CN116656056B - Rubber sealing material for automobile engine and preparation method thereof - Google Patents
Rubber sealing material for automobile engine and preparation method thereof Download PDFInfo
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- CN116656056B CN116656056B CN202310942645.6A CN202310942645A CN116656056B CN 116656056 B CN116656056 B CN 116656056B CN 202310942645 A CN202310942645 A CN 202310942645A CN 116656056 B CN116656056 B CN 116656056B
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 61
- 239000005060 rubber Substances 0.000 title claims abstract description 61
- 239000003566 sealing material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000006229 carbon black Substances 0.000 claims abstract description 34
- -1 polyethylene Polymers 0.000 claims abstract description 32
- 229920005560 fluorosilicone rubber Polymers 0.000 claims abstract description 25
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 24
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 24
- 239000004698 Polyethylene Substances 0.000 claims abstract description 21
- 229920000573 polyethylene Polymers 0.000 claims abstract description 21
- 229920000428 triblock copolymer Polymers 0.000 claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920002943 EPDM rubber Polymers 0.000 claims abstract description 15
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 15
- 229920002681 hypalon Polymers 0.000 claims abstract description 13
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 9
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 9
- 239000004014 plasticizer Substances 0.000 claims abstract description 7
- 238000004073 vulcanization Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims description 26
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 claims description 16
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 10
- 239000003431 cross linking reagent Substances 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 8
- GPXCORHXFPYJEH-UHFFFAOYSA-N 3-[[3-aminopropyl(dimethyl)silyl]oxy-dimethylsilyl]propan-1-amine Chemical compound NCCC[Si](C)(C)O[Si](C)(C)CCCN GPXCORHXFPYJEH-UHFFFAOYSA-N 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims description 5
- 238000004898 kneading Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- FGZFESWHQXSPJU-UHFFFAOYSA-N 2-methyl-2-(3,3,3-trifluoropropyl)-1,3,5,2,4,6-trioxatrisilinane Chemical compound FC(F)(F)CC[Si]1(C)O[SiH2]O[SiH2]O1 FGZFESWHQXSPJU-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- BIFQHCGLXZWNLN-UHFFFAOYSA-N 2,2,6-trifluoro-4-methyl-4-propyl-1,3,5,2,4,6-trioxatrisilinane Chemical compound CCC[Si]1(C)O[SiH](F)O[Si](F)(F)O1 BIFQHCGLXZWNLN-UHFFFAOYSA-N 0.000 claims description 3
- QDYGIMAMLUKRLQ-UHFFFAOYSA-N 4-methylbenzenesulfonic acid;hydrochloride Chemical compound Cl.CC1=CC=C(S(O)(=O)=O)C=C1 QDYGIMAMLUKRLQ-UHFFFAOYSA-N 0.000 claims description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 2
- 229940057995 liquid paraffin Drugs 0.000 claims description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical group CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-M toluenesulfonate group Chemical group C=1(C(=CC=CC1)S(=O)(=O)[O-])C LBLYYCQCTBFVLH-UHFFFAOYSA-M 0.000 claims description 2
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 17
- 238000012360 testing method Methods 0.000 description 15
- 239000000203 mixture Substances 0.000 description 8
- 238000007789 sealing Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 4
- 230000003712 anti-aging effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 208000005156 Dehydration Diseases 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- MYXKPFMQWULLOH-UHFFFAOYSA-M tetramethylazanium;hydroxide;pentahydrate Chemical compound O.O.O.O.O.[OH-].C[N+](C)(C)C MYXKPFMQWULLOH-UHFFFAOYSA-M 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Sealing Material Composition (AREA)
- Gasket Seals (AREA)
Abstract
The invention relates to the field of sealing materials, in particular to a rubber sealing material for an automobile engine and a preparation method thereof, and the rubber sealing material comprises the following components in parts by weight: 60-80 parts of ethylene propylene diene monomer rubber, 20-30 parts of epoxy-terminated nitrile rubber, 20-30 parts of fluorosilicone rubber, 5-10 parts of chlorosulfonated polyethylene rubber, 5-10 parts of polyethylene glycol-polybutadiene-polyethylene glycol triblock copolymer, 60-80 parts of white carbon black, 15-30 parts of carbon black, 1-2 parts of antioxidant RD, 1-2 parts of antioxidant MB, 1-3 parts of plasticizer and 1-3 parts of vulcanization component.
