CA2271128A1 - New targetable solids for polymer blends and methods of manufacturing the solids and blends containing the same - Google Patents
New targetable solids for polymer blends and methods of manufacturing the solids and blends containing the same Download PDFInfo
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- CA2271128A1 CA2271128A1 CA002271128A CA2271128A CA2271128A1 CA 2271128 A1 CA2271128 A1 CA 2271128A1 CA 002271128 A CA002271128 A CA 002271128A CA 2271128 A CA2271128 A CA 2271128A CA 2271128 A1 CA2271128 A1 CA 2271128A1
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- polymer
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- polymers
- curative
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- 239000000203 mixture Substances 0.000 title claims abstract description 92
- 239000007787 solid Substances 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 53
- 229920002959 polymer blend Polymers 0.000 title claims description 38
- 238000004519 manufacturing process Methods 0.000 title 1
- 229920000642 polymer Polymers 0.000 claims abstract description 135
- 239000000945 filler Substances 0.000 claims abstract description 88
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 63
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 58
- 229920001577 copolymer Polymers 0.000 claims description 39
- 239000005062 Polybutadiene Substances 0.000 claims description 30
- 229920002857 polybutadiene Polymers 0.000 claims description 30
- 239000000377 silicon dioxide Substances 0.000 claims description 28
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 13
- -1 and thereafter Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000440 bentonite Substances 0.000 claims description 4
- 229910000278 bentonite Inorganic materials 0.000 claims description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 4
- 229910052570 clay Inorganic materials 0.000 claims description 4
- 239000000454 talc Substances 0.000 claims description 4
- 229910052623 talc Inorganic materials 0.000 claims description 4
- 229920001169 thermoplastic Polymers 0.000 claims description 4
- 239000004416 thermosoftening plastic Substances 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 229920005610 lignin Polymers 0.000 claims description 3
- 229920001187 thermosetting polymer Polymers 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 abstract description 45
- 239000005060 rubber Substances 0.000 abstract description 29
- 239000000806 elastomer Substances 0.000 abstract description 16
- 229920000098 polyolefin Polymers 0.000 abstract description 9
- 238000001179 sorption measurement Methods 0.000 description 23
- 239000002243 precursor Substances 0.000 description 16
- 238000001723 curing Methods 0.000 description 10
- 238000005004 MAS NMR spectroscopy Methods 0.000 description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229920001195 polyisoprene Polymers 0.000 description 6
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 6
- 229960002447 thiram Drugs 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 6
- 229920000459 Nitrile rubber Polymers 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- PGAXJQVAHDTGBB-UHFFFAOYSA-N dibutylcarbamothioylsulfanyl n,n-dibutylcarbamodithioate Chemical compound CCCCN(CCCC)C(=S)SSC(=S)N(CCCC)CCCC PGAXJQVAHDTGBB-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 229920005557 bromobutyl Polymers 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000013007 heat curing Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000001029 thermal curing Methods 0.000 description 3
- MHKLKWCYGIBEQF-UHFFFAOYSA-N 4-(1,3-benzothiazol-2-ylsulfanyl)morpholine Chemical compound C1COCCN1SC1=NC2=CC=CC=C2S1 MHKLKWCYGIBEQF-UHFFFAOYSA-N 0.000 description 2
- HLBZWYXLQJQBKU-UHFFFAOYSA-N 4-(morpholin-4-yldisulfanyl)morpholine Chemical compound C1COCCN1SSN1CCOCC1 HLBZWYXLQJQBKU-UHFFFAOYSA-N 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- XMEKHKCRNHDFOW-UHFFFAOYSA-N O.O.[Na].[Na] Chemical compound O.O.[Na].[Na] XMEKHKCRNHDFOW-UHFFFAOYSA-N 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229920005556 chlorobutyl Polymers 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 150000001282 organosilanes Chemical class 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 229940124530 sulfonamide Drugs 0.000 description 2
- 150000003456 sulfonamides Chemical class 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- IFNXAMCERSVZCV-UHFFFAOYSA-L zinc;2-ethylhexanoate Chemical compound [Zn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O IFNXAMCERSVZCV-UHFFFAOYSA-L 0.000 description 2
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000000371 solid-state nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Solid, e.g., modified fillers and curatives, for polymers, elastomers, rubbers, polyolefins, and blends thereof, comprising a solid having the polymers, rubbers, polyolefins, and elastomers of the blend or polymers, rubbers, polyolefins, and elastomers compatible with the components of the blend coated or adsorbed thereon and methods of preparing the modified solids and blends containing the same.
Description
NEW TARGETABLE SOLIDS FOR POLYMER BLENDS
AND METHODS OF MAINUFACTURING THE SOLIDS AND
BLENDS CONTAINIhTG THE SAME
BACKGROUND OF THE INVENTION
Field of the Invention to This invention relates to new, modified solids, e.g. fillers and curatives, for polymers, elastomers, polyolefins, rubbers, and blends thereof and methods of preparing the modified solids and blends containing the same. Generally, the invention relates to targetable solids for addition to polymer blends, i. e., solids which may be custom designed to locate themselves in specific polymer components of the blend.
1s Description of Related Art Generally, solids have been utilized and/or incorporated into general purpose n~bber (GPR), polymers, elastomers, polyolefins, and/or mixtures of the above.
For example, in the tire industry, numerous solid fillers have been proposed for rubber and polymer blends in order to enhance the properties of tires, for example, to decrease the 2o rolling resistance of tires by modifying the rubber compositions used for the treads of tires. Reinforcing white fillers such as silica, bentonite, clay, titanium oxide, talc, etc., have been proposed for use in tire treads which tend to decrease the resistance to travel of the tires having a tread comprising such fillers. Various fillers and processes for blending the same into rubber compositions have been proposed. For example, 25 Rauline, in U.S. Patent No. 5,227,425, describes the use of a copolymer of a conju-gated dime with an aromatic vinyl compound prepared in solution with a special silica, known per se, to obtain dispersion of the silica in the elastomeric matrix.
Raines, et al., in U. S. Patent No. 5,017,630, describe an aqueous dispersion of silicone dioxide mixed with an emulsion latex polymer which is spray dried to achieve 3o free-flowing, fine-sized particles of the polymer containing very high amounts of the silicone dioxide therein.
AND METHODS OF MAINUFACTURING THE SOLIDS AND
BLENDS CONTAINIhTG THE SAME
BACKGROUND OF THE INVENTION
Field of the Invention to This invention relates to new, modified solids, e.g. fillers and curatives, for polymers, elastomers, polyolefins, rubbers, and blends thereof and methods of preparing the modified solids and blends containing the same. Generally, the invention relates to targetable solids for addition to polymer blends, i. e., solids which may be custom designed to locate themselves in specific polymer components of the blend.
1s Description of Related Art Generally, solids have been utilized and/or incorporated into general purpose n~bber (GPR), polymers, elastomers, polyolefins, and/or mixtures of the above.
For example, in the tire industry, numerous solid fillers have been proposed for rubber and polymer blends in order to enhance the properties of tires, for example, to decrease the 2o rolling resistance of tires by modifying the rubber compositions used for the treads of tires. Reinforcing white fillers such as silica, bentonite, clay, titanium oxide, talc, etc., have been proposed for use in tire treads which tend to decrease the resistance to travel of the tires having a tread comprising such fillers. Various fillers and processes for blending the same into rubber compositions have been proposed. For example, 25 Rauline, in U.S. Patent No. 5,227,425, describes the use of a copolymer of a conju-gated dime with an aromatic vinyl compound prepared in solution with a special silica, known per se, to obtain dispersion of the silica in the elastomeric matrix.
