CN101084258A - Modified natural rubber masterbatch and method for production thereof, and rubber composition and tire - Google Patents
Modified natural rubber masterbatch and method for production thereof, and rubber composition and tire Download PDFInfo
- Publication number
- CN101084258A CN101084258A CN200580043989.3A CN200580043989A CN101084258A CN 101084258 A CN101084258 A CN 101084258A CN 200580043989 A CN200580043989 A CN 200580043989A CN 101084258 A CN101084258 A CN 101084258A
- Authority
- CN
- China
- Prior art keywords
- natural rubber
- group
- modified
- modified natural
- rubber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 244000043261 Hevea brasiliensis Species 0.000 title claims abstract description 114
- 229920003052 natural elastomer Polymers 0.000 title claims abstract description 114
- 229920001194 natural rubber Polymers 0.000 title claims abstract description 114
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 86
- 229920001971 elastomer Polymers 0.000 title claims abstract description 77
- 239000005060 rubber Substances 0.000 title claims abstract description 77
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 45
- 239000000203 mixture Substances 0.000 title claims abstract description 12
- 239000002002 slurry Substances 0.000 claims abstract description 79
- 239000000178 monomer Substances 0.000 claims abstract description 67
- 239000000945 filler Substances 0.000 claims abstract description 49
- 229920006173 natural rubber latex Polymers 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 55
- -1 amino, imino- Chemical class 0.000 claims description 54
- 239000000839 emulsion Substances 0.000 claims description 49
- 239000000377 silicon dioxide Substances 0.000 claims description 26
- 239000002245 particle Substances 0.000 claims description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 21
- 239000006229 carbon black Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 18
- 235000012239 silicon dioxide Nutrition 0.000 claims description 18
- 229960001866 silicon dioxide Drugs 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 10
- 235000010755 mineral Nutrition 0.000 claims description 10
- 239000011707 mineral Substances 0.000 claims description 10
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 125000003700 epoxy group Chemical group 0.000 claims description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 9
- 239000013543 active substance Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 239000012530 fluid Substances 0.000 claims description 8
- 125000000623 heterocyclic group Chemical group 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 7
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 7
- 239000004411 aluminium Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 125000003368 amide group Chemical group 0.000 claims description 7
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 7
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 7
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 7
- 238000010559 graft polymerization reaction Methods 0.000 claims description 7
- 150000003949 imides Chemical class 0.000 claims description 7
- 239000000395 magnesium oxide Substances 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 7
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 7
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 claims description 7
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 claims description 7
- 125000000101 thioether group Chemical group 0.000 claims description 7
- 239000005995 Aluminium silicate Substances 0.000 claims description 6
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 235000012211 aluminium silicate Nutrition 0.000 claims description 6
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 6
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 125000005370 alkoxysilyl group Chemical group 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 125000005638 hydrazono group Chemical group 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims description 3
- 229910002012 Aerosil® Inorganic materials 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 229910017625 MgSiO Inorganic materials 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- 229960000892 attapulgite Drugs 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- FGZBFIYFJUAETR-UHFFFAOYSA-N calcium;magnesium;silicate Chemical compound [Mg+2].[Ca+2].[O-][Si]([O-])([O-])[O-] FGZBFIYFJUAETR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 239000000084 colloidal system Substances 0.000 claims description 3
- IQDXNHZDRQHKEF-UHFFFAOYSA-N dialuminum;dicalcium;dioxido(oxo)silane Chemical compound [Al+3].[Al+3].[Ca+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O IQDXNHZDRQHKEF-UHFFFAOYSA-N 0.000 claims description 3
- FSBVERYRVPGNGG-UHFFFAOYSA-N dimagnesium dioxido-bis[[oxido(oxo)silyl]oxy]silane hydrate Chemical compound O.[Mg+2].[Mg+2].[O-][Si](=O)O[Si]([O-])([O-])O[Si]([O-])=O FSBVERYRVPGNGG-UHFFFAOYSA-N 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 239000000391 magnesium silicate Substances 0.000 claims description 3
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 3
- 235000019792 magnesium silicate Nutrition 0.000 claims description 3
- 150000004682 monohydrates Chemical class 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052625 palygorskite Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 229910052903 pyrophyllite Inorganic materials 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 235000012222 talc Nutrition 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 235000010215 titanium dioxide Nutrition 0.000 claims description 3
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910001051 Magnalium Inorganic materials 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 21
- 235000019241 carbon black Nutrition 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 13
- OAASAJNCDIMPDW-UHFFFAOYSA-N 2-ethenyl-n-phenylaniline Chemical compound C=CC1=CC=CC=C1NC1=CC=CC=C1 OAASAJNCDIMPDW-UHFFFAOYSA-N 0.000 description 12
- 230000003014 reinforcing effect Effects 0.000 description 12
- 238000013329 compounding Methods 0.000 description 10
- 239000012764 mineral filler Substances 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- 239000007858 starting material Substances 0.000 description 9
- 230000006866 deterioration Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 229920000126 latex Polymers 0.000 description 7
- 239000004816 latex Substances 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- 235000021355 Stearic acid Nutrition 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 5
- 239000008117 stearic acid Substances 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- 235000014692 zinc oxide Nutrition 0.000 description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 125000004103 aminoalkyl group Chemical group 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229920003051 synthetic elastomer Polymers 0.000 description 4
- 239000005061 synthetic rubber Substances 0.000 description 4
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000007580 dry-mixing Methods 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 239000004636 vulcanized rubber Substances 0.000 description 3
- GXAAKXXCSOZTMN-UHFFFAOYSA-N 1-[dimethoxy(methyl)silyl]oxyethyl prop-2-enoate Chemical compound CC(O[Si](OC)(OC)C)OC(=O)C=C GXAAKXXCSOZTMN-UHFFFAOYSA-N 0.000 description 2
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 2
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910001679 gibbsite Inorganic materials 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- QENDLNJWYIFMIM-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]-n-methylprop-2-enamide Chemical compound CN(C)CCCN(C)C(=O)C=C QENDLNJWYIFMIM-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 125000001302 tertiary amino group Chemical group 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- OZWKZRFXJPGDFM-UHFFFAOYSA-N tripropoxysilane Chemical compound CCCO[SiH](OCCC)OCCC OZWKZRFXJPGDFM-UHFFFAOYSA-N 0.000 description 2
- GTMYOKVGMZSBOH-UHFFFAOYSA-M (2-methylphenyl)-diphenylstannanylium;prop-2-enoate Chemical compound [O-]C(=O)C=C.CC1=CC=CC=C1[Sn+](C=1C=CC=CC=1)C1=CC=CC=C1 GTMYOKVGMZSBOH-UHFFFAOYSA-M 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Tires In General (AREA)
Abstract
This invention provides a method for producing a modified natural rubber masterbatch, which comprises the step of mixing a modified natural rubber latex, which is formed by adding a polar group-containing monomer to a natural rubber latex to graft-polymerize the polar group-containing monomer onto a natural rubber molecule in the natural rubber latex, with a slurry solution formed by previously dispersing a filler into water, and a modified natural rubber masterbatch produced by the method and capable of highly improving a low loss factor, a wear resistance and fracture characteristics of a rubber composition.
Description
Technical field
The present invention relates to a kind of modified natural rubber masterbatch and production method thereof, and the rubber combination and the tire that use this modified natural rubber masterbatch, the modified natural rubber masterbatch that relates more specifically to comprise modified natural rubber and filler and can significantly improve low-loss, wear resistance and the anti-breaking property of rubber combination.
Background technology
Recently, strong request reduces the fuel consumption of motor vehicle, thereby need have the tire of low-rolling-resistance.For this purpose, need have the good rubber combination of low tan δ (low-loss hereinafter referred to as) and low-heat-generation as being used for the tyre surface of tire or the rubber combination of like.In addition, the rubber combination that requires to be used for tyre surface wear resistance and fracture characteristics except that low-loss is good.
In order to improve low-loss, wear resistance and the fracture characteristics by the rubber combination of the carbon black compounding being gone into rubber components formation, the avidity in the raising rubber combination between carbon black and the rubber components is effective.For example, in order to improve and to use the sooty reinforcing effect, developed wherein for the sooty avidity by the terminal-modified synthetic rubber that improves, wherein for the synthetic rubber of sooty avidity by improving with the copolymerization such as monomer that contain functional group by improving in the rubber combination avidity between the carbon black and rubber components.
