CN113402829A - Anti-aging rubber material and preparation method thereof - Google Patents
Anti-aging rubber material and preparation method thereof Download PDFInfo
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- CN113402829A CN113402829A CN202110558726.7A CN202110558726A CN113402829A CN 113402829 A CN113402829 A CN 113402829A CN 202110558726 A CN202110558726 A CN 202110558726A CN 113402829 A CN113402829 A CN 113402829A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/76—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from other polycondensation products
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
- D06M14/26—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin
- D06M14/30—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
- D06M15/256—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing fluorine
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- C—CHEMISTRY; METALLURGY
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
The invention discloses an anti-aging rubber material and a preparation method thereof. The preparation method comprises the steps of synthesizing polyaniline nanofibers with polyvinylidene fluoride by a solvent evaporation method to prepare a polyvinylidene fluoride polyaniline composite, grafting hexafluoropropylene onto the polyvinylidene fluoride polyaniline composite by an electron beam co-radiation grafting technology to obtain a grafted polyvinylidene fluoride polyaniline composite, modifying the grafted polyvinylidene fluoride polyaniline composite by dimethylformamide and benzoyl peroxide, and mixing with fluororubber to prepare the anti-aging rubber material. The anti-aging rubber material prepared by the invention has the effects of flexibility, wear resistance, refrigeration in summer and air freshening.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to an anti-aging rubber material and a preparation method thereof.
Background
Along with the improvement of social production efficiency, rubber materials are more and more widely applied in various industries, and the service life of the rubber materials is shortened due to the severe natural environment, so the aging resistance of the rubber materials is gradually valued by people, but along with the development of the times, the multielement high-speed utilization of the rubber materials is realized.
Disclosure of Invention
The invention aims to provide an anti-aging rubber material and a preparation method thereof, and aims to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme: an anti-aging rubber material mainly comprises the following components in parts by weight:
60-70 parts of fluororubber, 35-55 parts of grafted polyvinylidene fluoride polyaniline compound, 15-20 parts of dimethylformamide, 15-20 parts of benzoyl peroxide and 10-15 parts of curing agent.
Further, the grafted polyvinylidene fluoride polyaniline compound comprises a polyvinylidene fluoride polyaniline compound and hexafluoropropylene.
Further, the polyvinylidene fluoride polyaniline compound is prepared by reacting polyaniline nano-fibers with polyvinylidene fluoride through a solvent evaporation method.
Furthermore, the polyaniline nano-fiber is prepared by mixing aniline and sodium dodecyl benzene sulfonate aqueous solution, dissolving the mixture by hydrochloric acid and ammonium persulfate, reacting the mixture in an ice-water bath, and performing suction filtration, washing and drying.
Further, the curing agent is one of vinyl triamine and m-phenylenediamine.
Further, the preparation method of the anti-aging rubber material is characterized by mainly comprising the following preparation steps:
(1) preparing polyaniline nano-fibers: mixing aniline and sodium dodecyl benzene sulfonate aqueous solution, dissolving the mixture by hydrochloric acid and ammonium persulfate, reacting the mixture in an ice-water bath, and performing suction filtration, washing and drying on the reaction product to obtain the aqueous solution;
(2) preparing a polyvinylidene fluoride polyaniline compound: synthesizing polyaniline nano-fiber with polyvinylidene fluoride by a solvent evaporation method;
(3) preparing a grafted polyvinylidene fluoride polyaniline compound: mixing and dissolving polyvinylidene fluoride polyaniline compound and hexafluoropropylene in an acetone solution, and cooling after melting to obtain the polyvinylidene fluoride polyaniline/hexafluoropropylene composite material;
(4) preparing an anti-aging rubber material: melting the grafted polyvinylidene fluoride polyaniline compound and the fluororubber in a torque rheometer, adding dimethylformamide for continuous mixing, adding benzoyl peroxide for mixing until torque is balanced, stopping rotating, discharging, and curing by using m-phenylenediamine as a curing agent to obtain the final product.
