CN107266745B - Rubber composition containing modified nano white carbon black and preparation method thereof - Google Patents
Rubber composition containing modified nano white carbon black and preparation method thereof Download PDFInfo
- Publication number
- CN107266745B CN107266745B CN201610217661.9A CN201610217661A CN107266745B CN 107266745 B CN107266745 B CN 107266745B CN 201610217661 A CN201610217661 A CN 201610217661A CN 107266745 B CN107266745 B CN 107266745B
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- styrene
- rubber composition
- carbon black
- white carbon
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000006229 carbon black Substances 0.000 title claims abstract description 84
- 239000000203 mixture Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 60
- 229920001971 elastomer Polymers 0.000 title claims abstract description 46
- 239000005060 rubber Substances 0.000 title claims abstract description 46
- 239000000178 monomer Substances 0.000 claims abstract description 35
- 229920000126 latex Polymers 0.000 claims abstract description 32
- 239000004816 latex Substances 0.000 claims abstract description 32
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 29
- -1 aryl ethylene Chemical compound 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 11
- 235000019241 carbon black Nutrition 0.000 claims description 78
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 57
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 57
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 47
- 239000000839 emulsion Substances 0.000 claims description 47
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 45
- 239000003643 water by type Substances 0.000 claims description 28
- 230000018044 dehydration Effects 0.000 claims description 25
- 238000006297 dehydration reaction Methods 0.000 claims description 25
- 238000010792 warming Methods 0.000 claims description 21
- 239000002174 Styrene-butadiene Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 239000011115 styrene butadiene Substances 0.000 claims description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 230000033228 biological regulation Effects 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000003995 emulsifying agent Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 11
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 10
- 239000000872 buffer Substances 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 9
- 235000019394 potassium persulphate Nutrition 0.000 claims description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000008394 flocculating agent Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 claims description 3
- 239000003610 charcoal Substances 0.000 claims description 3
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- JWQPRMRTYLVVKK-UHFFFAOYSA-N 4,5-dihydro-1,3-oxazole;propane Chemical compound CCC.C1CN=CO1 JWQPRMRTYLVVKK-UHFFFAOYSA-N 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 150000001450 anions Chemical group 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000004665 fatty acids Chemical group 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- 150000003840 hydrochlorides Chemical class 0.000 claims description 2
- 239000012875 nonionic emulsifier Substances 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 239000000344 soap Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 claims description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 229940077388 benzenesulfonate Drugs 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 230000021615 conjugation Effects 0.000 claims 1
- 150000001993 dienes Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 239000005977 Ethylene Substances 0.000 abstract description 2
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 241000872198 Serjania polyphylla Species 0.000 abstract 1
- 230000001112 coagulating effect Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 26
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 16
- 238000004458 analytical method Methods 0.000 description 15
- 238000005070 sampling Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 238000004073 vulcanization Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 9
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229920003052 natural elastomer Polymers 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- 241000255964 Pieridae Species 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 210000000720 eyelash Anatomy 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- FHHJDRFHHWUPDG-UHFFFAOYSA-N peroxysulfuric acid Chemical compound OOS(O)(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C1/00—Treatment of rubber latex
- C08C1/14—Coagulation
- C08C1/15—Coagulation characterised by the coagulants used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention aims to provide a rubber composition containing modified nano white carbon black, which is prepared by adopting an unsaturated carboxylic acid polar monomer and an aryl ethylene monomer, preparing the modified nano white carbon black by using an in-situ polymerization method, and then directly mixing and coagulating the modified nano white carbon black with styrene butadiene rubber latex. The invention not only effectively solves the problem of easy agglomeration of the nano white carbon black, but also solves the problems of poor binding force and uneven dispersion of the nano white carbon black and the rubber matrix, and endows the composition with high wear resistance and low friction performance. The preparation method of the rubber composition is simple and easy to implement, has low cost, does not pollute the environment, and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of rubber compositions and preparation method thereof, fill fourth more particularly to a kind of modified white carbon black
Benzene rubber is used for the rubber composition and preparation method thereof of tire tread.
Background technique
It is well known that with the successive implementation of EU REACH Legislation and tire tag bill, synthetic rubber environmental protection is compeled
The eyebrows and eyelashes, along with the demand of light color article, the application study of white carbon black causes the attention of people.Nano silica is commonly called as white
Carbon black is the second largest reinforcing agent that dosage is only second to carbon black in rubber industry.From last century the nineties, white carbon black is as reinforcement
Filler is widely used in tire tread formula, obtains " devil's triangle " performance of above-mentioned tire tread requirement obvious
Balance.But Nano carbon white partial size is small, specific surface is big, surface energy is high, surface has a large amount of hydroxyl again, leads to a nanometer hard charcoal
It is black easily to reunite, it is not easy to be uniformly dispersed in the mixed process with rubber material, not only will affect filling-modified effect in this way, and
And it can also damage the performance of rubber material.
