CN104086902A - High-temperature-resistant rubber sealing ring for automobiles - Google Patents
High-temperature-resistant rubber sealing ring for automobiles Download PDFInfo
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- CN104086902A CN104086902A CN201410315258.0A CN201410315258A CN104086902A CN 104086902 A CN104086902 A CN 104086902A CN 201410315258 A CN201410315258 A CN 201410315258A CN 104086902 A CN104086902 A CN 104086902A
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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 discloses a high-temperature-resistant rubber sealing ring for automobiles. The high-temperature-resistant rubber sealing ring comprises the following raw materials in parts by weight: 70-90 parts of ethylene-propylene-diene-terpolymer rubber, 10-30 parts of chloroprene rubber, 1-4 parts of an anti-aging agent, 0.8-1.5 parts of active zinc oxide, 0.2-0.4 part of magnesium oxide, 0.5-1.0 part of calcium oxide, 0.6-1.5 parts of butyltin mercaptide, 30-40 parts of modified kaolin, 10-15 parts of magnesium methacrylate, 1-3 parts of a promoter, 6-10 parts of soybean oil, 1-2 parts of ethyl methacrylate, 40-80 parts of paraffin oil, 0.2-0.5 part of triallyl phosphate, 1.0-1.5 parts of a crosslinking agent BIBP, 0.5-1.2 parts of an assistant crosslinking agent TAIC, 0.3-0.5 part of microcrystalline wax, 2-3 parts of a vulcanizing agent and 0.5-1 part of phthalic anhydride. The sealing ring disclosed by the invention has strong weather resistance, corrosion resistance and ozone resistance, and can be suitable for being used as the high-temperature-resistant rubber sealing ring for the automobiles.
Description
Technical field
The present invention relates to rubber technology field, relate in particular to a kind of automobile high-temperature resistant rubber sealing-ring.
Background technology
Sealing-ring is the important composition element of rubber product, at present outside automobile, electrical equipment and electronics, office apparatus three large field application, also, in a large number for high-tech areas such as building, medical treatment, foodstuffs industry and Aeronautics and Astronautics, the elastomeric material of different field need to have different character.
Sealing-ring answers that rebound resilience is high, hardness is moderate, and compression set is little; There is good mechanical property: as tensile strength, determine tensile strength, elongation at break reaches certain standard; Have wear resistance, tear strength is strong; There is stable chemical nature, adapt to working medium ability strong, be not easy to produce swelling, decomposition, sclerosis; There is certain weathering resistance.The feature of ageing-resistant, corrosion-resistant, water-fast steam performance that terpolymer EP rubber has, hot water resistance energy and the high fillibility of low density, it has at present been the important materials of making sealing-ring, but blemish in an otherwise perfect thing is not oil resistant, slow with poor adhesion, the vulcanization rate of other materials of terpolymer EP rubber, there is certain deficiency in the sealing-ring of making, the resistance toheat of the sealing-ring on existing market and resistance to chemical corrosion are generally not good, easily cause premature aging and lose function, cause scrapping of rubber seal, increase cost.
Summary of the invention
In order to solve the technical problem existing in background technology, the present invention proposes a kind of automobile high-temperature resistant rubber sealing-ring, improve physical strength, chemical resistance, ozone resistance, weathering resistance and the thermotolerance of rubber hose, obtained the automobile high-temperature resistant rubber sealing-ring of good combination property.
