CN103013010A - Seal rubber for valve rod of automobile and preparation method of seal rubber - Google Patents
Seal rubber for valve rod of automobile and preparation method of seal rubber Download PDFInfo
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- CN103013010A CN103013010A CN2012104836738A CN201210483673A CN103013010A CN 103013010 A CN103013010 A CN 103013010A CN 2012104836738 A CN2012104836738 A CN 2012104836738A CN 201210483673 A CN201210483673 A CN 201210483673A CN 103013010 A CN103013010 A CN 103013010A
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Abstract
The invention discloses a seal rubber for a valve rod of an automobile. The seal rubber comprises the following raw materials by weight: 64 to 66 parts of acrylic rubber, 14 to 16 parts of butyl rubber BK-1675N (Yanshan Petrochemical), 10 to 12 parts of butadiene-acrylonitrile rubber N240, 8 to 10 parts of chlorosulfonated polyethylene rubber TS-930 (Tosoh), 1 to 2 parts of poly-4-methy-1-amylene, 10 to 20 parts of carbon black N440, 8 to 10 parts of super wear-resisting carbon black N110, 6 to 10 parts of heavy calcium carbonate, 1 to 3 parts of hard vinyl alcohol, 1 to 2 parts of calcium stearate, 0.5 to 0.8 parts of stearic acid, 1 to 2 parts of zinc oxide, 5 to 10 parts of wollastonite in powder, 2 to 4 parts of quartz powder, 9 to 11 parts of modified iron tailings powder, 1 to 2 parts of hexamethyldisilazane, 1 to 2 parts of vulcanizing agent DTBP (Di Tert Butyl Peroxide), 3 to 4 parts of N, N'-metabenzyl bismaleimide, 1 to 2 parts of antioxidant 4010NA, 1 to 2 parts of antioxidant ODA,1 to 3 parts of aminopropyltriethoxysilane, and 14 to 16 parts of epoxidized butyl oleate. The rubber material is excellent in ozone resistance, low-temperature resistance and heat resistance, wide in operating temperature range and environment-friendly in process, and can be used for manufacturing various seal components.
Description
Technical field
The present invention relates to the synthetic rubber field, be specifically related to a kind of automobile valve gasket sizing material and preparation method thereof.
Background technology
Automobile plays great role with rubber component to the riding stability of the vibrationproof of automobile, noise abatement, raising vehicle and riding comfort etc.The conventional rubber material usage of automobile is larger, but along with engine in recent years is tending towards high-power, miniaturization development, envrionment temperature around the engine raises, exhaust control laws and regulations requirement is stricter, the in addition use of alcohol fuel forces rubber component to improve heat-resisting, cold-resistant, oil resistant, the properties such as ageing-resistant.So the elastomeric consumption of high-performance special constantly increases, automobile is the principal market of these special synthetic rubbers.Therefore, automobile will be to the special gelatin future development with premium properties with the glue kind of rubber.
Acrylic elastomer (hereinafter to be referred as ACM) is the elastomerics that gets through copolymerization take acrylate as main monomer, and its main chain is saturated carbon chains, and side group is the polarity ester group.Because special construction gives its many excellences, such as heat-resisting, ageing-resistant, oil resistant, anti-ozone, uvioresistant etc., mechanical property and processing characteristics are better than viton and silicon rubber, and it is heat-resisting, ageing resistance and oil-proofness are better than paracril.ACM is widely used in various high temperature, the oil resistant environment, become automotive industry in recent years and focus on a kind of sealing material of develop and spread, especially for the high temperature resistant oil sealing of automobile, bent axle, valve rod, head gasket, hydraulic oil pipeline etc., at present domestic needs is whole dependence on import almost.
Cause engine room temperature rise, the envrionment temperature of auto parts machinery usually will reach more than 150 ℃ even 180 ℃ because car speed improves, the ACM rubber that therefore how to obtain using for a long time in the higher temperature environment becomes the focus that industry is paid close attention to.In order to give prominence to or improve the processing characteristics of ACM, in recent years ACM is carried out modification or selects ACM to one of other elastomer-modified study hotspots that become processed and applied.Existing rubber seal is under the operating modes such as high temperature, low temperature, the large temperature difference, corrosive medium and long lifetime, and it is satisfactory that its sealing property is difficult to, and works out the trend that high performance rubber unvulcanizate becomes present domestic rubber industry development.
Summary of the invention
The invention provides a kind of automobile valve rod caulking gum and preparation method thereof, sizing material of the present invention has excellent high-low temperature resistant, oil resistant, anti-solvent and chemical resistance, simultaneously good mechanical property.
