CN105860284A - Thermoplastic vulcanized rubber material for automobile turning dust cover and preparation method of thermoplastic vulcanized rubber material - Google Patents
Thermoplastic vulcanized rubber material for automobile turning dust cover and preparation method of thermoplastic vulcanized rubber material Download PDFInfo
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Abstract
The invention discloses a thermoplastic vulcanized rubber material for an automobile turning dust cover and a preparation method of the thermoplastic vulcanized rubber material. The thermoplastic vulcanized rubber material is prepared from, by weight, 100-300 parts of EPDM, 20-80 parts of polypropylene, 10-50 parts of linear low density polyethylene, 40-100 parts of thermoplastic polyurethane elastomers, 5-15 parts of ethylene-octylene copolymers, 5-15 parts of compatilizer, 10-80 parts of inorganic filler, 3-5 parts of silane coupling agent, 0.2-10 parts of cross-linking agent, 1-5 parts of activated zinc oxide, 1-3 parts of primary antioxidant, 0.5-1 part of auxiliary antioxidant, 1-3 parts of ultraviolet light absorber, 20-100 parts of processing oil and 2-6 parts of lubricating oil. The thermoplastic vulcanized rubber material has excellent strength, high temperature resistance, flexibility and blow molding performance.
Description
Technical field
The present invention relates to technical field of rubber material, particularly a kind of motor turning dust cover thermoplastic vulcanizate material and preparation method thereof.
Background technology
The major function of motor turning dust cover turns to machine system for preventing dust, moisture, oil product, mud, sandstone etc. from entering, and pull bar produces corrosion, sealing ring is produced abrasion and causes whole turning to inefficacy；Being affected by enging cabin high temperature and working environment and require that it manufactures material and has higher resistance to elevated temperatures, ozone resistance, resistance to oil property and weather resistance, therefore the requirement to material is the most extremely important.TPV has good elasticity and compression resistant morphotropism, and resistance to environment, resistance to ag(e)ing are equivalent to EP rubbers, and its oil resistant solvent resistance is equally matched with polychloroprene rubber for general purpose simultaneously.TPV body can use in-60 DEG C of-135 DEG C of temperature ranges, and TPV body need not sulfuration when using, and can shorten processing process directly by mode machine-shapings such as blowings, reduce processing cost.Main flow turns to dust cover product all to use thermoplastic vulcanizate material in the market.
United States Patent (USP) US4311628/0272871A1 discloses the method preparing TPV, described elastomer is EP rubbers, resin is polypropylene, vulcanizing system be Phenolic resin curative, two hydrated stannous chlorides be that vulcanization accelerator uses dynamic vulcanization technology to prepare TPV, but this vulcanite is relatively poor for the intensity of motor turning dust cover, heat-resisting quantity and flexility, blowing is processed or relatively difficult, is therefore not met by the performance requirement of motor turning dust cover.
Summary of the invention
Based on problem present in background technology, the present invention proposes a kind of motor turning dust cover thermoplastic vulcanizate material and preparation method thereof, described thermoplastic vulcanizate material has intensity, heat-resisting quantity and the pliability of excellence, and blow processability can be excellent.
A kind of motor turning dust cover thermoplastic vulcanizate material, its raw material includes by weight: EPDM100-300 part, polypropylene 20-80 part, linear low density polyethylene 10-50 part, Polyurethane Thermoplastic Elastomer 40-100 part, ethylene-octene copolymer 5-15 part, compatilizer 5-15 part, inorganic filler 10-80 part, silane coupler 3-5 part, cross-linking agent 0.2-10 part, activity Zinc Oxide 1-5 part, primary antioxidant 1-3 part, auxiliary anti-oxidant 0.5-1 part, UV absorbent 1-3 part, processing oil 20-100 part, lubricant 2-6 part；
Wherein, described EPDM is made up of the H type ethylene propylene diene rubber that Third monomer is Isosorbide-5-Nitrae-hexadiene of the E type ethylene propylene diene rubber that the Third monomer of 40-60wt% is ethenylidene norborene, the D type ethylene propylene diene rubber that Third monomer is dicyclopentadiene of 10-30wt% and 20-40wt%；
Described Polyurethane Thermoplastic Elastomer is graphite modified polyurethane elastomer, and its preparation method includes: added by graphite powder in the mixed acid solution of concentrated nitric acid and concentrated sulphuric acid composition, water-bath after supersound process, sucking filtration, and washing obtains graphite oxide；After being dehydrated by PTMEG, adding isocyanates, after being warming up to 80-100 DEG C, stirring reaction 1-3h, obtains the performed polymer of terminal isocyanate group；Described graphite oxide is added ultrasonic disperse in DMF; under conditions of nitrogen is protected; adding performed polymer and the catalyst dibutyl tin dilaurate of terminal isocyanate group, after being warming up to 60-80 DEG C, stirring reaction 1-3h, adds chain extender and accelerator trihydroxymethyl propane; quickly stir 0.01-0.02h; it is further continued for after evacuation stirring 0.01-0.02h, filters, washing; ripening, obtains described graphite modified polyurethane elastomer.