Description
Technical Field
The invention relates to the field of sealing materials, in particular to a rubber sealing material for an automobile engine and a preparation method thereof.
Background
The automobile sealing system plays an irreplaceable important role in the automobile structure, and has a key meaning for preventing leakage and improving the air barrier effect. In practice, although a part of metal products, silk products and the like are used as sealing materials, the rubber material structure has the characteristic of macromolecules, has the remarkable characteristics of good elasticity, recoverability, air tightness and the like, and has outstanding advantages in the aspects of shock absorption, sound insulation, sealing and the like, so that the rubber material product is always the most important material in automobile sealing.
In the aspect of an automobile engine, due to the special operation condition of the engine, the rubber sealing product is required to have certain advantages in the aspects of high temperature resistance and solvent resistance, so that higher requirements are put on the performance of the rubber sealing material.
Disclosure of Invention
The invention aims to: aiming at the technical problems, the invention provides a rubber sealing material for an automobile engine and a preparation method thereof.
The technical scheme adopted is as follows:
a rubber sealing material for an automobile engine comprises the following components in parts by weight:
60-80 parts of ethylene propylene diene monomer rubber, 20-30 parts of epoxy-terminated nitrile rubber, 20-30 parts of fluorosilicone rubber, 5-10 parts of chlorosulfonated polyethylene rubber, 5-10 parts of polyethylene glycol-polybutadiene-polyethylene glycol triblock copolymer, 60-80 parts of white carbon black, 15-30 parts of carbon black, 1-2 parts of antioxidant RD, 1-2 parts of antioxidant MB, 1-3 parts of plasticizer and 1-3 parts of vulcanization component.
Further, the number average molecular weight of the fluorosilicone rubber is 1-10 ten thousand, and the structural formula is as follows:
wherein m is the number of dimethyl siloxane units, and n is the number of trifluoropropyl methyl siloxane units;
m：n=1：1~10；
r is an aminoalkyl group having 1 to 4 carbon atoms.
Further, R is aminopropyl or aminobutyl.
Further, the fluorosilicone rubber is prepared from trifluoropropyl methyl cyclotrisiloxane, octamethyl cyclotrisiloxane, 1, 3-bis (3-aminopropyl) tetramethyl disiloxane and a catalyst;
wherein the dosage of the 1, 3-bis (3-aminopropyl) tetramethyl disiloxane is 0.5-1% of the total weight of the trifluoropropyl methyl cyclotrisiloxane and the octamethyl cyclotrisiloxane;
when the 1, 3-bis (3-aminopropyl) tetramethyl disiloxane is used as a blocking agent, the molecular chain growth is limited when the use level is more than 1%, and when the use level is less than 0.5%, the molecular weight is not increased continuously, probably because the copolymer is blocked in advance due to the chain transfer phenomenon, so that the use level of 1, 3-bis (3-aminopropyl) tetramethyl disiloxane is optimally 0.5-1% of the total weight of the trifluoropropyl methyl cyclotrisiloxane and the octamethyl cyclotrisiloxane in comprehensive consideration.
Further, the catalyst is fluorosilicone alcohol tetramethyl ammonium hydroxide.
Further, the preparation method of the polyethylene glycol-polybutadiene-polyethylene glycol triblock copolymer comprises the following steps:
the hydroxyl-terminated polybutadiene is modified into p-toluenesulfonate group which is easy to leave by utilizing the reaction of the hydroxyl-terminated polybutadiene and the p-toluenesulfonate chloride, and then the polyethylene glycol-polybutadiene-polyethylene glycol triblock copolymer can be obtained by utilizing the nucleophilic substitution reaction of the hydroxyl-terminated polyethylene glycol and the toluenesulfonate group.
Further, both the white carbon black and the carbon black are modified by a sulfur-containing silane coupling agent.
