CN115960418A - Rubber material for air conditioner hose and preparation method thereof - Google Patents
Rubber material for air conditioner hose and preparation method thereof Download PDFInfo
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 94
- 239000005060 rubber Substances 0.000 title claims abstract description 94
- 239000000463 material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 229920005989 resin Polymers 0.000 claims abstract description 47
- 239000011347 resin Substances 0.000 claims abstract description 47
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 37
- 238000004378 air conditioning Methods 0.000 claims abstract description 34
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 30
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 30
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229920002943 EPDM rubber Polymers 0.000 claims abstract description 27
- 229920005557 bromobutyl Polymers 0.000 claims abstract description 23
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 239000006229 carbon black Substances 0.000 claims abstract description 17
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002270 dispersing agent Substances 0.000 claims abstract description 13
- 239000005662 Paraffin oil Substances 0.000 claims abstract description 11
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 11
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 11
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000008117 stearic acid Substances 0.000 claims abstract description 11
- 239000011787 zinc oxide Substances 0.000 claims abstract description 11
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 9
- 150000002978 peroxides Chemical class 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims description 47
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000007599 discharging Methods 0.000 claims description 14
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 13
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 13
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 13
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 12
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 9
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 7
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 6
- 239000000194 fatty acid Substances 0.000 claims description 6
- 229930195729 fatty acid Natural products 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- 229920005906 polyester polyol Polymers 0.000 claims description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 5
- 238000009849 vacuum degassing Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 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 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- 238000001746 injection moulding Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 238000007711 solidification Methods 0.000 claims description 4
- 230000008023 solidification Effects 0.000 claims description 4
- 229920001567 vinyl ester resin Polymers 0.000 claims description 4
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- AQEFLFZSWDEAIP-UHFFFAOYSA-N di-tert-butyl ether Chemical compound CC(C)(C)OC(C)(C)C AQEFLFZSWDEAIP-UHFFFAOYSA-N 0.000 claims description 2
- -1 fatty acid ester Chemical class 0.000 claims description 2
- 238000013016 damping Methods 0.000 abstract description 12
- 238000010060 peroxide vulcanization Methods 0.000 abstract description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- 239000003507 refrigerant Substances 0.000 description 11
- 239000003963 antioxidant agent Substances 0.000 description 10
- 230000003078 antioxidant effect Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 239000003292 glue Substances 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 5
- VBICKXHEKHSIBG-UHFFFAOYSA-N beta-monoglyceryl stearate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 4
- 239000000945 filler Substances 0.000 description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 3
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 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 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000006038 hexenyl group Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229940037312 stearamide Drugs 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 description 1
- YLKFDHTUAUWZPQ-UHFFFAOYSA-N N-Nitrosodi-n-propylamine Chemical compound CCCN(N=O)CCC YLKFDHTUAUWZPQ-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Abstract
The invention relates to the technical field of rubber materials, and particularly discloses a rubber material for an air conditioner hose and a preparation method thereof. The rubber material for the air-conditioning hose comprises the following components in parts by weight: 30 to 70 parts of ethylene propylene diene monomer, 30 to 70 parts of brominated butyl rubber, 30 to 50 parts of paraffin oil, 1 to 2 parts of anti-aging agent, 50 to 80 parts of carbon black, 1 to 2 parts of peroxide vulcanizing agent, 1 to 2 parts of N, N' -m-phenylene bismaleimide, 3 to 8 parts of polyurethane-vinyl resin, 2 to 6 parts of maleic anhydride modified polybutadiene, 1 to 5 parts of zinc oxide, 1 to 2 parts of stearic acid, 0.1 to 0.5 part of scorch retarder and 1 to 2 parts of dispersant. According to the invention, the ethylene propylene diene monomer and the brominated butyl rubber are used together, an N, N' -m-phenylene bismaleimide/maleic anhydride modified polybutadiene peroxide vulcanization system is adopted, the polyurethane-vinyl resin is introduced, the compatibility is reasonable, and the high temperature resistance and the damping performance of the prepared rubber material are obviously improved.
