CN104530611A - Grinding roller sealing ring materials and preparation method thereof - Google Patents
Grinding roller sealing ring materials and preparation method thereof Download PDFInfo
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- CN104530611A CN104530611A CN201410848424.3A CN201410848424A CN104530611A CN 104530611 A CN104530611 A CN 104530611A CN 201410848424 A CN201410848424 A CN 201410848424A CN 104530611 A CN104530611 A CN 104530611A
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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
- 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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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
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- C—CHEMISTRY; METALLURGY
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention relates to grinding roller sealing ring materials. The grinding roller sealing ring materials are characterized by comprising, by weight, 100 parts of fluororubber, 10-20 parts of organic montmorillonite, 10-30 parts of wear-resisting carbon black, 5-20 parts of modified silicon carbide, 10-20 parts of graphene composites, 15-25 parts of magnesium oxide, 0.5-2 parts of hydroxyl silicone oil, 0.1-3 parts of microcrystalline wax, 0.5-2 parts of bisphenol AF and 0.5-1.5 parts of benzyl triphenyl phosphoric chloride. The graphene composites are graphene/ hydrogenated styrene- butadiene- styrene compounds subjected to in-situ reduction. The graphene/ hydrogenated styrene- butadiene- styrene compounds subjected to in-situ reduction are added, the graphene composites are dispersed easily, the problems of difficult stripping of graphene and difficult addition caused by low apparent density in the prior art are resolved, graphene can be evenly dispersed in the grinding roller sealing ring materials, the function of the graphene is fully played, and the wear resistance and heat resistance of the grinding roller sealing ring materials are effectively improved.
Description
Technical field
The present invention relates to grinding roller sealing ring material technical field, specifically refer to a kind of viton grinding roller sealing ring material and preparation method thereof.
Background technology
The carbon atom that viton (FKM) refers to main chain or side chain is connected to the one synthesis macromolecular elastomer of fluorine atom.The radius of fluorine atom is little, electronegativity is extremely strong, can be closely arranged in around carbon atom, generates the fluorine carbon bond that bond energy is very high, produces good shielding effect to carbon-carbon bond.Thus viton has very high thermostability and unreactiveness, is used as sealing material and is widely used in national defence, military project, space flight and aviation, automobile, field of petrochemical industry.Viton is used as grinding roller sealing-ring, has the advantage that other rubber is incomparable: high temperature resistant, fuel oil resistance, powerful oxidation corrosion resistance agent, resistance to natural weathering etc.But the wear resisting property of viton grinding roller sealing-ring of the prior art is poor, especially under high temperature, high velocity environment, cannot meet current demand.
Application publication number is that (application number: 201410374228.9) add graphene oxide in elastomeric material, Graphene passes through sp by monolayer carbon atom for the Chinese invention patent application " the explosion-proof rubber seal Jiao Gai of a kind of ultracapacitor " of CN104130541A
2the new Carbon Materials of one of hydridization tightly packed one-tenth bi-dimensional cellular shape crystalline network, is the hardest known in the world at present nano material, adds the wear resisting property that Graphene can improve elastomeric material in elastomeric material.But Graphene has the difficult feature peeled off, and its apparent density is lower, is directly joined by Graphene in other material, easily causes Graphene skewness in the material, greatly reduces the improving SNR of Graphene.Application publication number is that the Chinese invention patent application " a kind of high-strength high wear-resistant rubber " (application number: 201410487400.X) of CN104194240A adds Graphene equally in elastomeric material, and it has carried out modification to Graphene, to promote that other material is uniformly dispersed in elastomeric material, play the effect of Reinforced Rubber material wear-resistant performance simultaneously.But, its modified technique to Graphene is complicated, and its to promote other material to be uniformly dispersed in elastomeric material be make use of the large feature of Graphene specific surface area, if and Graphene originally disperses even not in elastomeric material, then directly affect Graphene to the uniform promoter action of other dispersion of materials.
Summary of the invention
Technical problem to be solved by this invention is the present situation for prior art, provides a kind of wear-resisting and grinding roller sealing ring material that resistance toheat is good.
