WO2001055254A1 - Elastomeric compositions containing polymer coated carbon products and other pigments - Google Patents
Elastomeric compositions containing polymer coated carbon products and other pigments Download PDFInfo
- Publication number
- WO2001055254A1 WO2001055254A1 PCT/US2001/002317 US0102317W WO0155254A1 WO 2001055254 A1 WO2001055254 A1 WO 2001055254A1 US 0102317 W US0102317 W US 0102317W WO 0155254 A1 WO0155254 A1 WO 0155254A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- carbon product
- polymer
- elastomeric composition
- modified carbon
- product
- Prior art date
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 227
- 239000000203 mixture Substances 0.000 title claims abstract description 151
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 91
- 239000000049 pigment Substances 0.000 title claims description 37
- 150000001721 carbon Chemical class 0.000 claims abstract description 238
- 125000000962 organic group Chemical group 0.000 claims abstract description 100
- 238000000576 coating method Methods 0.000 claims abstract description 77
- 238000000034 method Methods 0.000 claims abstract description 77
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 49
- 239000002904 solvent Substances 0.000 claims abstract description 42
- 229920001971 elastomer Polymers 0.000 claims abstract description 29
- 239000000806 elastomer Substances 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 239000006229 carbon black Substances 0.000 claims description 155
- 239000000178 monomer Substances 0.000 claims description 83
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 68
- 239000011248 coating agent Substances 0.000 claims description 67
- 239000003999 initiator Substances 0.000 claims description 54
- -1 sulfophenyl group Chemical group 0.000 claims description 53
- 239000004793 Polystyrene Substances 0.000 claims description 30
- 150000003839 salts Chemical class 0.000 claims description 27
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 24
- 125000003118 aryl group Chemical group 0.000 claims description 20
- 229920001577 copolymer Polymers 0.000 claims description 19
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 17
- 238000010526 radical polymerization reaction Methods 0.000 claims description 14
- 239000005060 rubber Substances 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 229920000098 polyolefin Polymers 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 8
- 125000001624 naphthyl group Chemical group 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 229920002223 polystyrene Polymers 0.000 claims description 7
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 6
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 6
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004917 carbon fiber Substances 0.000 claims description 6
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- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004677 Nylon Substances 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 229920001778 nylon Polymers 0.000 claims description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 4
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 229920001195 polyisoprene Polymers 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 239000004800 polyvinyl chloride Substances 0.000 claims description 4
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229920002397 thermoplastic olefin Polymers 0.000 claims description 4
- 229920006342 thermoplastic vulcanizate Polymers 0.000 claims description 4
- 229920001567 vinyl ester resin Polymers 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- 229920000106 Liquid crystal polymer Polymers 0.000 claims description 3
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 229920002292 Nylon 6 Polymers 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 239000004962 Polyamide-imide Substances 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 229920002367 Polyisobutene Polymers 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 3
- 229920000180 alkyd Polymers 0.000 claims description 3
- 150000001555 benzenes Chemical class 0.000 claims description 3
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 3
- 229920002313 fluoropolymer Polymers 0.000 claims description 3
- 239000004811 fluoropolymer Substances 0.000 claims description 3
- 125000000468 ketone group Chemical group 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920002312 polyamide-imide Polymers 0.000 claims description 3
- 229920000867 polyelectrolyte Polymers 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 229920006324 polyoxymethylene Polymers 0.000 claims description 3
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 125000000626 sulfinic acid group Chemical group 0.000 claims description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 3
- 229920006305 unsaturated polyester Polymers 0.000 claims description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 2
- 239000011324 bead Substances 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 claims description 2
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 3
- 230000008021 deposition Effects 0.000 claims 1
- 239000002356 single layer Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 8
- 239000000047 product Substances 0.000 description 234
- 235000019241 carbon black Nutrition 0.000 description 143
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 97
- 238000006243 chemical reaction Methods 0.000 description 67
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 44
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 32
- 229920001897 terpolymer Polymers 0.000 description 31
- 150000001875 compounds Chemical class 0.000 description 30
- 239000000243 solution Substances 0.000 description 29
- 238000001030 gas--liquid chromatography Methods 0.000 description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 27
- 239000000839 emulsion Substances 0.000 description 26
- 229920000638 styrene acrylonitrile Polymers 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000000463 material Substances 0.000 description 21
- 238000009472 formulation Methods 0.000 description 19
- 230000008569 process Effects 0.000 description 19
- 239000012954 diazonium Substances 0.000 description 18
- 150000001989 diazonium salts Chemical class 0.000 description 18
- 239000006185 dispersion Substances 0.000 description 18
- 239000002609 medium Substances 0.000 description 18
- 238000002474 experimental method Methods 0.000 description 17
- 239000002245 particle Substances 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000002156 mixing Methods 0.000 description 15
- 230000002378 acidificating effect Effects 0.000 description 14
- 238000000113 differential scanning calorimetry Methods 0.000 description 13
- 238000001704 evaporation Methods 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 11
- 235000019395 ammonium persulphate Nutrition 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 230000004907 flux Effects 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000004160 Ammonium persulphate Substances 0.000 description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 9
- 239000012736 aqueous medium Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000000605 extraction Methods 0.000 description 9
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- 239000000945 filler Substances 0.000 description 8
- 208000016261 weight loss Diseases 0.000 description 8
- 230000004580 weight loss Effects 0.000 description 8
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 7
- 150000001450 anions Chemical class 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 7
- 241000894007 species Species 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- 239000000010 aprotic solvent Substances 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 239000012429 reaction media Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- 102100039201 Constitutive coactivator of peroxisome proliferator-activated receptor gamma Human genes 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 101000813317 Homo sapiens Constitutive coactivator of peroxisome proliferator-activated receptor gamma Proteins 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 125000001072 heteroaryl group Chemical group 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
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- 238000002329 infrared spectrum Methods 0.000 description 4
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- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 4
- 150000003141 primary amines Chemical class 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
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- 125000001931 aliphatic group Chemical group 0.000 description 3
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- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
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- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
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- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
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- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
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- LCFYCLRCIJDYQD-UHFFFAOYSA-N 2-ethenyl-5-methylpyridine Chemical compound CC1=CC=C(C=C)N=C1 LCFYCLRCIJDYQD-UHFFFAOYSA-N 0.000 description 1
- XQGDNRFLRLSUFQ-UHFFFAOYSA-N 2H-pyranthren-1-one Chemical class C1=C(C2=C3C4=C56)C=CC3=CC5=C3C=CC=CC3=CC6=CC=C4C=C2C2=C1C(=O)CC=C2 XQGDNRFLRLSUFQ-UHFFFAOYSA-N 0.000 description 1
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- QWOVZHUJHAFOJS-UHFFFAOYSA-N 4-amino-2-(4-sulfophenyl)benzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C(C=2C=CC(=CC=2)S(O)(=O)=O)=C1 QWOVZHUJHAFOJS-UHFFFAOYSA-N 0.000 description 1
- UNYIAFAXSZQQOZ-UHFFFAOYSA-N 4-aminobutane-1,3-disulfonic acid Chemical compound NCC(S(O)(=O)=O)CCS(O)(=O)=O UNYIAFAXSZQQOZ-UHFFFAOYSA-N 0.000 description 1
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
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- VJOWMORERYNYON-UHFFFAOYSA-N 5-ethenyl-2-methylpyridine Chemical compound CC1=CC=C(C=C)C=N1 VJOWMORERYNYON-UHFFFAOYSA-N 0.000 description 1
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- 125000003710 aryl alkyl group Chemical group 0.000 description 1
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- 229910052788 barium Inorganic materials 0.000 description 1
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- 229910052792 caesium Inorganic materials 0.000 description 1
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- 230000001627 detrimental effect Effects 0.000 description 1
- LFINSDKRYHNMRB-UHFFFAOYSA-N diazanium;oxido sulfate Chemical compound [NH4+].[NH4+].[O-]OS([O-])(=O)=O LFINSDKRYHNMRB-UHFFFAOYSA-N 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001599 direct drying Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
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- 235000021384 green leafy vegetables Nutrition 0.000 description 1
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- 150000004820 halides Chemical class 0.000 description 1
- 125000005549 heteroarylene group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000010983 kinetics study Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000011177 media preparation Methods 0.000 description 1
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- 125000002757 morpholinyl group Chemical group 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
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- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical class C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
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- 239000003208 petroleum Substances 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
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- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002454 poly(glycidyl methacrylate) polymer Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 229940096055 prax Drugs 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000001422 pyrrolinyl group Chemical group 0.000 description 1
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- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
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- 239000012966 redox initiator Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
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- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000010512 small scale reaction Methods 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000007155 step growth polymerization reaction Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 150000008054 sulfonate salts Chemical class 0.000 description 1
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- 239000006228 supernatant Substances 0.000 description 1
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- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
-
- 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
- C08K9/04—Ingredients treated with organic substances
Definitions
- the present invention relates to carbon products and other pigments and polymers and more particularly relates to the coating of pigment products with polymers.