In the prior art, the research in relation to modified Nano white carbon black filled rubber material mainly passes through coupling agent or surface
Activating agent, graft polymers coating modification Nano carbon white particle surface filled rubber material method prepare.Such as: Qiu Quanfang
(" latex blending method " natural rubber/silicon dioxide nano composite material micro-structure and property control, 2010, University Of Hainan is large
Scholar's paper) study example high-performance NR composite material: natural rubber/silica nanometer composite wood is prepared using latex blending method
Material first uses γ-methacryloxypropyl trimethoxy silane coupling agent (MPS) modified manometer silicon dioxide (SiO2), then
Upper polymethyl methacrylate (PMMA), which is grafted, through emulsion polymerization obtains the nano-silicon dioxide particle (SiO of core-shell structure2-
MPS-PMMA finally it is directly blended with the modified Heveatex (NR-PMMA) of MMA), natural rubber/silica is made
Nanocomposite.Li Wen Ji et al. is prepared for clay/white carbon black compounded mix by drying process with atomizing, for substituting part
White carbon black, to enhance solution polymerized butadiene styrene rubber/butadiene rubber composite material jointly.Patent CN 101798473A uses multi-sulfur silane
Acceptor modified white carbon black then prepares silica/carbon black compounded mix.Patent CN201305854136A passes through poly-dopamine
Modified white carbon black is being kneaded with rubber raw rubber and auxiliary agent, is being vulcanized, and rubber composition is prepared.Although the above method is improved and is received
The compatibility of off-white carbon black and rubber matrix, but these methods are there are still certain limitation, using graft polymers it is modified and
When inorganic material surface coating modification Nano carbon white, it is longer that there are reaction time consumptions, and energy consumption is higher and causes serious pollution to the environment, operation
The disadvantages of complicated；And when utilizing coupling agent or surfactant-modified Nano carbon white, it will lead to rubber material vulcanization delay, draw
Playing cured properties reduces, and need to add vulcanizing agent and promotor causes processing cost to improve, and followed by dispersion stabilization is poor and easy
Again the disadvantages of reuniting.
Summary of the invention
It is an object of that present invention to provide a kind of rubber composition of white carbon black containing modified Nano, the rubber composition is for taking turns
There are preferable wearability, lower rolling resistance when tire tread.The invention uses unsaturated carboxylic acid polar monomer and aryl ethylene
Class monomer prepares modified Nano white carbon black using situ aggregation method, then directly mixes, is agglomerated to prepare with styrene butadiene rubber latex
The rubber composition of high-performance tire tread rubber.The invention not only efficiently solves the problems, such as the easy to reunite of Nano carbon white, and
And also solve the problems, such as Nano carbon white and rubber matrix binding force difference and dispersion is uneven, impart the composition high abrasion,
The performance of low friction.Present invention further propose that the preparation method of the composition.
A kind of rubber composition for tire tread of the present invention, with the quality of styrene butadiene rubber latex butt matter for percent
Hundred meters, mainly include following component:
(1) styrene butadiene rubber latex (butt matter) 100%
(2) modified Nano white carbon black 15~40%
Wherein, the modified Nano white carbon black is to use unsaturated carboxylic acid polar monomer and aryl ethylene class monomer,
It is prepared under initiator effect by situ aggregation method.White carbon black is selected from nanoscale, partial size are as follows: 20~60nm.It is unsaturated
Carboxylic acid polar monomer is selected from one of acrylic acid (AA), methacrylic acid (MAA), maleic anhydride (MAH), preferably acrylic acid
(AA), dosage are as follows: 1%~5%.Aryl ethylene class monomer is selected from styrene, α-methylstyrene, 2- propenyl benzene, ethylo benzene
The mixture of one or more of ethylene and their derivative, optimization styrene.Initiator is water-soluble thermal initiator, choosing
From bis- (the 2- amidine oxazoline propane) hydrochlorides of ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, 2,2- azo, 2,2- azo [2- (2- miaow
Oxazoline -2- base) propane] one or more of dihydrochloride mixture, preferred potassium peroxydisulfate.
Styrene butadiene rubber latex of the present invention is to pass through cream by conjugated diene hydrocarbon compound and aryl ethylene class compound
Liquid polymerization is copolymerized.Conjugated diene hydrocarbon compound is C4Class conjugated diene hydrocarbon compound.Aryl ethylene class compound can be
Styrene, α-methylstyrene, 2- propenyl benzene, ethyl styrene and their derivative.The wherein solid content 20 of styrene-butadiene latex
~45%, combinated styrene content content 15~25%, 50~200nm of latex particle size.
The preparation of rubber composition of the present invention carries out in condensing field, and specific preparation process includes the following steps:
(1) preparation of modified Nano white carbon black:
A. prepared by monomer pre-emulsion: based on the mass parts of aryl ethylene class monomer, by 100 parts of aryl ethylene class monomers, 2
~10 parts of emulsifiers, 200~300 parts of deionized waters, 1.0~2.0 parts of buffers, 0.01~0.1 part of initiator are put into togerther instead
It answers in device, when being warming up to 50~70 DEG C, is stirred to react 30~60 minutes and is prepared into monomer pre-emulsion.