Description
Technical Field
The invention relates to the technical field of rubber materials, in particular to a rubber material for an air conditioner hose and a preparation method thereof.
Background
Currently, R134a refrigerant, which has a GWP value (global warming potential) of 1300 and is defined as a greenhouse gas, is widely used as an air conditioning refrigerant in the automobile industry. With the improvement of environmental awareness, the R134a refrigerant is gradually replaced by the environment-friendly refrigerant, and compared with the R134a refrigerant, the carbon dioxide refrigerant has the characteristics of safety, no toxicity, environmental protection, low cost and the like.
Carbon dioxide refrigerant is commonly used in the industrial refrigeration industry, and the air conditioning pipelines of the carbon dioxide refrigerant all adopt metal hard pipes. However, when the automobile air conditioner compressor works, the refrigerant flows in the air conditioner pipe to generate pulse vibration and generate noise, so that the comfort level of people in the automobile is influenced, and in order to meet the low-noise requirement of a passenger car, the automobile air conditioner pipeline system cannot use a metal hard pipe. Due to CO 2 The critical temperature point is high, the compressor using the carbon dioxide refrigerant can generate high temperature as high as 180 ℃ instantly when working, the highest working temperature of the rubber materials of the air-conditioning hose commonly used for the automobile, such as hydrogenated nitrile rubber, ethylene propylene diene monomer, butyl rubber, chloroprene rubber and the like, is not more than 150 ℃, the damping effect is general, the requirements of high temperature resistance and NVH damping and noise reduction of the carbon dioxide refrigerant cannot be met, and the new challenge is provided for the pipeline design and manufacture of the automobile air-conditioning system.
Disclosure of Invention
In view of the above, the invention provides a rubber material for an air conditioner hose and a preparation method thereof, wherein ethylene propylene diene monomer rubber and brominated butyl rubber are used together, an N, N' -m-phenylene bismaleimide/maleic anhydride modified polybutadiene peroxide vulcanization system is adopted, polyurethane-vinyl resin is introduced, the compatibility is reasonable, and the high temperature resistance and the damping performance of the prepared rubber material are obviously improved.
In order to achieve the purpose of the invention, the embodiment of the invention adopts the following technical scheme:
in a first aspect, the invention provides a rubber material for an outer rubber layer of an air-conditioning hose, which comprises the following components in parts by weight: 30 to 70 parts of ethylene propylene diene monomer, 30 to 70 parts of brominated butyl rubber, 30 to 50 parts of paraffin oil, 1 to 2 parts of anti-aging agent, 50 to 80 parts of carbon black, 1 to 2 parts of peroxide vulcanizing agent, 1 to 2 parts of N, N' -m-phenylene bismaleimide, 3 to 8 parts of polyurethane-vinyl resin, 2 to 6 parts of maleic anhydride modified polybutadiene, 1 to 5 parts of zinc oxide, 1 to 2 parts of stearic acid, 0.1 to 0.5 part of scorch retarder and 1 to 2 parts of dispersant; wherein the sum of the parts by weight of the ethylene propylene diene monomer and the brominated butyl rubber is 100 parts; the ethylene content of the ethylene propylene diene monomer is 45wt% -70 wt%, and the VNB content is 1wt% -4 wt%.
Compared with the prior art, the rubber material for the air conditioner hose provided by the invention has the following advantages:
(1) According to the invention, the ethylene propylene diene monomer and the brominated butyl rubber are selected as rubber base materials, the molecular structures of the ethylene propylene diene monomer and the brominated butyl rubber are similar, the methyl groups on the upper side of the brominated butyl rubber molecular chain are dense, a higher loss factor can be provided in the system, and the system is ensured to have a higher damping coefficient; the ethylene propylene diene monomer has good comprehensive performance while having side methyl, and the active double bond of VNB in the ethylene propylene diene monomer is positioned at the tail end of the side group, so that the steric hindrance is small, free radicals are easily formed, and the crosslinking reaction is more complete. The ethylene propylene diene monomer rubber and the brominated butyl rubber are used together, so that the processability of rubber materials can be improved, the compatibility and the co-vulcanization property are good, the processing aid, resin, carbon black and the like are dispersed in the rubber more uniformly, and the viscosity, the high temperature resistance, the aging resistance, the damping property and the like of the composite material are greatly improved.