Another technical problem to be solved by this invention is the present situation for prior art, provides a kind of preparation method of above-mentioned grinding roller sealing ring material.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of grinding roller sealing ring material, it is characterized in that comprising following component by weight:
Wherein, described graphene composite material is the Graphene/hydrogenated styrene-butadiene-styrene mixture through in-situ reducing, this Graphene/hydrogenated styrene-butadiene-styrene mixture is obtained by following methods: under ultrasound condition by graphene oxide powder dispersion in organic solvent, after Graphene to be oxidized forms unformed suspension in organic solvent, in above-mentioned suspension, the reaction of hydrogenated styrene, divinyl and vinylbenzene is added again under agitation condition, also dry through underpressure distillation removing organic solvent after completion of the reaction; Described Graphene/hydrogenated styrene-butadiene-styrene mixture is completed in-situ reducing after melt blending 25min ~ 60min at 220 DEG C ~ 230 DEG C and obtains described graphene composite material.
As a further improvement on the present invention, in described Graphene/hydrogenated styrene-butadiene-styrene mixture, the weight ratio of Graphene and hydrogenated styrene-butadiene-styrene system is 1:1 ~ 1.2; The weight ratio of hydrogenated styrene in described hydrogenated styrene-butadiene-styrene system, divinyl and vinylbenzene three is 1:0.5 ~ 0.8:1.7 ~ 2.Adopt said ratio parameter, solve Graphene feed in raw material difficulty problem, Graphene is made to be easy to be evenly distributed in the material, give full play to the effect of Graphene, increase the wear resistance of elastomeric material on the one hand, promote that other component is uniformly dispersed in elastomeric material on the other hand, improve the overall performance of elastomeric material.
Further, described abrasion resistant carbon black is mixed to get 1:0.5 ~ 2 in mass ratio by high wear-resistant carbon black and intermediate super abrasion furnace black, the particle diameter of gained mixing abrasion resistant carbon black is 10 ~ 40nm, reinforcing property is excellent, the spherical abrasion resistant carbon black surface used in the present invention can further with matrix generation physics and chemically crosslinked, the polymer segment of flowing is impelled to integrate, be conducive to abrasion resistant carbon black better to disperse in elastomeric material, and give the good tensile property of material, tear resistance, wear resisting property and ageing resistance, effectively improve the mechanical property of elastomeric material.
As preferably, described carbon modified SiClx is through silane coupler modified silicon carbide micro-powder.Modified silicon carbide micro-powder has better avidity, is easy to disperse in elastomeric material, effectively improves the resistance toheat of elastomeric material.
A preparation method for above-mentioned grinding roller sealing ring material, is characterized in that comprising the following steps:
(1) preparation of graphene composite material:
Under ultrasound condition, by weight by 100 parts of graphene oxide powder dispersion in 150 ~ 200 parts of organic solvents, after Graphene to be oxidized forms unformed suspension in organic solvent, under agitation condition, add 100 parts ~ 120 parts hydrogenated styrene-butadiene-styrene system mixtures in above-mentioned suspension, the weight ratio of hydrogenated styrene in this mixture, divinyl and vinylbenzene three is 1:0.5 ~ 0.8:1.7 ~ 2;
Carry out underpressure distillation after reaction 1.5h ~ 2h, remove organic solvent and drying, obtain Graphene/hydrogenated styrene-butadiene-styrene mixture;
By described Graphene/hydrogenated styrene-butadiene-styrene mixture melt blending at 220 DEG C ~ 230 DEG C, carry out in-situ reducing reaction 25min ~ 60min, react complete and namely obtain described graphene composite material;
(2) preparation of carbon modified SiClx:
Get 60 parts of silicon carbide micro-powders cleaned, dry, add 0.1 ~ 1 part of silane coupling agent blending reaction 0.5h ~ 1h, wash after completion of the reaction, suction filtration drying;
(3) getting 100 parts of crude fluororubber is placed in mill, under roll spacing 0.5 ~ 1mm, and thin-pass 10 ~ 15 times, again roll spacing is put into 4 ~ 6mm, bottom sheet after roll-in 4 ~ 6min, wherein, the plasticating temperature of mill preliminary roller is 55 ~ 60 DEG C, and after mill, the plasticating temperature of roller is 50 ~ 55 DEG C;
(4) viton after step (3) being processed is placed in Banbury mixer, add 0.5 ~ 2 part of hydroxy silicon oil successively, graphene composite material, 10 ~ 30 parts of abrasion resistant carbon blacks prepared by carbon modified SiClx prepared by 0.1 ~ 3 part of Microcrystalline Wax, 15 ~ 25 parts of magnesium oxide, 10 ~ 20 parts of organo montmorillonites, 5 ~ 20 parts of steps (2), 10 ~ 20 parts of steps (1), mixing evenly after discharge; Wherein, melting temperature is 50 ~ 60 DEG C, and mixing time is 2 ~ 3min;
(5) compound after step (4) being processed is placed 24h and is placed in mill, add 0.5 ~ 2 part of bisphenol AF and 0.5 ~ 1.5 part of BPP carries out sulfuration, the curing temperature of one step cure is 140 ~ 160 DEG C, and curing time is 0.5h; Post vulcanization adopts cascade raising temperature mode, i.e. first sulfuration 1h at normal temperatures, is then warming up to 90 ~ 110 DEG C, 110 ~ 130 DEG C sulfuration 1h respectively successively, then is warming up to 150 DEG C of sulfuration 0.5h, continue to be warming up to 200 DEG C of sulfuration 12h, bottom sheet after being finally cooled to less than 80 DEG C;
(6) adopt vulcanizer shaping to step (5) gained material, molding pressure is 20MPa, and temperature is 170 ~ 180 DEG C, and the time is 10 ~ 15min.