Raines, et al., in U. S. Patent No. 5,017,630, describe an aqueous dispersion of silicone dioxide mixed with an emulsion latex polymer which is spray dried to achieve 3o free-flowing, fine-sized particles of the polymer containing very high amounts of the silicone dioxide therein.
Morocskowski, in U. S. Patent No. S,162,409, describes a rubber composition suitable for use in automobile tire treads wherein the composition comprises a halogenated isobutylene rubber which can be the sole rubber of the composition or one of a combination of rubbers. A preferred embodiment comprises a rubber component comprising 20 to 60 weight percent styrenelbutadiene rubber, 20 to 60 weight percent butadiene rubber, and 10 to 30 weight percent of a halogenated rubber, a silica filler, and an organosilane cross-linking agent. It is disclosed that in a preferred embodiment, the rubber compositions comprise 10 to 30 parts per 100 parts rubber of untreated, precipitated silica employed with an effective amount of organosilane coupling agent, for example, 1 to 8 parts per hundred rubber Preferably, the filler reinforces all phases, i. e., the polymeric phase of a blend, and curing can be controlled for each polymer phase component of the blend.
However, it is often discovered that the filler migrates from one polymer phase component to the other polymer phase component during processing.
Consequently, these effects greatly limit the enhancement of properties that can be achieved with fillers, and the curing and cure state of articles made therefrom.
Generally, polymer blends, e.g., those used to produce tires, are often crosslinked. It is known that the physical properties, performance characteristics, and durability of wlcanized rubber compounds are directly related to the number (crosslink density) and type of crosslinks formed during the wlcanization reaction. (See, e.g., The Post Vulcanization Stabilization for NR, W F. Helt, B.H. To & W W Paris, Rubber World, August 199l, pp. 18-23 which is incorporated by reference herein.) Generally, polymer blends may be crosslinked by adding curative molecules, for example sulfur, zinc, metals, radical initiators, etc. followed by heating. This method may be accelerated and is often used for the vulcanization of elastomer blends. The mechanism for accelerated wlcanization of natural rubber involves complex interactions between the curative, accelerator, activators and polymers. Ideally, all of the available curative is consumed in the formation of effective crosslinks which join together two polymer chains and enhance the overall strength of the polymer matrix. Numerous curatives are 3o known in the art and include, but are not limited to, the following: zinc oxide, stearic acid, tetramethylthiuram disulfide (TMTD), 4,4'-dithiodimorpholine (DTDM), tetrabutylthiuram disulfide (TBTD), benzothiazyl disulfide (MBTS), hexamethylene-1,6-bisthiosulfate disodium salt dihydrate (ERP 390), 2-(morpholinothio) benzothiazole (MB S or MOR), blends of 90% MOR and 10%
MBTS (MOR 90), N-oxydiethylene thiocarbamyl-N-oxydiethylene sulfonamide (OTOS) zinc 2-ethyl hexanoate (~; and MC sulfur. In addition, various vulcanization systems are lrnown in the art. (For example, see Formulation Design and Curing Characteristics of NBR Mixes for Seals, Rubber irYorld, September 1993, pp.
25-30 which is incorporated by reference herein). A possible major problem with these methods of crosslinking is often the concentration of the curative molecules in some l0 phase or phases of a blend is insuificient for good crosslinking due to migration or partitioning of the curative molecules between the phases of the blend during the mixing or blending process.
Therefore, there is a need for a method for the complete curing of polymer blends, elastomers, etc. wherein the concentration of curative in each polymer phase is i5 predictable and controllable. There is also a need for a method for the preparation of mechanical blends of filled polymers, elastomers, etc. in which the concentration of filler in each polymer phase component is predictable and controllable.
SUMMARY OF THE INVENTION
According to one aspect, the invention is directed toward a method for the 2o preparation of a targetable solid, i. e., a filler for addition to a rubber composition or a blend of at least two polymeric components. The method, according to one embodiment, comprises contacting or treating the filler with the polymer component of the blend having the least affinity for said filler as compared to the other polymer blend components, and thereafter contacting said first polymer treated filler with a second 25 polymer component having a greater affinity for the filler. According to another embodiment, the filler contacted with the polymer components is further subjected to thesmai curing under nitrogen atmosphere. It should be recognized that the invention is also directed to methods wherein the filler is contacted with a polymer or polymers which is/are not the same as either of the polymers of the blend but are compatible, i. e., 30 generally miscible, with one or both of the polymers of the blend. The invention is also directed to a filler produced according to the above-described methods.
WQ 98/27143 PCT/f3S97/22504 According to another aspect, the invention is directed toward a method for the preparation of a filled blend comprising polymer treated filler and polymers) blend components to produce a blend. The polymer blend comprises two or more polymer components with the treated filler dispersed throughout. The method comprises contacting or treating the filler with a minor amount of a polymer, which may, e.g., be the first component of the polymer blend. According to one embodiment of the invention, the first polymer has the least affinity for the filler as compared to other polymer for treatment of the filler. The filler, including said first polymer, is subsequently contacted with a minor amount of a second polymer having a greater 1o affinity for said filler than said first polymer . Thereafter, the coated filler is mixed with the polymers) for forming the blend. The invention is also directed to a filled blend produced according to the above-described methods.
According to a further aspect, the invention is directed to a filler, e.g., a particle, for addition to a polymer comprising a first polymer and/or a blend of a first polymer with a second polymer. The filler has a coating thereon comprised of at least one polymer compatible with at least one of the blend polyrner(s) or, e.g., at least one of the first or second polymer blend components.
According to a still further aspect, the invention is directed to a filled blend comprising a polymer blend comprising at least two polymers and a filler, said filler 2o having at least one polymer compatible with at least one of the polymer blend components coated thereon.
The invention, according to another embodiment, is directed to methods for crosslinking polymer blends comprising at least two polymers. The method generally comprises pretreating the solid with a curative, mixing the pretreated solid with the two polymers of the blend to form a curable polymer mixture, and subjecting the blend to curing conditions, such as suffciently heating the mixture to obtain crosslinldng and/or curing.
The method of forming a solid comprjsing curative may, according to an embodiment, be accomplished by precipitation of a polymer from a solution comprising 3o curative molecules, wherein the curative is the sole solid. According to a fiuther embodiment, the method of forming a solid comprising curative comprises adsorption WO 98/27143 PCT/US97l22504 of curative molecules onto an inert solid, isolation of the solid, and adsorption of a polymer onto the curative treated solid. According to a further embodiment, the method of forming a solid comprising curative may comprise adsorption of a polymer coating onto curative particles. According to a still further embodiment, the method of 5 forming a solid comprising curative may comprise mixing curative with a solid to form a mixture, and adsorbing a polymer onto the mixture.
According to a still fiarther embodiment, the present invention is also directed to polymer blends produced according to the above-described methods.