- the present invention further relates to the use of aqueous media polymerizations such as emulsion or suspension techniques or solvent based procedures to coat, at least partially, carbon products, such as carbon black and other pigments.
- carbon products, and more specifically, carbon black have been used in a variety of areas as a filler and/or reinforcer. While carbon black can advantageously contribute to the properties of various polymers in which it is present in, carbon black has been shown to contribute to certain detrimental properties such as impact properties, including tensile properties and stress and strain-related properties.
- carbon black when included in the polymers is usually added with the use of masterbatches since carbon black can be difficult to disperse in polymers due to its physical properties such as small primary particle sizes and highly structured aggregates.
- the present invention relates to a polymer coated modified carbon product, wherein the polymer at least partially coats a modified carbon product.
- the modified carbon product has at least one organic group attached to the carbon product.
- the organic group is preferably substituted with an ionic, ionizable, or polar groups which can facilitate the formation of a stable dispersion in an aqueous media.
- the polymer partially or fully encapsulates the modified carbon product, or the modified carbon product is the core and the polymer is the shell.
- the present invention further relates to a method of making a polymer coated modified carbon product which includes the steps of combining, in an aqueous-based medium, an initiator, at least one monomer, and a modified carbon product.
- the modified carbon product preferably has at least one organic group attached to the carbon product. Again, the organic group is preferably substituted with an ionic, ionizable, or polar group.
- the initiator, at least one monomer, and the modified carbon product are then subjected to an emulsion, suspension, or other aqueous based polymerization to form a polymer coated modified carbon product, wherein the monomer is capable of being polymerized in an aqueous environment and the modified carbon product is dispersible or dispersed in the aqueous- based medium.
- This method also relates to the use of a modified carbon product which can form stable aqueous dispersions and can also physically and/or chemically bond to the polymer formed during the polymerization of the monomers.
- the present invention in addition, relates to a method of making a polymer coated modified carbon product such as that described above, wherein a polymer is prepared separately and is then dissolved in an appropriate organic solvent. A modified carbon product is then combined with the solvent containing the polymer, followed by the removal of the solvent, such as by evaporation or other means. Further, the present invention relates to a method of making a polymer coated modified carbon product such as that described above, wherein a polymerizable monomer is present in an organic solvent and a modified carbon product is then combined with the solvent containing the monomer, followed by polymerization of the monomer and subsequent removal of the solvent. The present invention also relates to polymer coated modified pigments. • It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are intended to provide further explanation of the present invention, as claimed.
- RRTFF DESCRIPTION OF THF DRAWTNCS Figure 1 is a graph plotting the Young's Modulus vs. weight % of carbon black or polymer coated (20 nm) modified carbon black of the present invention.
- Figure 2 is a graph plotting the Fracture Energy vs. weight % of carbon black or a polymer coated (20 nm) modified carbon black of the present invention.
- Figure 3 and 4 are microphotographs of polymer coated modified carbon products of the present invention.
- Figure 5(a) - (c) are graphs depicting the variation in fracture energy for polymer matrices containing either conventional carbon black, solution polymer coated modified carbon black, and emulsion polymer coated modified carbon blacks.
- the present invention relates to a polymer coated modified carbon product.
- the modified carbon product is at least partially coated with one or more polymers and can be substantially or fully coated by one or more polymers.
- the use of the term "coated” includes partially and fully coated carbon products and modified carbon products.
- the polymer in this invention partially or fully encapsulates the modified carbon product, wherein the modified carbon product is the core and the polymer is the shell.
- the polymer(s) coated onto or used to encapsulate the modified carbon product is preferably present on the modified carbon product such that the polymer(s) is not substantially extractable by an organic solvent. More preferably, the polymer(s) on the modified carbon product is attached by physical (e.g., adsorption) and/or chemical means (e.g. chemical bonding, grafting).
- the carbon product coated with a polymer can be a modified carbon product having at least one organic group attached to the carbon product.
- the organic group is substituted with an ionic, ionizable, or polar group.
- the carbon product which has the organic group attached thereto can be any carbon product capable of having at least one organic group attached to the carbon product.
- the carbon product can be any carbon product capable of reacting with the diazonium salt to form the modified carbon product.
- the carbon may be of the crystalline or amorphous type. Examples include, but are not limited to, graphite, carbon black, vitreous carbon, activated charcoal, activated carbon, carbon fibers, and mixtures thereof. Finely divided forms of the above are preferred. It is also possible to utilize mixtures of different carbon products.
- the modified pigment is a pigment having attached at least one organic group.
- the pigment include, but are not limited to, any colored pigment, carbon black, carbon fibers, activated carbon, graphite, activated graphite, carbon cloth, vitreous carbon, and the like.
- the modified pigment is a modified carbon product, such as modified carbon black.
- the organic group which is attached onto the pigment can be any variety of organic groups such as those described in U.S. Patent Nos.
- a modified carbon product includes an aggregate comprising a carbon phase and a silicon-containing species phase.
- a description of this aggregate as well as means of making this aggregate are described in PCT Publication No. WO 96/37547 as well as U.S. Patent Nos. 5,830,930; 6,008,272; 5,977,213; 5,948,835; 5,919,841; 5,904,762; 5,877,238; and 5,869,550.
- This modified carbon product can be used as is or can have an organic group attached thereto. All of these patents, publications, and patent applications are hereby incorporated in their entireties herein by reference.
- the modified carbon product for purposes of the present invention, can also be an aggregate comprising a carbon phase and metal-containing species phase where the metal-containing species phase can be a variety of different metals such as magnesium, calcium, titanium, vanadium, cobalt, nickel, zirconium, tin, antimony, chromium, neodymium, lead, tellurium, barium, cesium, iron, molybdenum, aluminum, and zinc, and mixtures thereof.
- the aggregate comprising the carbon phase and a metal-containing species phase is described in U.S. Patent Application No. 08/828,785 filed March 27, 1997 and PCT Publication No. WO 98/42778 also hereby incorporated in their entireties herein by reference.
- This carbon product can be used as is or can hav.e an organic group attached thereto.
- a modified carbon product includes a silica-coated carbon black, such as that described in PCT Publication No. WO 96/37547, published November 28, 1996, and U.S. Patent No. 5,916,934 also hereby incorporated in their entireties herein by reference.
- This modified carbon product can be used as is or can have an organic group attached thereto.
- a modified pigment can be used.
- the modified pigment is a pigment having attached at least one organic group.
- the pigment include, but are not limited to, any colored pigment, carbon black, carbon fibers, activated carbon, graphite, activated graphite, carbon cloth, vitreous carbon, and the like.
- the modified pigment is a modified carbon product, such as modified carbon black.
- the organic group which is attached onto the pigment can be any variety of organic groups such as those described in U.S. Patent Nos.
- One process for attaching an organic group to the carbon product or modified pigment involves the reaction of at least one diazonium salt with a carbon product in the absence of an externally applied current sufficient to reduce the diazonium salt. That is, the reaction between the diazonium salt and the carbon product proceeds without an external source of electrons sufficient to reduce the diazonium salt. Mixtures of different diazonium salts may be used in the process of the invention. This process can be carried out under a variety of reaction conditions and in any type of reaction medium, including both protic and aprotic solvent systems or slurries.
- At least one diazonium salt reacts with a carbon product in a protic reaction medium.
- Mixtures of different diazonium salts may be used in this process of the invention. This process can also be carried out under a variety of reaction conditions.
- the diazonium salt can be formed in situ.
- the carbon product can be isolated and dried by means known in the art.
- the resultant carbon product can be treated to remove impurities by known techniques.
- the processes can be carried out in any reaction medium which allows the reaction between the diazonium salt and the carbon product to proceed.
- the reaction medium can be a solvent-based system.
- the solvent may be a protic solvent, an aprotic solvent, or a mixture of solvents.
- Protic solvents are solvents, like water or methanol, containing a hydrogen attached to an oxygen or nitrogen and thus are sufficiently acidic to form hydrogen bonds.
- Aprotic solvents are solvents which do not contain an acidic hydrogen as defined above.
- Aprotic solvents include, for example, solvents such as hexanes, tetrahydrofuran (THF), acetonitrile, and benzonitrile.
- solvents such as hexanes, tetrahydrofuran (THF), acetonitrile, and benzonitrile.
- THF tetrahydrofuran
- acetonitrile acetonitrile
- benzonitrile benzonitrile
- the reaction between a diazonium salt and a carbon product can take place with any type of carbon product, for example, in fluffy or pelleted fonn.
- the reaction between a diazonium salt and a carbon product forms a modified carbon product having an organic group attached to the carbon product.
- the diazonium salt may contain the organic group to be attached to the carbon product. It may be possible to produce the modified carbon products used in this invention by other means known to those skilled in the art.
