CN104341686A - Application of continuously prepared rubber master batch to car tire inner liner rubber - Google Patents
Application of continuously prepared rubber master batch to car tire inner liner rubber Download PDFInfo
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- CN104341686A CN104341686A CN201410609133.9A CN201410609133A CN104341686A CN 104341686 A CN104341686 A CN 104341686A CN 201410609133 A CN201410609133 A CN 201410609133A CN 104341686 A CN104341686 A CN 104341686A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 143
- 239000005060 rubber Substances 0.000 title claims abstract description 143
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 37
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 49
- 238000002156 mixing Methods 0.000 claims abstract description 42
- 239000000945 filler Substances 0.000 claims abstract description 41
- 239000002904 solvent Substances 0.000 claims abstract description 27
- 239000003921 oil Substances 0.000 claims abstract description 25
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 23
- 239000000654 additive Substances 0.000 claims abstract description 22
- 239000007822 coupling agent Substances 0.000 claims abstract description 14
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 10
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 10
- 229920001194 natural rubber Polymers 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 4
- 229920005555 halobutyl Polymers 0.000 claims abstract description 3
- 229920002681 hypalon Polymers 0.000 claims abstract description 3
- 229920001195 polyisoprene Polymers 0.000 claims abstract description 3
- 239000006229 carbon black Substances 0.000 claims description 35
- 238000002360 preparation method Methods 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 230000000996 additive effect Effects 0.000 claims description 17
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- 239000003963 antioxidant agent Substances 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 15
- 230000001737 promoting effect Effects 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000003292 glue Substances 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 230000003078 antioxidant effect Effects 0.000 claims description 10
- 235000021355 Stearic acid Nutrition 0.000 claims description 9
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 9
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 9
- 239000008117 stearic acid Substances 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- 238000005987 sulfurization reaction Methods 0.000 claims description 8
- -1 tetracol phenixin Chemical compound 0.000 claims description 8
- 239000011787 zinc oxide Substances 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920005615 natural polymer Polymers 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 229920001059 synthetic polymer Polymers 0.000 claims description 4
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 claims description 4
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 claims description 3
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 3
- 150000004657 carbamic acid derivatives Chemical class 0.000 claims description 3
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 3
- 229920001206 natural gum Polymers 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical class NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- LOVYCUYJRWLTSU-UHFFFAOYSA-N 2-(3,4-dichlorophenoxy)-n,n-diethylethanamine Chemical compound CCN(CC)CCOC1=CC=C(Cl)C(Cl)=C1 LOVYCUYJRWLTSU-UHFFFAOYSA-N 0.000 claims description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 2
- 239000000899 Gutta-Percha Substances 0.000 claims description 2
- VHOQXEIFYTTXJU-UHFFFAOYSA-N Isobutylene-isoprene copolymer Chemical group CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 240000000342 Palaquium gutta Species 0.000 claims description 2
- 241001495453 Parthenium argentatum Species 0.000 claims description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229960001701 chloroform Drugs 0.000 claims description 2
- 238000009795 derivation Methods 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000010419 fine particle Substances 0.000 claims description 2
- 229920000588 gutta-percha Polymers 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 238000010092 rubber production Methods 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 claims description 2
- 150000003557 thiazoles Chemical class 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 23
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000005062 Polybutadiene Substances 0.000 abstract 1
- 230000003213 activating effect Effects 0.000 abstract 1
- 229920005549 butyl rubber Polymers 0.000 abstract 1
- 230000015271 coagulation Effects 0.000 abstract 1
- 238000005345 coagulation Methods 0.000 abstract 1
- 239000002562 thickening agent Substances 0.000 abstract 1
- 239000004636 vulcanized rubber Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 37
- 235000019241 carbon black Nutrition 0.000 description 25
- 229940105289 carbon black Drugs 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- 239000000463 material Substances 0.000 description 10
- 238000004513 sizing Methods 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000013032 Hydrocarbon resin Substances 0.000 description 5
- 229920005557 bromobutyl Polymers 0.000 description 5
- 229920006270 hydrocarbon resin Polymers 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011877 solvent mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 238000003490 calendering Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000010074 rubber mixing Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 206010018612 Gonorrhoea Diseases 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000010058 rubber compounding Methods 0.000 description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 2