In a specific embodiment, the weight portion of EPDM can be 105,110,130,150,160,180,195,200,210,235,250,265,280,295；Polyacrylic weight portion can be 25,30,35,45,50,60,65,70,75；The weight portion of linear low density polyethylene can be 12,15,17,20,25,28,31,33,36,39,41,45,47；The weight portion of Polyurethane Thermoplastic Elastomer can be 45,50,55,60,65,70,75,80,85,90,95；, the weight portion of ethylene-octene copolymer can be 6,7,8,9,10,11,12,13,14；The weight portion of compatilizer can be 6,7,8,9,10,11,12,13,14；The weight portion of inorganic filler can be 12,16,18,20,24,30,35,42,56,60,65,70,75,78；The weight portion of cross-linking agent can be 0.3,0.5,0.7,1,3,4,5,6,7,8,9.5；The weight portion of processing oil can be 22,26,30,35,40,53,68,75,80,85,90,95,98.
Preferably, described graphite modified method for preparing polyurethane elastic body includes: graphite powder is added concentrated nitric acid that volume ratio is 1:1-3 with in the mixed acid solution of concentrated sulphuric acid, supersound process 1-3h at 20-40 DEG C, 1-3h is reacted again 80-100 DEG C of stirred in water bath, it is cooled to room temperature, sucking filtration, is washed with deionized to neutrality, obtains graphite oxide；Being dehydrated 3-5h after PTMEG being warming up to 90-120 DEG C and being evacuated to pressure≤-0.09Mpa, be cooled to 40-60 DEG C, add isocyanates, after being warming up to 80-100 DEG C, stirring reaction 1-3h, obtains the performed polymer of terminal isocyanate group；Described graphite oxide is added ultrasonic disperse 0.5-1h in DMF; under conditions of nitrogen is protected; add performed polymer and the catalyst dibutyl tin dilaurate of terminal isocyanate group; stirring reaction 1-3h after being warming up to 60-80 DEG C; add chain extender and accelerator trihydroxymethyl propane; 0.01-0.02h is quickly stirred under 1000-1200rpm; it is further continued for after evacuation stirring 0.01-0.02h; use politef membrane filtration; washing; ripening 5-10h in the drying baker of 100-120 DEG C, obtains described graphite modified polyurethane elastomer；Preferably, graphite powder, PTMEG, isocyanates, dibutyl tin dilaurate, the weight proportion of trihydroxymethyl propane are 1:50-70:20-35:10-20:0.05-0.1:2-4.
Preferably, described PTMEG be number-average molecular weight be tetrahydrofuran polyether PTMG or hydroquinone two (2-ethoxy) the ether HQEE of 800-1200；Described isocyanates be hexamethylene diisocyanate, 2,4 toluene diisocyanate, 2,6-toluene di-isocyanate(TDI), 2,4-methyl diphenylene diisocyanate, 4, at least one in 4-methyl diphenylene diisocyanate；Described chain extender be ethylene glycol, BDO, 1, at least one in 6-hexanediol.
Preferably, described polypropylene is made up of the copolymerized type propene polymer of 25-45wt% and the homopolymerization type polypropylene of 55-75wt%, and the melt index of described copolymerized type propene polymer is 0.5-10.0g/10min；The described polyacrylic melt index of homopolymerization type is 0.5-5.0g/10min.
Preferably, described compatilizer be maleic anhydride grafted ethene-octene copolymer POE-g-MAH, maleic anhydride graft phenylethene-ethylene-butadiene-styrene copolymer SEBS-g-MAH, maleic anhydride grafting ethylene propylene diene rubber EPDM-g-MAH at least one；Described inorganic filler is at least one in wollastonite, Pulvis Talci, glass microballoon, barium sulfate, mica powder, clay；Described silane coupler is at least one in Silane coupling reagent KH-570, silane coupling A-137.
Preferably, described cross-linking agent is made up of the peroxide cross-linking agent that weight proportion is 3-5:1 and assistant crosslinking agent；Preferably, described peroxide cross-linking agent is 2,5-dimethyl-2,5-bis(t-butylperoxy) hexin, 2,5-dimethyl-2, at least one in 5-bis(t-butylperoxy) hexane, cumyl peroxide；Described assistant crosslinking agent is at least one in polyesters material, polybutadiene species, cyanate material, isocyanates material, esters of acrylic acid material.
Preferably, at least one during described primary antioxidant is antioxidant 1010, antioxidant 3114, antioxidant DSTP；Described auxiliary anti-oxidant is 2-mercaptobenzimidazole MB, at least one in triphenyl phosphite TPP, dilauryl thiodipropionate DLTP.
Preferably, at least one during described UV absorbent is ultraviolet absorbent uv-326, UV absorbent UV-9；Described processing oil is at least one in paraffin oil, naphthenic oil, hydrocarbon oil；Described lubricant is at least one in ethylene bis stearic acid amide, oleamide, zinc stearate, calcium stearate.
A kind of preparation method of motor turning dust cover thermoplastic vulcanizate material, including: EPDM, polypropylene, linear low density polyethylene, Polyurethane Thermoplastic Elastomer, ethylene-octene copolymer, compatilizer, inorganic filler, silane coupler, primary antioxidant, auxiliary anti-oxidant, UV absorbent, processing oil and lubricant are added banburying in banbury uniform, it is re-fed in single screw extrusion machine carrying out plastics for the first time, wherein screw speed is 200-400r/min, the processing temperature plasticated for the first time is 160-180 DEG C, obtains rubber master batch after pelletizing；Described rubber master batch and cross-linking agent, activity Zinc Oxide are added in high mixer, 0.3-0.5h is mixed under the speed conditions of 400-500rpm, transferring to carry out second time in double screw extruder plasticate, wherein screw slenderness ratio is 55-64, and feeding rotating speed is 30-80rpm, screw speed is 300-500rpm, the processing temperature that second time is plasticated is 160-250 DEG C, tie rod, cooling, pelletizing, obtains described motor turning dust cover thermoplastic vulcanizate material.