- the organic group may be an aliphatic group, a cyclic organic group, or an organic compound having an aliphatic portion and a cyclic portion.
- the diazonium salt employed in the processes can be derived from a primary amine having one of these groups and being capable of forming, even transiently, a diazonium salt.
- the organic group may be substituted or unsubstituted, branched or unbranched.
- Aliphatic groups include, for example, groups derived from alkanes, alkenes, alcohols, ethers, aldehydes, ketones, carboxylic acids, and carbohydrates.
- Cyclic organic groups include, but are not limited to, alicyclic hydrocarbon groups (for example, cycloalkyls, cycloalkenyls), heterocyclic hydrocarbon groups (for example, pyrrolidinyl, pyrrolinyl, piperidinyl, morpholinyl, and the like), aryl groups (for example, phenyl, naphthyl, anthracenyl, and the like), and heteroaryl groups (imidazolyl, pyrazolyl, pyridinyl, thienyl, thiazolyl, furyl, indolyl, and the like).
- alicyclic hydrocarbon groups for example, cycloalkyls, cycloalkenyls
- heterocyclic hydrocarbon groups for example, pyrrolidinyl, pyrrolinyl, piperidinyl, morpholinyl, and the like
- aryl groups for example, phenyl, naphthyl, anthrac
- organic group When the organic group is substituted, it may contain any functional group compatible with the formation of a diazonium salt.
- R and R' which can be the same or different, are independently hydrogen, branched or unbranched C1-C20 substituted or unsubstituted, saturated or unsaturated hydrocarbon, e.g., alkyl, alkenyl, alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkylaryl, or substituted or unsubstituted arylalkyl.
- the integer k ranges from 1-8 and preferably from 2-4.
- the anion X " is a halide or an anion derived from a mineral or organic acid.
- Q is (CH2) neighbor, (CH 2 ) x O(CH2)z. (CH 2 ) x NR(CH 2 )z, or (CH 2 ) ⁇ S(CH ) z , where w is an integer from 2 to 6 and x and z are integers from 1 to 6.
- the organic group can be an aromatic group of the formula A y Ar-, which corresponds to a primary amine of the formula A y ArNH2.
- Ar is an aromatic radical such as an aryl or heteroaryl group.
- Ar is selected from the group consisting of phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl, pyridinyl, benzothiadiazolyl, and benzothiazolyl;
- A is a substituent on the aromatic radical independently selected from a preferred functional group described above or A is a linear, branched or cyclic hydrocarbon radical (preferably containing 1 to 20 carbon atoms), unsubstituted or substituted with one or more of those functional groups; and y is an integer from 1 to the total number of -CH radicals in the aromatic radical.
- y is an integer from 1 to 5 when Ar is phenyl, 1 to 7 when Ar is naphthyl, 1 to 9 when Ar is anthracenyl, phenanthrenyl, or biphenyl, or 1 to 4 when Ar is pyridinyl.
- R and R' are NH C ⁇ FLr, CH2CH2-C6H4-NH2, CH2-C6H4-NH2, and C 6 H 5 .
- Another set of organic groups which may be attached to the carbon product are organic groups substituted with an ionic or an ionizable group as a functional group.
- An ionizable group is one which is capable of forming an ionic group in the medium of use.
- the ionic group may be an anionic group or a cationic group and the ionizable group may form an anion or a cation.
- Ionizable functional groups forming anions include, for example, acidic groups or salts of acidic groups.
- the organic groups therefore, include groups derived from organic acids.
- such an organic group can have a) an aromatic group and b) at least one acidic group having a pKa of less than 11 , or at least one salt of an acidic group having a pKa of less than 11, or a mixture of at least one acidic group having a pKa of less than 11 and at least one salt of an acidic group having a pKa of less than 11.
- the pKa of the acidic group refers to the pKa of the organic group as a whole, not just the acidic substituent.
- the pKa is less than 10 and most preferably less than 9.
- the aromatic group of the organic group can be directly attached to the carbon product.
- the aromatic group may be further substituted or unsubstituted, for example, with alkyl groups.
- the organic group can be a phenyl or a naphthyl group and the acidic group is a sulfonic acid group, a sulfinic acid group, a phosphonic acid group, or a carboxylic acid group. Examples of these acidic groups and their salts are discussed above.
- the organic group can be a substituted or unsubstituted sulfophenyl group or a salt thereof; a substituted or unsubstituted (polysulfo)phenyl group or a salt thereof; a substituted or unsubstituted sulfonaphthyl group or a salt thereof; or a substituted or unsubstituted (polysulfo)naphthyl group or a salt thereof.
- An example of a substituted sulfophenyl group is hydroxysulfophenyl group or a salt thereof.
- organic groups having an ionizable functional group forming an anion are p-sulfophenyl (p-sulfanilic acid), 4-hydroxy-3-sulfophenyl (2- hydroxy-5-amino-benzenesulfonic acid), and 2-sulfoethyl (2-aminoethanesulfonic acid).
- p-sulfophenyl p-sulfanilic acid
- 4-hydroxy-3-sulfophenyl (2- hydroxy-5-amino-benzenesulfonic acid
- 2-sulfoethyl 2-aminoethanesulfonic acid
- Other organic groups having ionizable functional groups forming anions can also be used.
- Amines represent examples of ionizable functional groups that form cationic groups.
- amines may be protonated to form ammonium groups in acidic media.
- An organic group having an amine substituent can have a pKb of less than 5.
- Quaternary ammonium groups (-NR 3 + ) and quaternary phosphonium groups (-PR3 ) also represent examples of cationic groups.
- the organic group can contain an aromatic group such as a phenyl or a naphthyl group and a quaternary ammonium or a quaternary phosphonium group. The aromatic group can be directly attached to the carbon product.
- Quaternized cyclic amines can also be used as the organic group.
- N-substituted pyridinium compounds such as N-methyl-pyridyl
- organic groups include, but are not limited to, (CsHt Hs "1" ,
- modified carbon products having an attached organic group substituted with an ionic or an ionizable group may have increased water dispersibility relative to the corresponding untreated carbon product.
- Water dispersibility of a modified carbon product increases with the number of organic groups attached to the carbon black having an ionizable group or the number of ionizable groups attached to a given organic group.
- increasing the number of ionizable groups associated with the modified carbon product should increase its water dispersibility and permits control of the water dispersibility to a desired level.
- the water dispersibility of a modified carbon product containing an amine as the organic group attached to the carbon product may be increased by acidifying the aqueous medium.
- the ionic strength of the aqueous medium can be less than 0.1 molar.
- the ionic strength can also be less than 0.01 molar.
- the ionic, ionizable, or polar group can be ionized in the reaction medium.
- the resulting product solution or slurry may be used as is or diluted prior to use.
- the modified carbon product may be dried by techniques used for conventional carbon blacks. These techniques include, but are not limited to, drying in ovens and rotary kilns. Overdrying, however, may cause a loss in the degree of water dispersibility.
- modified carbon products having an organic group substituted with an ionic or an ionizable group may also be dispersible in polar organic solvents such as dimethylsulfoxide (DMSO), and formamide.
- polar organic solvents such as dimethylsulfoxide (DMSO), and formamide.
- DMSO dimethylsulfoxide
- use of complexing agents such as crown ethers increases the dispersibility of carbon black products having an organic group containing a metal salt of an acidic group.
- Aromatic sulfides encompass another group of organic groups. Modified carbon products having aromatic sulfide groups are particularly useful in rubber compositions. These aromatic sulfides can be represented by the formulas Ar(CH2) q Sk(CH 2 )rAr' or A-(CH 2 ) q S ⁇ (CH 2 ) r Ar" wherein Ar and Ar' are independently substituted or unsubstituted arylene or heteroarylene groups, Ar" is an aryl or heteroaryl group, k is 1 to 8 and q and r are 0-4. Substituted aryl groups would include . substituted alkylaryl groups. Arylene groups can include phenylene groups, particularly p-phenylene groups, or benzothiazolylene groups.
- Aryl groups can include phenyl, naphthyl and benzothiazolyl.
- the number of sulfurs present, defined by k preferably ranges from 2 to 4.
- Modified carbon products can have an attached aromatic sulfide organic group of the formula -(C6H4)-Sk-(CeH4)-, where k is an integer from 1 to 8, and more preferably where k ranges from 2 to 4.
- Aromatic sulfide groups can be bis-para- (C(_H.)-S2-(C6H4)- an d para-(C6H4)-S2-(C6H5).
- the diazonium salts of these aromatic sulfide groups may be conveniently prepared from their corresponding primary amines, H 2 N-Ar-Sk-Ar'-NH 2 or H 2 N- Ar-Sk-Ar".
