CN107722638B - Tear-resistant silicone rubber composite material and preparation method thereof - Google Patents

Tear-resistant silicone rubber composite material and preparation method thereof Download PDF

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CN107722638B
CN107722638B CN201711126997.5A CN201711126997A CN107722638B CN 107722638 B CN107722638 B CN 107722638B CN 201711126997 A CN201711126997 A CN 201711126997A CN 107722638 B CN107722638 B CN 107722638B
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carbon fiber
silicone rubber
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tear
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CN107722638A (en
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宋宏涛
安友
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Institute of Nuclear Physics and Chemistry China Academy of Engineering Physics
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/002—Methods
    • B29B7/007—Methods for continuous mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B29B7/72—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
    • B29C71/04—After-treatment of articles without altering their shape; Apparatus therefor by wave energy or particle radiation, e.g. for curing or vulcanising preformed articles
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C08L2312/06—Crosslinking by radiation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Abstract

The invention discloses a tear-resistant silicone rubber composite material and a preparation method thereof, wherein the silicone rubber composite material comprises the following components in parts by weight: 100 parts of silicon rubber, 10-40 parts of main reinforcing agent, 0.1-0.4 part of fluxing agent, 12-16 parts of structure control agent and 5-10 parts of reinforcing agent; the main reinforcing agent is a carbon fiber fabric with the pore space of 0.5-5.0 mm. The invention obviously improves the interface fusion of the carbon fiber fabric serving as the main reinforcing agent and the silicone rubber layer by surface pretreatment, and leads the carbon fiber to form connection with the cross-linked grid of the silicone rubber through the bridging action of the fluxing agent by means of radiation cross-linking, thereby realizing the strong combination of the carbon fiber and the silicone rubber layer.

Description

Tear-resistant silicone rubber composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of rubber materials and advanced composite materials thereof, and particularly relates to a tear-resistant silicone rubber composite material and a preparation method thereof.
Background
The silicone rubber has good high and low temperature resistance, oil resistance, air permeability, biological inertia and the like, but because the silicone rubber is a linear polymer and has poor mechanical strength, although the mechanical performance of the silicone rubber can be improved by a chemical crosslinking or radiation crosslinking mode, the intermolecular force of the silicone rubber is weak, so that the silicone rubber is difficult to prepare a self-supporting material with ideal mechanical strength, and the application of the silicone rubber is limited to a certain extent. Generally, white carbon black, chopped fiber and the like are added into a silicone rubber curing system for doping so as to effectively improve the mechanical properties (such as tearing strength) of the silicone rubber, so that the silicone rubber composite material with certain mechanical strength is prepared. However, the improvement range of the mechanical property of the silicone rubber material is limited, especially the tear resistance of the material is improved, and when the addition amount is excessive, the flexibility of the material is reduced sharply, and the difficulty and the safety risk of the mixing processing are increased greatly. Meanwhile, the particles or powder such as white carbon black, chopped fiber and the like are difficult to be uniformly dispersed in the silicon rubber matrix by means of the prior art, so that the mechanical strength deviation among batches of the prepared silicon rubber material is large and the process reproducibility is poor. How to maintain the performance advantages of the silicone rubber and avoid the performance disadvantages and processing difficulty of the silicone rubber is a difficult point of research. Therefore, the research on the novel silicon rubber composite material which is tear-resistant and has simple and environment-friendly preparation process has very positive significance.
Disclosure of Invention
An object of the present invention is to solve at least the above problems and/or disadvantages and to provide at least the advantages described hereinafter.
To achieve these objects and other advantages in accordance with the present invention, there is provided a tear-resistant silicone rubber composite having a formulation comprising, in parts by weight: 100 parts of silicon rubber, 10-40 parts of main reinforcing agent, 0.1-0.4 part of compatibilizer, 12-16 parts of structure control agent and 5-10 parts of reinforcing agent; the main reinforcing agent is carbon fiber, and is woven into a fabric with a pore space of 0.5-5.0 mm before use or similar carbon fiber fabric is directly used.
Preferably, the formula of the silicone rubber composite material comprises the following components in parts by weight: 100 parts of silicon rubber, 30 parts of main reinforcing agent, 0.3 part of compatibilizer, 14 parts of structure control agent and 6 parts of reinforcing agent.
Preferably, the silicone rubber is methyl vinyl silicone rubber or methyl vinyl phenyl silicone rubber;
the compatibilizer is any one of epoxy resins;
the structure control agent is hydroxyl silicone oil;
the reinforcing agent is any one of white carbon black, short carbon fiber or a mixture thereof, and the mixing ratio is 1-3: 1-3.
Preferably, the carbon fiber is one or a combination of several of polyacrylonitrile-based carbon fiber, pitch-based carbon fiber, viscose-based carbon fiber and phenolic-based carbon fiber.