(2) According to the invention, N' -m-phenylene bismaleimide and maleic anhydride modified polybutadiene are added into an ethylene propylene diene monomer/brominated butyl rubber combined system, on one hand, a maleic anhydride group can chemically react with an oxygen-containing group on the surface of carbon black, so that the surface energy of filler particles is reduced, the dispersibility of the filler is increased, and the interface combination of the carbon black and a rubber matrix is effectively improved; on the other hand, unsaturated double bonds in the maleic anhydride modified polybutadiene provide active crosslinking points for peroxide vulcanization, and can be co-crosslinked with unsaturated double bonds in rubber molecules, so that the crosslinking density of the co-mixed rubber is increased, and a crosslinking network is perfected; the N, N' -m-phenylene bismaleimide can introduce groups with good heat resistance, such as imide heterocyclic rings, benzene rings and the like, into a rubber material cross-linking network structure, so that the high-temperature resistance of the composite rubber is further improved; meanwhile, after the N, N ' -m-phenylene bismaleimide and the maleic anhydride modified polybutadiene are used together, the N, N ' -m-phenylene bismaleimide not only can play a role in cross-linking assistance, but also can play a role in compatibilization, and the N, N ' -m-phenylene bismaleimide and the maleic anhydride modified polybutadiene cooperate to accelerate the vulcanization speed, further improve the co-vulcanization property of the co-mixed rubber, enhance the compatibility of the resin, the carbon black and the rubber base material, enable the co-used rubber to form a stronger cross-linking network, and effectively improve the comprehensive performance of the co-used rubber.
(3) According to the invention, the polyurethane-vinyl resin with good damping performance is introduced into the formula, and the polarity of rubber molecules can be increased by utilizing the characteristic that the glass transition temperatures of the polyurethane-vinyl resin and rubber have a certain difference, so that the cohesive strength and the surface energy are improved, the internal loss of a molecular chain in the movement process is increased, and the damping performance of the rubber material is effectively improved.
Optionally, the specific preparation steps of the polyurethane-vinyl resin are as follows:
s1, mixing polyester polyol with toluene diisocyanate, and stirring to react to obtain a polyurethane prepolymer; wherein the mass fraction of-NCO in the polyurethane prepolymer is 9.0-9.5%;
s2, dissolving benzoyl peroxide and 1, 4-butanediol in ethyl acetate, adding a polyurethane prepolymer, vinyl resin, trimethylolpropane, N-dimethylaniline and a catalyst, uniformly stirring, vacuum degassing for 10-20 min, then injecting a mold, preserving heat at 80 ℃ for curing for 3-4 h, and cooling to obtain the polyurethane-vinyl resin; wherein the mass ratio of the polyurethane prepolymer to the vinyl resin is 3-4: 7.
optionally, in step S2, the styrene content in the vinyl resin is 30% to 40%; the adding amount of the benzoyl peroxide is 0.3-0.5% of the mass of the vinyl ester resin; the molar ratio of-OH in the 1, 4-butanediol alkyl to-NCO in the polyurethane prepolymer is 1: 2-3; the molar ratio of-OH in trimethylolpropane to-NCO in polyurethane prepolymer is 1: 2-3; the adding amount of the N, N-dimethylaniline is 0.2-0.3% of the mass of the vinyl ester resin.
