CN102936386B - Viton rubber master batch and preparation method thereof - Google Patents
Viton rubber master batch and preparation method thereof Download PDFInfo
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- CN102936386B CN102936386B CN201210447777.3A CN201210447777A CN102936386B CN 102936386 B CN102936386 B CN 102936386B CN 201210447777 A CN201210447777 A CN 201210447777A CN 102936386 B CN102936386 B CN 102936386B
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- 229920002449 FKM Polymers 0.000 title claims abstract description 82
- 229920001971 elastomer Polymers 0.000 title claims abstract description 53
- 239000005060 rubber Substances 0.000 title claims abstract description 47
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 32
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 24
- 229920001973 fluoroelastomer Polymers 0.000 claims abstract description 13
- 239000012763 reinforcing filler Substances 0.000 claims abstract description 8
- 238000002844 melting Methods 0.000 claims abstract description 6
- 230000008018 melting Effects 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 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
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000009413 insulation Methods 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- 235000019394 potassium persulphate Nutrition 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- 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 6
- 239000006229 carbon black Substances 0.000 claims description 6
- 239000000806 elastomer Substances 0.000 claims description 6
- 239000003995 emulsifying agent Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 230000033116 oxidation-reduction process Effects 0.000 claims description 6
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 6
- 238000004073 vulcanization Methods 0.000 claims description 6
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 5
- 239000004159 Potassium persulphate Substances 0.000 claims description 5
- -1 alcohol ether sulfosuccinates sodium salt Chemical class 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical group C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- IOJUPLGTWVMSFF-UHFFFAOYSA-N cyclobenzothiazole Natural products C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 3
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 claims description 3
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 claims description 3
- LPXFITACVAQQAL-UHFFFAOYSA-M sodium;prop-2-enoylazanide Chemical compound [Na+].[NH-]C(=O)C=C LPXFITACVAQQAL-UHFFFAOYSA-M 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 229960002447 thiram Drugs 0.000 claims description 3
- 239000012991 xanthate Substances 0.000 claims description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- SUOFREPYJDSUTJ-UHFFFAOYSA-N iron sulfurous acid Chemical compound [Fe].S(O)(O)=O SUOFREPYJDSUTJ-UHFFFAOYSA-N 0.000 claims description 2
- ATEAWHILRRXHPW-UHFFFAOYSA-J iron(2+);phosphonato phosphate Chemical compound [Fe+2].[Fe+2].[O-]P([O-])(=O)OP([O-])([O-])=O ATEAWHILRRXHPW-UHFFFAOYSA-J 0.000 claims description 2
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 2
- 230000002829 reductive effect Effects 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims 4
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims 1
- 239000011258 core-shell material Substances 0.000 abstract description 20
- 238000002156 mixing Methods 0.000 abstract description 8
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 239000003921 oil Substances 0.000 description 7
- 238000007789 sealing Methods 0.000 description 4
- 229920001774 Perfluoroether Polymers 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 229940069744 2,2'-dithiobisbenzothiazole Drugs 0.000 description 1
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920006169 Perfluoroelastomer Polymers 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 description 1
- STSDHUBQQWBRBH-UHFFFAOYSA-N n-cyclohexyl-1,3-benzothiazole-2-sulfonamide Chemical compound N=1C2=CC=CC=C2SC=1S(=O)(=O)NC1CCCCC1 STSDHUBQQWBRBH-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
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- 230000035882 stress Effects 0.000 description 1
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- Graft Or Block Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of viton rubber master batch and preparation method thereof, first prepare viton grafted maleic anhydride expanding material and Core-shell type double-active acrylate elastic body, again by crude fluororubber, viton grafted maleic anhydride expanding material, Core-shell type double-active acrylate elastic body and rubber reinforcing filler, join in Banbury mixer, at 120 ~ 170 DEG C, melting 50 ~ 120min is blended, obtained viton rubber master batch.Reacting property of active group increase-volume in viton grafted maleic anhydride expanding material and Core-shell type double-active acrylate elastic body, easily mixes time mixing with viton and produces in mechanical properties and coordinate same synergism, improving the high-temperature stability of rubber.<!--1-->
Description
Technical field
The invention belongs to viton, be a kind of viton rubber master batch specifically, also relate to the method utilizing viton grafted maleic anhydride expanding material and Core-shell type double-active acrylate elastic body to prepare viton rubber master batch.
