CN107266940A - Modification method of nano white carbon black - Google Patents
Modification method of nano white carbon black Download PDFInfo
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- CN107266940A CN107266940A CN201610217677.XA CN201610217677A CN107266940A CN 107266940 A CN107266940 A CN 107266940A CN 201610217677 A CN201610217677 A CN 201610217677A CN 107266940 A CN107266940 A CN 107266940A
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- Prior art keywords
- parts
- modifying
- white carbon
- white
- carbon black
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000006229 carbon black Substances 0.000 title abstract description 22
- 238000002715 modification method Methods 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 238000002360 preparation method Methods 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000002245 particle Substances 0.000 claims abstract description 27
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 150000001993 dienes Chemical class 0.000 claims abstract description 13
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 83
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 63
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical group CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 44
- 238000003756 stirring Methods 0.000 claims description 37
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000000839 emulsion Substances 0.000 claims description 34
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 29
- 239000000843 powder Substances 0.000 claims description 22
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 17
- 238000000227 grinding Methods 0.000 claims description 16
- 238000010792 warming Methods 0.000 claims description 16
- 239000003643 water by type Substances 0.000 claims description 15
- 230000018044 dehydration Effects 0.000 claims description 14
- 238000006297 dehydration reaction Methods 0.000 claims description 14
- 150000003926 acrylamides Chemical class 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 10
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 claims description 5
- 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 5
- 239000003995 emulsifying agent Substances 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000000872 buffer Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 2
- OAOZZYBUAWEDRA-UHFFFAOYSA-N 3,4-dimethylidenehexane Chemical compound CCC(=C)C(=C)CC OAOZZYBUAWEDRA-UHFFFAOYSA-N 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- IMJGQTCMUZMLRZ-UHFFFAOYSA-N buta-1,3-dien-2-ylbenzene Chemical compound C=CC(=C)C1=CC=CC=C1 IMJGQTCMUZMLRZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 claims description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 claims 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims 1
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims 1
- 229920001971 elastomer Polymers 0.000 abstract description 8
- 239000005060 rubber Substances 0.000 abstract description 8
- 238000012545 processing Methods 0.000 abstract description 5
- 238000005054 agglomeration Methods 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 4
- 239000000945 filler Substances 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 230000004888 barrier function Effects 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 241000872198 Serjania polyphylla Species 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 27
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 27
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 23
- 229920000642 polymer Polymers 0.000 description 19
- 238000004458 analytical method Methods 0.000 description 17
- 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 14
- 238000005070 sampling Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000009102 absorption Effects 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000004873 anchoring Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000003610 charcoal Substances 0.000 description 5
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000004945 emulsification Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- -1 neopelex Chemical compound 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 229910002808 Si–O–Si Inorganic materials 0.000 description 3
- 238000003556 assay Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000002242 deionisation method Methods 0.000 description 3
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical class CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- SIXWIUJQBBANGK-UHFFFAOYSA-N 4-(4-fluorophenyl)-1h-pyrazol-5-amine Chemical compound N1N=CC(C=2C=CC(F)=CC=2)=C1N SIXWIUJQBBANGK-UHFFFAOYSA-N 0.000 description 2
- HDONYZHVZVCMLR-UHFFFAOYSA-N N=C=O.N=C=O.CC1CCCCC1 Chemical compound N=C=O.N=C=O.CC1CCCCC1 HDONYZHVZVCMLR-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000013536 elastomeric material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- PEUWKAAVXXUTRM-UHFFFAOYSA-N 1-chloropenta-1,3-diene Chemical class CC=CC=CCl PEUWKAAVXXUTRM-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 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 description 1
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OMRDSWJXRLDPBB-UHFFFAOYSA-N N=C=O.N=C=O.C1CCCCC1 Chemical compound N=C=O.N=C=O.C1CCCCC1 OMRDSWJXRLDPBB-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- WJEIYVAPNMUNIU-UHFFFAOYSA-N [Na].OC(O)=O Chemical compound [Na].OC(O)=O WJEIYVAPNMUNIU-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920006247 high-performance elastomer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 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
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- BLUWRIUGZBUUHI-UHFFFAOYSA-N toluene;cyanide Chemical compound N#[C-].CC1=CC=CC=C1 BLUWRIUGZBUUHI-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 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 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/309—Combinations of treatments provided for in groups C09C1/3009 - C09C1/3081
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/3063—Treatment with low-molecular organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/3072—Treatment with macro-molecular organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a method for modifying high-dispersity rubber filler nano white carbon black. According to the preparation method, aliphatic diisocyanate is adopted to modify the nano white carbon black, acrylamide is added to carry out end-capping reaction, then conjugated diene monomer is pre-emulsified and subjected to in-situ polymerization with unsaturated bonds in the acrylamide, so that a barrier layer with a high connection strength and a high dispersion structure is formed on the surface of the nano white carbon black particles, and the preparation method can be used for separating the nano white carbon black particles under the action of high temperature or high shear. The method not only solves the problem of easy agglomeration of the nano white carbon black, endows the nano white carbon black with super-dispersibility, but also avoids the problem of agglomeration again in the processing and blending process, and ensures that the nano white carbon black particles can be uniformly dispersed into a rubber system. The invention has the advantages of simple operation method, low modification cost, small environmental pollution, suitability for industrial production and the like.