B. based on the mass parts of Nano carbon white, 100 parts of Nano carbon whites and 1.0 preparation of modified Nano white carbon black: are taken
~5.0 parts of unsaturated carboxylic acid polar monomers, 300~500 parts of deionized waters, 1~6 part of buffer are added to stir in polymeric kettle and mix
Close 10~30min；Then 1~5 part of emulsifier, 1~5 part of monomer pre-emulsion is added, stirring is warming up to 50~70 DEG C, is stirred for
It mixes 10~30min and generates and gathered centered on Nano carbon white powder by what carboxylic acid polar monomer and aryl ethylene class monomer coated
Zoarium, and using this as the seed of multiple emulsion；Then 20~40 parts of monomer pre-emulsions and 0.05~0.2 part of initiation are added
Agent after reacting 3.0~5.0h, is eventually adding 0.1~0.5 part of terminator, and modified Nano is made in washed, dehydration, dry, grinding
White carbon black.
(2) based on the mass parts of styrene-butadiene latex butt matter, 100 parts the tire tread preparation of butadiene-styrene rubber composition: are taken
Styrene-butadiene latex (butt matter) and 1~4 part of emulsifier, 100~200 parts of deionized waters are added in condensing field and are stirred 10~
Then 15~40 parts of modified Nano white carbon blacks are added in 30min, be 8~10 with buffer regulation system pH value, be warming up to 50~70
DEG C when, be stirred 30~60min, 3~6 parts of flocculating agents be then added and are condensed, last washed, dehydration, dry, briquetting
Tire tread butadiene-styrene rubber composition is made.
The present invention is not specially limited used emulsifier, flocculating agent, buffer, terminator etc., is all made of this
The general conven-tional adjuvants in field, additional amount are also the routine that those skilled in the art can be calculated according to the dosage of dry glue
Dosage, the present invention also do not do particular determination.
Cohesion of the present invention, poly- using acid cure, the technology is general for those skilled in the art, the flocculating agent
Usually inorganic acid, such as the mixture of one or more of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid.
Emulsifier of the present invention is known to those skilled in the art, is anion emulsifier and nonionic emulsifier
One or more of mixture, selected from fatty acid soaps, RA rosin acid, neopelex, lauryl sodium sulfate,
The mixture of one or more of polyoxyethylene sorbitol acid anhydride list olein, preferably neopelex.
Buffer of the present invention is selected from one of sodium carbonate, sodium bicarbonate, sodium hydroxide, ammonium hydroxide, ammonium hydrogen carbonate,
It is preferred that sodium hydroxide.
Terminator of the present invention is selected from the mixing of one or more of diethyl hydroxylamine, hydroxyl sulfate, Sodium Dimethyldithiocarbamate
Object.
The particle diameter for the Nano carbon white that the present invention uses is small, and the large specific surface area of particle, surface can be high, easily generation phase
Mutual agglomeration only is difficult to allow ultrafine particle in rubber by traditional method of modifying such as mechanical stirring or activating agent surface treatment
It is in nano-dispersion in matrix, Ultrafine effect is difficult to play.In order to solve this problem, first to Nano carbon white particle surface
Functional modification is carried out, foring one kind by " hydrogen bond action " in nanoparticle surface with anchoring group carboxylic acid is back, virtue
Base ethylene compounds are a kind of high dispersive structure of tail (see attached drawing one).Exist since this high dispersive structure contains benzene ring structure
The very big separation layer of one of steric hindrance is formed between nanoparticle, the mutual absorption that can significantly reduce particle surface silicone hydroxyl is made
With, hinder particle between mutual reunion, can be realized and steadily exist with single particle shape.Secondly, modified Nano is white
The aryl ethylene class compound as solvent chain on carbon black particle surface is identical as butadiene-styrene rubber molecular chain structure, according to similar
Compatibility principle has good compatibility, then changes without any later period between modified Nano hard charcoal black track producing particle and styrene-butadiene latex matrix
Property is achieved that Nano carbon white particle being uniformly dispersed in styrene-butadiene latex, to obtain the tire of high comprehensive performance
Face butadiene-styrene rubber composition.
Finally, Nano carbon white particle is not by opening in preparation process of the tire tread with butadiene-styrene rubber composition
Mill and mixer carry out mixing and mixing to process, but directly prepare with styrene-butadiene latex blending, cohesion.This avoid
The skidding of sizing material work in-process appearance, disperses the problems such as uneven at incipient scorch.Preparation method is simple and easy, low in cost, to environment
It is pollution-free, it is suitble to industrialized production.
Detailed description of the invention
Fig. 1 is the high dispersive structure chart of Nano carbon white particle surface.1 is using vinylaromatic polymer chain as tail in figure
Solvent chain；2 is using carboxylic acid groups as the anchoring group of anchor point；3 be Nano carbon white particle.
Specific embodiment
Following embodiment and comparative example are enumerated to illustrate invention effect of the invention, but protection scope of the present invention is not
It is only limitted in these embodiment and comparative examples." part " described in embodiment and comparative example each means mass parts.
(1) raw material sources:
(2) analysis test method:
0 DEG C and 60 DEG C of fissipation factors: being analyzed using the DMA Q800 type dynamic thermomechanical analysis apparatus of TA company,
Select double cantilever chucks.In -150 DEG C~100 DEG C temperature programmings, heating rate is 3 DEG C/min, amplitude 10
μm, test frequency is respectively 1Hz, 5Hz, 10Hz, dynamic force 1N.
