CN104045949A - Ultra-low temperature resistant fluororubber mixed rubber and preparation method thereof - Google Patents
Ultra-low temperature resistant fluororubber mixed rubber and preparation method thereof Download PDFInfo
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- CN104045949A CN104045949A CN201410233039.8A CN201410233039A CN104045949A CN 104045949 A CN104045949 A CN 104045949A CN 201410233039 A CN201410233039 A CN 201410233039A CN 104045949 A CN104045949 A CN 104045949A
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- viton
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/002—Methods
- B29B7/005—Methods for mixing in batches
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
- B29B7/7476—Systems, i.e. flow charts or diagrams; Plants
- B29B7/7495—Systems, i.e. flow charts or diagrams; Plants for mixing rubber
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
- B29B7/06—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices
- B29B7/10—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary
- B29B7/18—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary with more than one shaft
- B29B7/183—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary with more than one shaft having a casing closely surrounding the rotors, e.g. of Banbury type
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Abstract
The invention discloses an ultra-low temperature resistant fluororubber mixed rubber comprising the following components in parts by weight: 100 parts of fluororubber (A), 5-20 parts of an acid absorbing agent, 5-30 parts of a filler, 0.5-5 parts of a vulcanizing agent, 0.5-5 parts of a vulcanization accelerator and 1-15 parts of other auxiliary agents. The invention also discloses a preparation method of the ultra-low temperature resistant fluororubber mixed rubber; the preparation method comprises the steps: putting to raw fluororubber, the vulcanizing agent, the vulcanization accelerator and other auxiliary agents into an internal mixer, carrying out internal mixing for 8-12 min at the temperature of 100-130 DEG C, transferring the mixture in the internal mixer to an open mill, adjusting the roller distance of the open mill to 8-12 mm, and carrying out rubber milling; and successively adding the acid absorbing agent, the filler and other auxiliary agents into the fluororubber pre-mixed rubber prepared in the step (1) in the open mill, carrying out mill banding and plastication, packing the composite into triangular bags for 3-5 times, adjusting the roller distance to 2-5 mm, carrying out mill run for 2-5 times, and carrying out batch-off cooling to obtain the fluororubber mixed rubber.
Description
Technical field
The present invention relates to a kind of fluororubber compounded rubber of resistance to very low temperature and preparation method thereof.
Background technology
Viton refers to a kind of synthetic macromolecular elastomer that is connected with fluorine atom on the carbon atom of main chain or side chain.Viton molecular chain is all random structure, and degree of crystallinity is very low; Viton molecular chain all contains fluorine atom, due to the chemical property of fluorine atom uniqueness, has given viton a series of special performances.The characteristics such as that viton material has is heat-resisting, oil resistant, resistance to solvent, corrosion-resistant, powerful oxidation corrosion resistance agent, and there is good physical and mechanical properties, be widely used in many fields such as space flight and aviation, military project, national defence, automobile, petroleum and chemical industry.The property of viton is because the constructional feature that contains fluorine atom in its molecule determines, just because of this structure, also to viton, brought weak point, as elasticity, tearing toughness, low-temperature performance (temperature limit of brittleness is-30 ℃ of left and right), compression set, the defects such as rubber poor processability.But along with scientific and technical progress, the mankind, in exploring deep space and deep-sea activity, have higher requirement as thermotolerance, winter hardiness and chemicals-resistant to the performance of material.
Aspect fluororubber modified, do a large amount of and elaboration both at home and abroad, obtained very large achievement in research, improved greatly the performance deficiency of viton, expanded its utilization field.But also exist some shortcomings simultaneously.Mainly contain the following aspects: the blend of the viton of (1) different model can not need to consider the problems such as consistency between rubber and vulcanization system, but owing to being the rubber of same type, as all many-sides such as the low-temperature performance at viton, elasticity cannot be improved effectively.Due to because be all viton, just cannot realize the reduction on cost simultaneously.(2) now everybody about fluororubber modified research emphasis on viton and the better conventional rubber or specialty elastomer blend of other Performance Ratio.This modification is on the basis of possessing the original premium properties of viton, to its defect, effectively to supplement really, can also significantly reduce the production cost of viton simultaneously, expands its utilization field.But now the research about this respect much is all confined to improve the elasticity of viton, the improvement of the single performance such as processing characteristics, and for the improvement of viton low-temperature performance and to consider the research of a plurality of defects less.
