NO179951B - Sulfur-vulcanizable rubber compound, and a method of increasing the rate of vulcanization thereof - Google Patents
Sulfur-vulcanizable rubber compound, and a method of increasing the rate of vulcanization thereof Download PDFInfo
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- NO179951B NO179951B NO895244A NO895244A NO179951B NO 179951 B NO179951 B NO 179951B NO 895244 A NO895244 A NO 895244A NO 895244 A NO895244 A NO 895244A NO 179951 B NO179951 B NO 179951B
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- 229920001971 elastomer Polymers 0.000 title claims description 49
- 239000005060 rubber Substances 0.000 title claims description 40
- 238000000034 method Methods 0.000 title claims description 15
- 238000004073 vulcanization Methods 0.000 title claims description 12
- 150000001875 compounds Chemical class 0.000 title description 18
- 239000000203 mixture Substances 0.000 claims description 28
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 21
- 229910052717 sulfur Inorganic materials 0.000 claims description 13
- 239000011593 sulfur Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- -1 disulphides Chemical class 0.000 claims description 9
- 239000000806 elastomer Substances 0.000 claims description 9
- 239000005864 Sulphur Substances 0.000 claims description 5
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 claims description 4
- 229920001195 polyisoprene Polymers 0.000 claims description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 244000043261 Hevea brasiliensis Species 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000012990 dithiocarbamate Substances 0.000 claims description 3
- 229920003052 natural elastomer Polymers 0.000 claims description 3
- 229920001194 natural rubber Polymers 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 150000004659 dithiocarbamates Chemical class 0.000 claims description 2
- 150000002357 guanidines Chemical class 0.000 claims description 2
- 229920001021 polysulfide Polymers 0.000 claims description 2
- 150000003557 thiazoles Chemical class 0.000 claims description 2
- 239000012991 xanthate Substances 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 14
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 10
- 239000000654 additive Substances 0.000 description 10
- 238000009472 formulation Methods 0.000 description 10
- 239000006229 carbon black Substances 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
- 235000021355 Stearic acid Nutrition 0.000 description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 8
- 239000008117 stearic acid Substances 0.000 description 8
- 235000019270 ammonium chloride Nutrition 0.000 description 7
- 239000011787 zinc oxide Substances 0.000 description 7
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000005062 Polybutadiene Substances 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- 239000001993 wax Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 description 4
- 239000008380 degradant Substances 0.000 description 4
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 4
- 239000006057 Non-nutritive feed additive Substances 0.000 description 3
- 239000000378 calcium silicate Substances 0.000 description 3
- 229910052918 calcium silicate Inorganic materials 0.000 description 3
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 229920003051 synthetic elastomer Polymers 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 206010052904 Musculoskeletal stiffness Diseases 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- IPTLKMXBROVJJF-UHFFFAOYSA-N azanium;methyl sulfate Chemical compound N.COS(O)(=O)=O IPTLKMXBROVJJF-UHFFFAOYSA-N 0.000 description 2
- 229920005549 butyl rubber Polymers 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- XUUGSSQXYWMELT-UHFFFAOYSA-N 5-methylhexa-3,5-dien-2-one Chemical compound CC(=C)C=CC(C)=O XUUGSSQXYWMELT-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- WFYPICNXBKQZGB-UHFFFAOYSA-N butenyne Chemical group C=CC#C WFYPICNXBKQZGB-UHFFFAOYSA-N 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229920003211 cis-1,4-polyisoprene Polymers 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- CJSBUWDGPXGFGA-UHFFFAOYSA-N dimethyl-butadiene Natural products CC(C)=CC=C CJSBUWDGPXGFGA-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000002534 ethynyl group Chemical class [H]C#C* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N penta-1,3-diene Chemical compound CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical group [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
Landscapes
- Chemical & Material Sciences (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)
Description
Foreliggende oppfinnelse angår vulkaniseringen av en svovelherdbar gummiblanding. Nærmere bestemt angår foreliggende oppfinnelse en fremgangsmåte for økning av herdingshastigheten av en svovelvulkaniserbar gummi ved tilsetning av et metyl-trialkyl-ammoniumsalt. The present invention relates to the vulcanisation of a sulphur-curable rubber mixture. More specifically, the present invention relates to a method for increasing the curing rate of a sulphur-vulcanizable rubber by adding a methyl-trialkyl-ammonium salt.
