CN117362844A - Self-adhesive injection molding corner TPV material and preparation method thereof - Google Patents
Self-adhesive injection molding corner TPV material and preparation method thereof Download PDFInfo
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- CN117362844A CN117362844A CN202311269799.XA CN202311269799A CN117362844A CN 117362844 A CN117362844 A CN 117362844A CN 202311269799 A CN202311269799 A CN 202311269799A CN 117362844 A CN117362844 A CN 117362844A
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- 239000000463 material Substances 0.000 title claims abstract description 49
- 239000000853 adhesive Substances 0.000 title claims abstract description 34
- 238000001746 injection moulding Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims description 9
- 229920002943 EPDM rubber Polymers 0.000 claims abstract description 44
- -1 polypropylene Polymers 0.000 claims abstract description 29
- 239000004743 Polypropylene Substances 0.000 claims abstract description 28
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 28
- 229920001155 polypropylene Polymers 0.000 claims abstract description 27
- 229920006124 polyolefin elastomer Polymers 0.000 claims abstract description 21
- 239000003921 oil Substances 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 19
- 229920001971 elastomer Polymers 0.000 claims abstract description 18
- 239000005060 rubber Substances 0.000 claims abstract description 18
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 17
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 15
- 239000000945 filler Substances 0.000 claims abstract description 15
- 239000000314 lubricant Substances 0.000 claims abstract description 15
- 238000004073 vulcanization Methods 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 21
- 238000004132 cross linking Methods 0.000 claims description 16
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 12
- 239000005977 Ethylene Substances 0.000 claims description 12
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 12
- 239000000155 melt Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 150000001451 organic peroxides Chemical group 0.000 claims description 5
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000009775 high-speed stirring Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 claims description 2
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical group C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 claims description 2
- CCNDOQHYOIISTA-UHFFFAOYSA-N 1,2-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1C(C)(C)OOC(C)(C)C CCNDOQHYOIISTA-UHFFFAOYSA-N 0.000 claims description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 2
- ODBCKCWTWALFKM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-yne Chemical compound CC(C)(C)OOC(C)(C)C#CC(C)(C)OOC(C)(C)C ODBCKCWTWALFKM-UHFFFAOYSA-N 0.000 claims description 2
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 2
- HIJJQQSZGMTXFV-UHFFFAOYSA-N OCCO.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C Chemical compound OCCO.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C HIJJQQSZGMTXFV-UHFFFAOYSA-N 0.000 claims description 2
- 239000005662 Paraffin oil Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 229920005604 random copolymer Polymers 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 239000001993 wax Substances 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- PIMBTRGLTHJJRV-UHFFFAOYSA-L zinc;2-methylprop-2-enoate Chemical compound [Zn+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O PIMBTRGLTHJJRV-UHFFFAOYSA-L 0.000 claims description 2
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims 9
- 239000007924 injection Substances 0.000 claims 9
- KRDXTHSSNCTAGY-UHFFFAOYSA-N 2-cyclohexylpyrrolidine Chemical compound C1CCNC1C1CCCCC1 KRDXTHSSNCTAGY-UHFFFAOYSA-N 0.000 claims 1
- 235000010216 calcium carbonate Nutrition 0.000 claims 1
- 238000000465 moulding Methods 0.000 claims 1
- 239000004033 plastic Substances 0.000 claims 1
- 229920003023 plastic Polymers 0.000 claims 1
- 235000010215 titanium dioxide Nutrition 0.000 claims 1
- 238000007789 sealing Methods 0.000 abstract description 9
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- 229920006342 thermoplastic vulcanizate Polymers 0.000 description 27
- 239000002245 particle Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 9
- 239000012752 auxiliary agent Substances 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000002585 base Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- KNCZPLRYWQLPQT-UHFFFAOYSA-N 1-tert-butyl-2-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC=C1C(C)(C)C KNCZPLRYWQLPQT-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004408 titanium dioxide Substances 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—Ethene-propene or ethene-propene-diene copolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- 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)
Abstract
The self-adhesive injection molding corner TPV material comprises the following components in parts by weight: 30-60 parts of ethylene propylene diene monomer, 15-30 parts of polypropylene resin, 5-25 parts of polyolefin elastomer, 5-25 parts of rubber oil, 5-20 parts of filler, 0.5-5 parts of lubricant, 0.5-5 parts of cross-linking agent, 0.5-10 parts of auxiliary cross-linking agent and 0.1-3 parts of antioxidant. According to the invention, the polyolefin elastomer and the random polypropylene are added, so that the mechanical property of the original injection molding joint angle TPV material is maintained, the adhesive property of the material is greatly improved while the injection molding use temperature is reduced, the adhesive strength with the EPDM sealing strip is improved, and the material can be applied to higher-end application markets.