Further, the preparation method of the polyaniline nanofiber in the step (1) comprises the following steps: mixing sodium dodecyl benzene sulfonate and deionized water according to the mass ratio of 1: 10-1: 20, stirring to completely dissolve the sodium dodecyl benzene sulfonate, adding aniline with the mass being 3-5 times that of the sodium dodecyl benzene sulfonate, performing ultrasonic treatment for 25-35 min to obtain a uniformly dispersed solution A, placing the solution A in an ice water bath, and adding hydrochloric acid to adjust the pH value of the solution to 5; and simultaneously mixing and stirring ammonium persulfate and deionized water according to the mass ratio of 1: 5-1: 10 to dissolve the ammonium persulfate to obtain a solution B, dropwise adding the solution B with the volume of 0.6-0.8 time of that of the solution A into the solution A while stirring, controlling the dropwise adding time to be 20-30 min, standing and reacting for 10-12 h in an ice-water bath after stopping stirring to obtain a dark green solution, carrying out suction filtration on the obtained dark green solution, respectively washing for 2-3 times by using an acetone solution with the mass fraction of 10% and an ethanol solution with the mass fraction of 10%, and carrying out vacuum drying for 20-24 h at the temperature of 60-70 ℃ to obtain the polyaniline nanofiber.
Further, the preparation method of the polyvinylidene fluoride polyaniline compound in the step (2) comprises the following steps: mixing polyaniline nanofibers with a dimethylformamide solution with the mass fraction of 25% according to the mass ratio of 1: 10-1: 30, performing ultrasonic dispersion for 1-1.5 hours to obtain a dispersion solution, adding polyvinylidene fluoride with the mass of 2-3 times that of the polyaniline nanofibers into the dispersion solution, mixing and stirring for 10-12 hours to form a stable dark green dispersion solution, standing for 2.5-3 hours for defoaming, pouring the dispersion solution on a clean and horizontal glass plate, leveling, putting the dispersion solution in an oven with the temperature of 40-50 ℃ for 5-6 hours, and taking out the dispersion solution after the dimethylformamide component is completely evaporated to obtain the polyvinylidene fluoride polyaniline composite.
Further, the preparation method of the grafted polyvinylidene fluoride polyaniline compound in the step (3) comprises the following steps: mixing a polyvinylidene fluoride polyaniline compound and hexafluoropropylene according to a mass ratio of 10: 1-20: 1, adding the mixture into an acetone solvent with a mass fraction of 10% and a mass of 0.2-0.4 times of that of the polyvinylidene fluoride polyaniline compound, stirring for 2-3 hours at 50-60 ℃, inverting the solution in an aluminum foil after stirring, volatilizing, and melting at 180-200 ℃ to obtain the grafted polyvinylidene fluoride polyaniline compound.
Further, the preparation method of the anti-aging rubber material in the step (4) comprises the following steps: adjusting the temperature of a torque rheometer to 170-180 ℃, rotating at 80-90 r/min, weighing 35-55 parts by weight of a grafted polyvinylidene fluoride polyaniline composite, adding the grafted polyvinylidene fluoride polyaniline composite into the torque rheometer after the grafted polyvinylidene fluoride polyaniline composite is completely melted, blending with fluororubber 1-2 times the mass of the grafted polyvinylidene fluoride polyaniline composite for 5-6 min, adding dimethylformamide 0.3-0.5 times the mass of the grafted polyvinylidene fluoride polyaniline composite after a torque curve is basically balanced, blending for 3-4 min again, adding benzoyl peroxide 0.2-0.5 times the mass of the grafted polyvinylidene fluoride polyaniline composite after the torque curve is balanced, blending for 6-7 min, stopping rotating after the torque is balanced again, discharging, and curing with m-phenylenediamine 0.3-0.4 times the mass of the grafted polyvinylidene fluoride composite at normal temperature to obtain the anti-aging rubber material.