Preferably, described second time is plasticated processing temperature is particularly as follows: district's temperature 160-180 DEG C, two district's temperature 200-210 DEG C, three district's temperature 220-230 DEG C, four district's temperature 240-250 DEG C, five district's temperature 240-250 DEG C, six district's temperature 235-245 DEG C, seven district's temperature 225-235 DEG C, eight district's temperature 210-220 DEG C, nine district's temperature 205-215 DEG C, ten district's temperature 200-210 DEG C.
In the present invention, described thermoplastic vulcanizate material uses the E type ethylene propylene diene rubber of specific proportioning, D type ethylene propylene diene rubber and H type ethylene propylene diene rubber as the source of EPDM, make its hot strength, bending modulus and cross-linked polymeric degree all in a rational state, in motor turning dust cover, durability and the machine-shaping property of excellence can be obtained；The addition of polypropylene and linear low density polyethylene the most not only makes described elastomeric material can obtain required melt forming intensity, and can improve the blow processability energy of described material further；And owing to polypropylene has good solvent resistance, thermostability and processing fluidity, when compounding with EPDM, the pliability of elastomeric material itself can be substantially improved, thus meet the performance requirement of motor turning dust cover；The ethylene-octene copolymer being simultaneously introduced and compatilizer then can significantly improve the compatibility between each major ingredient, it is thus achieved that good combination property.
nullIn addition，In the present invention，Described Polyurethane Thermoplastic Elastomer utilizes graphite to be modified it，By molecule after graphite powder pickling has been entered into inside graphite,The interior layer spacing of graphite is widened，Interplanar distance increases，Graphite flakes shape structure is made to be destroyed after sonicated，Thus increase the spacing of graphite platelet structure,Make graphite internal structure become loose and volume to expand，And then the groups such as activity hydroxy are formed on surface，Again by with the polyurethane prepolymer precursor reactant with terminal isocyanate group，And add chain extender end-blocking，Thus obtain a kind of graphite modified polyurethane elastomer，While it realizes activating graphite surface，Also on the molecule of polyurethane elastomer, introduce graphite platelet structure，Thus obtained modified polyurethane elastomer can form densification on the surface of described vulcanized rubber material、Efficient carbon-coating structure，Thus effectively absorb heat，Heat is hindered to transmit to elastomeric material internal layer，Give the resistance to elevated temperatures that described material is good；And above-mentioned modified thermoplastic polyurethane elastomer makes graphite platelet structure be evenly dispersed in inside the matrixes such as EPDM with the state peeled off, the effect of skeletal support can be played, or serve as solid phase charcoal core, strengthen interfacial effect, beneficially elastomeric material and obtain the mechanical effects such as excellent intensity.
Further, the present invention, during preparing described thermoplastic vulcanizate material, uses dynamic vulcanization technology, using organic peroxide cross-linking system as vulcanizing agent, can efficiently control the crosslinking degree of cross-linked material and uniform performance；And use the processing technique of plasticating under special parameter so that Blending Processes is more abundant, and the rubber phase particle diameter in blend is less, it is more evenly distributed, the entanglement effect of molecule interchain is less, and solution twines relatively easily, avoids, with this, the mobility variation effect that causes because of elastomeric material over cure；The present invention is additionally added a certain amount of antioxidant, lubricant and UV absorbent, thus makes the thermoplastic vulcanizate material prepared have good weather resistance and mechanical property.
Detailed description of the invention
Below by specific embodiment, technical scheme is described in detail.