Preferably, the epoxy resin is any one of a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a phenol type epoxy resin, a rosin type epoxy resin, and a terpene type epoxy resin.
The invention provides a preparation method of the tear-resistant silicone rubber composite material, which comprises the following steps:
step one, adding a compatibilizer into an acetone or ethyl acetate solution according to parts by weight to prepare a treatment solution with the mass concentration of 1.0-2.0%; immersing the carbon fiber braided fabric with the pore space of 0.5-5.0 mm into the treatment liquid, soaking for 24-36 hours, and drying under reduced pressure at 60-80 ℃ for 4-8 hours to obtain a pretreated main reinforcing agent;
step two, putting 50 parts by weight of silicon rubber into a double-roller open mill, plasticating for 5-8 minutes at room temperature, then sequentially adding 6-8 parts by weight of a structure control agent and 2.5-5 parts by weight of a reinforcing agent, and mixing for 15-20 minutes; placing the mixed materials in a die frame, stamping the materials into rubber material sheets with the thickness of 0.3-0.6 mm on a tablet press, then clamping the pretreated main reinforcing agent between the two pressed rubber material sheets, and placing the rubber material sheets in the die frame under the pressure of 100-120 kg-2Maintaining the pressure for 5-10 minutes at the temperature of 80-100 ℃ to prepare a sheet with the thickness of 0.5-1.0 mm;
step three, after the sheet is cooled to room temperature, plastic packaging is carried out, and the sheet is placed in a gamma-ray irradiation field, so that the total absorbed dose of the sheet is kept at 50-100 kGy for radiation crosslinking; and after the irradiation is finished, removing the plastic package, and cutting off the edge to obtain the tear-resistant silicone rubber composite material.
Preferably, the silicone rubber is methyl vinyl silicone rubber or methyl vinyl phenyl silicone rubber; the compatibilizer is any one of epoxy resins; the structure control agent is hydroxyl silicone oil; the reinforcing agent is any one of white carbon black, short carbon fiber or a mixture thereof, and the mixing ratio is 1-3: 1-3.
Preferably, the carbon fiber is one or a combination of more of polyacrylonitrile-based carbon fiber, pitch-based carbon fiber, viscose-based carbon fiber and phenolic-based carbon fiber; the epoxy resin is any one of bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenolic aldehyde type epoxy resin, rosin-based epoxy resin and terpene-based epoxy resin.
Preferably, the carbon fibers are modified carbon fibers; the preparation method of the modified carbon fiber comprises the following steps: adding 20-30 parts by weight of carbon fiber and 50-80 parts by weight of 2-5 mol/L nitric acid solution into a sealed container with a stirrer, placing the sealed container in an electron accelerator with 1.5MeV and 30mA for irradiation stirring treatment for 60min, filtering, and adding the filtered carbon fiber into toluene for ultrasonic treatment for 30 min; then drying to obtain oxidized carbon fibers; adding 20-25 parts of oxidized carbon fiber and 5-10 parts of acidified carrageenan into a supercritical reaction device, adding 15-20 parts of butyl acrylate, 10-15 parts of allylthiourea, 0.05-0.25 part of ammonium persulfate and 80-100 parts of water, sealing the device, introducing carbon dioxide to 30-40 MPa, stirring and reacting for 2-3 hours at 70-80 ℃, removing the pressure of the carbon dioxide, adding 10-15 parts of dodecyl dimethyl benzyl ammonium chloride, injecting the carbon dioxide again until the pressure is 40-60 MPa, stirring for 0.5-1 hour, relieving the pressure, filtering, washing with ethanol, and drying to obtain the modified carbon fiber.
Preferably, 10-15 parts of 2-5 mol/L sulfuric acid is added into the nitric acid solution; the preparation method of the acidified carrageenan comprises the following steps: soaking 10-30 parts of carrageenan in 0.5-1 mol/L hydrochloric acid solution for 12-24 hours, then filtering and drying to obtain acidified carrageenan; the dosage of irradiation is 100-400 kGy, and the stirring speed is 100-200 r/min.
The invention at least comprises the following beneficial effects:
(1) the invention obviously improves the interface fusion of the carbon fiber fabric serving as the main reinforcing agent and the silicon rubber layer by surface pretreatment of the carbon fiber fabric serving as the main reinforcing agent and by means of radiation crossThe carbon fibers are connected with the cross-linked grids of the silicon rubber through the bridging effect of the compatibilizer, so that the carbon fibers and the cross-linked grids of the silicon rubber are strongly combined, meanwhile, a certain amount of white carbon black, short fibers or a mixture of the white carbon black and the short fibers are added as a reinforcing agent in the rubber mixing process to properly improve the mechanical strength of the silicon rubber layer, so that interface slippage caused by external force in the body phase is avoided, the mechanical strength of the silicon rubber composite material is greatly improved, and the tear strength can reach 20.63KN.m-1The tensile strength can reach 11.89 MPa.
