadiene rubber comprises the following steps: Step a, crushing 200g of aramid fiber to obtain short aramid fiber with a length of 1mm; dispersing the short aramid fiber in 800mL of acetone, filtering, drying, and performing thermal oxidation treatment at 200°C for 40min to obtain pretreated aramid fiber; Step b, kneading 3000 g of styrene butadiene rubber at 70° C. for 12 min to obtain kneaded styrene butadiene rubber; adding the pretreated aramid fiber to the kneaded styrene butadiene rubber, kneading at 75° C. for 20 min to obtain a mixed rubber; Step c, adding 80g of sodium hexamethylenediaminecarbamate, 45g of sodium dimethyldithiocarbamate and 200g of carbon black to the mixed rubber, mixing evenly, and vulcanizing at 165°C and 15MPa for 5min to obtain aramid fiber modified styrene-butadiene rubber.

[0058] Example 2 This embodiment provides a layered rubber material and a preparation method thereof, which specifically includes the following contents: The layered rubber material includes a puncture rubber layer, an antibacterial rubber layer and a contact rubber layer from top to bottom; wherein the puncture rubber layer includes the following raw material components in parts by weight: 45 parts of EPDM rubber, 10 parts of hydrogenated styrene-butadiene block copolymer, 12 parts of inorganic filler, 5 parts of antioxidant MB, 3 parts of stearic acid, and 2 parts of sulfur and ethylene sulfur in a mass ratio of 1:2.5; wherein the inorganic filler includes titanium powder and phlogopite powder in a mass ratio of 1:3; The antibacterial rubber layer comprises the following raw material components in parts by weight: 32 parts of aramid fiber modified styrene-butadiene rubber, 15 parts of paeonol microcapsule modified isoprene rubber, 5 parts of antioxidant MB, 3 parts of stearic acid, and 3 parts of sulfur and ethylene sulfur in a mass ratio of 1:2.5; The contact rubber layer comprises the following raw material components in parts by mass: 60 parts of butyl rubber, 5 parts of chitosan, 3 parts of antioxidant MB, 2 parts of stearic acid, and 2 parts of sulfur and ethylene thiourea in a mass ratio of 1:2.

[0059] The method for preparing the layered rubber material comprises the following steps: Step 1: weigh the raw materials of each component of the puncture rubber layer according to the designed ratio, mix them evenly, vulcanize them at 160° C. and 10 MPa for 8 min, and extrude them to obtain a puncture rubber layer material with a thickness of 560 μm; Step 2: weigh the various components of the antibacterial rubber layer according to the designed ratio, mix them evenly, vulcanize them at 165° C. and 12 MPa for 7 min, and extrude them to obtain an antibacterial rubber layer material with a thickness of 470 μm; Step 3: Weigh the raw materials of the contact rubber layer according to the designed ratio, mix them evenly, vulcanize them at 175° C. and 13 MPa for 6 min, and extrude them to obtain a contact rubber layer material with a thickness of 600 μm; Step 4: stack the puncture rubber layer material, the antibacterial rubber layer material and the contact rubber layer material in sequence, and extrude and shape them to obtain a layered rubber material.

[0060] The preparation method of the paeonol microcapsule modified isoprene rubber comprises the following steps: S1, dissolving 30g of gum arabic in 800g of deionized water, heating to dissolve, to obtain a wall material solution; adding 50g of paeonol alcohol solution to the wall material solution, mixing evenly, to obtain a core-wall mixed solution; spray drying the core-wall mixed solution, setting the spray drying inlet air temperature to 100°C, the outlet air temperature to 90°C, the feed rate to 3mL / min; the atomization pressure to 0.3MPa, to obtain paeonol microcapsules; S2, kneading 1 kg of isoprene rubber at 55° C. for 8 min to obtain kneaded rubber; adding 50 g of the paeonol microcapsules to the kneaded rubber, and kneading at 75° C. for 12 min to obtain a mixed rubber; S3, adding 50g of tetramethylthiuram disulfide, 30g of zinc diethyldithiocarbamate and 100g of carbon black to the mixed rubber, mixing evenly, and vulcanizing at 110°C and 9MPa for 5min to obtain paeonol microcapsule modified isoprene rubber.

[0061] The preparation method of the aramid fiber modified styrene butadiene rubber comprises the following steps: Step a, crushing 200g of aramid fiber to obtain short aramid fiber with a length of 1mm; dispersing the short aramid fiber in 800mL of acetone, filtering, drying, and performing thermal oxidation treatment at 200°C for 40min to obtain pretreated aramid fiber; Step b, kneading 3000 g of styrene butadiene rubber at 70° C. for 12 min to obtain kneaded styrene butadiene rubber; adding the pretreated aramid fiber to the kneaded styrene butadiene rubber, kneading at 75° C. for 20 min to obtain a mixed rubber; Step c, adding 80g of sodium hexamethylenediaminecarbamate, 45g of sodium dimethyldithiocarbamate and 200g of carbon black to the mixed rubber, mixing evenly, and vulcanizing at 165°C and 15MPa for 5min to obtain aramid fiber modified styrene-butadiene rubber.