In addition, by mineral filler such as silicon-dioxide or similar substance compounding are gone into rubber components, the tan δ that can reduce rubber combination is to reduce heat generation.Yet, because mineral filler is lower usually for the avidity of rubber components, therefore can not obtain enough reinforcing properties, thereby the wear resistance of rubber combination and fracture characteristics deterioration.On the contrary, in order to improve the reinforcing effect that uses mineral filler, developed wherein for the avidity of mineral filler by the terminal-modified synthetic rubber that improves, wherein for the avidity of mineral filler synthetic rubber by improving with the copolymerization such as monomer that contain functional group by mineral filler and the avidity between the rubber components that improves in the rubber combination.
On the other hand, use natural rubber to utilize its good physical property simultaneously in large quantities, but also do not have such technology: in this technology, for the avidity of carbon black or mineral filler by the modification of natural rubber own being improved significantly to improve the reinforcing effect that uses filler.
For example, propose to make the epoxidised technology of natural rubber.Yet in this technology, the avidity between natural rubber and the filler can not be improved fully, so that uses the reinforcing effect of filler not strengthen fully.In addition, known wherein by adding the technology (referring to JP-A-H05-287121, JP-A-H06-329702, JP-A-H09-25468, JP-A-2000-319339, JP-A-2002-138266 and JP-A-2002-348559) that graft polymerization is carried out in the natural rubber latex Ruzhong based on the monomer of vinyl.To drop into practical application as tackiness agent or similar substance by the grafting natural rubber that this technology obtains.Yet, in this grafting natural rubber, will be as monomeric a large amount of vinyl compounds (20-50 quality %) grafting to change the characteristic of natural rubber itself, consequently when it and filler compounding, improved viscosity greatly and made the processing characteristics deterioration.In addition, owing to the molecular chain of a large amount of vinyl compounds being introduced natural rubber, the good physical property (stress-strain curve in visco-elasticity, the tension test etc.) of infringement natural rubber inherent.
On the other hand, as being used for improving the technology of filler, known by natural rubber latex is produced natural rubber masterbatch with mixing by the slurry that in advance fillers dispersed is formed in water in the dispersiveness of natural rubber.Yet, use rubber combination deficiency aspect reinforcing property of natural rubber masterbatch, so still there is the space of improving wear resistance and fracture characteristics.
Summary of the invention
Therefore, the objective of the invention is to solve the problems referred to above of conventional art, and the master batch of low-loss, wear resistance and the fracture characteristics that can significantly improve rubber combination and the method that is used to produce this rubber master batch are provided.In addition, another object of the present invention provides avidity and reinforcing property height and the good rubber combination of low-loss, wear resistance and fracture characteristics that uses between this master batch and rubber components and the filler, and the tire that uses this rubber combination.
In order to achieve the above object, the inventor has carried out multiple research, and find the low-loss of rubber combination, wear resistance and fracture characteristics can improve greatly by using modified natural rubber masterbatch, this modified natural rubber masterbatch obtains by the slurry blended step with specific modified rubber-emulsion and filler, and the result has finished the present invention.
Promptly, production method according to modified natural rubber masterbatch of the present invention is characterized in that: it comprises modified rubber-emulsion and slurry blended step, this modified rubber-emulsion forms with the monomer of this polar functionalities of graft polymerization on the natural rubber molecule in natural rubber latex Ruzhong by the monomer of polar functionalities being added the natural rubber latex Ruzhong, and this slurry forms in water by at least a fillers dispersed in the group that will be selected from carbon black, silicon-dioxide in advance and be made up of the mineral compound of following general formula (I) expression:
nM·xSiO
y·zH
2O...(I)
[wherein, M is selected from least a by in the following group of forming: the metal of aluminium, manganese, titanium, calcium or zirconium, the oxide compound of these metals and oxyhydroxide, the carbonate of their hydrate and these metals, n is the integer of 1-5, x is the integer of 0-10, and y is that integer and the z of 2-5 is the integer of 0-10].
In preferred embodiment according to the production method of modified natural rubber masterbatch of the present invention, filler in slurry has volume average particle size (volume meanparticle size) and (mv) is not more than 25 μ m, 90% particle volume diameter (D90) is not more than 30 μ m, from the 24M4DBP of the filler of slurry fluid drying and recovery absorb remain on be scattered in the water before 24M4DBP absorb more than 93%.
In another preferred embodiment according to the production method of modified natural rubber masterbatch of the present invention; this filler is a carbon black, and the monomeric polar group of this polar functionalities is to be selected from least a by in the following group of forming: amino, imino-, itrile group, ammonium, imide, amide group, hydrazono-, azo-group, diazo, hydroxyl, carboxyl, carbonyl, epoxy group(ing), oxygen carbonyl (oxycarbonyl group), sulfide group, disulphide group, alkylsulfonyl, sulfinyl, thiocarbonyl, nitrogen heterocycle, oxygen-containing heterocycle and contain tin group.
In other preferred embodiment according to the production method of modified natural rubber masterbatch of the present invention; filler is for being selected from least a in the group of being made up of the mineral compound of silicon-dioxide and general formula (I) expression, and the monomeric polar group of polar functionalities is to be selected from least a by in the following group of forming: amino; imino-; itrile group; ammonium; imide; amide group; hydrazono-; azo-group; diazo; hydroxyl; carboxyl; carbonyl; epoxy group(ing); oxygen carbonyl (oxycarbonyl group); sulfide group; the disulphide group; alkylsulfonyl; sulfinyl; thiocarbonyl; nitrogen heterocycle; oxygen-containing heterocycle and alkoxysilyl.
In the further embodiment preferred according to the production method of modified natural rubber masterbatch of the present invention, the monomeric grafting amount of this polar functionalities is 0.01-5.0 quality %, based on the rubber components in natural rubber latex Ruzhong.
In another preferred embodiment according to the production method of modified natural rubber masterbatch of the present invention, wherein, this modified rubber-emulsion and/or slurry further contain tensio-active agent.
In production method according to modified natural rubber masterbatch of the present invention, as silicon-dioxide, preferred sedimentary silicon-dioxide, aerosil and colloid silica, and as the mineral compound by general formula (I) expression, preferred aluminum oxide (Al
2O
3), monohydrate alumina (Al
2O
3H
2O), aluminium hydroxide [Al (OH)
3], aluminium carbonate [Al
2(CO
3)
3], magnesium hydroxide [Mg (OH)
2], magnesium oxide (MgO), magnesiumcarbonate (MgCO
3), talcum (3MgO4SiO
2H
2O), attapulgite (5MgO8SiO
29H
2O), titanium white (TiO
2), the black (TiO of titanium
2n-1), calcium oxide (CaO), calcium hydroxide [Ca (OH)
2], magnalium oxide compound (MgO.Al
2O
3), clay (Al
2O
32SiO
2), kaolin (Al
2O
32SiO
22H
2O), pyrophyllite (Al
2O
34SiO
2H
2O), wilkinite (Al
2O
34SiO
22H
2O), pure aluminium silicate (Al
2SiO
5, Al
43SiO
45H
2O), Magnesium Silicate q-agent (Mg
2SiO
4, MgSiO
3), Calucium Silicate powder (Ca
2SiO
4), Aluminum calcium silicate (Al
2O
3CaO2SiO
2), calcium magnesium silicate (CaMgSiO
4), lime carbonate (CaCO
3), zirconium white (ZrO
2), zirconium hydroxide [ZrO (OH)
2NH
2O], zirconium carbonate [Zr (CO
3)
2] and crystalline aluminosilicate.In addition, the M in general formula (I) is preferably selected from least a in the group that the carbonate of the oxide compound of aluminum metal, aluminium and oxyhydroxide, their hydrate and aluminium forms.
Production method according to modified natural rubber masterbatch of the present invention preferably further comprises the step of the mixture of modified rubber-emulsion and slurry being solidified and the coagulated substance drying of gained is applied simultaneously mechanical shear stress.At this moment, the dry preferred continuous mixer that uses carries out, and this continuous mixer is preferably the twin shaft mixing extruder.
In addition, modified natural rubber masterbatch according to the present invention is characterised in that by aforesaid method production, rubber combination according to the present invention is characterised in that and uses this modified natural rubber masterbatch that tire according to the present invention is characterised in that this rubber combination is used for any tyre parts.