(2) According to the invention, the carbon fiber fabric is introduced between the two silicon rubber sheets, so that the tear resistance of the silicon rubber composite material is effectively and greatly improved, and meanwhile, the pressure maintaining in the forming stage is beneficial to not only the interface fusion of the carbon fiber fabric and the silicon rubber, but also the elimination of air bubbles in the fabric tows and at the interface, so that the silicon rubber composite material with excellent flexibility and stable mechanical properties among batches is very beneficial to be obtained.
(3) According to the invention, only a small amount of reinforcing agent is added in the mixing processing stage, and the main reinforcing agent is introduced after the mixing processing is completed, so that the excellent characteristics of the carbon fiber fabric are maintained to the maximum extent, and the difficulty and safety risk of the mixing processing are greatly reduced.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Description of the drawings:
fig. 1 is a scanning electron microscope image of a cross section of the tear-resistant silicone rubber composite material prepared in example 1 of the present invention.
The specific implementation mode is as follows:
the present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1:
the tear-resistant silicone rubber composite material comprises the following components in parts by weight: 100 parts of silicon rubber, 20 parts of main reinforcing agent, 0.2 part of compatibilizer, 12 parts of structure control agent and 5 parts of reinforcing agent; the main reinforcing agent is polyacrylonitrile-based carbon fiber; the silicone rubber is methyl vinyl silicone rubber; the compatibilizer is bisphenol A epoxy resin; the structure control agent is hydroxyl silicone oil; the reinforcing agent is white carbon black.
The tear-resistant silicone rubber composite material comprises the following steps:
step one, adding a compatibilizer into acetone according to parts by weight to prepare a treatment solution with the mass concentration of 1.0%; soaking 20 parts of carbon fiber fabric with the pore space of 1 mm in 30 parts of treatment liquid for 24 hours, and drying at 60 ℃ under reduced pressure for 8 hours to obtain a pretreated main reinforcing agent; weighing the carbon fibers before and after treatment, wherein the weight part difference is 0.2 parts, namely the amount of the compatibilizer is 0.2 parts;
step two, putting 50 parts by weight of silicon rubber into a double-roll open mill, plasticating for 5 minutes at room temperature, then sequentially adding 6 parts of structure control agent and 2.5 parts of reinforcing agent, and mixing for 15 minutes; placing the mixed material in a die frame, stamping the mixed material into a sizing material sheet with the thickness of 0.3 mm on a tablet press, clamping the pretreated main reinforcing agent between the two pressed sizing material sheets, and placing the two pressed sizing material sheets in the die frame under the pressure of 100kg.cm-2Maintaining the temperature at 80 ℃ for 10 minutes to prepare a sheet with the thickness of 0.5 mm;
step three, after the sheet is cooled to room temperature, plastic packaging is carried out, and the sheet is placed in a gamma-ray irradiation field, so that the total absorbed dose of the sheet is kept at 50kGy for radiation crosslinking; and after the irradiation is finished, removing the plastic package, and cutting off the edge to obtain the tear-resistant silicone rubber composite material.
And (3) carrying out performance test on the prepared tear-resistant silicone rubber foam material: tear Strength, 20.04KN.m-1(ii) a Tensile strength, 11.33 MPa.
Example 2:
the tear-resistant silicone rubber composite material comprises the following components in parts by weight: 100 parts of silicon rubber, 10 parts of main reinforcing agent, 0.3 part of compatibilizer, 16 parts of structure control agent and 7 parts of reinforcing agent; the main reinforcing agent is polyacrylonitrile-based carbon fiber; the silicone rubber is methyl vinyl silicone rubber; the compatibilizer is bisphenol A epoxy resin; the structure control agent is hydroxyl silicone oil; the reinforcing agent is white carbon black.