[0062] Example 3 This embodiment provides a layered rubber material and a preparation method thereof, which specifically includes the following contents: The layered rubber material includes a puncture rubber layer, an antibacterial rubber layer and a contact rubber layer from top to bottom; wherein the puncture rubber layer includes the following raw material components in parts by weight: 40 parts of EPDM rubber, 15 parts of hydrogenated styrene-butadiene block copolymer, 20 parts of inorganic filler, 3 parts of antioxidant MB, 2 parts of stearic acid, and 3 parts of sulfur and ethylene sulfur in a mass ratio of 1:2; wherein the inorganic filler includes titanium powder and phlogopite powder in a mass ratio of 1:3.5; The antibacterial rubber layer comprises the following raw material components in parts by weight: 40 parts of aramid fiber modified styrene-butadiene rubber, 15 parts of paeonol microcapsule modified isoprene rubber, 3 parts of antioxidant MB, 3 parts of stearic acid, and 3 parts of sulfur and ethylene sulfur in a mass ratio of 1:2.5; The contact rubber layer comprises the following raw material components in parts by mass: 40 parts of butyl rubber, 5 parts of chitosan, 5 parts of antioxidant MB, 3 parts of stearic acid, and 2 parts of sulfur and ethylene thiourea in a mass ratio of 1:2.5.

[0063] The method for preparing the layered rubber material comprises the following steps: Step 1: weigh the raw materials of each component of the puncture rubber layer according to the designed ratio, mix them evenly, vulcanize them at 170° C. and 10 MPa for 8 minutes, and extrude them to obtain a puncture rubber layer material with a thickness of 540 μm; Step 2: weigh the various components of the antibacterial rubber layer according to the designed ratio, mix them evenly, vulcanize them at 165° C. and 12 MPa for 8 min, and extrude them to obtain an antibacterial rubber layer material with a thickness of 390 μm; Step 3: Weigh the raw materials of the contact rubber layer according to the designed ratio, mix them evenly, vulcanize them at 175° C. and 13 MPa for 6 min, and extrude them to obtain a contact rubber layer material with a thickness of 600 μm; Step 4: stack the puncture rubber layer material, the antibacterial rubber layer material and the contact rubber layer material in sequence, and extrude and shape them to obtain a layered rubber material.

[0064] The preparation method of the paeonol microcapsule modified isoprene rubber comprises the following steps: S1. Dissolve 30 g of gum arabic in 800 g of deionized water, heat and dissolve to obtain a wall material solution; add 50 g of paeonol alcohol solution to the wall material solution, mix well, and obtain a core-wall mixed solution; spray dry the core-wall mixed solution, set the spray drying inlet air temperature to 90° C., the outlet air temperature to 80° C., the feed rate to 3 mL / min; the atomization pressure to 0.3 MPa, and obtain paeonol microcapsules; S2, kneading 1 kg of isoprene rubber at 55° C. for 8 min to obtain kneaded rubber; adding 50 g of the paeonol microcapsules to the kneaded rubber, and kneading at 75° C. for 12 min to obtain a mixed rubber; S3, adding 50g of tetramethylthiuram disulfide, 30g of zinc diethyldithiocarbamate and 100g of carbon black to the mixed rubber, mixing evenly, and vulcanizing at 100°C and 10MPa for 5min to obtain paeonol microcapsule modified isoprene rubber.

[0065] The preparation method of the aramid fiber modified styrene butadiene rubber comprises the following steps: Step a, crushing 200g of aramid fiber to obtain short aramid fiber with a length of 1mm; dispersing the short aramid fiber in 800mL of acetone, filtering, drying, and performing thermal oxidation treatment at 200°C for 40min to obtain pretreated aramid fiber; Step b, kneading 3000 g of styrene butadiene rubber at 70° C. for 12 min to obtain kneaded styrene butadiene rubber; adding the pretreated aramid fiber to the kneaded styrene butadiene rubber, kneading at 75° C. for 20 min to obtain a mixed rubber; Step c, adding 80g of sodium hexamethylenediaminecarbamate, 45g of sodium dimethyldithiocarbamate and 200g of carbon black to the mixed rubber, mixing evenly, and vulcanizing at 165°C and 15MPa for 5min to obtain aramid fiber modified styrene-butadiene rubber.