Above-mentioned magnesium oxide is acid-acceptor, can absorb the acid produced in vulcanizable fluororubber process, and preferable particle size is less, the activated magnesia of vesicular structure.
Compared with prior art, the invention has the advantages that:
(1) the present invention with the addition of the Graphene/hydrogenated styrene-butadiene-styrene mixture through in-situ reducing, this graphene composite material is easy to dispersion, solve the reinforced difficult problem that in prior art, Graphene difficulty is peeled off, caused because apparent density is low, make Graphene can be dispersed at grinding roller sealing ring material, give full play to the effect of Graphene, effectively improve wear resistance and the thermotolerance of grinding roller sealing ring material;
(2) in grinding roller sealing ring material, with similar staple fibre, size exists much smaller than the whisker structure of staple fibre carbon modified SiClx, this structure can not only strongthener mechanical property, improve the thermotolerance of material, materials processing performance can also be improved to a certain extent; And, graphene composite material in the present invention and carbon modified SiClx all have good affinity, therebetween synergy makes the effect of graphene composite material and carbon modified SiClx be given full play to, and further increases wear resistance and the thermotolerance of material on the whole;
(3) because Graphene passes through sp by monolayer carbon atom
2the bi-dimensional cellular shape crystalline network that hydridization is tightly packed, it has higher specific surface area, intensity, elasticity etc., and the nanometer size effect under the laminated structure of organo montmorillonite and nano-dispersed form makes its interface interaction power in rubber matrix stronger, graphene composite material and organo montmorillonite interact, utilize the high-ratio surface sum affinity of graphene composite material, grinding roller sealing ring material is made to form a kind of material had compared with strong interfacial tension on the whole, not only there is good toughening effect, also grinding roller sealing ring material is made to have good dimensional stability and thermostability.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1:
The grinding roller sealing ring material of the present embodiment comprises following component by weight:
The preparation method of the grinding roller sealing ring material of the present embodiment comprises the following steps:
(1) preparation of graphene composite material:
Under ultrasound condition, by weight by 100 parts of graphene oxide powder dispersion in 150 parts of tetrahydrofuran (THF)s, after Graphene to be oxidized forms unformed suspension in tetrahydrofuran (THF), under agitation condition, add 100 parts of hydrogenated styrene-butadiene-styrene system mixtures in above-mentioned suspension, the weight ratio of hydrogenated styrene in this mixture, divinyl and vinylbenzene three is 1:0.5:1.7;
Carry out underpressure distillation after reaction 1.5h, remove organic solvent and drying, obtain Graphene/hydrogenated styrene-butadiene-styrene mixture;
By Graphene/hydrogenated styrene-butadiene-styrene mixture melt blending at 220 DEG C, carry out in-situ reducing reaction 25min, react complete and namely obtain graphene composite material;
(2) preparation of carbon modified SiClx:
Get 60 parts of silicon carbide micro-powders cleaned, dry, add 0.1 part of silane coupling agent blending reaction 0.5h, wash after completion of the reaction, suction filtration drying;
(3) getting 100 parts of crude fluororubber is placed in mill, under roll spacing 0.5mm, and thin-pass 10 times, then roll spacing is put into 4mm, bottom sheet after roll-in 4min, wherein, the plasticating temperature of mill preliminary roller is 55 DEG C, and after mill, the plasticating temperature of roller is 50 DEG C;