Background technology
Viton (FKM) be main chain or side chain carbon atom on containing the synthesis macromolecular elastomer of fluorine atom, it is widely used in many fields such as space flight, military project, national defence, automobile, petrochemical complex.Viton goods are mainly used in sealing member, packing ring, pad, barrier film, sebific duct, oil sealing, lining, anticorrosive products and electrical isolation goods.
Viton is most widely used is automotive field, accounts for 60 ~ 70% of application total amount.On automobile component, can be used as motor spirit flexible pipe, refueling hose, petrolift, O shape circle, and jet apparatus, power piston, valve stem, bent axle, compressor of air conditioner sealing material.The automotive sealant that rubber is made in use, except the effect by stress, strain, high temperature and low temperature, also by the erosion of oil product (oil fuel, lubricating oil), chemicals (alcohol, deicing fluid, scavenging solution, braking fluid) and biology (mould, bacterium, insect) etc.During product design, as can not be considered the independent of working conditions and synergy comprehensively, damage intensity will be caused to accelerate, cause shorten work-ing life.Particularly along with the development of automotive industry and motorway, the travel speed of automobile significantly improves, make the use temperature of oil sealing significantly increase, the oil temperature at the bent axle place of engine substantially more than 110 DEG C, therefore to the specification of quality also corresponding raising of the rubber seal to automobile accessories.Traditional viton elaxtic seal cannot meet high temperature, at a high speed, the actual operation requirements of high abrasion.
China started to develop viton from the sixties in 20th century, successively successfully developed the viton based on polyolefine such as 23 types, 26 types, 246 types, TP-2 type and carboxyl Asia pin base viton.The eighties in 20th century has developed again perfluoroelastomers and has fluoridized phosphorus rubber etc.
In order to improve the performance of viton and goods, a large amount of research work is carried out to the modification of viton and processing both at home and abroad.At present, the modification of viton mainly contains both direction: one is, pass through backbone modification, as the exploitation of fluoroether rubber, trifluoropropyl siloxane, ehter bond is introduced viton main chain, increase the flexibility of molecule, while its low-temperature performance is improved greatly, remain the original feature of viton, but due to Development and Production high cost, significantly limit its promotion and application; Two are, rubber blending, by viton and some conventional rubbers, specialty elastomer use, so that it is more excellent to obtain performance, and the material that cost is lower.
Blending and modifying is a kind of method preferably, but has the following disadvantages: the cost performance that (1) makes novel type fluorubber is not high.Fluoroether rubber, trifluoropropyl siloxane are too high due to cost of development, make its price even higher than viton, and under can only being used in the harsher environment of condition, promotion and application are restricted; (2) modification of the blending and modifying between viton to viton performance is restricted.Rubber of the same type determines it to be caused on performance deficiency by rubber self structure in improvement and is restricted, and cost difficulty reduces.Though and the blended low-temperature performance well improving viton of viton and fluoroether rubber, cost is higher; (3) the blended difficulty of the low-temperature performance to viton of viton and other rubber is kind.Blending and modifying can improve the elasticity of viton, the improvement of the single performance such as processing characteristics, but very few to improving viton low-temperature performance and considering multiple defect aspect research.
Viton itself has excellent resistance to elevated temperatures, but the use temperature of oil sealing increases substantially with automobile running velocity and significantly rises, and proposes requirements at the higher level to the heat resisting temperature of automotive sealant.Polar acrylate's rubber has heat-resisting, oil resistant, ageing-resistant and ozone resistance, good processability, the features such as elasticity is splendid, and price is only 10% of viton.If by blended for the double activated acrylic elastomer of viton and modification, then the performance of viton product will be improved.
Summary of the invention
For the deficiency that prior art exists, the object of this invention is to provide the method for the high viton grafted maleic anhydride expanding material of a kind of consistency and Core-shell type double-active acrylate elastic body blending and modifying viton.
Technical scheme of the present invention is achieved in that a kind of viton rubber master batch, prepare by the following method: first prepare viton grafted maleic anhydride expanding material and Core-shell type double-active acrylate elastic body, again by crude fluororubber, viton grafted maleic anhydride expanding material, Core-shell type double-active acrylate elastic body and rubber reinforcing filler, join in Banbury mixer, at 120 ~ 170 DEG C, melting 50 ~ 120min is blended, obtained viton rubber master batch.