Compared with the prior art, the invention has the following beneficial effects:
the invention firstly synthesizes polyaniline nanometer fiber by emulsion polymerization, and synthesizes the polyaniline nanometer fiber with polyvinylidene fluoride by solvent evaporation method to prepare polyvinylidene fluoride polyaniline compound, the polyaniline nanometer fiber presents disordered net structure and is dispersed in polyvinylidene fluoride network structure, and is compactly cross-linked with the polyvinylidene fluoride network structure, and is mutually twisted together, the compatibility is good, the polyaniline nanometer fiber can link the spherulites between the polyvinylidene fluoride and the polyaniline nanometer fiber along with the proceeding of reaction, at the same time, the network structure is formed in the amorphous region of the polyvinylidene fluoride, the heat conduction structure of the polyvinylidene fluoride is strengthened, thereby the heat conductivity of the rubber is enhanced, the invention prepares the aging resistant rubber material which is applied on the subway seat, the refrigeration effect is achieved when people sit on in summer, and the polyaniline nanometer fiber can also play a connecting role in the aspect of grafting polyvinylidene fluoride polyaniline compound and fluororubber, thereby increasing the tensile strength of the rubber.
And then, hexafluoropropylene is grafted to the polyvinylidene fluoride polyaniline compound by an electron beam co-radiation grafting technology, so that the arrangement of polyvinylidene fluoride chain segments can be effectively hindered, the crystallinity of polyvinylidene fluoride molecules is reduced, polyaniline nanofibers are effectively prevented from being extruded out of a crystallization area by polyvinylidene fluoride as impurities, a connection dense net structure is formed, the wear resistance of the polyaniline compound is enhanced, and the interaction between the polyaniline nanofibers and polyvinylidene fluoride can be effectively improved by carbon-fluorine bonds existing in the grafted polyvinylidene fluoride polyaniline compound, so that the material has better flexibility.
Finally, the grafted polyvinylidene fluoride polyaniline compound is modified by dimethylformamide and benzoyl peroxide and then mixed with fluororubber, the modified compound can be in a microspherical shape on the surface of the fluororubber due to the block copolymer formed by block grafting carboxyl groups and blending and compatible polyvinylidene fluoride components, so that the surface of the fluororubber can be uneven, holes are uniformly distributed in a convex structure to achieve the effect of absorbing moisture, the defect that the original grafted polyvinylidene fluoride polyaniline compound is fragile and difficult to stretch is overcome, the tensile strength is increased, the flexibility of the compound is improved, the sitting comfort of people is met, the grafted polyvinylidene fluoride molecular chains in the modified compound can be mutually wound and interpenetrated with the molecular chains at the interface of the fluororubber, better compatibility is achieved, and under the joint action of the polyaniline nanofibers and the block grafting hydrophilic carboxyl groups, on the premise of enhancing the wear resistance of the rubber, the rubber can absorb hydrogen sulfide skatole and ammonia gas in the flatus, so that the air is fresh, and the phenomenon that people die due to flatus odor in a subway is solved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to more clearly illustrate the method provided by the present invention, the following examples are provided, and the method for testing each index of the aging resistant rubber material prepared in the following examples is as follows:
the aging-resistant rubber materials prepared by the components of example 1, example 2 and comparative example 1 are subjected to an ammonia gas purification test; controlling the air inlet flow to be 120L/h at the room temperature of 20-25 ℃ under the standard atmospheric pressure, measuring the ammonia gas purification efficiency of the three components in the same time, wherein the higher the ammonia gas purification efficiency is, the fresher the air is, and the specific data are shown in the table I.
The flexibility performance test is carried out on the ageing-resistant rubber materials prepared by the components of example 1, example 2 and comparative example 1; the clamping distance of a chuck of a control measuring machine is 100mm, the testing speed is 400mm/min, the pre-tension is 0.07cN/dtex, the higher the tensile strength is, the better the flexibility is, and the specific data are shown in the second table.
