CN105419180A - High-performance fluorine rubber composite material - Google Patents
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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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Abstract
The invention discloses a high-performance fluorine rubber composite material. The high-performance fluorine rubber composite material comprises the following components: fluorine rubber, methyl phenyl vinyl silicone rubber, ethylene-acrylate rubber, polyvinylidene fluoride, polycaprolactone, a compatibilizer, 2,4-dichlorobenzoyl peroxide, t-butyl peroxybenzoate, triallyl cyanurate, zinc oxide, stearic acid, calcium hydroxide, fumed silica, graphene, kieselguhr, boron nitride, molybdenum disulfide, hydroxyl silicone oil, an anti-aging agent, an accelerant and a silane coupling agent. The high-performance fluorine rubber composite material disclosed by the invention is good in heat resistance, ageing resistance, low temperature resistance and oil resistance, excellent in processing performance and long in service life.
Description
Technical field
The present invention relates to viton technical field, particularly relate to a kind of high performance fluorine rubber composite.
Background technology
Viton be main chain or side chain carbon atom on containing the rubber of fluorine atom, it is high temperature resistant, corrosion-resistant and have excellent weather resistance, and is widely used in automotive industry, aerospace, field of petrochemical industry.In recent years along with the rubber item of the field uses such as automobile, machinery, Aeronautics and Astronautics, chemical industry is towards high-performance, less energy-consumption and long lifetime future development, have higher requirement to the performance of rubber item, traditional single elastomeric material can not meet the service requirements developed rapidly completely.
Summary of the invention
Based on the technical problem that background technology exists, the present invention proposes a kind of high performance fluorine rubber composite, its thermotolerance, ageing resistance, lower temperature resistance and oil-proofness are good, and processing characteristics is excellent, long service life.
A kind of high performance fluorine rubber composite that the present invention proposes, its raw material comprises following component by weight: viton 50-75 part, methyl vinyl phenyl silicon rubber 20-35 part, ethylene-acrylate rubber 5-15 part, polyvinylidene difluoride (PVDF) 3-12 part, polycaprolactone 3-10 part, expanding material 5-10 part, 2, 4-dichlorobenzoperoxide 0.5-1.2 part, peroxidized t-butyl perbenzoate 0.6-1 part, triallylcyanurate 0.2-0.5 part, zinc oxide 2-5 part, stearic acid 0.5-1 part, calcium hydroxide 3-10 part, gas-phase silica 10-20 part, Graphene 5-10 part, diatomite 2-10 part, boron nitride 5-20 part, molybdenumdisulphide 2-10 part, hydroxy silicon oil 2-5 part, anti-aging agent 1-2.5 part, promotor 0.5-2 part, silane coupling agent 2-5 part.
Preferably, in its raw material, the weight ratio of viton, methyl vinyl phenyl silicon rubber, ethylene-acrylate rubber, polyvinylidene difluoride (PVDF), polycaprolactone is 55-70:24-32:7-13:5-10:5-10.
Preferably, in its raw material, the weight ratio of 2,4-dichlorobenzoperoxide, peroxidized t-butyl perbenzoate, triallylcyanurate is 0.8-1.2:0.7-1:0.3-0.5.
Preferably, its raw material comprises following component by weight: viton 60-65 part, methyl vinyl phenyl silicon rubber 26-30 part, ethylene-acrylate rubber 10-13 part, polyvinylidene difluoride (PVDF) 7-8.5 part, polycaprolactone 6-8 part, expanding material 7-8 part, 2, 4-dichlorobenzoperoxide 0.8-1.1 part, peroxidized t-butyl perbenzoate 0.7-1 part, triallylcyanurate 0.35-0.42 part, zinc oxide 3.2-4 part, stearic acid 0.6-0.8 part, calcium hydroxide 5.8-7 part, gas-phase silica 12-17 part, Graphene 6.8-7.3 part, diatomite 5.5-6.2 part, boron nitride 12-16 part, molybdenumdisulphide 5.3-6 part, hydroxy silicon oil 3.2-4 part, anti-aging agent 1.8-2.2 part, promotor 1.3-1.6 part, silane coupling agent 3.1-3.5 part.