CN101412835A has described a kind of viton, Silicone Rubber Blends, it is mainly by the lower temperature resistance and the processibility that add to improve viton of silicon rubber, but there is many deficiencies in this technical scheme, owing to having added viton and silicon rubber in co-mixing system, need different vulcanization systems, thereby increased the complicacy of cross-linked rubber system, and vulcanized article is easily separated afterwards in sulfuration, affected the package stability of viton, chemicals-resistant and the oil-proofness of viton have been had a strong impact on, after making rubber item, tensile strength and compression set poor-performing due to silicon rubber, affect the fundamental property of goods, its Application Areas is restricted, because silicon rubber gross rubber is easy to structurizing in storage process, so fluorine, Silicone Rubber Blends shortens storage period greatly.
Functional rubber auxiliary agent can be given the special physics of rubber item, chemical property, can be scattered among sizing material well, and have good economy, is the feasible a kind of technique means of modified rubber.In the low temperature resistant modification of fluororubber compounded rubber, add suitable low temperature resistant auxiliary agent and can realize the resistance to ultralow warm nature of viton, the Application Areas of viton is further expanded.
Summary of the invention
The invention provides a kind of fluororubber compounded rubber of resistance to very low temperature and preparation method thereof, it not only can resistance to-50 ℃ low temperature, and can chemical resistance excellent.
The present invention has adopted following technical scheme: a kind of fluororubber compounded rubber of resistance to very low temperature, and the component that it comprises following weight parts:
Viton (A) 100
Acid-acceptor 5～20
Filler 5～30
Vulcanizing agent 0.5～5
Vulcanization accelerator 0.5～5
Other auxiliary agents 1～15
Mooney viscosity (the ML of described viton (A)
1+10, 121 ℃) and be 10～190, molecular structure skeleton symbol is:
Wherein,
A, b, c are 1,2, the integer of 3....n;
D, e are 0,1,2, the integer of 3....n;
Rf is that carbonatoms is 1～8 perfluoroalkyl;
R1, R2, R3 be-H or-F;
R4 is-Br ,-CF
2br ,-CF
2cF
2br or-I ,-CF
2i ,-CF
2cF
2i.
Described acid-acceptor be in magnesium oxide, calcium oxide, zinc oxide, magnesium hydroxide, aluminium hydroxide and calcium hydroxide any one or more than one mix, the specific surface area of acid-acceptor is 5m
2/ g～20m
2/ g.
Described filler be in carbon black, white carbon black, barium sulfate, Calcium Fluoride (Fluorspan), Calucium Silicate powder, pure aluminium silicate, Magnesium Silicate q-agent, aluminum borate and glass fibre any one or more than one mix, wherein the specific surface area of carbon black, white carbon black is 5m
2/ g～200m
2/ g, barium sulfate, Calcium Fluoride (Fluorspan), Calucium Silicate powder, pure aluminium silicate, Magnesium Silicate q-agent, aluminum borate, glass fibre specific surface area are 5m
2/ g～20m
2/ g.