The present invention is fizrther directed to curative precursors used in 1o crosslinking polymer blends, said precursors produced from: (1) the precipitation of a polymer from a solution comprising dissolved or suspended curative molecules;
(2) adsorbing curative molecules onto a solid, and adsorbing a polymer onto the solid; (3) adso~ing a polymer onto curative particles; or (4) mixing or grinding curative molecules together with an inert solid to form a mixture, and adsorbing a polymer onto the mixture. The invention is also directed to methods for making curative molecules.
DETAILED DESCRIPTION OF THE INVENTION
According to one embodiment, the present invention provides a composition based on a mixture or blend of rubbers, elastomers, polyolefins, polymers, etc.
comprising a polymer blend or mixture and a solid. The solid may, for example, be a 2o filler, such as silica, wherein the filler has coated thereon or has adsorbed on its surface one or more of the components of the polymer phase. According to another embodiment, the solid may be pretreated with a curative .
Rubbers, polymers (thermoplastic, thermoset and mixtures thereof, elastomers, and polyolefins and products produced therefrom useful in the practice of the invention include, but are not limited to, brominated butyl rubber (commonly called bromobutyl and as used herein, the term "butyl rubber" means a copolymer of isobutylene and a diene such as isoprene); chlorinated butyl rubber (commonly called chlorobutyl where isoprene is the diene copolymerized with isobutylene); star-branched polyisobutylene comprising branched or star-shaped polyisobutylene subunits, such as star-branched bromobutyl; isobutylene-bromomethylstyrene copolymers such as isobutylene~para-bromomethylstyrene, isobutylene/chloromethylstyrene copolymers such as isobutyleneJpara-chloromethylstyrene, and the like halomethylated aromatic interpolymers disclosed in U. S. Patent No. 5,162,445 which is hereby incorporated by reference; isoprene and halogenated isobutylene copolymers (chlorinated or brominated); polychloroprene (neoprene); and the like, and mixtures thereof.
The invention is also preferably directed to blends comprising haiogenated isobutylene rubbers including halogenated terpolymers comprising isobutylene such as halogenated isobutylene/styreneldienes, for example, isobutylenelstyrenehsoprene, and halogenated isobutylene/methylstyreneJdienes, for example, isobutyleneJmethylstyrenehsoprene; isobutylenelt~alomethylstyrene/diene terpolymers to including isobutylene/bromomethylstyren~soprene;
isobutylenelhaloisobutyleneJdienes, including isobutylene/bromobutylenef soprene; and the like, and mixtures thereof with other halogenated isobutylene rubbers.
Other elastomers useful in the invention include: polybutadiene, BR; styrene butadiene rubber, SBR; nitrile-butadiene rubber, NBR; natural rubber, NR;
polyisoprene, IR; and ethylene-alphaolefin elastomers like ethylene-propylene rubber, EPR
Thermoplastics usefizl in this invention include polyethylene, polypropylene, polystyrene, polycarbonate, and nylon.
Fillers which can be utilized in the practice of the present invention include, but 2o are not limited to, silica, pumice, bentonite, clay, titanium oxide, talc, calcium carbonate, high styrene resins, coumarone-indene resin, phenolic resin, lignin, modified melamine resins, and petroleum resins. The fillers of the present invention may be any size and typically range, e.g., in the tire industry, from about 0.0001 to about 100 microns. As used herein, silica is meant to refer to any type or particle size silica or another silicic acid derivative, or silicic acid, processed by solution, pyrogenic or the like methods and having a surface area, including untreated, precipitated silica, crystalline silica, colloidal silica, aluminum or calcium silicates, flamed silica, and the like.
The curatives useful in the practice of the present invention generally include 3o curatives used in the rubber industry, e.g., sulfur compounds, zinc compounds, metal compounds, radical initiators, etc. and include, but are not limited to, zinc oxide, stearic WO 98l27143 PCT/US97/Z2504 acid, tetramethylthiuram disulfide (TMTD), 4,4'-dithiodimorpholine (DTDM), tetrabutylthiuram disulfide (TBTD), benzothiazyl disulfide (MBTS), hexamethylene-1,6-bisthiosulfate disodium salt dihydrate (EItP 390), 2-(morpholinothio) benzothiazole (MBS or MOR), blends comprising 90% MOR and 10% MBTS (MOR 90), N-oxydiethylene thiocarbamyl-N-oxydiethylene sulfonamide (OTOS) zinc 2-ethyl hexanoate (ZEIT); and MC sulfur.
The compositions producxd in accordance with the present invention may also contain other components and additives customarily used in rubber mixes, such as plasticizers, pigments, anti-oxidants, vulcanization accelerators, napthenic or aromatic to extender oils if the presence of an extension oil is desired, and silane coupling agents, etc.
In a preferred embodiment, the polymer blend is comprised of a blend of two components, for example, polybutadiene and a brominated copolymer of isobutene and 4-methylstyrene or polymers compatible with polybutadiene and brominated copolymer of isobutene and 4-methylstyrene. Preferably, the filler utilized in the above-described preferred embodiment is silica having co-adsorbed thereon minor amounts of polybutadiene and brominated copolymer of isobutene and 4-methylstyrene.
In accordance with the practice of the present invention, a method is provided for the preparation of filler for addition to a blend of at least two polymer components 2o selected from the goup consisting of elastomers, rubbers, polyolefins, polymers and mixtures thereof. In accordance, a preferred embodiment of the invention before blending the filler with the polymer blend component(s), the filler is contacted with a minor amount of the polymer component which has the least affinity for the filler as compared to the other polymer components to form a stable surface saturated layer.
The thickness of the layer may be varied by varying adsorption conditions.
Depending upon the filler and the polymer(s), the adsorption time may range from about one second to several hours. It should be noted that depending upon the polymer, different solvents may be utilized including, but not limited to, aliphatic and aromatic solvents like pentane, hexane, and toluene. The adsorption may be conducted at low 3o temperatures, e.g., -40~ C Where the amount of polymer to be adsorbed is large, to high temperatures, e.g., up to 200~0 C when the amount of polymer to be adsorbed is small.
However, it is often discovered that the filler migrates from one polymer phase component to the other polymer phase component during processing.
Consequently, these effects greatly limit the enhancement of properties that can be achieved with fillers, and the curing and cure state of articles made therefrom.
Generally, polymer blends, e.g., those used to produce tires, are often crosslinked. It is known that the physical properties, performance characteristics, and durability of wlcanized rubber compounds are directly related to the number (crosslink density) and type of crosslinks formed during the wlcanization reaction. (See, e.g., The Post Vulcanization Stabilization for NR, W F. Helt, B.H. To & W W Paris, Rubber World, August 199l, pp. 18-23 which is incorporated by reference herein.) Generally, polymer blends may be crosslinked by adding curative molecules, for example sulfur, zinc, metals, radical initiators, etc. followed by heating. This method may be accelerated and is often used for the vulcanization of elastomer blends. The mechanism for accelerated wlcanization of natural rubber involves complex interactions between the curative, accelerator, activators and polymers. Ideally, all of the available curative is consumed in the formation of effective crosslinks which join together two polymer chains and enhance the overall strength of the polymer matrix. Numerous curatives are 3o known in the art and include, but are not limited to, the following: zinc oxide, stearic acid, tetramethylthiuram disulfide (TMTD), 4,4'-dithiodimorpholine (DTDM), tetrabutylthiuram disulfide (TBTD), benzothiazyl disulfide (MBTS), hexamethylene-1,6-bisthiosulfate disodium salt dihydrate (ERP 390), 2-(morpholinothio) benzothiazole (MB S or MOR), blends of 90% MOR and 10%
MBTS (MOR 90), N-oxydiethylene thiocarbamyl-N-oxydiethylene sulfonamide (OTOS) zinc 2-ethyl hexanoate (~; and MC sulfur. In addition, various vulcanization systems are lrnown in the art. (For example, see Formulation Design and Curing Characteristics of NBR Mixes for Seals, Rubber irYorld, September 1993, pp.