Optionally, the structural formula of the maleic anhydride modified polybutadiene is as follows:
optionally, the structural formula of the maleic anhydride modified polybutadiene is as follows:
optionally, the number average molecular weight of the maleic anhydride modified polybutadiene is 1000-4000, and the acid value is 100-150 mgKOH/g.
The optimized maleic anhydride modified polybutadiene has good adhesive property, has good compatibility with rubber base materials, carbon black and resin, and can improve the vulcanization rate of rubber materials, so that the co-vulcanization effect of ethylene propylene diene monomer and brominated butyl rubber is improved, the adhesive property of rubber materials can be improved, the use requirement is met, and the reinforcing effect of fillers and resin can be further improved.
Optionally, the peroxide vulcanizing agent is at least one of benzoyl peroxide, 2, 4-dichlorobenzoyl peroxide, dicumyl peroxide or di-tert-butyl oxide.
Optionally, the dispersant is at least one of a fatty acid dispersant, a fatty acid amide dispersant or a fatty acid ester dispersant.
Optionally, the antioxidant can be conventional antioxidant in the art, preferably at least one of quinoline antioxidant, p-phenylenediamine antioxidant or naphthylamine antioxidant, such as antioxidant 4020, antioxidant D, antioxidant BLE, antioxidant H or antioxidant RD.
Alternatively, the scorch retarder can be a scorch retarder conventional in the art, such as scorch retarder CTP, scorch retarder E, scorch retarder APR, phthalic anhydride, or scorch retarder NDPA, and the like.
The present invention in a preferred example may be further configured to: the rubber material for the air-conditioning hose further comprises 0-40 parts of microcrystalline talc by weight.
In a second aspect, the invention also provides a preparation method of the rubber material for the outer rubber layer of the air-conditioning hose, which comprises the following steps:
weighing the components according to a designed ratio, mixing the ethylene propylene diene monomer rubber and the brominated butyl rubber, and plasticating to obtain a compounded rubber;
mixing the rubber compound, paraffin oil, an anti-aging agent, carbon black, N' -m-phenylene bismaleimide, polyurethane-vinyl resin, maleic anhydride modified polybutadiene, zinc oxide, stearic acid, an anti-scorching agent and a dispersing agent, and carrying out primary mixing to obtain a rubber compound;
and step three, mixing the first-stage mixing rubber and a peroxide vulcanizing agent, mixing for the second time, then discharging rubber to an open mill, turning over, discharging, and cooling to obtain the rubber material for the air-conditioning hose.
Compared with the prior art, the preparation method of the rubber material for the air-conditioning hose provided by the invention has the following advantages:
according to the invention, the ethylene propylene diene monomer and the brominated butyl rubber are used together, an N, N' -m-phenylene bismaleimide/maleic anhydride modified polybutadiene peroxide vulcanization system is adopted, and meanwhile, the polyurethane-vinyl resin and the carbon black are added, so that the compatibility is reasonable, the blending degree is high, the high temperature resistance and the damping performance of the prepared rubber material are obviously improved, the preparation method is simple to operate, no complex process is required, and the industrial popularization is facilitated.
Optionally, in the step one, the plastication conditions are as follows: the plasticating time is 3min to 5min, the initial temperature is 50 ℃ to 60 ℃, and the rotating speed is 30rpm to 50rpm.
Optionally, in the second step, the conditions of the first mixing are as follows: the mixing time is 5 min-10 min, the initial temperature is 60-70 ℃, and the rotating speed is 30-40 rpm.
Optionally, in the third step, the conditions of the second mixing are as follows: the mixing time is 3 min-5 min, the initial temperature is 50-60 ℃, the rotating speed is 30-40 rpm, and the rubber discharging temperature is 80-100 ℃.