Carbon black dispension degree: method in standard GB/T6030-1985 is executed.
Akron abrasion volume；Method in execution standard GB/T 25262-2010.
Embodiment 1
(1) preparation of modified Nano white carbon black:
A. the preparation of monomer pre-emulsion: in terms of the mass parts of styrene, by 100 parts of styrene, 2.5 parts of detergent alkylates
Sodium sulfonate, 200 parts of deionized waters, 1.2 parts of sodium hydroxides, 0.03 part of potassium peroxydisulfate are put into togerther in reactor, are warming up to 60 DEG C
When, it is stirred to react and is prepared within 35 minutes styrene pre-emulsion a.
B. in terms of the mass parts of Nano carbon white, 100 parts of Nano carbon whites and 2.0 preparation of modified Nano white carbon black: are taken
Part acrylic acid (AA), 300 parts of deionized waters, 1.0 parts of sodium hydroxides are added in polymeric kettle and are stirred 20min；Then it is added
1.2 parts of neopelexes, 1.5 parts of styrene pre-emulsion a, stirring are warming up to 65 DEG C, are stirred for mixing 20min and generate
The seed of multiple emulsion centered on Nano carbon white powder；Then 25 parts of styrene pre-emulsion a and 0.07 part are added
Potassium peroxydisulfate after reacting 3.0h, is eventually adding 0.1 part of diethyl hydroxylamine, and modified Nano is made in washed, dehydration, dry, grinding
White carbon black.
(2) tire tread is with the preparation of butadiene-styrene rubber composition: in terms of the mass parts of styrene-butadiene latex, taking 100 parts of butadiene-styrene rubbers
Newborn SBR1500 (butt matter) and 1.5 parts of neopelexes, 150 parts of deionized waters are added in condensing field and are stirred
Then 17 parts of modified Nano white carbon blacks are added in 15min, be 8.5 with sodium hydroxide regulation system pH value, when being warming up to 60 DEG C, stir
Mixing 35min is mixed, 3.5 parts of sulfuric acid are then added and are condensed, last washed, dehydration, dry, briquetting are made tire tread and use
Butadiene-styrene rubber composition.Sampling analysis: standard sample is made through vulcanization, test performance is shown in Table 1.
Embodiment 2
(1) preparation of modified Nano white carbon black:
A. the preparation of monomer pre-emulsion: with embodiment 1.
B. in terms of the mass parts of Nano carbon white, 100 parts of Nano carbon whites and 1.0 preparation of modified Nano white carbon black: are taken
Part acrylic acid (AA), 350 parts of deionized waters, 2.0 parts of sodium hydroxides are added in polymeric kettle and are stirred 20min；Then it is added
2.5 parts of neopelexes, 2.0 parts of styrene pre-emulsion a, stirring are warming up to 65 DEG C, are stirred for mixing 25min and generate
The seed of multiple emulsion centered on Nano carbon white powder；Then 20 parts of styrene pre-emulsion a and 0.09 part are added
Potassium peroxydisulfate after reacting 4.0h, is eventually adding 0.2 part of diethyl hydroxylamine, and modified Nano is made in washed, dehydration, dry, grinding
White carbon black.Sampling analysis: standard sample is made, performance is shown in Table 1 after tested.
(2) tire tread is with the preparation of butadiene-styrene rubber composition: in terms of the mass parts of styrene-butadiene latex, taking 100 parts of butadiene-styrene rubbers
Newborn SBR1500 (butt matter) and 1.0 parts of neopelexes, 120 parts of deionized waters are added in condensing field and are stirred
Then 15 parts of modified Nano white carbon blacks are added in 10min, be 8.6 with sodium hydroxide regulation system pH value, when being warming up to 60 DEG C, stir
Mixing 40min is mixed, 3.0 parts of sulfuric acid are then added and are condensed, last washed, dehydration, dry, briquetting are made tire tread and use
Butadiene-styrene rubber composition.Sampling analysis: standard sample is made through vulcanization, test performance is shown in Table 1.
Embodiment 3
(1) preparation of modified Nano white carbon black:
A. the preparation of monomer pre-emulsion: in terms of the mass parts of styrene, by 100 parts of styrene, 5 parts of detergent alkylate sulphurs
Sour sodium, 240 parts of deionized waters, 1.5 parts of sodium hydroxides, 0.05 part of potassium peroxydisulfate are put into togerther in reactor, when being warming up to 55 DEG C,
It is stirred to react and is prepared within 40 minutes styrene pre-emulsion b.
The preparation of b modified Nano white carbon black: in terms of the mass parts of Nano carbon white, 100 parts of Nano carbon whites and 2.5 parts are taken
Acrylic acid (AA), 370 parts of deionized waters, 2.5 parts of sodium hydroxides are added in polymeric kettle and are stirred 25min；Then 3 parts are added
Neopelex, 2.5 parts of styrene pre-emulsion b, stirring are warming up to 65 DEG C, are stirred for mixing 25min and generate to receive
The seed of multiple emulsion centered on rice white carbon black powder；Then 30 parts of styrene pre-emulsion b and 0.12 part of over cure are added
Sour potassium after reacting 4.0h, is eventually adding 0.25 part of diethyl hydroxylamine, washed, dehydration, dry, the obtained modified Nano of grinding is white
Carbon black.