Description
Technical field
The present invention relates to a kind of method of modifying as the ultra-dispersed property of synthetic rubber filler nanometer white carbon.
Background technology
It is well known that from the point of view of the Expected Results of inorganic powder filling-modified conjunction rubber, the particle diameter chi of inorganic particle particle
The effect of very little smaller modification is also better, but a technology is inevitably run into the application process of ultrafine inorganic powder
Problem, i.e. superfine powder can be improved with the reduction of particle diameter, specific surface area increase, surface, and autohemagglutination ability is stronger, is more difficult to by rubber
Material is mixed into, infiltrates and disperseed.Therefore scattering problem of the ultrafine inorganic powder in rubber, it has also become prepare high-performance rubber material
The bottleneck of material.
Nano carbon white is porous material, and its composition can use SiO2·nH2O represents, wherein nH2O is with surface hydroxyl
Form is present, and is a kind of white, nontoxic, amorphous, porous attritive powder, with internal surface area is big, dispersible, light weight, resistance to
High temperature, do not burn, the characteristic such as electrical insulating property is good, chemical property is stable.White carbon as it is a kind of environmental protection, excellent performance auxiliary agent,
It is mainly used in the fields such as rubber.Nano carbon white particle diameter is small, bigger than surface, the surface high, surface of energy has substantial amounts of hydroxyl again
Base, causes Nano carbon white easily to be reunited, and is difficult to be uniformly dispersed in the mixed process with elastomeric material, so can not only influence
Filling-modified effect, but also the performance of elastomeric material can be damaged.
In the prior art using common are coupling agent or surfactant-modified, silane coupler, toluene isocyanide are utilized
Acid esters, inorganic mineral, oligomer dialogue are carbon black modified (such as：CN101798473A、CN101817529A、CN101704967A
Deng)；Also graft polymers is modified and inorganic material surface coating modification, such as：Che Jianfei et al. is using paraformaldehyde and a contracting
Diethylene glycol condensation polymerization prepares polyacetals oligomer, using Toluene-2,4-diisocyanate, after 4- diisocyanate activates silica surface
Grafted polyacetal oligomer (South China Science ＆ Engineering University journal 2005,29,33-333).Yellow loyalty soldier et al. uses methacryl (3- tri-
Methoxy silane) propyl ester is to silica surface modified, then by being aggregated in improved silica Surface coating polyphenyl without soap lye
Pvdf layer (macromolecule journal 2004,6,835-835).Although the above method improves the dispersiveness of Nano carbon white particle, increases
The strong compatibility with rubber matrix, but these methods still suffer from certain limitation, are modified using graft polymers and inorganic
During material surface coating modification Nano carbon white, there is that reaction time consumption is longer, energy consumption is higher, the shortcomings of complex operation；And utilize
When coupling agent or surfactant-modified Nano carbon white, there is also consumption is big and production cost is high, dispersion stabilization difference and easy
Again the shortcomings of reuniting.
The content of the invention
Present invention aims at provide a kind of method of modifying of ultra-dispersed property gum filler Nano carbon white.The invention is used
Aliphatic diisocyanate is modified to Nano carbon white, is then added acrylamide and is carried out end capping reaction, then again to altogether
Yoke diolefinic monomer carries out pre-emulsification processing and occurs in-situ polymerization with the unsaturated bond in acrylamide, thus in nanometer hard charcoal
Black track producing particle surface forms a kind of barrier layer of the high ultra-dispersed structure of bonding strength, and reaching can under high temperature or high shear forces
Separate the preparation method of Nano carbon white particle.This method not only solves the easy agglomeration traits of Nano carbon white, imparts
The ultra-dispersed property of Nano carbon white, but also prevent because processing the problem of reuniting once more in blending procedure, it is ensured that receive
Off-white carbon black particle can be evenly dispersed into rubbery system.
" part " of the present invention each means mass parts.
A kind of method of modifying of Nano carbon white as gum filler of the present invention, specific preparation process is：
(1) prepared by monomer pre-emulsion：In parts by mass, by 100 parts of conjugated diene monomers, 5~10 parts of emulsifying agents,
150~200 parts of deionized waters, 1.0~2.0 parts of buffers, 0.01~0.1 part of initiator are put into reactor together, are warming up to
At 40~60 DEG C, stirring reaction is prepared into monomer pre-emulsion in 30~50 minutes.