Embodiment 1
A kind of motor turning dust cover thermoplastic vulcanizate material, its raw material includes by weight: EPDM100 part, polypropylene 80 parts, linear low density polyethylene 10 parts, Polyurethane Thermoplastic Elastomer 100 parts, ethylene-octene copolymer 5 parts, maleic anhydride grafted ethene-octene copolymer POE-g-MAH 15 parts, wollastonite 10 parts, Silane coupling reagent KH-570 5 parts, cross-linking agent 0.2 part, activity Zinc Oxide 5 parts, antioxidant 1010 1 part, 2-mercaptobenzimidazole MB 1 part, ultraviolet absorbent uv-326 1 part, paraffin oil 100 parts, ethylene bis stearic acid amide 2 parts；
Wherein, described EPDM is made up of the H type ethylene propylene diene rubber that Third monomer is Isosorbide-5-Nitrae-hexadiene of the E type ethylene propylene diene rubber that the Third monomer of 40wt% is ethenylidene norborene, the D type ethylene propylene diene rubber that Third monomer is dicyclopentadiene of 30wt% and 30wt%；
Described Polyurethane Thermoplastic Elastomer is graphite modified polyurethane elastomer, its preparation method includes: graphite powder is added concentrated nitric acid that volume ratio is 1:1 with in the mixed acid solution of concentrated sulphuric acid, supersound process 1h at 40 DEG C, 1h is reacted again 100 DEG C of stirred in water bath, it is cooled to room temperature, sucking filtration, is washed with deionized to neutrality, obtains graphite oxide；Being dehydrated 3h after PTMEG being warming up to 120 DEG C and being evacuated to pressure≤-0.09Mpa, be cooled to 60 DEG C, add isocyanates, after being warming up to 80 DEG C, stirring reaction 3h, obtains the performed polymer of terminal isocyanate group；Described graphite oxide is added ultrasonic disperse 0.5h in DMF; under conditions of nitrogen is protected; adding performed polymer and the catalyst dibutyl tin dilaurate of terminal isocyanate group, after being warming up to 80 DEG C, stirring reaction 1h, adds chain extender and accelerator trihydroxymethyl propane; 0.01h is quickly stirred under 1200rpm; it is further continued for after evacuation stirring 0.02h, uses politef membrane filtration, washing; ripening 10h in the drying baker of 100 DEG C, obtains described graphite modified polyurethane elastomer；Wherein, graphite powder, PTMEG, isocyanates, dibutyl tin dilaurate, the weight proportion of trihydroxymethyl propane are 1:50:35:10:0.1:2；Described PTMEG be number-average molecular weight be tetrahydrofuran polyether PTMG of 800；Described isocyanates is hexamethylene diisocyanate；Described chain extender is ethylene glycol；
Described polypropylene is made up of the copolymerized type propene polymer of 25wt% and the homopolymerization type polypropylene of 75wt%, and the melt index of described copolymerized type propene polymer is 0.5g/10min；The described polyacrylic melt index of homopolymerization type is 5.0g/10min；Described cross-linking agent is made up of the 2,5-dimethyl-2,5-bis(t-butylperoxy) hexin that weight proportion is 3:1 and polyesters material；Described UV absorbent is ultraviolet absorbent uv-326.
Embodiment 2
A kind of motor turning dust cover thermoplastic vulcanizate material, its raw material includes by weight: EPDM300 part, polypropylene 20 parts, linear low density polyethylene 50 parts, Polyurethane Thermoplastic Elastomer 40 parts, ethylene-octene copolymer 15 parts, maleic anhydride graft phenylethene-ethylene-butadiene-styrene copolymer SEBS-g-MAH 5 parts, Pulvis Talci 80 parts, silane coupling A-137 3 parts, cross-linking agent 10 parts, activity Zinc Oxide 1 part, antioxidant 3114 3 parts, triphenyl phosphite TPP 0.5 part, UV absorbent UV-93 part, naphthenic oil 20 parts, oleamide 6 parts；
Wherein, described EPDM is made up of the H type ethylene propylene diene rubber that Third monomer is Isosorbide-5-Nitrae-hexadiene of the E type ethylene propylene diene rubber that the Third monomer of 60wt% is ethenylidene norborene, the D type ethylene propylene diene rubber that Third monomer is dicyclopentadiene of 10wt% and 30wt%；
Described Polyurethane Thermoplastic Elastomer is graphite modified polyurethane elastomer, its preparation method includes: graphite powder is added concentrated nitric acid that volume ratio is 1:3 with in the mixed acid solution of concentrated sulphuric acid, supersound process 3h at 20 DEG C, 3h is reacted again 80 DEG C of stirred in water bath, it is cooled to room temperature, sucking filtration, is washed with deionized to neutrality, obtains graphite oxide；Being dehydrated 5h after PTMEG being warming up to 90 DEG C and being evacuated to pressure≤-0.09Mpa, be cooled to 40 DEG C, add isocyanates, after being warming up to 100 DEG C, stirring reaction 1h, obtains the performed polymer of terminal isocyanate group；Described graphite oxide is added ultrasonic disperse 1h in DMF; under conditions of nitrogen is protected; adding performed polymer and the catalyst dibutyl tin dilaurate of terminal isocyanate group, after being warming up to 60 DEG C, stirring reaction 3h, adds chain extender and accelerator trihydroxymethyl propane; 0.02h is quickly stirred under 1000rpm; it is further continued for after evacuation stirring 0.01h, uses politef membrane filtration, washing; ripening 5h in the drying baker of 120 DEG C, obtains described graphite modified polyurethane elastomer；Wherein, graphite powder, PTMEG, isocyanates, dibutyl tin dilaurate, the weight proportion of trihydroxymethyl propane are 1:70:20:20:0.05:4；Described PTMEG be number-average molecular weight be hydroquinone two (2-ethoxy) the ether HQEE of 1200；Described isocyanates is 2,4 toluene diisocyanate；Described chain extender is BDO；
Described polypropylene is made up of the copolymerized type propene polymer of 45wt% and the homopolymerization type polypropylene of 55wt%, and the melt index of described copolymerized type propene polymer is 10.0g/10min；The described polyacrylic melt index of homopolymerization type is 0.5g/10min；Described compatilizer is maleic anhydride graft phenylethene-ethylene-butadiene-styrene copolymer SEBS-g-MAH；Described inorganic filler is Pulvis Talci；Described silane coupler is silane coupling A-137；Described cross-linking agent is made up of the 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane that weight proportion is 5:1 and polybutadiene species.