Optionally, in the third step, the turning time is 3min to 5min, and the turning temperature is 60 ℃ to 80 ℃.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The embodiment of the invention provides a rubber material for an outer rubber layer of an air-conditioning hose, which comprises the following components in parts by weight: 60 parts of ethylene propylene diene monomer (60 wt% of ethylene content and 3wt% of VNB content), 40 parts of brominated butyl rubber, 40 parts of paraffin oil, 1.5 parts of antioxidant RD, 60 parts of carbon black, 1.5 parts of benzoyl peroxide, 1.5 parts of N, N' -m-phenylene bismaleimide, 5 parts of polyurethane-vinyl resin, 4 parts of maleic anhydride modified polybutadiene, 3 parts of zinc oxide, 1.5 parts of stearic acid, 0.3 part of scorch retarder CTP and 1.5 parts of stearic acid monoglyceride.
The preparation method of the polyurethane-vinyl resin comprises the following specific steps:
s1, mixing polyester polyol with toluene diisocyanate, and stirring to react to obtain a polyurethane prepolymer; wherein the mass fraction of-NCO in the polyurethane prepolymer is 9.5%;
s2, dissolving 0.28 part of benzoyl peroxide and 0.269 part of 1, 4-butanediol in ethyl acetate, adding 35 parts of polyurethane prepolymer, 70 parts of vinyl resin (the content of styrene is 35%), 0.179 part of trimethylolpropane, 0.175 part of N, N-dimethylaniline and 0.175 part of stannous octoate, uniformly stirring, carrying out vacuum degassing for 15min, then carrying out injection molding, carrying out heat preservation and solidification at 80 ℃ for 3.5h, and cooling to obtain the polyurethane-vinyl resin.
The structural formula of the maleic anhydride modified polybutadiene is as follows, wherein n is 15:
the preparation method of the rubber material for the air-conditioning hose comprises the following steps:
weighing the components according to the proportion, mixing ethylene propylene diene monomer and brominated butyl rubber, plasticating in an open mill for 4min at the initial temperature of 55 ℃ and the rotation speed of 40rpm to obtain compounded rubber;
secondly, putting the rubber compound, paraffin oil, an anti-aging agent RD, carbon black, N' -m-phenylene bismaleimide, polyurethane-vinyl resin, maleic anhydride modified polybutadiene, zinc oxide, stearic acid, an anti-scorching agent CTP and stearic acid monoglyceride into an internal mixer for first mixing, controlling the mixing time to be 8min, controlling the initial temperature to be 65 ℃ and the rotating speed to be 35rpm, and obtaining a rubber compound;
and step three, mixing the first-stage mixing glue and benzoyl peroxide in an internal mixer, and mixing for the second time, wherein the mixing time is controlled to be 4min, the initial temperature is 55 ℃, the rotating speed is 35rpm, and the glue discharging temperature is 90 ℃. Discharging the mixed materials into an open mill for turning, controlling the turning time to be 4min and the turning temperature to be 70 ℃, discharging the sheets, and cooling to obtain the rubber material for the air conditioning hose.
Example 2
The embodiment of the invention provides a rubber material for an outer rubber layer of an air-conditioning hose, which comprises the following components in parts by weight: 30 parts of ethylene propylene diene monomer (ethylene content is 45wt%, VNB content is 1 wt%), 70 parts of brominated butyl rubber, 30 parts of paraffin oil, 1 part of antioxidant RD, 50 parts of carbon black, 1 part of benzoyl peroxide, 1 part of N, N' -m-phenylene bismaleimide, 3 parts of polyurethane-vinyl resin, 2 parts of maleic anhydride modified polybutadiene, 1 part of zinc oxide, 1 part of stearic acid, 0.1 part of scorch retarder CTP and 1 part of stearic acid monoglyceride.