Preferably, its raw material comprises following component by weight: viton 63 parts, 27 parts, methyl vinyl phenyl silicon rubber, ethylene-acrylate rubber 10 parts, polyvinylidene difluoride (PVDF) 8 parts, polycaprolactone 7.2 parts, expanding material 7.3 parts, 2, 4-dichlorobenzoperoxide 1 part, peroxidized t-butyl perbenzoate 0.85 part, triallylcyanurate 0.4 part, 3.6 parts, zinc oxide, stearic acid 0.7 part, 6 parts, calcium hydroxide, gas-phase silica 15 parts, Graphene 7 parts, 6 parts, diatomite, boron nitride 13 parts, molybdenumdisulphide 5.6 parts, hydroxy silicon oil 3.8 parts, 2 parts, anti-aging agent, promotor 1.4 parts, silane coupling agent 3.2 parts.
Preferably, described expanding material is prepared according to following technique: add in 30-50 part ethanol by 5-10 part cerous hydroxide by weight, then add 4-10 part vinyltrimethoxy silane, at 40-55 DEG C, stir 30-50min, filtration, washing, drying obtain modification cerous hydroxide; By weight by 100 parts of viton, 2-4 part γ-methacryloxypropyl trimethoxy silane, 3-10 part modification cerous hydroxide, 2-5 part methacrylic acid-2,2,2-trifluoro ethyl ester and 0.6-1.2 part dicumyl peroxide add in Haake rheometer, mixing 3-7min at 120-140 DEG C, then obtains described expanding material through dehydrated alcohol extracting 30-45h at 60-75 DEG C.
Preferably, described expanding material is prepared according to following technique: added in 40 parts of ethanol by 8 parts of cerous hydroxides by weight, then adds 6.5 parts of vinyltrimethoxy silanes, at 50 DEG C, stirs 45min, and filtration, washing, drying obtain modification cerous hydroxide; By weight by 100 parts of viton, 3.2 parts of γ-methacryloxypropyl trimethoxy silane, 8 parts of modification cerous hydroxides, 3.5 parts of methacrylic acids-2,2,2-trifluoro ethyl ester and 1 part of dicumyl peroxide add in Haake rheometer, mixing 5min at 135 DEG C, then obtains described expanding material through dehydrated alcohol extracting 40h at 70 DEG C.
Preferably, described anti-aging agent is one or more the mixture in antioxidant MB, antioxidant A W, anti-aging agent RD, antioxidant MC.
Preferably, described promotor is one or more the mixture in accelerant CZ, vulkacit D, Vulcanization accelerator TMTD, altax.