(2) tire tread is with the preparation of butadiene-styrene rubber composition: in terms of the mass parts of styrene-butadiene latex, taking 100 parts of butadiene-styrene rubbers
Newborn SBR1500 (butt matter) and 2.0 parts of neopelexes, 160 parts of deionized waters are added in condensing field and are stirred
Then 25 parts of modified Nano white carbon blacks are added in 20min, be 8.9 with sodium hydroxide regulation system pH value, when being warming up to 60 DEG C, stir
Mixing 45min is mixed, 4.0 parts of sulfuric acid are then added and are condensed, last washed, dehydration, dry, briquetting are made tire tread and use
Butadiene-styrene rubber composition.Sampling analysis: standard sample is made through vulcanization, test performance is shown in Table 1.
Embodiment 4
(1) preparation of modified Nano white carbon black:
The preparation of a monomer pre-emulsion: with embodiment 3.
The preparation of b modified Nano white carbon black: in terms of the mass parts of Nano carbon white, 100 parts of Nano carbon whites and 3.0 parts are taken
Acrylic acid (AA), 380 parts of deionized waters, 2.7 parts of sodium hydroxides are added in polymeric kettle and are stirred 25min；Then 4 parts are added
Neopelex, 3.8 parts of styrene pre-emulsion b, stirring are warming up to 65 DEG C, are stirred for mixing 25min and generate to receive
The seed of multiple emulsion centered on rice white carbon black powder；Then 32 parts of styrene pre-emulsion b and 0.14 part of over cure are added
Sour potassium after reacting 4.0h, is eventually adding 0.27 part of diethyl hydroxylamine, washed, dehydration, dry, the obtained modified Nano of grinding is white
Carbon black.
(2) tire tread is with the preparation of butadiene-styrene rubber composition: in terms of the mass parts of styrene-butadiene latex, taking 100 parts of butadiene-styrene rubbers
Newborn SBR1500 (butt matter) and 3.0 parts of neopelexes, 170 parts of deionized waters are added in condensing field and are stirred
Then 30 parts of modified Nano white carbon blacks are added in 25min, be 8.7 with sodium hydroxide regulation system pH value, when being warming up to 65 DEG C, stir
Mixing 50min is mixed, 4.5 parts of hydrochloric acid are then added and are condensed, last washed, dehydration, dry, briquetting are made tire tread and use
Butadiene-styrene rubber composition.Sampling analysis: standard sample is made through vulcanization, test performance is shown in Table 1.
Embodiment 5
(1) preparation of modified Nano white carbon black:
A. prepared by monomer pre-emulsion: in terms of the mass parts of α-methylstyrene, by 100 parts of α-methylstyrenes, 10 parts
Neopelex, 300 parts of deionized waters, 1.8 parts of sodium hydroxides, 0.1 part of ammonium persulfate are put into togerther in reactor, are risen
When temperature is to 70 DEG C, it is stirred to react 60 minutes and is prepared into α-methylstyrene pre-emulsion.
B. in terms of the mass parts of Nano carbon white, 100 parts of Nano carbon whites and 4.5 preparation of modified Nano white carbon black: are taken
Part maleic anhydride (MAH), 400 parts of deionized waters, 2.8 parts of sodium hydroxides are added in polymeric kettle and are stirred 25min；Then plus
Enter 4.5 parts of neopelexes, 4.2 parts of α-methylstyrene pre-emulsion c, stirring is warming up to 65 DEG C, is stirred for mixing
30min generates the seed of the multiple emulsion centered on Nano carbon white powder；Then it is pre- that 37 parts of α-methylstyrenes are added
Emulsion and 0.17 part of ammonium persulfate are eventually adding 0.29 part of diethyl hydroxylamine after reacting 4.0h, washed, dehydration, it is dry,
It grinds and modified Nano white carbon black is made.
(2) tire tread is with the preparation of butadiene-styrene rubber composition: in terms of the mass parts of styrene-butadiene latex, taking 100 parts of butadiene-styrene rubbers
Newborn SBR1502 (butt matter) and 3.5 parts of neopelexes, 190 parts of deionized waters are added in condensing field and are stirred
Then 35 parts of modified Nano white carbon blacks are added in 25min, be 9.2 with sodium hydroxide regulation system pH value, when being warming up to 65 DEG C, stir
Mixing 55min is mixed, 5.0 parts of hydrochloric acid are then added and are condensed, last washed, dehydration, dry, briquetting are made tire tread and use
Butadiene-styrene rubber composition.Sampling analysis: standard sample is made through vulcanization, test performance is shown in Table 1.