- 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
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004807 desolvation 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
- 239000000428 dust Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229920006173 natural rubber latex Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- 230000008698 shear stress Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 238000005406 washing Methods 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
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
- C08L23/283—Iso-olefin halogenated homopolymers or copolymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General 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 invention relates to application of continuously prepared rubber master batch to car tire inner liner rubber. The application comprises the following steps: a) adding fillers in rubber solution, evenly mixing and dispersing the mixture, injecting the mixture into a coagulator for coagulation, removing solvent and conducting drying to obtain rubber master batch; b) adding the rubber master batch into an internal mixer, adding vulcanizing agent and accelerant and evenly mixing the mixture to obtain a car tire inner liner rubber compound; c) vulcanizing the car tire inner liner rubber compound under vulcanizing conditions to obtain car tire inner liner vulcanized rubber. The application further comprises the step of adding additives, wherein the additives are added in step a and/or step b; the additives comprise one or more of coupling agent, anti-aging agent, activating agent, oil, homogenizing agent and thickening agent; rubber in the rubber solution comprises one or more of butyl rubber, halogenated butyl rubber, chlorosulfonated polyethylene rubber, natural rubber, polyisoprene rubber, polystyrene-butadiene rubber and polybutadiene rubber.
Description
Technical field
The present invention relates to rubber for tire sizing material production field, the preparation of the rubber masterbatch particularly prepared containing a kind of continous way in Inner liner rubber for passenger car tyre and the application of this air/tight layer rubber in tyres for passenger cars.
Background technology
In tyre airtight layer glue preparation process, by formula in filler and the additive conventional approach be mixed in rubber be with large-scale mixing facilities, such as Banbury mixer, milling machine and opening rubber mixing machine etc., be mixed into Powdered or liquid filler and additive in solid rubber.This kind of technique mixing time be long, it is high to consume energy, dust is many and bad dispersibility, and the degree of scatter of filler directly decides the performance of sizing material, and the mechanics fatigue property and tire product quality that make air retaining wall cross-linked rubber are very restricted by fillers dispersed difference.
In recent years, the master batch of the relevant mixing preparation of liquid phase, in the application of tire production, has introduction in some documents and patent.The application of wet masterbatch rubber combination in tire is refer in CN102414270A, the wet method rubber master batch preparation technology related in this patent is prepared respectively: A, gonorrhoea shape rubber pharmaceutical chemicals dispersion liquid (anti-aging agent, wax, at least one in stearic acid and resin), B, rubber latex, C, filler slurries, then by after two kinds of liquid mixing wherein preparing, again with another kind of liquid mixing, this kind of complicated process of preparation, need preparation gonorrhoea shape rubber pharmaceutical chemicals dispersion liquid separately, and pharmaceutical chemicals kind is wherein restricted, only be mentioned to anti-aging agent, wax, at least one in stearic acid and resin.A kind of application of wet method rubber master batch in the tread glue formula of mine containing solution dispersion white carbon black latex mixture is referred in CN102807689A, the wet method rubber master batch mentioned in this patent refers to: carry out mixing through solidifying with a small amount of rubber latex used in formula in advance by a small amount of filler used in tyre surface formula and for white carbon black and silane, dehydration, the rubber master batch that washing is obtained, the section of plasticating is have passed through in tread mix preparation process, mixing one section, supplement mixing two sections, add sulphur totally four sections mixing, the wet method rubber master batch mentioned in this patent carries out pre-dispersed to white carbon black, white carbon black can be made to disperse in sizing material more even, but this kind of wet method rubber master batch packing variety and content are all restricted, and the calendering process of tread mix is not simplified." application of liquid-phase mixing NR/ carbon black composite material in tread rubber " that " tire industry " second phase in 2005 delivers, the application of NR/ carbon black composite material (CEC) is referred in this document, CEC one-stage process is relate to mixing mixing with CEC two-phase method in document, female refining medicine and whole refining medicine need be added at this mixing process, the NR/ carbon black composite material mentioned in this document is that the technique that Cabot Co., Ltd of U.S. natural rubber latex and carbon black water slurry adopt liquid phase to manufacture natural gum/carbonblack master batch continuously obtains, the method that this liquid phase continuous mixing prepares rubber/filler master batch simplifies rubber mixing technique, mixing time, reduce energy consumption with artificial, but rubber used in rubber master batch preparation, packing variety and content are restricted, and the additives such as rubber master batch medicine still need add in rubber compounding process.