Description
Technical Field
The invention relates to the field of dynamic vulcanization thermoplastic elastomers, in particular to a self-adhesive injection molding corner TPV material and a preparation method thereof.
Background
Ethylene Propylene Diene Monomer (EPDM) has the softness and elasticity of conventional rubber and also has good weatherability. Can be used for a long time within the temperature range of minus 60 ℃ to 135 ℃ and has the advantages of excellent mechanical properties such as fatigue resistance, tearing resistance, acid and alkali resistance, ozone resistance and the like.
TPV thermoplastic elastomer is a thermoplastic elastomer produced by blending EPDM (ethylene propylene diene monomer) and PP (polypropylene) through a double screw extruder and dynamically vulcanizing, and in order to meet the ever-increasing requirements of environmental protection and recycling, TPV slowly plays an important role and starts to replace EPDM in certain fields. TPVs are currently mainly used in the automotive industry, where they account for over 50% of the sealing tape used to make them. The corners of the sealing strips usually require a joint angle, and some whole factories start pushing EPDM as a base material and TPV as a design requirement of the joint angle material on the window guide groove, however, they are two distinct materials, and the joint angle is difficult. TPV joint angle material has certain market share, and the location ratio is higher, and technical content is higher.
For the joint angle of EPDM sealing strips, there are mainly the following problems: (1) the adhesive strength is insufficient and the adhesive is easy to crack; (2) has shrinkage marks; (3) easy gate breakage. If the bonding effect is good, a relatively high injection molding temperature is generally required and is generally not lower than 230 ℃, but the problems (2) and (3) are relatively easy to occur at the relatively high injection molding temperature. The TPV joint material, while not a large percentage of the overall TPV market share, affects the use of conventional TPV weatherstrip materials.
Therefore, how to solve the above-mentioned drawbacks of the prior art is a subject to be studied and solved by the present invention.
Disclosure of Invention
The invention aims to provide a self-adhesive injection molding corner TPV material and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
the self-adhesive injection molding corner TPV material comprises the following components in parts by weight:
30-60 parts of ethylene propylene diene monomer rubber;
15-30 parts of polypropylene resin;
5-25 parts of polyolefin elastomer;
5-25 parts of rubber oil;
5-20 parts of filler;
0.5-5 parts of lubricant;
0.5-5 parts of a cross-linking agent;
0.5-10 parts of auxiliary cross-linking agent;
0.1-3 parts of an antioxidant.
According to a further technical scheme, the EPDM with low Mooney viscosity and high ethylene content is selected and compounded with the EPDM with medium viscosity, the main constituent monomers are ethylene and propylene, and the third monomer is ethylidene norbornene;
wherein, the Mooney viscosity ML (1+4) of the low Mooney viscosity EPDM is between 20 and 35 ℃, the ethylene content is between 50 and 70 percent, and the crosslinking monomer content is between 1 and 5 percent; the Mooney viscosity ML (1+4) of the medium viscosity EPDM is between 35 and 60 at 125 ℃; the weight ratio of the low-Mooney EPDM to the medium-viscosity EPDM is (1-3): (1-3).
According to a further technical scheme, the polypropylene resin is a random copolymer with the crystallinity lower than 30%, and is formed by polymerizing ethylene and propylene, wherein the ethylene content is 1% -7%; the melt index of the polypropylene resin is 10.0-30.0 g/10min, and the melt temperature is 120-150 ℃.
According to a further technical scheme, the polyolefin elastomer is an ethylene-octene copolymer, the melting temperature of the polyolefin elastomer is 50-120 ℃, the melt index is 5.0-30.0 g/10min, and the octene content is 10% -40%.
According to a further technical scheme, the rubber oil is one or a combination of more of white oil, paraffin oil and naphthenic oil.
According to a further technical scheme, the filler is one or a combination of more of active calcium carbonate, titanium dioxide, talcum powder, montmorillonite, kaolin and carbon black.
According to a further technical scheme, the lubricant is one or a combination of more of stearic acid, zinc stearate, calcium stearate, polyethylene wax, paraffin wax, erucamide and silicone.