The preparation method of the polyurethane-vinyl resin comprises the following specific steps:
s1, mixing polyester polyol with toluene diisocyanate, and stirring to react to obtain a polyurethane prepolymer; wherein the mass fraction of-NCO in the polyurethane prepolymer is 9.0%;
s2, dissolving 0.21 part of benzoyl peroxide and 0.273 part of 1, 4-butanediol in ethyl acetate, adding 30 parts of polyurethane prepolymer, 70 parts of vinyl resin (the content of styrene is 30 percent), 0.182 part of trimethylolpropane, 0.14 part of N, N-dimethylaniline and 0.15 part of stannous octoate, uniformly stirring, vacuum degassing for 10min, then carrying out injection molding, carrying out heat preservation and solidification at 80 ℃ for 3h, and cooling to obtain the polyurethane-vinyl resin.
The structural formula of the maleic anhydride modified polybutadiene is as follows, wherein n is 10:
the preparation method of the rubber material for the air-conditioning hose comprises the following steps:
weighing the components according to the proportion, mixing ethylene propylene diene monomer and brominated butyl rubber, plasticating in an open mill for 3min at the initial temperature of 50 ℃ and the rotation speed of 30rpm to obtain compounded rubber;
step two, putting the rubber compound, paraffin oil, an anti-aging agent RD, carbon black, N' -m-phenylene bismaleimide, polyurethane-vinyl resin, maleic anhydride modified polybutadiene, zinc oxide, stearic acid, an anti-scorching agent CTP and stearic acid monoglyceride into an internal mixer for primary mixing, controlling the mixing time to be 5min, the initial temperature to be 60 ℃ and the rotating speed to be 30rpm, and obtaining a rubber compound;
and step three, mixing the first-stage mixing glue and benzoyl peroxide in an internal mixer, and mixing for the second time, wherein the mixing time is controlled to be 3min, the initial temperature is 50 ℃, the rotating speed is 30rpm, and the glue discharging temperature is 80 ℃. Discharging the mixed materials into an open mill for turning, controlling the turning time to be 3min and the turning temperature to be 60 ℃, discharging sheets, and cooling to obtain the rubber material for the air conditioning hose.
Example 3
The embodiment of the invention provides a rubber material for an outer rubber layer of an air-conditioning hose, which comprises the following components in parts by weight: 70 parts of ethylene propylene diene monomer (the ethylene content is 70wt%, and the VNB content is 4 wt%), 30 parts of brominated butyl rubber, 50 parts of paraffin oil, 2 parts of an anti-aging agent 4020, 80 parts of carbon black, 2 parts of dicumyl peroxide, 2 parts of N, N' -m-phenylene bismaleimide, 8 parts of polyurethane-vinyl resin, 6 parts of maleic anhydride modified polybutadiene, 5 parts of zinc oxide, 2 parts of stearic acid, 0.5 part of an anti-scorching agent E and 2 parts of hexenyl bis stearamide.
The preparation method of the polyurethane-vinyl resin comprises the following specific steps:
s1, mixing polyester polyol and toluene diisocyanate, and stirring for reaction to obtain a polyurethane prepolymer; wherein the mass fraction of-NCO in the polyurethane prepolymer is 9.2%;
s2, dissolving 0.35 part of benzoyl peroxide and 0.248 part of 1, 4-butanediol in ethyl acetate, adding 40 parts of polyurethane prepolymer, 70 parts of vinyl resin (the content of styrene is 40 percent), 0.165 part of trimethylolpropane, 0.21 part of N, N-dimethylaniline and 0.2 part of stannous octoate, uniformly stirring, vacuum degassing for 20min, then carrying out injection molding, carrying out heat preservation and solidification at 80 ℃ for 4h, and cooling to obtain the polyurethane-vinyl resin.