Summary of the invention
For the problem of prior art, first object of the present invention is to provide a kind of Inner liner rubber for passenger car tyre sizing material containing rubber masterbatch prepared by method for continuously producing, and after this rubber vulcanization, fillers dispersed is good, and fatigue performance improves.Second object of the present invention is to provide the above-mentioned preparation method containing the air retaining wall sizing material of rubber masterbatch prepared by method for continuously producing, apply this preparation method can simplify rubber mixing technique, shorten mixing time, reduce energy consumption and artificial, the 3rd object of the present invention is to provide the application of above-mentioned air/tight layer rubber in tyres for passenger cars.
Have employed continous way in the present invention and prepare the manufacturing process of rubber masterbatch to prepare tyres for passenger cars air/tight layer rubber and tire, compare with air/tight layer rubber with traditional dry method calendering process, this method improves the dispersion of filler in rubber size, decrease mixing step, solve the mixing problem of not easily disperseing of filler, air/tight layer rubber prepared by use this method is in fillers dispersed, mechanics fatigue performance aspect is all very superior, the tyre airtight layer glue using this legal system standby is applied to after in tire, its end properties is under the prerequisite ensureing tire basic security performance, because the fatigue performance of air retaining wall sizing material increases, make tire driving process air-tightness and life cycle improve further, thus indirectly reduce the traveling rolling resistance of tire, reduce oil consumption.
The application of rubber masterbatch in car tire air/tight layer rubber prepared by a kind of continous way of the present invention comprises following steps:
A) in rubber solutions, add filler, blending dispersion evenly injects cohesion in knockouts afterwards, then desolventizing drying obtains rubber masterbatch;
B) rubber masterbatch is joined in Banbury mixer, add vulcanizing agent and promotor, after mixing, obtain car tire air retaining wall rubber unvulcanizate;
C) car tire air retaining wall rubber unvulcanizate is carried out sulfuration under cure conditions, obtain car tire air retaining wall cross-linked rubber;
Above-mentioned steps also comprises adding of additive, additive step a) and/or step b) in add; Additive comprises one or more of coupling agent, anti-aging agent, promoting agent, oil and tackifier.Rubber in wherein said rubber solutions comprise in isoprene-isobutylene rubber, halogenated butyl rubber, chlorosulfonated polyethylene rubber, natural rubber, polyisoprene rubber, styrene-butadiene rubber, polybutadiene rubber one or more also use.
Preferably, the step of aforesaid method comprises:
A) in rubber solutions, add anti-aging agent, carbon black or add anti-aging agent, white carbon black and coupling agent, blending dispersion evenly injects cohesion in knockouts afterwards, then desolventizing drying obtains rubber masterbatch;
B) rubber masterbatch is joined in Banbury mixer, add anti-aging agent, promoting agent and tackifier or add anti-aging agent, promoting agent, oil and tackifier, then adding vulcanizing agent and promotor, after mixing, obtain car tire air retaining wall rubber unvulcanizate;
C) car tire air retaining wall rubber unvulcanizate is carried out sulfuration under cure conditions, obtain car tire air retaining wall cross-linked rubber.
Preferably, step b) in anti-aging agent, promoting agent and tackifier or add anti-aging agent, promoting agent, oil and tackifier step a) in add.
Rubber solutions of the present invention is directly obtain from preparing solution polymerized rubber production line, or the dry glue of any type is dissolved preparation in the good solvent of this rubber.When wherein preparing rubber solutions with dry glue, described dry glue is natural polymer or synthetic polymer, described natural polymer comprises at least one of natural gum, gutta-percha, guayule, described synthetic polymer is that monomer is polymerized gained in the solution, and monomer in emulsion, be polymerized gained or monomer body carries out polymerization gained.Wherein in rubber solutions, rubber consumption is 100 weight parts, and wherein the consumption of natural rubber is below 50 weight parts.