The present invention is achieved by the following technical solutions: a kind of automobile high-temperature resistant rubber sealing-ring, its raw materials by weight portion comprises: terpolymer EP rubber 70-90 part, chloroprene rubber 10-30 part, anti-aging agent 1-4 part, active oxidation zinc 0.8-1.5 part, magnesium oxide 0.2-0.4 part, calcium oxide 0.5-1.0 part, butanethiol tin 0.6-1.5 part, modified kaolin 30-40 part, magnesinm methacrylate 10-15 part, promotor 1-3 part, soybean oil 6-10 part, β-dimethyl-aminoethylmethacrylate 1-2 part, paraffin oil 40-80 part, triallyl phosphoesterase 30 .2-0.5 part, crosslinking agent B IBP1.0-1.5 part, additional crosslinker TAIC0.5-1.2 part, Microcrystalline Wax 0.3-0.5 part, vulcanizing agent 2-3 part, Tetra hydro Phthalic anhydride 0.5-1 part,
Proportioning according to above-mentioned each raw material, is prepared according to following steps:
S1, mill is heated to 30-35 ℃, roll spacing is made as 0.2-0.8mm, and terpolymer EP rubber and chloroprene rubber are added to the 10-15min that plasticates in mill simultaneously, then through binder removal, compressing tablet, lower, cool to room temperature and park 4-5h and obtain broken-(down)rubber one time;
S2, mill is heated to 25-30 ℃, roll spacing is made as 0.4-0.6mm, and the broken-(down)rubber obtaining in S1 is added to the mill 10-20min that plasticates, then through binder removal, compressing tablet, lower, cool to room temperature and park 3-5h and obtain secondary broken-(down)rubber;
S3, the temperature of mill is made as to room temperature, roll spacing is made as 0.5-1mm, and the secondary broken-(down)rubber obtaining in S2 is added to the mill 15-20min that plasticates, then through binder removal, compressing tablet, lower, cool to room temperature and park 5-10h and obtain broken-(down)rubber three times;
S4, Banbury mixer is warming up to 120-140 ℃, roll spacing is made as 0.5-1mm, adds three broken-(down)rubbers described in S3, and banburying 2-5min is by binder removal, cool to room temperature and park 8-15h and obtain broken-(down)rubber;
S5, Banbury mixer is warming up to 80-90 ℃, roll spacing rises to 100-115 ℃ by temperature after being adjusted into and adding the mixing 2-5min of the broken-(down)rubber described in S4 after 3-8mm, add successively modified kaolin, magnesium oxide and active zinc flower, after mixing 1-2min, temperature is risen to 120-135 ℃, then add soybean oil simultaneously, magnesinm methacrylate, the mixing 1-2min of β-dimethyl-aminoethylmethacrylate and paraffin oil, then add anti-aging agent simultaneously, after the mixing 2-5min of Microcrystalline Wax, add Tetra hydro Phthalic anhydride that temperature is risen to 140-165 ℃, then add successively calcium oxide, butanethiol tin, triallyl phosphoric acid ester, crosslinking agent B IBP and additional crosslinker TAIC, after mixing 2-5min, add vulcanizing agent and promotor, after mixing 2-5min binder removal, put into mill thin-pass and obtain rubber unvulcanizate 5-8 time,
S6, pack the rubber unvulcanizate described in S5 into mould, at 15-20MPa pressure, at 145-150 ℃ of temperature, sulfuration 5-20min, obtains described automobile high-temperature resistant rubber sealing-ring after die sinking.
Preferably, its raw materials by weight portion comprises: terpolymer EP rubber 75-85 part, chloroprene rubber 15-25 part, anti-aging agent 2-3 part, active oxidation zinc 1.0-1.4 part, magnesium oxide 0.23-0.34 part, calcium oxide 0.6-0.9 part, butanethiol tin 0.7-1.4 part, modified kaolin 35-39 part, magnesinm methacrylate 12-14 part, promotor 1.2-2.8 part, soybean oil 7-8.5 part, β-dimethyl-aminoethylmethacrylate 1.2-1.8 part, paraffin oil 45-75 part, triallyl phosphoesterase 30 .22-0.4 part, crosslinking agent B IBP1.2-1.45 part, additional crosslinker TAIC0.7-1.0 part, Microcrystalline Wax 0.32-0.4 part, vulcanizing agent 2.2-2.8 part, Tetra hydro Phthalic anhydride 0.7-0.9 part.
Preferably, its raw materials by weight portion comprises: 80 parts of terpolymer EP rubbers, 20 parts of chloroprene rubbers, 2.5 parts, anti-aging agent, 1.2 parts, active oxidation zinc, 0.33 part, magnesium oxide, 0.7 part, calcium oxide, 0.9 part, butanethiol tin, 38 parts of modified kaolins, 13 parts of magnesinm methacrylates, 1.8 parts of promotor, 8 parts of soybean oil, 1.4 parts of β-dimethyl-aminoethylmethacrylates, 50 parts of paraffin oils, triallyl phosphoesterase 30 .28 part, crosslinking agent B IBP1.3 part, additional crosslinker TAIC0.9 part, 0.35 part of Microcrystalline Wax, 2.5 parts of vulcanizing agents, 0.8 part of Tetra hydro Phthalic anhydride.
Preferably, the roller speed of plasticating in S1, S2 and S3 is 15-25r/min, and roller speed ratio is 1:1.1-1.4.
Preferably, in S4, filling glue amount is 30-55%, and pressure is 0.2-0.7MPa.