Further, described crude fluororubber 100 weight part, Core-shell type double-active acrylate elastic body 20 ~ 50 weight part, viton grafted maleic anhydride expanding material 3 ~ 8 weight part, rubber reinforcing filler 10 ~ 30 weight part.
The preparation process of described viton grafted maleic anhydride joins in Banbury mixer by crude fluororubber, maleic anhydride, initiator, vulcanizing agent, promotor, at 120 ~ 160 DEG C, under the condition of rotating speed 50 ~ 100r/min, and reaction 10 ~ 30min.
Described crude fluororubber 80 ~ 130 weight part, maleic anhydride 3 ~ 8 weight part, initiator 0.5 ~ 2 weight part, vulcanizing agent 0.2 ~ 0.5 weight part, promotor 0.1 ~ 0.3 weight part.
The preparation process of described Core-shell type double-active acrylate elastic body is by acrylate monomer, joins in kneader containing the acrylate of active group, compound emulsifying agent; be warming up to 60 ~ 90 DEG C; insulation reaction 0.8 ~ 1.2h; then vulcanizing agent and oxidation-reduction initiator is added; under nitrogen protection; be warming up to 80 ~ 100 DEG C, insulation reaction 1.5 ~ 2.0h, be finally cooled to 40 ~ 50 DEG C and obtain.
Described acrylate monomer 70 ~ 100 weight part, containing acrylate 50 ~ 80 weight part of active group, compound emulsifying agent 15 ~ 30 weight part, vulcanizing agent 8 ~ 20 weight part, oxidation-reduction initiator 5 ~ 8 weight part.
Described rubber reinforcing filler comprises one or more in carbon black, white carbon black, nano-calcium carbonate, hard (china) clay.
Described initiator be benzoyl peroxide (BPO), dilauroyl peroxide (LPO), Diisopropyl azodicarboxylate (AIBN), Potassium Persulphate (KPS), dicumyl peroxide (DCP) or oxidation di-t-butyl one or more; Described vulcanizing agent be benzoyl peroxide (BPO), BPP (BPP), calcium hydroxide or magnesian one or more; Described promotor is 2-benzothiazolyl mercaptan (accelerator M), 2, one or more of 2 '-dithio-bis-benzothiazole (accelerator DM), N-cyclohexyl-2-benzothiazole sulfonamide (aniline fluid bed), N tert butyl benzothiazole 2 sulfenamide (vulcanization accelerator TBBS), tetramethyl-thiuram disulfide (vulcanization accelerator TMTD), N-cyclohexyl-2-benzene (CZ).
Described compound emulsifying agent is one or more in acrylamide sodium isopropyl xanthate, double bond containing alcohol ether sulfosuccinates sodium salt, sodium vinyl sulfonate, sodium laurylsulfonate, polyoxyethylenated alcohol sodium sulfate; Oxygenant in described oxidation-reduction initiator is one or more in Potassium Persulphate, benzoyl peroxide, dilauroyl peroxide, and reductive agent is one or more in sodium bisulfite, ferrous pyrophosphate, sulfurous acid iron.
Compared with prior art, the present invention has the following advantages:
(1) reacting property of the active group increase-volume in viton grafted maleic anhydride expanding material and Core-shell type double-active acrylate elastic body, easily mix time mixing with viton and produce in mechanical properties and coordinate same synergism, simultaneously two by the crosslinked cross-linking density and the tear resistance that wait raising rubber unvulcanizate, the introducing of ether-containing group, improves the high-temperature stability of rubber.The present invention is by the modification acrylate blend rubber of rubber master batch and weathering resistance and tear-resistant excellent property, and improving viton has resistance to low temperature; By carrying out modification to acrylate, introducing containing ether and active functional group wherein, constructing the modification acrylate of double activated (double cross connection), improve the resistance to elevated temperatures of viton further.
(2) the present invention is by adding viton grafted maleic anhydride expanding material, and compatibilization effect is good, improves the mechanics of viton and stability and reduction viton cost.
(3) the present invention by acid-acceptor, vulcanizing agent, rubber reinforcing filler, promotor with the use of, reduce the second-order transition temperature of Core-shell type double-active acrylate elastic body blending and modifying viton, improve its resistance to low temperature.