The step of preparation method of the present invention a) adopts the method for continuously producing of rubber rubber master batch, and the method specifically comprises the steps:
Step 1): filler being joined in rubber solutions, forming rubber/filler/solvent mixture by stirring;
Step 2): by step 1) in rubber/filler/solvent mixture send in knockouts, and contact with nitrogen, water, water vapour, filler water slurry and one or more fluid-phases in oil in knockouts and mix rear cohesion, obtain the mixture of rubber/filler compound and solvent;
Step 3): desolvation also carries out drying to described mixture, obtains rubber/filler master batch.Wherein optional recycling step 3) solvent that removes, recycle.In step 1) and/or step 2) in optional add one or more and be selected from but be not limited to coupling agent, anti-aging agent, promoting agent, tackifier and/or oil additives.
Wherein, step 1) can be specially filler is joined in rubber solutions, form rubber/filler/solvent mixture by stirring, and to described rubber/filler/solvent mixture further finely divided and smart dispersion to improve the degree of scatter of filler in rubber solutions.
Described finely dividedly can to implement in the following way: the mixture of above-mentioned stirring gained is sprayed, to improve the dispersion of filler and/or additive when high pressure high-shear by a nozzle; And then make above-mentioned ejecta make mixed solution clash into the dispersiveness increasing filler and/or additive at Guan Zhongyu tube wall by swan neck more than; Or make ejecta convert shear-stress by the bore pipeline that repeatedly folding and unfolding changes and increase the dispersion of filler and/or additive.Pressure range used from 0.5MPa to 60MPa, preferred 10MPa to 40MPa.
Described finely divided rear formed mixture can also improve filler and/or the dispersion of additive in rubber solutions further by following essence dispersion:
I. by described finely divided after mixture add continuously in ball mill and/or colloidal mill and disperse, filler and/or additive are dispersed in rubber solutions uniformly;
Ii. by described finely divided after mixture join continuously in shredder and carry out grinding to make filler and/or additive be well dispersed in rubber solutions, this shredder has the plane mill of one or more groups high-speed rotation and to be fixed on shredder sleeve and the fixing pin alternate with plane mill or price fixing.
Iii. by described finely divided after mixture join in shredder continuously and grind, this shredder has two contrary blades of turning direction, described blade has pore chute, under high pressure can improve filler and/or the degree of scatter of additive in rubber solutions by the blade rotated.Pressure range used from 0.5MPa to 60MPa, preferred 10MPa to 40MPa.
Iv. by described finely divided after mixture join in multi-layer high-voltage slit dispersion machine continuously, mixture is under high pressure extruded from slit between two-layer, and the Strong shear power now produced can improve filler and/or the degree of scatter of additive in rubber solutions.Pressure range used from 0.5MPa to 60MPa, preferred 10MPa to 40MPa.
V. by described finely divided after mixture join continuously in power decentralized device and disperse, the rotor of the high speed rotating of described power decentralized device has many radially-arranged slits or hole, mixture with high-speed impact on stator surface to make filler and/or additive be evenly dispersed in rubber solutions.
Two or more use of can mutually connecting of above-mentioned five kinds of finely divided methods.
The solvent of rubber of the present invention is the good solvent of various rubber, solvent comprises at least one of aliphatic solvents, aromatic hydrocarbon solvent, chlorinated hydrocarbon solvent, ketones solvent, ether solvent and esters solvent, described aliphatic solvents comprises at least one of gasoline, naphthenic hydrocarbon, substituted ring alkane, normal alkane, described aromatic hydrocarbon solvent comprises benzene,toluene,xylene, cinnamic at least one, and described chlorinated hydrocarbon solvent comprises at least one of methylene dichloride, trichloromethane, tetracol phenixin, ethylene dichloride, chlorobenzene, zellon, toluene(mono)chloride.Rubber concentration range is in the solution 1 % by weight to 60 % by weight, preferably 5 % by weight to 40 % by weight, more preferably 10 % by weight to 30 % by weight.Described anti-aging agent comprise in amines antioxidants, quinoline type antioxidant, phenolic type antioxidant and protection wax one or more also use, amines antioxidants comprises Ursol D class, the preferred antioxidant 4020 of amines antioxidants, the preferred anti-aging agent RD of quinoline type antioxidant, the preferred antioxidant 264 of phenolic type antioxidant, the consumption of anti-aging agent is 0 to 8 weight part, preferably 0 to 3 weight part.Described promoting agent comprises stearic acid, and the consumption of promoting agent is 0 to 5 weight part, preferably 0.5 to 3 weight part.