According to the present invention, can provide modified natural rubber masterbatch by the slurry of particular modification natural rubber latex and filler is mixed with the fillers dispersed that in modified natural rubber, improves.In addition, can be by using this modified natural rubber masterbatch to provide to have the rubber combination of low-loss, wear resistance and the breaking property of raising, and the tire that uses this rubber combination.
Embodiment
The present invention will be described in detail belows.Comprise modified rubber-emulsion and the slurry blended step that forms in water by at least a fillers dispersed that will be selected from advance in the group of being made up of the mineral compound of carbon black, silicon-dioxide and general formula (I) expression according to the production method of modified natural rubber masterbatch of the present invention, this modified rubber-emulsion is by forming the monomer adding natural rubber latex Ruzhong of the polar functionalities monomer with this polar functionalities of graft polymerization on the natural rubber molecule in natural rubber latex Ruzhong.In addition, modified natural rubber masterbatch according to the present invention is characterised in that by this method and produces.
In modified natural rubber masterbatch according to the present invention, because filler is had in the master batch of rubber components (i.e. modified natural rubber in modified rubber-emulsion), the dispersiveness of filler in rubber components is improved.In addition, because the monomeric polar group of polar functionalities is good for the avidity of filler, so compare with unmodified natural rubber, the modified natural rubber in modified rubber-emulsion is for the avidity height of filler.In addition, in modified natural rubber masterbatch of the present invention, the dispersiveness of filler in rubber components is by being formed the effect of master batch and using the synergy of effect of modified rubber-emulsion and significantly raising by rubber components and filler.Therefore, in modified natural rubber masterbatch according to the present invention, the reinforcing effect of filler obtains performance fully, thereby makes wear resistance and anti-breaking property good and significantly improve low-heat-generation (low-loss).In addition, the modified natural rubber masterbatch of the application of the invention, can significantly improve the wear resistance of rubber combination, anti-breaking property and low-loss, further, by in tire, particularly use this rubber combination in tire tread, anti-breaking property and wear resistance can improve significantly, significantly reduce rolling resistance simultaneously.
The natural rubber latex that is used for modified rubber-emulsion is not particularly limited, and for example can comprise the latex of the latex of field latex, ammonia treatment, centrifugal spissated latex, the deproteinization handled with tensio-active agent or enzyme, and combination.
The monomer that adds the polar functionalities in natural rubber latex Ruzhong has at least one polar group in its molecule, and does not have special restriction, if it can with the graft polymerization of natural rubber molecule.The monomer of polar functionalities preferably in its molecule, have carbon-to-carbon double bond with the graft polymerization of natural rubber molecule, and the monomer based on vinyl of preferred polar functionalities.As the specific examples of polar group, preferably mention amino, imino-, itrile group, ammonium, imide, amide group, hydrazono-, azo-group, diazo, hydroxyl, carboxyl, carbonyl, epoxy group(ing), oxygen carbonyl, sulfide group, disulphide group, alkylsulfonyl, sulfinyl, thiocarbonyl, nitrogen heterocycle, oxygen-containing heterocycle, contain tin group and alkoxysilyl or the like.In addition; when filler was carbon black, this polar group was preferably amino, imino-, itrile group, ammonium, imide, amide group, hydrazono-, azo-group, diazo, hydroxyl, carboxyl, carbonyl, epoxy group(ing), oxygen carbonyl, sulfide group, disulphide group, alkylsulfonyl, sulfinyl, thiocarbonyl, nitrogen heterocycle, oxygen-containing heterocycle, contains tin group.In addition; when filler is a silicon-dioxide or during by the mineral compound of general formula (I) expression, this polar group is preferably amino, imino-, itrile group, ammonium, imide, amide group, hydrazono-, azo-group, diazo, hydroxyl, carboxyl, carbonyl, epoxy group(ing), oxygen carbonyl, sulfide group, disulphide group, alkylsulfonyl, sulfinyl, thiocarbonyl, nitrogen heterocycle, oxygen-containing heterocycle and alkoxysilyl.The monomer of these polar functionalities can use separately or being used in combination with two or more.
As containing amino monomer, mention and in their molecule, contain at least one the amino polymerisable monomer that is selected from primary amino, secondary amino group and uncle's amino.In having amino polymerisable monomer, the monomer of tertiary-amino-containing is particularly preferred as (methyl) vinylformic acid dialkylaminoalkyl ester or similar substance.These contain amino monomer and can use separately or being used in combination with two or more.
As the monomer that contains primary amino, mention acrylamide, Methacrylamide, 4-vinyl aniline, (methyl) acrylic-amino methyl esters, (methyl) acrylic-amino ethyl ester, (methyl) acrylic-amino propyl ester, (methyl) acrylic-amino butyl ester or the like.
As the monomer that contains secondary amino group, mention (1) anilino vinylbenzene such as anilino vinylbenzene, beta-phenyl-to anilino vinylbenzene, beta-cyano-to anilino vinylbenzene, beta-cyano-Beta-methyl-to anilino vinylbenzene, β-chloro-is to anilino vinylbenzene, β-carboxyl-to anilino vinylbenzene, the 'beta '-methoxy carbonyl-to anilino vinylbenzene, β-(2-hydroxyl-oxethyl) carbonyl-to anilino vinylbenzene, β-formyl-to anilino vinylbenzene, β-formyl-Beta-methyl-to anilino vinylbenzene, α-carboxyl-β-carboxyl-beta-phenyl-to anilino vinylbenzene etc., (2) anilino phenyl butadiene such as 1-anilino phenyl-1, the 3-divinyl, 1-anilino phenyl-3-methyl isophthalic acid, the 3-divinyl, 1-anilino phenyl-3-chloro-1, the 3-divinyl, 3-anilino phenyl-2-methyl isophthalic acid, the 3-divinyl, 1-anilino phenyl-2-chloro-1, the 3-divinyl, 2-anilino phenyl-1, the 3-divinyl, 2-anilino phenyl-3-methyl isophthalic acid, the 3-divinyl, 2-anilino phenyl-3-chloro-1,3-divinyl etc., and mono-substituted (methyl) acrylamide of (3) N-such as N-methyl (methyl) acrylamide, N-ethyl (methyl) acrylamide, N hydroxymethyl acrylamide, N-(4-anilino phenyl) Methacrylamide etc.
As the monomer of tertiary-amino-containing, mention N, the dibasic aminoalkyl of N-(methyl) acrylate, N, the dibasic aminoalkyl of N-(methyl) acrylamide or the like.
As N, the dibasic aminoalkyl of N-(methyl) acrylate, the ester of mentioning acrylic or methacrylic acid is as (methyl) vinylformic acid N, N-dimethylamino methyl esters, (methyl) vinylformic acid N, the N-dimethylamino ethyl ester, (methyl) vinylformic acid N, N-dimethylamino propyl ester, (methyl) vinylformic acid N, N-dimethylamino butyl ester, (methyl) vinylformic acid N, N-diethylamino ethyl ester, (methyl) vinylformic acid N, N-diethylamino propyl ester, (methyl) vinylformic acid N, N-diethylamino butyl ester, (methyl) vinylformic acid N-methyl-N-ethylamino ethyl ester, (methyl) vinylformic acid N, N-dipropyl amino ethyl ester, (methyl) vinylformic acid N, N-dibutylamino ethyl ester, (methyl) vinylformic acid N, N-dibutylamino propyl ester, (methyl) vinylformic acid N, N-dibutylamino butyl ester, (methyl) vinylformic acid N, N-dihexyl amino ethyl ester, (methyl) vinylformic acid N, N-dioctyl amino ethyl ester, acryloyl morpholine or the like.Wherein, (methyl) vinylformic acid N, N-dimethylamino ethyl ester, (methyl) vinylformic acid N, N-diethylamino ethyl ester, (methyl) vinylformic acid N, N-dipropyl amino ethyl ester, (methyl) vinylformic acid N, N-dioctyl amino ethyl ester, (methyl) vinylformic acid N-methyl-N-ethylamino ethyl ester etc. is particularly preferred.