In the present invention, have selected viton is major ingredient, and cooperation with the addition of methyl vinyl phenyl silicon rubber, ethylene-acrylate rubber as blend compounds, make matrix material with the advantage of viton, methyl vinyl phenyl silicon rubber and ethylene-acrylate rubber, give the lower temperature resistance of matrix material excellence, processing characteristics and oil-proofness, polyvinylidene difluoride (PVDF), polycaprolactone add in system, improve the tensile strength of blend compounds, tear strength and hardness, improve mobility and the solvent resistance of system simultaneously, and with the addition of expanding material, the homogeneity of Blend rubber is improved, interface binding power strengthens, reach the object of each material performance complementation, in hot environment, rubber molecular chain is easy fracture not, the weathering resistance of matrix material excellence is given while improving the processing characteristics of matrix material, thermotolerance, ageing resistance and lower temperature resistance, in the expanding material of optimal way, first have selected cerous hydroxide and vinyltrimethoxy silane carries out being obtained by reacting modification cerous hydroxide, afterwards and viton, γ-methacryloxypropyl trimethoxy silane, methacrylic acid-2, 2, after the mixing of 2-trifluoro ethyl ester, under the effect of dicumyl peroxide, by γ-methacryloxypropyl trimethoxy silane, methacrylic acid-2, 2, 2-trifluoro ethyl ester and modification cerous hydroxide have been grafted in viton molecule, add after in system, because containing fluorine in molecule simultaneously, Siliciumatom, improve the consistency of system, improve the thermotolerance of matrix material simultaneously, weathering resistance and ageing resistance, simultaneously due to the cerous hydroxide of expanding material neutral and alkali and the existence of acyloxy, improve 2, 4-dichlorobenzoperoxide, peroxidized t-butyl perbenzoate and triallylcyanurate are as curability during vulcanizing agent, shorten curing time and time of scorch, accelerate vulcanization rate, Blend rubber is made to have excellent processing safety, good cross-linking density, physical and mechanical properties, thermotolerance and ageing-resistant performance, Graphene and molybdenumdisulphide add in system and have synergy, improve wear resistance and the thermostability of matrix material, add calcium hydroxide, gas-phase silica, after diatomite, relatively advanced filler network is defined in system, effectively improve the tensile strength of matrix, hardness, modulus of compression, give the mechanical property of matrix material excellence, overcome viton, methyl vinyl phenyl silicon rubber and ethylene-acrylate rubber intensity low, the defect of wear resistance and lear energy deficiency, and effectively prevent nonpolar oil molecule to infiltrate in Blend rubber, improve intensity and the oil-proofness of matrix material, facilitate the carrying out of rubber vulcanization reaction in addition to a certain extent, improve the processing fluidity of matrix material and the reliability of goods.
Embodiment
Below, by specific embodiment, technical scheme of the present invention is described in detail.
Embodiment 1
A kind of high performance fluorine rubber composite that the present invention proposes, its raw material comprises following component by weight: viton 75 parts, 20 parts, methyl vinyl phenyl silicon rubber, ethylene-acrylate rubber 15 parts, polyvinylidene difluoride (PVDF) 3 parts, polycaprolactone 10 parts, expanding material 5 parts, 2, 4-dichlorobenzoperoxide 0.5 part, peroxidized t-butyl perbenzoate 1 part, triallylcyanurate 0.2 part, 5 parts, zinc oxide, stearic acid 1 part, 10 parts, calcium hydroxide, gas-phase silica 10 parts, Graphene 10 parts, 2 parts, diatomite, boron nitride 20 parts, molybdenumdisulphide 2 parts, hydroxy silicon oil 5 parts, 1 part, anti-aging agent, promotor 2 parts, silane coupling agent 2 parts.
Embodiment 2
A kind of high performance fluorine rubber composite that the present invention proposes, its raw material comprises following component by weight: viton 50 parts, 35 parts, methyl vinyl phenyl silicon rubber, ethylene-acrylate rubber 5 parts, polyvinylidene difluoride (PVDF) 12 parts, polycaprolactone 3 parts, expanding material 10 parts, 2, 4-dichlorobenzoperoxide 1.2 parts, peroxidized t-butyl perbenzoate 0.6 part, triallylcyanurate 0.5 part, 2 parts, zinc oxide, stearic acid 0.5 part, 3 parts, calcium hydroxide, gas-phase silica 20 parts, Graphene 5 parts, 10 parts, diatomite, boron nitride 5 parts, molybdenumdisulphide 10 parts, hydroxy silicon oil 2 parts, antioxidant MB 0.3 part, antioxidant A W0.2 part, anti-aging agent RD 1 part, antioxidant MC 1 part, accelerant CZ 0.5 part, silane coupling agent 5 parts.