Preferably, described anti-aging agent be the mixture of anti-aging agent RD, MB, DNP, 4010NA and by weight RD:MB:DPN be 2:1:1.
Preferably, described modified kaolin is coupling agent and tensio-active agent and uses modification; Most preferably, described coupling agent is any one or the multiple composition in A187, A1100, A174; Described tensio-active agent is glycol ether, PEG400, any one in polyethers 330N or multiple composition.
Preferably, in S5, Banbury mixer is warming up to 81-89 ℃, roll spacing rises to 103-110 ℃ by temperature after being adjusted into and adding the mixing 2.5-4.5min of the broken-(down)rubber described in S4 after 3.3-7.8mm, add successively modified kaolin, magnesium oxide and active zinc flower, after mixing 1.1-1.7min, temperature is risen to 126-131 ℃, then add soybean oil simultaneously, magnesinm methacrylate, the mixing 1.2-1.8min of β-dimethyl-aminoethylmethacrylate and paraffin oil, then add anti-aging agent simultaneously, after the mixing 2.5-4.7min of Microcrystalline Wax, add Tetra hydro Phthalic anhydride that temperature is risen to 146-163 ℃, then add successively calcium oxide, butanethiol tin, triallyl phosphoric acid ester, crosslinking agent B IBP and additional crosslinker TAIC, after mixing 2.4-4.5min, add vulcanizing agent and promotor, after mixing 2.1-4.7min binder removal, put into mill thin-pass and obtain rubber unvulcanizate 6-7 time.
Preferably, in S5, Banbury mixer is warming up to 85 ℃, roll spacing rises to 108 ℃ by temperature after being adjusted into and adding the mixing 4min of the broken-(down)rubber described in S4 after 5mm, add successively modified kaolin, magnesium oxide and active zinc flower, after mixing 1.5min, temperature is risen to 128 ℃, then add soybean oil simultaneously, magnesinm methacrylate, the mixing 1.7min of β-dimethyl-aminoethylmethacrylate and paraffin oil, then add anti-aging agent simultaneously, after the mixing 3.5min of Microcrystalline Wax, add Tetra hydro Phthalic anhydride that temperature is risen to 148 ℃, then add successively calcium oxide, butanethiol tin, triallyl phosphoric acid ester, crosslinking agent B IBP and additional crosslinker TAIC, after mixing 3min, add vulcanizing agent and promotor, after mixing 3min binder removal, put into mill thin-pass and obtain rubber unvulcanizate 6 times.
Preferably, in S6, pack the rubber unvulcanizate described in S5 into mould, at 15.3-1.92MPa pressure, at 142-149 ℃ of temperature, sulfuration 6-17min, obtains described automobile high-temperature resistant rubber sealing-ring after die sinking; Most preferably, in S6, pack the rubber unvulcanizate described in S5 into mould, at 18MPa pressure, at 146 ℃ of temperature, sulfuration 15min, obtains described automobile high-temperature resistant rubber sealing-ring after die sinking.
In the present invention, selecting terpolymer EP rubber is rubber, and added chloroprene rubber, can make the performance complement of two kinds of rubber, oil-proofness, flame resistivity and the adhesive while of improving terpolymer EP rubber also improved the ozone resistance of chloroprene rubber, heat-resisting, resistance to steam, the low temperature resistant performance such as subdue, the mixture that utilizes RD, MB, DNP, 4010NA is anti-aging agent, anti-aging agent RD has splendid protective benefits to thermo-oxidative ageing, and DNP has superior ageing-resistant and Weather performance, and the effect that improves other anti-aging agent usefulness, also with thering is better heat-resisting ageing-resisting performance, improve the ageing-resistant performance of sealing-ring with RD, MB, 4010NA, add active zinc flower, both accelerated vulcanization rate and also improved state of vulcanization, reduced the consumption of vulcanizing agent, simultaneously as activator, improved the ageing-resistant performance of sealing-ring, added magnesium oxide, not only improved active but also improved the scorching quality