In addition, as N, the dibasic aminoalkyl of N-(methyl) acrylamide, mention acrylamide compound and methacryloyl amine compound, as N, N-dimethylaminomethyl (methyl) acrylamide, N, N-dimethyl aminoethyl (methyl) acrylamide, N, N-dimethylaminopropyl (methyl) acrylamide, N, N-dimethylamino butyl (methyl) acrylamide, N, N-diethylamino ethyl (methyl) acrylamide, N, N-diethylamino propyl group (methyl) acrylamide, N, N-diethylamino butyl (methyl) acrylamide, N-methyl-N-ethylamino ethyl (methyl) acrylamide, N, N-dipropyl amino-ethyl (methyl) acrylamide, N, N-dibutylamino ethyl (methyl) acrylamide, N, N-dibutylamino propyl group (methyl) acrylamide, N, N-dibutylamino butyl (methyl) acrylamide, N, N-dihexyl amino-ethyl (methyl) acrylamide, N, N-dihexyl aminopropyl (methyl) acrylamide, N, N-dioctyl aminopropyl (methyl) acrylamide or the like.Wherein, N, N-dimethylaminopropyl (methyl) acrylamide, N, N-diethylamino propyl group (methyl) acrylamide, N, N-dioctyl aminopropyl (methyl) acrylamide etc. is particularly preferred.
As the monomer of nitrile group-containing, mention (methyl) vinyl cyanide, vinylidene nitrile compound or the like.The monomer of these nitrile group-containings can use separately or two or more are used in combination.
As the monomer of hydroxyl, mention in a molecule, have be selected from primary, the polymerisable monomer of at least a hydroxyl of the second month in a season and tert-hydroxyl.As such monomer, mention the monomer based on unsaturated carboxylic acid, the hydroxyl of hydroxyl the monomer based on vinyl ether, hydroxyl based on monomer of vinyl ketone etc.As the monomer of hydroxyl, mention that specifically (methyl) acrylic acid hydroxy alkyl ester is as (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 3-hydroxypropyl acrylate, (methyl) vinylformic acid 2-hydroxy butyl ester, (methyl) vinylformic acid 3-hydroxy butyl ester, (methyl) vinylformic acid 4-hydroxy butyl ester etc.; Polyalkylene glycol (for example, aklylene glycol unit number is 2-13) is as list (methyl) acrylate of polyoxyethylene glycol, polypropylene glycol etc.; The unsaturated amides of hydroxyl such as N-methylol (methyl) acrylamide, N-(2-hydroxyethyl) (methyl) acrylamide, N, two (2-methylol) (methyl) acrylamides of N-etc.; The vinyl aromatic compounds of hydroxyl such as neighbour-hydroxy styrenes ,-hydroxy styrenes, right-hydroxy styrenes, neighbour-hydroxyl-alpha-methyl styrene ,-hydroxyl-alpha-methyl styrene, right-hydroxyl-alpha-methyl styrene, right-vinyl benzyl alcohol etc.Wherein, the vinyl aromatic compounds of the monomer based on unsaturated carboxylic acid of hydroxyl, (methyl) acrylic acid hydroxy alkyl ester and hydroxyl is preferred, and the monomer based on unsaturated carboxylic acid of hydroxyl is particularly preferred.As the acid mono based on unsaturated carboxylic acid of hydroxyl, mention ester, acid amides, acid anhydrides of derivative such as vinylformic acid, methacrylic acid, methylene-succinic acid, fumaric acid, toxilic acid etc. etc.Wherein, the ester of vinylformic acid, methacrylic acid etc. is particularly preferred.The monomer of these hydroxyls can use separately or being used in combination with two or more.
As carboxylic monomer, mention that unsaturated carboxylic acid is as (methyl) vinylformic acid, toxilic acid, fumaric acid, methylene-succinic acid, tetraconic acid, styracin etc.; The unsaturated compound that contains the monoesters of the ester of free carboxy such as non-polymerizable polycarboxylic acid such as phthalic acid, succsinic acid, hexanodioic acid etc. and hydroxyl is as (methyl) allyl alcohol, (methyl) vinylformic acid 2-hydroxyl ethyl ester or its analogue, and salt.Wherein, unsaturated carboxylic acid is particularly preferred.These carboxylic monomers can use separately or two or more are used in combination.
As the monomer that contains epoxy group(ing), mention (methyl) glycidyl allyl ether, (methyl) glycidyl acrylate, (methyl) vinylformic acid 3,4-oxygen cyclohexyl or the like.These monomers that contain epoxy group(ing) can use separately or two or more are used in combination.
As the nitrogen heterocyclic ring in containing the monomer of nitrogen heterocycle, mention pyrroles, Histidine, imidazoles, triazolidine, triazole, triazine, pyridine, pyrimidine, pyrazine, indoles, quinoline, purine, azophenlyene, pteridine, trimeric cyanamide or the like.In addition, nitrogenous heterocyclic ring can comprise another heteroatoms in its ring.Contain pyridyl and comprise the vinyl compound that contains pyridyl such as 2-vinyl pyridine, 3-vinyl pyridine, 4-vinylpridine, 5-methyl-2-vinyl pyridine, 5-ethyl-2-vinyl pyridine or the like as the monomer of nitrogen heterocycle.Wherein, 2-vinyl pyridine, 4-vinylpridine etc. are particularly preferred.These monomers that contain nitrogen heterocycle can use separately or being used in combination with two or more.
As having the monomer that closes tin group, for example mention the stanniferous monomer: allyl group three-normal-butyl tin, allyl group tin trimethyl, allyl group triphenyltin, allyl group three-n-octyl tin, (methyl) acryloxy-normal-butyl tin, (methyl) acryloxy tin trimethyl, (methyl) acryloxy triphenyltin, (methyl) acryloxy n-octyl tin, vinyl three-normal-butyl tin, vinyl tin trimethyl, vinyl triphenyltin, vinyl three-n-octyl tin or the like.These stanniferous monomers can use separately or being used in combination with two or more.
As the monomer that contains alkoxysilyl, mention (methyl) acryloxy methyltrimethoxy silane, (methyl) acryloxy methyl dimethoxy silane, (methyl) acryloxy methyl dimethoxy methoxylsilane, (methyl) acryloxy Union carbide A-162, (methyl) acryloxy methyl diethoxy silane, (methyl) acryloxy methyl dimethoxy base oxethyl silane, (methyl) acryloyl-oxy ylmethyl tripropoxy silane, (methyl) acryloxy methyl dipropoxy silane, (methyl) acryloxy methyl dimethoxy base propoxy-silane, γ-(methyl) acryloxy propyl trimethoxy silicane, γ-(methyl) acryloxy propyl group methyl dimethoxysilane, γ-(methyl) acryloxy propyl-dimethyl methoxy silane, γ-(methyl) acryloxy propyl-triethoxysilicane, γ-(methyl) acryloxy propyl group methyldiethoxysilane, γ-(methyl) acryloxy propyl-dimethyl Ethoxysilane, γ-(methyl) acryloxy propyl group tripropoxy silane, γ-(methyl) acryloxy propyl group methyl dipropoxy silane, γ-(methyl) acryloxy propyl-dimethyl propoxy-silane, γ-(methyl) acryloxy propyl group methyldiphenyl TMOS, γ-(methyl) acryloxy propyl-dimethyl phenoxy group silane, γ-(methyl) acryloxy propyl group methyl benzyloxy silane, γ-(methyl) acryloxy propyl-dimethyl benzyloxy silane, the trimethoxy vinyl silanes, the triethoxy vinyl silanes, 6-trimethoxysilyl-1, the 2-hexene, right-trimethoxysilyl vinylbenzene or the like.These monomers that contain the siloxanes silyl can use separately or two or more are used in combination.
In the present invention, the graft polymerization of the monomer of polar functionalities on the natural rubber molecule carried out with letex polymerization.In letex polymerization, usually preferably to adding the monomer of polar functionalities and further add polymerization starter, to the monomer that stirs under the fixed temperature with the polymerization polar functionalities by water and emulsifying agent in case of necessity being added in the solution that the natural rubber latex Ruzhong forms.When the monomer with polar functionalities adds natural rubber latex, emulsifying agent can be added natural rubber latex earlier, perhaps can be added to natural rubber latex then with the monomer of emulsifying agent emulsification polar functionalities.The monomeric emulsifying agent that can be used for emulsification natural rubber latex and/or polar functionalities does not have special restriction, comprises nonionogenic tenside such as polyoxyethylene lauryl ether etc.