According to a further technical scheme, the cross-linking agent is an organic peroxide, and the organic peroxide is one of 2, 5-bis (tert-butyl peroxy) -2, 5-dimethyl-3-hexyne or 2, 5-bis (tert-butyl peroxy) -2, 5-dimethylhexane or dicumyl peroxide or tert-butyl peroxyisopropyl carbonate or tert-butyl isopropylbenzene peroxide or di- (tert-butyl peroxyisopropyl) benzene.
According to a further technical scheme, the auxiliary crosslinking agent which is matched with the crosslinking system of the organic peroxide is one or a combination of a plurality of trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethylene glycol triacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, zinc diacrylate, zinc dimethacrylate and N-N-bismaleimide.
According to a further technical scheme, the antioxidant is one or a combination of more of antioxidants 1098, 1010, 3450, 2246, 225, 405 and 445.
Further, the invention also comprises the technical scheme of the method:
a preparation method of a self-adhesive injection molding joint angle TPV material comprises the following steps:
step one, preparing an intermediate:
mixing ethylene propylene diene monomer rubber, polypropylene resin, polyolefin elastomer, filler, rubber oil, lubricant and antioxidant in parts by weight, and putting into an internal mixer; the banburying temperature is 170-190 ℃, banburying is carried out for 20-35 min, after the components are uniformly mixed, the mixture is fed into a single screw extruder with the same set temperature as the banburying temperature for granulation, and therefore an uncrosslinked thermoplastic elastomer intermediate is obtained;
step two, crosslinking reaction:
and (3) placing the thermoplastic elastomer intermediate, the auxiliary crosslinking agent and the crosslinking agent which are prepared according to parts by weight into a high-speed stirring pot, stirring for 3-5 minutes, extruding and granulating on a double-screw extruder by adopting a dynamic vulcanization process after uniformly mixing, wherein the vulcanization temperature is 160-220 ℃, and the rotation speed is 200-400 r/min, and carrying out a crosslinking reaction on the thermoplastic elastomer intermediate, the auxiliary crosslinking agent and the crosslinking agent, so that the self-adhesive injection molding joint angle TPV material is obtained.
The working principle and the advantages of the invention are as follows:
according to the invention, the injection molding use temperature is reduced by selecting the EPDM with low Mooney viscosity and high ethylene content, compounding the EPDM with medium viscosity and blending the EPDM with the random polypropylene with lower crystallinity. The strength of the joint angle is improved by reducing shrinkage through the addition of a maleic anhydride grafted tackifying resin material to the TPV.
Compared with the prior art, the invention has the following beneficial effects:
(1) The self-adhesive injection molding joint angle TPV material is prepared by taking polypropylene and ethylene propylene rubber as base materials and adopting dynamic vulcanization. The EPDM with low Mooney viscosity and high ethylene content is selected, and is compounded with the EPDM with medium viscosity to be blended with the random polypropylene with lower crystallinity, so that the injection molding use temperature is reduced, the curing time is prolonged, the contact surfaces between materials can be better fused and combined, and the problems of shrinkage marks and easy gate breakage are solved.
(2) According to the invention, the adhesive resin material grafted by maleic anhydride is added into the TPV, so that the cohesiveness of the product in a high-temperature environment is improved, the curing time is prolonged, and the strength of the joint angle between the product and the EPDM sealing strip is improved.
Detailed Description
The invention is further described below with reference to examples:
the following detailed description will clearly illustrate the present invention, and it will be apparent to those skilled in the art from this disclosure that various changes and modifications can be made in the technology taught herein without departing from the spirit and scope of the present invention.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present disclosure. Singular forms such as "a," "an," "the," and "the" are intended to include the plural forms as well, as used herein. As used herein, the terms "comprising," "including," "having," and the like are intended to be open-ended terms, meaning including, but not limited to.
The term (terms) as used herein generally has the ordinary meaning of each term as used in this field, in this disclosure, and in the special context, unless otherwise noted. Certain terms used to describe the present disclosure are discussed below, or elsewhere in this specification, to provide additional guidance to those skilled in the art in connection with the description herein.