Example 1
An anti-aging rubber material mainly comprises the following components in parts by weight: 70 parts of fluororubber, 55 parts of a grafted polyvinylidene fluoride polyaniline compound, 20 parts of dimethylformamide, 20 parts of benzoyl peroxide and 15 parts of a curing agent.
The preparation method of the anti-aging rubber material mainly comprises the following preparation steps:
(1) preparing polyaniline nano-fibers: mixing aniline and sodium dodecyl benzene sulfonate aqueous solution, dissolving the mixture by hydrochloric acid and ammonium persulfate, reacting the mixture in an ice-water bath, and performing suction filtration, washing and drying on the reaction product to obtain the aqueous solution;
(2) preparing a polyvinylidene fluoride polyaniline compound: the polyaniline nano-fiber is prepared by the reaction of a solvent evaporation method and polyvinylidene fluoride;
(3) preparing a grafted polyvinylidene fluoride polyaniline compound: mixing and dissolving polyvinylidene fluoride polyaniline compound and hexafluoropropylene in an acetone solution, and cooling after melting to obtain the polyvinylidene fluoride polyaniline/hexafluoropropylene composite material;
(4) preparing an anti-aging rubber material: melting the grafted polyvinylidene fluoride polyaniline compound and the fluororubber in a torque rheometer, adding dimethylformamide for continuous mixing, adding benzoyl peroxide for mixing until torque is balanced, stopping rotating, discharging, and curing by using m-phenylenediamine as a curing agent to obtain the final product.
Further, the preparation method of the polyaniline nanofiber in the step (1) comprises the following steps: mixing sodium dodecyl benzene sulfonate and deionized water according to a mass ratio of 1:20, stirring to completely dissolve the sodium dodecyl benzene sulfonate, adding aniline with the mass 5 times that of the sodium dodecyl benzene sulfonate, performing ultrasonic treatment for 35min to obtain a uniformly dispersed solution A, placing the solution A in an ice-water bath, and adding hydrochloric acid to adjust the pH value of the solution to 5; and simultaneously mixing and stirring ammonium persulfate and deionized water according to the mass ratio of 1:10 to dissolve the ammonium persulfate to obtain a solution B, dropwise adding the solution B with the volume of 0.8 time of that of the solution A into the solution A while stirring, controlling the dropwise adding time to be 30min, standing and reacting for 12h in an ice water bath after stopping stirring to obtain a dark green solution, carrying out suction filtration on the obtained dark green solution, respectively washing for 3 times by using an acetone solution with the mass fraction of 10% and an ethanol solution with the mass fraction of 10%, and then carrying out vacuum drying for 24h at 70 ℃ to obtain the polyaniline nanofiber.
Further, the preparation method of the polyvinylidene fluoride polyaniline compound in the step (2) comprises the following steps: mixing polyaniline nanofibers with a dimethylformamide solution with the mass fraction of 25% according to the mass ratio of 1:30, performing ultrasonic dispersion for 1.5 hours to obtain dispersion liquid, then adding polyvinylidene fluoride with the mass of 3 times that of the polyaniline nanofibers into the dispersion liquid, mixing and stirring for 12 hours to form stable dark green dispersion liquid, standing for 3 hours for defoaming, pouring the stable dark green dispersion liquid on a clean and horizontal glass plate, leveling and putting the glass plate into a 50 ℃ oven for 6 hours, and taking out the dispersion liquid after the dimethylformamide component is completely evaporated to obtain the polyvinylidene fluoride polyaniline composite.
Further, the preparation method of the grafted polyvinylidene fluoride polyaniline compound in the step (3) comprises the following steps: mixing a polyvinylidene fluoride polyaniline compound and hexafluoropropylene according to a mass ratio of 20:1, adding the mixture into an acetone solvent with the mass fraction of 10% and the mass of 0.4 time that of the polyvinylidene fluoride polyaniline compound, stirring the mixture for 3 hours at 60 ℃, inverting the stirred solution in an aluminum foil, volatilizing the solution, and melting the solution at 200 ℃ to obtain the grafted polyvinylidene fluoride polyaniline compound.