There is no particular restriction for polymerization starter, can comprise the various polymerization starters that are used for letex polymerization, and its adding method does not have special restriction yet.As polymerization starter commonly used, mention benzoyl peroxide, hydrogen peroxide, cumene hydroperoxide, t-butyl hydroperoxide, peroxidation two-tertiary butyl, 2,2-azobis isobutyronitrile, 2, two (2-diaminopropanes) hydrochlorides, 2 of 2-azo, two (2-diaminopropanes) dihydrochlorides, 2 of 2-azo, 2-azo two (2,4-dimethyl-valeronitrile), Potassium Persulphates, Sodium Persulfate, ammonium persulphate or the like.In addition, preferably use redox class polymerization starter to reduce polymerization temperature.As in redox class polymerization starter will with the reductive agent of superoxide combination, mention for example tetren, mercaptan, sodium acid sulfite, reducing metal ion, xitix or the like.As the preferably combination of superoxide in the oxidation-reduction type polymerization starter and reductive agent, mention combination of t-butyl hydroperoxide and tetren or the like.
In order not make the processing characteristics deterioration, importantly the monomer of a small amount of polar functionalities is introduced in each natural rubber molecule equably by using modified natural rubber masterbatch according to the present invention to improve the low-loss of rubber combination and wear resistance.Therefore, the preferred 1-100mol% of the amount of the polymerization starter that is added, more preferably 10-100mol% is based on the monomer of polar functionalities.
Aforementioned component is dropped in the reaction vessel and at 30 to 80 ℃ to descend to react 10 minutes to 7 hours, to obtain the wherein modified rubber-emulsion of polar functionalities monomer graft copolymerization on the natural rubber molecule.
In modified rubber-emulsion, the monomeric grafting amount of polar functionalities preferably in the scope of 0.01-5.0 quality %, more preferably 0.02-3.0 quality %, 0.03-2.0 quality % most preferably is based on the rubber components in natural rubber latex Ruzhong.When the monomeric grafting amount of polar functionalities was lower than 0.01 quality %, rubber combination low-loss and wear resistance can not be improved fully.And the monomeric grafting amount of working as polar functionalities surpasses 5.0 quality %, to change widely for natural rubber inherent physicals such as visco-elasticity, S-S characteristic (stress-strain curve in tensile testing machine) or the like, thereby reduce, and the also working ability of deterioration rubber combination widely for the good physicals of natural rubber inherent.
Be used for slurry according to modified natural rubber masterbatch of the present invention by in advance fillers dispersed being formed at water.The production of slurry can be undertaken by well-known method, can use high shear mixer, high-pressure homogenizer, ultrasonic homogenizer, colloidal mill or its similar devices of mixing machine for example such as rotor-stator type.Slurry can under agitation slowly drip filler for example by in the colloidal mill that water is packed into, and circulating with tensio-active agent in homogenizer under constant voltage and constant temperature then prepares.In this case, pressure is generally 10-1000kPa, preferred 200-800kPa.In addition, can be by with constant mixed filler and water and the end production that its mixture is introduced in the slender pipeline of powerful waterpower under stirring is had the continuous slurry fluid of even composition.In addition, the preferred 0.5-60 quality of the concentration of filler in slurry %, more preferably 1-30 quality %.
About slurry, filler in slurry preferably has volume average particle size (mv) and is not more than 25 μ m, 90% particle volume diameter (D90) is not more than 30 μ m, more preferably have volume average particle size (mv) and be not more than 20 μ m, 90% particle volume diameter (D90) is not more than 25 μ m, from the 24M4DBP of the filler of slurry fluid drying and recovery absorb preferably remain on be scattered in the water before 24M4DBP absorb more than 93%, more preferably more than 96%.It is the value of measuring according to ISO 6894 that 24M4DBP absorbs, and volume average particle size and 90 volume % particle diameters be by the specific refractory power of using laser diffraction type particle size distribution analyser and supposing water be 1.33 and the specific refractory power of filler be 1.57 values of measuring.If the particle diameter of the filler in the slurry (volume average particle size and 90 volume % particle diameters) is too big, the dispersed deterioration of filler in the mixture of modified rubber-emulsion and slurry, reinforcing property and wear resistance may deteriorations.And be applied to slurry so that particle diameter when diminishing when excessive shearing force, destroy the structure of filler and cause the reinforcing property deterioration, thus from the 24M4DBP of the filler of slurry fluid drying and recovery absorb preferably remain on be scattered in the water before 24M4DBP absorb more than 93%.
Consider the stability that improves modified rubber-emulsion, modified rubber-emulsion and/or slurry preferably further contain tensio-active agent.As tensio-active agent, mention negatively charged ion, positively charged ion, nonionic and amphoterics.Wherein, negatively charged ion and nonionogenic tenside are preferred.The amount of the tensio-active agent that is added is generally 0.01-2 quality %, and preferred 0.02-1 quality % is based on modified rubber-emulsion.
Carbon black does not have special restriction, comprises for example GPF, FEF, HAF, ISAF and SAF level carbon black.These carbon blacks can use separately or be used in combination with two or more.
Be used for mineral filler of the present invention for being selected from least a of the group be made up of the mineral compound of silicon-dioxide and general formula (I) expression, the M in the general formula (I) is preferably and is selected from least a by in the following group of forming: the carbonate of the oxide compound of aluminum metal, aluminium and oxyhydroxide, their hydrate and aluminium.As silicon-dioxide, preferably mention precipitated silica, aerosil, colloid silica or the like.On the other hand, as the mineral compound of formula (I), mention aluminum oxide (Al
2O
3) as gama-alumina, Alpha-alumina or its analogue; Alumina monohydrate (Al
2O
3H
2O) as boehmite, diaspore or its analogue; Aluminium hydroxide [Al (OH)
3] as gibbsite, bayerite or its analogue; Aluminium carbonate [Al
2(CO
3)
3], magnesium hydroxide [Mg (OH)
2], magnesium oxide (MgO), magnesiumcarbonate (MgCO
3), talcum (3MgO4SiO
2H
2O), attapulgite (5MgO8SiO
29H
2O), titanium white (TiO
2), the black (TiO of titanium
2n-1), calcium oxide (CaO), calcium hydroxide [Ca (OH)
2], magnesium aluminium oxide (MgOAl
2O
3), clay (Al
2O
32SiO
2), kaolin (Al
2O
32SiO
22H
2O), pyrophyllite (Al
2O
34SiO
2H
2O), wilkinite (Al
2O
34SiO
22H
2O), pure aluminium silicate (Al
2SiO
5, Al
43SiO
45H
2O, or the like), Magnesium Silicate q-agent (Mg
2SiO
4, MgSiO
3, or the like), Calucium Silicate powder (Ca
2SiO
4, or the like), Aluminum calcium silicate (Al
2O
3CaO2SiO
2, or the like), calcium magnesium silicate (CaMgSiO
4), lime carbonate (CaCO
3), zirconium white (ZrO
2), zirconium hydroxide [ZrO (OH)
2NH
2O], zirconium carbonate [Zr (CO
3)
2] and contain the crystalline aluminosilicate such as the various zeolite of hydrogen, basic metal or the alkaline-earth metal of charge compensation.These mineral fillers can be used separately or be used in combination with two or more.
As the method for mixed and modified natural rubber latex and slurry, mention the method that also under agitation drips the method for modified rubber-emulsion in the blending mill of for example wherein slurry being packed into and wherein under agitation in modified rubber-emulsion, drip slurry on the contrary.In addition, also can use wherein modified rubber-emulsion stream and slurry stream under powerful waterpower stirring with constant throughput ratio blended method.In this case, modified natural rubber that will be in modified rubber-emulsion and the filler compounding in slurry, so that the preferred 5-100 mass parts of amount of the filler in slurry, more preferably 10-70 mass parts is based on the rubber components in the 100 mass parts modified rubber-emulsions (being modified natural rubber).When the amount of the filler of compounding is lower than 5 mass parts, can not obtain enough reinforcing properties, and when it surpasses 100 mass parts, the possible deterioration of processing characteristics.
Modified natural rubber masterbatch forms by following manner usually: modified rubber-emulsion is mixed with slurry, solidify then and further dry they.Solidifying of the mixture of modified rubber-emulsion and slurry usually by using acid to carry out as peptizer as formic acid, sulfuric acid etc. or salt such as sodium-chlor etc.Yet solidifying can be by mixed and modified natural rubber latex and slurry and do not add peptizer and carry out, and in this case, needn't add peptizer.