25-30 which is incorporated by reference herein). A possible major problem with these methods of crosslinking is often the concentration of the curative molecules in some l0 phase or phases of a blend is insuificient for good crosslinking due to migration or partitioning of the curative molecules between the phases of the blend during the mixing or blending process.
Therefore, there is a need for a method for the complete curing of polymer blends, elastomers, etc. wherein the concentration of curative in each polymer phase is i5 predictable and controllable. There is also a need for a method for the preparation of mechanical blends of filled polymers, elastomers, etc. in which the concentration of filler in each polymer phase component is predictable and controllable.
SUMMARY OF THE INVENTION
According to one aspect, the invention is directed toward a method for the 2o preparation of a targetable solid, i. e., a filler for addition to a rubber composition or a blend of at least two polymeric components. The method, according to one embodiment, comprises contacting or treating the filler with the polymer component of the blend having the least affinity for said filler as compared to the other polymer blend components, and thereafter contacting said first polymer treated filler with a second 25 polymer component having a greater affinity for the filler. According to another embodiment, the filler contacted with the polymer components is further subjected to thesmai curing under nitrogen atmosphere. It should be recognized that the invention is also directed to methods wherein the filler is contacted with a polymer or polymers which is/are not the same as either of the polymers of the blend but are compatible, i. e., 30 generally miscible, with one or both of the polymers of the blend. The invention is also directed to a filler produced according to the above-described methods.
WQ 98/27143 PCT/f3S97/22504 According to another aspect, the invention is directed toward a method for the preparation of a filled blend comprising polymer treated filler and polymers) blend components to produce a blend. The polymer blend comprises two or more polymer components with the treated filler dispersed throughout. The method comprises contacting or treating the filler with a minor amount of a polymer, which may, e.g., be the first component of the polymer blend. According to one embodiment of the invention, the first polymer has the least affinity for the filler as compared to other polymer for treatment of the filler. The filler, including said first polymer, is subsequently contacted with a minor amount of a second polymer having a greater 1o affinity for said filler than said first polymer . Thereafter, the coated filler is mixed with the polymers) for forming the blend. The invention is also directed to a filled blend produced according to the above-described methods.
According to a further aspect, the invention is directed to a filler, e.g., a particle, for addition to a polymer comprising a first polymer and/or a blend of a first polymer with a second polymer. The filler has a coating thereon comprised of at least one polymer compatible with at least one of the blend polyrner(s) or, e.g., at least one of the first or second polymer blend components.
According to a still further aspect, the invention is directed to a filled blend comprising a polymer blend comprising at least two polymers and a filler, said filler 2o having at least one polymer compatible with at least one of the polymer blend components coated thereon.
The invention, according to another embodiment, is directed to methods for crosslinking polymer blends comprising at least two polymers. The method generally comprises pretreating the solid with a curative, mixing the pretreated solid with the two polymers of the blend to form a curable polymer mixture, and subjecting the blend to curing conditions, such as suffciently heating the mixture to obtain crosslinldng and/or curing.
The method of forming a solid comprjsing curative may, according to an embodiment, be accomplished by precipitation of a polymer from a solution comprising 3o curative molecules, wherein the curative is the sole solid. According to a fiuther embodiment, the method of forming a solid comprising curative comprises adsorption WO 98/27143 PCT/US97l22504 of curative molecules onto an inert solid, isolation of the solid, and adsorption of a polymer onto the curative treated solid. According to a further embodiment, the method of forming a solid comprising curative may comprise adsorption of a polymer coating onto curative particles. According to a still further embodiment, the method of 5 forming a solid comprising curative may comprise mixing curative with a solid to form a mixture, and adsorbing a polymer onto the mixture.
According to a still fiarther embodiment, the present invention is also directed to polymer blends produced according to the above-described methods.
The present invention is fizrther directed to curative precursors used in 1o crosslinking polymer blends, said precursors produced from: (1) the precipitation of a polymer from a solution comprising dissolved or suspended curative molecules;
(2) adsorbing curative molecules onto a solid, and adsorbing a polymer onto the solid; (3) adso~ing a polymer onto curative particles; or (4) mixing or grinding curative molecules together with an inert solid to form a mixture, and adsorbing a polymer onto the mixture. The invention is also directed to methods for making curative molecules.
DETAILED DESCRIPTION OF THE INVENTION
According to one embodiment, the present invention provides a composition based on a mixture or blend of rubbers, elastomers, polyolefins, polymers, etc.
comprising a polymer blend or mixture and a solid. The solid may, for example, be a 2o filler, such as silica, wherein the filler has coated thereon or has adsorbed on its surface one or more of the components of the polymer phase. According to another embodiment, the solid may be pretreated with a curative .
Rubbers, polymers (thermoplastic, thermoset and mixtures thereof, elastomers, and polyolefins and products produced therefrom useful in the practice of the invention include, but are not limited to, brominated butyl rubber (commonly called bromobutyl and as used herein, the term "butyl rubber" means a copolymer of isobutylene and a diene such as isoprene); chlorinated butyl rubber (commonly called chlorobutyl where isoprene is the diene copolymerized with isobutylene); star-branched polyisobutylene comprising branched or star-shaped polyisobutylene subunits, such as star-branched bromobutyl; isobutylene-bromomethylstyrene copolymers such as isobutylene~para-bromomethylstyrene, isobutylene/chloromethylstyrene copolymers such as isobutyleneJpara-chloromethylstyrene, and the like halomethylated aromatic interpolymers disclosed in U. S. Patent No. 5,162,445 which is hereby incorporated by reference; isoprene and halogenated isobutylene copolymers (chlorinated or brominated); polychloroprene (neoprene); and the like, and mixtures thereof.
The invention is also preferably directed to blends comprising haiogenated isobutylene rubbers including halogenated terpolymers comprising isobutylene such as halogenated isobutylene/styreneldienes, for example, isobutylenelstyrenehsoprene, and halogenated isobutylene/methylstyreneJdienes, for example, isobutyleneJmethylstyrenehsoprene; isobutylenelt~alomethylstyrene/diene terpolymers to including isobutylene/bromomethylstyren~soprene;
isobutylenelhaloisobutyleneJdienes, including isobutylene/bromobutylenef soprene; and the like, and mixtures thereof with other halogenated isobutylene rubbers.
Other elastomers useful in the invention include: polybutadiene, BR; styrene butadiene rubber, SBR; nitrile-butadiene rubber, NBR; natural rubber, NR;
polyisoprene, IR; and ethylene-alphaolefin elastomers like ethylene-propylene rubber, EPR
Thermoplastics usefizl in this invention include polyethylene, polypropylene, polystyrene, polycarbonate, and nylon.