(4) viton after step (3) being processed is placed in Banbury mixer, add hydroxy silicon oil successively, graphene composite material, high wear-resistant carbon black, intermediate super abrasion furnace black prepared by carbon modified SiClx prepared by Microcrystalline Wax, magnesium oxide, organo montmorillonite, 15 parts of steps (2), 12 parts of steps (1), mixing evenly after discharge; Wherein, melting temperature is 50 DEG C, and mixing time is 2min;
(5) compound after step (4) being processed is placed 24h and is placed in mill, and add bisphenol AF and BPP carries out sulfuration, the curing temperature of one step cure is 140 DEG C, and curing time is 0.5h; Post vulcanization adopts cascade raising temperature mode, i.e. first sulfuration 1h at normal temperatures, is then warming up to 90 DEG C, 110 DEG C sulfuration 1h respectively successively, then is warming up to 150 DEG C of sulfuration 0.5h, continue to be warming up to 200 DEG C of sulfuration 12h, bottom sheet after being finally cooled to less than 80 DEG C;
(6) adopt vulcanizer shaping to step (5) gained material, molding pressure is 20MPa, and temperature is 170 DEG C, and the time is 10min.
Embodiment 2:
The grinding roller sealing ring material of the present embodiment comprises following component by weight:
The preparation method of the grinding roller sealing ring material of the present embodiment comprises the following steps:
(1) preparation of graphene composite material:
Under ultrasound condition, by weight by 100 parts of graphene oxide powder dispersion in 160 parts of tetrahydrofuran (THF)s, after Graphene to be oxidized forms unformed suspension in tetrahydrofuran (THF), under agitation condition, add 110 parts of hydrogenated styrene-butadiene-styrene system mixtures in above-mentioned suspension, the weight ratio of hydrogenated styrene in this mixture, divinyl and vinylbenzene three is 1:0.8:1.7;
Carry out underpressure distillation after reaction 1.8h, remove organic solvent and drying, obtain Graphene/hydrogenated styrene-butadiene-styrene mixture;
By Graphene/hydrogenated styrene-butadiene-styrene mixture melt blending at 225 DEG C, carry out in-situ reducing reaction 40min, react complete and namely obtain graphene composite material;
(2) preparation of carbon modified SiClx:
Get 60 parts of silicon carbide micro-powders cleaned, dry, add 0.4 part of silane coupling agent blending reaction 0.8h, wash after completion of the reaction, suction filtration drying;
(3) getting 100 parts of crude fluororubber is placed in mill, under roll spacing 0.7mm, and thin-pass 12 times, then roll spacing is put into 5mm, bottom sheet after roll-in 5min, wherein, the plasticating temperature of mill preliminary roller is 57 DEG C, and after mill, the plasticating temperature of roller is 52 DEG C;
(4) viton after step (3) being processed is placed in Banbury mixer, add hydroxy silicon oil successively, graphene composite material, high wear-resistant carbon black, intermediate super abrasion furnace black prepared by carbon modified SiClx prepared by Microcrystalline Wax, magnesium oxide, organo montmorillonite, 10 parts of steps (2), 20 parts of steps (1), mixing evenly after discharge; Wherein, melting temperature is 55 DEG C, and mixing time is 2.5min;
(5) compound after step (4) being processed is placed 24h and is placed in mill, and add bisphenol AF and BPP carries out sulfuration, the curing temperature of one step cure is 150 DEG C, and curing time is 0.5h; Post vulcanization adopts cascade raising temperature mode, i.e. first sulfuration 1h at normal temperatures, is then warming up to 100 DEG C, 120 DEG C sulfuration 1h respectively successively, then is warming up to 150 DEG C of sulfuration 0.5h, continue to be warming up to 200 DEG C of sulfuration 12h, bottom sheet after being finally cooled to less than 80 DEG C;
(6) adopt vulcanizer shaping to step (5) gained material, molding pressure is 20MPa, and temperature is 175 DEG C, and the time is 12min.