of sizing material, added calcium oxide and carried the highly active while and can also absorb the moisture producing in rubber vulcanization process, prevented that sizing material from bubbling, and affects the performance of sizing material, having added modified kaolin is strengthening agent, what adopt is the method for modifying of coupling agent and tensio-active agent use, kaolin after modification has stronger effect of contraction to ethylene-propylene-diene monomer xanthan molecule, the cross-linked rubber obtaining has the large indeformable ability of opposing external force, the kaolin of modification can make cross-linked rubber obtain suitable cross-linking density, improve inner structure, reduce the weak link of cross-linked rubber inside, stop and slowed down crackle or the breach in material and when stressed, expand cracking rapidly and cause destroying, make cross-linked rubber there is large tensile yield, tensile strength and the tear strength of rubber have been improved, improved the over-all properties of rubber, add stablizer butanethiol tin, improved the stability of sulfuration, add triallyl phosphoric acid ester, improved the curability of peroxide vulcanizing agent, described vulcanizing agent is organic amine vulcanizing agent, and the cross-linked rubber physical strength that obtains is large, compression set is little, still can keep physical and mechanical properties after high temperature long-term aging, the sealing-ring good sealing effect obtaining, and duration of service is long, adopted the method for multi stage mastication, reduced molecular weight and the viscosity of terpolymer EP rubber and chloroprene rubber, improved its plasticity-, and obtain suitable mobility, to meet needs mixing and that moulding is further processed, when mixing, controlled reinforced order, according to the feature of sulfuration, selected suitable curing temperature and curing time, guarantee to prevent under the crosslinked prerequisite of rubber molecule rubber molecular chain too much fracture and the ruckbildung that causes.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail; should understand; embodiment is only for the present invention is described, rather than for the present invention is limited, and any modification of making on basis of the present invention, is equal to replacement etc. all in protection scope of the present invention.
Automobile described in the present invention high-temperature resistant rubber sealing-ring, its raw materials by weight portion terpolymer EP rubber can also be 71, 72, 73.5, 74, 76, 77, 77.8, 79, 81, 82, 83, 84, 86, 87, 88, 89 parts, chloroprene rubber can also be 11, 12, 13.6, 14, 16, 17.2, 18, 19, 21, 22, 23, 24, 26, 27, 28, 29 parts, anti-aging agent can also be 1.1, 1.3, 1.4, 1.5, 1.6, 1.8, 1.9, 2.1, 2.2, 2.3, 2.4, 2.7, 2.8, 2.9, 3.1, 3.2, 3.3, 3.4, 3.5, 3.7, 3.8, 3.9 part, active oxidation zinc can also be 0.9, 1.1, 1.3 part, magnesium oxide can also be 0.22, 0.24, 0.25, 0.26, 0.28, 0.29, 0.3, 0.31, 0.35, 0.36, 0.38, 0.39 part, calcium oxide can also be 0.8 part, butanethiol tin can also be 0.8, 1.0, 1.1, 1.2, 1.3 part, modified kaolin can also be 31, 32, 33, 34.2, 36, 37, 39.4 parts, magnesinm methacrylate can also be 11, 11.5, 12.6 parts, promotor can also be 1.1, 1.4, 1.5, 1.9, 2.0, 2.1, 2.4, 2.5, 2.6, 2.9 part, soybean oil can also be 6.2, 7.4, 8.9, 9.3 part, β-dimethyl-aminoethylmethacrylate can also be 1.1, 1.3, 1.5, 1.6, 1.7, 1.9 part, paraffin oil can also be 41, 42, 43.9, 46, 47, 48.2, 51, 52, 54, 55, 57.6, 59, 60, 61.3, 63, 64, 66.7, 68, 68.7, 70, 72, 74, 76, 78, 79 parts, triallyl phosphoric acid ester can also be 0.3, 0.35, 0.44 part, crosslinking agent B IBP can also be 1.1, 1.4 part, additional crosslinker TAIC can also be 0.6, 0.8, 1.1 part, Microcrystalline Wax can also be 0.33, 0.46, 0.48 part, vulcanizing agent can also be 2.1, 2.3, 2.4, 2.6, 2.7, 2.9 part, Tetra hydro Phthalic anhydride can also be 0.6 part.