The structural formula of the maleic anhydride modified polybutadiene is as follows, wherein n is 23:
the preparation method of the rubber material for the air-conditioning hose comprises the following steps:
weighing the components according to the ratio, mixing ethylene propylene diene monomer rubber and brominated butyl rubber, and plasticating in an open mill at the initial temperature of 60 ℃ for 5min and the rotation speed of 50rpm to obtain a compounded rubber;
secondly, putting the rubber compound, paraffin oil, an anti-aging agent 4020, carbon black, N' -m-phenylene bismaleimide, polyurethane-vinyl resin, maleic anhydride modified polybutadiene, zinc oxide, stearic acid, an anti-scorching agent E and hexenyl bis-stearamide into an internal mixer for first mixing, controlling the mixing time to be 10min, the initial temperature to be 70 ℃ and the rotating speed to be 40rpm, and obtaining a rubber compound;
and step three, mixing the first-stage mixing glue with dicumyl peroxide in an internal mixer, and mixing for the second time, wherein the mixing time is controlled to be 5min, the initial temperature is 60 ℃, the rotating speed is 40rpm, and the glue discharging temperature is 100 ℃. Discharging the mixed materials into an open mill for turning, controlling the turning time to be 5min and the turning temperature to be 80 ℃, discharging the sheets, and cooling to obtain the rubber material for the air conditioning hose.
Comparative example 1
The comparative example provides a rubber material for an outer rubber layer of an air-conditioning hose, which is different from example 1 in that: the maleic anhydride-modified polybutadiene was replaced with an equal amount of coumarone resin.
Comparative example 2
The comparative example provides a rubber material for an outer rubber layer of an air-conditioning hose, which is different from example 1 in that: the N, N' -m-phenylenedimaleimide was replaced with an equivalent amount of trimethylolpropane trimethacrylate (TMPTMA).
Comparative example 3
The comparative example provides a rubber material for an outer rubber layer of an air-conditioning hose, which is different from example 1 in that: the polyurethane-vinyl resin was replaced with an equal amount of petroleum resin.
To better illustrate the characteristics of the rubber materials provided in the examples of the present invention, the rubber materials prepared in examples 1 to 3 and comparative examples 1 to 3 were tested for their properties using the following criteria:
tensile strength and elongation at break: GB/T528;
hot air aged tensile strength change rate and elongation at break change rate: GB/T3512;
compression set: GB/T7759.1;
low temperature performance: GB/T15256;
damping performance: the dissipation factor was tested according to the DMA test method.
The results of the measurements are shown in Table 1 below.
Table 1 results of performance testing
As can be seen from the table 1, the N, N '-m-phenylene bismaleimide and the maleic anhydride modified polybutadiene are added into the ethylene propylene diene monomer/brominated butyl rubber combined system, and the N, N' -m-phenylene bismaleimide and the maleic anhydride modified polybutadiene are cooperated to effectively improve the high temperature resistance of the rubber material and can meet the aging requirement at 180 ℃; by adding the polyurethane-vinyl resin to be matched with other components in the rubber material, the damping performance can be obviously improved. The rubber material for the outer rubber layer of the air-conditioning hose provided by the invention has the advantages of reasonable compatibility of all components, good high-temperature resistance and damping performance, and can meet the use requirements of carbon dioxide air-conditioning pipes of passenger vehicles.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The rubber material for the air conditioner hose is characterized by comprising the following components in parts by weight: 30 to 70 parts of ethylene propylene diene monomer, 30 to 70 parts of brominated butyl rubber, 30 to 50 parts of paraffin oil, 1 to 2 parts of anti-aging agent, 50 to 80 parts of carbon black, 1 to 2 parts of peroxide vulcanizing agent, 1 to 2 parts of N, N' -m-phenylene bismaleimide, 3 to 8 parts of polyurethane-vinyl resin, 2 to 6 parts of maleic anhydride modified polybutadiene, 1 to 5 parts of zinc oxide, 1 to 2 parts of stearic acid, 0.1 to 0.5 part of scorch retarder and 1 to 2 parts of dispersant;
wherein the sum of the parts by weight of the ethylene propylene diene monomer and the brominated butyl rubber is 100 parts; the ethylene content of the ethylene propylene diene monomer is 45wt% -70 wt%, and the VNB content is 1wt% -4 wt%.