"Herdingshastigheten" er definert som hastigheten ved hvilken tverrbinding og utvikling av stivhet (modulus) av en gummiforbindelse finner sted. Når gummiforbindelsen opp- The "curing rate" is defined as the rate at which cross-linking and development of stiffness (modulus) of a rubber compound takes place. When the rubber compound up-
varmes endres egenskapene av gummiforbindelsen fra et bløtt plastisk materiale til et seigt elastisk materiale. Under herdingstrinnet innføres tverrbindinger som forbinder de lange polymere kjeder av gummien. Når flere tverrbindinger innføres blir polymerkjedene knyttet fastere sammen og stivheten eller modulus av forbindelsen øker. Herdingshastigheten er en viktig vulkaniseringsparameter fordi den delvis bestemmer hvor lang tid forbindelsen må herdes, dvs. "herdingstiden". Ved produksjon av vulkaniserte gummiartikler kan vesentlige om-kostningsbesparelser realiseres gjennom en reduksjon av herdingstid. Gjennom økte herdingshastigheter kan herdingstiden som er påkrevet for å tilfredsstille minimale herdingsgrader reduseres. I overensstemmelse med dette er omfattende for-skning utført for å forkorte herdingstidene for gummiforbindelser. Det foreligger derfor et behov for forbedrede fremgangsmåter som øker herdingshastigheten uten å bibringe uønskede egenskaper til vulkanisatet. when heated, the properties of the rubber compound change from a soft plastic material to a tough elastic material. During the curing step, crosslinks are introduced that connect the long polymer chains of the rubber. When more crosslinks are introduced, the polymer chains are bound together more tightly and the stiffness or modulus of the compound increases. The cure rate is an important vulcanization parameter because it partly determines how long the compound must be cured, i.e. the "cure time". In the production of vulcanized rubber articles, significant cost savings can be realized through a reduction in curing time. Through increased curing speeds, the curing time required to satisfy minimum curing degrees can be reduced. In accordance with this, extensive research has been carried out to shorten the curing times for rubber compounds. There is therefore a need for improved methods which increase the curing rate without imparting undesirable properties to the vulcanizate.
Foreliggende oppfinnelse angår en fremgangsmåte for økning av vulkaniseringshastigheten av en gummiblanding, omfattende at det til en svovel-vulkaniserbar gummi tilsettes et metyl-trialkyl-ammoniumsalt av formel: The present invention relates to a method for increasing the vulcanization rate of a rubber mixture, comprising adding a methyl-trialkyl-ammonium salt of the formula to a sulphur-vulcanisable rubber:
hvori R<1> R2 og R3 uavhengig av hverandre er alkylradikaler med 8 til 10 karbonatomer, og M er utvalgt fra gruppen omfattende Cl, Br, CH3S04 og HS04. Oppfinnelsen angår dessuten svovel- wherein R<1> R2 and R3 are independently alkyl radicals of 8 to 10 carbon atoms, and M is selected from the group consisting of Cl, Br, CH3SO4 and HS04. The invention also relates to sulphur-
vulkaniserbar gummiblanding omfattende en elastomer inneholdende olefinisk umettethet, et svovel-vulkaniserende middel, en akselerator og et metyl-trialkyl-ammoniumsalt utvalgt fra saltene med den ovenfor angitte formel. vulcanizable rubber composition comprising an elastomer containing olefinic unsaturation, a sulfur vulcanizing agent, an accelerator and a methyl trialkyl ammonium salt selected from the salts of the above formula.
Foreliggende oppfinnelse an går anvendelsen av et metyl-trialkyl-ammoniumsalt som en aktivator for svovelherd-bare gummiblandinger. Et spesielt foretrukket metyltrialkyl-ammoniumsalt er metyl-trialkyl (C8-C10)-ammoniumklorid som er kommersielt tilgjengelig under varemerket Adogen<®> 464 fra Sherex Chemical Company, Dublin, Ohio og fra Henkel Corporation, Minneapolis, Minnesota, under varemerket Aliquot<® >336. Metyl-trialkyl-ammoniumsalter er generelt kjent som fase-overføringskatalysatorer og er beskrevet i US patent 3 992 432 som i sin helhet er innbefattet heri ved referanse. The present invention relates to the use of a methyl trialkyl ammonium salt as an activator for sulphur-curable rubber compounds. A particularly preferred methyl trialkyl ammonium salt is methyl trialkyl (C8-C10) ammonium chloride which is commercially available under the trade name Adogen<®> 464 from Sherex Chemical Company, Dublin, Ohio and from Henkel Corporation, Minneapolis, Minnesota, under the trade name Aliquot<® >336. Methyl trialkyl ammonium salts are generally known as phase transfer catalysts and are described in US Patent 3,992,432 which is hereby incorporated by reference in its entirety.
For å lette anvendelsen kan metyl-trialkyl-ammoniumsaltet anbringes på egnede bærere. Eksempler på bærere som kan anvendes ved foreliggende oppfinnelse innbefatter silisiumoksid, sot, aluminiumoksid, kiselgur, silikagel og kalsium-silikat. To facilitate use, the methyl trialkyl ammonium salt can be placed on suitable supports. Examples of carriers that can be used in the present invention include silicon oxide, carbon black, aluminum oxide, diatomaceous earth, silica gel and calcium silicate.
Anvendelse av et metyl-trialkyl-ammoniumsalt synes ikke å påvirke tverrbindingsfordelingen når det anvendes i kombinasjon med primære og eventuelt sekundære akseleratorer. Sammen med den økte herdingshastighet observeres imidlertid en økt herdingseffektivitet i form av en økt herdingstilstand eller herdingrad. Use of a methyl-trialkyl-ammonium salt does not seem to affect the cross-linking distribution when used in combination with primary and possibly secondary accelerators. Together with the increased curing speed, however, an increased curing efficiency is observed in the form of an increased curing state or degree of curing.