A kind of automobile high-temperature resistant rubber sealing-ring disclosed in this invention, in each embodiment, the parts by weight of component are as shown in table 1:
Table 1 is the parts by weight that in each embodiment, automobile is used high-temperature resistant rubber sealing-ring component
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Terpolymer EP rubber | 72 | 88 | 80 |
| Chloroprene rubber | 28 | 12 | 20 |
| Anti-aging agent | 1.5 | 3.5 | 2.5 |
| Active oxidation zinc | 0.9 | 1.3 | 1.2 |
| Magnesium oxide | 0.4 | 0.2 | 0.33 |
| Calcium oxide | 0.5 | 0.8 | 0.7 |
| Butanethiol tin | 0.8 | 1.4 | 0.9 |
| Modified kaolin | 35 | 30 | 38 |
| Magnesinm methacrylate | 14 | 11 | 13 |
| Promotor | 1.7 | 2.8 | 1.8 |
| Soybean oil | 10 | 6.5 | 8 |
| β-dimethyl-aminoethylmethacrylate | 1.2 | 1.8 | 1.4 |
| Paraffin oil | 75 | 41 | 50 |
| Triallyl phosphoric acid ester | 0.5 | 0.3 | 0.28 |
| Crosslinking agent B IBP | 1.5 | 1.1 | 1.3 |
| Additional crosslinker TAIC | 1.2 | 0.6 | 0.9 |
| Microcrystalline Wax | 0.3 | 0.5 | 0.35 |
| Vulcanizing agent | 2.8 | 2.2 | 2.5 |
| Tetra hydro Phthalic anhydride | 0.5 | 1 | 0.8 |
Embodiment 1
Automobile described in the present invention comprises the steps: with its preparation of high-temperature resistant rubber sealing-ring
S1, mill is heated to 30 ℃, roll spacing is made as 0.3mm, by the parts by weight of embodiment in table 11, terpolymer EP rubber and chloroprene rubber are added to the 14min that plasticates in mill simultaneously, then through binder removal, compressing tablet, lower, cool to room temperature and park 4.3h and obtain broken-(down)rubber one time;
S2, mill is heated to 30 ℃, roll spacing is made as 0.6mm, and the broken-(down)rubber obtaining in S1 is added to the mill 11min that plasticates, then through binder removal, compressing tablet, lower, cool to room temperature and park 3.5h and obtain secondary broken-(down)rubber;
S3, the temperature of mill is made as to room temperature, roll spacing is made as 0.8mm, and the secondary broken-(down)rubber obtaining in S2 is added to the mill 18min that plasticates, then through binder removal, compressing tablet, lower, cool to room temperature and park 6h and obtain broken-(down)rubber three times;
S4, Banbury mixer is warming up to 125 ℃, roll spacing is made as 0.7mm, adds three broken-(down)rubbers described in S3, and banburying 2.5min is by binder removal, cool to room temperature and park 8h and obtain broken-(down)rubber;
S5, Banbury mixer is warming up to 85 ℃, roll spacing rises to 102 ℃ by temperature after being adjusted into and adding the mixing 2.5min of the broken-(down)rubber described in S4 after 3mm, add successively modified kaolin, magnesium oxide and active zinc flower, after mixing 1.2min, temperature is risen to 122 ℃, then add soybean oil simultaneously, magnesinm methacrylate, the mixing 1.8min of β-dimethyl-aminoethylmethacrylate and paraffin oil, then add anti-aging agent simultaneously, after the mixing 2.2min of Microcrystalline Wax, add Tetra hydro Phthalic anhydride that temperature is risen to 165 ℃, then add successively calcium oxide, butanethiol tin, triallyl phosphoric acid ester, crosslinking agent B IBP and additional crosslinker TAIC, after mixing 2.5min, add vulcanizing agent and promotor, after mixing 5min binder removal, put into mill thin-pass and obtain rubber unvulcanizate 5 times,
S6, pack the rubber unvulcanizate described in S5 into mould, at 15MPa pressure, at 150 ℃ of temperature, sulfuration 18min, obtains described automobile high-temperature resistant rubber sealing-ring after die sinking.