The preparation method of the self-adhesive injection molding corner TPV material specifically comprises the following steps:
step one, preparing an intermediate:
mixing ethylene propylene diene monomer, polypropylene resin, polyolefin elastomer, filler, rubber oil, lubricant and antioxidant according to parts by weight, putting the materials into an internal mixer, banburying at 170-190 ℃ for 20-35 min, uniformly blending the components, and then granulating the components in a single screw extruder with the same set temperature as the banburying temperature, thereby obtaining an uncrosslinked thermoplastic elastomer intermediate;
step two, crosslinking reaction:
and (3) placing the thermoplastic elastomer intermediate obtained in the step (A), the auxiliary crosslinking agent and the crosslinking agent which are prepared according to parts by weight into a high-speed stirring pot, stirring for 3-5 minutes, and extruding and granulating on a double-screw extruder by adopting a dynamic vulcanization process after uniformly mixing, wherein the vulcanization temperature is 160-220 ℃ and the rotating speed is 200-400 r/min. The dynamic vulcanization process is that unvulcanized raw rubber in the thermoplastic elastomer intermediate and unvulcanized thermoplastic resin are melt-blended in a high-temperature and high-shear double screw, and simultaneously, under the action of a cross-linking agent, the rubber is completely subjected to cross-linking reaction and broken into micron-sized vulcanized rubber particles, and the micron-sized vulcanized rubber particles are uniformly dispersed in a resin phase.
The following examples 1-5 and comparative examples 1 and 2 all adopt the preparation methods of the self-adhesive injection molding corner TPV material, and the difference is that the proportion of the raw materials is different.
Example 1: 50 parts of ethylene propylene diene monomer, 25 parts of polypropylene resin, 5 parts of polyolefin elastomer, 6 parts of rubber oil, 15 parts of filler, 2 parts of lubricant and 1 part of antioxidant are added into an internal mixer, the internal mixing is carried out for 30min at the internal mixing temperature of 180 ℃, and then the mixture is added into a single screw extruder to form intermediate particles; the prepared intermediate particles, 1 part of cross-linking agent and 3 parts of cross-linking auxiliary agent are uniformly mixed in a mixer, and are added into a double-screw extruder for dynamic vulcanization, so that the self-adhesive injection molding joint angle TPV material is obtained, the rotating speed is 350 revolutions per minute, the extrusion finished product particles are extruded, the vulcanization temperature is 190 ℃, and the test results of sample performance are shown in Table 2.
Example 2: adding 45 parts of ethylene propylene diene monomer, 25 parts of polypropylene resin, 10 parts of polyolefin elastomer, 8 parts of rubber oil, 12 parts of filler, 2 parts of lubricant and 1 part of antioxidant into an internal mixer, carrying out internal mixing for 30min at the internal mixing temperature of 180 ℃, and then adding into a single screw extruder to form intermediate particles; the prepared intermediate particles, 1 part of cross-linking agent and 3 parts of cross-linking auxiliary agent are uniformly mixed in a mixer, and are added into a double-screw extruder for dynamic vulcanization, so that the self-adhesive injection molding joint angle TPV material is obtained, the rotating speed is 350 revolutions per minute, the extrusion finished product particles are extruded, the vulcanization temperature is 190 ℃, and the test results of sample performance are shown in Table 2.
Example 3: adding 40 parts of ethylene propylene diene monomer, 25 parts of polypropylene resin, 15 parts of polyolefin elastomer, 10 parts of rubber oil, 10 parts of filler, 2 parts of lubricant and 0.5 part of antioxidant into an internal mixer, carrying out internal mixing for 30min at the internal mixing temperature of 180 ℃, and then adding into a single screw extruder to form intermediate particles; the prepared intermediate particles, 1 part of cross-linking agent and 3 parts of cross-linking auxiliary agent are uniformly mixed in a mixer, and are added into a double-screw extruder for dynamic vulcanization, so that the self-adhesive injection molding joint angle TPV material is obtained, the rotating speed is 350 revolutions per minute, the extrusion finished product particles are extruded, the vulcanization temperature is 190 ℃, and the test results of sample performance are shown in Table 2.
Example 4: adding 35 parts of ethylene propylene diene monomer, 20 parts of polypropylene resin, 20 parts of polyolefin elastomer, 12 parts of rubber oil, 8 parts of filler, 1.5 parts of lubricant and 0.3 part of antioxidant into an internal mixer, carrying out internal mixing for 30min at the internal mixing temperature of 180 ℃, and then adding into a single screw extruder to form intermediate particles; the prepared intermediate particles, 1 part of cross-linking agent and 3 parts of cross-linking auxiliary agent are uniformly mixed in a mixer, and are added into a double-screw extruder for dynamic vulcanization, so that the self-adhesive injection molding joint angle TPV material is obtained, the rotating speed is 350 revolutions per minute, the extrusion finished product particles are extruded, the vulcanization temperature is 190 ℃, and the test results of sample performance are shown in Table 2.