Foreliggende oppfinnelse kan anvendes for å herde svovel-vulkaniserbare gummiblandinger eller elastomerer inneholdende olefinisk umettethet. Uttrykket "gummi eller elastomer inneholdende olefinisk umettethet" er ment å innbefatte både naturlig gummi og dens forskjellige råformer og regene-rerte former, så vel som forskjellige syntetiske gummiblandinger. Representative syntetiske polymerer er homopolymeriser-ingsproduktene av butadien og dens homologer og derivater, f.eks. metylbutadien, dimetylbutadien og pentadien så vel som kopolymerer, slik som de som dannes fra butadien eller dens homologer eller derivater med andre umettede monomerer. Blant de sistnevnte er acetylener, f.eks. vinylacetylen; olefiner, f.eks. isobutylen, som kopolymeriserer med isopren under dannelse, av butylgummi; vinylforbindelser, f.eks. akrylsyre, akrylonitril (som polymeriserer med butadien under dannelse av NBR), metakrylsyre og styren, den sistnevnte forbindelse polymeriserer med butadien under dannelse av SBR, så vel som vinylestere og forskjellige umettede aldehyder, ketoner og etere, f.eks. akrolein, metylisoprenylketon og vinyletyl eter. Spesifikke eksempler på syntetiske gummiforbindelser innbefatter neopren (polykloropren), polybutadien (innbefattet cis-1,4-polybutadien), polyisopren (innbefattet cis-1,4-polyisopren), butylgummi, kopolymerer av 1,3-butadien eller isopren med monomerer som styren, akrylonitril og metylmet-akrylat, så vel som etylen/propylen-terpolymerer, også kjent som etylen/propylen/dienmonomer (EPDM), og spesielt etylen/propylen/disyklopentadien-terpolymerer. The present invention can be used to cure sulphur-vulcanizable rubber compounds or elastomers containing olefinic unsaturation. The term "rubber or elastomer containing olefinic unsaturation" is intended to include both natural rubber and its various raw and regenerated forms, as well as various synthetic rubber compounds. Representative synthetic polymers are the homopolymerization products of butadiene and its homologues and derivatives, e.g. methylbutadiene, dimethylbutadiene and pentadiene as well as copolymers such as those formed from butadiene or its homologues or derivatives with other unsaturated monomers. Among the latter are acetylenes, e.g. vinyl acetylene; olefins, e.g. isobutylene, which copolymerizes with isoprene to form butyl rubber; vinyl compounds, e.g. acrylic acid, acrylonitrile (which polymerizes with butadiene to form NBR), methacrylic acid and styrene, the latter compound polymerizing with butadiene to form SBR, as well as vinyl esters and various unsaturated aldehydes, ketones and ethers, e.g. acrolein, methyl isoprenyl ketone and vinyl ethyl ether. Specific examples of synthetic rubber compounds include neoprene (polychloroprene), polybutadiene (including cis-1,4-polybutadiene), polyisoprene (including cis-1,4-polyisoprene), butyl rubber, copolymers of 1,3-butadiene or isoprene with monomers such as styrene , acrylonitrile and methyl methacrylate, as well as ethylene/propylene terpolymers, also known as ethylene/propylene/diene monomer (EPDM), and especially ethylene/propylene/dicyclopentadiene terpolymers.
Den anvendte aktivator i foreliggende oppfinnelse kan tilsettes til gummiforbindelse n ved hjelp av enhver konven-sjonell fremgangsmåte slik som i et blandeverk eller i en Banbury-mikser. Mengde metyl-trialkyl-ammoniumsalt kan variere i stor grad, avhengig av gummi type og andre forbindelser som er til stede i den vulkaniserbare blanding. Vanligvis er den anvendte mengde metyl-trialkyl-ammoniumsalt i et område fra tilnærmet 0,05 til 5,0 vektdeler, med et foretrukket område på 0,1 til 1,5 vektdeler. The activator used in the present invention can be added to rubber compound n using any conventional method such as in a mixing plant or in a Banbury mixer. The amount of methyl-trialkyl-ammonium salt can vary greatly, depending on the type of rubber and other compounds present in the vulcanizable mixture. Generally, the amount of methyl trialkyl ammonium salt used is in a range from approximately 0.05 to 5.0 parts by weight, with a preferred range of 0.1 to 1.5 parts by weight.
Vulkanisering av gummien ut føres vanligvis ved temperaturer mellom 100 "C og 200 °C. Fortrinnsvis utføres vulkaniseringen ved temperaturer fra tilnærmet 110 °C til 180 °C. Enhver av de vanlige vulkaniseringsfremgangsmåter kan anvendes, slik som oppvarming i en presse eller støpeform, oppvarming med overhetet damp eller varmluft, eller i et saltbad. Vulcanization of the rubber is usually carried out at temperatures between 100 °C and 200 °C. Preferably, the vulcanization is carried out at temperatures from approximately 110 °C to 180 °C. Any of the usual vulcanization methods can be used, such as heating in a press or mold, heating with superheated steam or hot air, or in a salt bath.