Embodiment 3
A kind of motor turning dust cover thermoplastic vulcanizate material, its raw material includes by weight: EPDM200 part, polypropylene 50 parts, linear low density polyethylene 30 parts, Polyurethane Thermoplastic Elastomer 70 parts, ethylene-octene copolymer 10 parts, maleic anhydride grafting ethylene propylene diene rubber EPDM-g-MAH 10 parts, glass microballoon 45 parts, Silane coupling reagent KH-570 4 parts, cross-linking agent 5 parts, activity Zinc Oxide 3 parts, antioxidant DSTP 2 parts, dilauryl thiodipropionate DLTP 0.7 part, ultraviolet absorbent uv-326 2 parts, hydrocarbon oil 60 parts, zinc stearate 4 parts；
Wherein, described EPDM is made up of the H type ethylene propylene diene rubber that Third monomer is Isosorbide-5-Nitrae-hexadiene of the E type ethylene propylene diene rubber that the Third monomer of 50wt% is ethenylidene norborene, the D type ethylene propylene diene rubber that Third monomer is dicyclopentadiene of 10wt% and 40wt%；
Described Polyurethane Thermoplastic Elastomer is graphite modified polyurethane elastomer, its preparation method includes: graphite powder is added concentrated nitric acid that volume ratio is 1:2 with in the mixed acid solution of concentrated sulphuric acid, supersound process 2h at 30 DEG C, 2h is reacted again 90 DEG C of stirred in water bath, it is cooled to room temperature, sucking filtration, is washed with deionized to neutrality, obtains graphite oxide；Being dehydrated 4h after PTMEG being warming up to 105 DEG C and being evacuated to pressure≤-0.09Mpa, be cooled to 50 DEG C, add isocyanates, after being warming up to 90 DEG C, stirring reaction 2h, obtains the performed polymer of terminal isocyanate group；Described graphite oxide is added ultrasonic disperse 0.7h in DMF, under conditions of nitrogen is protected, add performed polymer and the catalyst dibutyl tin dilaurate of terminal isocyanate group, stirring reaction 2h after being warming up to 70 DEG C, add chain extender and accelerator trihydroxymethyl propane, 0.015h is quickly stirred under 1100rpm, it is further continued for after evacuation stirring 0.015h, use politef membrane filtration, washing, ripening 7h in the drying baker of 110 DEG C, obtain described graphite modified polyurethane elastomer, wherein graphite powder, PTMEG, isocyanates, dibutyl tin dilaurate, the weight proportion of trihydroxymethyl propane is 1:60:25:15:0.07:3；Described PTMEG be number-average molecular weight be tetrahydrofuran polyether PTMG of 1000；Described isocyanates is 2,6-toluene di-isocyanate(TDI)；Described chain extender is 1,6-hexanediol；
Described polypropylene is made up of the copolymerized type propene polymer of 35wt% and the homopolymerization type polypropylene of 65wt%, and the melt index of described copolymerized type propene polymer is 5.0g/10min；The described polyacrylic melt index of homopolymerization type is 3.0g/10min；Described cross-linking agent is made up of the cumyl peroxide that weight proportion is 4:1 and cyanate material.
Embodiment 4
A kind of motor turning dust cover thermoplastic vulcanizate material, its raw material includes by weight: EPDM250 part, polypropylene 60 parts, linear low density polyethylene 20 parts, Polyurethane Thermoplastic Elastomer 80 parts, ethylene-octene copolymer 12 parts, compatilizer 8 parts, inorganic filler 40 parts, silane coupler 4 parts, cross-linking agent 3 parts, activity Zinc Oxide 2 parts, primary antioxidant 2 parts, auxiliary anti-oxidant 0.8 part, UV absorbent 2 parts, processing oil 50 parts, lubricant 3 parts；
Wherein, described EPDM is made up of the H type ethylene propylene diene rubber that Third monomer is Isosorbide-5-Nitrae-hexadiene of the E type ethylene propylene diene rubber that the Third monomer of 60wt% is ethenylidene norborene, the D type ethylene propylene diene rubber that Third monomer is dicyclopentadiene of 20wt% and 20wt%；
Described Polyurethane Thermoplastic Elastomer is graphite modified polyurethane elastomer, its preparation method includes: graphite powder is added concentrated nitric acid that volume ratio is 1:2 with in the mixed acid solution of concentrated sulphuric acid, supersound process 1.5h at 25 DEG C, 2.5h is reacted again 95 DEG C of stirred in water bath, it is cooled to room temperature, sucking filtration, is washed with deionized to neutrality, obtains graphite oxide；Being dehydrated 4.5h after PTMEG being warming up to 100 DEG C and being evacuated to pressure≤-0.09Mpa, be cooled to 45 DEG C, add isocyanates, after being warming up to 95 DEG C, stirring reaction 1h, obtains the performed polymer of terminal isocyanate group；Described graphite oxide is added ultrasonic disperse 0.8h in DMF; under conditions of nitrogen is protected; adding performed polymer and the catalyst dibutyl tin dilaurate of terminal isocyanate group, after being warming up to 75 DEG C, stirring reaction 2h, adds chain extender and accelerator trihydroxymethyl propane; 0.01h is quickly stirred under 1100rpm; it is further continued for after evacuation stirring 0.02h, uses politef membrane filtration, washing; ripening 8h in the drying baker of 110 DEG C, obtains described graphite modified polyurethane elastomer；Wherein, graphite powder, PTMEG, isocyanates, dibutyl tin dilaurate, the weight proportion of trihydroxymethyl propane are 1:60:30:10:0.08:3；Described PTMEG be number-average molecular weight be hydroquinone two (2-ethoxy) the ether HQEE of 1000；Described isocyanates is 2,4-methyl diphenylene diisocyanate and 4, the mixture of 4-methyl diphenylene diisocyanate；Described chain extender is BDO and 1, the mixture of 6-hexanediol；