In the drying of solidifying the back mixture, can use drying machine commonly used such as Vacuumdrier, blast dryer, rotary drum dryer and conveyor dryer or its similar devices, but consider the dispersiveness and the homogeneity of further raising filler, preferably carry out exsiccant and apply mechanical shear stress simultaneously.Apply the modified natural rubber masterbatch that mechanical shear stress can obtain to have excellent processing characteristics, reinforcing property and low-loss simultaneously by exsiccant.Exsiccant applies mechanical shear stress simultaneously can be undertaken by mixing machinery commonly used, still from the viewpoint of industrial productivity, preferably uses the screw type continuous mixer, more preferably uses the twin shaft mixing extruder of rotation in the same way or reverse rotation.As the screw type continuous mixer, can use commercially available product, for example, and by Kobe Steel, twin shaft mixing extruder that Ltd. makes or the like.In addition, moisture content is not less than 10% in the modified natural rubber masterbatch before dry.When moisture content was lower than 10% in the dry preceding master batch, in drying step, the raising of fillers dispersed was very little.
Except that modified rubber-emulsion, slurry and tensio-active agent, can in modified natural rubber masterbatch, add additive such as vulcanizing agent, antioxidant, tinting material, dispersion agent etc.
Rubber combination according to the present invention is characterized in that using this modified natural rubber masterbatch.Because the homogeneity of this modified natural rubber masterbatch is good, therefore, good according to homogeneity, low-loss, wear resistance and the fracture characteristics of rubber combination of the present invention as mentioned above.In addition, except that modified natural rubber masterbatch, in the scope of not damaging the object of the invention, can in rubber combination of the present invention, add the additive that is generally used for rubber industry such as vulcanizing agent, vulcanization accelerator, antioxidant, scorch retarder, zinc white, stearic acid, silane coupling agent etc.As these additives, can preferably use commercially available additive.Rubber combination of the present invention can by with modified natural rubber masterbatch and the various additive compoundings of suitably selecting in case of necessity and mixing, heat, extrude to wait and produce.
Tire according to the present invention is characterized in that using this rubber combination in any tyre element.In tire according to the present invention, rubber combination is preferred for tread-rubber, uses the anti-breaking property and the wear resistance height of the tire of this rubber combination in tyre surface, and the cloudy power of rolling is low and low fuel consumption is good.In addition, as the gas that charges into, can use air commonly used or have the air of oxygen partial pressure of adjustment and rare gas element such as nitrogen, argon, helium or the like according to tire of the present invention.
Embodiment
Provide the following example and be not intended to qualification with explanation the present invention as it.
The production example of the female coal refining of modified natural rubber glue
(production example 1 of modified rubber-emulsion)
Field latex is carried out centrifugation with latex separator [by Saito Enshin Kogyo Co., Ltd. makes] under the rotating speed of 7500rpm, to obtain revertex with dry rubber concentrations 60%.The 1000g revertex packed into be provided with in the stainless steel reactor of agitator and temperature regulation chuck, add by [Emulgen 1108 with 10mL water and 90mg emulsifying agent, make by Kao Corporation] adding 3.0g methacrylic acid N, in the N-diethyl amino ethyl ester and preformed emulsion and 990mL water at room temperature stir then and replaced with nitrogen simultaneously in 30 minutes.Subsequently, 1.2g t-butyl hydroperoxide and 1.2g tetren are added as polymerization starter, under 40 ℃, reacted 30 minutes, obtain modified rubber-emulsion A thus.
Then, the modified rubber-emulsion A with preparation as mentioned above solidifies pH regulator to 4.7 by adding formic acid.Thus obtained solid is handled 5 times with clappers (clapper), by shredding machine break into pieces and by hot air dryer 110 ℃ dry 210 minutes down, obtain modified natural rubber a.Quality determination from thus obtained modified natural rubber a: as the methacrylic acid N that monomer adds, the transformation efficiency of N-diethyl amino ethyl ester is 100%.In addition, by also further using 2: 1 the acetone and the mixed extractant solvent of methyl alcohol to attempt separating of homopolymer with the petroleum ether extraction modified natural rubber, but from the analysis of extract, do not detect homopolymer, therefore, confirm that adding monomer with 100% introduces in the natural rubber molecule.Therefore, monomeric grafting amount is 0.5 quality % in modified natural rubber a, based on the rubber components in natural rubber latex Ruzhong.
(production example 2 of modified rubber-emulsion)
Replace 3.0g methacrylic acid N except adding the 1.7g 4-vinylpridine as monomer, outside the N-diethyl amino ethyl ester, with production example 1 in identical mode obtain modified rubber-emulsion B.In addition, modified natural rubber b obtains from modified rubber-emulsion B in the same way, as the result who analyzes, confirms that adding monomer with 100% introduces in the natural rubber molecule.Therefore, monomeric grafting amount is 0.28 quality % in modified natural rubber b, based on the rubber components in natural rubber latex Ruzhong.
(production example 3 of modified rubber-emulsion)
Replace 3.0g methacrylic acid N except adding the 1.7g vinyl cyanide as monomer, outside the N-diethyl amino ethyl ester, with production example 1 in identical mode obtain modified rubber-emulsion C.In addition, modified natural rubber c obtains from modified rubber-emulsion C in the same way, as the result who analyzes, confirms that adding monomer with 100% introduces in the natural rubber molecule.Therefore, monomeric grafting amount is 0.28 quality % in modified natural rubber c, based on the rubber components in natural rubber latex Ruzhong.
(production example 4 of modified rubber-emulsion)
Replace 3.0g methacrylic acid N except adding 2.1g methacrylic acid 2-hydroxyl ethyl ester as monomer, outside the N-diethyl amino ethyl ester, with production example 1 in identical mode obtain modified rubber-emulsion D.In addition, modified natural rubber d obtains from modified rubber-emulsion D in the same way, as the result who analyzes, confirms that adding monomer with 100% introduces in the natural rubber molecule.Therefore, monomeric grafting amount is 0.35 quality % in modified natural rubber d, based on the rubber components in natural rubber latex Ruzhong.
(production example 5 of modified rubber-emulsion)
Replace 3.0g methacrylic acid N except adding the 1.4g methacrylic acid as monomer, outside the N-diethyl amino ethyl ester, with production example 1 in identical mode obtain modified rubber-emulsion E.In addition, modified natural rubber e obtains from modified rubber-emulsion E in the same way, as the result who analyzes, confirms that adding monomer with 100% introduces in the natural rubber molecule.Therefore, monomeric grafting amount is 0.23 quality % in modified natural rubber e, based on the rubber components in natural rubber latex Ruzhong.
(production example 6 of modified rubber-emulsion)
Replace 3.0g methacrylic acid N except adding the 2.3g glycidyl methacrylate as monomer, outside the N-diethyl amino ethyl ester, with production example 1 in identical mode obtain modified rubber-emulsion F.In addition, modified natural rubber f obtains from modified rubber-emulsion F in the same way, as the result who analyzes, confirms that adding monomer with 100% introduces in the natural rubber molecule.Therefore, monomeric grafting amount is 0.38 quality % in modified natural rubber f, based on the rubber components in natural rubber latex Ruzhong.
(the preparation embodiment 1 of slurry)
In colloidal mill, pack into 1425g deionized water and 75g carbon black (N110) with rotor diameter 50mm, under rotor-stator gap 1mm and rotating speed 1500rpm, stirred 10 minutes, the slurry that is obtained further adds 0.05% anion surfactant [Demol N, make by Kao Corporation] and applying pressure type homogenizer under the pressure of 500kPa, circulate three times, to prepare slurry 1 (carbon black slurry).In addition, absorb, measure according to ISO 6894 as used sooty 24M4DBP, in being scattered in water before 24M4DBP be absorbed as 98mL/100g, from the slurry fluid drying with reclaim back 24M4DBP and be absorbed as 96mL/100g (conservation rate: 98.0%).In addition, as sooty size distribution in slurry, after dispersion at once by use laser diffraction type particle size distribution analyser [MICROTRAC FRA type] and the specific refractory power of supposing water be 1.33 and the particulate specific refractory power be 1.57 to measure, volume average particle size (mv) is 15.1 μ m, and 90% particle volume diameter (D90) is 19.5 μ m.