I tillegg til metyl-trialkyl-ammoniumsalt kan andre gummitilsetninger også innbefattes i det svovel-vulkaniserbare materiale. De vanligst anvend te tilsetningsmidler i gummi-vulkanisater er f.eks., sot, klebriggjøringsharpikser, bearbeidelseshjelpemidler, antioksidanter, antiozonanter, stearinsyre, aktivatorer, voks, oljer og peptiseringsmidler. Det er kjent for fagmannen at visse av de ovenfor angitte tilsetningsmidler er vanlig brukt i konvensjonelle mengder. Typiske tilsetnirtgsmengder av sot, omfatter tilnærmet 20 til 100 vektdeler diengummi, fortrinnsvis 50 til 70 vektdeler. Typiske mengder klebriggjøringsharpikser omfatter tilnærmet 5 til 10 vektdeler. Typiske mengder bearbeidelseshjelpemidler omfatter tilnærmet 1 til 5 vektdeler. Typiske mengder antioksidanter omfatter 1 til 10 vektdeler. Typiske mengder antiozonanter omfatter 1 til 10 vektdeler. Typiske mengder stearinsyre omfatter 1 til 2 vektdeler. Typiske mengder sinkoksid omfatter 2 til 5 vektdeler. Typiske mengder voks omfatter 1 til 5 vektdeler. Typiske mengder oljer omfatter 5 til 30 vektdeler. Typiske mengder peptiseringsmidler omfatter 0,1 til 1 vektdeler. Tilstedeværelse og de relative mengder av de ovenfor angitte tilsetningsmidler er ikke et trekk ved foreliggende oppfinnelse. In addition to methyl trialkyl ammonium salt, other rubber additives can also be included in the sulphur-vulcanizable material. The most commonly used additives in rubber vulcanizates are, for example, carbon black, tackifying resins, processing aids, antioxidants, antiozonants, stearic acid, activators, waxes, oils and peptizing agents. It is known to the person skilled in the art that certain of the above-mentioned additives are commonly used in conventional amounts. Typical added amounts of carbon black comprise approximately 20 to 100 parts by weight of diene gum, preferably 50 to 70 parts by weight. Typical amounts of tackifying resins comprise approximately 5 to 10 parts by weight. Typical amounts of processing aids comprise approximately 1 to 5 parts by weight. Typical amounts of antioxidants comprise 1 to 10 parts by weight. Typical amounts of antiozonants comprise 1 to 10 parts by weight. Typical amounts of stearic acid comprise 1 to 2 parts by weight. Typical amounts of zinc oxide comprise 2 to 5 parts by weight. Typical amounts of wax comprise 1 to 5 parts by weight. Typical amounts of oils comprise 5 to 30 parts by weight. Typical amounts of peptizing agents comprise 0.1 to 1 part by weight. The presence and the relative amounts of the above-mentioned additives are not a feature of the present invention.
Vulkaniseringen utføres under nærvær av et svovel-vulkaniserende middel. Eksempler på egnede svovel-vulkaniserende midler innbefatter elementært svovel (fritt svovel) eller svovelavgivende vulkaniserende midler, f.eks. et amindisulfid, polymere polysulfid- eller svovel-olefinadukter. Fortrinnsvis er det svovel-vulkaniserende middel elementært svovel. Som kjent for fagmannen anvendes de svovel-vulkaniserende midler i en mengde fra til nærmet 0,5 til 8 vektdeler, med et fore.-trukket område fra 1,5 til 2,25 vektdeler. The vulcanization is carried out in the presence of a sulfur vulcanizing agent. Examples of suitable sulfur vulcanizing agents include elemental sulfur (free sulfur) or sulfur-releasing vulcanizing agents, e.g. an amine disulfide, polymeric polysulfide or sulfur-olefin adducts. Preferably, the sulfur vulcanizing agent is elemental sulfur. As is known to the person skilled in the art, the sulfur vulcanizing agents are used in an amount from to approximately 0.5 to 8 parts by weight, with a preferred range from 1.5 to 2.25 parts by weight.