The tear-resistant silicone rubber composite material comprises the following steps:
step one, adding a compatibilizer into ethyl acetate according to parts by weight to prepare a treatment solution with the mass concentration of 2.0%; soaking 10 parts of carbon fiber fabric with a pore space of 1 mm in 10 parts of treatment liquid for 24 hours, and drying at 60 ℃ under reduced pressure for 8 hours to obtain a pretreated main reinforcing agent; weighing the carbon fibers before and after treatment, wherein the weight part difference is 0.3 part, namely the amount of the compatibilizer is 0.3 part;
step two, putting 50 parts by weight of silicon rubber into a double-roll open mill, plasticating for 5 minutes at room temperature, then sequentially adding 6 parts by weight of structure control agent and 3.5 parts by weight of reinforcing agent, and mixing for 20 minutes; placing the mixed material in a die frame, stamping the mixed material into a sizing material sheet with the thickness of 0.6 mm on a tablet press, clamping the pretreated main reinforcing agent between the two pressed sizing material sheets, and placing the two pressed sizing material sheets in the die frame under the pressure of 120kg.cm-2Maintaining the temperature at 100 ℃ for 8 minutes to prepare a sheet with the thickness of 1 mm;
step three, after the sheet is cooled to room temperature, plastic packaging is carried out, and the sheet is placed in a gamma ray irradiation field, so that the total absorbed dose of the sheet is kept at 100kGy for radiation crosslinking; and after the irradiation is finished, removing the plastic package, and cutting off the edge to obtain the tear-resistant silicone rubber composite material.
And (3) carrying out performance test on the prepared tear-resistant silicone rubber foam material: tear Strength, 12.05KN.m-1(ii) a Tensile strength, 8.63 MPa.
Example 3:
the tear-resistant silicone rubber composite material comprises the following components in parts by weight: 100 parts of silicon rubber, 30 parts of main reinforcing agent, 0.3 part of compatibilizer, 16 parts of structure control agent and 5 parts of reinforcing agent; the main reinforcing agent is polyacrylonitrile-based carbon fiber; the silicone rubber is methyl vinyl silicone rubber; the compatibilizer is bisphenol A epoxy resin; the structure control agent is hydroxyl silicone oil; the reinforcing agent is chopped carbon fiber.
The tear-resistant silicone rubber composite material comprises the following steps:
step one, adding a compatibilizer into ethyl acetate according to parts by weight to prepare a treatment solution with the mass concentration of 1.0%; soaking 30 parts of carbon fiber fabric with a pore space of 1 mm in 40 parts of treatment liquid for 30 hours, and drying at 70 ℃ under reduced pressure for 6 hours to obtain a pretreated main reinforcing agent; weighing the carbon fibers before and after treatment, wherein the weight part difference is 0.3 part, namely the amount of the compatibilizer is 0.3 part;
step two, putting 50 parts by weight of silicon rubber into a double-roll open mill, plastifying for 8 minutes at room temperature, then sequentially adding 8 parts of structure control agent and 2.5 parts of reinforcing agent, and mixing for 15 minutes; placing the mixed material in a die frame, stamping the mixed material into a sizing material sheet with the thickness of 0.3 mm on a tablet press, clamping the pretreated main reinforcing agent between the two pressed sizing material sheets, and placing the two pressed sizing material sheets in the die frame under the pressure of 120kg.cm-2Maintaining the temperature at 100 ℃ for 10 minutes to prepare a sheet with the thickness of 0.5 mm;
step three, after the sheet is cooled to room temperature, plastic packaging is carried out, and the sheet is placed in a gamma-ray irradiation field, so that the total absorbed dose of the sheet is kept at 80kGy for radiation crosslinking; and after the irradiation is finished, removing the plastic package, and cutting off the edge to obtain the tear-resistant silicone rubber composite material.
And (3) carrying out performance test on the prepared tear-resistant silicone rubber foam material: tear Strength, 17.63KN.m-1(ii) a Tensile strength, 8.97 MPa.
Example 4:
the tear-resistant silicone rubber composite material comprises the following components in parts by weight: 100 parts of silicon rubber, 40 parts of main reinforcing agent, 0.3 part of compatibilizer, 16 parts of structure control agent and 10 parts of reinforcing agent; the main reinforcing agent is polyacrylonitrile-based carbon fiber; the silicone rubber is methyl vinyl silicone rubber; the compatibilizer is bisphenol A epoxy resin; the structure control agent is hydroxyl silicone oil; the reinforcing agent is chopped carbon fiber and white carbon black.
The tear-resistant silicone rubber composite material comprises the following steps:
step one, adding a compatibilizer into acetone according to parts by weight to prepare a treatment solution with the mass concentration of 1.0%; soaking 40 parts of carbon fiber braided fabric with the pore space of 1 mm in 40 parts of treatment liquid for 36 hours, and drying at 60 ℃ under reduced pressure for 8 hours to obtain a pretreated main reinforcing agent; weighing the carbon fibers before and after treatment, wherein the weight part difference is 0.3 part, namely the amount of the compatibilizer is 0.3 part;
secondly, putting 50 parts by weight of silicon rubber into a double-roll open mill, plasticating for 5 minutes at room temperature, then sequentially adding 8 parts of structure control agent, 2.5 parts of chopped carbon fiber and 2.5 parts of white carbon black, and mixing for 20 minutes; placing the mixed material in a die frame, stamping the mixed material into a sizing material sheet with the thickness of 0.3 mm on a tablet press, clamping the pretreated main reinforcing agent between the two pressed sizing material sheets, and placing the two pressed sizing material sheets in the die frame under the pressure of 120kg.cm-2Maintaining the temperature at 100 ℃ for 8 minutes to prepare a sheet with the thickness of 0.5 mm;
step three, after the sheet is cooled to room temperature, plastic packaging is carried out, and the sheet is placed in a gamma-ray irradiation field, so that the total absorbed dose of the sheet is kept at 60kGy for radiation crosslinking; and after the irradiation is finished, removing the plastic package, and cutting off the edge to obtain the tear-resistant silicone rubber composite material.