Fillers which can be utilized in the practice of the present invention include, but 2o are not limited to, silica, pumice, bentonite, clay, titanium oxide, talc, calcium carbonate, high styrene resins, coumarone-indene resin, phenolic resin, lignin, modified melamine resins, and petroleum resins. The fillers of the present invention may be any size and typically range, e.g., in the tire industry, from about 0.0001 to about 100 microns. As used herein, silica is meant to refer to any type or particle size silica or another silicic acid derivative, or silicic acid, processed by solution, pyrogenic or the like methods and having a surface area, including untreated, precipitated silica, crystalline silica, colloidal silica, aluminum or calcium silicates, flamed silica, and the like.
The curatives useful in the practice of the present invention generally include 3o curatives used in the rubber industry, e.g., sulfur compounds, zinc compounds, metal compounds, radical initiators, etc. and include, but are not limited to, zinc oxide, stearic WO 98l27143 PCT/US97/Z2504 acid, tetramethylthiuram disulfide (TMTD), 4,4'-dithiodimorpholine (DTDM), tetrabutylthiuram disulfide (TBTD), benzothiazyl disulfide (MBTS), hexamethylene-1,6-bisthiosulfate disodium salt dihydrate (EItP 390), 2-(morpholinothio) benzothiazole (MBS or MOR), blends comprising 90% MOR and 10% MBTS (MOR 90), N-oxydiethylene thiocarbamyl-N-oxydiethylene sulfonamide (OTOS) zinc 2-ethyl hexanoate (ZEIT); and MC sulfur.
The compositions producxd in accordance with the present invention may also contain other components and additives customarily used in rubber mixes, such as plasticizers, pigments, anti-oxidants, vulcanization accelerators, napthenic or aromatic to extender oils if the presence of an extension oil is desired, and silane coupling agents, etc.
In a preferred embodiment, the polymer blend is comprised of a blend of two components, for example, polybutadiene and a brominated copolymer of isobutene and 4-methylstyrene or polymers compatible with polybutadiene and brominated copolymer of isobutene and 4-methylstyrene. Preferably, the filler utilized in the above-described preferred embodiment is silica having co-adsorbed thereon minor amounts of polybutadiene and brominated copolymer of isobutene and 4-methylstyrene.
In accordance with the practice of the present invention, a method is provided for the preparation of filler for addition to a blend of at least two polymer components 2o selected from the goup consisting of elastomers, rubbers, polyolefins, polymers and mixtures thereof. In accordance, a preferred embodiment of the invention before blending the filler with the polymer blend component(s), the filler is contacted with a minor amount of the polymer component which has the least affinity for the filler as compared to the other polymer components to form a stable surface saturated layer.
The thickness of the layer may be varied by varying adsorption conditions.
Depending upon the filler and the polymer(s), the adsorption time may range from about one second to several hours. It should be noted that depending upon the polymer, different solvents may be utilized including, but not limited to, aliphatic and aromatic solvents like pentane, hexane, and toluene. The adsorption may be conducted at low 3o temperatures, e.g., -40~ C Where the amount of polymer to be adsorbed is large, to high temperatures, e.g., up to 200~0 C when the amount of polymer to be adsorbed is small.
For example, as further described below, when a polymer blend is comprised of a brominated copolymer of isobutene and 4-methylstyrene and polybutadiene, the filler, e.g., silica, is preferably first contacted with a minor amount of the brominated copolymer of isobutene and 4-methylstyrene. This copolymer has less affinity for said filler as compared to the polybutadiene. As used herein, the term "minor amount"
means in an amount suffcient to provide a stable surface saturated layer on the filler.
After contacting the filler with the brominated copolymer of isobutene and 4-methylstyrene, preferably forming a layer by the adsorption of the same onto the filler surface, the filler is contacted with a minor amount of the second component of the to polymer blend and/or the polybutadiene. In this manner, a filler is provided which will not completely migrate from the brominated copolymer of isobutene and 4-methylstyrene during the blending of the two components of the polymer phase.
Preferably, depending upon the application, after the filler has been contacted with the polymer blend components, the contacted filler is subjected to curing conditions such as to heat or thermal curing under a nitrogen atmosphere at temperatures ranging from about 60~ C to about 120~ C.
In order to determine which polymer has the least affinity for the filler as compared to the other polymer, it is usefizl to measure rates of competitive adsorption or co-adsorption of polymers, etc. onto solid particles. For example, to determine 2o whether the brominated copolymer of isobutene and 4-methylstyrene has a greater or weaker affinity for the filler as compared to polybutadiene, the following test is performed which may be modified in accordance with that which is well-known in the art for other polymer phase component systems. Specifically, the exchange of elastomers on a silica filler was measured using a practical and rapid method comprising solid state H MAS-NMR. This method allows the possibility to monitor and rank polymer interactions with solid fillers by measuring the exchange.
The exchange was performed from both directions, that is, adsorbing from solution the brominated copolymer of isobutene and 4-methylstyrene (hereinafter "brominated copolymer") first and then placing the brominated copolymer-loaded silica 3o filler into a solution of polybutadiene and vice versa. The polymer-loaded filler sample remained wet with solvent, e.g., one weight percent solution of pentane, during the transfer to a solution, e.g., one weight percent solution, of the second polymer. After exposure to the solution of the second polymer for a time interval, a sample of the polymer-loaded filler was removed and washed in an excess of solvent. The composition of the resulting solvent was monitored by solid state H MAS NMR
which was used to measure the ratio of one polymer to another. This quantity can be measured precisely without any other standards. The total polymer composition was deterniined by carbon elemental analysis, and polymers in the same molecular weight were used.
The results of the exchange experiment in which the brominated copolymer was loaded first are shown in Table 1. To summarize, the polybutadiene rapidly replaced some, but not all of the brominated copolymer. The fact that some of the brominated copolymer was exchanged can be concluded by comparison of the elemental and H
MAS-NMR analysis as follows: if all the carbon weight gain of Sample 3 represented adsorption of polybutadiene, then the Sample should be only [ 100 x (6. S-3 .
7) divided by 6.5] equals 43% polybutadiene. Since there was a much greater percentage of polybutadiene than 43% in Sample 3, polybutadiene had replaced some of the brominated copolymer. Most of the braminated copolymer, about 65% of the initial amount, was exchanged.
WO 98I27143 PCT/(TS97/22504 Exchange of Brominated Copolymer-Loaded (EXXFRO~: brominated copolymer of isobutene and 4-methylstyrene)1 ITISiI 233 (silica) with Polybutadiene (Budene 1207) Sample Composition* Time for SecondWeight % Carbon by MAS-NMR Adsorption (Iir) 1 100% E 0 3.7 i 2 67% B 0.25 6.7 3 76% B 24 6.5 5 '' Brominat~i poly(isobutylene-co-4-methylstyrene) containing 7.5 wt%
4-methylstyrene and 2 wt% having a Mooney viscosity ML,(1+8) 125~ of 45~S
* E = EXXI'RO~ 90-10 (Brominated Copolymer of Isobutene and 4-l0 methylstyrene) B = Budene I207 (Polybutadiene) The results of the exchange experiment in which polybutadiene is loaded first is shown in Table 2. No H MAS NMR signals for the brominated copolymer were observed in the samples. Thus, no exchange of adsorbed polybutadiene by the 1s brominated copolymer occurred.