Described filler comprises at least one of white carbon black, carbon black and other fine particle filler.The consumption of described filler is 20 to 180 weight parts, and wherein the consumption of white carbon black is 0 to 150 weight part, preferably 10 to 120 weight parts, and the consumption of carbon black is 0 to 180 weight part, preferably 10 to 150 weight parts.The specific surface area of described carbon black is 4 to 200m
2/ g, preferably 10 to 100m
2/ g, the oil-absorption(number) of described carbon black is 20 to 250ml/100g, preferably 25 to 200ml/100g, more preferably 30 to 150ml/100g.The specific surface area of described white carbon black is 10 to 500m
2/ g, preferably 15 to 250m
2/ g, more preferably 30 to 200m
2/ g, the oil-absorption(number) of described white carbon black is 20 to 350ml/100g, preferably 25 to 300ml/100g, more preferably 30 to 290ml/100g.
Described vulcanizing agent comprises one or more and use in Sulfur, zinc oxide, sulfur donor and superoxide, and the consumption of vulcanizing agent is 0.2 to 10 weight part, preferably 0.5 to 8 weight part.Described promotor comprise in thiazoles, sulfenamide, thiurams, Carbamates promotor and hexichol guanidine acclerators one or more also use, wherein thiazole accelerator is as altax, sulphenamide accelerators is as accelerant CZ, accelerator NS, thiuram type accelerator is as TMTD, Carbamates promotor is as promotor PX, hexichol guanidine acclerators is as vulkacit D PG, and the consumption of promotor is 0.2 to 5 weight part, preferably 0.5 to 3 weight part.Described tackifier comprise phenolic tackifying resin, petroleum derivation resin, timber resins derived therefrom, the consumption of tackifier is 0 to 25 weight part preferably 2 to 20 weight parts, described oil comprises the aromatic hydrocarbon oil of petroleum or at least one of naphthenic oil, the consumption of oil is 0 to 30 weight part, preferably 0 to 15 weight part.Described coupling agent comprise in two (triethoxy propyl silane) tetrasulfide and disulphide, 3-thiocyanogen propyl-triethoxysilane, γ-mercapto propyl-trimethoxysilane, zirconium ester coupling agent, titanate coupling agent and nitro coupling agent one or more also use.
Apply the preparation method of this kind of tyre airtight layer glue, simplify the calendering process of sizing material, reduce the labour intensity of rubber compounding.Improve the dispersion of filler and the fatigue performance of cross-linked rubber in sizing material, strength and extension property and resilience slightly improve, and the gas permeation rate of sulfide film slightly reduces simultaneously.From the viewpoint of tire end properties, because the fatigue performance of air retaining wall sizing material increases, make tire driving process air-tightness and life cycle improve further, thus indirectly reduce the traveling rolling resistance of tire, reduce oil consumption.
Embodiment
Further describe the present invention by embodiment below, but scope of the present invention is not by the restriction of these embodiments.