(2) preparation of ultra-dispersed type Nano carbon white：In parts by mass, 100 parts of Nano carbon whites and 200~400 parts are taken
Deionized water is added to 10~30min of stirring mixing in polymeric kettle；Then add 5~10 parts of aliphatic diisocyanates, 1.0~
2.0 parts of catalyst, are warming up to 40~60 DEG C, then 1~2h of stirring reaction adds 6~12 parts of acrylamides and 0.5~1.0
Generated after 30~60min of part catalyst reaction centered on Nano carbon white powder by aliphatic diisocyanate and acrylamide
The performed polymer coated；20~40 parts of monomer pre-emulsions and 0.5~1.5 part of initiator are finally added, 4.0~6.0h is reacted
0.1~0.5 part of terminator is added afterwards, and ultra-dispersed type Nano carbon white is made in scrubbed, dehydration, dry, grinding.
White carbon of the present invention is nano level, and its particle diameter is：20~60nm.
It is different that aliphatic diisocyanate of the present invention is selected from hexamethylene diisocyanate (HDI), isophorone two
In cyanate (IPDI), dicyclohexyl methyl hydride -4,4'- diisocyanate (MDI), methylcyclohexane diisocyanate (HTDI)
One or more of mixtures, preferably HDI.
Acrylamide of the present invention, its purity >=99%.
Conjugated diene of the present invention is C4~Cl2Conjugated diene, selected from 1,3-butadiene；Isoprene；2,3- bis-
Methyl isophthalic acid, 3 butadiene；2,3- diethyl -1,3 butadiene；2- methyl -3- ethyl -1,3 butadiene；The chloro- 1,3-pentadienes of 2-；
1,3-pentadiene；3- butyl -1,3- octadienes；2- phenyl -1,3-butadiene；One or more of mixing in 1,3- hexadiene
Thing, more preferably isoprene.
Initiator of the present invention is water-soluble thermal initiator, in ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate
One kind, initiator system of ammonium persulfate.
Catalyst of the present invention can be in sodium carbonate, sodium acid carbonate, sodium hydroxide, ammoniacal liquor, ammonium hydrogen carbonate
One kind, preferably sodium hydroxide.
The present invention can use conven-tional adjuvants generally in the art to emulsifying agent, buffer, terminator for being used etc.,
Its addition is also that those skilled in the art can calculate obtained conventional amount used according to the consumption of latex, and the present invention does not do special
Limit.Emulsifying agent as described in the present invention is known to those skilled in the art, can be anion emulsifier and nonionic Emulsion
One or more in agent.Such as：Fatty acid soaps, RA rosin acid, neopelex, dodecyl sulphate can be selected from
One or more in sodium, polyoxyethylene sorbitol acid anhydride list olein, preferably neopelex.
Buffer of the present invention can be selected from one kind in sodium carbonate, sodium acid carbonate, ammonium hydrogen carbonate, preferably carbonic acid
Sodium.
Terminator of the present invention can be selected from the one or more in diethyl hydroxylamine, HAS, Sodium Dimethyldithiocarbamate.
The method of modifying of a kind of super-dispersed nano white carbon of the present invention, with the cyanic acid in aliphatic diisocyanate
Ester group (- NCO) is anchoring group, under the conditions of weak alkaline aqueous solution, and it is anti-to occur chemistry with the hydroxyl on white carbon particle surface
Carbamate should be generated, acrylamide is subsequently added and end-blocking effect is played to cyanic acid ester group, prevent diisocyanate mutually certainly
Inhale and cause the adhesion of hard charcoal black track producing particle, be copolymerized next to that introducing unsaturated bond with conjugated diene monomer, so
It is to carry on the back with conjugated diene polymer as tail using anchoring group-NCO just to be formed a kind of in Nano carbon white particle surface, and logical
Cross " covalent bond " close ultra-dispersed structure for connecting into an entirety (see accompanying drawing 1).Although aliphatic diisocyanate is with single-point
The form of anchoring is adsorbed in white carbon surface, but this anchor point is realized by covalent bond, due to the bond energy of covalent bond
Greatly, there are enough adsorption strengths, also be difficult to depart under high temperature and shear action.Next to that conjugated diene polymer
The characteristics of backbone structure has nonpolar and chain segment length, can effectively hinder Nano carbon white particle because being collided with polyhydroxy
During and occur bonding phenomenon.Therefore, Nano carbon white particle adds with rubber blending under both mutually " synergy "
Can very stably exist with single particle shape during work.In addition, the anchoring group in the present invention can not select fragrance
(cyclo) aliphatic diisocyanates, contain benzene ring structure mainly due to aromatic series (cyclo) aliphatic diisocyanates, and molecule space steric effect is big, hinders
Chemically reacted with the hydroxyl on white carbon particle surface, the anchoring dot density on white carbon surface can be reduced, so in banburying
During the high temperature and shearing of machine and double screw extruder, Nano carbon white particle easily occurs to reunite again, influences its point
Dissipate property.