Described polypropylene is made up of the copolymerized type propene polymer of 30wt% and the homopolymerization type polypropylene of 70wt%, and the melt index of described copolymerized type propene polymer is 4.0g/10min；The described polyacrylic melt index of homopolymerization type is 2.0g/10min；Described compatilizer is maleic anhydride grafted ethene-octene copolymer POE-g-MAH and the mixture of maleic anhydride grafting ethylene propylene diene rubber EPDM-g-MAH；Described inorganic filler is the mixture of barium sulfate, mica powder and clay；Described silane coupler is the mixture of Silane coupling reagent KH-570 and silane coupling A-137；Described cross-linking agent is made up of the peroxide cross-linking agent that weight proportion is 4:1 and assistant crosslinking agent, and described peroxide cross-linking agent is 2,5-dimethyl-2,5-bis(t-butylperoxy) hexin and the mixture of cumyl peroxide, described assistant crosslinking agent is isocyanates material and the mixture of esters of acrylic acid material；Described primary antioxidant is antioxidant 1010 and the mixture of antioxidant DSTP；Described auxiliary anti-oxidant is triphenyl phosphite TPP and the mixture of dilauryl thiodipropionate DLTP；Described UV absorbent is ultraviolet absorbent uv-326；Described processing oil is the mixture of paraffin oil, naphthenic oil and hydrocarbon oil；Described lubricant is the mixture of zinc stearate and calcium stearate.
The preparation method of motor turning dust cover thermoplastic vulcanizate material described in above-described embodiment 1-4, including: by EPDM, polypropylene, linear low density polyethylene, Polyurethane Thermoplastic Elastomer, ethylene-octene copolymer, compatilizer, inorganic filler, silane coupler, primary antioxidant, auxiliary anti-oxidant, UV absorbent, it is uniform that processing oil and lubricant add banburying in banbury, it is re-fed in single screw extrusion machine carrying out plastics for the first time, wherein screw speed is 200-400r/min, the processing temperature plasticated for the first time is 160-180 DEG C, rubber master batch is obtained after pelletizing；Described rubber master batch and cross-linking agent, activity Zinc Oxide are added in high mixer, 0.3-0.5h is mixed under the speed conditions of 400-500rpm, transferring to carry out second time in double screw extruder plasticate, wherein screw slenderness ratio is 55-64, and feeding rotating speed is 30-80rpm, screw speed is 300-500rpm, the processing temperature that second time is plasticated is 160-250 DEG C, tie rod, cooling, pelletizing, obtains described motor turning dust cover thermoplastic vulcanizate material；Wherein, described second time is plasticated processing temperature is particularly as follows: district's temperature 160-180 DEG C, two district's temperature 200-210 DEG C, three district's temperature 220-230 DEG C, four district's temperature 240-250 DEG C, five district's temperature 240-250 DEG C, six district's temperature 235-245 DEG C, seven district's temperature 225-235 DEG C, eight district's temperature 210-220 DEG C, nine district's temperature 205-215 DEG C, ten district's temperature 200-210 DEG C.
Motor turning dust cover thermoplastic vulcanizate material described in above-described embodiment 1-4 is carried out performance test, and result is as follows:
In the present invention, described thermoplastic vulcanizate material uses the E type ethylene propylene diene rubber of specific proportioning, D type ethylene propylene diene rubber and H type ethylene propylene diene rubber as the source of EPDM, make its hot strength, bending modulus and cross-linked polymeric degree all in a rational state, in motor turning dust cover, durability and the machine-shaping property of excellence can be obtained；The addition of polypropylene and linear low density polyethylene the most not only makes described elastomeric material can obtain required melt forming intensity, and can improve the blow processability energy of described material further；And owing to polypropylene has good solvent resistance, thermostability and processing fluidity, when compounding with EPDM, the pliability of elastomeric material itself can be substantially improved, thus meet the performance requirement of motor turning dust cover；The ethylene-octene copolymer being simultaneously introduced and compatilizer then can significantly improve the compatibility between each major ingredient, it is thus achieved that good combination property.
nullIn addition，In the present invention，Described Polyurethane Thermoplastic Elastomer utilizes graphite to be modified it，By molecule after graphite powder pickling has been entered into inside graphite,The interior layer spacing of graphite is widened，Interplanar distance increases，Graphite flakes shape structure is made to be destroyed after sonicated，Thus increase the spacing of graphite platelet structure,Make graphite internal structure become loose and volume to expand，And then the groups such as activity hydroxy are formed on surface，Again by with the polyurethane prepolymer precursor reactant with terminal isocyanate group，And add chain extender end-blocking，Thus obtain a kind of graphite modified polyurethane elastomer，While it realizes activating graphite surface，Also on the molecule of polyurethane elastomer, introduce graphite platelet structure，Thus obtained modified polyurethane elastomer can form densification on the surface of described vulcanized rubber material、Efficient carbon-coating structure，Thus effectively absorb heat，Heat is hindered to transmit to elastomeric material internal layer，Give the resistance to elevated temperatures that described material is good；And above-mentioned modified thermoplastic polyurethane elastomer makes graphite platelet structure be evenly dispersed in inside the matrixes such as EPDM with the state peeled off, the effect of skeletal support can be played, or serve as solid phase charcoal core, strengthen interfacial effect, beneficially elastomeric material and obtain the mechanical effects such as excellent intensity.