Further, the plasticizer is any one or a combination of more than one of liquid paraffin, dioctyl phthalate, dibutyl phthalate and coumarone resin.
Further, the vulcanizing component comprises a vulcanizing agent DCP and a auxiliary crosslinking agent TAIC, wherein the weight ratio of the vulcanizing agent DCP to the auxiliary crosslinking agent TAIC is 2-4: 1.
the invention also provides a preparation method of the rubber sealing material for the automobile engine, which comprises the following steps:
uniformly mixing fluorosilicone rubber and white carbon black on a two-roll open mill, kneading for 4-8 hours at the temperature of 120-140 ℃ and the vacuum degree of-0.1 to-0.05 MPa in a kneader, standing for 18-24 hours, mixing with ethylene propylene diene monomer, epoxy nitrile rubber, chlorosulfonated polyethylene rubber, polyethylene glycol-polybutadiene-polyethylene glycol triblock copolymer and plasticizer, mixing for 1-2 minutes, adding carbon black, an antioxidant RD and an antioxidant MB, continuously mixing for 4-8 minutes, discharging rubber, adding the obtained rubber into the two-roll open mill, carrying out back mixing for 3-6 minutes, adding a vulcanization component, carrying out sheet thinning for 5-10 times, standing for 12-24 hours, vulcanizing for 10-20 minutes at the temperature of 150-170 ℃ and the pressure of 10-15 MPa in a flat vulcanizing machine, and taking out the rubber from a die.
The invention has the beneficial effects that:
the ethylene propylene diene monomer rubber has excellent ozone resistance, weather aging resistance and high chemical stability, but the oil resistance is poor, the fluorosilicone rubber has excellent high temperature resistance, oil resistance, wear resistance, chemical corrosion resistance and other performances, but the fluorosilicone rubber and the ethylene propylene diene monomer rubber have large polarity difference and poor compatibility, the inventor takes epoxy-terminated nitrile rubber as a medium, and forms a co-crosslinking structure through the crosslinking reaction of epoxy groups and amino groups, so that the interfacial binding force and compatibility among the three are increased, the performance is improved, the chlorosulfonated polyethylene rubber main chain is chemically stable saturated hydrocarbon, the chlorosulfonyl rubber can be entangled with the ethylene propylene diene monomer rubber, the side group is a chlorine atom with polarity, the compatibility with the end-capped nitrile rubber is good, the chlorosulfonyl group with high activity can provide crosslinking points for vulcanization, can promote the formation of a co-crosslinking network, and the polyethylene glycol-polybutadiene-polyethylene glycol triblock copolymer as a block copolymer structure has a polar chain segment and a nonpolar chain segment, can be used as a compatilizer, the rheological property of the fluorosilicone rubber, the mechanical property of the rubber and the ethylene propylene diene monomer rubber and the end-capped nitrile rubber are improved, the processability of the rubber is improved, the high-temperature resistance sealing material is good, and the sealing material is suitable for preparing an engine with good high temperature resistance.
Detailed Description
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. The technology not mentioned in the present invention refers to the prior art, and unless otherwise indicated, the following examples and comparative examples are parallel tests, employing the same processing steps and parameters.