Present invention efficiently solves the easy agglomeration traits of Nano carbon white, while ensureing point of Nano carbon white particle again
Dissipate processing stability.The present invention has operating method simple, and modified cost is low, and environmental pollution is small, is adapted to industrialized production etc. excellent
Point.
Brief description of the drawings
Fig. 1 is the high dispersive structure chart of Nano carbon white particle surface.1 represents using conjugated diene polymer as tail in figure
Solvent chain, 2 represent anchoring group using cyanic acid ester group as anchor point, and 3 represent hard charcoal black track producing particles.
Fig. 2 is the infrared spectrum spectrogram of white carbon (a) and modified white carbon black (b).It is 1099cm in wave number on a-1Place goes out
Existing Si-O-Si asymmetric stretching vibration absworption peak, is 804cm in wave number-1The symmetrical stretching vibration that Si-O-Si occurs in place absorbs
Peak, is 465cm in wave number-1There is Si-O-Si flexural vibrations absworption peak in place.On b, wave number is 1715-1730cm-1Place goes out
The sharp absworption peak of ester group is showed；Wave number is 3400~3250cm-1Place occurs in that the sharp absworption peak of amide groups；Wave number be 1950~
2150cm-1Place occurs in that the sharp absworption peak of cyanic acid ester group.It can be seen that aliphatic diisocyanate and acrylamide polar monomer
The polymer of generation successful deposition in Nano carbon white particle surface.
Embodiment
Following examples and comparative example is enumerated to illustrate the invention effect of the present invention, but protection scope of the present invention is not
It is only limitted in these embodiments and comparative example." part " described in embodiment and comparative example each means mass parts.
(1) raw material sources：
Other reagents are commercially available industrial goods
(2) analysis test method：
Sample infrared spectrum analysis：Nano carbon white is modified using German Bruke spectral instruments company infrared spectrometer
Front and rear sample carries out functional group analysis.Sample is dried at 100 DEG C in vacuum drying oven, using pressing potassium bromide troche, wave number is gathered
Scope 400-4000cm-1。
The assay method of settling volume：Weigh the tool plug graduated cylinder that 10g modified Nano white carbons are placed in graduated 100mL
It is interior, a certain amount of dispersant (atoleine) is added, Nano carbon white to be modified adds liquid by after atoleine complete wetting
Body paraffin fully vibrates 5min to 100mL scale with 30 times/1min frequency of oscillation, makes modified Nano white carbon in liquid
It is uniformly dispersed, then stands in paraffin, reads the solid volume of different time.The settling volume of same time can be in certain journey
Reflect the quality of compatibility between particle and organic solvent on degree, settling volume is big, it is good to make carbon black dispersion clear, easily compatible.
The assay method of oil absorption：Reference《The assay method of YS/T618-2007 aluminium hydroxide used as filling material oil absorptions》, take
Quantitative modified Nano white carbon is put into surface plate, and diisooctyl phthalate is added dropwise by each 0.2mL, after being added dropwise every time,
It is fully ground, can be sticked into untill agglomerate do not split to powder, oil absorption is with the volume V of every 100g samples institute oil suction with toolsetting0
(mL) represent, be calculated as follows:
In formula, υ is the volume (mL) of the diisooctyl phthalate consumed；M is the quality (g) of sample.Oil absorption exists
The specific surface area of modified Nano white carbon is reflected in a way, and specific surface area is lower, and oil absorption is lower, and wettability is got over
Good, vice versa.
Embodiment 1
(1) preparation of monomer pre-emulsion：By 100 parts of isoprene, 6 parts of neopelexes, 160 parts of deionizations
Water, 1.2 parts of sodium carbonate, 0.01 part of ammonium persulfate are put into reactor together, when being warming up to 45 DEG C, and stirring reaction is prepared for 30 minutes
Into isoprene pre-emulsion a.
(2) preparation of ultra-dispersed type Nano carbon white：Counted using Nano carbon white quality as 100 parts, take 100 parts of nanometer hard charcoals
Black and 200 parts of deionized waters are added to stirring mixing 10min in polymeric kettle；Then 5 parts of HDI, 1.0 parts of sodium hydroxides are added, are risen
Temperature is to 40 DEG C, and stirring reaction 1h is generated with nanometer after then adding 6 parts of acrylamides and 0.5 part of sodium hydroxide reaction 30min
The performed polymer coated centered on white carbon black powder by HDI and acrylamide；Finally add 20 parts of isoprene pre-emulsion a
With 0.5 part of ammonium persulfate, react and 0.1 part of Sodium Dimethyldithiocarbamate is added after 4.0h, scrubbed, dehydration, the obtained ultra-dispersed type of dry, grinding are received
Off-white carbon black.Sampling analysis：Standard specimen is made, performance is shown in Table 1 after tested.