The present invention adopts following technical scheme:
A kind of automobile valve rod caulking gum, made by following raw materials in part by weight: acrylic elastomer 64-66, isoprene-isobutylene rubber BK-1675N(Yanshan Petrochemical) 14-16, butadiene-acrylonitrile rubber N240 10-12, eastern Cao of chlorosulfonated polyethylene rubber TS-930(Japan) 8-10, poly--4-methyl-1-pentene 1-2, carbon black N440 10-20, super abrasion resistant carbon black N110 8-10, water-ground limestone 6-10, polyvinyl alcohol 1-3, calcium stearate 1-2, stearic acid 0.5-0.8, zinc oxide 1-2, wollastonite powder 5-10, silica powder 2-4, Modified Iron mine tailing ground-slag 9-11, hexamethyldisilazane 1-2, vulcanizing agent DTBP1～2, N, a N '-penylene bismaleimides 3-4, antioxidant 4010NA 1-2, anti-aging agent ODA 1-2, aminopropyl triethoxysilane 1-3, epoxyoleic acid butyl ester 14-16.
Described a kind of automobile valve rod caulking gum, it is characterized in that, made by following raw materials in part by weight: acrylic elastomer 65, isoprene-isobutylene rubber BK-1675N(Yanshan Petrochemical) 15, butadiene-acrylonitrile rubber N240 11, eastern Cao of chlorosulfonated polyethylene rubber TS-930(Japan) 9, poly--4-methyl-1-pentene 1.5, carbon black N440 15, super abrasion resistant carbon black N1109, water-ground limestone 9, polyvinyl alcohol 2, calcium stearate 1.5, stearic acid 0.6, zinc oxide 1.5, wollastonite powder 8, silica powder 3, Modified Iron mine tailing ground-slag 10, hexamethyldisilazane 1.3, vulcanizing agent DTBP1.2, N, a N '-penylene bismaleimides 3.6, antioxidant 4010NA 1.1, anti-aging agent ODA 1.4, aminopropyl triethoxysilane 1.8, epoxyoleic acid butyl ester 15.
Described a kind of automobile valve rod is characterized in that with the preparation method of caulking gum, may further comprise the steps:
(1) preparation method of modification trees ash:
The sericite-tridymite-cristobalite of trees ashes weight 1-2% joined in the trees ash mix, using 15-20% salt acid soak 1-2 hour, wash with water to neutrality, after the oven dry, add trisodium phosphate, 1-2% iso-octyl phenyl Soxylat A 25-7, the 3-5% zinc oxide of the aluminate coupling agent DL-411, the 1-2% that are equivalent to solid weight 0.5-1.0%, the speed high-speed stirring with 1200-1500 rev/min obtains dispersion liquid, dispersion liquid is dried, is ground into powder, obtains modification trees ash;
(2) preparation of Modified Iron mine tailings:
With 900-1000 ℃ of lower scaling loss 4-6 of iron tailings slag hour, then grind to form nanometer powder, admix again the ptfe micropowder, the sodium lignosulfonate of 1-2%, the 1-2% machine oil agitating that are equivalent to powder weight 1-2% even, oven dry, grind to form nanometer powder, obtain Modified Iron mine tailing ground-slag;
(3) press the 1:1 quality than diluted ammonia propyl-triethoxysilicane with machine oil;
(4) press formula rate with modification trees ashes, carbon black N440, super abrasion resistant carbon black N110, drop in the high-speed mixer, speed high-speed stirring with 1000-1200 rev/min, the coupling agent that step (2) dilution is good is sprayed onto in the mixed fillers simultaneously, continue to stir 5-6 minute, the discharging cooling is for subsequent use, obtains mixture;
(5) with acrylic elastomer, isoprene-isobutylene rubber BK-1675N(Yanshan Petrochemical), butadiene-acrylonitrile rubber N240, chlorosulfonated polyethylene rubber (Japanese eastern Cao TS-930), Modified Iron mine tailings, drop in the Banbury mixer, under 65-73 ℃ temperature, plasticate, after plasticating 10-14 minute, when temperature reaches 82-95 ℃, the beginning discharge is parked cooling 10-12 hour behind the discharge;
(6) by formula rate above-mentioned cooled broken-(down)rubber is joined in the Banbury mixer, the compound that adds again step (4), after mixing 2-3 minute, after the mixing 10-15 of other leftover materials minute during adding is filled a prescription again except vulcanizing agent and promotor class, when temperature reaches 90-118 ℃, the beginning discharge is parked cooling 12-14 hour behind the discharge;
(7) above-mentioned mixing materials is dropped in the mill, vulcanizing agent, promotor class are added in the rubber unvulcanizate again, thin-pass 6-8 is all over getting final product, the processing temperature of mill≤56 ℃.