Further, the preparation method of the anti-aging rubber material in the step (4) comprises the following steps: adjusting the temperature of a torque rheometer to 180 ℃, adjusting the rotating speed to 90r/min, weighing 55 parts of grafted polyvinylidene fluoride polyaniline compound by weight, adding the grafted polyvinylidene fluoride polyaniline compound into the torque rheometer, adding fluororubber 2 times the mass of the grafted polyvinylidene fluoride polyaniline compound after the grafted polyvinylidene fluoride polyaniline compound is completely melted, blending for 6min, adding dimethylformamide 0.5 times the mass of the grafted polyvinylidene fluoride polyaniline compound after a torque curve is basically balanced, blending for 4min again, adding benzoyl peroxide 0.5 times the mass of the grafted polyvinylidene fluoride polyaniline compound after the torque is balanced, blending for 7min, stopping rotating after the torque is balanced again, discharging, and curing m-phenylenediamine 0.4 times the mass of the grafted polyvinylidene fluoride polyaniline compound at normal temperature to obtain the anti-aging rubber material.
Example 2
An anti-aging rubber material mainly comprises the following components in parts by weight: 60 parts of fluororubber, 35 parts of a grafted polyvinylidene fluoride polyaniline compound, 15 parts of dimethylformamide, 15 parts of benzoyl peroxide and 10 parts of a curing agent.
The preparation method of the anti-aging rubber material mainly comprises the following preparation steps:
(1) preparing polyaniline nano-fibers: mixing aniline and sodium dodecyl benzene sulfonate aqueous solution, dissolving the mixture by hydrochloric acid and ammonium persulfate, reacting the mixture in an ice-water bath, and performing suction filtration, washing and drying on the reaction product to obtain the aqueous solution;
(2) preparing a polyvinylidene fluoride polyaniline compound: the polyaniline nano-fiber is prepared by the reaction of a solvent evaporation method and polyvinylidene fluoride;
(3) preparing a grafted polyvinylidene fluoride polyaniline compound: mixing and dissolving polyvinylidene fluoride polyaniline compound and hexafluoropropylene in an acetone solution, and cooling after melting to obtain the polyvinylidene fluoride polyaniline/hexafluoropropylene composite material;
(4) preparing an anti-aging rubber material: melting the grafted polyvinylidene fluoride polyaniline compound and the fluororubber in a torque rheometer, adding dimethylformamide for continuous mixing, adding benzoyl peroxide for mixing until torque is balanced, stopping rotating, discharging, and curing by using m-phenylenediamine as a curing agent to obtain the final product.
Further, the preparation method of the polyaniline nanofiber in the step (1) comprises the following steps: mixing sodium dodecyl benzene sulfonate and deionized water according to a mass ratio of 1:10, stirring to completely dissolve the sodium dodecyl benzene sulfonate, adding aniline with the mass of 3 times that of the sodium dodecyl benzene sulfonate, performing ultrasonic treatment for 25min to obtain a uniformly dispersed solution A, placing the solution A in an ice-water bath, and adding hydrochloric acid to adjust the pH value of the solution to 5; and simultaneously mixing and stirring ammonium persulfate and deionized water according to the mass ratio of 1:5 to dissolve the ammonium persulfate to obtain a solution B, dropwise adding the solution B with the volume of 0.6 time of that of the solution A into the solution A while stirring, controlling the dropwise adding time to be 20min, standing and reacting for 10h in an ice water bath after stopping stirring to obtain a dark green solution, carrying out suction filtration on the obtained dark green solution, respectively washing for 2 times by using an acetone solution with the mass fraction of 10% and an ethanol solution with the mass fraction of 10%, and then carrying out vacuum drying for 20h at the temperature of 60 ℃ to obtain the polyaniline nanofiber.