Embodiment 3
A kind of high performance fluorine rubber composite that the present invention proposes, its raw material comprises following component by weight: viton 60 parts, 30 parts, methyl vinyl phenyl silicon rubber, ethylene-acrylate rubber 10 parts, polyvinylidene difluoride (PVDF) 8.5 parts, polycaprolactone 6 parts, expanding material 8 parts, 2, 4-dichlorobenzoperoxide 0.8 part, peroxidized t-butyl perbenzoate 1 part, triallylcyanurate 0.35 part, 4 parts, zinc oxide, stearic acid 0.8 part, 7 parts, calcium hydroxide, gas-phase silica 12 parts, Graphene 7.3 parts, 5.5 parts, diatomite, boron nitride 16 parts, molybdenumdisulphide 5.3 parts, hydroxy silicon oil 4 parts, antioxidant A W0.3 part, anti-aging agent RD 0.5 part, antioxidant MC 1 part, vulkacit D 1 part, Vulcanization accelerator TMTD 0.6 part, silane coupling agent 3.1 parts,
Wherein, described expanding material is prepared according to following technique: added in 50 parts of ethanol by 5 parts of cerous hydroxides by weight, then adds 4 parts of vinyltrimethoxy silanes, at 55 DEG C, stirs 30min, and filtration, washing, drying obtain modification cerous hydroxide; By weight by 100 parts of viton, 2 parts of γ-methacryloxypropyl trimethoxy silane, 10 parts of modification cerous hydroxides, 2 parts of methacrylic acids-2,2,2-trifluoro ethyl ester and 1.2 parts of dicumyl peroxides add in Haake rheometer, mixing 7min at 120 DEG C, then obtains described expanding material through dehydrated alcohol extracting 45h at 60 DEG C.
Embodiment 4
A kind of high performance fluorine rubber composite that the present invention proposes, its raw material comprises following component by weight: viton 65 parts, 26 parts, methyl vinyl phenyl silicon rubber, ethylene-acrylate rubber 13 parts, polyvinylidene difluoride (PVDF) 7 parts, polycaprolactone 8 parts, expanding material 7 parts, 2, 4-dichlorobenzoperoxide 1.1 parts, peroxidized t-butyl perbenzoate 0.7 part, triallylcyanurate 0.42 part, 3.2 parts, zinc oxide, stearic acid 0.6 part, 5.8 parts, calcium hydroxide, gas-phase silica 17 parts, Graphene 6.8 parts, 6.2 parts, diatomite, boron nitride 12 parts, molybdenumdisulphide 6 parts, hydroxy silicon oil 3.2 parts, antioxidant A W2 part, anti-aging agent RD 0.2 part, vulkacit D 0.3 part, Vulcanization accelerator TMTD 0.7 part, altax 0.3 part, silane coupling agent 3.5 parts,
Wherein, described expanding material is prepared according to following technique: added in 30 parts of ethanol by 10 parts of cerous hydroxides by weight, then adds 10 parts of vinyltrimethoxy silanes, at 40 DEG C, stirs 50min, and filtration, washing, drying obtain modification cerous hydroxide; By weight by 100 parts of viton, 4 parts of γ-methacryloxypropyl trimethoxy silane, 3 parts of modification cerous hydroxides, 5 parts of methacrylic acids-2,2,2-trifluoro ethyl ester and 0.6 part of dicumyl peroxide add in Haake rheometer, mixing 3min at 140 DEG C, then obtains described expanding material through dehydrated alcohol extracting 30h at 75 DEG C.