WO-98/271d3 PCT/US97I22504 Exchange ofPolybutadiene (Budene 1207)-Loaded Silica (I-fiSil 233) with Brominated Copolymer of Isobutene and 4-Methylstyrene (EXXPRO~' 90-10)' Sample Composition* Tune for SecondWeight % Carbon by MAS-NMR Adsorption (Hr) 4 100% B 0 6.0 5 100% B 0.25 5.9 6 >94% B 24 5.8 '~ Brominated poly(isobutylene-co-4-methylstyrene) containing 7.5 wt%
4-methylstyrene and 2 wt% having a Mooney viscosity ML(1+8) 125~ of 45~5 to * B = Budene 1207 (polybutadiene) As a result, it can be stated from the above that Budene 1207 (polybutadiene) tends to have a greater amity or interaction with HiSil (silica) than does EXXI'RO~
90-10 (brominated copolymer of isobutene and 4-methylstyrene).
Polymer blends exemplifying the present invention and analytical data supporting the same are set forth below. The examples illustrate that the modified or coated silica filler is well dispersed in a blend of brominated copolymer of isobutene and 4-methylstyrene and polybutadiene elastomers, whereas a conventional silica filler is not.
EXAMPLES I (Comnarativel & II
Example I is the control in which EXXPRO~ 90-10 (30 phr), Budene 1207 (70 phr) and conventional I~SiI 233 (30 phr) are blended by milling together.
The dispersion of the silica filler can be detected by scanning electron microscopy The scanning electron microscopy showed that the conventional silica filler was not found to be present in the EXXPRO~ phase of the blend. Coated silica used in this example was prepared by stirring for 30 minutes a suspension of 100 g. ~Sil 233 in a 0.5 wt%
to polymer in cyclohexane solution. The coated filler was removed and washed with cyclohexane three times. On the other hand, when the modified silica filler of the present invention is used to make a similar~blend, as in Example II, the modified silica filler of the present invention is found to be well dispersed in the EXXPRO~
phase and the Budene phase.
Example II: Modified silica filler was prepared by adsorption of poly(isoprene) from dilute solution 0.5% polymer in cyclohexane, with vigorous stirring at about 22~
C for approximately 1 hour. The coated silica was washed three times in cyclohexane.
The weight percent carbon of the product was 6.18%. The above-described product was then subjected to heat or thermal curing under a nitrogen atmosphere at 2o temperatures ranging from 60~ C to 120~ C for 60 minutes. The polyisoprene layer was extensively crosslinked because polyisoprene signals of the adsorbed polyisoprene layer were no longer observed in the solid state NMR spectrum. Crosslinked coatings formed in this example are stable to exchange by other polymers including poiar polymers with a high affinity for the filler like NBR. These coated fillers will be primarily found in the polyisoprene regions when used in blends of polyisoprene and NBR
The present invention also relates and generally applies, e.g., to various curing or vulcanization systems including, but not limited to, conventional systems (polysulfidic crosslinks produced by sulfur system); conventional systems with post 3o vulcanization stabilizers, e.g., dihydrate of the sodium salt of hexamethylene-1, 6-bisthiosulfate-s-ester; EV systems (low concentration of sulfur and high concentration of an organic accelerator); sulfurless or sulfur donor systems (using, for example, TMTD); Semi-EV (intermediate system between conventional and EV systems);
Soluble EV and Soluble Semi-EV systems; and the EV System of Hofinann (combination of sulfur donors, like TMTD and DTDM, in conjunction with sulfenamide (OTOS).
The curative precursors of the present invention are generally comprised of a solid containing or comprising curative. The curative precursor of the present invention may be formed by, e.g., the following methods: (1) precipitation of a polymer from a solution containing dissolved or suspended curative(s); (2) adsorption of curatives) to onto an inert solid, e.g., alumina or silica, followed by isolation of the curative-loaded solid, and adsorption of a polymer coating to the surface of the loaded solid;
(3) adsorption of a polymer coating to the surface of curative particles; or (4) mixing and/or grinding together curatives) with an inert solid, followed by adsorption of a polymer coating to the surface of the resulting solid curative mixture. The polymers useful in the preparation of the curative precursors of the present invention may be comprised of the same polymers of the blend and/or polymers compatible with one or more polymers of the blend. The term "compatible" as used herein means generally considered miscible.
While the following discussion is in terms of a single embodiment, it is 2o understood that the scope of the invention shall not be limited thereby In accordance with the practice of the present invention, a method is provided for the preparation of curative precursors for addition to a blend of at least two polymers selected from the group consisting of, for example, but not limited to elastomers, rubbers, polyolefins, polymers and mixtures thereof. In accordance with the present invention, a curative loaded solid or solid curative is, according to one embodiment, contacted with one of the polymers of the blend and/or a polymer compatible with one or both of the polymers of the blend and the polymer is adsorbed onto the surface of the curative loaded solid or solid curative. According to a preferred embodiment, the solid curative precursor is contacted with a minor amount of the polymer of the blend which has the "least aff nity" for the curative solid as compared to the other polymers) of the blend to form a stable surface saturated layer, e.g., which preferably is not removed by any subsequent solvent extractions. The thickness of the layer may be varied by varying adsorption conditions. Depending upon the solid utilized to form the curative-loaded solid and the polymer(s), the adsorption time may range from about one second to several hours. It should be noted that depending upon the polymer, different solvents may be utilized including, but not limited to, aliphatic and aromatic solvents like pentane, hexane, and toluene. The adsorption may be conducted at low temperatures, e.g., -40~ C where the amount of polymer to be adsorbed is large, to high temperatures, e. g., up to 200~ C when the amount of polymer to be adsorbed is small. For example, as further described below, when the polymers are brominated copolymer of isobutene to and 4-methylstyrene and polybutadiene, the curative loaded silica solid, is preferably first contacted with a minor amount of the brominated copolymer of isobutene and 4-methylstyrene. This copolymer has the "least affinity" for said loaded solid as compared to the polybutadiene. As used herein, the term "minor amount" means in an amount sufficient to provide a stable surface saturated layer on the filler. After contacting the curative-loaded solid with the brominated copolymer of isobutene and 4-methyistyrene, preferably forming a layer by the adsorption of the same onto the curative-loaded solid surface, the curative-loaded polymer coated solid is contacted with a minor amount of the second polymer of the blend and/or the polybutadiene. In this manner, a precursor is provided which will not completely migrate from the brominated copolymer of 2o isobutene and 4-methylstyrene during the blending of the two polymers.
Preferably, depending upon the application, after the curative loaded solid has been contacted with the polymers of the blend, the curative precursor is subjected to heat or thermal curing under a nitrogen atmosphere at temperatures ranging fi om about 60~ C to about 120~
C.
In order to determine which polymer of the polymer blend has the "least aff pity" for the solid comprising curative as compared to the other polymer(s), it is useful to measure rates of competitive adsorption or co-adsorption of polymers, etc.
onto solid particles. For example, to deterniine whether the brominated copolymer of isobutene and 4-methylstyrene has a Beater or weaker affinity for the curative-loaded 3o solid (which later forms the curative precursor) as compared to polybutadiene, the following test is performed which may be modified, if needed, for other polymer 1$
systems. Specifically, the exchange of elastomers on a solid precursor may be measured using a practical and rapid method comprising solid state H MAS-NMR.