Embodiment 2
Automobile described in the present invention comprises the steps: with its preparation of high-temperature resistant rubber sealing-ring
S1, mill is heated to 35 ℃, roll spacing is made as 0.7mm, by the parts by weight of embodiment in table 12, terpolymer EP rubber and chloroprene rubber are added to the 12min that plasticates in mill simultaneously, then through binder removal, compressing tablet, lower, cool to room temperature and park 4.7h and obtain broken-(down)rubber one time;
S2, mill is heated to 27 ℃, roll spacing is made as 0.4mm, and the broken-(down)rubber obtaining in S1 is added to the mill 19min that plasticates, then through binder removal, compressing tablet, lower, cool to room temperature and park 4.2h and obtain secondary broken-(down)rubber;
S3, the temperature of mill is made as to room temperature, roll spacing is made as 0.5mm, and the secondary broken-(down)rubber obtaining in S2 is added to the mill 16min that plasticates, then through binder removal, compressing tablet, lower, cool to room temperature and park 9h and obtain broken-(down)rubber three times;
S4, Banbury mixer is warming up to 140 ℃, roll spacing is made as 1mm, adds three broken-(down)rubbers described in S3, and banburying 4.8min is by binder removal, cool to room temperature and park 8h and obtain broken-(down)rubber;
S5, Banbury mixer is warming up to 89 ℃, roll spacing rises to 110 ℃ by temperature after being adjusted into and adding the mixing 4.5min of the broken-(down)rubber described in S4 after 8mm, add successively modified kaolin, magnesium oxide and active zinc flower, after mixing 2min, temperature is risen to 135 ℃, then add soybean oil simultaneously, magnesinm methacrylate, the mixing 1min of β-dimethyl-aminoethylmethacrylate and paraffin oil, then add anti-aging agent simultaneously, after the mixing 3min of Microcrystalline Wax, add Tetra hydro Phthalic anhydride that temperature is risen to 140 ℃, then add successively calcium oxide, butanethiol tin, triallyl phosphoric acid ester, crosslinking agent B IBP and additional crosslinker TAIC, after mixing 4min, add vulcanizing agent and promotor, after mixing 2min binder removal, put into mill thin-pass and obtain rubber unvulcanizate 8 times,
S6, pack the rubber unvulcanizate described in S5 into mould, at 20MPa pressure, at 149 ℃ of temperature, sulfuration 7min, obtains described automobile high-temperature resistant rubber sealing-ring after die sinking.
Embodiment 3
Automobile described in the present invention comprises the steps: with its preparation of high-temperature resistant rubber sealing-ring
S1, mill is heated to 33 ℃, roll spacing is made as 0.5mm, and terpolymer EP rubber and chloroprene rubber are added to the 13min that plasticates in mill simultaneously, then through binder removal, compressing tablet, lower, cool to room temperature and park 4.5h and obtain broken-(down)rubber one time;
S2, mill is heated to 28 ℃, roll spacing is made as 0.5mm, and the broken-(down)rubber obtaining in S1 is added to the mill 18min that plasticates, then through binder removal, compressing tablet, lower, cool to room temperature and park 4h and obtain secondary broken-(down)rubber;
S3, the temperature of mill is made as to room temperature, roll spacing is made as 0.6mm, and the secondary broken-(down)rubber obtaining in S2 is added to the mill 16min that plasticates, then through binder removal, compressing tablet, lower, cool to room temperature and park 7.5h and obtain broken-(down)rubber three times;
S4, Banbury mixer is warming up to 130 ℃, roll spacing is made as 0.75mm, adds three broken-(down)rubbers described in S3, and banburying 3.5min is by binder removal, cool to room temperature and park 8h and obtain broken-(down)rubber;
S5, Banbury mixer is warming up to 85 ℃, roll spacing rises to 108 ℃ by temperature after being adjusted into and adding the mixing 4min of the broken-(down)rubber described in S4 after 5mm, add successively modified kaolin, magnesium oxide and active zinc flower, after mixing 1.5min, temperature is risen to 128 ℃, then add soybean oil simultaneously, magnesinm methacrylate, the mixing 1.7min of β-dimethyl-aminoethylmethacrylate and paraffin oil, then add anti-aging agent simultaneously, after the mixing 3.5min of Microcrystalline Wax, add Tetra hydro Phthalic anhydride that temperature is risen to 148 ℃, then add successively calcium oxide, butanethiol tin, triallyl phosphoric acid ester, crosslinking agent B IBP and additional crosslinker TAIC, after mixing 3min, add vulcanizing agent and promotor, after mixing 3min binder removal, put into mill thin-pass and obtain rubber unvulcanizate 6 times,
S6, pack the rubber unvulcanizate described in S5 into mould, at 18MPa pressure, at 146 ℃ of temperature, sulfuration 15min, obtains described automobile high-temperature resistant rubber sealing-ring after die sinking.