And (3) carrying out performance test on the prepared tear-resistant silicone rubber foam material: tear Strength, 20.63KN.m-1(ii) a Tensile strength, 11.89 MPa.
Example 5:
the tear-resistant silicone rubber composite material comprises the following components in parts by weight: 100 parts of silicon rubber, 40 parts of main reinforcing agent, 0.3 part of compatibilizer, 16 parts of structure control agent and 9 parts of reinforcing agent; the main reinforcing agent is polyacrylonitrile-based carbon fiber; the silicone rubber is methyl vinyl silicone rubber; the compatibilizer is bisphenol A epoxy resin; the structure control agent is hydroxyl silicone oil; the reinforcing agent is chopped carbon fiber and white carbon black.
The tear-resistant silicone rubber composite material comprises the following steps:
step one, adding a compatibilizer into ethyl acetate according to parts by weight to prepare a treatment solution with the mass concentration of 1.0%; soaking 40 parts of carbon fiber fabric with the pore space of 1 mm in 40 parts of treatment liquid for 36 hours, and drying at 60 ℃ under reduced pressure for 8 hours to obtain a pretreated main reinforcing agent; weighing the carbon fibers before and after treatment, wherein the weight part difference is 0.3 part, namely the amount of the compatibilizer is 0.3 part;
secondly, putting 50 parts by weight of silicon rubber into a double-roll open mill, plastifying for 6 minutes at room temperature, then sequentially adding 8 parts of structure control agent, 1.5 parts of chopped carbon fiber and 3 parts of white carbon black, and mixing for 18 minutes; placing the mixed material in a die frame, stamping the mixed material into a sizing material sheet with the thickness of 0.6 mm on a tablet press, clamping the pretreated main reinforcing agent between the two pressed sizing material sheets, and placing the two pressed sizing material sheets in the die frame under the pressure of 120kg.cm-2Maintaining the temperature at 100 ℃ for 10 minutes to prepare a sheet with the thickness of 1 mm;
step three, after the sheet is cooled to room temperature, plastic packaging is carried out, and the sheet is placed in a gamma-ray irradiation field, so that the total absorbed dose of the sheet is kept at 50kGy for radiation crosslinking; and after the irradiation is finished, removing the plastic package, and cutting off the edge to obtain the tear-resistant silicone rubber composite material.
And (3) carrying out performance test on the prepared tear-resistant silicone rubber foam material: tear Strength, 17.82KN.m-1(ii) a Tensile strength, 9.14 MPa.
Example 6:
the tear-resistant silicone rubber composite material comprises the following components in parts by weight: 100 parts of silicon rubber, 30 parts of main reinforcing agent, 0.3 part of compatibilizer, 16 parts of structure control agent and 6 parts of reinforcing agent; the main reinforcing agent is asphalt-based carbon fiber; the silicone rubber is methyl vinyl silicone rubber; the compatibilizer is bisphenol A epoxy resin; the structure control agent is hydroxyl silicone oil; the reinforcing agent is chopped carbon fiber and white carbon black.
The tear-resistant silicone rubber composite material comprises the following steps:
step one, adding a compatibilizer into ethyl acetate according to parts by weight to prepare a treatment solution with the mass concentration of 1.0%; soaking 30 parts of carbon fiber fabric with a pore space of 1 mm in 40 parts of treatment liquid for 36 hours, and drying at 60 ℃ under reduced pressure for 8 hours to obtain a pretreated main reinforcing agent; weighing the carbon fibers before and after treatment, wherein the weight part difference is 0.3 part, namely the amount of the compatibilizer is 0.3 part;
secondly, putting 50 parts by weight of silicon rubber into a double-roll open mill, plastifying for 6 minutes at room temperature, then sequentially adding 8 parts of structure control agent, 1.5 parts of chopped carbon fiber and 1.5 parts of white carbon black, and mixing for 18 minutes; placing the mixed material in a die frame, stamping the mixed material into a sizing material sheet with the thickness of 0.6 mm on a tablet press, clamping the pretreated main reinforcing agent between the two pressed sizing material sheets, and placing the two pressed sizing material sheets in the die frame under the pressure of 120kg.cm-2Maintaining the temperature at 100 ℃ for 10 minutes to prepare a sheet with the thickness of 1 mm;
step three, after the sheet is cooled to room temperature, plastic packaging is carried out, and the sheet is placed in a gamma-ray irradiation field, so that the total absorbed dose of the sheet is kept at 80kGy for radiation crosslinking; and after the irradiation is finished, removing the plastic package, and cutting off the edge to obtain the tear-resistant silicone rubber composite material.