Example 1:
a rubber sealing material for an automobile engine comprises the following components in parts by weight:
70 parts of ethylene propylene diene monomer rubber, 25 parts of epoxy-terminated nitrile rubber, 25 parts of fluorosilicone rubber, 10 parts of chlorosulfonated polyethylene rubber, 5 parts of polyethylene glycol-polybutadiene-polyethylene glycol triblock copolymer, 60 parts of white carbon black, 20 parts of carbon black, 2 parts of an anti-aging agent RD, 1 part of an anti-aging agent MB, 1.5 parts of dibutyl phthalate, 1.5 parts of coumarone resin, 1 part of a vulcanizing agent DCP and 0.5 part of a crosslinking assistant TAIC. Wherein, the structural formula of the fluorosilicone rubber is as follows:
the preparation method comprises the following steps:
1000g of trifluoro propyl methyl cyclotrisiloxane is added into a reaction bottle, high-purity nitrogen is introduced after vacuumizing, stirring and heating are carried out to 60 ℃ and keeping for 1h, dehydration treatment is carried out, then 20g of tetramethyl ammonium hydroxide pentahydrate is added into the reaction bottle, the temperature is increased to 80 ℃ for 1h under-0.05 MPa, the vacuum degree is increased to-0.1 MPa, the fluorosilicone alcohol tetramethyl ammonium hydroxide is obtained after removing low boiling substances, the reaction bottle is sealed and placed for standby, 2966g of octamethyl cyclotrisiloxane, 46854g of trifluoro propyl methyl cyclotrisiloxane and 498g of fluorosilicone alcohol tetramethyl ammonium hydroxide are added into the reaction bottle, stirring and mixing are carried out uniformly, the temperature is increased to 80 ℃ for polymerization reaction for 8h, then 364g of 1, 3-bis (3-aminopropyl) tetramethyl disiloxane is added, the reaction is continued for 1.5h under-0.1 MPa, and the low boiling substances are removed for 2h under-0.1 MPa, and the fluorosilicone rubber is obtained, m: n (theoretical value) =1:7.5, m: n (found) =1:7.52, number average molecular weight 46500.
The preparation method of the polyethylene glycol-polybutadiene-polyethylene glycol triblock copolymer comprises the following steps:
47g of hydroxyl-terminated polybutadiene (Mn=2350, 20mmol, from Zigbaolone chemical Co., ltd.) were dissolved thoroughly in 150mL of THF solution, 33.3mL of triethylamine were added thereto, and the reaction system was transferred into an ice-water bath. After the temperature had equilibrated, 100mL of a solution of p-toluenesulfonyl chloride (45.8 g,240 mmol) in THF was dropwise added using a constant pressure dropping funnel for 2h. After the dripping is finished, the mixture is reacted in an ice water bath for 1h, and then the mixture is moved into a constant temperature oil bath at 40 ℃ for continuous reaction for 24h. After the reaction was completed, triethylamine salt was removed by suction filtration, the crude product was precipitated in methanol, the supernatant was removed, THF and methanol were distilled off by a rotary evaporator to obtain tosylate-terminated polybutadiene, 12g of polyethylene glycol (mn=600, 2mmol, purchased from the eastern sea-ampere petrochemical plant, jiangsu province) was dissolved in 200mL of lthf, 22.4g of potassium hydroxide was added, the system was transferred to a 65 ℃ constant temperature oil bath, 150mL of a THF solution of tosylate-terminated polybutadiene (23.5 g,10 mmol) was slowly dropped into the above reaction system, and the reaction was continued at 65 ℃ for 48 hours after the dropping was completed. After the reaction is finished, filtering, steaming, dissolving the crude product in dichloromethane, washing to be neutral by using HCl solution and distilled water in sequence, drying by using anhydrous magnesium sulfate, filtering, and steaming to obtain the polyethylene glycol-polybutadiene-polyethylene glycol triblock copolymer.
The white carbon black and the carbon black are subjected to modification pretreatment by a silane coupling agent Si-69. The method comprises the following steps:
adding white carbon black and carbon black into a three-neck flask respectively, dropwise adding a silane coupling agent Si-69 (solid-liquid weight ratio is 100:16) while stirring, heating to 143 ℃, preserving heat, continuing stirring for 30min, cooling, discharging, and sealing for later use.
The preparation method of the rubber sealing material for the automobile engine comprises the following steps:
firstly, mixing fluorosilicone rubber and white carbon black on a two-roll open mill for 10min, then adding the mixture into a kneader, kneading for 5h under the conditions that the temperature is 130 ℃ and the vacuum degree is minus 0.1MPa, standing for 24h, then mixing the mixture with ethylene propylene diene monomer rubber, epoxy nitrile rubber, chlorosulfonated polyethylene rubber, polyethylene glycol-polybutadiene-polyethylene glycol triblock copolymer, dibutyl phthalate and coumarone resin, then mixing for 2min, adding carbon black, an antioxidant RD and an antioxidant MB, continuously mixing for 5min, discharging rubber, adding the obtained rubber into the two-roll open mill, carrying out back mixing for 4min, adding a vulcanizing agent DCP and an auxiliary cross-linking agent TAIC, carrying out sheet thinning for 8 times, and vulcanizing the rubber on a flat vulcanizing machine for 15min at 160 ℃ and 10-15 MPa after the rubber is parked for 24h.