Embodiment 6
(1) preparation of modified Nano white carbon black:
A. prepared by monomer pre-emulsion: with embodiment 6
B. in terms of the mass parts of Nano carbon white, 100 parts of Nano carbon whites and 5.0 preparation of modified Nano white carbon black: are taken
Part maleic anhydride (MAH), 500 parts of deionized waters, 6.0 parts of sodium hydroxides are added in polymeric kettle and are stirred 30min；Then plus
Enter 5.0 parts of neopelexes, 5.0 parts of α-methylstyrene pre-emulsion c, stirring is warming up to 70 DEG C, is stirred for mixing
30min generates the seed of the multiple emulsion centered on Nano carbon white powder；Then it is pre- that 40 parts of α-methylstyrenes are added
Emulsion c and 0.2 part of ammonium persulfate after reacting 5.0h, are eventually adding 0.5 part of diethyl hydroxylamine, and washed, dehydration, is ground at drying
Grind to obtain modified Nano white carbon black.
(2) tire tread is with the preparation of butadiene-styrene rubber composition: in terms of the mass parts of styrene-butadiene latex, taking 100 parts of butadiene-styrene rubbers
Newborn SBR1502 (butt matter) and 4.0 parts of neopelexes, 200 parts of deionized waters are added in condensing field and are stirred
Then 40 parts of modified Nano white carbon blacks are added in 30min, be 9.5 with sodium hydroxide regulation system pH value, when being warming up to 70 DEG C, stir
Mixing 60min is mixed, 6.0 parts of nitric acid are then added and are condensed, last washed, dehydration, dry, briquetting are made tire tread and use
Butadiene-styrene rubber composition.Sampling analysis: standard sample is made through vulcanization, test performance is shown in Table 1.
Comparative example 1
(1) preparation of modified Nano white carbon black:
The preparation of a monomer pre-emulsion: with embodiment 1.
The preparation of b modified Nano white carbon black: with embodiment 1.
(2) preparation of tire tread butadiene-styrene rubber composition: other conditions are same as Example 1, the difference is that
The additional amount of modified Nano white carbon black is 10 parts in preparation process, it may be assumed that takes 100 parts of styrene-butadiene latex SBR1500 (butt matter) and 1.5
Part neopelex, 150 parts of deionized waters are added in condensing field and are stirred 15min, and 10 parts of modifications are then added
Nano carbon white is 8.5 with sodium hydroxide regulation system pH value, when being warming up to 60 DEG C, is stirred 35min, is then added 3.5
Part sulfuric acid is condensed, and tire tread butadiene-styrene rubber composition is made in last washed, dehydration, dry, briquetting.Sampling point
Analysis: standard sample is made through vulcanization, test performance is shown in Table 1.
Comparative example 2
The preparation of tire tread butadiene-styrene rubber composition: other conditions are same as Example 2, the difference is that preparation
Modified Nano white carbon black is not added in the process, but is directly added into unmodified Nano carbon white, additional amount is 15 parts, it may be assumed that is taken
100 parts of styrene-butadiene latex SBR1500 (butt matter) and 1.0 parts of neopelexes, 120 parts of deionized waters are added to condensing field
In be stirred 10min, then be added 15 parts of unmodified Nano carbon whites, with sodium hydroxide regulation system pH value be 8.6, heating
When to 60 DEG C, it is stirred 40min, 3.0 parts of sulfuric acid are then added and are condensed, last washed, dehydration, dry, briquetting system
Obtain tire tread butadiene-styrene rubber composition.Sampling analysis: standard sample is made through vulcanization, test performance is shown in Table 1.
Comparative example 3
(1) preparation of modified Nano white carbon black: other conditions are same as Example 3, the difference is that in-situ polymerization mistake
Styrene pre-emulsion b is not added in journey, it may be assumed that take 100 parts of Nano carbon whites and 2.5 parts of acrylic acid (AA), 370 parts of deionized waters,
2.5 parts of sodium hydroxides are added in polymeric kettle and are stirred 25min；Then 3 parts of neopelexes, stirring heating is added
To 65 DEG C, it is stirred for the seed that mixing 25min generates the multiple emulsion centered on Nano carbon white powder；Then it adds
0.12 part of potassium peroxydisulfate after reacting 4.0h, is eventually adding 0.25 part of diethyl hydroxylamine, and washed, dehydration, dry, grinding are made
Modified Nano white carbon black a.
(2) preparation of tire tread butadiene-styrene rubber composition: other conditions are same as Example 3, the difference is that
Modified Nano white carbon black is not added in preparation process, but is directly added into modified Nano white carbon black a, additional amount is 25 parts, it may be assumed that is taken
100 parts of styrene-butadiene latex SBR1500 (butt matter) and 2.0 parts of neopelexes, 160 parts of deionized waters are added to condensing field
In be stirred 20min, then be added 25 parts of modified Nano white carbon black a, with sodium hydroxide regulation system pH value be 8.9, heating
When to 60 DEG C, it is stirred 45min, 4.0 parts of sulfuric acid are then added and are condensed, last washed, dehydration, dry, briquetting system
Obtain tire tread butadiene-styrene rubber composition.Sampling analysis: standard sample is made through vulcanization, test performance is shown in Table 1.