Claims (10)
1. an automobile high-temperature resistant rubber sealing-ring, it is characterized in that, its raw materials by weight portion comprises: terpolymer EP rubber 70-90 part, chloroprene rubber 10-30 part, anti-aging agent 1-4 part, active oxidation zinc 0.8-1.5 part, magnesium oxide 0.2-0.4 part, calcium oxide 0.5-1.0 part, butanethiol tin 0.6-1.5 part, modified kaolin 30-40 part, magnesinm methacrylate 10-15 part, promotor 1-3 part, soybean oil 6-10 part, β-dimethyl-aminoethylmethacrylate 1-2 part, paraffin oil 40-80 part, triallyl phosphoesterase 30 .2-0.5 part, crosslinking agent B IBP1.0-1.5 part, additional crosslinker TAIC0.5-1.2 part, Microcrystalline Wax 0.3-0.5 part, vulcanizing agent 2-3 part, Tetra hydro Phthalic anhydride 0.5-1 part,
Proportioning according to above-mentioned each raw material, is prepared according to following steps:
S1, mill is heated to 30-35 ℃, roll spacing is made as 0.2-0.8mm, and terpolymer EP rubber and chloroprene rubber are added to the 10-15min that plasticates in mill simultaneously, then through binder removal, compressing tablet, lower, cool to room temperature and park 4-5h and obtain broken-(down)rubber one time;
S2, mill is heated to 25-30 ℃, roll spacing is made as 0.4-0.6mm, and the broken-(down)rubber obtaining in S1 is added to the mill 10-20min that plasticates, then through binder removal, compressing tablet, lower, cool to room temperature and park 3-5h and obtain secondary broken-(down)rubber;
S3, the temperature of mill is made as to room temperature, roll spacing is made as 0.5-1mm, and the secondary broken-(down)rubber obtaining in S2 is added to the mill 15-20min that plasticates, then through binder removal, compressing tablet, lower, cool to room temperature and park 5-10h and obtain broken-(down)rubber three times;
S4, Banbury mixer is warming up to 120-140 ℃, roll spacing is made as 0.5-1mm, adds three broken-(down)rubbers described in S3, and banburying 2-5min is by binder removal, cool to room temperature and park 8-15h and obtain broken-(down)rubber;
S5, Banbury mixer is warming up to 80-90 ℃, roll spacing rises to 100-115 ℃ by temperature after being adjusted into and adding the mixing 2-5min of the broken-(down)rubber described in S4 after 3-8mm, add successively modified kaolin, magnesium oxide and active zinc flower, after mixing 1-2min, temperature is risen to 120-135 ℃, then add soybean oil simultaneously, magnesinm methacrylate, the mixing 1-2min of β-dimethyl-aminoethylmethacrylate and paraffin oil, then add anti-aging agent simultaneously, after the mixing 2-5min of Microcrystalline Wax, add Tetra hydro Phthalic anhydride that temperature is risen to 140-165 ℃, then add successively calcium oxide, butanethiol tin, triallyl phosphoric acid ester, crosslinking agent B IBP and additional crosslinker TAIC, after mixing 2-5min, add vulcanizing agent and promotor, after mixing 2-5min binder removal, put into mill thin-pass and obtain rubber unvulcanizate 5-8 time,
S6, pack the rubber unvulcanizate described in S5 into mould, at 15-20MPa pressure, at 145-150 ℃ of temperature, sulfuration 5-20min, obtains described automobile high-temperature resistant rubber sealing-ring after die sinking.
2. automobile according to claim 1 high-temperature resistant rubber sealing-ring, it is characterized in that, its raw materials by weight portion comprises: terpolymer EP rubber 75-85 part, chloroprene rubber 15-25 part, anti-aging agent 2-3 part, active oxidation zinc 1.0-1.4 part, magnesium oxide 0.23-0.34 part, calcium oxide 0.6-0.9 part, butanethiol tin 0.7-1.4 part, modified kaolin 35-39 part, magnesinm methacrylate 12-14 part, promotor 1.2-2.8 part, soybean oil 7-8.5 part, β-dimethyl-aminoethylmethacrylate 1.2-1.8 part, paraffin oil 45-75 part, triallyl phosphoesterase 30 .22-0.4 part, crosslinking agent B IBP1.2-1.45 part, additional crosslinker TAIC0.7-1.0 part, Microcrystalline Wax 0.32-0.4 part, vulcanizing agent 2.2-2.8 part, Tetra hydro Phthalic anhydride 0.7-0.9 part.