[0066] Comparative Example 1 This comparative example provides a layered rubber material, which is different from Example 1 in that the hydrogenated styrene-butadiene block copolymer is replaced by an equal amount of styrene-butadiene block copolymer, and other components and processes remain unchanged, which will not be described again.

[0067] Comparative Example 2 This comparative example provides a layered rubber material, which is different from Example 1 in that the inorganic filler is replaced with an equal amount of attapulgite, and other components and processes remain unchanged, which will not be described again.

[0068] Comparative Example 3 This comparative example provides a layered rubber material, which differs from Example 1 in that the aramid fiber-modified styrene-butadiene rubber is replaced with an equal amount of styrene-butadiene rubber, and other components and processes remain unchanged, which will not be described in detail here.

[0069] Comparative Example 4 This comparative example provides a layered rubber material, which differs from Example 1 in that the paeonol microcapsule-modified isoprene rubber is replaced with an equal amount of chitosan quaternary ammonium salt-modified isoprene rubber, and other components and processes remain unchanged and will not be described in detail here.

[0070] The preparation method of the chitosan quaternary ammonium salt modified isoprene rubber comprises the following steps: S1, kneading 1 kg of isoprene rubber at 55° C. for 8 min to obtain kneaded rubber; adding 50 g of chitosan quaternary ammonium salt to the kneaded rubber, kneading at 75° C. for 12 min to obtain a mixed rubber; S2. Add 50 g of tetramethylthiuram disulfide, 30 g of zinc diethyldithiocarbamate and 100 g of carbon black to the mixed rubber, mix well, and vulcanize at 105° C. and 9 MPa for 2 h to obtain chitosan quaternary ammonium salt modified isoprene rubber.

[0071] In order to further reflect the technical effect of the present invention, the present invention performs the following tests on the layered rubber materials obtained in Examples 1-3 and Comparative Examples 1-4: According to the standard provisions of YBB00052005-2015, the rubber stoppers prepared in each embodiment and comparative example are respectively subjected to performance tests, and the ammonium ion and zinc ion tests in the chemical performance tests are performed. After the test solution is prepared according to the standard provisions of YBB00052005-2015, it is tested by a quantitative detection method, and the contents of ammonium ions and zinc ions in the test solution are calculated; the rubber material is subjected to an Escherichia coli antibacterial test, and the specific test process is as follows: the rubber material is cleaned with sterile physiological saline, dried, and placed in a sterile culture dish, and 1 mL of the cultured Escherichia coli solution (concentration of 10 7CFU / mL) was dripped around the rubber material, and the inoculated culture dish was placed in a constant temperature incubator at 37°C for culture. The growth of colonies on the surface of the rubber material was observed, the number of colonies was recorded, and the antibacterial effect of the rubber material was evaluated. The control group was a culture dish without rubber material. The calculation formula for the antibacterial rate was: antibacterial rate (%) = (number of colonies in the control group - number of colonies in the experimental group) / number of colonies in the control group × 100%. The test results are shown in Table 1.

[0072] Table 1 Performance test results of various layered rubber materials

[0073] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modification, equivalent substitution or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A layered rubber material, characterized in that: The layered rubber material includes a puncture rubber layer, an antibacterial rubber layer and a contact rubber layer from top to bottom; wherein the puncture rubber layer includes the following raw material components in parts by weight: 40-50 parts of ethylene propylene rubber, 10-15 parts of hydrogenated styrene-butadiene block copolymer, 10-20 parts of inorganic filler, 1-5 parts of antioxidant, 1-3 parts of activator and 1-3 parts of vulcanization aid; wherein the inorganic filler includes titanium powder and phlogopite powder; The antibacterial rubber layer comprises the following raw material components in parts by weight: 30-50 parts of aramid fiber modified styrene-butadiene rubber, 15-20 parts of paeonol microcapsule modified isoprene rubber, 1-5 parts of antioxidant, 1-3 parts of activator and 1-3 parts of vulcanization aid; The contact rubber layer comprises the following raw material components in parts by mass: 40-60 parts of butyl rubber, 1-5 parts of chitosan, 1-5 parts of antioxidant, 1-3 parts of activator and 1-3 parts of vulcanization aid.

2. The layered rubber material according to claim 1, characterized in that: The preparation method of the paeonol microcapsule modified isoprene rubber comprises the following steps: S1, dissolving the wall material in deionized water to obtain a wall material solution; adding an alcohol solution of paeonol to the wall material solution, mixing evenly, to obtain a core-wall mixed solution; spray drying the core-wall mixed solution to obtain paeonol microcapsules; S2, kneading the isoprene rubber at 50-60° C. to obtain kneaded rubber; adding the paeonol microcapsules to the kneaded rubber, and kneading to obtain a mixed rubber; S3, adding a vulcanizing agent, an accelerator and a reinforcing agent to the mixed rubber, mixing them evenly, and vulcanizing them at 100° C.-110° C. to obtain paeonol microcapsule modified isoprene rubber.