And (3) carrying out performance test on the prepared tear-resistant silicone rubber foam material: tear Strength, 20.40KN.m-1(ii) a Tensile strength, 10.32 MPa.
Example 7:
the carbon fiber is modified polypropylene carbon fiber; the preparation method of the modified polypropylene carbon fiber comprises the following steps: adding 30 parts by weight of carbon fiber and 80 parts by weight of 5mol/L nitric acid solution into a sealed container with a stirrer, then placing the sealed container into an electron accelerator with 1.5MeV and 30mA for irradiation stirring treatment for 60min, filtering, and adding the filtered carbon fiber into toluene for ultrasonic treatment for 30 min; then drying to obtain oxidized carbon fibers; adding 20 parts of oxidized carbon fiber and 10 parts of acidified carrageenan into a supercritical reaction device, simultaneously adding 20 parts of butyl acrylate, 10 parts of allyl thiourea, 0.15 part of ammonium persulfate and 80 parts of water, sealing the device, introducing carbon dioxide to 30MPa, stirring and reacting at 70 ℃ for 3 hours, then removing the pressure of carbon dioxide, adding 15 parts of dodecyl dimethyl benzyl ammonium chloride, then injecting the carbon dioxide again until the pressure is 60MPa, stirring for 1 hour, relieving the pressure, filtering, washing with ethanol, and drying to obtain the modified carbon fiber. Adding 15 parts of 5mol/L sulfuric acid into the nitric acid solution; the preparation method of the acidified carrageenan comprises the following steps: soaking 20 parts of carrageenan in 0.5mol/L hydrochloric acid solution for 24 hours, then filtering and drying to obtain acidified carrageenan; the dosage of the irradiation is 100kGy, and the stirring speed is 200 r/min. By the modification method, the modified carbon fiber fabric layer is arranged between the two layers of rubber sheets, so that the tensile strength and the tear resistance of the silicone rubber foam material are greatly improved.
The rest of the process parameters and procedures are exactly the same as in example 1; and (3) carrying out performance test on the prepared tear-resistant silicone rubber foam material: tear Strength, 21.25KN.m-1(ii) a Tensile strength, 12.58 MPa.
Example 8:
the carbon fiber is modified polypropylene carbon fiber; the preparation method of the modified polypropylene carbon fiber comprises the following steps: adding 25 parts by weight of carbon fiber and 60 parts by weight of 4mol/L nitric acid solution into a sealed container with stirring, then placing the sealed container into an electron accelerator with 1.5MeV and 30mA for irradiation stirring treatment for 60min, filtering, and adding the filtered carbon fiber into toluene for ultrasonic treatment for 30 min; then drying to obtain oxidized carbon fibers; adding 25 parts of oxidized carbon fiber and 8 parts of acidified carrageenan into a supercritical reaction device, adding 15 parts of butyl acrylate, 15 parts of allyl thiourea, 0.1 part of ammonium persulfate and 100 parts of water, sealing the device, introducing carbon dioxide to 35MPa, stirring and reacting at 70 ℃ for 3 hours, removing the pressure of carbon dioxide, adding 12 parts of dodecyl dimethyl benzyl ammonium chloride, injecting the carbon dioxide again until the pressure is 50MPa, stirring for 1 hour, relieving the pressure, filtering, washing with ethanol, and drying to obtain modified carbon fiber; adding 15 parts of 5mol/L sulfuric acid into the nitric acid solution; the preparation method of the acidified carrageenan comprises the following steps: soaking 10 parts of carrageenan in 0.5mol/L hydrochloric acid solution for 24 hours, then filtering and drying to obtain acidified carrageenan; the dosage of the irradiation is 200kGy, and the stirring speed is 200 r/min.
The rest of the process parameters and procedures are exactly the same as in example 1; and (3) carrying out performance test on the prepared tear-resistant silicone rubber foam material: tear Strength, 21.15KN.m-1(ii) a Tensile strength, 12.87 MPa.