Embodiment 5
A kind of high performance fluorine rubber composite that the present invention proposes, its raw material comprises following component by weight: viton 63 parts, 27 parts, methyl vinyl phenyl silicon rubber, ethylene-acrylate rubber 10 parts, polyvinylidene difluoride (PVDF) 8 parts, polycaprolactone 7.2 parts, expanding material 7.3 parts, 2, 4-dichlorobenzoperoxide 1 part, peroxidized t-butyl perbenzoate 0.85 part, triallylcyanurate 0.4 part, 3.6 parts, zinc oxide, stearic acid 0.7 part, 6 parts, calcium hydroxide, gas-phase silica 15 parts, Graphene 7 parts, 6 parts, diatomite, boron nitride 13 parts, molybdenumdisulphide 5.6 parts, hydroxy silicon oil 3.8 parts, antioxidant MB 2 parts, accelerant CZ 0.2 part, vulkacit D 0.3 part, Vulcanization accelerator TMTD 0.5 part, altax 0.4 part, silane coupling agent 3.2 parts,
Wherein, described expanding material is prepared according to following technique: added in 40 parts of ethanol by 8 parts of cerous hydroxides by weight, then adds 6.5 parts of vinyltrimethoxy silanes, at 50 DEG C, stirs 45min, and filtration, washing, drying obtain modification cerous hydroxide; By weight by 100 parts of viton, 3.2 parts of γ-methacryloxypropyl trimethoxy silane, 8 parts of modification cerous hydroxides, 3.5 parts of methacrylic acids-2,2,2-trifluoro ethyl ester and 1 part of dicumyl peroxide add in Haake rheometer, mixing 5min at 135 DEG C, then obtains described expanding material through dehydrated alcohol extracting 40h at 70 DEG C.
The above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technical scheme of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.
Claims (9)
1. a high performance fluorine rubber composite, it is characterized in that, its raw material comprises following component by weight: viton 50-75 part, methyl vinyl phenyl silicon rubber 20-35 part, ethylene-acrylate rubber 5-15 part, polyvinylidene difluoride (PVDF) 3-12 part, polycaprolactone 3-10 part, expanding material 5-10 part, 2, 4-dichlorobenzoperoxide 0.5-1.2 part, peroxidized t-butyl perbenzoate 0.6-1 part, triallylcyanurate 0.2-0.5 part, zinc oxide 2-5 part, stearic acid 0.5-1 part, calcium hydroxide 3-10 part, gas-phase silica 10-20 part, Graphene 5-10 part, diatomite 2-10 part, boron nitride 5-20 part, molybdenumdisulphide 2-10 part, hydroxy silicon oil 2-5 part, anti-aging agent 1-2.5 part, promotor 0.5-2 part, silane coupling agent 2-5 part.
2. high performance fluorine rubber composite according to claim 1, it is characterized in that, in its raw material, the weight ratio of viton, methyl vinyl phenyl silicon rubber, ethylene-acrylate rubber, polyvinylidene difluoride (PVDF), polycaprolactone is 55-70:24-32:7-13:5-10:5-10.
3. high performance fluorine rubber composite according to claim 1 or 2, is characterized in that, in its raw material, the weight ratio of 2,4-dichlorobenzoperoxide, peroxidized t-butyl perbenzoate, triallylcyanurate is 0.8-1.2:0.7-1:0.3-0.5.
4. high performance fluorine rubber composite according to any one of claim 1-3, it is characterized in that, its raw material comprises following component by weight: viton 60-65 part, methyl vinyl phenyl silicon rubber 26-30 part, ethylene-acrylate rubber 10-13 part, polyvinylidene difluoride (PVDF) 7-8.5 part, polycaprolactone 6-8 part, expanding material 7-8 part, 2, 4-dichlorobenzoperoxide 0.8-1.1 part, peroxidized t-butyl perbenzoate 0.7-1 part, triallylcyanurate 0.35-0.42 part, zinc oxide 3.2-4 part, stearic acid 0.6-0.8 part, calcium hydroxide 5.8-7 part, gas-phase silica 12-17 part, Graphene 6.8-7.3 part, diatomite 5.5-6.2 part, boron nitride 12-16 part, molybdenumdisulphide 5.3-6 part, hydroxy silicon oil 3.2-4 part, anti-aging agent 1.8-2.2 part, promotor 1.3-1.6 part, silane coupling agent 3.1-3.5 part.