3. The layered rubber material according to claim 2, characterized in that: In S1, the wall material is gum arabic or gelatin; and / or In S1, the mass ratio of the wall material to the deionized water is 1:20-1:30; and / or In S1, the mass ratio of the alcohol solution of paeonol to the wall material solution is 1:10-1:20; and / or In S1, the mass percentage of paeonol in the alcohol solution of paeonol is 60%-70%.

4. The layered rubber material according to claim 2, characterized in that: In S1, the inlet air temperature of the spray drying is 90°C-100°C, the outlet air temperature is 80°C-90°C, the feed rate is 2mL / min-5mL / min; the atomization pressure is 0.2MPa-0.4MPa; and / or In S2, the banburying time is 5 min-10 min; and / or In S2, the mass ratio of the paeonol microcapsules to the isoprene rubber is 3:100-8:100; and / or In S2, the mixing temperature is 70°C-80°C, and the mixing time is 10min-15min.

5. The layered rubber material according to claim 2, characterized in that: In S3, the amount of the vulcanizing agent added is 2%-3% of the mass of the mixed rubber; and / or In S3, the amount of the accelerator added is 1%-2% of the mass of the mixed rubber; and / or In S3, the amount of the reinforcing agent added is 5%-10% of the mass of the mixed rubber; and / or In S3, the vulcanization time is 4 min-6 min, and the vulcanization pressure is 8 MPa-10 MPa.

6. The layered rubber material according to claim 1, characterized in that: The preparation method of the aramid fiber modified styrene butadiene rubber comprises the following steps: Step a, crushing the aramid fiber to obtain short aramid fiber; dispersing the short aramid fiber in a low boiling point organic solvent, filtering, drying, and performing thermal oxidation treatment at 180° C. to 220° C. for 30 min to 50 min to obtain pretreated aramid fiber; Step b, kneading the styrene-butadiene rubber at 65° C.-75° C. for 10 min-15 min to obtain kneaded styrene-butadiene rubber; adding the pretreated aramid fiber to the kneaded styrene-butadiene rubber, kneading at 60° C.-85° C. for 20 min-25 min to obtain a mixed rubber; Step c, adding a vulcanizing agent, an accelerator and a reinforcing agent to the mixed rubber, mixing them evenly, and vulcanizing them at 150° C.-170° C. to obtain aramid fiber modified styrene butadiene rubber.

7. The layered rubber material according to claim 6, characterized in that: In step a, the length of the short aramid fiber is 0.5 mm to 1.5 mm; and / or In step a, the low boiling point solvent is acetone; and / or In step a, the mass volume ratio of the short aramid fiber to the low boiling point organic solvent is 1g:3mL-1g:5mL; and / or In step b, the mass ratio of the pretreated aramid fiber to the styrene-butadiene rubber is 1:10-1:20; and / or In step c, the vulcanization pressure is 10MPa-20MPa, and the vulcanization time is 4min-8min.

8. The layered rubber material according to claim 1, characterized in that: The inorganic filler comprises titanium dioxide powder and phlogopite powder in a mass ratio of 1:2-1:5; and / or The thickness of the puncture rubber layer is 450 μm-800 μm; and / or The thickness of the antibacterial rubber layer is 250 μm-500 μm; and / or The thickness of the contact rubber layer is 450 μm-600 μm.

9. A method for preparing a layered rubber material according to any one of claims 1 to 8, characterized in that: The steps include: Step 1, weigh the raw materials of each component of the puncture rubber layer according to the designed ratio, mix them evenly, vulcanize them at 160° C.-180° C., and extrude them to obtain the puncture rubber layer material; Step 2: weigh the various components of the antibacterial rubber layer according to the designed ratio, mix them evenly, perform vulcanization at 160° C.-180° C., and extrude them to obtain the antibacterial rubber layer material; Step 3, weigh the raw materials of the contact rubber layer according to the designed ratio, mix them evenly, vulcanize them at 160° C.-180° C., and extrude them to obtain the contact rubber layer material; Step 4: stack the puncture rubber layer material, the antibacterial rubber layer material and the contact rubber layer material in sequence, and extrude and shape them to obtain a layered rubber material.

10. Use of the layered rubber material according to any one of claims 1 to 8 or the layered rubber material prepared by the method for preparing the layered rubber material according to claim 9 in the field of preparing medical rubber plug materials.

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