Example 9:
the carbon fiber is modified asphalt-based carbon fiber; the preparation method of the modified asphalt-based carbon fiber comprises the following steps: adding 30 parts by weight of carbon fiber and 60 parts by weight of 5mol/L nitric acid solution into a sealed container with stirring, then placing the sealed container into an electron accelerator with 1.5MeV and 30mA for irradiation stirring treatment for 60min, filtering, and adding the filtered carbon fiber into toluene for ultrasonic treatment for 30 min; then drying to obtain oxidized carbon fibers; adding 25 parts of oxidized carbon fiber and 8 parts of acidified carrageenan into a supercritical reaction device, simultaneously adding 20 parts of butyl acrylate, 15 parts of allyl thiourea, 0.1 part of ammonium persulfate and 100 parts of water, sealing the device, introducing carbon dioxide to 35MPa, stirring and reacting at 70 ℃ for 3 hours, then removing the pressure of carbon dioxide, adding 12 parts of dodecyl dimethyl benzyl ammonium chloride, then injecting the carbon dioxide again until the pressure is 50MPa, stirring for 1 hour, relieving the pressure, filtering, washing with ethanol, and drying to obtain modified carbon fiber; adding 15 parts of 5mol/L sulfuric acid into the nitric acid solution; the preparation method of the acidified carrageenan comprises the following steps: soaking 10 parts of carrageenan in 0.5mol/L hydrochloric acid solution for 24 hours, then filtering and drying to obtain acidified carrageenan; the dosage of the irradiation is 400kGy, and the stirring speed is 200 r/min.
The rest of the process parameters and procedures are exactly the same as in example 6; and (3) carrying out performance test on the prepared tear-resistant silicone rubber foam material: tear Strength, 22.55KN.m-1(ii) a Tensile strength, 12.27 MPa.
Example 10:
the carbon fiber is modified asphalt-based carbon fiber; the preparation method of the modified asphalt-based carbon fiber comprises the following steps: adding 28 parts by weight of carbon fiber and 60 parts by weight of 5mol/L nitric acid solution into a sealed container with stirring, then placing the sealed container into an electron accelerator with 1.5MeV and 30mA for irradiation stirring treatment for 60min, filtering, and adding the filtered carbon fiber into toluene for ultrasonic treatment for 30 min; then drying to obtain oxidized carbon fibers; adding 20 parts of oxidized carbon fiber and 5 parts of acidified carrageenan into a supercritical reaction device, simultaneously adding 18 parts of butyl acrylate, 12 parts of allyl thiourea, 0.15 part of ammonium persulfate and 100 parts of water, sealing the device, introducing carbon dioxide to 35MPa, stirring and reacting at 70 ℃ for 3 hours, then removing the pressure of carbon dioxide, adding 12 parts of dodecyl dimethyl benzyl ammonium chloride, then injecting the carbon dioxide again until the pressure is 50MPa, stirring for 1 hour, relieving the pressure, filtering, washing with ethanol, and drying to obtain modified carbon fiber; adding 15 parts of 5mol/L sulfuric acid into the nitric acid solution; the preparation method of the acidified carrageenan comprises the following steps: soaking 10 parts of carrageenan in 1mol/L hydrochloric acid solution for 24 hours, then filtering and drying to obtain acidified carrageenan; the dosage of the irradiation is 200kGy, and the stirring speed is 200 r/min.
The rest of the process parameters and procedures are exactly the same as in example 6; and (3) carrying out performance test on the prepared tear-resistant silicone rubber foam material: tear Strength, 22.35KN.m-1(ii) a Tensile strength, 12.38 MPa.
Example 11:
replacing the carbon fiber in example 2 with the modified polyacrylonitrile-based carbon fiber prepared in example 7; the remaining process parameters and procedures were exactly the same as in example 2.
And (3) carrying out performance test on the prepared tear-resistant silicone rubber foam material: tear Strength, 14.62KN.m-1(ii) a Tensile strength, 10.58 MPa.
Example 12:
replacing the carbon fiber in example 3 with the modified polyacrylonitrile-based carbon fiber prepared in example 7; the remaining process parameters and procedures were exactly the same as in example 3.
And (3) carrying out performance test on the prepared tear-resistant silicone rubber foam material: tear Strength, 18.72KN.m-1Tensile strength, 10.58 MPa.
Example 13:
replacing the carbon fiber in example 4 with the modified polyacrylonitrile-based carbon fiber prepared in example 7; the remaining process parameters and procedures were exactly the same as in example 4.
And (3) carrying out performance test on the prepared tear-resistant silicone rubber foam material: tear Strength, 22.65KN.m-1Tensile strength, 13.89 MPa.
Example 14:
replacing the carbon fiber in example 5 with the modified polyacrylonitrile-based carbon fiber prepared in example 7; the remaining process parameters and procedures were exactly the same as in example 5.
And (3) carrying out performance test on the prepared tear-resistant silicone rubber foam material: tear Strength, 20.38KN.m-1Tensile strength, 12.38 MPa.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.