(the preparation embodiment 2 of slurry)
The sedimentary silicon-dioxide of 1425g deionized water and 75g in colloidal mill, pack into [by Nippon Silica Industrial Co. with rotor diameter 50mm, Ltd. make, Nipsil LP], under rotor-stator gap 0.3mm and rotating speed 7000rpm, stirred 10 minutes, with preparation slurry 2 (SiO 2 slurry liquid).In addition, absorb, measure according to ISO 6894 as the 24M4DBP of used silicon-dioxide, in being scattered in water before 24M4DBP be absorbed as 150mL/100g, from the slurry fluid drying with reclaim back 24M4DBP and be absorbed as 144mL/100g (conservation rate: 96.0%).In addition, size distribution as silicon-dioxide in slurry, after dispersion at once by use laser diffraction type particle size distribution analyser [MICROTRAC FRA type] and the specific refractory power of supposing water be 1.33 and the particulate specific refractory power be 1.57 to measure, volume average particle size (mv) is 13.2 μ m, and 90% particle volume diameter (D90) is 24.0 μ m.
(the preparation embodiment 3 of slurry)
Pack in the colloidal mill with rotor diameter 50mm 1425g deionized water and 75g gibbsite type aluminum hydroxide [made by Showa Denko K.K., HigiliteH-43M], under rotor-stator gap 0.5mm and rotating speed 1500rpm, stirred 10 minutes preparation slurry 3 (aluminium hydroxide slurry).In addition, absorb, measure according to ISO 6894 as the 24M4DBP of used aluminium hydroxide, in being scattered in water before 24M4DBP be absorbed as 52mL/100g, from the slurry fluid drying with reclaim back 24M4DBP and be absorbed as 52mL/100g (conservation rate: 100.0%).In addition, as the size distribution of aluminium hydroxide in slurry, be 1.57 to measure by supposition particulate specific refractory power in the same way, volume average particle size (mv) is 5.1 μ m, 90% particle volume diameter (D90) is 8.8 μ m.
(solidifying and drying step)
The modified rubber-emulsion that is shown in the combination in the table 1,2 and 3 and the slurry of packing in homomixer and being that the amount of 50 mass parts adds carbon black, silicon-dioxide or aluminium hydroxide based on 100 mass parts rubber components reaches 4.7 up to pH and solidifies by under agitation adding formic acid.The coagulated substance of gained is collected, wash with water, dehydration reaches about 40% up to moisture content, further by using by Kobe Steel, Ltd. the twin shaft mixing extruder [homodromal screw diameter=30mm of Zhi Zaoing, L/D=35, three venting holes] dry under 120 ℃ of barrel zone temperatures and rotating speed 100rpm, to obtain modified natural rubber masterbatch.
The production example of natural rubber masterbatch
In order to compare, natural rubber latex G does not only have above-mentioned modification procedure by dilute with water and prepares to have the rubber components concentration identical with above-mentioned latex.Natural rubber masterbatch is to obtain by using natural rubber latex G and slurry 1,2 or 3 with mode identical in the production example of modified natural rubber masterbatch.
(embodiment 1-3 and comparative example 1)
By in plastics processing mill (plastomill), based on the rubber master batch of 150 mass parts according to the combination manufacturing of table 1, compounding and mixing 5 mass parts perfume oil, 2 mass parts stearic acid, 1 mass parts antioxidant 6C[N-(1, the 3-dimethylbutyl)-N '-phenyl-Ursol D], 3 mass parts zinc white, 0.8 mass parts accelerator CZ [N cyclohexyl 2 benzothiazole sulfenamide] and 1 mass parts sulphur prepares rubber combination.
(comparative example 2)
By in plastics processing mill, based on 100 mass parts modified natural rubbers, compounding and drying-mixing 50 mass parts carbon blacks (N110), 5 mass parts perfume oil, 2 mass parts stearic acid, 1 mass parts antioxidant 6C, 3 mass parts zinc white, 0.8 mass parts accelerator CZ and 1 mass parts sulphur prepare rubber combination.
(embodiment 4-15 and comparative example 3 and 5)
By in plastics processing mill, based on the rubber master batch of 150 mass parts according to the manufacturing of the combination in table 2 or 3, compounding and mixing 4 mass parts silane coupling agents [being made Si69 by Degussa], 2 mass parts stearic acid, 1 mass parts antioxidant 6C, 3 mass parts zinc white, 1 mass parts vulcanization accelerator NS [N tert butyl benzothiazole 2 sulfenamide] and 1.2 mass parts sulphur prepare rubber combination.
(comparative example 4 and 6)
By in plastics processing mill, based on 100 mass parts modified natural rubbers, compounding and drying-mixing 50 mass parts silicon-dioxide are [by Nippon Silica Industrial Co., Ltd. make Nipsil LP], 4 mass parts silane coupling agents, 2 mass parts stearic acid, 1 mass parts antioxidant 6C, 3 mass parts zinc white, 1 mass parts vulcanization accelerator NS and 1.2 mass parts sulphur prepare the rubber combination of comparative example 4.In addition, except using aluminium hydroxide [making Higilite H-43M by Showa Denko K.K.] to replace obtaining the rubber combination of comparative example 6 in the same way outside the silicon-dioxide.
The performance evaluation of rubber combination
For the rubber combination of gained, measure and estimate mooney viscosity, tensile strength (Tb), tan δ and wear resistance by following method.The results are shown in table 1-3.
(1) mooney viscosity
The mooney viscosity ML of rubber combination
1+4(130 ℃) are measured according to JISK6300-1994 under 130 ℃.
(2) tensile strength
For vulcanized rubber, carry out tension test to measure tensile strength (Tb) according to JIS K 6301-199 5 by obtaining in 33 minutes at 145 ℃ of following vulcanizate compositions.Tensile strength is big more, and anti-breaking property is good more.
(3)Tanδ
For vulcanized rubber by obtaining in 33 minutes at 145 ℃ of following vulcanizate compositions, by using viscoelasticity measurement equipment [making] by RHEOMETRICS Corporation, 50 ℃ of temperature, strain 5% and frequency 15Hz measure loss tangent (tan δ) down.Tan δ is more little, and low-loss is good more.