Akseleratorer anvendes for å kontrollere tiden Accelerators are used to control time
og/ eller temperaturen som er påkrevet for vulkanisering og for å forbedre egenskapene til vulkanisatet. I en utførelses-form kan et enkelt akseleratorsystem anvendes, dvs. primær akselerator. Vanligvis anvendes en primær akselerator i mengder fra tilnærmet 0,5 til 2,0 vektdeler. I en annen utfør-elsesform kan blandinger av to eller flere akseleratorer anvendes som kan omfatte en primær akselerator som vanligvis anvendes i en større mengde (0,5 til 1,0 vektdeler), og en sekundær akselerator som vanligvis anvendes i mindre mengder (0,05 0,5 vektdeler) for å aktivere og forbedre vulkanisatets egenskaper. Blandinger av disse akseleratorer er kjent for å produsere en synergistisk effekt på de sluttelige egenskaper og er noe bedre enn de egenskaper som produseres ved anvendelse av hver akselerator alene. I tillegg kan anvendes akseleratorer med forsinket virkning som ikke påvirkes av normale prosesstemperaturer, men produserer tilfredsstillende herd-inger ved vanlige vulkaniseringstemperaturer. Egnede typer and/or the temperature required for vulcanization and to improve the properties of the vulcanizate. In one embodiment, a single accelerator system can be used, i.e. primary accelerator. Usually a primary accelerator is used in amounts from approximately 0.5 to 2.0 parts by weight. In another embodiment, mixtures of two or more accelerators can be used which can comprise a primary accelerator which is usually used in a larger amount (0.5 to 1.0 parts by weight), and a secondary accelerator which is usually used in smaller amounts (0 .05 0.5 parts by weight) to activate and improve the properties of the vulcanizate. Mixtures of these accelerators are known to produce a synergistic effect on the final properties and are somewhat better than the properties produced by using each accelerator alone. In addition, accelerators with a delayed effect can be used which are not affected by normal process temperatures, but produce satisfactory cures at normal vulcanization temperatures. Suitable types
akseleratorer som kan anvendes ved foreliggende oppfinnelse er aminer, disulfider, guanidiner, tiourea, tiazoler, tiouramer, sulfenamider, ditiokarbamater og xanthater. Fortrinnsvis er den primære akselerator et sulfenamid. Dersom en sekundær akselerator anvendes er denne fortrinnsvis et guanidin, ditio-karbamat eller tiuram. accelerators that can be used in the present invention are amines, disulphides, guanidines, thiourea, thiazoles, thiourams, sulfenamides, dithiocarbamates and xanthates. Preferably, the primary accelerator is a sulfenamide. If a secondary accelerator is used, this is preferably a guanidine, dithiocarbamate or thiuram.
De følgende eksempler presenteres for å illustrere foreliggende oppfinnelse. The following examples are presented to illustrate the present invention.
Eksempler 1- 11 Examples 1-11
Disse eksperimenter stiller effektiviteten ved anvendelse av metyl-trialkyl(C8-C10)-ammoniumklorid (MTAAC) ved forskjellige nivåer opp mot anvendelse av en ekvivalent mengde tetraetyl-ammoniumbromid (TEABr) som kontroll. MTAAC og TEABr ble anvendt i et typisk sidegummiråstoff omfattende 40 vektdeler polyisopren, 60 vektdeler cis-l,4-polybutadien, 0,5 vektdeler av en primær akselerator og konvensjonelle mengder sot, klebriggjører, bearbeidelseshjelpemidler, antinedbryt-ningsmiddel, stearinsyre, sinkoksid og svovel. De forskjellige tilsetningsmidler ble blandet ved anvendelse av konvensjonelle fremgangsmåter. Herdingstest ble utført ved 150 °C på en Monsanto herdingsreometer i overensstemmelse med ASTM-test-metoden D-2084-87. Anvulkanisasjonen av forbindelsen ble målt i overensstemmelse m ed ASTM testmetode Dl64687. Tabell 1 viser resultatene for eksempler 1-11. These experiments pit the effectiveness of using methyl trialkyl (C8-C10) ammonium chloride (MTAAC) at various levels against using an equivalent amount of tetraethyl ammonium bromide (TEABr) as a control. MTAAC and TEABr were used in a typical side rubber stock comprising 40 parts by weight of polyisoprene, 60 parts by weight of cis-1,4-polybutadiene, 0.5 part by weight of a primary accelerator and conventional amounts of carbon black, tackifier, processing aids, antidegradant, stearic acid, zinc oxide and sulphur. . The various additives were mixed using conventional methods. Curing test was performed at 150°C on a Monsanto curing rheometer in accordance with ASTM test method D-2084-87. The vulcanization of the compound was measured in accordance with ASTM test method D164687. Table 1 shows the results for examples 1-11.
Dataene i tabell I viser at kontrollforbindelsen (tetraetylammoniumbromid) viste liten eller ingen effekt på herdingstiden som evaluert ved t25 og t90. Anvendelse av metyl-trialkyl (C8-C10)-ammoniumklorid (MTAAC), resulterte imidlertid i vesentlig reduserte herdingstider. The data in Table I show that the control compound (tetraethylammonium bromide) showed little or no effect on the cure time as evaluated at t25 and t90. Use of methyl-trialkyl (C8-C10)-ammonium chloride (MTAAC), however, resulted in significantly reduced curing times.