Further, the present invention, during preparing described thermoplastic vulcanizate material, uses dynamic vulcanization technology, using organic peroxide cross-linking system as vulcanizing agent, can efficiently control the crosslinking degree of cross-linked material and uniform performance；And use the processing technique of plasticating under special parameter so that Blending Processes is more abundant, and the rubber phase particle diameter in blend is less, it is more evenly distributed, the entanglement effect of molecule interchain is less, and solution twines relatively easily, avoids, with this, the mobility variation effect that causes because of elastomeric material over cure；The present invention is additionally added a certain amount of antioxidant, lubricant and UV absorbent, thus makes the thermoplastic vulcanizate material prepared have good weather resistance and mechanical property.
The above; it is only the present invention preferably detailed description of the invention; but protection scope of the present invention is not limited thereto; any those familiar with the art is in the technical scope that the invention discloses; according to technical scheme and inventive concept equivalent or change in addition thereof, all should contain within protection scope of the present invention.
Claims (10)
1. a motor turning dust cover thermoplastic vulcanizate material, it is characterised in that its raw material is by weight
Amount part includes: EPDM 100-300 part, polypropylene 20-80 part, linear low density polyethylene 10-50 part,
Polyurethane Thermoplastic Elastomer 40-100 part, ethylene-octene copolymer 5-15 part, compatilizer 5-15 part,
Inorganic filler 10-80 part, silane coupler 3-5 part, cross-linking agent 0.2-10 part, activity Zinc Oxide 1-5 part,
Primary antioxidant 1-3 part, auxiliary anti-oxidant 0.5-1 part, UV absorbent 1-3 part, processing oil 20-100 part,
Lubricant 2-6 part；
Wherein, described EPDM is by the E type ternary that the Third monomer of 40-60wt% is ethenylidene norborene
EP rubbers, the D type ethylene propylene diene rubber that Third monomer is dicyclopentadiene of 10-30wt% and 20-40wt%
The H type ethylene propylene diene rubber that Third monomer is Isosorbide-5-Nitrae-hexadiene composition；
Described Polyurethane Thermoplastic Elastomer is graphite modified polyurethane elastomer, and its preparation method includes: will
Graphite powder adds in the mixed acid solution of concentrated nitric acid and concentrated sulphuric acid composition, water-bath after supersound process, sucking filtration,
Washing, obtains graphite oxide；After being dehydrated by PTMEG, add isocyanates, after being warming up to 80-100 DEG C
Stirring reaction 1-3h, obtains the performed polymer of terminal isocyanate group；Described graphite oxide is added in DMF ultrasonic
Dispersion, under conditions of nitrogen is protected, adds performed polymer and the catalyst dibutyl tin of terminal isocyanate group
Cinnamic acid stannum, after being warming up to 60-80 DEG C, stirring reaction 1-3h, adds chain extender and accelerator trihydroxymethyl propane,
Quickly stir 0.01-0.02h, be further continued for after evacuation stirring 0.01-0.02h, filter, washing, ripening,
Obtain described graphite modified polyurethane elastomer.
Motor turning dust cover thermoplastic vulcanizate material the most according to claim 1, its feature
Being, described graphite modified method for preparing polyurethane elastic body includes: it is 1 that graphite powder adds volume ratio:
In the concentrated nitric acid of 1-3 and the mixed acid solution of concentrated sulphuric acid, supersound process 1-3h at 20-40 DEG C, then
80-100 DEG C of stirred in water bath reaction 1-3h, is cooled to room temperature, sucking filtration, is washed with deionized to neutrality,
Obtain graphite oxide；It is dehydrated after PTMEG being warming up to 90-120 DEG C and being evacuated to pressure≤-0.09Mpa
3-5h, is cooled to 40-60 DEG C, adds isocyanates, stirring reaction 1-3h after being warming up to 80-100 DEG C,
Obtain the performed polymer of terminal isocyanate group；Described graphite oxide is added ultrasonic disperse 0.5-1h in DMF,
Under conditions of nitrogen protection, add performed polymer and the catalyst dibutyl tin dilaurate of terminal isocyanate group,
After being warming up to 60-80 DEG C, stirring reaction 1-3h, adds chain extender and accelerator trihydroxymethyl propane,
Quickly stir 0.01-0.02h under 1000-1200rpm, be further continued for after evacuation stirring 0.01-0.02h, use
Politef membrane filtration, washing, ripening 5-10h in the drying baker of 100-120 DEG C, obtain described graphite
Modified polyurethane elastomer；Preferably, graphite powder, PTMEG, isocyanates, dibutyl tin cinnamic acid
Stannum, the weight proportion of trihydroxymethyl propane are 1:50-70:20-35:10-20:0.05-0.1:2-4.