(4) wear resistance
Wear resistance is estimated by measuring by the wear loss of the vulcanized rubber that obtained in 33 minutes at 145 ℃ of following vulcanizate compositions by the Lan Pengshi wear testing machine under slip ratio 60% and room temperature, its each freedom based on the inverse of the wear loss of comparative example in the table 11 be 100, in the table 2 inverse of the wear loss of comparative example 3 be 100 and table 3 in the inverse of wear loss of comparative example 5 be that 100 index is represented.Desired value is big more, and wear loss is low more and wear resistance is good more.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | |
| The method of mixed carbon black | Master batch | Master batch | Master batch | Master batch | Dry mixing |
| (modification) natural rubber latex | A | B | C | G | - |
| Slurry | Slurry 1 | Slurry 1 | Slurry 1 | Slurry 1 | - |
| Modified natural rubber | - | - | - | - | a |
| Mooney viscosity ML 1+4(130℃) | 76 | 73 | 74 | 75 | 87 |
| Tb(MPa) | 29.2 | 29.3 | 29.0 | 27.5 | 27.9 |
| tanδ | 0.125 | 0.121 | 0.128 | 0.153 | 0.144 |
| Wear resistance (index) | 125 | 126 | 122 | 100 | 108 |
Table 2
| Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Comparative example 3 | Comparative example 4 | |
| The method of mixed silica | Master batch | Master batch | Master batch | Master batch | Master batch | Master batch | Master batch | Dry mixing |
| (modification) natural rubber latex | A | D | B | E | C | F | G | - |
| Slurry | Slurry 2 | Slurry 2 | Slurry 2 | Slurry 2 | Slurry 2 | Slurry 2 | Slurry 2 | - |
| Modified natural rubber | - | - | - | - | - | - | - | a |
| Mooney viscosity ML 1+4(130℃) | 84 | 84 | 80 | 81 | 81 | 83 | 82 | 93 |
| Tb(MPa) | 28.1 | 28.0 | 27.9 | 28.0 | 28.2 | 28.3 | 26.2 | 26.9 |
| tanδ | 0.112 | 0.114 | 0.109 | 0.115 | 0.116 | 0.113 | 0.146 | 0.135 |
| Wear resistance (index) | 127 | 123 | 128 | 122 | 125 | 123 | 100 | 109 |
Table 3
| Embodiment 10 | Embodiment 11 | Embodiment 12 | Embodiment 13 | Embodiment 14 | Embodiment 15 | Comparative example 5 | Comparative example 6 | |
| The method of mixing aluminium hydroxide | Master batch | Master batch | Master batch | Master batch | Master batch | Master batch | Master batch | Dry mixing |
| (modification) natural rubber latex | A | D | B | E | C | F | G | - |
| Slurry | Slurry 3 | Slurry 3 | Slurry 3 | Slurry 3 | Slurry 3 | Slurry 3 | Slurry 3 | - |
| Modified natural rubber | - | - | - | - | - | - | - | a |
| Mooney viscosity ML 1+4(130℃) | 68 | 65 | 64 | 67 | 67 | 69 | 67 | 74 |
| Tb(MPa) | 24.8 | 24.5 | 24.9 | 24.2 | 24.5 | 24.1 | 22.5 | 23.0 |
| tanδ | 0.108 | 0.110 | 0.108 | 0.115 | 0.111 | 0.113 | 0.138 | 0.130 |
| Wear resistance (index) | 124 | 126 | 125 | 124 | 122 | 129 | 100 | 108 |
As from the embodiment 1-3 of table 1 and the contrast of comparative example 1, embodiment 4-9 and the contrast of comparative example 3 and the contrast finding of embodiment 10-15 in the table 3 and comparative example 5 the table 2, the fracture characteristics of rubber combination, low-loss and wear resistance can be by using modified natural rubber masterbatch to replace natural rubber masterbatch and significantly improving.In addition, as from the embodiment 1-3 of table 1 and the contrast of comparative example 2, embodiment 4-9 and the contrast of comparative example 4 and the contrast finding of embodiment 10-15 in the table 3 and comparative example 6 the table 2, the blended situation is compared by drying is mixing with filler with modified natural rubber, when using modified natural rubber masterbatch, can improve processing characteristics, fracture characteristics, low-loss and the wear resistance of rubber combination by a larger margin.
Claims (15)
1. the production method of a modified natural rubber masterbatch, it comprises modified rubber-emulsion and slurry blended step, this modified rubber-emulsion forms with the monomer of this polar functionalities of graft polymerization on the natural rubber molecule in natural rubber latex Ruzhong by the monomer of polar functionalities being added the natural rubber latex Ruzhong, and this slurry forms in water by at least a fillers dispersed in the group that will be selected from carbon black, silicon-dioxide in advance and be made up of the mineral compound of following general formula (I) expression:
nM·xSiO
y·zH
2O...(I)
[wherein, M is selected from least a by in the following group of forming: the metal of aluminium, manganese, titanium, calcium or zirconium, the oxide compound of these metals and oxyhydroxide, the carbonate of their hydrate and these metals, n is the integer of 1-5, x is the integer of 0-10, and y is that integer and the z of 2-5 is the integer of 0-10].
2. the production method of modified natural rubber masterbatch according to claim 1, wherein, this filler in slurry has volume average particle size (mv) and is not more than 25 μ m, 90% particle volume diameter (D90) is not more than 30 μ m, from the 24M4DBP of the filler of slurry fluid drying and recovery absorb remain on be scattered in the water before 24M4DBP absorb more than 93%.
3. the production method of modified natural rubber masterbatch according to claim 1; wherein; this filler is a carbon black, and the monomeric polar group of this polar functionalities is to be selected from least a by in the following group of forming: amino, imino-, itrile group, ammonium, imide, amide group, hydrazono-, azo-group, diazo, hydroxyl, carboxyl, carbonyl, epoxy group(ing), oxygen carbonyl, sulfide group, disulphide group, alkylsulfonyl, sulfinyl, thiocarbonyl, nitrogen heterocycle, oxygen-containing heterocycle and contain tin group.
4. the production method of modified natural rubber masterbatch according to claim 1; wherein; this filler is for being selected from least a in the group of being made up of the mineral compound of silicon-dioxide and general formula (I) expression, and the monomeric polar group of this polar functionalities is to be selected from least a by in the following group of forming: amino; imino-; itrile group; ammonium; imide; amide group; hydrazono-; azo-group; diazo; hydroxyl; carboxyl; carbonyl; epoxy group(ing); the oxygen carbonyl; sulfide group; the disulphide group; alkylsulfonyl; sulfinyl; thiocarbonyl; nitrogen heterocycle; oxygen-containing heterocycle and alkoxysilyl.
5. the production method of modified natural rubber masterbatch according to claim 1, wherein, the monomeric grafting amount of this polar functionalities is 0.01-5.0 quality %, based on the rubber components in natural rubber latex Ruzhong.
6. the production method of modified natural rubber masterbatch according to claim 1, wherein, this modified rubber-emulsion and/or slurry further contain tensio-active agent.
7. the production method of modified natural rubber masterbatch according to claim 1, wherein, silicon-dioxide is any one of precipitated silica, aerosil and colloid silica.
8. the production method of modified natural rubber masterbatch according to claim 1 wherein, is to be selected from least a by in the following group of forming by the mineral compound of general formula (I) expression: aluminum oxide (Al
2O
3), monohydrate alumina (Al
2O
3H
2O), aluminium hydroxide [Al (OH)
3], aluminium carbonate [Al
2(CO
3)
3], magnesium hydroxide [Mg (OH)
2], magnesium oxide (MgO), magnesiumcarbonate (MgCO
3), talcum (3MgO4SiO
2H
2O), attapulgite (5MgO8SiO
29H
2O), titanium white (TiO
2), the black (TiO of titanium
2n-1), calcium oxide (CaO), calcium hydroxide [Ca (OH)
2], magnalium oxide compound (MgOAl
2O
3), clay (Al
2O
32SiO
2), kaolin (Al
2O
32SiO
22H
2O), pyrophyllite (Al
2O
34SiO
2H
2O), wilkinite (Al
2O
34SiO
22H
2O), pure aluminium silicate (Al
2SiO
5, Al
43SiO
45H
2O), Magnesium Silicate q-agent (Mg
2SiO
4, MgSiO
3), Calucium Silicate powder (Ca
2SiO
4), Aluminum calcium silicate (Al
2O
3CaO2SiO
2), calcium magnesium silicate (CaMgSiO
4), lime carbonate (CaCO
3), zirconium white (ZrO
2), zirconium hydroxide [ZrO (OH)
2NH
2O], zirconium carbonate [Zr (CO
3)
2] and crystalline aluminosilicate.
9. the production method of modified natural rubber masterbatch according to claim 1, wherein, the M in the general formula (I) is selected from least a by in the following group of forming: the carbonate of the oxide compound of aluminum metal, aluminium and oxyhydroxide, their hydrate and aluminium.
10. the production method of modified natural rubber masterbatch according to claim 1, it further comprises the step of the mixture of modified rubber-emulsion and slurry being solidified and the coagulated substance drying of gained is applied simultaneously mechanical shear stress.
11. the production method of modified natural rubber masterbatch according to claim 10, wherein, drying is undertaken by continuous mixer.
12. the production method of modified natural rubber masterbatch according to claim 11, wherein, this continuous mixer is the twin shaft mixing extruder.
13. a modified natural rubber masterbatch, it passes through according to each described method production of claim 1-12.
14. a rubber combination, it uses modified rubber master batch according to claim 13.
15. a tire is characterized in that, uses rubber combination according to claim 14 in any tyre element.
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| JP2004335706A JP4810085B2 (en) | 2004-11-19 | 2004-11-19 | Modified natural rubber masterbatch and method for producing the same, rubber composition and tire |
| JP335706/2004 | 2004-11-19 | ||
| PCT/JP2005/021280 WO2006054713A1 (en) | 2004-11-19 | 2005-11-18 | Modified natural rubber masterbatch and method for production thereof, and rubber composition and tire |
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2004
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Also Published As
| Publication number | Publication date |
|---|---|
| CN101084258B (en) | 2010-09-29 |
| JP2006143879A (en) | 2006-06-08 |
| JP4810085B2 (en) | 2011-11-09 |
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