Described vulcanizing agent is vulcanizing agent (A), vulcanizing agent (B) or vulcanizing agent (C), vulcanizing agent (A) is diphenols vulcanizing agent, diphenols vulcanizing agent is hexafluoroisopropyli,ene-bis-(4-hydroxyl-benzene), Resorcinol, 2,2-bis-(4-hydroxy phenyl) propane and N, the two Chinese cassia tree fork of N-base-1, one or more mixing of 6-hexanediamine, vulcanizing agent (B) is peroxide vulcanizing agent, peroxide vulcanizing agent is 1, 1-bis(t-butylperoxy)-3, 3, 5-trimethyl-cyclohexane, 2, 5-dimethyl-2, 5-bis-(tert-butyl hydroperoxide) hexane, 2, 5-bis-(t-butyl peroxy)-2, 5-dimethyl-3-hexin, 3, 3, 5, 7, 7-pentamethyl--1, 2, 4-trioxane, 4, 4-bis-(tert-butyl hydroperoxide) n-butyl pentanoate, peroxidation two (2, 4-dichloro-benzoyl), peroxidation two (4-toluyl), two (tert-butyl peroxy) p-Diisopropylbenzene, benzoyl peroxide, dicumyl peroxide, ditertiary butyl peroxide, tert-butyl peroxide isopropyl benzene, tert-butyl hydroperoxide-3, 5, 5-tri-methyl hexanoic acid ester, peroxidized t-butyl perbenzoate, tert-butyl hydroperoxide carbonic acid-2-ethylhexyl, vulcanizing agent (C) is Diamines vulcanizing agent, Diamines vulcanizing agent is hexyl diamino carbamate, quadrol carbaminate, any one in cyclohexanediamine carbaminate, when wherein in viton (A) molecular structural formula, e is 0, select vulcanizing agent (A) or vulcanizing agent (C), when e is not 0, select vulcanizing agent (B), described vulcanization accelerator is vulcanization accelerator (A) or vulcanization accelerator (B), wherein vulcanization accelerator (A) is BPP, 1-phthalic imidine-4-butyl triphenyl bromo-phosphonium, one benzyl-3, 5 dimethyl chlorination pyridines, 5-nitrogen [4, 4] bromination nonane, 4-butyl ammonium hydrogen sulfate and one or more mixing wherein of tetrabutyl bromine ammonium, vulcanization accelerator (B) is cyanacrylate, tridecylene propyl group cyanurate, paraquinonedioxime, P, P-dibenzoyl paraquinonedioxime, maleimide, N-phenylene maleimide and N, one or more mixing in N-phenylene bismaleimides, if while wherein selecting vulcanizing agent (A), coordinate vulcanization accelerator (A), if while selecting vulcanizing agent (B), coordinate vulcanization accelerator (B).
Other described auxiliary agents be in releasing agent, pigment, low-temperature flexibility agent any one or more than one, wherein releasing agent be that lauric acid, stearylamide, amine hydroxybenzene, Lay mattress are loose, a kind of in polyethylene wax, carnauba wax, sodium stearate, lead stearate, wherein pigment be in red iron oxide, titanium oxide, nigrosine, cadmium yellow, titan yellow, chrome green, cobalt blue, cadmium red any one or more than one, wherein low-temperature flexibility agent is K type, Y type, D type and Z-type perfluoro polyether oil, and low-temperature flexibility agent preferred viscosities is 20～2000mPa.s.
A preparation method for the fluororubber compounded rubber of resistance to very low temperature, comprises the steps:
(1) in Banbury mixer, drop into crude fluororubber, vulcanizing agent, vulcanization accelerator and other auxiliary agents, at 100～130 ℃ of banburying 8～12min, again the mixture in Banbury mixer is transferred in mill, mill roll spacing is adjusted to 8～12mm and refines glue, in mill, refine after cementing bundle, mixture is obtained to viton premixing glue after rubber strainer filtration is cooling;
(2) the viton premixing glue of being prepared by step (1) adds successively acid-acceptor, filler and other auxiliary agents in mill, and bag roller is plasticated and played triangle bag 3～5 times, adjusts roll spacing 2～5mm thin-pass 2～5 times, the lower cooling fluororubber compounded rubber that obtains.
Compared with prior art, the beneficial effect of technical scheme of the present invention is as follows:
The selected viton (A) of the present invention adopts and in its molecular structure, adds the method for the group that contains ehter bond, make its molecule keep at low temperatures good kindliness, thereby improve its resistance to low temperature, both solved the shortcoming of the outstanding poor performance at low temperatures of common viton, keep again the oil resistant that common viton has, high temperature resistant, resistance to solvent, resistance to strong acid, powerful oxidation corrosion resistance agent, a series of premium propertiess such as fire-retardant, ageing-resistant, greatly expanded the Application Areas of viton.
Selected filler had both improved the mechanical property of viton, had improved again the dimensional stability of viton goods, had also reduced the production cost of viton goods.