- Groups include dithiodi-4,1 -phenylene, tetrathiodi-4,1 -phenylene, phenyldithiophenylene, dithiodi-4,l-(3-chlorophenylene), -(4-C6H,)-S-S-(2-C 7 H4NS), -(4-C6H4)-S-S-(4-C6H4)-OH, -6-(2- C 7 H 3 NS)-SH, -(4-C 6 H4)-CH2CH 2 -S-S-CH 2 CH2-(4-C 6 H4)-, -(4-C 6 H4)-CH 2 CH 2 -S-S-S-CH2CH2-(4- C 6 H 4
- Organic groups also include aromatic sulfides, represented by the formulas Ar-S n -Ar' or Ar-S n -Ar", wherein Ar and Ar' are independently arylene groups, Ar” is an aryl and n is 1 to 8.
- the organic group comprises an aromatic group and/or a Ci-Cmo alkyl group (and more preferably a Ci-C ⁇ alkyl group) directly attached to the carbon product, with or without an ionic, ionizable, or polar group to improve dispersion in aqueous media.
- the attached group would be non-polar or non-ionic.
- More than one type of organic group can be attached to the carbon product, or two or more modified carbon products with different attached organic groups can be used. Using two or more different types of organic groups permits a combination of properties. If two different types of organic groups are attached, for example, a sulfanilic group and a styrenic group, the sulfanilic group promotes dispersibility and the styrenic group serves as a radical grafting site.
- the ratio of the different organic groups can be the same or different.
- only the minimum treatment level of the ionic, ionizable, or polar group is used to impart stability to the dispersion.
- groups such as ionic species (e.g., sulphates, phosphates, alkali salts of organic acids or quaternary ammonium salts), non-ionic species (e.g., hydroxyl, organic acids) or surfactant stabilizers (e.g., SDMS, SDS, Antarox) can be used to provide stable carbon product dispersions in aqueous media. Dispersion of the modified carbon products in organic liquids can be facilitated in a similar manner but employing treatments which are more compatible with these less polar environments. Treatment levels of the organic group for purposes of radical grafting sites would depend on material uses.
- attachment of epoxy groups would facilitate grafting to hydroxyl bearing polymer matrices such as polyurethanes or polycarbonates or amine matrices such as nylon.
- Other examples include the attachment of radical sensitive vinyl groups such as styrenics or acrylates, to facilitate crosslinking type reactions in radical polymerizations.
- These attached groups would ultimately affect the properties of the materials containing these modified carbon products. The properties that would be affected include, but are not limited to, impact behaviour, modulus response, and dispersibility in plastics.
- modified carbon products can be used.
- a modified carbon product having one type of organic group attached thereto can be used in combination with another modified carbon product having a different organic group attached thereto.
- a modified carbon product such as an aggregate comprising a carbon phase and a silicon-containing species phase can be used in combination with a modified carbon product having an attached organic group, and so on.
- the modified carbon product which is coated with one or more polymers can have any particle size and/or surface area so long as the particle is capable of being at least partially coated with one or more polymers.
- the primary particle size of the modified carbon product is from about 5 nm to about 100 nm and more preferably from about 8 nm to about 75 nm.
- the nitrogen surface area as measured by the BET method, of the modified carbon product is preferably from about 20 m 2 /g to about 1500 m 2 /g and more preferably from about 25 m 2 /g to about 700 m 2 /g and most preferably from about 30 m /g to about 250 m /g. If the modified carbon product is not a particle, such as a fiber, preferably the modified carbon product has the following preferred properties: reinforcement or conduction properties or other physical properties associated with filler particles.
- the thickness of the coating on the modified carbon product can be uniformed or can vary in thickness.
- the thickness of the coating can be about 1 nm or more.
- the polymer coated onto the modified carbon product is substantially uniform in thickness.
- the thickness of the polymer coating on the modified carbon product is from about 10 nm to about 100 nm, more preferably from about 20 nm to about 75 nm, and most preferably from about 30 nm to about 50 nm.
- Figures 3 and 4 are microphotographs showing the coating around the carbon black.
- the modified carbon product can have more than one coating or shell.
- the modified carbon product can have multiple layers of shells or coatings which partially or fully encapsulate the modified carbon product or a previous coating or shell.
- the polymers comprising the various layers can be the same or different. For instance, one layer can be cross-linked while the next layer can be not cross-linked.
- Each of the various coatings, if more than one is present on the modified carbon product, can be substantially the same or vary in thickness if desired.
- the polymer which is coated onto the modified carbon product can be a homo-polymer, copolymer, terpolymer, and/or a polymer containing any number of different repeating units.
- the polymer can be any type of polymer, such as a random polymer, alternating polymer, graft polymer, block polymer, star-like polymer, and/or comb-like polymer.
- the polymer can also be one or more polyblends.
- the polymer can be an interpenetrating polymer network (IPN); simultaneous interpenetrating polymer network (SIN); or interpenetrating elastomeric network (IEN).
- IPN interpenetrating polymer network
- SIEN simultaneous interpenetrating polymer network
- the polymer can be thermoplastic or thermosettable.
- polymers include, but are not limited to, linear and non-linear polymers such as polyethylene, poly(vinylchloride), polyisobutylene, polystyrene, polycaprolactam (nylon), polyisoprene, and the like.
- polymers include polyamides, polycarbonates, polyelectrolytes, polyesters, polyethers, (polyhydroxy)benzenes, polyimides, polymers containing sulfur (such as polysulfides, (polyphenylene) sulfide, and polysulfones, polyolefins, polymethylbenzenes, polystyrene and styrene copolymers (ABS included), acetal polymers, acrylic polymers, acrylonitrile polymers and copolymers, polyolefins containing halogen (such as polyvinyl chloride and polyvinylidene chloride), fluoropolymers, ionomeric polymers, polymers containing ketone group(s), liquid crystal polymers, polyamide-imides, polymers containing olefinic double bond(s) (such as polybutadiene, polydicyclopentadiene), polyolefin copolymers, polyphenylene oxides, poly
- the polymer is an acrylic polymer, a methacrylic polymer, or a styrenic polymer, but would largely depend upon the intended application.
- reinforcement applications would generally involve the formation of a rubber product that could be attached to the modified carbon product in a manner such that the rubber product is preferably not extractable, e.g., not extractable in solvents. This can be accomplished by using a modified carbon product that has styrenic groups attached to the surface. During an aqueous media radical polymerization, the propagating chains could graft to these sites on the surface of the modified carbon product and generate a rubbery coated particle.
- the polymer coated modified carbon products can be made by a number of ways.
- the modified carbon products are made by, but are not limited to, aqueous mediated polymerization environments such as emulsion polymerization or suspension polymerization processes as well as solvent based polymerizations.
- the polymerization involved are generally chain growth polymerizations and/or step growth polymerizations. Examples of the aqueous based polymerization processes are described below.
- an initiator, at least one monomer, and a modified carbon product as described above are combined or added into an aqueous- based medium.
- the components can be added in any order but it is preferred that the modified carbon product be added to the aqueous-based medium first and then the initiator and then the monomer. Then, an emulsion polymerization is conducted to form a polymer coated modified carbon product.
- an initiator can optionally be added to ensure continuing and/or complete polymerization of the monomer(s).
- the monomer(s) used in this polymerization is capable of being polymerized by any type of free radical polymerization including highly specialized free radical polymerizations such as stable free radical polymerization (SFRP) and atom transfer radical polymerization (ATRP).
- free radical polymerization SFRP
- ATRP atom transfer radical polymerization
- olefinic type monomers include, but are not limited to, acrylates, methacrylates, styrenics, dienes, or vinyl esters as well as monomers such as maleic anhydride or vinyl sulfone, vinyl pyridine, or vinylpyrolidinone.
- the monomer is styrenic, acrylic, or methacrylic or mixtures or combinations thereof.
- the amount of monomer present is an amount sufficient to at least polymerize and partially coat the modified carbon products in the aqueous-based or solvent based medium.
- this amount of monomer is from about 20 % to about 80 % by volume, more preferably from about 25 % to about 60% by volume, and most preferably from about 30 % to about 50% by volume, based on the total volume.
- the aqueous-based medium used can be any aqueous-based medium capable of permitting a free radical polymerization to occur.
- the aqueous-based medium is water or water-based, and more preferably is deionized water.
- the amount of the aqueous-based medium is an amount sufficient to permit at least free radical polymerization to occur such that at least a portion of the modified carbon product is partially coated with the polymerized monomer.
- any initiator capable of initiating a radical polymerization of at least a portion of the monomers present can be used.
- examples include, but are not limited to, peroxides such as hydrogen peroxide, and ammonium peroxysulfate.
- Other examples include azo compounds, for example, azobisisobutylnitrile, redox initiators such as ferrous ions (e.g. FeCl ⁇ ) , silver alkyl reagents, and other methods of initiation such as photo induced or electrolytic transfer process.
- the initiator is present in an amount to at least partially if not completely initiate to polymerization of the monomers present in the aqueous-based medium such as to at least partially coat the modified carbon product with the polymerized monomer(s).