Example 5: adding 35 parts of ethylene propylene diene monomer, 20 parts of polypropylene resin, 25 parts of polyolefin elastomer, 10 parts of rubber oil, 8 parts of filler, 1.5 parts of lubricant and 0.3 part of antioxidant into an internal mixer, carrying out internal mixing for 30min at the internal mixing temperature of 180 ℃, and then adding into a single screw extruder to form intermediate particles; the prepared intermediate particles, 1 part of cross-linking agent and 3 parts of cross-linking auxiliary agent are uniformly mixed in a mixer, and are added into a double-screw extruder for dynamic vulcanization, so that the self-adhesive injection molding joint angle TPV material is obtained, the rotating speed is 350 revolutions per minute, the extrusion finished product particles are extruded, the vulcanization temperature is 190 ℃, and the test results of sample performance are shown in Table 2.
Comparative example 1: adding 35 parts of ethylene propylene diene monomer, 20 parts of polypropylene resin, 0 part of polyolefin elastomer, 12 parts of rubber oil, 8 parts of filler, 1.5 parts of lubricant and 0.5 part of antioxidant into an internal mixer, banburying for 30min at 180 ℃, and then adding into a single screw extruder to form intermediate particles; the prepared intermediate particles, 1 part of cross-linking agent and 3 parts of cross-linking auxiliary agent are uniformly mixed in a mixer, and are added into a double-screw extruder for dynamic vulcanization, so that the self-adhesive injection molding joint angle TPV material is obtained, the rotating speed is 350 revolutions per minute, the extrusion finished product particles are extruded, the vulcanization temperature is 190 ℃, and the test results of sample performance are shown in Table 2.
Comparative example 2: the random polypropylene is replaced by isotactic polypropylene, specifically, 35 parts of ethylene propylene diene monomer, 20 parts of isotactic polypropylene resin, 25 parts of polyolefin elastomer, 10 parts of rubber oil, 8 parts of filler, 1.5 parts of lubricant and 0.3 part of antioxidant are added into an internal mixer, the internal mixing is carried out for 30min, the internal mixing temperature is 180 ℃, and then the mixture is added into a single screw extruder to form intermediate particles; the prepared intermediate particles, 1 part of cross-linking agent and 3 parts of cross-linking auxiliary agent are uniformly mixed in a mixer, and are added into a double-screw extruder for dynamic vulcanization, so that the self-adhesive injection molding joint angle TPV material is obtained, the rotating speed is 350 revolutions per minute, the extrusion finished product particles are extruded, the vulcanization temperature is 190 ℃, and the test results of sample performance are shown in Table 2.
Wherein the specific composition of examples 1 to 5 and comparative examples 1 and 2 is shown in Table 1
Table 1: raw material formulations (unit: parts by weight) of examples 1 to 5 and comparative examples
Table 2: performance test results of the self-adhesive injection molding joint angle TPV materials prepared in examples 1 to 5 and comparative examples 1 and 2
As can be seen from the performance test results of Table 2, the comparative example 1 has lower bonding strength with the EPDM sealing strip due to the fact that the polyolefin elastomer is not added, and cannot meet the use requirement that the bonding strength is greater than or equal to 1.5MPa, and as the adding proportion of the polyolefin elastomer increases, the bonding strength between the samples of examples 1-5 and the EPDM sealing strip gradually increases, so that the bonding strength of the materials in a high-temperature environment can be increased by adding the polyolefin elastomer, and the bonding strength with the EPDM sealing strip is improved.
As can be seen by comparing the properties of the samples of comparative example 2 and example 5, the bond strength of the sample of comparative example 2 to the EPDM sealing strip is smaller because the random polypropylene is selected for example 5 instead of isotactic polypropylene, the melting point of the sample is lower, the curing time is longer at the same 220 ℃ injection molding service temperature, and the contact surface between the materials can be better melt-bonded, resulting in a greater bond strength of the sample. Therefore, the use of the random polypropylene can reduce the injection molding use temperature, save energy and reduce emission, and simultaneously lead the material to have better bonding performance.
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
Claims (11)
1. The utility model provides a self-adhesion formula connects angle TPV material of moulding plastics which characterized in that: the formula of the feed comprises the following components in parts by weight:
30-60 parts of ethylene propylene diene monomer rubber;
15-30 parts of polypropylene resin;
5-25 parts of polyolefin elastomer;
5-25 parts of rubber oil;
5-20 parts of filler;
0.5-5 parts of lubricant;
0.5-5 parts of a cross-linking agent;
0.5-10 parts of auxiliary cross-linking agent;
0.1-3 parts of an antioxidant.