Embodiment 2
(1) preparation of monomer pre-emulsion：Be the same as Example 1.
(2) preparation of ultra-dispersed type Nano carbon white：Counted using Nano carbon white quality as 100 parts, take 100 parts of nanometer hard charcoals
Black and 230 parts of deionized waters are added to stirring mixing 13min in polymeric kettle；Then 6 parts of HDI, 1.2 parts of sodium hydroxides are added, are risen
Temperature is to 45 DEG C, and stirring reaction 1h generates to receive after then adding 7 parts of acrylamides and 0.55 part of sodium hydroxide reaction 40min
The performed polymer coated centered on rice white carbon black powder by HDI and acrylamide；Finally add 24 parts of isoprene pre-emulsifications
0.2 part of Sodium Dimethyldithiocarbamate is added after liquid a and 0.7 part of ammonium persulfate, reaction 4.5h, scrubbed, dehydration, dry, grinding are made ultra-dispersed
Type Nano carbon white.Sampling analysis：Standard specimen is made, performance is shown in Table 1 after tested.
Embodiment 3
(1) preparation of monomer pre-emulsion：Be the same as Example 1.
(2) preparation of ultra-dispersed type Nano carbon white：Counted using Nano carbon white quality as 100 parts, take 100 parts of nanometer hard charcoals
Black and 250 parts of deionized waters are added to stirring mixing 15min in polymeric kettle；Then 6.5 parts of HDI, 1.3 parts of sodium hydroxides are added,
Be warming up to 45 DEG C, stirring reaction 1h, then add generated after 8 parts of acrylamides and 0.65 part of sodium hydroxide reaction 45min with
The performed polymer coated centered on Nano carbon white powder by HDI and acrylamide；Finally add 29 parts of pre- breasts of isoprene
Change and 0.2 part of Sodium Dimethyldithiocarbamate is added after liquid a and 0.75 part of ammonium persulfate, reaction 4.5h, oversubscription is made in scrubbed, dehydration, dry, grinding
Dissipate type Nano carbon white.Sampling analysis：Standard specimen is made, performance is shown in Table 1 after tested.
Embodiment 4
(1) preparation of monomer pre-emulsion：By 100 parts of isoprene, 8 parts of neopelexes, 180 parts of deionizations
Water, 1.4 parts of sodium carbonate, 0.03 part of ammonium persulfate are put into reactor together, when being warming up to 50 DEG C, and stirring reaction is prepared for 40 minutes
Into isoprene pre-emulsion b.
(2) preparation of ultra-dispersed type Nano carbon white：Counted using Nano carbon white quality as 100 parts, take 100 parts of nanometer hard charcoals
Black and 260 parts of deionized waters are added to stirring mixing 16min in polymeric kettle；Then 7 parts of HDI, 1.4 parts of sodium hydroxides are added, are risen
Temperature is to 45 DEG C, and stirring reaction 1h is generated with nanometer after then adding 9 parts of acrylamides and 0.7 part of sodium hydroxide reaction 45min
The performed polymer coated centered on white carbon black powder by HDI and acrylamide；Finally add 32 parts of isoprene pre-emulsion b
With 0.8 part of ammonium persulfate, react and 0.2 part of Sodium Dimethyldithiocarbamate is added after 4.5h, scrubbed, dehydration, the obtained ultra-dispersed type of dry, grinding are received
Off-white carbon black.Sampling analysis：Standard specimen is made, performance is shown in Table 1 after tested.
Embodiment 5
(1) preparation of monomer pre-emulsion：Be the same as Example 4.
(2) preparation of ultra-dispersed type Nano carbon white：Counted using Nano carbon white quality as 100 parts, take 100 parts of nanometer hard charcoals
Black and 260 parts of deionized waters are added to stirring mixing 16min in polymeric kettle；Then 8 parts of HDI, 1.5 parts of sodium hydroxides are added, are risen
Temperature is to 50 DEG C, and stirring reaction 1h generates to receive after then adding 10 parts of acrylamides and 0.8 part of sodium hydroxide reaction 45min
The performed polymer coated centered on rice white carbon black powder by HDI and acrylamide；Finally add 35 parts of isoprene pre-emulsifications
0.3 part of Sodium Dimethyldithiocarbamate is added after liquid b and 0.85 part of ammonium persulfate, reaction 5.0h, scrubbed, dehydration, dry, grinding are made ultra-dispersed
Type Nano carbon white.Sampling analysis：Standard specimen is made, performance is shown in Table 1 after tested.
Embodiment 6
(1) preparation of monomer pre-emulsion：Be the same as Example 4.