Selected low-temperature flexibility agent is perfluor ether oil, and fluorine atom has replaced hydrogen atom, and the C-F key larger with bond energy replaced c h bond, makes PFPE have higher thermostability, oxidative stability, good unreactiveness and insulativity.PFPE also has low volatility, wider temperature use range and excellent viscosity-temperature characteristics.And there is good consistency with viton, thus guarantee its stable existence in viton goods, when improving viton processing characteristics, also greatly improved the winter hardiness of viton.
Embodiment
The invention provides a kind of fluororubber compounded rubber of resistance to very low temperature, the component that it comprises following weight parts:
Viton (A) 100
Acid-acceptor 5～20
Filler 5～30
Vulcanizing agent 0.5～5
Vulcanization accelerator 0.5～5
Other auxiliary agents 1～15
Mooney viscosity (the ML of described viton (A)
1+10, 121 ℃) and be 10～190, molecular structure skeleton symbol is:
Wherein,
A, b, c are 1,2, the integer of 3....n;
D, e are 0,1,2, the integer of 3....n;
Rf is that carbonatoms is 1～8 perfluoroalkyl;
R1, R2, R3 be-H or-F;
R4 is-Br ,-CF
2br ,-CF
2cF
2br or-I ,-CF
2i ,-CF
2cF
2i.Described acid-acceptor be in magnesium oxide, calcium oxide, zinc oxide, magnesium hydroxide, aluminium hydroxide and calcium hydroxide any one or more than one mix, the specific surface area of acid-acceptor is 5m
2/ g～20m
2/ g.Described filler be in carbon black, white carbon black, barium sulfate, Calcium Fluoride (Fluorspan), Calucium Silicate powder, pure aluminium silicate, Magnesium Silicate q-agent, aluminum borate and glass fibre any one or more than one mix, wherein the specific surface area of carbon black, white carbon black is 5m
2/ g～200m
2/ g, barium sulfate, Calcium Fluoride (Fluorspan), Calucium Silicate powder, pure aluminium silicate, Magnesium Silicate q-agent, aluminum borate, glass fibre specific surface area are 5m
2/ g～20m
2/ g.Described vulcanizing agent is vulcanizing agent (A), vulcanizing agent (B) or vulcanizing agent (C), vulcanizing agent (A) is diphenols vulcanizing agent, diphenols vulcanizing agent is hexafluoroisopropyli,ene-bis-(4-hydroxyl-benzene), Resorcinol, 2,2-bis-(4-hydroxy phenyl) propane and N, the two Chinese cassia tree fork of N-base-1, one or more mixing of 6-hexanediamine, vulcanizing agent (B) is peroxide vulcanizing agent, peroxide vulcanizing agent is 1, 1-bis(t-butylperoxy)-3, 3, 5-trimethyl-cyclohexane, 2, 5-dimethyl-2, 5-bis-(tert-butyl hydroperoxide) hexane, 2, 5-bis-(t-butyl peroxy)-2, 5-dimethyl-3-hexin, 3, 3, 5, 7, 7-pentamethyl--1, 2, 4-trioxane, 4, 4-bis-(tert-butyl hydroperoxide) n-butyl pentanoate, peroxidation two (2, 4-dichloro-benzoyl), peroxidation two (4-toluyl), two (tert-butyl peroxy) p-Diisopropylbenzene, benzoyl peroxide, dicumyl peroxide, ditertiary butyl peroxide, tert-butyl peroxide isopropyl benzene, tert-butyl hydroperoxide-3, 5, 5-tri-methyl hexanoic acid ester, peroxidized t-butyl perbenzoate, tert-butyl hydroperoxide carbonic acid-2-ethylhexyl, vulcanizing agent (C) is Diamines vulcanizing agent, Diamines vulcanizing agent is hexyl diamino carbamate, quadrol carbaminate, any one in cyclohexanediamine carbaminate, when wherein in viton (A) molecular structural formula, e is 0, select vulcanizing agent (A) or vulcanizing agent (C), when e is not 0, select vulcanizing agent (B), described vulcanization accelerator is vulcanization accelerator (A) or vulcanization accelerator (B), wherein vulcanization accelerator (A) is BPP, 1-phthalic imidine-4-butyl triphenyl