5. high performance fluorine rubber composite according to any one of claim 1-4, it is characterized in that, its raw material comprises following component by weight: viton 63 parts, 27 parts, methyl vinyl phenyl silicon rubber, ethylene-acrylate rubber 10 parts, polyvinylidene difluoride (PVDF) 8 parts, polycaprolactone 7.2 parts, expanding material 7.3 parts, 2, 4-dichlorobenzoperoxide 1 part, peroxidized t-butyl perbenzoate 0.85 part, triallylcyanurate 0.4 part, 3.6 parts, zinc oxide, stearic acid 0.7 part, 6 parts, calcium hydroxide, gas-phase silica 15 parts, Graphene 7 parts, 6 parts, diatomite, boron nitride 13 parts, molybdenumdisulphide 5.6 parts, hydroxy silicon oil 3.8 parts, 2 parts, anti-aging agent, promotor 1.4 parts, silane coupling agent 3.2 parts.
6. high performance fluorine rubber composite according to any one of claim 1-5, it is characterized in that, described expanding material is prepared according to following technique: add in 30-50 part ethanol by 5-10 part cerous hydroxide by weight, then 4-10 part vinyltrimethoxy silane is added, at 40-55 DEG C, stir 30-50min, filtration, washing, drying obtain modification cerous hydroxide; By weight by 100 parts of viton, 2-4 part γ-methacryloxypropyl trimethoxy silane, 3-10 part modification cerous hydroxide, 2-5 part methacrylic acid-2,2,2-trifluoro ethyl ester and 0.6-1.2 part dicumyl peroxide add in Haake rheometer, mixing 3-7min at 120-140 DEG C, then obtains described expanding material through dehydrated alcohol extracting 30-45h at 60-75 DEG C.
7. high performance fluorine rubber composite according to any one of claim 1-6, it is characterized in that, described expanding material is prepared according to following technique: add in 40 parts of ethanol by 8 parts of cerous hydroxides by weight, then 6.5 parts of vinyltrimethoxy silanes are added, at 50 DEG C, stir 45min, filtration, washing, drying obtain modification cerous hydroxide; By weight by 100 parts of viton, 3.2 parts of γ-methacryloxypropyl trimethoxy silane, 8 parts of modification cerous hydroxides, 3.5 parts of methacrylic acids-2,2,2-trifluoro ethyl ester and 1 part of dicumyl peroxide add in Haake rheometer, mixing 5min at 135 DEG C, then obtains described expanding material through dehydrated alcohol extracting 40h at 70 DEG C.
8. high performance fluorine rubber composite according to any one of claim 1-7, is characterized in that, described anti-aging agent is one or more the mixture in antioxidant MB, antioxidant A W, anti-aging agent RD, antioxidant MC.
9. high performance fluorine rubber composite according to any one of claim 1-8, is characterized in that, described promotor is one or more the mixture in accelerant CZ, vulkacit D, Vulcanization accelerator TMTD, altax.
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| CN115895145A (en) * | 2022-11-29 | 2023-04-04 | 芜湖集拓橡胶技术有限公司 | Low-pollution and fuel-resistant oil filler sheath formula |
| CN116082770A (en) * | 2022-11-14 | 2023-05-09 | 中国第一汽车股份有限公司 | Fluororubber composition and preparation method and application thereof |
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| CN106188992A (en) * | 2016-08-29 | 2016-12-07 | 宁波江东甬风工业设计有限公司 | A kind of preparation method of microcrystalline Cellulose modification fluorubber |
| US10889727B1 (en) | 2018-06-14 | 2021-01-12 | Southwire Company, Llc | Electrical cable with improved installation and durability performance |
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| CN113801411B (en) * | 2021-11-19 | 2022-02-15 | 北京橡胶工业研究设计院有限公司 | Wear-resistant fluororubber, application thereof and traceless sectional vulcanization method of sealing product |
| CN116082770A (en) * | 2022-11-14 | 2023-05-09 | 中国第一汽车股份有限公司 | Fluororubber composition and preparation method and application thereof |
| CN115895145A (en) * | 2022-11-29 | 2023-04-04 | 芜湖集拓橡胶技术有限公司 | Low-pollution and fuel-resistant oil filler sheath formula |
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