Beneficial effect
The present invention is with acrylic elastomer and other several compounding rubbers, improve the over-all properties of rubber unvulcanizate, the trees ash is improved, simultaneously the tail iron ore is carried out modification, then mix with carbon black, use again coupling agent treatment, use as strengthening agent, improved the dispersiveness of filler at rubber unvulcanizate, ozone resistance and the resistance to low temperature of rubber unvulcanizate have been improved, resistance toheat has wider use temperature scope than acrylic elastomer itself and butadiene-acrylonitrile rubber simultaneously, better processing performance, lower starting material and production cost meet the performance requriements of the component that domesticize.
Embodiment
The preparation of caulking gum of a kind of automobile valve rod,
Take by weighing acrylic elastomer (AR-100) 65kg, isoprene-isobutylene rubber BK-1675N(Yanshan Petrochemical) 15kg, butadiene-acrylonitrile rubber N240 11kg, eastern Cao of chlorosulfonated polyethylene rubber TS-930(Japan) 9kg, poly--4-methyl-1-pentene 1.5kg, carbon black N440 15kg, super abrasion resistant carbon black N110 9kg, water-ground limestone 9kg, polyvinyl alcohol 2kg, calcium stearate 1.5kg, stearic acid 0.6kg, zinc oxide 1.5kg, wollastonite powder 8kg, silica powder 3kg, Modified Iron mine tailing ground-slag 10kg, hexamethyldisilazane 1.3kg, vulcanizing agent DTBP1.2kg, N, a N '-penylene bismaleimides 3.6kg, antioxidant 4010NA 1.1kg, anti-aging agent ODA 1.4kg, aminopropyl triethoxysilane 1.8kg, epoxyoleic acid butyl ester 15kg.
The preparation method may further comprise the steps:
(1) preparation method of modification trees ash:
The sericite-tridymite-cristobalite of trees ashes weight 1-2% joined in the trees ash mix, using 15-20% salt acid soak 1-2 hour, wash with water to neutrality, after the oven dry, add trisodium phosphate, 1-2% iso-octyl phenyl Soxylat A 25-7, the 3-5% zinc oxide of the aluminate coupling agent DL-411, the 1-2% that are equivalent to solid weight 0.5-1.0%, the speed high-speed stirring with 1200-1500 rev/min obtains dispersion liquid, dispersion liquid is dried, is ground into powder, obtains modification trees ash;
(2) preparation of Modified Iron mine tailings:
With 900-1000 ℃ of lower scaling loss 4-6 of iron tailings slag hour, then grind to form nanometer powder, admix again the ptfe micropowder, the sodium lignosulfonate of 1-2%, the 1-2% machine oil agitating that are equivalent to powder weight 1-2% even, oven dry, grind to form nanometer powder, obtain Modified Iron mine tailing ground-slag;
(3) press the 1:1 quality than diluted ammonia propyl-triethoxysilicane with machine oil;
(4) press formula rate with modification trees ashes, carbon black N440, super abrasion resistant carbon black N110, drop in the high-speed mixer, speed high-speed stirring with 1000-1200 rev/min, the coupling agent that step (2) dilution is good is sprayed onto in the mixed fillers simultaneously, continue to stir 5-6 minute, the discharging cooling is for subsequent use, obtains mixture;
(5) with acrylic elastomer, isoprene-isobutylene rubber BK-1675N(Yanshan Petrochemical), butadiene-acrylonitrile rubber N240, chlorosulfonated polyethylene rubber (Japanese eastern Cao TS-930), Modified Iron mine tailings, drop in the Banbury mixer, under 65-73 ℃ temperature, plasticate, after plasticating 10-14 minute, when temperature reaches 82-95 ℃, the beginning discharge is parked cooling 10-12 hour behind the discharge;
(6) by formula rate above-mentioned cooled broken-(down)rubber is joined in the Banbury mixer, the compound that adds again step (4), after mixing 2-3 minute, after the mixing 10-15 of other leftover materials minute during adding is filled a prescription again except vulcanizing agent and vulkacit D TDM class, when temperature reaches 90-118 ℃, the beginning discharge is parked cooling 12-14 hour behind the discharge;
(7) above-mentioned mixing materials is dropped in the mill, vulcanizing agent, promotor class are added in the rubber unvulcanizate again, thin-pass 6-8 is all over getting final product, the processing temperature of mill≤56 ℃.。
Experimental data
Make the sizing material detection that makes a service test by the formula for raw stock of embodiment, detected result sees Table 1.