Eksempler 12- 19 Examples 12-19
Eksperimenter (eksempler 12 -19) ble utført for å vise de økte herdingshastigheter ved tilsetningen av et metyltrialkyl (C8-C10)-ammoniumsalt til en svovel-vulkaniserbar gummi. Et eksperiment (eksempel 12, kontroll) ble utført for sammenlignende formål. Eksperimenter (eksempler 13 og 14) ble utført for a demonstrere effektiviteten ved anvendelse av 68 vekt% metyl-trialkyl(C8-C10)ammoniumklorid belagt på kalsium-silikat. Eksperimenter (eksempler 15 og 16) ble utført for å demonstrere effektiviteten ved anvendelse av 72 vekt% metyl-trialkyl (C8-C10) ammoniumklorid belagt på silisiumoksid. Eksperimenter (eksempler 17-19) ble utført for å demonstrere effektiviteten ved anvendelse av metyl-trialkyl(C8-C10)ammonium metylsulfat. De åtte gummiforbindelser ble fremstilt ved anvendelse av forskjellige nivåer av metyl-trialkyl-ammoniumsalt (vektdeler) og et typisk sidegummiråstoff omfattende 40 vektdeler polyisopren 60 vektdeler cis-1,4-polybutadien, 0,5 vektdeler av en primær akselerator og konvensjonelle mengder sot, klebriggjører, prosessolje, anti-nedbrytningsmiddel, stearinsyre, sinkoksid og svovel. De forskjellige tilsetningsmidler ble blandet ved anvendelse av konvensjonelle fremgangsmåter og prøvene ble evaluert ved anvendelse av herdingsfremgangsmåtene ifølge eksemplene 111. Tabell II viser herdingsegenskapene for forbindelsene ifølge eksempler 12-19 som resulterte i lignende herdingsgrader med forskjellige herdingshastigheter som vist Experiments (Examples 12-19) were conducted to demonstrate the increased cure rates of the addition of a methyltrialkyl (C8-C10) ammonium salt to a sulfur vulcanizable rubber. An experiment (Example 12, control) was performed for comparative purposes. Experiments (Examples 13 and 14) were conducted to demonstrate the effectiveness of using 68% by weight of methyl trialkyl (C 8 -C 10 ) ammonium chloride coated on calcium silicate. Experiments (Examples 15 and 16) were conducted to demonstrate the effectiveness of using 72% by weight methyl trialkyl (C8-C10) ammonium chloride coated on silicon oxide. Experiments (Examples 17-19) were conducted to demonstrate the effectiveness of using methyl trialkyl(C8-C10)ammonium methyl sulfate. The eight rubber compounds were prepared using different levels of methyl trialkyl ammonium salt (parts by weight) and a typical side rubber feedstock comprising 40 parts by weight polyisoprene, 60 parts by weight cis-1,4-polybutadiene, 0.5 parts by weight of a primary accelerator and conventional amounts of carbon black, tackifier, process oil, anti-degradant, stearic acid, zinc oxide and sulphur. The various additives were mixed using conventional methods and the samples were evaluated using the curing procedures of Examples 111. Table II shows the curing properties of the compounds of Examples 12-19 which resulted in similar degrees of cure at different curing rates as shown
ved t25 og t90. at t25 and t90.
Eksempler 13-19 viser at metyl-trialkyl(C8-C10)-ammoniumsalter er effektive for økning av herdingshastig-hetene. Dataene i eksempler 13-16 viser at anvendelse av forskjellige bærere ikke er ugunstige for effektiviteten av metyl-trialkyl(C8-C10)-ammoniumklorid. Eksempler 17-19 antyder at metyl-trialkyl(C8-C10)-ammoniummetylsulfat er like effektiv som de andre metyl- rialkyl-ammoniumsalter anvendt ved foreliggende oppfinnelse. Examples 13-19 show that methyl-trialkyl (C8-C10) ammonium salts are effective for increasing the curing rates. The data in Examples 13-16 show that the use of different carriers is not detrimental to the effectiveness of methyltrialkyl (C8-C10) ammonium chloride. Examples 17-19 suggest that methyl trialkyl (C8-C10) ammonium methyl sulfate is as effective as the other methyl trialkyl ammonium salts used in the present invention.
Eksempler 20- 21 Examples 20-21
De følgende eksperimenter ble utført for å vise herd-ingsaktiveringen av metyl-trialkyl-ammoniumklorid (MTAAC). Formuleringen som ble anvendt i eksempel 20 (kontroll) inneholdt ikke MTAAC og formuleringen anvendt i eksempel 21 inneholdt 0,30 vektdeler MTAAC. Begge formuleringer omfattet et typisk sidegummiråstoff inneholdende 20 vektdeler naturlig gummi, 20 vektdeler syntetisk polyisopren, 60 vektdeler polybutadien, 0,5 vektdeler av en primær akselerator og konvensjonelle mengder sot, voks, oljer, anti-nedbrytningsmidler, klebriggjøringsharpiks, stearinsyre, sinkoksid og svovel. De forskjellige tilsetningsmidler ble blandet sammen og prøvene ble vulkanisert ved pressforming i 18 minutter ved 150 °C. Herdingsegenskapene ble evaluert på den samme måte som i eksemplene 1-11. Strekkforlengelsesegenskapene ble testet i overensstemmelse med ASTM metode nr. D412-87. Dataene er vist i tabell III. The following experiments were carried out to show the curing activation of methyl trialkyl ammonium chloride (MTAAC). The formulation used in Example 20 (control) did not contain MTAAC and the formulation used in Example 21 contained 0.30 parts by weight of MTAAC. Both formulations comprised a typical side rubber stock containing 20 parts by weight natural rubber, 20 parts by weight synthetic polyisoprene, 60 parts by weight polybutadiene, 0.5 parts by weight of a primary accelerator and conventional amounts of carbon black, waxes, oils, anti-degradants, tackifier resin, stearic acid, zinc oxide and sulphur. The different additives were mixed together and the samples were vulcanized by compression molding for 18 minutes at 150 °C. The curing properties were evaluated in the same way as in Examples 1-11. The tensile elongation properties were tested in accordance with ASTM Method No. D412-87. The data are shown in Table III.