(1) embodiment uses following plant and instrument and measuring method to measure:
Plant and instrument prepared by table 1 rubber sample
| Sequence number | Device name | Specifications and models | Manufacturer |
| 1 | Banbury mixer | XSM-1/10-120 | Shanghai Kechuang rubber and plastics machine equipment company limited |
| 2 | Mill | 152.5*320 | Zhanjiang Machine Factory, Guangdong Prov. |
| 3 | Vulcanizing press | XLB-D600*600 | Zhejiang Huzhou east Machinery Co., Ltd. |
The testing method of table 2 properties of rubber and instrument
The testing method of table 3 tire end properties and equipment
(2) embodiment and comparative example
Raw material:
Natural rubber, SMR20; SENG HIN RUBBER (M) SDN BHD (Cheng Xing);
Brominated butyl rubber, BB2222, ExxonMobil Chemical Asia Pacific;
White carbon black, Newsil HD165MP, Q & C Silicon Chemical Co., Ltd.;
Carbon black, N660, Cabot (China) Investment Co., Ltd;
Naphthenic oil, Shandong Tianyuan Chemical Co., Ltd.;
Indirect process zinc oxide, Dalian zinc oxide factory;
Stearic acid, PF1808, Malaysian Li Cheng company limited;
Antioxidant 264, Huangyan, Zhejiang East Zhejiang province rubber ingredients company limited;
Silane coupling agent Si69, NanJing Shuguang Chemical Group Co., Ltd.;
Octyl group phenolic tackifying resins, Wuhan Jinghe Chemical Co., Ltd;
Hydrocarbon resin blend, 40MSF, STRUKTOR company of the U.S.;
Accelerator NS, Shandong Sunsine Chemical Co., Ltd.;
Vulkacit D PG, Dan County, Shandong Chemical Co., Ltd.;
Sulfur flour, Lin Yiluo Zhuan Xin Anhua factory;
Described in following examples and comparative example, number is weight part.
Comparative example 1
In Banbury mixer, 60 parts of carbon blacks are joined carry out in 10 parts of natural rubbers and 90 parts of brominated butyl rubbers mixing, mixing certain hour, add 1 part of stearic acid, 2 parts of antioxidant 264s, 2 parts of octyl group phenolic tackifying resins, 7 parts of hydrocarbon resin blend and 8 parts of naphthenic oils, rubber unvulcanizate is mixing add 0.7 part of accelerator NS, 0.5 part of Sulfur and 4 parts of zinc oxide after parking 8 hours again in Banbury mixer after, rubber unvulcanizate is parked after 8 hours and under 165 DEG C of conditions, after sulfuration to plateau cure, is obtained dry pre-sulfiding glue 1 with vulcanizing press.Tire 195/60R14 is obtained with dry method air retaining wall rubber unvulcanizate 1.
Embodiment 1
60 parts of carbon blacks, 8 parts of naphthenic oils, 2 parts of antioxidant 264s, 1 part of stearic acid, 2 parts of octyl group phenolic tackifying resins, 7 parts of hydrocarbon resin blend to be joined in the hexane solution of 90 parts of brominated butyl rubbers and 10 parts of natural rubbers after mixing, inject cohesion in knockouts continuously, afterwards desolventizing drying obtains rubber master batch 1.
Rubber master batch 1 is joined after mixing in Banbury mixer, mixing after adding 4 parts of zinc oxide, 0.7 part of accelerator NS, 0.5 part of Sulfur, cross roller bottom sheet after mixing, rubber unvulcanizate is parked after 8 hours and is used vulcanizing press under 165 DEG C of conditions after sulfuration to plateau cure, and obtained continous way prepares cross-linked rubber 1.Prepare air retaining wall rubber unvulcanizate 1 by continous way and obtain tire 195/60R14.
Comparative example 2
In Banbury mixer, 60 parts of white carbon blacks and 4.8 parts of silane coupling agent Si69 are joined carry out in 10 parts of natural rubbers and 90 parts of brominated butyl rubbers mixing, mixing certain hour, add 1 part of stearic acid, 2 parts of antioxidant 264s, 2 parts of octyl group phenolic tackifying resins, 7 parts of hydrocarbon resin blend and 8 parts of naphthenic oils, rubber unvulcanizate adds 0.7 part of accelerator NS after parking 8 hours again in Banbury mixer, 1 part of vulkacit D PG, mixing after 0.5 part of Sulfur and 4 parts of zinc oxide, rubber unvulcanizate to be parked after 8 hours with vulcanizing press under 165 DEG C of conditions after sulfuration to plateau cure, obtained dry pre-sulfiding glue 2.Tire 195/60R14 is obtained with dry method air retaining wall rubber unvulcanizate 2.
Embodiment 2
60 parts of white carbon blacks, 4.8 parts of silane coupling agents, 8 parts of naphthenic oils, 2 parts of antioxidant 264s, 1 part of stearic acid, 2 parts of octyl group phenolic tackifying resins, 7 parts of hydrocarbon resin blend to be joined in the hexane solution of 90 parts of brominated butyl rubbers and 10 parts of natural rubbers after mixing, inject cohesion in knockouts continuously, afterwards desolventizing drying obtains rubber master batch 1.