Table 1
As can be seen from the table the lower temperature resistance of sizing material of the present invention, resistance toheat, and resistance to tearing all good than conventional gasket material, can be used as various sealing member materials.
Claims (3)
1. automobile valve rod caulking gum, it is characterized in that, made by following raw materials in part by weight: acrylic elastomer 64-66, isoprene-isobutylene rubber BK-1675N(Yanshan Petrochemical) 14-16, butadiene-acrylonitrile rubber N240 10-12, chlorosulfonated polyethylene rubber (Japanese eastern Cao TS-930) 8-10, poly--4-methyl-1-pentene 1-2, carbon black N440 10-20, super abrasion resistant carbon black N110 8-10, water-ground limestone 6-10, polyvinyl alcohol 1-3, calcium stearate 1-2, stearic acid 0.5-0.8, zinc oxide 1-2, wollastonite powder 5-10, silica powder 2-4, Modified Iron mine tailing ground-slag 9-11, hexamethyldisilazane 1-2, vulcanizing agent DTBP1～2, N, a N '-penylene bismaleimides 3-4, antioxidant 4010NA 1-2, anti-aging agent ODA 1-2, aminopropyl triethoxysilane 1-3, epoxyoleic acid butyl ester 14-16.
2. a kind of automobile valve rod caulking gum according to claim 1, it is characterized in that, made by following raw materials in part by weight: acrylic elastomer 65, isoprene-isobutylene rubber BK-1675N(Yanshan Petrochemical) 15, butadiene-acrylonitrile rubber N240 11, chlorosulfonated polyethylene rubber (Japanese eastern Cao TS-930) 9, poly--4-methyl-1-pentene 1.5, carbon black N440 15, super abrasion resistant carbon black N110 9, water-ground limestone 9, polyvinyl alcohol 2, calcium stearate 1.5, stearic acid 0.6, zinc oxide 1.5, wollastonite powder 8, silica powder 3, Modified Iron mine tailing ground-slag 10, hexamethyldisilazane 1.3, vulcanizing agent DTBP1.2, N, a N '-penylene bismaleimides 3.6, antioxidant 4010NA 1.1, anti-aging agent ODA 1.4, aminopropyl triethoxysilane 1.8, epoxyoleic acid butyl ester 15.
3. a kind of automobile valve rod according to claim 1 and 2 is characterized in that with the preparation method of caulking gum, may further comprise the steps:
(1) preparation method of modification trees ash:
The sericite-tridymite-cristobalite of trees ashes weight 1-2% joined in the trees ash mix, using 15-20% salt acid soak 1-2 hour, wash with water to neutrality, after the oven dry, add trisodium phosphate, 1-2% iso-octyl phenyl Soxylat A 25-7, the 3-5% zinc oxide of the aluminate coupling agent DL-411, the 1-2% that are equivalent to solid weight 0.5-1.0%, the speed high-speed stirring with 1200-1500 rev/min obtains dispersion liquid, dispersion liquid is dried, is ground into powder, obtains modification trees ash;
(2) preparation of Modified Iron mine tailings:
With 900-1000 ℃ of lower scaling loss 4-6 of iron tailings slag hour, then grind to form nanometer powder, admix again the ptfe micropowder, the sodium lignosulfonate of 1-2%, the 1-2% machine oil agitating that are equivalent to powder weight 1-2% even, oven dry, grind to form nanometer powder, obtain Modified Iron mine tailing ground-slag;
(3) press the 1:1 quality than diluted ammonia propyl-triethoxysilicane with machine oil;
(4) press formula rate with modification trees ashes, carbon black N440, super abrasion resistant carbon black N110, drop in the high-speed mixer, speed high-speed stirring with 1000-1200 rev/min, the aminopropyl triethoxysilane that step (2) dilution is good is sprayed onto in the mixed fillers simultaneously, continue to stir 5-6 minute, the discharging cooling is for subsequent use, obtains mixture;
(5) with acrylic elastomer, isoprene-isobutylene rubber BK-1675N(Yanshan Petrochemical), butadiene-acrylonitrile rubber N240, chlorosulfonated polyethylene rubber (Japanese eastern Cao TS-930), Modified Iron mine tailings, drop in the Banbury mixer, under 65-73 ℃ temperature, plasticate, after plasticating 10-14 minute, when temperature reaches 82-95 ℃, the beginning discharge is parked cooling 10-12 hour behind the discharge;