Example 2:
a rubber sealing material for an automobile engine comprises the following components in parts by weight:
80 parts of ethylene propylene diene monomer, 30 parts of epoxy nitrile rubber, 30 parts of fluorosilicone rubber, 10 parts of chlorosulfonated polyethylene rubber, 10 parts of polyethylene glycol-polybutadiene-polyethylene glycol triblock copolymer, 80 parts of white carbon black, 30 parts of carbon black, 2 parts of an anti-aging agent RD, 2 parts of an anti-aging agent MB, 1.5 parts of dibutyl phthalate, 1.5 parts of coumarone resin, 1 part of a vulcanizing agent DCP and 0.5 part of a crosslinking auxiliary agent TAIC.
Wherein, the preparation method of the fluorosilicone rubber and the polyethylene glycol-polybutadiene-polyethylene glycol triblock copolymer is the same as that of the example 1;
the method of the preparation method is the same as that of the example 1, wherein the white carbon black and the carbon black are subjected to modification pretreatment of a silane coupling agent Si-69;
the preparation method of the rubber sealing material for the automobile engine comprises the following steps:
firstly, mixing fluorosilicone rubber and white carbon black on a two-roll open mill for 10min, then adding the mixture into a kneader, kneading for 8h under the conditions that the temperature is 140 ℃ and the vacuum degree is minus 0.1MPa, standing for 24h, then mixing the mixture with ethylene propylene diene monomer rubber, epoxy nitrile rubber, chlorosulfonated polyethylene rubber, polyethylene glycol-polybutadiene-polyethylene glycol triblock copolymer, dibutyl phthalate and coumarone resin, then mixing for 2min, adding carbon black, an antioxidant RD and an antioxidant MB, continuously mixing for 8min, discharging rubber, adding the obtained rubber into the two-roll open mill, back mixing for 6min, adding a vulcanizing agent DCP and an auxiliary cross-linking agent TAIC, discharging sheets after 10 times of thinning, and vulcanizing the rubber on a flat vulcanizing machine for 20min at 170 ℃ after the rubber is parked for 24h.
Example 3:
a rubber sealing material for an automobile engine comprises the following components in parts by weight:
60 parts of ethylene propylene diene monomer rubber, 20 parts of epoxy-terminated nitrile rubber, 20 parts of fluorosilicone rubber, 5 parts of chlorosulfonated polyethylene rubber, 5 parts of polyethylene glycol-polybutadiene-polyethylene glycol triblock copolymer, 60 parts of white carbon black, 15 parts of carbon black, 1 part of antioxidant RD, 1 part of antioxidant MB, 1.5 parts of dibutyl phthalate, 1.5 parts of coumarone resin, 1 part of vulcanizing agent DCP and 0.5 part of auxiliary crosslinking agent TAIC.
Wherein, the preparation method of the fluorosilicone rubber and the polyethylene glycol-polybutadiene-polyethylene glycol triblock copolymer is the same as that of the example 1;
the method of the preparation method is the same as that of the example 1, wherein the white carbon black and the carbon black are subjected to modification pretreatment of a silane coupling agent Si-69;
the preparation method of the rubber sealing material for the automobile engine comprises the following steps:
firstly, mixing fluorosilicone rubber and white carbon black on a two-roll open mill for 10min, then adding the mixture into a kneader, kneading for 4h under the conditions that the temperature is 120 ℃ and the vacuum degree is minus 0.05MPa, standing for 18h, then mixing the mixture with ethylene propylene diene monomer rubber, epoxy nitrile rubber, chlorosulfonated polyethylene rubber, polyethylene glycol-polybutadiene-polyethylene glycol triblock copolymer, dibutyl phthalate and coumarone resin, then mixing for 1min, adding carbon black, an antioxidant RD and an antioxidant MB, continuously mixing for 4min, discharging rubber, adding the obtained rubber into the two-roll open mill, carrying out back mixing for 3min, adding a vulcanizing agent DCP and an auxiliary cross-linking agent TAIC, carrying out sheet discharging after 5 times of thinning, standing the rubber, and vulcanizing for 10min on a flat vulcanizing machine at 150 ℃ and 10 MPa.