Embodiment 3:
The grinding roller sealing ring material of the present embodiment comprises following component by weight:
The preparation method of the grinding roller sealing ring material of the present embodiment comprises the following steps:
(1) preparation of graphene composite material:
Under ultrasound condition, by weight by 100 parts of graphene oxide powder dispersion in 180 parts of tetrahydrofuran (THF)s, after Graphene to be oxidized forms unformed suspension in tetrahydrofuran (THF), under agitation condition, add 120 parts of hydrogenated styrene-butadiene-styrene system mixtures in above-mentioned suspension, the weight ratio of hydrogenated styrene in this mixture, divinyl and vinylbenzene three is 1:0.8:2;
Carry out underpressure distillation after reaction 2h, remove organic solvent and drying, obtain Graphene/hydrogenated styrene-butadiene-styrene mixture;
By Graphene/hydrogenated styrene-butadiene-styrene mixture melt blending at 230 DEG C, carry out in-situ reducing reaction 50min, react complete and namely obtain graphene composite material;
(2) preparation of carbon modified SiClx:
Get 60 parts of silicon carbide micro-powders cleaned, dry, add 0.6 part of silane coupling agent blending reaction 0.6h, wash after completion of the reaction, suction filtration drying;
(3) getting 100 parts of crude fluororubber is placed in mill, under roll spacing 1mm, and thin-pass 15 times, then roll spacing is put into 6mm, bottom sheet after roll-in 6min, wherein, the plasticating temperature of mill preliminary roller is 60 DEG C, and after mill, the plasticating temperature of roller is 55 DEG C;
(4) viton after step (3) being processed is placed in Banbury mixer, add hydroxy silicon oil successively, graphene composite material, high wear-resistant carbon black, intermediate super abrasion furnace black prepared by carbon modified SiClx prepared by Microcrystalline Wax, magnesium oxide, organo montmorillonite, 5 parts of steps (2), 15 parts of steps (1), mixing evenly after discharge; Wherein, melting temperature is 60 DEG C, and mixing time is 3min;
(5) compound after step (4) being processed is placed 24h and is placed in mill, and add bisphenol AF and BPP carries out sulfuration, the curing temperature of one step cure is 160 DEG C, and curing time is 0.5h; Post vulcanization adopts cascade raising temperature mode, i.e. first sulfuration 1h at normal temperatures, is then warming up to 110 DEG C, 130 DEG C sulfuration 1h respectively successively, then is warming up to 150 DEG C of sulfuration 0.5h, continue to be warming up to 200 DEG C of sulfuration 12h, bottom sheet after being finally cooled to less than 80 DEG C;
(6) adopt vulcanizer shaping to step (5) gained material, molding pressure is 20MPa, and temperature is 180 DEG C, and the time is 15min.
Embodiment 4:
The grinding roller sealing ring material of the present embodiment comprises following component by weight:
The preparation method of the grinding roller sealing ring material of the present embodiment comprises the following steps:
(1) preparation of graphene composite material:
Under ultrasound condition, by weight by 100 parts of graphene oxide powder dispersion in 170 parts of tetrahydrofuran (THF)s, after Graphene to be oxidized forms unformed suspension in tetrahydrofuran (THF), under agitation condition, add 120 parts of hydrogenated styrene-butadiene-styrene system mixtures in above-mentioned suspension, the weight ratio of hydrogenated styrene in this mixture, divinyl and vinylbenzene three is 1:0.5:2;
Carry out underpressure distillation after reaction 1.7h, remove organic solvent and drying, obtain Graphene/hydrogenated styrene-butadiene-styrene mixture;
By Graphene/hydrogenated styrene-butadiene-styrene mixture melt blending at 225 DEG C, carry out in-situ reducing reaction 60min, react complete and namely obtain graphene composite material;
(2) preparation of carbon modified SiClx:
Get 60 parts of silicon carbide micro-powders cleaned, dry, add 1 part of silane coupling agent blending reaction 0.8h, wash after completion of the reaction, suction filtration drying;
(3) getting 100 parts of crude fluororubber is placed in mill, under roll spacing 0.7mm, and thin-pass 13 times, then roll spacing is put into 5mm, bottom sheet after roll-in 6min, wherein, the plasticating temperature of mill preliminary roller is 58 DEG C, and after mill, the plasticating temperature of roller is 53 DEG C;
(4) viton after step (3) being processed is placed in Banbury mixer, add hydroxy silicon oil successively, graphene composite material, high wear-resistant carbon black, intermediate super abrasion furnace black prepared by carbon modified SiClx prepared by Microcrystalline Wax, magnesium oxide, organo montmorillonite, 20 parts of steps (2), 10 parts of steps (1), mixing evenly after discharge; Wherein, melting temperature is 54 DEG C, and mixing time is 3min;
(5) compound after step (4) being processed is placed 24h and is placed in mill, and add bisphenol AF and BPP carries out sulfuration, the curing temperature of one step cure is 155 DEG C, and curing time is 0.5h; Post vulcanization adopts cascade raising temperature mode, i.e. first sulfuration 1h at normal temperatures, is then warming up to 105 DEG C, 125 DEG C sulfuration 1h respectively successively, then is warming up to 150 DEG C of sulfuration 0.5h, continue to be warming up to 200 DEG C of sulfuration 12h, bottom sheet after being finally cooled to less than 80 DEG C;
(6) adopt vulcanizer shaping to step (5) gained material, molding pressure is 20MPa, and temperature is 177 DEG C, and the time is 15min.