Further, the preparation method of the polyvinylidene fluoride polyaniline compound in the step (2) comprises the following steps: mixing polyaniline nanofibers with a dimethylformamide solution with the mass fraction of 25% according to the mass ratio of 1:10, performing ultrasonic dispersion for 1h to obtain a dispersion solution, adding polyvinylidene fluoride with the mass of 2 times that of the polyaniline nanofibers into the dispersion solution, mixing and stirring for 10h to form a stable dark green dispersion solution, standing for 2.5h for defoaming, pouring the dispersion solution on a clean and horizontal glass plate, leveling and putting the dispersion solution into a 40 ℃ oven for 5h, and taking out the dispersion solution after the dimethylformamide component is completely evaporated to obtain the polyvinylidene fluoride polyaniline composite.
Further, the preparation method of the grafted polyvinylidene fluoride polyaniline compound in the step (3) comprises the following steps: mixing a polyvinylidene fluoride polyaniline compound and hexafluoropropylene according to a mass ratio of 10:1, adding the mixture into an acetone solvent with a mass fraction of 10% and 0.2 times of that of the polyvinylidene fluoride polyaniline compound, stirring for 2 hours at 50 ℃, inverting the solution in an aluminum foil after stirring, volatilizing, and melting at 180 ℃ to obtain the grafted polyvinylidene fluoride polyaniline compound.
Further, the preparation method of the anti-aging rubber material in the step (4) comprises the following steps: adjusting the temperature of a torque rheometer to 170 ℃, adjusting the rotating speed to 80r/min, weighing 35 parts of grafted polyvinylidene fluoride polyaniline compound by weight, adding the grafted polyvinylidene fluoride polyaniline compound into the torque rheometer, adding fluororubber with the mass 1 time that of the grafted polyvinylidene fluoride polyaniline compound after the grafted polyvinylidene fluoride polyaniline compound is completely melted, blending for 5min, adding dimethylformamide with the mass 0.3 time that of the grafted polyvinylidene fluoride polyaniline compound after a torque curve is basically balanced, blending for 3min again, adding benzoyl peroxide with the mass 0.2 time that of the grafted polyvinylidene fluoride polyaniline compound after the torque is balanced, stopping rotating and discharging after the torque is balanced again, and curing by using m-phenylenediamine with the mass 0.3 time that of the grafted polyvinylidene fluoride polyaniline compound at normal temperature to obtain the anti-aging rubber material.
Comparative example 1:
the formulation of comparative example 1 was the same as example 1. The preparation method of the aging-resistant rubber material is different from that of the example 1 only in that the preparation process of the step (2) is not carried out, and the rest of the preparation steps are the same as those of the example 1.
Comparative example 2:
the formulation of comparative example 1 was the same as example 1. The preparation method of the aging-resistant rubber material is different from that of the example 1 only in that the preparation process of the step (3) is not carried out, and the rest of the preparation steps are the same as those of the example 1.
Test example 1:
the aging-resistant rubber materials prepared by the components of example 1, example 2 and comparative example 1 are subjected to an ammonia gas purification test; controlling the air inlet flow to be 120L/h at the room temperature of 20-25 ℃ under the standard atmospheric pressure, measuring the ammonia gas purification efficiency of the three components in the same time, wherein the higher the ammonia gas purification efficiency is, the fresher the air is, and the data are as follows:
watch 1
| Purification efficiency of Ammonia (%) | |
| Example 1 | 96.3％ |
| Example 2 | 94.7％ |
| Comparative example 1 | 44.4％ |
The above table shows that the ammonia gas purification efficiency of the embodiment 1 and the embodiment 2 is relatively high, and the effect of the comparative example 2 is not obvious, which indicates that the connection effect between the polyvinylidene fluoride and the polyaniline nanofiber enables the rubber material to absorb hydrogen sulfide skatole and ammonia gas in the fart after a network structure is formed in the amorphous region of the polyvinylidene fluoride and the block is under the combined action of hydrophilic carboxyl groups, so that the air is fresh, and the social death phenomenon that people release fart in subways is solved.