Embodiment
In following embodiment, the number of material is all expressed with weight part.
Embodiment 1
(1) viton grafted maleic anhydride expanding material is prepared.Crude fluororubber 80 parts, maleic anhydride 3 part, part dicumyl peroxide (DCP) 0.5,0.2 part, magnesium oxide, tetramethyl-thiuram disulfide 0.1 part (vulcanization accelerator TMTD) are joined in Banbury mixer, temperature be 120 DEG C, under rotating speed is the condition of 50r/min, reaction 15min, obtain viton grafted maleic anhydride (KFM-g-MAH) expanding material, recording its percentage of grafting is 1.65%.
(2) Core-shell type double-active acrylate elastic body.Preparation is by methyl acrylate 70 parts, methoxyethyl acrylate 55 parts, acrylamide sodium isopropyl xanthate 15 parts; join in kneader; be warming up to 62 DEG C; insulation reaction 0.8h, then adds benzoyl peroxide 10 parts and Potassium Persulphate-sodium bisulfite 5 parts, under nitrogen protection; be warming up to 83 DEG C; insulation reaction 1.7h, is finally cooled to 43 DEG C, obtains Core-shell type double-active acrylate elastic body.
(3) blendedly viton rubber master batch is prepared.By crude fluororubber 100 parts, Core-shell type double-active acrylate elastic body 20 parts, viton grafted maleic anhydride expanding material 3 parts, white carbon black 10 parts, be sequentially added in Banbury mixer, melting 80min at DEG C, obtains viton rubber master batch.
Embodiment 2
(1) viton grafted maleic anhydride expanding material is prepared.By viton 120 parts, maleic anhydride 6 parts, Potassium Persulphate (KPS) 1 part, benzoyl peroxide (BPO) 0.3 part, 2,2 '-dithio-bis-benzothiazole 0.2 part (accelerator DM) joins in Banbury mixer, temperature be 140 DEG C, under rotating speed is the condition of 80r/min, reaction 18min, obtain viton grafted maleic anhydride (KFM-g-MAH) expanding material, recording its percentage of grafting is 3.5%.
(2) Core-shell type double-active acrylate elastic body.By ethyl propenoate 80 parts, methyl methacrylate 75 parts, double bond containing alcohol ether sulfosuccinates sodium salt 20 parts; join in kneader; be warming up to 90 DEG C; insulation reaction 1.2h, then added BPP 8 parts and ammonium persulfate-sodium bisulfite 6 parts, under nitrogen protection; be warming up to 80 DEG C; insulation reaction 1.5h, is finally cooled to 40 DEG C, obtains Core-shell type double-active acrylate elastic body.
(3) blendedly viton rubber master batch is prepared.By crude fluororubber 100 parts, Core-shell type double-active acrylate elastic body 30 parts, viton grafted maleic anhydride expanding material 5 parts, nano-calcium carbonate 20 parts, be sequentially added in Banbury mixer, melting 100min at 150 DEG C, obtains viton rubber master batch.
Embodiment 3
(1) viton grafted maleic anhydride expanding material is prepared.By crude fluororubber 130 parts, maleic anhydride 7 part, part dilauroyl peroxide 1.5(LPO), BPP 0.5 part (BPP), N tert butyl benzothiazole 2 sulfenamide 0.3 part (vulcanization accelerator TBBS) join in Banbury mixer, temperature be 160 DEG C, under rotating speed is the condition of 100r/min, reaction 20min, obtain viton grafted maleic anhydride (KFM-g-MAH) expanding material, recording its percentage of grafting is 3.15%.
(2) Core-shell type double-active acrylate elastic body.By butyl acrylate 100 parts, hydroxyethyl methylacrylate 80 parts, sodium vinyl sulfonate 30 parts; join in kneader; be warming up to 70 DEG C; insulation reaction 1.0h, then adds 17 parts, calcium hydroxide and sodium chlorate-S-WAT 8 parts, under nitrogen protection; be warming up to 100 DEG C; insulation reaction 2.0h, is finally cooled to 50 DEG C, obtains Core-shell type double-active acrylate elastic body.
(3) blendedly viton rubber master batch is prepared.By viton 100 parts, Core-shell type double-active acrylate elastic body 45 parts, viton grafted maleic anhydride expanding material 7 parts, carbon black 30 parts, be sequentially added in Banbury mixer, melting 120min at 140 DEG C, obtains viton rubber master batch.