Embodiment 5:
The grinding roller sealing ring material of the present embodiment comprises following component by weight:
The preparation method of the grinding roller sealing ring material of the present embodiment comprises the following steps:
(1) preparation of graphene composite material:
Under ultrasound condition, by weight by 100 parts of graphene oxide powder dispersion in 200 parts of tetrahydrofuran (THF)s, after Graphene to be oxidized forms unformed suspension in tetrahydrofuran (THF), under agitation condition, add 120 parts of hydrogenated styrene-butadiene-styrene system mixtures in above-mentioned suspension, the weight ratio of hydrogenated styrene in this mixture, divinyl and vinylbenzene three is 1:0.6:1.9;
Carry out underpressure distillation after reaction 2h, remove organic solvent and drying, obtain Graphene/hydrogenated styrene-butadiene-styrene mixture;
By Graphene/hydrogenated styrene-butadiene-styrene mixture melt blending at 225 DEG C, carry out in-situ reducing reaction 60min, react complete and namely obtain graphene composite material;
(2) preparation of carbon modified SiClx:
Get 60 parts of silicon carbide micro-powders cleaned, dry, add 1 part of silane coupling agent blending reaction 1h, wash after completion of the reaction, suction filtration drying;
(3) getting 100 parts of crude fluororubber is placed in mill, under roll spacing 0.7mm, and thin-pass 12 times, then roll spacing is put into 5mm, bottom sheet after roll-in 6min, wherein, the plasticating temperature of mill preliminary roller is 58 DEG C, and after mill, the plasticating temperature of roller is 53 DEG C;
(4) viton after step (3) being processed is placed in Banbury mixer, add hydroxy silicon oil successively, graphene composite material, high wear-resistant carbon black, intermediate super abrasion furnace black prepared by carbon modified SiClx prepared by Microcrystalline Wax, magnesium oxide, organo montmorillonite, 12 parts of steps (2), 18 parts of steps (1), mixing evenly after discharge; Wherein, melting temperature is 54 DEG C, and mixing time is 3min;
(5) compound after step (4) being processed is placed 24h and is placed in mill, and add bisphenol AF and BPP carries out sulfuration, the curing temperature of one step cure is 155 DEG C, and curing time is 0.5h; Post vulcanization adopts cascade raising temperature mode, i.e. first sulfuration 1h at normal temperatures, is then warming up to 105 DEG C, 125 DEG C sulfuration 1h respectively successively, then is warming up to 150 DEG C of sulfuration 0.5h, continue to be warming up to 200 DEG C of sulfuration 12h, bottom sheet after being finally cooled to less than 80 DEG C;
(6) adopt vulcanizer shaping to step (5) gained material, molding pressure is 20MPa, and temperature is 180 DEG C, and the time is 15min.