- Typical ingredients and levels will be apparent to one skilled in the art of emulsion polymerization.
- the modified carbon product in order to be substantially encapsulated or coated with the polymer during the emulsion polymerization, should be adequately dispersed in the aqueous-based medium.
- the modified carbon product can be dispersed by mechanical means such as by stirring in order to keep the modified carbon product substantially suspended in the aqueous-based medium and/or one or more surfactants can be added to the aqueous-based medium in order to stabilize the suspension.
- a dispersion aid can be applied onto the modified carbon products prior to their introduction into the aqueous-based medium in order to provide a better dispersion in the aqueous-based medium.
- the modified carbon product used has an attached organic group which is substituted with an ionic, ionizable, or polar group
- no surfactant or dispersion aid is used, or at the very least, a lower amount of surfactant and/or dispersion aid can be used.
- the modified carbon product having an organic group with a substituted ionic, ionizable, or polar group is sufficiently water dispersible and thus no surfactant or dispersion aid is needed.
- this makes for an economical system for aqueous mediated polymerizations as well as provides uniform coverage, if desired, on the modified carbon products.
- no stirring would be necessary either.
- a surfactant can be used to further stabilize the emulsion.
- surfactants include, but are not limited to, ethoxylated alcohols such as polyethylene glycol, SDS, SDMS, and/or antarox surfactants.
- the surfactant, if used, can be present in amounts ranging from about 0.01 to about 30, more preferably from about 0.1 to about 10, and most preferably from about 1 to about 5, based on the weight of the modified carbon product.
- ingredients typically used with free radical polymerization reactions can also be present such as surface active agents (for aqueous media preparations such as suspension or emulsion techniques) and inhibiting or quenching agents (e.g., quinones or hydroquinones), crosslinking agents such as divinylbenzene, as well as chain-transfer agents such as mercaptans, CBr4 or other modifiers typically employed in free radical polymerizations and known to those skilled in the art of polymer synthesis and modification.
- surface active agents for aqueous media preparations such as suspension or emulsion techniques
- inhibiting or quenching agents e.g., quinones or hydroquinones
- crosslinking agents such as divinylbenzene
- chain-transfer agents such as mercaptans, CBr4 or other modifiers typically employed in free radical polymerizations and known to those skilled in the art of polymer synthesis and modification.
- the amounts of these various optional ingredients can vary depending upon the initiator, monomer, and modified carbon product used.
- the emulsion polymerization is preferably conducted where the aqueous-based medium, e.g., water, and the modified carbon black are charged into a flask kept in a water bath at approximately 70°C.
- the flask is purged with nitrogen and then an initiator is added to the flask.
- the monomers are then introduced at a fixed rate into the reacting flask using a peristaltic pump, such as a Watson-Marlow peristaltic pump, or other suitable introduction means such as gravametric devices, e.g., either flow controlled or manually adjusted.
- the reactions are allowed to proceed until completion such as for 10 hours, before the flask is cooled to room temperature.
- additional amounts of initiator can be added while stirring the flask at about 70°C to ensure complete polymerization of the monomer.
- the polymer coated modified carbon products can then be separated from the aqueous-based medium and any unreacted monomers or by-products by any means such as filtering or evaporation, or by other direct drying methods such as freeze drying and spray drying.
- the material can be allowed to settle once it is of sufficient coating weight and the aqueous supernatant can be decanted off.
- the residual wet solid can be dried using conventional techniques such as oven batch drying or continuous drying such as that achieved in fluidized bed dryers.
- the monomer(s) can be added at any rate, but preferably at rates such that the monomer(s) is completely added over a period from about 15 minutes to about 24 hours, more preferably from about 1 hour to about 10 hours, and most preferably from about 2 hours to about 5 hours in order to obtain an optimized coating on the modified carbon product.
- the conditions for conducting the polymerizations described above can be optimized by a number of factors such as temperature, agitation, atmosphere in which the polymerization occurs, pressure, and the like. These factors and their effects would be the same or similar to the knowledge possessed by those skilled in the art with respect to general polymerizations and would be easily determinable in view of this knowledge coupled with the details provided herein.
- the atmosphere is inert and the temperatures during polymerization are somewhat dependent on the initiator system used.
- General polymerization factors and parameters, that can be applied to the present invention in view of the disclosure herein, are set forth in "The Chemistry of Free Radical Polymerization," G. Moad and D.
- Polymer coated modified carbon products can also be formed by solvent based polymerization processes which are similar to the aqueous based polymerization procedures. Modified carbon products bearing groups that enhance dispersion in solvents, such as toluene, and/or allow for the grafting of the propagating polymer to the carbon products are preferred.
- solvents include but are not limited to solvents having a low chain transfer constant, such as toluene, xylenes, THF, and ethyl acetate.
- solvent-based polymerizations include, but are not limited to, solution polymerization and solution coating.
- solution coating generally, once the polymerization is complete, the modified carbon product is added by any means and preferably is dispersed in the polymer solution for a time sufficient to at least partially coat the modified carbon product with the polymer present in solution. Then, controlled separation of the solvent from the polymer and polymer coated modified carbon product occurs such as by controlled evaporation or precipitation into a non-solvent. The polymer coated modified carbon product is then subjected to drying for instance at 40°C under vacuum.
- one type of solution coating process involves the preparation of a polymer in solution (e.g., a solvent), wherein the modified carbon product is then added to the polymer solution and the solvent containing the polymer is then removed, such as by evaporation or other means.
- a polymer in solution e.g., a solvent
- the solvent used in the coating process is generally an organic solvent such as toluene but can include polar solvents such as methanol depending upon the nature of the polymer material intended to cover the modified carbon product.
- the polymerization of the monomer(s) occurs in situ in the presence of the modified carbon product in an organic solvent.
- Other conventional ingredients typically used in such solvent-based polymerizations can also be present in conventional amounts.
- the initiator is present in amounts higher than conventional.
- the solvent based solution contains free radical initiators as described above, and the desired monomer(s).
- the reaction solution is heated, e.g., to approximately 70° C for several hours. This type of polymerization is generally allowed to proceed until completion such as for 30 hours at 60° C under a nitrogen atmosphere.
- the final product would be collected using conventional recovery techniques, such as evaporative techniques.
- the polymer coated modified carbon products of the present invention can also be prepared through a bulk polymerization.
- a polymerizable monomer is present along with the modified carbon products and an initiator.
- a controlled amount of initiator is present in order to have unreacted monomer remaining at all times in order to act as the solvent.
- no formal solvent needs to be present since the unreacted monomer acts as the solvent.
- the various types of monomers that can be used in this process include, but are not limited to, the monomers described earlier.
- the polymer coated modified carbon products of the present invention can be made by dispersing the modified carbon products in a latex formulation which, due to the dispersibility of the carbon products, will be coated and then can be separated by separating means known to those skilled in the art such as evaporation, freeze drying, spray drying, coagulation, centrifugation, filtration, and the like.
- the polymer coated modified carbon products of the present invention can be used in a number of ways.
- the polymeric coated modified carbon products can be used in masterbatches which contain from low to high concentrations of carbon products, such as carbon black.
- the polymeric coated modified carbon products can be introduced into a masterbatch in the same manner as conventional carbon black is formed into a polymeric masterbatch.
- the polymeric coated modified carbon products can themselves act as a highly concentrated or standard masterbatches in view of the amount of polymer already present and coated onto the modified carbon products.
- the polymer coated modified carbon product of the present invention is formed into a masterbatch just as conventional masterbatches are formed. Accordingly, the polymer coated modified carbon product can be added with standard masterbatch ingredients which may include waxes and polymers as well as other optional ingredients.
- the amount of modified carbon product present can be amounts traditionally used with conventional carbon products, such as carbon black, in masterbatches.
- masterbatches with higher loadings of carbon products are possible and thus masterbatches of the present invention can contain from about 10 wt% to about 95 wt% or more carbon product, and more preferably from about 50 wt% to about 90 wt% carbon product, based on the weight of the masterbatch.
- the modified carbon products of the present invention can be incorporated or dispersed in the polymer to form the polymeric product using any means which permit the introduction of conventional reinforcement agents, fillers, or colorants like carbon black.
- Examples include hopper feeding of the modified carbon product into an extruder such as a single screw or multi-screw extruder, or an injection molder.
- Other means of introducing the modified carbon product into the polymer include mixers, like internal mixers, such as Banbury and Brabender mixers.
- Other means of introducing, and preferably dispersing the modified carbon product in the polymer include, but are not limited to, long continuous mixers, continuous compounding extruders (e.g., Buss Kneader), tumble blenders, pelletizers, and the like.