2. A self-adhesive injection molded corner TPV material according to claim 1, characterized in that: the EPDM is selected from EPDM with low Mooney viscosity and high ethylene content, and is compounded with EPDM with medium viscosity for use, wherein main constituent monomers are ethylene and propylene, and a third monomer is ethylidene norbornene;
wherein, the Mooney viscosity ML (1+4) of the low Mooney viscosity EPDM is between 20 and 35 ℃, the ethylene content is between 50 and 70 percent, and the crosslinking monomer content is between 1 and 5 percent;
the Mooney viscosity ML (1+4) of the medium viscosity EPDM is between 35 and 60 at 125 ℃;
the weight ratio of the low-Mooney EPDM to the medium-viscosity EPDM is (1-3): (1-3).
3. A self-adhesive injection molded corner TPV material according to claim 1, characterized in that: the polypropylene resin is a random copolymer with the crystallinity lower than 30 percent, and is formed by polymerizing ethylene and propylene, and the ethylene content is 1-7 percent; the melt index of the polypropylene resin is 10.0-30.0 g/10min, and the melt temperature is 120-150 ℃.
4. A self-adhesive injection molded corner TPV material according to claim 1, characterized in that: the polyolefin elastomer is an ethylene-octene copolymer, the melting temperature of the polyolefin elastomer is 50-120 ℃, the melt index is 5.0-30.0 g/10min, and the octene content is 10% -40%.
5. A self-adhesive injection molded corner TPV material according to claim 1, characterized in that: the rubber oil is one or a combination of more of white oil, paraffin oil and naphthenic oil.
6. A self-adhesive injection molded corner TPV material according to claim 1, characterized in that: the filler is one or a combination of more of active calcium carbonate, titanium white, talcum powder, montmorillonite, kaolin and carbon black.
7. A self-adhesive injection molded corner TPV material according to claim 1, characterized in that: the lubricant is one or more of stearic acid, zinc stearate, calcium stearate, polyethylene wax, paraffin, erucamide and silicone.
8. A self-adhesive injection molded corner TPV material according to claim 1, characterized in that: the cross-linking agent is organic peroxide, and the organic peroxide is one of 2, 5-bis (tert-butyl peroxy) -2, 5-dimethyl-3-hexyne or 2, 5-bis (tert-butyl peroxy) -2, 5-dimethylhexane or dicumyl peroxide or tert-butyl peroxyisopropyl carbonate or tert-butyl cumyl peroxide or di- (tert-butyl peroxyisopropyl) benzene.
9. A self-adhesive injection molded corner TPV material according to claim 1, characterized in that: the auxiliary cross-linking agent is one or a combination of a plurality of trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethylene glycol triacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, zinc diacrylate, zinc dimethacrylate and N-N-bismaleimide.
10. A self-adhesive injection molded corner TPV material according to claim 1, characterized in that: the antioxidant is one or a combination of more of antioxidants 1098, 1010, 3450, 2246, 225, 405 and 445.
11. A preparation method of a self-adhesive injection molding corner TPV material is characterized by comprising the following steps: a self-adhesive injection molding joint angle TPV material according to any one of claims 1 to 10, the preparation method comprising:
step one, preparing an intermediate:
mixing ethylene propylene diene monomer rubber, polypropylene resin, polyolefin elastomer, filler, rubber oil, lubricant and antioxidant in parts by weight, and putting into an internal mixer; the banburying temperature is 170-190 ℃, banburying is carried out for 20-35 min, after the components are uniformly mixed, the mixture is fed into a single screw extruder with the same set temperature as the banburying temperature for granulation, and therefore an uncrosslinked thermoplastic elastomer intermediate is obtained;
step two, crosslinking reaction:
and (3) placing the thermoplastic elastomer intermediate, the auxiliary crosslinking agent and the crosslinking agent which are prepared according to parts by weight into a high-speed stirring pot, stirring for 3-5 minutes, extruding and granulating on a double-screw extruder by adopting a dynamic vulcanization process after uniformly mixing, wherein the vulcanization temperature is 160-220 ℃, and the rotation speed is 200-400 r/min, and carrying out a crosslinking reaction on the thermoplastic elastomer intermediate, the auxiliary crosslinking agent and the crosslinking agent, so that the self-adhesive injection molding joint angle TPV material is obtained.
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