Motor turning dust cover thermoplastic vulcanizate material the most according to claim 2, its feature
Be, described PTMEG be number-average molecular weight be tetrahydrofuran polyether PTMG of 800-1200 or to benzene two
Phenol two (2-ethoxy) ether HQEE；Described isocyanates be hexamethylene diisocyanate, 2,4-toluene two is different
Cyanate, 2,6-toluene di-isocyanate(TDI), 2,4-methyl diphenylene diisocyanate, 4,4-diphenylmethyl
At least one in alkane diisocyanate；Described chain extender be ethylene glycol, BDO, 1,6-oneself two
At least one in alcohol.
4. according to the motor turning dust cover thermoplastic vulcanizate material described in any one of claim 1-3,
It is characterized in that, described polypropylene is that the homopolymerization type of the copolymerized type propene polymer by 25-45wt% and 55-75wt% gathers
Propylene forms, and the melt index of described copolymerized type propene polymer is 0.5-10.0g/10min；Described homopolymerization type gathers
The melt index of propylene is 0.5-5.0g/10min.
5. according to the motor turning dust cover thermoplastic vulcanizate material described in any one of claim 1-4,
It is characterized in that, described compatilizer is maleic anhydride grafted ethene-octene copolymer POE-g-MAH, maleic acid
Acid anhydride graft phenylethene-ethylene-butadiene-styrene copolymer SEBS-g-MAH, maleic anhydride grafting EPDM
At least one in rubber EPDM-g-MAH；Described inorganic filler be wollastonite, Pulvis Talci, glass microballoon,
At least one in barium sulfate, mica powder, clay；Described silane coupler be Silane coupling reagent KH-570,
At least one in silane coupling A-137.
6. according to the motor turning dust cover thermoplastic vulcanizate material described in any one of claim 1-5,
It is characterized in that, described cross-linking agent is by the peroxide cross-linking agent that weight proportion is 3-5:1 and assistant crosslinking agent
Composition；Preferably, described peroxide cross-linking agent is 2,5-dimethyl-2,5-bis(t-butylperoxy) hexin,
At least one in 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane, cumyl peroxide；Described
Assistant crosslinking agent be polyesters material, polybutadiene species, cyanate material, isocyanates material,
At least one in esters of acrylic acid material.
7. according to the motor turning dust cover thermoplastic vulcanizate material described in any one of claim 1-6,
It is characterized in that, described primary antioxidant be in antioxidant 1010, antioxidant 3114, antioxidant DSTP extremely
Few one；Described auxiliary anti-oxidant is 2-mercaptobenzimidazole MB, triphenyl phosphite TPP, thio-2 acid
At least one in dilauryl DLTP.
8. according to the motor turning dust cover thermoplastic vulcanizate material described in any one of claim 1-7,
It is characterized in that, described UV absorbent is in ultraviolet absorbent uv-326, UV absorbent UV-9
At least one；Described processing oil is at least one in paraffin oil, naphthenic oil, hydrocarbon oil；Described
Lubricant is at least one in ethylene bis stearic acid amide, oleamide, zinc stearate, calcium stearate.
9. one kind according to the motor turning dust cover TPV described in any one of claim 1-8
The preparation method of material, it is characterised in that including: by EPDM, polypropylene, linear low density polyethylene,
Polyurethane Thermoplastic Elastomer, ethylene-octene copolymer, compatilizer, inorganic filler, silane coupler, master
It is uniform that antioxidant, auxiliary anti-oxidant, UV absorbent, processing oil and lubricant add banburying in banbury,
Being re-fed in single screw extrusion machine carrying out plastics for the first time, wherein screw speed is 200-400r/min, first
The secondary processing temperature plasticated is 160-180 DEG C, obtains rubber master batch after pelletizing；By described rubber master batch and crosslinking
Agent, activity Zinc Oxide add in high mixer, mix 0.3-0.5h under the speed conditions of 400-500rpm, then
Being transferred in double screw extruder carry out second time plasticate, wherein screw slenderness ratio is 55-64, and feeding rotating speed is
30-80rpm, screw speed is 300-500rpm, and the processing temperature that second time is plasticated is 160-250 DEG C, draws
Bar, cooling, pelletizing, obtain described motor turning dust cover thermoplastic vulcanizate material.
The preparation of motor turning dust cover thermoplastic vulcanizate material the most according to claim 9
Method, processing temperature that described second time is plasticated is particularly as follows: district's temperature 160-180 DEG C, two district's temperature
200-210 DEG C, three district's temperature 220-230 DEG C, four district's temperature 240-250 DEG C, five district's temperature 240-250 DEG C,
Six district's temperature 235-245 DEG C, seven district's temperature 225-235 DEG C, eight district's temperature 210-220 DEG C, nine district's temperature
205-215 DEG C, ten district's temperature 200-210 DEG C.
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| CN115926436A (en) * | 2023-02-16 | 2023-04-07 | 河北华密新材科技股份有限公司 | Super-wear-resistant rubber and plastic material and preparation method and application thereof |
| CN117089143A (en) * | 2023-10-19 | 2023-11-21 | 广东腾业科技有限公司 | Low-energy-consumption recyclable blend and application thereof in production of all-plastic foam pump head |
| CN117089143B (en) * | 2023-10-19 | 2024-04-09 | 广东腾业科技有限公司 | Low-energy-consumption recyclable blend and application thereof in production of all-plastic foam pump head |
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