- each individual primary aggregate is preferably evenly coated. This allows for good surface wetting characteristics of the polymer coated modified carbon product in the matrix material it is diluted with. This effect results in superior dispersion characteristics when compared to the identical procedure carried out with untreated or conventional carbon products or with comparable commercial masterbatches. Moreover, the ease at which these materials are prepared in view of the process for preparing masterbatches, makes the polymer coated modified carbon products superior additives. Additionally, since the modified carbon particles are located within discrete polymer coatings, and when the formulation of the coating resin is properly designed, unique properties can be attained which are not necessarily attained with a direct mixture of the polymer and the carbon particles. For instance, properties such as reinforcement of rigid matrices can be attained when compared to materials having separate carbon particles and polymer compounded into them separately.
- the polymer coated modified carbon products of the present invention have the ability to chemically interact with the polymer coating and this coating, when adequately formulated can also interact with the matrix polymer product in which it is introduced to.
- the interaction between modified carbon product and polymer coating has been described above.
- the coated modified carbon products can attach to the polymer matrix, e.g., graft onto the polymer matrix of the polymeric product.
- This ability can lead to improved properties such as impact strength and tensile strength.
- Other properties such as melt flow viscosities can be influenced in this way.
- Advantanges of this method include but are not strictly limited to, the ability to produce materials of superior impact strength, controlled flow properties, beneficial material surface adhesion, and improved color characteristics.
- FIGS 1 and 2 show the ability of a polymer coated modified carbon product to provide improved properties with respect to tensile and impact strength once the polymer coated modified carbon products are incorporated into a polymer matrix, like SAN.
- the "Sterling” is conventional carbon black
- the "coated Sterling” is modified carbon black having attached-styrene groups and subsequently coated with about 20 nm of PS/BA GMA polymer.
- the polymeric products of the present invention like any conventional polymer, can be formed and shaped into any desired article or shape.
- polymeric products of the present invention include solvent-borne and solvent- free polymeric coatings as well as polymeric foams.
- polymeric coatings typically an aqueous or non-aqueous medium will be present in amounts typically found with respect to conventional polymeric coatings.
- polymeric foams typically a foaming agent will be present in amounts conventionally found with respect to conventional polymeric foams.
- the polymeric products of the present invention can include additional conventional ingredients typically found in polymers such as anti-oxidants, stabilizers (e.g., light/UV and thermal types), plasticizers, fillers, impact modifiers, lubricants, biocides, flame retardants, process modifiers, antistatic agents, blowing (foaming) agents, colorants, antimicrobials, antiblocking agents, organic peroxides, optical brighteners, coupling agents, compatibilizers, process acids, mold release aids, tack additives, viscosity suppressants, reactive additives fibers, antifogging agents, antihazing agents, bacteriocides, conductivity agents, cross-linking agents, delustering agents, dispersants, flexibilizers, flow control agents, fluorescent agents, fusion promoters, mildewcides and fungicides, nucleating agents, organic chelating agents, surface treatments, and the like, or other materials as described in Plastic Additives and Modifiers Handbook, Jesse Edenbaum, Ed., pp. 193
- the polymer coated modified carbon products preferably have improved properties compared to untreated carbon black and/or the polymers themselves which are coated onto the carbon product when added to a polymeric product.
- polymeric products containing the polymer coated modified carbon products of the present invention preferably have improved impact properties and/or tensile properties compared to polymeric products containing untreated carbon black.
- the polymer coated modified carbon products are capable of improving ultimate impact strength of resins such as SAN (styrene acrylonitrile) when compared to SAN containing unmodified carbon black and rubber reinforcing agents.
- resins such as SAN (styrene acrylonitrile)
- Other advantages include the ability to act as easily (low shear) dispersible colorants or reinforcing agents when compared to conventional masterbatches with controlled viscosity and better colour characteristic.
- the resultant weight percentage of modified carbon product in a resin produced in situ is in the range of 0.01 % wt to 3.0 % wt., the resin can be considered a direct letdown material with excellent dispersion characteristics without the use of shear intensive mixing.
- modified pigments other than carbon products can be used as well to form polymer coated modified pigments.
- modified pigments would encompass all types of pigments capable of having at least one organic group attached thereto.
- the colored pigment is any pigment which can be modified with the attachment of an organic group, like an aromatic group or an alkyl group.
- the colored pigments other than carbon products include, but are not limited to, black, blue, white, cyan, green, violet, magenta, red, yellow, tones and/or shades thereof as well as mixtures thereof.
- Suitable classes of colored pigments include, but are not limited to, anthraquinones, phthalocyanine blues, phthalocyanine greens, diazos, monoazos, pyranthrones, perylenes, heterocyclie yellows, quinacridones, and (thio)indigoids. Specific examples and further information concerning the colored pigments and methods of making colored pigments with attached organic groups are described in U.S. Patent No. 5,837,045 and PCT Publication No. WO 97/47699, both incorporated in their entireties by reference herein.
- the polymer coated modified carbon products and pigments can be used in rubber and elastomeric compositions according to the present invention.
- Rubbers suitable for use with the present invention are natural rubber and its derivatives such as chlorinated rubber.
- the modified pigment products of the invention may also be used with synthetic rubbers such as: copolymers of from about 10 to about 70 percent by weight of styrene and from about 90 to about 30 percent by weight of butadiene such as copolymer of 19 parts styrene and 81 parts butadiene, a copolymer of 30 parts styrene and 70 parts butadiene, a copolymer of 43 parts styrene and 57 parts butadiene and a copolymer of 50 parts styrene and 50 parts butadiene; polymers and copolymers of conjugated dienes such as polybutadiene, polyisoprene, polychloroprene, and the like, and copolymers of such conjugated dienes
- the rubber composition of the present invention can therefore contain at least one elastomer, curing agents, reinforcing filler, a coupling agent, and, optionally, various processing aids, oil extenders, and antidegradents.
- the elastomer can be, but is not limited to, polymers (e.g., homopolymers, copolymers, and terpolymers) manufactured from 1,3 butadiene, styrene, isoprene, isobutylene, 2,3-dimethyl-l,3 butadiene, acrylonitrile, ethylene, propylene, and the like.
- these elastomers have a glass transition point (Tg), as measured by DSC, between -120° C and 0° C.
- Tg glass transition point
- examples of such elastomers include poly(butadiene), poly(styrene-co-butadiene), poly(isoprene), styrene-butadiene rubber (SBR), natural rubber, and their oil-extended derivatives. Blends of any of the foregoing may also be used.
- Elastomeric compositions disclosed in the present invention and which can be prepared include, but are not limited to, vulcanized compositions (VR), thermoplastic vulcanizates (TPV), thermoplastic elastomers (TPE) and thermoplastic polyolefins (TPO), TPV, TPE, and TPO materials are further classified by their ability to be extruded and molded several times without loss of performance characteristics.
- VR vulcanized compositions
- TPV thermoplastic vulcanizates
- TPE thermoplastic elastomers
- TPO thermoplastic polyolefins
- the elastomeric composition may include one or more curing agents such as, for example, sulfur, sulfur donors, activators, accelerators, peroxides, and other systems used to effect vulcanization of the elastomer composition.
- curing agents such as, for example, sulfur, sulfur donors, activators, accelerators, peroxides, and other systems used to effect vulcanization of the elastomer composition.
- the resultant elastomeric compounds containing the modified pigment, and preferably modified carbon black of the present invention and optionally containing one or more coupling agents may be used for various elastomeric products, including tires and components thereof, such as a tread compound, undertread compound, sidewall compound, wire skim compound, innerliner compound, bead, apex, any compound used in carcass and other components for vehicle tires, industrial rubber products, seals, timing belts, power transmission belting, and other rubber goods.
- the modified pigment products, and especially the modified carbon black products of the present invention can impart improved abrasion resistance and/or reduced hysteresis to rubber or elastomeric compositions containing them.
- S represents Sterling® carbon black
- R represents Regal® carbon blacks
- nf ' represents an organic group attached
- the first number represents the thickness of the polymer coating on the carbon product and the second number represents the amount of carbon black and any polymer coated onto the carbon black as a percent by weight of the polymer matrix with filler.
- R-nf-0-50 would mean Regal carbon black which was untreated (no organic groups attached) and 0 is the polymer coating thickness and 50 is the amount of carbon product by weight percent.
- Homopolymers of styrene (PS), acrylonitrile (PAN) and glycidyl methacrylate (PGMA), and a terpolymer of the three of them (PS/AN/GMA) were prepared by solution polymerisation in toluene at a solvent to monomer ratio of 70:30 by weight.
- AZBN was used as the initiator at a level of 0.1% by weight of monomer.
- the polymerisation was allowed to proceed for 16 hours at 60 °C under a nitrogen atmosphere.
- the resulting polymers were separated and purified by precipitation into a large excess of petroleum ether (60/80) and dried at 40 °C under vacuum to constant weight.
- the comonomer compositions used are given in Table 1.
- Table l The compositions of the styrene, acrylonitryle and glycidyl methacrylate used in individual polymerization's.