(6) by formula rate above-mentioned cooled broken-(down)rubber is joined in the Banbury mixer, the compound that adds again step (4), after mixing 2-3 minute, after the mixing 10-15 of other leftover materials minute during adding is filled a prescription again except vulcanizing agent and promotor class, when temperature reaches 90-118 ℃, the beginning discharge is parked cooling 12-14 hour behind the discharge;
(7) above-mentioned mixing materials is dropped in the mill, vulcanizing agent, promotor class are added in the rubber unvulcanizate again, thin-pass 6-8 is all over getting final product, the processing temperature of mill≤56 ℃.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103254849A (en) * | 2013-05-08 | 2013-08-21 | 安徽艳阳电气集团有限公司 | Brominated butyl rubber high temperature-resistant waterproof sealant and preparation method thereof |
| CN103254848A (en) * | 2013-05-08 | 2013-08-21 | 安徽艳阳电气集团有限公司 | Butyl rubber fluorescent lamp waterproof glue and preparation method thereof |
| CN103613865A (en) * | 2013-11-12 | 2014-03-05 | 铜陵市肆得科技有限责任公司 | High-strength rubber sealing gasket material and preparation method thereof |
| CN103613864A (en) * | 2013-10-28 | 2014-03-05 | 蚌埠市鸿安精密机械有限公司 | Mixed rubber sealing ring for capacitor, and making method thereof |
| CN104059253A (en) * | 2014-01-21 | 2014-09-24 | 四川远星橡胶有限责任公司 | Wear-resistant rubber material combination of tire tread and preparation method thereof |
| CN105254949A (en) * | 2013-11-01 | 2016-01-20 | 国网河南省电力公司漯河供电公司 | Anti-pressure wear-resistant corrosion-resistant transformer sealing ring |
| CN109207098A (en) * | 2017-06-30 | 2019-01-15 | 株式会社自动网络技术研究所 | Vehicle containment member and vehicle electricity consumption relay part |
| CN110713726A (en) * | 2019-11-03 | 2020-01-21 | 霍山汇能汽车零部件制造有限公司 | Preparation method of high-pressure-resistant sealing element for automobile parts |
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| CN102504366A (en) * | 2011-10-31 | 2012-06-20 | 铜陵新特阀门有限责任公司 | Rubber slurry used for producing parallel gate valve end face O-shaped sealing ring and preparation method thereof |
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| CN102504366A (en) * | 2011-10-31 | 2012-06-20 | 铜陵新特阀门有限责任公司 | Rubber slurry used for producing parallel gate valve end face O-shaped sealing ring and preparation method thereof |
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| CN103254849A (en) * | 2013-05-08 | 2013-08-21 | 安徽艳阳电气集团有限公司 | Brominated butyl rubber high temperature-resistant waterproof sealant and preparation method thereof |
| CN103254848A (en) * | 2013-05-08 | 2013-08-21 | 安徽艳阳电气集团有限公司 | Butyl rubber fluorescent lamp waterproof glue and preparation method thereof |
| CN103254848B (en) * | 2013-05-08 | 2015-11-25 | 安徽艳阳电气集团有限公司 | butyl rubber fluorescent lamp waterproof glue and preparation method thereof |
| CN103613864A (en) * | 2013-10-28 | 2014-03-05 | 蚌埠市鸿安精密机械有限公司 | Mixed rubber sealing ring for capacitor, and making method thereof |
| CN103613864B (en) * | 2013-10-28 | 2016-03-23 | 蚌埠市鸿安精密机械有限公司 | A kind of electrical condenser mixing of rubber sealing-ring and preparation method thereof |
| CN105254949A (en) * | 2013-11-01 | 2016-01-20 | 国网河南省电力公司漯河供电公司 | Anti-pressure wear-resistant corrosion-resistant transformer sealing ring |
| CN103613865A (en) * | 2013-11-12 | 2014-03-05 | 铜陵市肆得科技有限责任公司 | High-strength rubber sealing gasket material and preparation method thereof |
| CN104059253A (en) * | 2014-01-21 | 2014-09-24 | 四川远星橡胶有限责任公司 | Wear-resistant rubber material combination of tire tread and preparation method thereof |
| CN109207098A (en) * | 2017-06-30 | 2019-01-15 | 株式会社自动网络技术研究所 | Vehicle containment member and vehicle electricity consumption relay part |
| CN109207098B (en) * | 2017-06-30 | 2021-05-18 | 株式会社自动网络技术研究所 | Sealing member for vehicle and power relay component for vehicle |
| CN110713726A (en) * | 2019-11-03 | 2020-01-21 | 霍山汇能汽车零部件制造有限公司 | Preparation method of high-pressure-resistant sealing element for automobile parts |
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