Claims (4)

1. The tear-resistant silicone rubber composite material is characterized by comprising the following components in parts by weight: 100 parts of silicon rubber, 10-40 parts of main reinforcing agent, 0.1-0.4 part of compatibilizer, 12-16 parts of structure control agent and 5-10 parts of reinforcing agent; the main reinforcing agent is carbon fiber, and is woven into a fabric with a pore space of 0.5-5.0 mm before use or similar carbon fiber fabric is directly used;
the preparation method of the tear-resistant silicone rubber composite material comprises the following steps:
step one, adding a compatibilizer into an acetone or ethyl acetate solution according to parts by weight to prepare a treatment solution with the mass concentration of 1.0-2.0%; immersing the carbon fiber braided fabric with the pore space of 0.5-5.0 mm into the treatment liquid, soaking for 24-36 hours, and drying under reduced pressure at 60-80 ℃ for 4-8 hours to obtain a pretreated main reinforcing agent;
step two, putting 50 parts by weight of silicon rubber into a double-roller open mill, plasticating for 5-8 minutes at room temperature, then sequentially adding 6-8 parts by weight of a structure control agent and 2.5-5 parts by weight of a reinforcing agent, and mixing for 15-20 minutes; placing the mixed materials in a die frame, stamping the materials into rubber material sheets with the thickness of 0.3-0.6 mm on a tablet press, then clamping the pretreated main reinforcing agent between the two pressed rubber material sheets, and placing the rubber material sheets in the die frame under the pressure of 100-120 kg-2Maintaining the pressure for 5-10 minutes at the temperature of 80-100 ℃ to prepare a sheet with the thickness of 0.5-1.0 mm;
step three, after the sheet is cooled to room temperature, plastic packaging is carried out, and the sheet is placed in a gamma-ray irradiation field, so that the total absorbed dose of the sheet is kept at 50-100 kGy for radiation crosslinking; after the irradiation is finished, removing the plastic package, and cutting off the edge to obtain the tear-resistant silicone rubber composite material;
the silicone rubber is methyl vinyl silicone rubber or methyl vinyl phenyl silicone rubber;
the compatibilizer is any one of epoxy resins;
the structure control agent is hydroxyl silicone oil;
the reinforcing agent is any one of white carbon black, short carbon fiber or a mixture thereof, and the mixing ratio is 1-3: 1-3;
the carbon fiber is one or a combination of more of polyacrylonitrile-based carbon fiber, asphalt-based carbon fiber, viscose-based carbon fiber and phenolic-based carbon fiber;
the carbon fiber is modified carbon fiber; the preparation method of the modified carbon fiber comprises the following steps: adding 20-30 parts by weight of carbon fiber and 50-80 parts by weight of 2-5 mol/L nitric acid solution into a sealed container with a stirrer, placing the sealed container in an electron accelerator with 1.5MeV and 30mA for irradiation stirring treatment for 60min, filtering, and adding the filtered carbon fiber into toluene for ultrasonic treatment for 30 min; then drying to obtain oxidized carbon fibers; adding 20-25 parts of oxidized carbon fiber and 5-10 parts of acidified carrageenan into a supercritical reaction device, adding 15-20 parts of butyl acrylate, 10-15 parts of allylthiourea, 0.05-0.25 part of ammonium persulfate and 80-100 parts of water, sealing the device, introducing carbon dioxide to 30-40 MPa, stirring and reacting for 2-3 hours at 70-80 ℃, removing the pressure of the carbon dioxide, adding 10-15 parts of dodecyl dimethyl benzyl ammonium chloride, injecting the carbon dioxide again until the pressure is 40-60 MPa, stirring for 0.5-1 hour, relieving the pressure, filtering, washing with ethanol, and drying to obtain the modified carbon fiber.
2. The tear-resistant silicone rubber composite material of claim 1, wherein the silicone rubber composite material is formulated from, by weight: 100 parts of silicon rubber, 30 parts of main reinforcing agent, 0.3 part of compatibilizer, 14 parts of structure control agent and 6 parts of reinforcing agent.
3. The tear-resistant silicone rubber composite material according to claim 1, wherein the epoxy resin is any one of a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a phenol type epoxy resin, a rosin type epoxy resin, and a terpene type epoxy resin.
4. The tear-resistant silicone rubber composite material according to claim 1, wherein 10 to 15 parts of 2 to 5mol/L sulfuric acid is added to the nitric acid solution; the preparation method of the acidified carrageenan comprises the following steps: soaking 10-30 parts of carrageenan in 0.5-1 mol/L hydrochloric acid solution for 12-24 hours, then filtering and drying to obtain acidified carrageenan; the dosage of irradiation is 100-400 kGy, and the stirring speed is 100-200 r/min.
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