Dataene i tabell III viser at tilsetning av et metyl-trialkyl-ammoniumklorid reduserer herdingstiden som kreves for å nå optimal herding. Anvendelse av metyl-trialkylammoniumsalt har liten effekt på tverrbindingsfordelingen og tillater bedre anvendelse av svovel som er vist ved en økning i tverrbind-ingstetthet (v x IO<4>) og øket 300 % modulus. The data in Table III show that the addition of a methyl trialkyl ammonium chloride reduces the cure time required to reach optimum cure. Use of methyl trialkylammonium salt has little effect on the crosslink distribution and allows better utilization of sulfur as shown by an increase in crosslink density (v x 10<4>) and increased 300% modulus.
Eksempler 22- 23 Examples 22-23
Følgende eksperimenter ble utført for å vise effektiviteten av MTAAC i en annen svovel-vulkaniserbar blanding. Den anvendte formulering i eksempel 22 (kontroll) inneholdt ikke MTAAC og den anvendte formulering i eksempel 23 inneholdt 0,50 vektdeler MTAAC. Begge formuleringer omfattet et typisk dekkbane-gummiråstoff inneholdende 30 vektdeler polybutadien, 70 vektdeler SBr, 1 vektdel av en primær akselerator, 0,15 vektdeler av en sekundær akselerator og konvensjonelle mengder sot, voks, olje, peptiseringsmiddel, stearinsyre, anti-nedbrytningsmiddel, sinkoksid og svovel. De forskjellige tilsetningsmidler ble blandet og prøvene ble vulkanisert ved pres-støping i 18 minutter ved 150 °C. Etter herding ble disse prøver evaluert ved anvendelse av testfremgangsmåter ifølge eksemplene 20-21. Dataene er vist i tabell IV. The following experiments were conducted to demonstrate the effectiveness of MTAAC in another sulfur-vulcanizable mixture. The formulation used in Example 22 (control) did not contain MTAAC and the formulation used in Example 23 contained 0.50 parts by weight of MTAAC. Both formulations comprised a typical tire rubber raw material containing 30 parts by weight polybutadiene, 70 parts by weight SBr, 1 part by weight of a primary accelerator, 0.15 parts by weight of a secondary accelerator and conventional amounts of carbon black, wax, oil, peptizer, stearic acid, anti-degradant, zinc oxide and sulfur. The different additives were mixed and the samples were vulcanized by pressure casting for 18 minutes at 150 °C. After curing, these samples were evaluated using the test procedures of Examples 20-21. The data are shown in Table IV.
Eksemplene 22 og 23 viser effektiviteten av MTAAC i en polybutadien/SBR-blanding. Examples 22 and 23 demonstrate the effectiveness of MTAAC in a polybutadiene/SBR blend.
Eksempler 24 og 25 Examples 24 and 25
De følgende eksempler ble utført for å vise effektiviteten av MTAAC i en annen svovel-vulkaniserbar blanding. Den anvendte formulering i eksempel 24 (kontroll) inneholdt ikke MTAAC og den anvendte formulering i eksempel 25 inneholdt 0,2 vektdeler MTAAC. Begge formuleringer omfattet et typisk dekkbane-gummiråstoff inneholdende 70 vektdeler medium vinyl-polybutadien, 30 vektdeler cis-1,4-polybutadien, 1,1 vektdeler av en primær akselerator, 0,16 vektdeler av en sekundær akselerator og konvensjonelle mengder sot, voks, olje, anti-nedbrytningsmidler, stearinsyre, sinkoksid og svovel. De forskjellige tilsetningsmidler ble dannet ved anvendelse av konvensjonelle fremgangsmåter. The following examples were conducted to demonstrate the effectiveness of MTAAC in another sulfur vulcanizable mixture. The formulation used in Example 24 (control) did not contain MTAAC and the formulation used in Example 25 contained 0.2 parts by weight of MTAAC. Both formulations comprised a typical tire rubber stock containing 70 parts by weight of medium vinyl polybutadiene, 30 parts by weight of cis-1,4-polybutadiene, 1.1 parts by weight of a primary accelerator, 0.16 parts by weight of a secondary accelerator and conventional amounts of carbon black, wax, oil, anti-degradants, stearic acid, zinc oxide and sulphur. The various additives were formed using conventional methods.
Disse prøver ble evaluert ved hjelp av herdingstest-fremgangsmåtene anvendt i eksemplene 20 og 21. Dataene er vist i tabell V. These samples were evaluated using the curing test procedures used in Examples 20 and 21. The data are shown in Table V.