(2) preparation of ultra-dispersed type Nano carbon white：Counted using Nano carbon white quality as 100 parts, take 100 parts of nanometer hard charcoals
Black and 350 parts of deionized waters are added to stirring mixing 25min in polymeric kettle；Then 9 parts of HDI, 1.8 parts of sodium hydroxides are added, are risen
Temperature is to 50 DEG C, and stirring reaction 1h generates to receive after then adding 11 parts of acrylamides and 0.9 part of sodium hydroxide reaction 50min
The performed polymer coated centered on rice white carbon black powder by HDI and acrylamide；Finally add 38 parts of isoprene pre-emulsifications
0.4 part of Sodium Dimethyldithiocarbamate is added after liquid b and 1.2 parts of ammonium persulfates, reaction 5.5h, scrubbed, dehydration, dry, grinding are made ultra-dispersed
Type Nano carbon white.Sampling analysis：Standard specimen is made, performance is shown in Table 1 after tested.
Embodiment 7
(1) preparation of monomer pre-emulsion：100 parts of 1,3- hexadienes, 10 parts of neopelexes, 200 parts are gone
Ionized water, 2.0 parts of sodium carbonate, 0.1 part of ammonium persulfate are put into reactor together, when being warming up to 60 DEG C, stirring reaction 50 minutes
It is prepared into 1,3- hexadiene pre-emulsions c.
(2) preparation of ultra-dispersed type Nano carbon white：Counted using Nano carbon white quality as 100 parts, take 100 parts of nanometer hard charcoals
Black and 400 parts of deionized waters are added to stirring mixing 30min in polymeric kettle；Then 10 parts of methylcyclohexane diisocyanates are added
(HTDI), 2.0 parts of sodium hydroxides, are warming up to 60 DEG C, then stirring reaction 2h adds 12 parts of acrylamides and 1.0 parts of hydrogen-oxygens
The performed polymer coated centered on Nano carbon white powder by HTDI and acrylamide is generated after changing sodium reaction 60min；Finally
0.5 part of Sodium Dimethyldithiocarbamate is added after adding 40 parts of 1,3- hexadiene pre-emulsion c and 1.5 parts of ammonium persulfates, reaction 6.0h, through washing
Wash, be dehydrated, drying, grinding obtained ultra-dispersed type Nano carbon white.Sampling analysis：Standard specimen is made, performance is shown in Table after tested
1。
Comparative example 1
(1) preparation of monomer pre-emulsion：Be the same as Example 1.
(2) preparation of ultra-dispersed type Nano carbon white：Other conditions are same as Example 1, and difference is to prepare
HDI is not added with journey, but adds 5 parts of PPDIs, i.e.,：Counted using Nano carbon white quality as 100 parts, take 100 parts to receive
Off-white carbon black and 200 parts of deionized waters are added to stirring mixing 10min in polymeric kettle；Then add 5 parts of PPDIs,
1.0 parts of sodium hydroxides, are warming up to 40 DEG C, then stirring reaction 1h adds 6 parts of acrylamides and 0.5 part of sodium hydroxide reaction
The performed polymer coated centered on Nano carbon white powder by HDI and acrylamide is generated after 30min；Finally add 20 parts
Isoprene pre-emulsion a and 0.5 part of ammonium persulfate, reaction 4.0h after add 0.1 part of Sodium Dimethyldithiocarbamate, it is scrubbed, dehydration, dry,
Ultra-dispersed type Nano carbon white is made in grinding.Sampling analysis：Standard specimen is made, performance is shown in Table 1 after tested.
Comparative example 2
(1) preparation of monomer pre-emulsion：Be the same as Example 1.
(2) preparation of ultra-dispersed type Nano carbon white：Other conditions are same as Example 1, and difference is to prepare
Isoprene pre-emulsion a addition is 15 parts in journey, i.e.,：Counted using Nano carbon white quality as 100 parts, take 100 parts of nanometers
White carbon and 230 parts of deionized waters are added to stirring mixing 13min in polymeric kettle；Then 6 parts of HDI, 1.2 parts of hydroxides are added
Sodium, is warming up to 45 DEG C, stirring reaction 1h is generated after then adding 7 parts of acrylamides and 0.55 part of sodium hydroxide reaction 40min
The performed polymer coated centered on Nano carbon white powder by HDI and acrylamide；Finally add 15 parts of isoprene pre-
0.2 part of Sodium Dimethyldithiocarbamate is added after emulsion a and 0.7 part of ammonium persulfate, reaction 4.5h, scrubbed, dehydration, dry, grinding are made super
Decentralized Nano carbon white.Sampling analysis：Standard specimen is made, performance is shown in Table 1 after tested.
Comparative example 3
(1) preparation of monomer pre-emulsion：Be the same as Example 1.