Rubber master batch 1 is joined after mixing in Banbury mixer, mixing after adding 4 parts of zinc oxide, 0.7 part of accelerator NS, 1 part of vulkacit D PG, 0.5 part of Sulfur, roller bottom sheet is crossed after mixing, rubber unvulcanizate is parked after 8 hours and is used vulcanizing press under 165 DEG C of conditions after sulfuration to plateau cure, and obtained continous way prepares cross-linked rubber 2.Prepare air retaining wall rubber unvulcanizate 2 by continous way and obtain tire 195/60R14.
Table 4 dry method and continous way prepare the test performance of air retaining wall cross-linked rubber
Table 5 dry method and continous way are prepared air retaining wall rubber unvulcanizate and are prepared tyre performance test
Table 4 is the contrast table of application continous way preparation technology and the mechanical property applying dry preparation process gained air/tight layer rubber, dynamic property and air-tightness, as can be seen from the table, under same recipe, after application continous way preparation technology, the degree of scatter of filler in rubber improves, and the hardness of cross-linked rubber slightly reduces, tensile strength and tensile yield increase, elasticity is higher, and fatigue performance is good, and gas permeation rate is low.
The tire indoor performance contrast table that table 5 is prepared with application dry preparation process gained air retaining wall rubber unvulcanizate for application continous way preparation technology, as can be seen from the table, under same recipe, tire prepared by application dry method and continous way preparation technology, the basic security performance of tire all can ensure.Its end properties is under the prerequisite ensureing tire basic security performance, because the fatigue performance of air retaining wall sizing material increases, make tire driving process air-tightness and life cycle improve further, thus indirectly reduce the traveling rolling resistance of tire, reduce oil consumption.
Claims (18)
1. the application of rubber masterbatch in car tire air/tight layer rubber prepared of continous way, it comprises following steps:
A) in rubber solutions, add filler, blending dispersion evenly injects cohesion in knockouts afterwards, then desolventizing drying obtains rubber masterbatch;
B) rubber masterbatch is joined in Banbury mixer, add vulcanizing agent and promotor, after mixing, obtain car tire air retaining wall rubber unvulcanizate;
C) car tire air retaining wall rubber unvulcanizate is carried out sulfuration under cure conditions, obtain car tire air retaining wall cross-linked rubber;
Above-mentioned steps also comprises adding of additive, additive step a) and/or step b) in add; Additive comprises one or more of coupling agent, anti-aging agent, promoting agent, oil and tackifier;
Rubber in wherein said rubber solutions comprise in isoprene-isobutylene rubber, halogenated butyl rubber, chlorosulfonated polyethylene rubber, natural rubber, polyisoprene rubber, styrene-butadiene rubber, polybutadiene rubber one or more also use.
2. application according to claim 1, its step comprises:
A) in rubber solutions, add anti-aging agent, carbon black or add anti-aging agent, white carbon black and coupling agent, blending dispersion evenly injects cohesion in knockouts afterwards, then desolventizing drying obtains rubber masterbatch;
B) rubber masterbatch is joined in Banbury mixer, add anti-aging agent, promoting agent and tackifier or add anti-aging agent, promoting agent, oil and tackifier, then adding vulcanizing agent and promotor, after mixing, obtain car tire air retaining wall rubber unvulcanizate;
C) car tire air retaining wall rubber unvulcanizate is carried out sulfuration under cure conditions, obtain car tire air retaining wall cross-linked rubber.
3. application according to claim 2, is characterized in that: step b) in anti-aging agent, promoting agent and tackifier or add anti-aging agent, promoting agent, oil and tackifier step a) in add.
4. application according to claim 1, wherein said rubber solutions directly obtains from preparing solution polymerized rubber production line, or the dry glue of any type is dissolved in the good solvent of this rubber preparation and obtain.
5. application according to claim 4, when wherein preparing rubber solutions with dry glue, described dry glue is natural polymer or synthetic polymer, described natural polymer comprises at least one of natural gum, gutta-percha, guayule, described synthetic polymer is that monomer is polymerized gained in the solution, and monomer in emulsion, be polymerized gained or monomer body carries out polymerization gained.