bromo-phosphonium, one benzyl-3, 5 dimethyl chlorination pyridines, 5-nitrogen [4, 4] bromination nonane, 4-butyl ammonium hydrogen sulfate and one or more mixing wherein of tetrabutyl bromine ammonium, vulcanization accelerator (B) is cyanacrylate, tridecylene propyl group cyanurate, paraquinonedioxime, P, P-dibenzoyl paraquinonedioxime, maleimide, N-phenylene maleimide and N, one or more mixing in N-phenylene bismaleimides, if while wherein selecting vulcanizing agent (A), coordinate vulcanization accelerator (A), if while selecting vulcanizing agent (B), coordinate vulcanization accelerator (B).Other described auxiliary agents be in releasing agent, pigment, low-temperature flexibility agent any one or more than one, wherein releasing agent be that lauric acid, stearylamide, amine hydroxybenzene, Lay mattress are loose, a kind of in polyethylene wax, carnauba wax, sodium stearate, lead stearate, wherein pigment be in red iron oxide, titanium oxide, nigrosine, cadmium yellow, titan yellow, chrome green, cobalt blue, cadmium red any one or more than one, wherein low-temperature flexibility agent is K type, Y type, D type and Z-type perfluoro polyether oil, and low-temperature flexibility agent preferred viscosities is 20～2000mPa.s.
The invention also discloses a kind of preparation method of the fluororubber compounded rubber of resistance to very low temperature, comprise the steps: that (1) drop into crude fluororubber, vulcanizing agent, vulcanization accelerator and other auxiliary agents in Banbury mixer, at 100～130 ℃ of banburying 8～12min, again the mixture in Banbury mixer is transferred in mill, mill roll spacing is adjusted to 8～12mm and refines glue, in mill, refine after cementing bundle, mixture is obtained to viton premixing glue after rubber strainer filtration is cooling; (2) the viton premixing glue of being prepared by step (1) adds successively acid-acceptor, filler and other auxiliary agents in mill, and bag roller is plasticated and played triangle bag 3～5 times, adjusts roll spacing 2～5mm thin-pass 2～5 times, the lower cooling fluororubber compounded rubber that obtains.
Below by embodiment, further illustrate the present invention:
Embodiment 1
Viton (A) 100
Magnesium oxide 3
Calcium hydroxide 6
Spray carbon black 7
N, the two Chinese cassia tree fork of N-base-1,6-hexanediamine 2.5
Low-temperature flexibility agent 8
Mooney viscosity (the ML of described viton (A)
1+10, 121 ℃) and be 10～190, molecular structure skeleton symbol is:
Wherein,
A, b, c are 1,2, the integer of 3....n;
D, e are 0,1,2, the integer of 3....n;
Rf is that carbonatoms is 1～8 perfluoroalkyl;
R1, R2, R3 be-H or-F;
R4 is-Br ,-CF
2br ,-CF
2cF
2br or-I ,-CF
2i ,-CF
2cF
2i,
Low-temperature flexibility agent is K type, Y type, D type and Z-type perfluoro polyether oil, and low-temperature flexibility agent preferred viscosities is 20～2000mPa.s.
Embodiment 2
Viton (A) 100
Magnesium oxide 3
Calcium hydroxide 6
Spray carbon black 20
BPP 1.2
2,2-bis-(4-hydroxy phenyl) propane 2
N, the two Chinese cassia tree fork of N-base-1,6-hexanediamine 0.3
Mooney viscosity (the ML of described viton (A)
1+10, 121 ℃) and be 10～190, molecular structure skeleton symbol is:
Wherein,
A, b, c are 1,2, the integer of 3....n;
D, e are 0,1,2, the integer of 3....n;
Rf is that carbonatoms is 1～8 perfluoroalkyl;
R1, R2, R3 be-H or-F;
R4 is-Br ,-CF
2br ,-CF
2cF
2br or-I ,-CF
2i ,-CF
2cF
2i,
Low-temperature flexibility agent is K type, Y type, D type and Z-type perfluoro polyether oil, and low-temperature flexibility agent preferred viscosities is 20～2000mPa.s.