Comparative example 4
(1) preparation of modified Nano white carbon black:
A. prepared by monomer pre-emulsion: with embodiment 3.
B. the preparation of modified Nano white carbon black: other conditions are same as Example 4, the difference is that in-situ polymerization process
In initiator potassium persulfate is not added, 1,3- hexadiene pre-emulsion b is that dialogue carbon black particle surface is coated, it may be assumed that takes 100
Part Nano carbon white and 3.0 parts of acrylic acid (AA), 380 parts of deionized waters, 2.7 parts of sodium hydroxides are added to stir in polymeric kettle and mix
Close 25min；Then 4 parts of neopelexes, 3.8 parts of styrene pre-emulsion b are added, stirring is warming up to 65 DEG C, then stirs
Mix the seed that mixing 25min generates the multiple emulsion centered on Nano carbon white powder；Then it is pre- that 32 parts of styrene are added
Emulsion b after reacting 4.0h, is eventually adding 0.27 part of diethyl hydroxylamine, and modified Nano is made in washed, dehydration, dry, grinding
White carbon black b.
(2) preparation of tire tread butadiene-styrene rubber composition: other conditions are same as Example 4, the difference is that
Modified Nano white carbon black is not added in preparation process, but is directly added into modified Nano white carbon black b, additional amount is 30 parts, it may be assumed that is taken
100 parts of styrene-butadiene latex SBR1500 (butt matter) and 3.0 parts of neopelexes, 170 parts of deionized waters are added to condensing field
In be stirred 25min, then be added 30 parts of modified Nano white carbon black b, with sodium hydroxide regulation system pH value be 8.7, heating
When to 65 DEG C, it is stirred 50min, 4.5 parts of hydrochloric acid are then added and are condensed, last washed, dehydration, dry, briquetting system
Obtain tire tread butadiene-styrene rubber composition.Sampling analysis: standard sample is made through vulcanization, test performance is shown in Table 1.
Comparative example 5
(1) preparation of modified Nano white carbon black:
A. prepared by monomer pre-emulsion: with embodiment 5.
B. the preparation of modified Nano white carbon black: other conditions are same as Example 5, the difference is that in preparation process not
Add maleic anhydride (MAH), it may be assumed that 100 parts of Nano carbon whites, 400 parts of deionized waters, 2.8 parts of sodium hydroxides is taken to be added to polymeric kettle
In be stirred 25min；Then 4.5 parts of neopelexes, 4.2 parts of α-methylstyrene pre-emulsion c, stirring is added
65 DEG C are warming up to, the seed that mixing 30min generates the multiple emulsion centered on Nano carbon white powder is stirred for；Then add again
Enter 37 parts of α-methylstyrene pre-emulsions and 0.17 part of ammonium persulfate, after reacting 4.0h, is eventually adding 0.29 part of diethyl hydroxyl
Modified Nano white carbon black c is made in amine, washed, dehydration, dry, grinding.
(2) preparation of tire tread butadiene-styrene rubber composition: other conditions are same as Example 5, the difference is that
Modified Nano white carbon black is not added in preparation process, but is directly added into modified Nano white carbon black c, additional amount is 35 parts, it may be assumed that is taken
100 parts of styrene-butadiene latex SBR1502 (butt matter) and 3.5 parts of neopelexes, 190 parts of deionized waters are added to condensing field
In be stirred 25min, then be added 35 parts of modified Nano white carbon black c, with sodium hydroxide regulation system pH value be 9.2, heating
When to 65 DEG C, it is stirred 55min, 5.0 parts of hydrochloric acid are then added and are condensed, last washed, dehydration, dry, briquetting system
Obtain tire tread butadiene-styrene rubber composition.Sampling analysis: standard sample is made through vulcanization, test performance is shown in Table 1.
Comparative example 6
The preparation of tire tread butadiene-styrene rubber composition: other conditions are same as Example 6, the difference is that preparation
Modified Nano white carbon black is not added in the process, but is directly added into unmodified Nano carbon white, additional amount is 40 parts, it may be assumed that is taken
100 parts of styrene-butadiene latex SBR1502 (butt matter) and 4.0 parts of neopelexes, 200 parts of deionized waters are added to condensing field
In be stirred 30min, then be added 40 parts of unmodified Nano carbon whites, with sodium hydroxide regulation system pH value be 9.5, heating
When to 70 DEG C, it is stirred 60min, 6.0 parts of nitric acid are then added and are condensed, last washed, dehydration, dry, briquetting system
Obtain tire tread butadiene-styrene rubber composition.Sampling analysis: standard sample is made through vulcanization, test performance is shown in Table 1.
The performance of table 1 tire tread butadiene-styrene rubber composition
As shown in Table 1: 0 DEG C of tan δ of embodiment is higher than comparative example, illustrates that the wet-sliding resistant performance for tire preparation is good；It is real
60 DEG C of fissipation factors (tan δ) and the wear volume for applying example are all lower than comparative example, illustrate for tire preparation rolling resistance it is low,
Wearability is good.