6. application according to claim 4, wherein in rubber solutions, rubber consumption is 100 weight parts, and wherein the consumption of natural rubber is below 50 weight parts.
7. application according to claim 4, the solvent of wherein said rubber comprises at least one of aliphatic solvents, aromatic hydrocarbon solvent, chlorinated hydrocarbon solvent, ketones solvent, ether solvent and esters solvent, and described aliphatic solvents comprises at least one of gasoline, naphthenic hydrocarbon, substituted ring alkane, normal alkane; Described aromatic hydrocarbon solvent comprises benzene,toluene,xylene, cinnamic at least one, and described chlorinated hydrocarbon solvent comprises at least one of methylene dichloride, trichloromethane, tetracol phenixin, ethylene dichloride, chlorobenzene, zellon, toluene(mono)chloride; Rubber concentration range is in the solution 1 % by weight to 60 % by weight, preferably 5 % by weight to 40 % by weight, more preferably 10 % by weight to 30 % by weight.
8. application according to claim 1, wherein said anti-aging agent comprise in amines antioxidants, quinoline type antioxidant, phenolic type antioxidant and protection wax one or more also use, amines antioxidants comprises Ursol D class, and the consumption of anti-aging agent is 0 to 8 weight part, preferably 0 to 3 weight part.
9. application according to claim 1, wherein said promoting agent comprises stearic acid, and the consumption of promoting agent is 0 to 5 weight part, preferably 0.5 to 3 weight part.
10. application according to claim 1, wherein said filler comprises at least one of white carbon black, carbon black and other fine particle filler.
11. application according to claim 10, the specific surface area of wherein said carbon black is 4 to 200m
2/ g, preferably 10 to 100m
2/ g, the oil-absorption(number) of described carbon black is 20 to 250ml/100g, preferably 25 to 200ml/100g, more preferably 30 to 150ml/100g.
12. application according to claim 10, the specific surface area of wherein said white carbon black is 10 to 500m
2/ g, preferably 15 to 250m
2/ g, more preferably 30 to 200m
2/ g, the oil-absorption(number) of described white carbon black is 20 to 350ml/100g, preferably 25 to 300ml/100g, more preferably 30 to 290ml/100g.
13. application according to claim 10, the total consumption of wherein said filler is 20 to 180 weight parts, and wherein the consumption of white carbon black is 0 to 150 weight part, preferably 10 to 120 weight parts, and the consumption of carbon black is 0 to 180 weight part, preferably 10 to 150 weight parts.
14. application according to claim 1, wherein said vulcanizing agent comprises one or more and use in Sulfur, zinc oxide, sulfur donor and superoxide, and the consumption of vulcanizing agent is 0.2 to 10 weight part, preferably 0.5 to 8 weight part.
15. application according to claim 1, wherein said promotor comprise in thiazoles, sulfenamide, thiurams, Carbamates and hexichol guanidine acclerators one or more also use, the consumption of promotor is 0.2 to 5 weight part, preferably 0.5 to 3 weight part.
16. application according to claim 1, wherein said tackifier comprise phenolic tackifying resin, petroleum derivation resin, and one or more and use in timber resins derived therefrom, the consumption of tackifier is 0 to 25 weight part, preferably 2 to 20 weight parts.
17. application according to claim 1, wherein said oil comprises the aromatic hydrocarbon oil of petroleum or at least one of naphthenic oil, and the consumption of oil is 0 to 30 weight part, preferably 0 to 15 weight part.
18. application according to claim 1, wherein said coupling agent comprise in two (triethoxy propyl silane) tetrasulfide and disulphide, 3-thiocyanogen propyl-triethoxysilane, γ-mercapto propyl-trimethoxysilane, zirconium ester coupling agent, titanate coupling agent and nitro coupling agent one or more also use.
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| CN110734612A (en) * | 2019-09-30 | 2020-01-31 | 德州玲珑轮胎有限公司 | fatigue-resistant chlorosulfonated polyethylene rubber composition, and preparation method and application thereof |
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Application publication date: 20150211 |