Comparative example 1:
The grinding roller sealing ring material of this comparative example comprises following component by weight:
The preparation method of the grinding roller sealing ring material of this comparative example comprises the following steps:
(1) getting 100 parts of crude fluororubber is placed in mill, under roll spacing 0.7mm, and thin-pass 12 times, then roll spacing is put into 5mm, bottom sheet after roll-in 6min, wherein, the plasticating temperature of mill preliminary roller is 58 DEG C, and after mill, the plasticating temperature of roller is 53 DEG C;
(2) viton after step (1) being processed is placed in Banbury mixer, adds hydroxy silicon oil, Microcrystalline Wax, magnesium oxide, high wear-resistant carbon black successively, mixing evenly rear discharge; Wherein, melting temperature is 54 DEG C, and mixing time is 3min;
(3) compound after step (2) being processed is placed 24h and is placed in mill, and add bisphenol AF and BPP carries out sulfuration, the curing temperature of one step cure is 155 DEG C, and curing time is 0.5h; Post vulcanization adopts cascade raising temperature mode, i.e. first sulfuration 1h at normal temperatures, is then warming up to 105 DEG C, 125 DEG C sulfuration 1h respectively successively, then is warming up to 150 DEG C of sulfuration 0.5h, continue to be warming up to 200 DEG C of sulfuration 12h, bottom sheet after being finally cooled to less than 80 DEG C;
(6) adopt vulcanizer shaping to step (5) gained material, molding pressure is 20MPa, and temperature is 180 DEG C, and the time is 15min.
Resistance toheat and wear resisting property (GB/T9867) test are carried out to material prepared by the various embodiments described above and comparative example.Wherein, resistance toheat test condition: according to (GB/T3512-2001) test, material is placed in climatic chamber, at 70 DEG C, through 72h air oven aging test; Wear resisting property test condition: adopt Akron abrasion machine (TY-4069 type, Jiangsu Tian Yuan testing installation company limited produces), measure the wear loss of material by GB/T1689-1998.
Test result is as shown in table 1.
Table 1
| Tensile strength velocity of variation/% | Changes in hardness rate/% | Wear index/mm | |
| Viton material | -24 | 9 | 102 |
| Embodiment 1 | -8 | 1 | 151 |
| Embodiment 2 | -10 | 1 | 147 |
| Embodiment 3 | -9 | 2 | 160 |
| Embodiment 4 | -9 | 1 | 155 |
| Embodiment 5 | -8 | 2 | 158 |
| Comparative example 1 | -15 | 6 | 115 |
Visible, grinding roller sealing ring material of the present invention has good wear resistance and thermotolerance.
Organo montmorillonite in the various embodiments described above buys from Beijing happy luxuriant specialization development in science and technology company limited, high wear-resistant carbon black and intermediate super abrasion furnace black are bought and are shown moral carbon black company limited from Zhejiang, graphene oxide is bought from Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences, hydroxy silicon oil is bought from Jiaxing Ke Rui organosilicon company limited, Microcrystalline Wax is bought from Quanzhou Zhong Xin Industrial Co., Ltd., bisphenol AF is bought from Hubei Yuancheng Saichuang Technology Co., Ltd., and BPP is bought from Yantai Heng Nuo Chemical Co., Ltd..
Claims (5)
1. a grinding roller sealing ring material, is characterized in that comprising following component by weight:
Wherein, described graphene composite material is the Graphene/hydrogenated styrene-butadiene-styrene mixture through in-situ reducing, this Graphene/hydrogenated styrene-butadiene-styrene mixture is obtained by following methods: under ultrasound condition by graphene oxide powder dispersion in organic solvent, after Graphene to be oxidized forms unformed suspension in organic solvent, in above-mentioned suspension, the reaction of hydrogenated styrene, divinyl and vinylbenzene is added again under agitation condition, also dry through underpressure distillation removing organic solvent after completion of the reaction; Described Graphene/hydrogenated styrene-butadiene-styrene mixture is completed in-situ reducing after melt blending 25min ~ 60min at 220 DEG C ~ 230 DEG C and obtains described graphene composite material.
2. grinding roller sealing ring material according to claim 1, is characterized in that: in described Graphene/hydrogenated styrene-butadiene-styrene mixture, and the weight ratio of Graphene and hydrogenated styrene-butadiene-styrene system is 1:1 ~ 1.2; The weight ratio of hydrogenated styrene in described hydrogenated styrene-butadiene-styrene system, divinyl and vinylbenzene three is 1:0.5 ~ 0.8:1.7 ~ 2.
3. grinding roller sealing ring material according to claim 1, is characterized in that: described abrasion resistant carbon black is mixed to get 1:0.5 ~ 2 in mass ratio by high wear-resistant carbon black and intermediate super abrasion furnace black.