Claims (19)
1. a kind of rubber composition of white carbon black containing modified Nano, main to wrap in terms of the mass parts of styrene butadiene rubber latex butt matter
Include following component:
(1) 100 parts of styrene butadiene rubber latex
(2) 15~40 parts of modified Nano white carbon black
It is characterized in that, the modified Nano white carbon black the preparation method comprises the following steps:
Based on the mass parts of Nano carbon white, take 100 parts of Nano carbon whites and 1.0~5.0 parts of unsaturated carboxylic acid polar monomers,
300~500 parts of deionized waters, 1~6 part of buffer are added in polymeric kettle and are stirred 10~30min；Then it is added 1~5 part
Emulsifier, 1~5 part of aryl ethylene class monomer pre-emulsion, stirring are warming up to 50~70 DEG C, and it is raw to be stirred for 10~30min of mixing
At the condensate coated centered on Nano carbon white powder by carboxylic acid polar monomer and aryl ethylene class monomer, and using this as
The seed of multiple emulsion；Then 20~40 parts of aryl ethylene class monomer pre-emulsions and 0.05~0.2 part of initiator are added, instead
After answering 3.0~5.0h, it is eventually adding 0.1~0.5 part of terminator, modified Nano hard charcoal is made in washed, dehydration, dry, grinding
It is black.
2. rubber composition as described in claim 1, which is characterized in that the partial size of the modified Nano white carbon black are as follows: 20~
60nm。
3. rubber composition as described in claim 1, which is characterized in that the unsaturated carboxylic acid polar monomer is selected from propylene
One of acid, methacrylic acid, maleic anhydride.
4. rubber composition as claimed in claim 3, which is characterized in that the unsaturated carboxylic acid polar monomer is acrylic acid.
5. rubber composition as described in claim 1, which is characterized in that the aryl ethylene class monomer is selected from styrene, α-
The mixture of one or more of methyl styrene, 2- propenyl benzene, ethyl styrene and their derivative.
6. rubber composition as claimed in claim 5, which is characterized in that the aryl ethylene class monomer is styrene.
7. rubber composition as described in claim 1, which is characterized in that the initiator is water-soluble thermal initiator, is selected from
Bis- (the 2- amidine oxazoline propane) hydrochlorides of ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, 2,2- azo, 2,2- azo [2- (2- imidazoles
Quinoline -2- base) propane] dihydrochloride one or more of mixtures.
8. rubber composition as claimed in claim 7, which is characterized in that the initiator is potassium peroxydisulfate.
9. rubber composition as described in claim 1, which is characterized in that the styrene butadiene rubber latex is by conjugated diene hydrocarbonylation
It closes object and aryl ethylene class compound is copolymerized by emulsion polymerization.
10. rubber composition as claimed in claim 9, which is characterized in that the conjugated diene hydrocarbon compound is C4Class conjugation two
Olefin(e) compound.
11. rubber composition as claimed in claim 9, which is characterized in that the aryl ethylene class compound be selected from styrene,
One of α-methylstyrene, 2- propenyl benzene, ethyl styrene and their derivative.
12. such as the described in any item rubber compositions of claim 9~11, which is characterized in that the styrene butadiene rubber latex is consolidated
Content is 20~45%, and combinated styrene content content is 15~25%, and latex particle size is 50~200nm.
13. a kind of preparation method of the rubber composition as described in one of claim 1~12, includes the following steps:
(1) in terms of the mass parts of styrene-butadiene latex butt matter, take 100 parts of styrene-butadiene latexes and 1~4 part of emulsifier, 100~200 parts go from
Sub- water, which is added in condensing field, is stirred 10~30min；
(2) 15~40 parts of modified Nano white carbon blacks are added in condensing field, is 8~10 with buffer regulation system pH value, rises
When temperature is to 50~70 DEG C, it is stirred 30~60min；
(3) 3~6 parts of flocculating agents are added in condensing field to be condensed, the rubber is made in last washed, dehydration, dry, briquetting
Glue composition.
14. method as claimed in claim 13, which is characterized in that the flocculating agent is hydrochloric acid, in sulfuric acid, phosphoric acid, nitric acid
One or more of mixtures.
15. method as claimed in claim 13, which is characterized in that the emulsifier is anion emulsifier and non-ionic emulsifier
The mixture of one or more of agent.
16. method as claimed in claim 15, which is characterized in that the emulsifier is selected from fatty acid soaps, RA rosin acid, 12
The mixture of one or more of sodium alkyl benzene sulfonate, lauryl sodium sulfate, polyoxyethylene sorbitol acid anhydride list olein.
17. the method described in claim 16, which is characterized in that the emulsifier is neopelex.
18. method as claimed in claim 13, which is characterized in that the buffer is selected from sodium carbonate, sodium bicarbonate, hydroxide
One of sodium, ammonium hydroxide, ammonium hydrogen carbonate.
19. method as claimed in claim 18, which is characterized in that the buffer is sodium hydroxide.
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| CA3084127A1 (en) * | 2017-12-21 | 2019-06-27 | Compagnie Generale Des Etablissements Michelin | Diacid-crosslinked rubber composition comprising a phenolic compound |
| CN111073079B (en) * | 2018-10-18 | 2022-03-29 | 中国石油天然气股份有限公司 | Rubber composition for anti-slippery tire and preparation method thereof |
| CN119119585A (en) * | 2023-06-13 | 2024-12-13 | 中国石油天然气股份有限公司 | Rubber filler, rubber composite material containing the same, and preparation method and application thereof |
| CN117986407B (en) * | 2024-01-10 | 2025-04-01 | 青岛福诺化工科技有限公司 | A latex flocculation method, rubber masterbatch and preparation method and rubber composition |
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