Test example 2:
the flexibility performance test is carried out on the ageing-resistant rubber materials prepared by the components of example 1, example 2 and comparative example 1; the control measuring machine had a chuck grip of 100mm, a measuring speed of 400mm/min, a pre-tension of 0.07cN/dtex, and the higher the tensile strength, the better the flexibility, the data are as follows:
watch two
| Tensile Strength (MPa) | |
| Example 1 | 44 |
| Example 2 | 40 |
| Comparative example 2 | 14 |
As can be seen from the above table, the tensile strength of examples 1 and 2 is relatively high, and the tensile strength of comparative example 2 is lower than that of examples 1 and 2, which illustrates that hexafluoropropylene is grafted to a polyvinylidene fluoride polyaniline composite, so that the arrangement of polyvinylidene fluoride chain segments can be effectively hindered, the crystallinity of polyvinylidene fluoride molecules is reduced, polyaniline nanofibers are effectively prevented from being extruded out of a crystallization region by polyvinylidene fluoride as impurities, a connection dense mesh structure is formed, the wear resistance of the polyaniline nanofibers is enhanced, and the interaction between polyaniline nanofibers and polyvinylidene fluoride can be effectively improved by carbon-fluorine bonds existing in the grafted polyvinylidene fluoride polyaniline composite, so that the material shows better flexibility.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (10)
1. An anti-aging rubber material is characterized by mainly comprising, by weight, 60-70 parts of fluororubber, 35-55 parts of grafted polyvinylidene fluoride polyaniline compound, 15-20 parts of dimethylformamide, 15-20 parts of benzoyl peroxide and 10-15 parts of curing agent.
2. The aging-resistant rubber material of claim 1, wherein the grafted polyvinylidene fluoride polyaniline composite comprises polyvinylidene fluoride polyaniline composite, hexafluoropropylene.
3. The aging-resistant rubber material as claimed in claim 2, wherein the polyvinylidene fluoride polyaniline composite is prepared by reacting polyaniline nanofibers with polyvinylidene fluoride through a solvent evaporation method.
4. The aging-resistant rubber material of claim 3, wherein the polyaniline nanofibers are prepared by mixing aniline and a sodium dodecyl benzene sulfonate aqueous solution, dissolving the mixture with hydrochloric acid and ammonium persulfate, reacting the mixture in an ice-water bath, filtering, washing and drying.
5. The aging-resistant rubber material as claimed in claim 4, wherein the curing agent is one of vinyl triamine and m-phenylenediamine.
6. The preparation method of the anti-aging rubber material is characterized by mainly comprising the following preparation steps:
(1) preparing polyaniline nano-fibers: mixing aniline and sodium dodecyl benzene sulfonate aqueous solution, dissolving the mixture by hydrochloric acid and ammonium persulfate, reacting the mixture in an ice-water bath, and performing suction filtration, washing and drying on the reaction product to obtain the aqueous solution;
(2) preparing a polyvinylidene fluoride polyaniline compound: the polyaniline nano-fiber is prepared by the reaction of a solvent evaporation method and polyvinylidene fluoride;
(3) preparing a grafted polyvinylidene fluoride polyaniline compound: mixing and dissolving polyvinylidene fluoride polyaniline compound and hexafluoropropylene in an acetone solution, and cooling after melting to obtain the polyvinylidene fluoride polyaniline/hexafluoropropylene composite material;
(4) preparing an anti-aging rubber material: melting the grafted polyvinylidene fluoride polyaniline compound and the fluororubber in a torque rheometer, adding dimethylformamide for continuous mixing, adding benzoyl peroxide for mixing until torque is balanced, stopping rotating, discharging, and curing by using m-phenylenediamine as a curing agent to obtain the final product.