- wts % is the percentage weight of styrene in the total monomer mixture
- tAN % is the percentage weight of acrylonitrile in the total monomer mixture
- wtGMA % is the percentage weight of glycidyl methacrylate in the total monomer mixture
- the structure of the terpolymer prepared had the following structure:
- Coating of the carbon black or the modified carbon black particles was achieved via a solution evaporation method. There were three main steps in the procedure for coating the particles: first, the dissolution of the terpolymer (PS/AN/GMA) in a suitable solvent (100:5 wt% solvent:wt% terpolymer); next, the dispersion of the washed particles into the solution; and finally, the controlled evaporation of the solvent.
- the dispersion of the particles into the toluene-dissolved copolymer was carried out using a Silverson L4R high-shear mixer. The solvent was removed from the mixture under water pump vacuum using a rotary-film evaporator at 70° C. Three different samples were prepared from each carbon black grade or modified carbon black.
- Table 2A shows the mass of terpolymer used to prepare the coated samples relative to 1 g of carbon black or modified carbon black. Table 2A. Coated samples indicating the mass of terpolymer used in their preparation with respect to 1 g of carbon black.
- Styrene was selected as the monomer and 4,4'-azobis(4-cyanopentanoic acid) as the initiator.
- the carbon black was Sterling® 4620 grade (Cabot Corporation) with -C6H4S ⁇ 3Na groups attached to the carbon black.
- Three emulsion polymerization's were carried out, with the only difference being the amount of initiator used.
- the formulations used are given in Table 2B.
- the amount of polymer used was calculated to give a 20 nm coating, based upon the surface area and volume of the equivalent non- porous sphere with the same diameter as the modified carbon black.
- El, E2 and E3 denotes the three different emulsion polymerization's perfonned.
- the polymerization's were performed under nitrogen in a 5-necked flanged reaction flask at 70
- Cycolac SAN 29283 was blended with the two grades (Regal 80® and Sterling 4620® carbon black) of the coated and uncoated modified carbon blacks.
- the compounding was carried out using a Banbury mixer with the mixing conditions summarised in Table 3.
- the prepared compounds and their analytical data are summarised in Table 4. Table 3.
- 6B S-nf-0-30 20.6 20.47 12.0 3 6 1060
- Example 3 Studies were carried out in order to synthesise a terpolymer (PS/BA/GMA) of styrene, butyl acrylate and glycidyl methacrylate with a lower Tg than the one described in Example 1.
- Styrene (Aldrich, 98%) was washed several times with 10% sodium hydroxide solution in a separating funnel, then several times with distilled water. The inhibitor-free monomer was dried over anhydrous calcium chloride before being distilled under nitrogen at reduced-pressure. Butyl acrylate (Aldrich, 97%) was washed several times with 2% sodium hydroxide solution in a separating funnel, then several times with distilled water. The inhibitor-free monomer was dried over anhydrous calcium chloride before filtering off. Azo-bis(isobutyronitrile) (AZBN) was purified by forming a saturated solution in toluene at 30 °C and then cooling the solution to 0 °C in an ice-water bath. Glycidyl methacrylate (Aldrich, 97%) was used as supplied.
- AZBN Azo-bis(isobutyronitrile)
- the terpolymer was prepared by solution polymerisation in toluene at an initial solvent to monomer ratio of 70:30 by weight.
- AZBN was used as the initiator at a level of 0.1% by weight of monomer.
- the polymerisation was allowed to proceed with stirring for 30 hours at 60 °C under a nitrogen atmosphere.
- Two different terpolymers were prepared with different comonomer composition.
- Table 5 shows the comonomer compositions used.
- (a) wt ⁇ A % is the percentage weight of butyl acrylate in the total monomer mixture
- wts % is the percentage weight of styrene in the total monomer mixture
- wtQMA % is th e percentage weight of glycidyl methacrylate in the total monomer mixture.
- wt ⁇ A % is the percentage weight of butyl acrylate in the terpolymer
- wts % is the percentage weight of styrene in the terpolymer
- wtGMA % is the percentage weight of glycidyl methacrylate in the terpolymer
- the terpolymer (PS/BA/GMA) i shows a Tg at 14° C while the terpolymer (PS/BA/GMA)2, which has greater amount of butyl acrylate, has a Tg at -30° C.
- Terpolymer (PS/BA/GMA)2 was selected as the one for coating the carbon black or modified carbon black particles due to its low Tg (-30° C).
- the coating was carried out via the solution evaporation method using the same procedure as described in the previous report.
- the various particles were dispersed into the as-prepared terpolymer solution, followed by the controlled evaporation of the solvent.
- the coating of the samples resulted in a 20 nm thick coat and a hard solid after drying at 40° C under vacuum.
- coated samples were characterised by DSC which show similar traces to that of the terpolymer exhibiting a single Tg around -30° C.
- the polymer used for the coating was the terpolymer (PS/BA/GMA)2 of styrene, butyl acrylate and glycidyl methacrylate.
- the targeted coating thickness of the modified carbon blacks with the specially-synthesised terpolymer was 20 nm.
- a mortar was used for grinding the coated, modified carbon blacks into fine powders. The coated, modified carbon blacks were subsequently compounded with SAN.
- Cycolac SAN 29283 was blended with the two grades (Regal 80® and Sterling 4620® carbon blacks) of coated and uncoated carbon blacks. The compounding was carried out using a Banbury mixer with the mixing conditions summarised in Table 7. The prepared compounds and their analytical data are summarised in Table 8.
- the materials used in the emulsion polymerization's were styrene (Aldrich, 98%), butyl acrylate (Aldrich, 97%) (purified as described in Section 3.1.1), deionised water which was boiled under a N2 atmosphere in order to eliminate dissolved 02, modified carbon black which was washed with methanol and dried to constant weight, and the initiators, 4,4'-azobis (4-cyanopentanoic acid) (Aldrich, 75+%) and ammonium persulphate (Aldrich, 99.0%), both used as supplied. Thirty emulsion polymerization's were carried out in total for the three monomer / initiator combinations studied.
- a reaction flask was initially charged with water (25 g) and modified carbon black (10 g). The contents of the reaction flask were stirred continuously and a flow of nitrogen established. After the contents of the flask attained bath temperature, a solution of the initiator in water (5 g) was added and the system sealed. The total quantity of monomer was then added via a dropping funnel over a period of 15 minutes. After 10 hours the reaction flask was cooled to room temperature and the reaction product collected by filtration through a No. 4 sinter, followed by drying under vacuum at 60 °C. Before filtering an aliquot was removed in order to calculate the conversion of the reaction using gas-liquid chromatography (GLC).
- GLC gas-liquid chromatography
- the formulations used in the emulsion polymerization's are given in Tables 9, 10 and 11.
- GLC was used to determine the amount of unreacted monomer in the aliquot removed after reaction in order to calculate the conversion level of the emulsion polymerisation.
- Anala R methanol was added to the aliquot in order to induce the miscibility of the water and monomer.
- GLC was carried out using a Perkin-Elmer Autosystem Gas Chromatograph. Quantitative analysis was carried out using propan-1-ol as an internal standard.
- Initiator content varies between 0.0007 and 1.0000 g for the 11 reactions carried out.
- Table 10 Formulations used in the emulsion polymerization's of the styrene / ammonium persulphate combination.
- Deionised water which was boiled under a N2 atmosphere in order to eliminate dissolved O2, was used in all preparations.
- the two monomers used were butyl acrylate (BA, Aldrich, 97%) and allyl methacrylate (ALMA, Aldrich, 98%).
- Butyl acrylate was used after being washed several times with 2% sodium hydroxide. Allyl methacrylate was used as supplied.
- the modified carbon black (Sterling 4620® carbon black with attached -C ⁇ HtSOsNa groups, and attached groups) was washed with methanol and dried to constant weight, and the initiator, ammonium persulphate (Aldrich, 99.0%) was used as supplied. Polymerization's were carried out using a form of semi- continuos emulsion polymerisation.
- the water and modified carbon black were charged in a round-bottomed flask kept in a water bath at 70° C. The flask was purged with nitrogen. After the mixture had reached bath temperature, the initiator was added and the monomers were pumped at a fixed rate into the reactor using a Watson- Marlow peristaltic pump. The reactions were allowed to proceed for 10 hours before cooling to room temperature and filtering through a No. 4 sinter and drying under vacuum at 60° C. Extra initiator in water was added after 3 hours reaction time for preparing coating of thickness greater than 15 nm.
- Emulsion polymerisation products were analysed by weight-loss and extraction experiments, gas-liquid chromatography (GLC) and differential scanning calorimetry (DSC). • A gravimetric method, based on weight loss of the sample, and an extraction experiment were used to calculate quantitatively the amount of polymer present in the samples. These methods are the followings: a) Furnace method
- the temperature of the oven was increased from 60 to 160° C at a rate of 7° C min"l.