(2) preparation of ultra-dispersed type Nano carbon white：Other conditions are same as Example 1, and difference is to prepare
The addition of acrylamide is 4 parts in journey, i.e.,：Counted using Nano carbon white quality as 100 parts, take 100 parts of Nano carbon whites and 250
Part deionized water is added to stirring mixing 15min in polymeric kettle；Then 6.5 parts of HDI, 1.3 parts of sodium hydroxides are added, 45 are warming up to
DEG C, stirring reaction 1h is generated with nanometer hard charcoal after then adding 4 parts of acrylamides and 0.65 part of sodium hydroxide reaction 45min
The performed polymer coated centered on black powder by HDI and acrylamide；Finally add 29 parts of isoprene pre-emulsion a and
0.2 part of Sodium Dimethyldithiocarbamate is added after 0.75 part of ammonium persulfate, reaction 4.5h, scrubbed, dehydration, dry, grinding are made ultra-dispersed type and received
Off-white carbon black.Sampling analysis：Standard specimen is made, performance is shown in Table 1 after tested.
Comparative example 4
The preparation of ultra-dispersed type Nano carbon white：Other conditions are same as Example 4, and difference is in preparation process
Isoprene pre-emulsion b is not added with, but is directly added into isoprene, i.e.,：Counted using Nano carbon white quality as 100 parts, take 100
Part Nano carbon white and 260 parts of deionized waters are added to stirring mixing 16min in polymeric kettle；Then 7 parts of HDI, 1.4 parts of hydrogen are added
Sodium oxide molybdena, is warming up to 45 DEG C, then stirring reaction 1h is added after 9 parts of acrylamides and 0.7 part of sodium hydroxide reaction 45min
Generate the performed polymer coated centered on Nano carbon white powder by HDI and acrylamide；Finally add 32 parts of isoamyls two
0.2 part of Sodium Dimethyldithiocarbamate is added after alkene and 0.8 part of ammonium persulfate, reaction 4.5h, ultra-dispersed type is made in scrubbed, dehydration, dry, grinding
Nano carbon white.Sampling analysis：Standard specimen is made, performance is shown in Table 1 after tested.
Comparative example 5
(1) preparation of monomer pre-emulsion：Be the same as Example 4.
(2) preparation of ultra-dispersed type Nano carbon white：Other conditions are same as Example 5, and difference is to prepare
Initiator ammonium persulfate is not added with journey, isoprene pre-emulsion b is that dialogue carbon black particle surface is only coated, i.e.,：With
Nano carbon white quality is 100 parts of meters, takes 100 parts of Nano carbon whites and 260 parts of deionized waters to be added in polymeric kettle and stirs mixed
Close 16min；Then 8 parts of HDI, 1.5 parts of sodium hydroxides are added, 50 DEG C are warming up to, then stirring reaction 1h adds 10 parts of propylene
Generate centered on Nano carbon white powder and to be coated by HDI and acrylamide after acid amides and 0.8 part of sodium hydroxide reaction 45min
Performed polymer；0.3 part of Sodium Dimethyldithiocarbamate is added after finally adding 35 parts of isoprene pre-emulsion b, reaction 5.0h, it is scrubbed, de-
Ultra-dispersed type Nano carbon white is made in water, drying, grinding.Sampling analysis：Standard specimen is made, performance is shown in Table 1 after tested.
Comparative example 6
(1) preparation of monomer pre-emulsion：Be the same as Example 4.
(2) preparation of ultra-dispersed type Nano carbon white：Other conditions are same as Example 4, and difference is to prepare
Acrylamide is not added with journey, i.e.,：Counted using Nano carbon white quality as 100 parts, take 100 parts of Nano carbon whites and 350 parts of deionizations
Water is added to stirring mixing 25min in polymeric kettle；Then 9 parts of HDI, 1.8 parts of sodium hydroxides are added, 50 DEG C are warming up to, stirring is anti-
1h is answered, then adds to generate after 0.9 part of sodium hydroxide reaction 50min and is coated centered on Nano carbon white powder by HDI
Performed polymer；0.4 part of good fortune is added after finally adding 38 parts of isoprene pre-emulsion b and 1.2 parts of ammonium persulfates, reaction 5.5h
Ultra-dispersed type Nano carbon white is made in U.S. sodium, scrubbed, dehydration, dry, grinding.Sampling analysis：Standard specimen is made, after tested
Performance is shown in Table 1.