Eksempler 26- 29 Examples 26-29
Disse eksperimenter viser forskjellen mellom effektiviteten av metyl-trialkyl(C8-C10)-ammoniumklorid (MTAAC) i These experiments show the difference between the effectiveness of methyl-trialkyl(C8-C10)-ammonium chloride (MTAAC) in
nærvær eller fravær av en akselerator. Den resterende bestand-del av de anvendte formuleringer i eksempler 26-29 omfatter et gummiråstoff inneholdende 50 vektdeler SBR, 50 vektdeler poly- presence or absence of an accelerator. The remaining component of the formulations used in examples 26-29 comprises a rubber raw material containing 50 parts by weight SBR, 50 parts by weight poly
isopren og konvensjonelle mengder olje (28,75 vektdeler), sot (50 vektdeler), sinkoksid (3 vektdeler), svovel (2 vektdeler) og stearinsyre (2 vektdeler). I eksempel 26 ble det 14 ikke isoprene and conventional amounts of oil (28.75 parts by weight), carbon black (50 parts by weight), zinc oxide (3 parts by weight), sulfur (2 parts by weight) and stearic acid (2 parts by weight). In example 26, there were 14 not
anvendt verken akselerator eller MTAAC. I eksempel 27 ble det ikke anvendt akselerator, men 0,50 vektdeler MTAAC (68 veikt % Adogen 464 på kalsiumsilikatbærer) ble anvendt. I eksempeil 28, ble det anvendt 1,5 vektdeler akselerator, men ikke noe MTAAC. I eksempel 29 ble det anvendt 1,5 vektdeler akselerator og 0,50 vektdeler MTAAC (den samme mengde som i eksempel 27). De forskjellige tilsetningsmidler ble blandet ved anvendelse av konvensjonelle fremgangsmåter. Herdingstesting ble utført ved 150 °C. På et Monsanto herdingsreometer ifølge ASTM-test-metoden nr. D-2084. Herdingsegenskapene er vist i tabell VI. used neither accelerator nor MTAAC. In Example 27 no accelerator was used, but 0.50 parts by weight of MTAAC (68 weak % Adogen 464 on calcium silicate carrier) was used. In Example 28, 1.5 parts by weight of accelerator was used, but no MTAAC. In Example 29, 1.5 parts by weight of accelerator and 0.50 parts by weight of MTAAC were used (the same amount as in Example 27). The various additives were mixed using conventional methods. Curing testing was performed at 150 °C. On a Monsanto Curing Rheometer according to ASTM Test Method No. D-2084. The curing properties are shown in Table VI.
Eksempel 26 viser den meget dårlige herding som Example 26 shows the very poor curing which
finner sted når det ikke anvendes MTAAC eller akselerator. takes place when no MTAAC or accelerator is used.
Dataene fra eksempel 27 viser at anvendelse av MTAAC i fravær The data from Example 27 show that application of MTAAC in the absence
av en akselerator ikke fører noen vesentlig herding. Dataene i eksempel 28 viser en typisk akseleratoreffekt. Dataene i eksempel 29 viser en dramatisk reduksjon i herdingstid når det anvendes både en akselerator og MTAAC-aktivator. of an accelerator does not cause any significant hardening. The data in Example 28 shows a typical accelerator effect. The data in Example 29 show a dramatic reduction in cure time when both an accelerator and MTAAC activator are used.
Claims (13)
Applications Claiming Priority (1)
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|---|---|---|---|
| US29079688A | 1988-12-28 | 1988-12-28 |
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| NO179951C NO179951C (en) | 1997-01-15 |
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| NO895244A NO179951C (en) | 1988-12-28 | 1989-12-22 | Sulfur-vulcanizable rubber compound, and a method of increasing the rate of vulcanization thereof |
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| KR (1) | KR900009701A (en) |
| CN (2) | CN1062574C (en) |
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| KR101411114B1 (en) * | 2012-08-29 | 2014-06-25 | 유태우 | Pad and it's making method for acupuncture of a imagenation cure |
| CN104961982A (en) * | 2015-07-28 | 2015-10-07 | 太仓市晨洲塑业有限公司 | Modified butyl rubber |
| CN114854057B (en) * | 2022-04-26 | 2024-06-07 | 濮阳林氏医疗制品有限公司 | Low-temperature vulcanizing bag set and preparation method and application thereof |
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- 1989-12-28 CN CN89106900A patent/CN1062574C/en not_active Expired - Fee Related
- 1989-12-28 IE IE419189A patent/IE66562B1/en not_active IP Right Cessation
-
1998
- 1998-09-28 CN CN98120866A patent/CN1277210A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| PT92754B (en) | 1995-11-30 |
| AR247219A1 (en) | 1994-11-30 |
| NO179951C (en) | 1997-01-15 |
| FI896047A0 (en) | 1989-12-18 |
| CN1043726A (en) | 1990-07-11 |
| CN1277210A (en) | 2000-12-20 |
| FI99134B (en) | 1997-06-30 |
| CN1062574C (en) | 2001-02-28 |
| NO895244L (en) | 1990-06-29 |
| IE66562B1 (en) | 1996-01-24 |
| PT92754A (en) | 1990-06-29 |
| MY105906A (en) | 1995-02-28 |
| BR8906667A (en) | 1990-09-11 |
| ZA899579B (en) | 1990-09-26 |
| DK668089A (en) | 1990-06-29 |
| FI99134C (en) | 1997-10-10 |
| CA1340497C (en) | 1999-04-13 |
| NO895244D0 (en) | 1989-12-22 |
| ATE105001T1 (en) | 1994-05-15 |
| DK668089D0 (en) | 1989-12-27 |
| KR900009701A (en) | 1990-07-05 |
| MA21696A1 (en) | 1990-07-01 |
| IE894191L (en) | 1990-06-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MM1K | Lapsed by not paying the annual fees |
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