3. according to the automobile high-temperature resistant rubber sealing-ring described in any one in claim 1-2, it is characterized in that, its raw materials by weight portion comprises: 80 parts of terpolymer EP rubbers, 20 parts of chloroprene rubbers, 2.5 parts, anti-aging agent, 1.2 parts, active oxidation zinc, 0.33 part, magnesium oxide, 0.7 part, calcium oxide, 0.9 part, butanethiol tin, 38 parts of modified kaolins, 13 parts of magnesinm methacrylates, 1.8 parts of promotor, 8 parts of soybean oil, 1.4 parts of β-dimethyl-aminoethylmethacrylates, 50 parts of paraffin oils, triallyl phosphoesterase 30 .28 part, crosslinking agent B IBP1.3 part, additional crosslinker TAIC0.9 part, 0.35 part of Microcrystalline Wax, 2.5 parts of vulcanizing agents, 0.8 part of Tetra hydro Phthalic anhydride.
4. according to the automobile high-temperature resistant rubber sealing-ring described in any one in claim 1-3, it is characterized in that, the roller speed of plasticating in S1, S2 and S3 is 15-25r/min, and roller speed ratio is 1:1.1-1.4.
5. according to the automobile high-temperature resistant rubber sealing-ring described in any one in claim 1-4, it is characterized in that, in S4, filling glue amount is 30-55%, and pressure is 0.2-0.7MPa.
6. according to the automobile high-temperature resistant rubber sealing-ring described in any one in claim 1-5, it is characterized in that, described anti-aging agent be the mixture of anti-aging agent RD, MB, DNP, 4010NA and by weight RD:MB:DPN be 2:1:1.
7. according to the automobile high-temperature resistant rubber sealing-ring described in any one in claim 1-6, it is characterized in that, described modified kaolin is coupling agent and tensio-active agent and uses modification; Preferably, described coupling agent is any one or the multiple composition in A187, A1100, A174, and described tensio-active agent is glycol ether, PEG400, any one in polyethers 330N or multiple composition.
8. according to the automobile high-temperature resistant rubber sealing-ring described in any one in claim 1-7, it is characterized in that, in S5, Banbury mixer is warming up to 81-89 ℃, roll spacing rises to 103-110 ℃ by temperature after being adjusted into and adding the mixing 2.5-4.5min of the broken-(down)rubber described in S4 after 3.3-7.8mm, add successively modified kaolin, magnesium oxide and active zinc flower, after mixing 1.1-1.7min, temperature is risen to 126-131 ℃, then add soybean oil simultaneously, magnesinm methacrylate, the mixing 1.2-1.8min of β-dimethyl-aminoethylmethacrylate and paraffin oil, then add anti-aging agent simultaneously, after the mixing 2.5-4.7min of Microcrystalline Wax, add Tetra hydro Phthalic anhydride that temperature is risen to 146-163 ℃, then add successively calcium oxide, butanethiol tin, triallyl phosphoric acid ester, crosslinking agent B IBP and additional crosslinker TAIC, after mixing 2.4-4.5min, add vulcanizing agent and promotor, after mixing 2.1-4.7min binder removal, put into mill thin-pass and obtain rubber unvulcanizate 6-7 time.
9. according to the automobile high-temperature resistant rubber sealing-ring described in any one in claim 1-8, it is characterized in that, in S5, Banbury mixer is warming up to 85 ℃, roll spacing rises to 108 ℃ by temperature after being adjusted into and adding the mixing 4min of the broken-(down)rubber described in S4 after 5mm, add successively modified kaolin, magnesium oxide and active zinc flower, after mixing 1.5min, temperature is risen to 128 ℃, then add soybean oil simultaneously, magnesinm methacrylate, the mixing 1.7min of β-dimethyl-aminoethylmethacrylate and paraffin oil, then add anti-aging agent simultaneously, after the mixing 3.5min of Microcrystalline Wax, add Tetra hydro Phthalic anhydride that temperature is risen to 148 ℃, then add successively calcium oxide, butanethiol tin, triallyl phosphoric acid ester, crosslinking agent B IBP and additional crosslinker TAIC, after mixing 3min, add vulcanizing agent and promotor, after mixing 3min binder removal, put into mill thin-pass and obtain rubber unvulcanizate 6 times.
10. according to the automobile high-temperature resistant rubber sealing-ring described in any one in claim 1-9, it is characterized in that, in S6, pack the rubber unvulcanizate described in S5 into mould, at 15.3-1.92MPa pressure, at 142-149 ℃ of temperature, sulfuration 6-17min, obtains described automobile high-temperature resistant rubber sealing-ring after die sinking; Preferably, in S6, pack the rubber unvulcanizate described in S5 into mould, at 18MPa pressure, at 146 ℃ of temperature, sulfuration 15min, obtains described automobile high-temperature resistant rubber sealing-ring after die sinking.
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