This method allows the possibility to monitor and rank polymer interactions with solids by measuring the exchange.
According to one embodiment of the method of the invention, the curative-loaded, first polymer-coated solid of the precursor is kept wet with solvent, e.g., one weight percent solution of pentane, during transfer to a solution, e.g., one weight percent solution, of the second polymer. After exposure to the solution of the second polymer for a time interval, a sample of the polymer-coated precursor should be to removed and washed in an excess of solvent. The composition of the resulting solvent may be monitored by solid state H MAS-NMR which can measure the ratio of one polymer to another. This quantity can be measured precisely without any other standards. The total polymer composition may be deternvned by carbon elemental analysis.
After the curative precursor is prepared, it is mixed together with the polymers of the blend. The required mixing and heating varies as a function of the polymers utilized, the curative precursor, and the operating conditions employed by the person of ordinary skill in the art, the essential factor being complete and excellent dispersing of the curative precursor. Therefore, depending upon the devices utilized (like BanburyTM
2o mixers) to effect the mixing, the time may vary and may be determined by the person of ordinary skill in the art on the basis of his/her general knowledge and control of the properties of the composition used in the particular application, e.g., in the form of tire tread, knowing, e.g., that it is advisable to maximize the ratio of the 300~!~
elongation modulus to the 100~!o elongation modulus for each composition: Thus, the thenmomechanical work can include only a single step of suitable duration, temperature and intensity, or it can include several steps which can, if desired, be separated by at least a cooling step.
The final heating step of the method of the present invention is generally carried out using typical procedures known to one of ordinary skill in the art for crosslinlcing 3o and curing polymer blends. In any event, the blend is heated sufficiently to obtain crosslinlang, i.e., cure of the blend.
Although the invention has been illustrated by typical examples, it is not limited thereto. Changes and modifications of the examples of the invention herein chosen for purposes of disclosure can be made which do not constitute departure from the spirit and scope of the invention.
means in an amount suffcient to provide a stable surface saturated layer on the filler.
After contacting the filler with the brominated copolymer of isobutene and 4-methylstyrene, preferably forming a layer by the adsorption of the same onto the filler surface, the filler is contacted with a minor amount of the second component of the to polymer blend and/or the polybutadiene. In this manner, a filler is provided which will not completely migrate from the brominated copolymer of isobutene and 4-methylstyrene during the blending of the two components of the polymer phase.
Preferably, depending upon the application, after the filler has been contacted with the polymer blend components, the contacted filler is subjected to curing conditions such as to heat or thermal curing under a nitrogen atmosphere at temperatures ranging from about 60~ C to about 120~ C.
In order to determine which polymer has the least affinity for the filler as compared to the other polymer, it is usefizl to measure rates of competitive adsorption or co-adsorption of polymers, etc. onto solid particles. For example, to determine 2o whether the brominated copolymer of isobutene and 4-methylstyrene has a greater or weaker affinity for the filler as compared to polybutadiene, the following test is performed which may be modified in accordance with that which is well-known in the art for other polymer phase component systems. Specifically, the exchange of elastomers on a silica filler was measured using a practical and rapid method comprising solid state H MAS-NMR. This method allows the possibility to monitor and rank polymer interactions with solid fillers by measuring the exchange.
The exchange was performed from both directions, that is, adsorbing from solution the brominated copolymer of isobutene and 4-methylstyrene (hereinafter "brominated copolymer") first and then placing the brominated copolymer-loaded silica 3o filler into a solution of polybutadiene and vice versa. The polymer-loaded filler sample remained wet with solvent, e.g., one weight percent solution of pentane, during the transfer to a solution, e.g., one weight percent solution, of the second polymer. After exposure to the solution of the second polymer for a time interval, a sample of the polymer-loaded filler was removed and washed in an excess of solvent. The composition of the resulting solvent was monitored by solid state H MAS NMR
which was used to measure the ratio of one polymer to another. This quantity can be measured precisely without any other standards. The total polymer composition was deterniined by carbon elemental analysis, and polymers in the same molecular weight were used.
The results of the exchange experiment in which the brominated copolymer was loaded first are shown in Table 1. To summarize, the polybutadiene rapidly replaced some, but not all of the brominated copolymer. The fact that some of the brominated copolymer was exchanged can be concluded by comparison of the elemental and H
MAS-NMR analysis as follows: if all the carbon weight gain of Sample 3 represented adsorption of polybutadiene, then the Sample should be only [ 100 x (6. S-3 .
7) divided by 6.5] equals 43% polybutadiene. Since there was a much greater percentage of polybutadiene than 43% in Sample 3, polybutadiene had replaced some of the brominated copolymer. Most of the braminated copolymer, about 65% of the initial amount, was exchanged.
WO 98I27143 PCT/(TS97/22504 Exchange of Brominated Copolymer-Loaded (EXXFRO~: brominated copolymer of isobutene and 4-methylstyrene)1 ITISiI 233 (silica) with Polybutadiene (Budene 1207) Sample Composition* Time for SecondWeight % Carbon by MAS-NMR Adsorption (Iir) 1 100% E 0 3.7 i 2 67% B 0.25 6.7 3 76% B 24 6.5 5 '' Brominat~i poly(isobutylene-co-4-methylstyrene) containing 7.5 wt%
4-methylstyrene and 2 wt% having a Mooney viscosity ML,(1+8) 125~ of 45~S
* E = EXXI'RO~ 90-10 (Brominated Copolymer of Isobutene and 4-l0 methylstyrene) B = Budene I207 (Polybutadiene) The results of the exchange experiment in which polybutadiene is loaded first is shown in Table 2. No H MAS NMR signals for the brominated copolymer were observed in the samples. Thus, no exchange of adsorbed polybutadiene by the 1s brominated copolymer occurred.
WO-98/271d3 PCT/US97I22504 Exchange ofPolybutadiene (Budene 1207)-Loaded Silica (I-fiSil 233) with Brominated Copolymer of Isobutene and 4-Methylstyrene (EXXPRO~' 90-10)' Sample Composition* Tune for SecondWeight % Carbon by MAS-NMR Adsorption (Hr) 4 100% B 0 6.0 5 100% B 0.25 5.9 6 >94% B 24 5.8 '~ Brominated poly(isobutylene-co-4-methylstyrene) containing 7.5 wt%
4-methylstyrene and 2 wt% having a Mooney viscosity ML(1+8) 125~ of 45~5 to * B = Budene 1207 (polybutadiene) As a result, it can be stated from the above that Budene 1207 (polybutadiene) tends to have a greater amity or interaction with HiSil (silica) than does EXXI'RO~
90-10 (brominated copolymer of isobutene and 4-methylstyrene).
Polymer blends exemplifying the present invention and analytical data supporting the same are set forth below. The examples illustrate that the modified or coated silica filler is well dispersed in a blend of brominated copolymer of isobutene and 4-methylstyrene and polybutadiene elastomers, whereas a conventional silica filler is not.
EXAMPLES I (Comnarativel & II
Example I is the control in which EXXPRO~ 90-10 (30 phr), Budene 1207 (70 phr) and conventional I~SiI 233 (30 phr) are blended by milling together.