Comparative example 7
The preparation of ultra-dispersed type Nano carbon white：Other conditions are same as Example 7, and difference is in preparation process
1,3- hexadiene pre-emulsion c are not added with, but are directly added into 1,3- hexadienes, i.e.,：Counted using Nano carbon white quality as 100 parts,
100 parts of Nano carbon whites and 400 parts of deionized waters are taken to be added to stirring mixing 30min in polymeric kettle；Then 10 parts of methyl are added
Cyclohexane diisocyanate (HTDI), 2.0 parts of sodium hydroxides, are warming up to 60 DEG C, then stirring reaction 2h adds 12 parts of propylene
Generate centered on Nano carbon white powder and to be wrapped by HTDI and acrylamide after acid amides and 1.0 parts of sodium hydroxides reaction 60min
The performed polymer covered；0.5 part of Sodium Dimethyldithiocarbamate is added after finally adding 40 parts of 1,3- hexadienes and 1.5 parts of ammonium persulfates, reaction 6.0h,
Ultra-dispersed type Nano carbon white is made in scrubbed, dehydration, dry, grinding.Sampling analysis：Standard specimen is made, after tested performance
It is shown in Table 1.
The settling volume and oil absorbency of the ultra-dispersed type Nano carbon white of table 1
As shown in Table 1：The settling volume of embodiment is big than comparative example under same time, and oil absorption is below contrast
Example, illustrates that the modified effect of the present invention is obvious.Secondly from embodiment 1~7 it can be seen that modified Nano white carbon passes through twin-screw
The settling volume (120min) and oil absorbency that are measured after extruder extrusion and the change do not extruded are little, illustrate modified Nano hard charcoal
Black processing dispersion stabilization is good.
Certainly, the present invention can also have other various embodiments, ripe in the case of without departing substantially from spirit of the invention and its essence
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
The protection domain of the claims in the present invention should all be belonged to.
Claims (12)
1. a kind of method of modifying of Nano carbon white, it is characterised in that mainly include the following steps that：
(1) prepared by monomer pre-emulsion：In parts by mass, by 100 parts of conjugated diene monomers, 5~10 parts of emulsifying agents, 150~
200 parts of deionized waters, 1.0~2.0 parts of buffers, 0.01~0.1 part of initiator are put into reactor together, are warming up to 40~60
DEG C when, stirring reaction is prepared into monomer pre-emulsion in 30~50 minutes；
(2) the preparation of modified Nano white carbon：In parts by mass, 100 parts of Nano carbon whites and 200~400 parts of deionized waters are taken to add
Enter into polymeric kettle 10~30min of stirring mixing；Then 5~10 parts of aliphatic diisocyanates, 1.0~2.0 parts of catalysis are added
Agent, is warming up to 40~60 DEG C, 1~2h of stirring reaction, then adds 6~12 parts of acrylamides and 0.5~1.0 part of catalyst is anti-
Answer generated after 30~60min centered on Nano carbon white powder by aliphatic diisocyanate and acrylamide coated it is pre-
Aggressiveness；0.1 is added after finally adding 20~40 parts of monomer pre-emulsions and 0.5~1.5 part of initiator, 4.0~6.0h of reaction
Modified Nano white carbon is made in~0.5 part of terminator, scrubbed, dehydration, dry, grinding.
2. method of modifying as claimed in claim 1, it is characterised in that the white carbon is nano level, and its particle diameter is：20~
60nm。
3. the method for modifying as described in claim 1 or 2 is any, it is characterised in that it is sub- that the aliphatic diisocyanate is selected from six
Methyl diisocyanate, IPDI, dicyclohexyl methyl hydride -4,4'- diisocyanate, hexahydrotoluene two are different
One or more of mixture in cyanate.
4. method of modifying as claimed in claim 3, it is characterised in that the aliphatic diisocyanate is that hexa-methylene two is different
Cyanate.
5. the method for modifying as described in claim 1,2 or 4 are any, it is characterised in that the purity of the acrylamide be more than or
Equal to 99%.
6. method of modifying as claimed in claim 1, it is characterised in that the conjugated diene is C4~Cl2Conjugated diene.
7. method of modifying as claimed in claim 6, it is characterised in that the conjugated diene is 1,3-butadiene；Isoamyl two
Alkene；2,3- dimethyl -1,3 butadiene；2,3- diethyl -1,3 butadiene；2- methyl -3- ethyl -1,3 butadiene；2- chloro- 1,
3- pentadienes；1,3-pentadiene；3- butyl -1,3- octadienes；2- phenyl -1,3-butadiene；One kind in 1,3- hexadiene or
Several mixtures.
8. method of modifying as claimed in claim 7, it is characterised in that the conjugated diene is isoprene.
9. method of modifying as claimed in claim 1, it is characterised in that the initiator is ammonium persulfate, potassium peroxydisulfate, over cure
One kind in sour sodium.
10. method of modifying as claimed in claim 9, it is characterised in that the initiator is ammonium persulfate.
11. the method for modifying as described in claim 1,2,4,6~10 is any, it is characterised in that the catalyst be sodium carbonate,
One kind in sodium acid carbonate, sodium hydroxide, ammoniacal liquor, ammonium hydrogen carbonate.
12. method of modifying as claimed in claim 11, it is characterised in that the catalyst is sodium hydroxide.
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