Embodiment 3
Viton (A) 100
Magnesium oxide 3
Calcium hydroxide 6
Spray carbon black 10
Calcium Fluoride (Fluorspan) 20
BPP 1.2
2,2-bis-(4-hydroxy phenyl) propane 2.5
Mooney viscosity (the ML of described viton (A)
1+10, 121 ℃) and be 10～190, molecular structure skeleton symbol is:
Wherein,
A, b, c are 1,2, the integer of 3....n;
D, e are 0,1,2, the integer of 3....n;
Rf is that carbonatoms is 1～8 perfluoroalkyl;
R1, R2, R3 be-H or-F;
R4 is-Br ,-CF
2br ,-CF
2cF
2br or-I ,-CF
2i ,-CF
2cF
2i,
Low-temperature flexibility agent is K type, Y type, D type and Z-type perfluoro polyether oil, and low-temperature flexibility agent preferred viscosities is 20～2000mPa.s.
Embodiment 4
Viton (A) 100
Magnesium oxide 3
Calcium hydroxide 2
Spray carbon black 45
BPP 0.8
Hexafluoroisopropyli,ene-bis-(4-hydroxyl-benzene) 2.2
Low-temperature flexibility agent 10
Mooney viscosity (the ML of described viton (A)
1+10, 121 ℃) and be 10～190, molecular structure skeleton symbol is:
Wherein,
A, b, c are 1,2, the integer of 3....n;
D, e are 0,1,2, the integer of 3....n;
Rf is that carbonatoms is 1～8 perfluoroalkyl;
R1, R2, R3 be-H or-F;
R4 is-Br ,-CF
2br ,-CF
2cF
2br or-I ,-CF
2i ,-CF
2cF
2i,
Low-temperature flexibility agent is K type, Y type, D type and Z-type perfluoro polyether oil, and low-temperature flexibility agent preferred viscosities is 20～2000mPa.s.
Embodiment 5
Viton (A) 100
Magnesium oxide 10
Calcium hydroxide 2
Spray carbon black 20
Tridecylene propyl group cyanurate 2
Dicumyl peroxide 2
Low-temperature flexibility agent 5
Mooney viscosity (the ML of described viton (A)
1+10, 121 ℃) and be 10～190, molecular structure skeleton symbol is:
Wherein,
A, b, c are 1,2, the integer of 3....n;
D, e are 0,1,2, the integer of 3....n;
Rf is that carbonatoms is 1～8 perfluoroalkyl;
R1, R2, R3 be-H or-F;
R4 is-Br ,-CF
2br ,-CF
2cF
2br or-I ,-CF
2i ,-CF
2cF
2i,
Low-temperature flexibility agent is K type, Y type, D type and Z-type perfluoro polyether oil, and low-temperature flexibility agent preferred viscosities is 20～2000mPa.s.
Embodiment 6
Viton (A) 100
Magnesium oxide 10
Spray carbon black 10
Tridecylene propyl group cyanurate 2
Benzoyl peroxide 3
Comparative example
Fluororubber 246 100
Magnesium oxide 3
Calcium hydroxide 6
Spray carbon black 20
BPP 0.8
Hexafluoroisopropyli,ene-bis-(4-hydroxyl-benzene) 2.2
Mooney viscosity (the ML of described viton (A)
1+10, 121 ℃) and be 10～190, molecular structure skeleton symbol is:
Wherein,
A, b, c are 1,2, the integer of 3....n;
D, e are 0,1,2, the integer of 3....n;
Rf is that carbonatoms is 1～8 perfluoroalkyl;
R1, R2, R3 be-H or-F;
R4 is-Br ,-CF
2br ,-CF
2cF
2br or-I ,-CF
2i ,-CF
2cF
2i, low-temperature flexibility agent is K type, Y type, D type and Z-type perfluoro polyether oil, low-temperature flexibility agent preferred viscosities is 20～2000mPa.s.