7. The method for preparing the aging-resistant rubber material according to claim 6, wherein the method for preparing the polyaniline nanofibers in step (1) comprises the following steps: mixing sodium dodecyl benzene sulfonate and deionized water according to the mass ratio of 1: 10-1: 20, stirring to completely dissolve the sodium dodecyl benzene sulfonate, adding aniline with the mass being 3-5 times that of the sodium dodecyl benzene sulfonate, performing ultrasonic treatment for 25-35 min to obtain a uniformly dispersed solution A, placing the solution A in an ice water bath, and adding hydrochloric acid to adjust the pH value of the solution to 5; and simultaneously mixing and stirring ammonium persulfate and deionized water according to the mass ratio of 1: 5-1: 10 to dissolve the ammonium persulfate to obtain a solution B, dropwise adding the solution B with the volume of 0.6-0.8 time of that of the solution A into the solution A while stirring, controlling the dropwise adding time to be 20-30 min, standing and reacting for 10-12 h in an ice-water bath after stopping stirring to obtain a dark green solution, carrying out suction filtration on the obtained dark green solution, respectively washing for 2-3 times by using an acetone solution with the mass fraction of 10% and an ethanol solution with the mass fraction of 10%, and carrying out vacuum drying for 20-24 h at the temperature of 60-70 ℃ to obtain the polyaniline nanofiber.
8. The method for preparing an aging-resistant rubber material according to claim 6, wherein the method for preparing the polyvinylidene fluoride polyaniline composite in the step (2) comprises the following steps: mixing polyaniline nanofibers with a dimethylformamide solution with the mass fraction of 25% according to the mass ratio of 1: 10-1: 30, performing ultrasonic dispersion for 1-1.5 hours to obtain a dispersion solution, adding polyvinylidene fluoride with the mass of 2-3 times that of the polyaniline nanofibers into the dispersion solution, mixing and stirring for 10-12 hours to form a stable dark green dispersion solution, standing for 2.5-3 hours for defoaming, pouring the dispersion solution on a clean and horizontal glass plate, leveling, putting the dispersion solution in an oven with the temperature of 40-50 ℃ for 5-6 hours, and taking out the dispersion solution after the dimethylformamide component is completely evaporated to obtain the polyvinylidene fluoride polyaniline composite.
9. The method for preparing an aging-resistant rubber material according to claim 6, wherein the method for preparing the grafted polyvinylidene fluoride polyaniline composite in the step (3) comprises the following steps: mixing a polyvinylidene fluoride polyaniline compound and hexafluoropropylene according to a mass ratio of 10: 1-20: 1, adding the mixture into an acetone solvent with a mass fraction of 10% and a mass of 0.2-0.4 times of that of the polyvinylidene fluoride polyaniline compound, magnetically stirring for 2-3 hours at 50-60 ℃, inverting the solution in an aluminum foil after stirring, volatilizing, and melting at 180-200 ℃ to obtain the grafted polyvinylidene fluoride polyaniline compound.
10. The method for preparing an aging-resistant rubber material according to claim 6, wherein the method for preparing an aging-resistant rubber material in the step (4) comprises the following steps: adjusting the temperature of a torque rheometer to 170-180 ℃, rotating at 80-90 r/min, weighing 35-55 parts by weight of a grafted polyvinylidene fluoride polyaniline composite, adding the grafted polyvinylidene fluoride polyaniline composite into the torque rheometer after the grafted polyvinylidene fluoride polyaniline composite is completely melted, blending with fluororubber 1-2 times the mass of the grafted polyvinylidene fluoride polyaniline composite for 5-6 min, adding dimethylformamide 0.3-0.5 times the mass of the grafted polyvinylidene fluoride polyaniline composite after a torque curve is basically balanced, blending for 3-4 min again, adding benzoyl peroxide 0.2-0.5 times the mass of the grafted polyvinylidene fluoride polyaniline composite after the torque curve is balanced, blending for 6-7 min, stopping rotating after the torque is balanced again, discharging, and curing with m-phenylenediamine 0.3-0.4 times the mass of the grafted polyvinylidene fluoride composite at normal temperature to obtain the anti-aging rubber material.
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| CN105849180A (en) * | 2013-12-27 | 2016-08-10 | 日本华尔卡工业株式会社 | Fluorine rubber composition, crosslinked rubber molded body and method for producing same |
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