Comparative example 1:
substantially the same as in example 1, except that the terminal epoxy nitrile rubber was not added.
Comparative example 2:
substantially the same as in example 1, except that a commercially available fluorosilicone elastomer AFS was used ® -R-H2100 replaces homemade fluorosilicone rubber.
Comparative example 3:
substantially the same as in example 1, except that the fluorosilicone rubber was not added.
Comparative example 4:
substantially the same as in example 1, except that chlorosulfonated polyethylene rubber was not added.
Comparative example 5:
substantially the same as in example 1, except that the polyethylene glycol-polybutadiene-polyethylene glycol triblock copolymer was not added.
Performance test:
(1) performance test is carried out by taking the rubber sealing materials prepared in the examples 1-3 and the comparative examples 1-4 as test samples;
tensile properties were tested according to GB/T528-2009;
the tearing strength is tested according to GB/T529-2008, and a right-angle sample is adopted;
compression set was tested according to GB/T7759.1-2015;
DIN abrasion was tested according to GB/T9867-2008.
Table 1:
| tensile Strength/MPa | Elongation at break/% | Tear strength/(kN.m) -1 ） | Compression set/% | DIN abrasion loss/mm 3 | |
| Example 1 | 20.4 | 325 | 52 | 10.3 | 110 |
| Example 2 | 19.8 | 309 | 47 | 12.6 | 118 |
| Example 3 | 18.4 | 288 | 47 | 14.5 | 121 |
| Comparative example 1 | 17.6 | 260 | 41 | 20.2 | 132 |
| Comparative example 2 | 19.4 | 310 | 48 | 15.1 | 124 |
| Comparative example 3 | 18.6 | 303 | 44 | 18.4 | 140 |
| Comparative example 4 | 17.9 | 290 | 49 | 23.6 | 125 |
| Comparative example 5 | 19.0 | 312 | 48 | 19.7 | 115 |
As can be seen from the above Table 1, the rubber sealing material prepared by the invention has excellent properties and is suitable for sealing automobile engines.
(2) The oil resistance test is carried out by referring to national standard GB/T15005-1995 "vulcanized rubber humid Heat ageing test".
And (3) carrying out an oil resistance test on the sample at 80 ℃ for 100 hours, adopting an HK-80L constant temperature and humidity test box to carry out the test, hanging the sample in the box in a free state, putting a beaker in the test box, pouring 92# gasoline into the beaker, heating the test box after sealing to enable the test box to be full of gasoline steam, starting timing, finishing the test to be tested, taking out the sample, placing for 6 hours, testing each performance of the sample, recording data, comparing the data with the data before the test, and obtaining the oil resistance coefficient of the sample.
The oil resistance is represented by E: e=c/d×100%
Wherein: e is oil resistance (%), C is performance data after test of the sample, and D is performance data before test of the sample.