4. grinding roller sealing ring material according to claim 1, is characterized in that: described carbon modified SiClx is through silane coupler modified silicon carbide micro-powder.
5. a preparation method for grinding roller sealing ring material described in claim 1, is characterized in that comprising the following steps:
(1) preparation of graphene composite material:
Under ultrasound condition, by weight by 100 parts of graphene oxide powder dispersion in 150 ~ 200 parts of organic solvents, after Graphene to be oxidized forms unformed suspension in organic solvent, under agitation condition, add 100 parts ~ 120 parts hydrogenated styrene-butadiene-styrene system mixtures in above-mentioned suspension, the weight ratio of hydrogenated styrene in this mixture, divinyl and vinylbenzene three is 1:0.5 ~ 0.8:1.7 ~ 2;
Carry out underpressure distillation after reaction 1.5h ~ 2h, remove organic solvent and drying, obtain Graphene/hydrogenated styrene-butadiene-styrene mixture;
By described Graphene/hydrogenated styrene-butadiene-styrene mixture melt blending at 220 DEG C ~ 230 DEG C, carry out in-situ reducing reaction 25min ~ 60min, react complete and namely obtain described graphene composite material;
(2) preparation of carbon modified SiClx:
Get 60 parts of silicon carbide micro-powders cleaned, dry, add 0.1 ~ 1 part of silane coupling agent blending reaction 0.5h ~ 1h, wash after completion of the reaction, suction filtration drying;
(3) getting 100 parts of crude fluororubber is placed in mill, under roll spacing 0.5 ~ 1mm, and thin-pass 10 ~ 15 times, again roll spacing is put into 4 ~ 6mm, bottom sheet after roll-in 4 ~ 6min, wherein, the plasticating temperature of mill preliminary roller is 55 ~ 60 DEG C, and after mill, the plasticating temperature of roller is 50 ~ 55 DEG C;
(4) viton after step (3) being processed is placed in Banbury mixer, add 0.5 ~ 2 part of hydroxy silicon oil successively, graphene composite material, 10 ~ 30 parts of abrasion resistant carbon blacks prepared by carbon modified SiClx prepared by 0.1 ~ 3 part of Microcrystalline Wax, 15 ~ 25 parts of magnesium oxide, 10 ~ 20 parts of organo montmorillonites, 5 ~ 20 parts of steps (2), 10 ~ 20 parts of steps (1), mixing evenly after discharge; Wherein, melting temperature is 50 ~ 60 DEG C, and mixing time is 2 ~ 3min;
(5) compound after step (4) being processed is placed 24h and is placed in mill, add 0.5 ~ 2 part of bisphenol AF and 0.5 ~ 1.5 part of BPP carries out sulfuration, the curing temperature of one step cure is 140 ~ 160 DEG C, and curing time is 0.5h; Post vulcanization adopts cascade raising temperature mode, i.e. first sulfuration 1h at normal temperatures, is then warming up to 90 ~ 110 DEG C, 110 ~ 130 DEG C sulfuration 1h respectively successively, then is warming up to 150 DEG C of sulfuration 0.5h, continue to be warming up to 200 DEG C of sulfuration 12h, bottom sheet after being finally cooled to less than 80 DEG C;
(6) adopt vulcanizer shaping to step (5) gained material, molding pressure is 20MPa, and temperature is 170 ~ 180 DEG C, and the time is 10 ~ 15min.
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| CN113667245A (en) * | 2021-07-21 | 2021-11-19 | 佛山市天禄智能装备科技有限公司 | Flexible high-temperature-resistant sealing material and preparation method thereof |
| CN115624955A (en) * | 2022-10-25 | 2023-01-20 | 广州怀特远科技有限公司 | Biochar soil heavy metal restoration agent and preparation method thereof |
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| CN113667245A (en) * | 2021-07-21 | 2021-11-19 | 佛山市天禄智能装备科技有限公司 | Flexible high-temperature-resistant sealing material and preparation method thereof |
| CN113667245B (en) * | 2021-07-21 | 2023-08-29 | 佛山市天禄智能装备科技有限公司 | Flexible high-temperature-resistant sealing material and preparation method thereof |
| CN115624955A (en) * | 2022-10-25 | 2023-01-20 | 广州怀特远科技有限公司 | Biochar soil heavy metal restoration agent and preparation method thereof |
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