- an aliquot was removed from a reaction in order to calculate the conversion level in the emulsion polymerisation.
- AnalaR methanol was added to the aliquot in order to induce the miscibility of the water and monomer. Quantitative analysis was carried out using propan-1-ol as an internal standard.
- the targeted coating thickness was 10 nm in all cases.
- Three representative examples of the emulsions polymerization's carried out are shown in Table 12.
- E6 polymerization did not go to complete reaction with the amount of initiator used, indicating that the addition of an extra initiator was necessary for the emulsion polymerization's with a coating thickness of 20 nm or higher.
- the targeted coating thickness was 10 nm.
- the polymerisation procedure was as described above. After the reaction, the products obtained were filtered off, dried and ground into fine powders.
- Cycolac SAN 29283 was blended with the coated modified carbon black. The compounding was carried out using a Banbury mixed with the mixer conditions sumi ⁇ arized in Table 17. The prepared compounds and their analytical data are summarised in Table 18.
- compositions also injection moulded.
- the polymer used for the coating was the terpolymer (PS/BA GMA) of styrene, acrylonitrile and glycidyl methacrylate previously described in Example 3. Two grades of modified carbon black were coated by this method.
- Table 20 shows the tensile properties of the compounds.
- the values of the unfilled SAN and uncoated-carbon black filled SAN compounds are also given for comparative purposes.
- PS/BA/GMA has a composition of 2/95/3 % and BA/ALMA of 98/2 % by weight
- E is the tensile modulus calculated as the secant at 0.1 % elongation
- compositions also injection moulded.
- Three-point bend single edge-notched impact testing was performed using a Ceast 6545 digital pendulum, (release angle set at 15°) interfaced to a MK4 microprocessor together with a PC.
- the notch-to-depth ratio, (a/w) was 0.50 ⁇ 0.05 and for each material at least 6 specimens were analysed and mean results calculated.
- the measured values of the fracture energy, G ⁇ c as calculated from ASTM D 5045-95, are presented in Table 21. Table 21. Variation of fracture energy, G ⁇ c , with weight percentage of carbon black, wt(CB).
- Gic is the fracture energy as calculated from ASTM D 5045-95
- Figures 5(a) - (c) shows the effect of carbon black content upon Gfc. There is a significant decrease in the G c value with increasing carbon black content for the uncoated carbon black compounds. This trend is the same for the emulsion-coated modified carbon blacks. In contrast the solution-coated compounds show the opposite trend, with G ⁇ c increasing as the filler content increases. The filled SAN was shown to be tougher than the unfilled material even at 50 % filler content.
- Polymerizations were carried out using a form of semi-continuous emulsion polymerisation.
- the water and carbon black were charged in a round-bottomed flask kept in a water bath at 70°C. The flask was purged with nitrogen. After the mixture had reached bath temperature, the initiator was added and the monomers were pumped at a fixed rate into the reactor using a Watson-Marlow peristaltic pump. The extra amount of initiator (disolved in water) was also added in a continuous way over a 3 hours period using a syringe pump. This slow rate of adding of the initiator ( ⁇ 0.23 ml min"*) was chosen to avoid destabilisation of the reaction which may occur when all the initiator is added in one step.
- DSC experiments were performed on the reaction products in order to detect the polymer- coating. Experiments were performed under nitrogen at a heating rate of 20°C min"l using a DuPont Thermal Analyst 2000 instrument with a DuPont 910 cell base fitted with a DSC cell. The products were well dried in a vacuum oven at 40°C to constant weight before analysis.
- Dispersibility experiments were also carried out on the scaling-up products. Small amounts (-1 g) of the dried products (E-100A-10, E-100A-20 and E-100A-30) were dispersed in water (-10 g) and allowed to settle. The experiment showed that the dispersibility in water was poorer with increasing coating thickness, observing that the sedimentation of E-100A-30 and E-100A-20 is very quick. The sedimentation of E-100A-10 required longer periods of time. These experiments showed that the polymer was successfully coated onto the carbon black and also showed, qualitatively, the effects of the different coating thicknesses.
- Two sets of compounds were prepared; the first set was prepared by blending Cycolac SAN 29283 with the coated carbon black (E-100A-20) in various proportions, and the second set by blending the SAN with E-100A-30.
- the compounding was carried out using a Banbury with the mixing conditions summarized in Table 24.
- the prepared compounds and their analytical data are summarized in Table 25.
- Table 24 Banbury mixing conditions of SAN with the coated carbon black E-100A-20 and E-100A- 30.
- Tensile tests were performed according to ASTM D638 using an Instron 1 122 tensile testing machine in order to obtain the tensile properties of the various compounds. The tests were carried out using a gauge length of 64 mm and a crosshead speed of 10 mm min"'. An Instron 2630-30 extensometer was used to measure strains up to 10% accurately. A total of six specimens were tested for each material and the mean values of the mechanical properties calculated.
- Table 26 shows the tensile properties of the compounds.
- the values of the SAN and uncoated carbon black-filled SAN compounds are also given for comparative purposes.
- Figures 4-6 show the variation of Young's modulus, E, ultimate stress, 0 " u, and ultimate strain, £ u> >th carbon black content for the compounds.
- the values obtained from the compounds prepared with E-lOOA-10 are also showed for comparative purposes.
- E is the tensile modulus calculated as the secant at 0.1 % elongation
- Table 27 Tensile properties of the filled and unfilled SAN injection-moulded tensile specimens according to ISO R527 type II. The values between parenthesis corresponds to specimens ISO R527 type I and they were tested using a gauge length of 120 mm.
- E is the tensile modulus calculated as the secant at 0.1 % elongation
- Tables 26 and 27 showed that Young's modulus, ultimate stress and ultimate strain follow the same trend with carbon black content as those described for the compression molded specimens, however it is noticeable that there are significant differences between the behaviour of the coated samples E-100A-30 and the others (E-lOOA-10 and E-100A-20). Samples containing E-100A-30 display slightly lower values of Young's modulus and significantly higher values of ultimate stress and strain. This indicates that the ratio of polymer-coating to carbon black ( ⁇ 0.4 g polymer / 1 g CB) used in these samples is appropriate for changing the mechanical properties. This same ratio of polymer- coating to carbon black was also used in the solution-coated blacks which displayed improved mechanical properties.
- Three-point bend single edge-notched impact testing was performed using a Ceast 6545 digital pendulum, (release angle set at 15°) interfaced to a MK4 microprocessor together with a PC.
- the notch-to-depth ratio, (a/w) was 0.50 ⁇ 0.05 and for each material at least 6 specimens were analyzed and mean results calculated.
- the measured values of the fracture energy, G ⁇ c as calculated from ASTM D 5045-95, are presented in Table 28.
- Gic is the fracture energy as calculated from ASTM D 5045-95
- the 30 nm coating thickness was selected in order to have a ratio of the weight percent coating polymer (wt% polymer) to weight percent carbon black (wt% CB) of approximately 0.4 g polymer / 1 g CB. This ratio is similar to that used in the solution evaporation method [S-NH2- 20(BA) and R-NH2-20(BA)] which showed improved mechanical properties over the uncoated carbon black.
- Table 29 shows the compositions of the most representative polymerizations.
- Polymerisation E5 is similar to E4 but in this case the BA:ALMA ratio was 99: 1 mol%.
- the instantaneous conversions indicated that between the reaction time of 20-80 min, more than 90 % conversion was achieved. This was followed by a decrease and as the addition of extra amount of initiator started the conversion increased again until 100 % at approximately 220 minutes.
- compositions of E4, E5 and E6 were the selected ones for the scaling-up of the coating process.
- Two batches of the polymer-coated carbon black were prepared for each of the scaling-ups (E-
- Table 30 Composition details of the polymer-coated carbon black, grade Sterling (-C6H4S ⁇ 3Na) (sample number T016-84A), with a 30 nm coating thickness.
- Sample Code Polymer-Coating Composition Composition of Coated mol% CB wt%
- E-16A-30 and E-16A-30(99BA) had a Tg of —43 °C (similar to that obtained for the reaction E-lOOA-30 which was — 44° C).
- the scaling-up E-16A-30(94BA) had a Tg of — 30°C. This increase in the Tg is due to the lower content of BA in the copolymer (94 mol%) and the presence of MMA and S which has a more glassy and less rubbe y features than the BA.
- the scaling-up products were also characterised by IR spectroscopy. The main feature of the IR spectra of the sca ⁇ ng-up samples were the peaks due to the presence of BA in the polymer coating
Abstract
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Also Published As
Publication number | Publication date |
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US6479571B1 (en) | 2002-11-12 |
JP5088999B2 (en) | 2012-12-05 |
EP1255787A1 (en) | 2002-11-13 |
JP2004501209A (en) | 2004-01-15 |
AU2001231116A1 (en) | 2001-08-07 |
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