The results are shown in Table 2 below:
table 2:
| tensile Strength/MPa | Elongation at break/% | Tear strength/(kN.m) -1 ） | Compression set/% | DIN abrasion loss/mm 3 | |
| Example 1 | 0.73 | 0.79 | 0.65 | 1.46 | 0.87 |
| Example 2 | 0.70 | 0.75 | 0.62 | 1.50 | 0.85 |
| Example 3 | 0.69 | 0.72 | 0.61 | 1.49 | 0.85 |
| Comparative example 1 | 0.65 | 0.70 | 0.58 | 1.55 | 0.81 |
| Comparative example 2 | 0.62 | 0.54 | 0.57 | 1.60 | 0.76 |
| Comparative example 3 | 0.58 | 0.60 | 0.55 | 1.64 | 0.73 |
| Comparative example 4 | 0.71 | 0.77 | 0.62 | 1.48 | 0.83 |
| Comparative example 5 | 0.70 | 0.74 | 0.61 | 1.51 | 0.86 |
As shown in the table 2, the rubber sealing material prepared by the invention has better oil resistance and high temperature resistance.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (6)
1. The rubber sealing material for the automobile engine is characterized by comprising the following components in parts by weight:
60-80 parts of ethylene propylene diene monomer rubber, 20-30 parts of epoxy-terminated nitrile rubber, 20-30 parts of fluorosilicone rubber, 5-10 parts of chlorosulfonated polyethylene rubber, 5-10 parts of polyethylene glycol-polybutadiene-polyethylene glycol triblock copolymer, 60-80 parts of white carbon black, 15-30 parts of carbon black, 1-2 parts of antioxidant RD, 1-2 parts of antioxidant MB, 1-3 parts of plasticizer and 1-3 parts of vulcanization component;
the number average molecular weight of the fluorosilicone rubber is 1-10 ten thousand, and the structural formula is shown as follows:
wherein m is the number of dimethyl siloxane units, and n is the number of trifluoropropyl methyl siloxane units;
m：n=1：1~10；
r is aminopropyl or aminobutyl;
the preparation method of the polyethylene glycol-polybutadiene-polyethylene glycol triblock copolymer comprises the following steps:
modifying the hydroxyl-terminated group of the hydroxyl-terminated polybutadiene into a p-toluenesulfonate group which is easy to leave by utilizing the reaction of the hydroxyl-terminated polybutadiene and the p-toluenesulfonate chloride, and obtaining a polyethylene glycol-polybutadiene-polyethylene glycol triblock copolymer by utilizing the nucleophilic substitution reaction of the hydroxyl-terminated group of the polyethylene glycol and the toluenesulfonate group;
the preparation method of the rubber sealing material for the automobile engine comprises the following steps:
uniformly mixing fluorosilicone rubber and white carbon black on a two-roll open mill, kneading for 4-8 hours at the temperature of 120-140 ℃ and the vacuum degree of-0.1 to-0.05 MPa in a kneader, standing for 18-24 hours, mixing with ethylene propylene diene monomer, epoxy nitrile rubber, chlorosulfonated polyethylene rubber, polyethylene glycol-polybutadiene-polyethylene glycol triblock copolymer and plasticizer, mixing for 1-2 minutes, adding carbon black, an antioxidant RD and an antioxidant MB, continuously mixing for 4-8 minutes, discharging rubber, adding the obtained rubber into the two-roll open mill, carrying out back mixing for 3-6 minutes, adding a vulcanization component, carrying out sheet thinning for 5-10 times, standing for 12-24 hours, vulcanizing for 10-20 minutes at the temperature of 150-170 ℃ and the pressure of 10-15 MPa in a flat vulcanizing machine, and taking out the rubber from a die.
2. The rubber sealing material for an automobile engine according to claim 1, wherein the fluorosilicone rubber is prepared from trifluoropropyl methyl cyclotrisiloxane, octamethyl cyclotetrasiloxane, 1, 3-bis (3-aminopropyl) tetramethyldisiloxane and a catalyst;
wherein the dosage of the 1, 3-bis (3-aminopropyl) tetramethyl disiloxane is 0.5-1% of the total weight of the trifluoro propyl methyl cyclotrisiloxane and the octamethyl cyclotrisiloxane.
3. The rubber sealing material for an automobile engine according to claim 2, wherein the catalyst is fluorosilicone alcohol tetramethyl ammonium hydroxide.
4. The rubber sealing material for an automobile engine according to claim 1, wherein both the white carbon black and the carbon black are subjected to a sulfur-containing silane coupling agent modification treatment.
5. The rubber sealing material for an automobile engine according to claim 1, wherein the plasticizer is any one or a combination of a plurality of liquid paraffin, dioctyl phthalate, dibutyl phthalate and coumarone resin.
6. The rubber sealing material for an automobile engine according to claim 1, wherein the vulcanization component comprises a vulcanizing agent DCP and a auxiliary crosslinking agent TAIC, and the weight ratio of the vulcanizing agent DCP to the auxiliary crosslinking agent TAIC is 2-4: 1.
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