The preparation method of the fluororubber compounded rubber in above-described embodiment and comparative example, comprises the steps:
(1) in Banbury mixer, drop into crude fluororubber, vulcanizing agent, vulcanization accelerator and other auxiliary agents, at 100～130 ℃ of banburying 8～12min, again the mixture in Banbury mixer is transferred in mill, mill roll spacing is adjusted to 8～12mm and refines glue, in mill, refine after cementing bundle, mixture is obtained to viton premixing glue after rubber strainer filtration is cooling;
(2) the viton premixing glue of being prepared by step (1) adds successively acid-acceptor, filler and other auxiliary agents in mill, and bag roller is plasticated and played triangle bag 3～5 times, adjusts roll spacing 2～5mm thin-pass 2～5 times, the lower cooling fluororubber compounded rubber that obtains.
The performance test results of the fluororubber compounded rubber of resistance to very low temperature
Claims (6)
1. the fluororubber compounded rubber of resistance to very low temperature, the component that it comprises following weight parts:
Viton (A) 100
Acid-acceptor 5～20
Filler 5～30
Vulcanizing agent 0.5～5
Vulcanization accelerator 0.5～5
Other auxiliary agents 1～15
According to the fluororubber compounded rubber of resistance to very low temperature under claim 1, it is characterized in that the mooney viscosity (ML of described viton (A)
1+10, 121 ℃) and be 10～190, molecular structure skeleton symbol is:
Wherein,
A, b, c are 1,2, the integer of 3....n;
D, e are 0,1,2, the integer of 3....n;
Rf is that carbonatoms is 1～8 perfluoroalkyl;
R1, R2, R3 be-H or-F;
R4 is-Br ,-CF
2br ,-CF
2cF
2br or-I ,-CF
2i ,-CF
2cF
2i.
2. the fluororubber compounded rubber of resistance to very low temperature according to claim 1, it is characterized in that described acid-acceptor be in magnesium oxide, calcium oxide, zinc oxide, magnesium hydroxide, aluminium hydroxide and calcium hydroxide any one or more than one mix, the specific surface area of acid-acceptor is 5m
2/ g～20m
2/ g.
3. the fluororubber compounded rubber of resistance to very low temperature according to claim 1, it is characterized in that described filler be in carbon black, white carbon black, barium sulfate, Calcium Fluoride (Fluorspan), Calucium Silicate powder, pure aluminium silicate, Magnesium Silicate q-agent, aluminum borate and glass fibre any one or more than one mix, wherein the specific surface area of carbon black, white carbon black is 5m
2/ g～200m
2/ g, barium sulfate, Calcium Fluoride (Fluorspan), Calucium Silicate powder, pure aluminium silicate, Magnesium Silicate q-agent, aluminum borate, glass fibre specific surface area are 5m
2/ g～20m
2/ g.
4. the fluororubber compounded rubber of resistance to very low temperature according to claim 1, it is characterized in that described vulcanizing agent is vulcanizing agent (A), vulcanizing agent (B) or vulcanizing agent (C), vulcanizing agent (A) is diphenols vulcanizing agent, diphenols vulcanizing agent is hexafluoroisopropyli,ene-bis-(4-hydroxyl-benzene), Resorcinol, 2,2-bis-(4-hydroxy phenyl) propane and N, the two Chinese cassia tree fork of N-base-1, one or more mixing of 6-hexanediamine, vulcanizing agent (B) is peroxide vulcanizing agent, peroxide vulcanizing agent is 1, 1-bis(t-butylperoxy)-3, 3, 5-trimethyl-cyclohexane, 2, 5-dimethyl-2, 5-bis-(tert-butyl hydroperoxide) hexane, 2, 5-bis-(t-butyl peroxy)-2, 5-dimethyl-3-hexin, 3, 3, 5, 7, 7-pentamethyl--1, 2, 4-trioxane, 4, 4-bis-(tert-butyl hydroperoxide) n-butyl pentanoate, peroxidation two (2, 4-dichloro-benzoyl), peroxidation two (4-toluyl), two (tert-butyl peroxy) p-Diisopropylbenzene, benzoyl peroxide, dicumyl peroxide, ditertiary butyl peroxide, tert-butyl peroxide isopropyl benzene, tert-butyl hydroperoxide-3, 5, 5-tri-methyl hexanoic acid ester, peroxidized t-butyl perbenzoate, tert-butyl hydroperoxide carbonic acid-2-ethylhexyl, vulcanizing