2. The rubber material for air-conditioning hoses according to claim 1, wherein the polyurethane-vinyl resin is prepared by the following specific steps:
s1, mixing polyester polyol with toluene diisocyanate, and stirring to react to obtain a polyurethane prepolymer; wherein the mass fraction of-NCO in the polyurethane prepolymer is 9.0-9.5%;
s2, dissolving benzoyl peroxide and 1, 4-butanediol in ethyl acetate, adding a polyurethane prepolymer, vinyl resin, trimethylolpropane, N-dimethylaniline and a catalyst, uniformly stirring, vacuum degassing for 10-20 min, then carrying out injection molding, carrying out heat preservation and solidification at 80 ℃ for 3-4 h, and cooling to obtain the polyurethane-vinyl resin; wherein the mass ratio of the polyurethane prepolymer to the vinyl resin is 3-4: 7.
3. the rubber material for air-conditioning hoses according to claim 2, wherein in the step S2, the styrene content in the vinyl resin is 30-40%; the adding amount of the benzoyl peroxide is 0.3-0.5% of the mass of the vinyl ester resin; the molar ratio of-OH in the 1, 4-butanediol alkyl to-NCO in the polyurethane prepolymer is 1: 2-3; the molar ratio of-OH in trimethylolpropane to-NCO in polyurethane prepolymer is 1: 2-3; the adding amount of the N, N-dimethylaniline is 0.2-0.3% of the mass of the vinyl ester resin.
4. The rubber material for air-conditioning hoses according to claim 1, wherein the maleic anhydride-modified polybutadiene has the following structural formula:
5. The rubber material for air-conditioning hoses according to claim 1 or 4, wherein the maleic anhydride-modified polybutadiene has a number-average molecular weight of 1000 to 4000 and an acid value of 100mgKOH/g to 150mgK OH/g.
6. The rubber material for air-conditioning hoses of claim 1, wherein the peroxide curing agent is at least one of benzoyl peroxide, 2, 4-dichlorobenzoyl peroxide, dicumyl peroxide or di-tert-butyl oxide.
7. The rubber material for air-conditioning hoses as claimed in claim 1, wherein the dispersant is at least one of a fatty acid-based dispersant, a fatty acid amide-based dispersant or a fatty acid ester-based dispersant.
8. A method for preparing a rubber material for air-conditioning hoses according to any one of claims 1 to 7, comprising the steps of:
step one, weighing all components according to a designed ratio, mixing the ethylene propylene diene monomer rubber and the brominated butyl rubber, and plasticating to obtain a rubber compound;
mixing the rubber compound, paraffin oil, an anti-aging agent, carbon black, N' -m-phenylene bismaleimide, polyurethane-vinyl resin, maleic anhydride modified polybutadiene, zinc oxide, stearic acid, an anti-scorching agent and a dispersing agent, and performing primary mixing to obtain a rubber compound;
and step three, mixing the first-stage mixing rubber and a peroxide vulcanizing agent, mixing for the second time, then discharging rubber to an open mill, turning over, discharging, and cooling to obtain the rubber material for the air-conditioning hose.
9. The rubber material for air-conditioning hoses as claimed in claim 8, wherein in the first step, the plastication conditions are as follows: plasticating time is 3 min-5 min, initial temperature is 50-60 ℃, and rotating speed is 30 rpm-50 rpm; and/or
In the second step, the first mixing conditions are as follows: the mixing time is 5 min-10 min, the initial temperature is 60-70 ℃, and the rotating speed is 30 rpm-40 rpm.
10. The method for preparing a rubber material for air-conditioning hoses according to claim 8, wherein in the third step, the conditions of the second mixing are as follows: the mixing time is 3min to 5min, the initial temperature is 50 ℃ to 60 ℃, the rotating speed is 30rpm to 40rpm, and the rubber discharge temperature is 80 ℃ to 100 ℃; and/or
The time of the tumbling is 3 min-5 min, and the temperature of the tumbling is 60 ℃ to 80 ℃.
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