Claims (7)
1. the preparation method of a viton rubber master batch, it is characterized in that, first prepare viton grafted maleic anhydride expanding material and double activated acrylate elastomer, again by crude fluororubber, viton grafted maleic anhydride expanding material, double activated acrylate elastomer and rubber reinforcing filler, join in Banbury mixer, at 120 ~ 170 DEG C, melting 50 ~ 120 minutes is blended;
Described crude fluororubber 100 weight part, double activated acrylate elastomer 20 ~ 50 weight part, viton grafted maleic anhydride expanding material 3 ~ 8 weight part, rubber reinforcing filler 10 ~ 30 weight part;
The process preparing viton grafted maleic anhydride joins in Banbury mixer by crude fluororubber, maleic anhydride, initiator, vulcanizing agent, promotor, at 120 ~ 160 DEG C, under the condition of rotating speed 50 ~ 100r/min, and reaction 10 ~ 30min;
The process preparing double activated acrylate elastomer is by acrylate monomer, joins in kneader containing the acrylate of active group, emulsifying agent; be warming up to 60 ~ 90 DEG C; insulation reaction 0.8 ~ 1.2h; then vulcanizing agent and oxidation-reduction initiator is added; under nitrogen protection; be warming up to 80 ~ 100 DEG C, insulation reaction 1.5 ~ 2.0h, be finally cooled to 40 ~ 50 DEG C and obtain.
2. the preparation method of rubber rubber master batch according to claim 1, is characterized in that, described crude fluororubber 80 ~ 130 weight part, maleic anhydride 3 ~ 8 weight part, initiator 0.5 ~ 2 weight part, vulcanizing agent 0.2 ~ 0.5 weight part, promotor 0.1 ~ 0.3 weight part.
3. the preparation method of viton rubber master batch according to claim 1, it is characterized in that, described acrylate monomer 70 ~ 100 weight part, containing acrylate 50 ~ 80 weight part of active group, emulsifying agent 15 ~ 30 weight part, vulcanizing agent 8 ~ 20 weight part, oxidation-reduction initiator 5 ~ 8 weight part.
4. the preparation method of viton rubber master batch according to claim 1, is characterized in that, described rubber reinforcing filler comprises one or more in carbon black, white carbon black, nano-calcium carbonate, hard (china) clay.
5. the preparation method of viton rubber master batch according to claim 1, it is characterized in that, described initiator is one or more of benzoyl peroxide (BPO), dilauroyl peroxide (LPO), Diisopropyl azodicarboxylate (AIBN), Potassium Persulphate (KPS), dicumyl peroxide (DCP) or di-t-butyl peroxide;
Described vulcanizing agent be benzoyl peroxide (BPO), BPP (BPP), calcium hydroxide or magnesian one or more;
Described promotor is 2-benzothiazolyl mercaptan (accelerator M), 2, one or more of 2 '-dithio-bis-benzothiazole (accelerator DM), N-cyclohexyl-2-[4-morpholinodithio sulphenamide (aniline fluid bed), N tert butyl benzothiazole 2 sulfenamide (vulcanization accelerator TBBS), tetramethyl-thiuram disulfide (vulcanization accelerator TMTD).
6. the preparation method of viton rubber master batch according to claim 1, it is characterized in that, described emulsifying agent is one or more in acrylamide sodium isopropyl xanthate, double bond containing alcohol ether sulfosuccinates sodium salt, sodium vinyl sulfonate, sodium laurylsulfonate, polyoxyethylenated alcohol sodium sulfate;
Oxygenant in described oxidation-reduction initiator is one or more in Potassium Persulphate, benzoyl peroxide, dilauroyl peroxide, and reductive agent is one or more in sodium bisulfite, ferrous pyrophosphate, sulfurous acid iron.
7. a viton rubber master batch, is characterized in that, is obtained by preparation method according to claim 1.
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| CN106632868A (en) * | 2016-10-21 | 2017-05-10 | 兰州理工大学 | Maleic anhydride-grafted compatibilizer and its preparation method, and polytetrafluoroethylene composite |
| CN115028952A (en) * | 2022-06-24 | 2022-09-09 | 四川道弘新材料有限公司 | Fluororubber with high performance retention rate at high temperature and preparation method thereof |
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