agent (C) is Diamines vulcanizing agent, Diamines vulcanizing agent is hexyl diamino carbamate, quadrol carbaminate, any one in cyclohexanediamine carbaminate, when wherein in viton (A) molecular structural formula, e is 0, select vulcanizing agent (A) or vulcanizing agent (C), when e is not 0, select vulcanizing agent (B), described vulcanization accelerator is vulcanization accelerator (A) or vulcanization accelerator (B), wherein vulcanization accelerator (A) is BPP, 1-phthalic imidine-4-butyl triphenyl bromo-phosphonium, one benzyl-3, 5 dimethyl chlorination pyridines, 5-nitrogen [4, 4] bromination nonane, 4-butyl ammonium hydrogen sulfate and one or more mixing wherein of tetrabutyl bromine ammonium, vulcanization accelerator (B) is cyanacrylate, tridecylene propyl group cyanurate, paraquinonedioxime, P, P-dibenzoyl paraquinonedioxime, maleimide, N-phenylene maleimide and N, one or more mixing in N-phenylene bismaleimides, if while wherein selecting vulcanizing agent (A), coordinate vulcanization accelerator (A), if while selecting vulcanizing agent (B), coordinate vulcanization accelerator (B).
5. the fluororubber compounded rubber of resistance to very low temperature according to claim 1, it is characterized in that other described auxiliary agents are releasing agent, pigment, in low-temperature flexibility agent any one or more than one, wherein releasing agent is lauric acid, stearylamide, amine hydroxybenzene, Lay mattress is loose, polyethylene wax, carnauba wax, sodium stearate, a kind of in lead stearate, wherein pigment is red iron oxide, titanium oxide, nigrosine, cadmium yellow, titan yellow, chrome green, cobalt blue, any one in cadmium red or more than one, wherein low-temperature flexibility agent is K type, Y type, D type and Z-type perfluoro polyether oil, low-temperature flexibility agent preferred viscosities is 20～2000mPa.s.
6. a preparation method for the fluororubber compounded rubber of resistance to very low temperature, comprises the steps:
(1) in Banbury mixer, drop into crude fluororubber, vulcanizing agent, vulcanization accelerator and other auxiliary agents, at 100～130 ℃ of banburying 8～12min, again the mixture in Banbury mixer is transferred in mill, mill roll spacing is adjusted to 8～12mm and refines glue, in mill, refine after cementing bundle, mixture is obtained to viton premixing glue after rubber strainer filtration is cooling;
(2) the viton premixing glue of being prepared by step (1) adds successively acid-acceptor, filler and other auxiliary agents in mill, and bag roller is plasticated and played triangle bag 3～5 times, adjusts roll spacing 2～5mm thin-pass 2～5 times, the lower cooling fluororubber compounded rubber that obtains.
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| CN108641241A (en) * | 2018-04-20 | 2018-10-12 | 镇江科特新材料有限公司 | A kind of modified fluorubber and preparation method thereof |
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| CN113717481A (en) * | 2021-07-26 | 2021-11-30 | 青岛凯通密封件有限公司 | Fluororubber banburying process |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103772859A (en) * | 2014-01-24 | 2014-05-07 | 中昊晨光化工研究院有限公司 | Modified fluororubber rubber compound and preparation method thereof |
| CN103788363A (en) * | 2013-12-25 | 2014-05-14 | 上海艾肯化工科技有限公司 | Method for preparing perfluoropolyether with high molecular weight |
-
2014
- 2014-05-29 CN CN201410233039.8A patent/CN104045949A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103788363A (en) * | 2013-12-25 | 2014-05-14 | 上海艾肯化工科技有限公司 | Method for preparing perfluoropolyether with high molecular weight |
| CN103772859A (en) * | 2014-01-24 | 2014-05-07 | 中昊晨光化工研究院有限公司 | Modified fluororubber rubber compound and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 王珍 等: ""氟醚橡胶的结构和高低温性能研究"", 《世界橡胶工业》 * |
| 肖风亮: ""新型氟弹性体在航空密封领域内的应用进展（上）"", 《世界橡胶工业》 * |
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