The dispersion of the silica filler can be detected by scanning electron microscopy The scanning electron microscopy showed that the conventional silica filler was not found to be present in the EXXPRO~ phase of the blend. Coated silica used in this example was prepared by stirring for 30 minutes a suspension of 100 g. ~Sil 233 in a 0.5 wt%
to polymer in cyclohexane solution. The coated filler was removed and washed with cyclohexane three times. On the other hand, when the modified silica filler of the present invention is used to make a similar~blend, as in Example II, the modified silica filler of the present invention is found to be well dispersed in the EXXPRO~
phase and the Budene phase.
Example II: Modified silica filler was prepared by adsorption of poly(isoprene) from dilute solution 0.5% polymer in cyclohexane, with vigorous stirring at about 22~
C for approximately 1 hour. The coated silica was washed three times in cyclohexane.
The weight percent carbon of the product was 6.18%. The above-described product was then subjected to heat or thermal curing under a nitrogen atmosphere at 2o temperatures ranging from 60~ C to 120~ C for 60 minutes. The polyisoprene layer was extensively crosslinked because polyisoprene signals of the adsorbed polyisoprene layer were no longer observed in the solid state NMR spectrum. Crosslinked coatings formed in this example are stable to exchange by other polymers including poiar polymers with a high affinity for the filler like NBR. These coated fillers will be primarily found in the polyisoprene regions when used in blends of polyisoprene and NBR
The present invention also relates and generally applies, e.g., to various curing or vulcanization systems including, but not limited to, conventional systems (polysulfidic crosslinks produced by sulfur system); conventional systems with post 3o vulcanization stabilizers, e.g., dihydrate of the sodium salt of hexamethylene-1, 6-bisthiosulfate-s-ester; EV systems (low concentration of sulfur and high concentration of an organic accelerator); sulfurless or sulfur donor systems (using, for example, TMTD); Semi-EV (intermediate system between conventional and EV systems);
Soluble EV and Soluble Semi-EV systems; and the EV System of Hofinann (combination of sulfur donors, like TMTD and DTDM, in conjunction with sulfenamide (OTOS).
The curative precursors of the present invention are generally comprised of a solid containing or comprising curative. The curative precursor of the present invention may be formed by, e.g., the following methods: (1) precipitation of a polymer from a solution containing dissolved or suspended curative(s); (2) adsorption of curatives) to onto an inert solid, e.g., alumina or silica, followed by isolation of the curative-loaded solid, and adsorption of a polymer coating to the surface of the loaded solid;
(3) adsorption of a polymer coating to the surface of curative particles; or (4) mixing and/or grinding together curatives) with an inert solid, followed by adsorption of a polymer coating to the surface of the resulting solid curative mixture. The polymers useful in the preparation of the curative precursors of the present invention may be comprised of the same polymers of the blend and/or polymers compatible with one or more polymers of the blend. The term "compatible" as used herein means generally considered miscible.
While the following discussion is in terms of a single embodiment, it is 2o understood that the scope of the invention shall not be limited thereby In accordance with the practice of the present invention, a method is provided for the preparation of curative precursors for addition to a blend of at least two polymers selected from the group consisting of, for example, but not limited to elastomers, rubbers, polyolefins, polymers and mixtures thereof. In accordance with the present invention, a curative loaded solid or solid curative is, according to one embodiment, contacted with one of the polymers of the blend and/or a polymer compatible with one or both of the polymers of the blend and the polymer is adsorbed onto the surface of the curative loaded solid or solid curative. According to a preferred embodiment, the solid curative precursor is contacted with a minor amount of the polymer of the blend which has the "least aff nity" for the curative solid as compared to the other polymers) of the blend to form a stable surface saturated layer, e.g., which preferably is not removed by any subsequent solvent extractions. The thickness of the layer may be varied by varying adsorption conditions. Depending upon the solid utilized to form the curative-loaded solid and the polymer(s), the adsorption time may range from about one second to several hours. It should be noted that depending upon the polymer, different solvents may be utilized including, but not limited to, aliphatic and aromatic solvents like pentane, hexane, and toluene. The adsorption may be conducted at low temperatures, e.g., -40~ C where the amount of polymer to be adsorbed is large, to high temperatures, e. g., up to 200~ C when the amount of polymer to be adsorbed is small. For example, as further described below, when the polymers are brominated copolymer of isobutene to and 4-methylstyrene and polybutadiene, the curative loaded silica solid, is preferably first contacted with a minor amount of the brominated copolymer of isobutene and 4-methylstyrene. This copolymer has the "least affinity" for said loaded solid as compared to the polybutadiene. As used herein, the term "minor amount" means in an amount sufficient to provide a stable surface saturated layer on the filler. After contacting the curative-loaded solid with the brominated copolymer of isobutene and 4-methyistyrene, preferably forming a layer by the adsorption of the same onto the curative-loaded solid surface, the curative-loaded polymer coated solid is contacted with a minor amount of the second polymer of the blend and/or the polybutadiene. In this manner, a precursor is provided which will not completely migrate from the brominated copolymer of 2o isobutene and 4-methylstyrene during the blending of the two polymers.
Preferably, depending upon the application, after the curative loaded solid has been contacted with the polymers of the blend, the curative precursor is subjected to heat or thermal curing under a nitrogen atmosphere at temperatures ranging fi om about 60~ C to about 120~
C.
In order to determine which polymer of the polymer blend has the "least aff pity" for the solid comprising curative as compared to the other polymer(s), it is useful to measure rates of competitive adsorption or co-adsorption of polymers, etc.
onto solid particles. For example, to deterniine whether the brominated copolymer of isobutene and 4-methylstyrene has a Beater or weaker affinity for the curative-loaded 3o solid (which later forms the curative precursor) as compared to polybutadiene, the following test is performed which may be modified, if needed, for other polymer 1$
systems. Specifically, the exchange of elastomers on a solid precursor may be measured using a practical and rapid method comprising solid state H MAS-NMR.
This method allows the possibility to monitor and rank polymer interactions with solids by measuring the exchange.
According to one embodiment of the method of the invention, the curative-loaded, first polymer-coated solid of the precursor is kept wet with solvent, e.g., one weight percent solution of pentane, during transfer to a solution, e.g., one weight percent solution, of the second polymer. After exposure to the solution of the second polymer for a time interval, a sample of the polymer-coated precursor should be to removed and washed in an excess of solvent. The composition of the resulting solvent may be monitored by solid state H MAS-NMR which can measure the ratio of one polymer to another. This quantity can be measured precisely without any other standards. The total polymer composition may be deternvned by carbon elemental analysis.
After the curative precursor is prepared, it is mixed together with the polymers of the blend. The required mixing and heating varies as a function of the polymers utilized, the curative precursor, and the operating conditions employed by the person of ordinary skill in the art, the essential factor being complete and excellent dispersing of the curative precursor. Therefore, depending upon the devices utilized (like BanburyTM
2o mixers) to effect the mixing, the time may vary and may be determined by the person of ordinary skill in the art on the basis of his/her general knowledge and control of the properties of the composition used in the particular application, e.g., in the form of tire tread, knowing, e.g., that it is advisable to maximize the ratio of the 300~!~
elongation modulus to the 100~!o elongation modulus for each composition: Thus, the thenmomechanical work can include only a single step of suitable duration, temperature and intensity, or it can include several steps which can, if desired, be separated by at least a cooling step.
The final heating step of the method of the present invention is generally carried out using typical procedures known to one of ordinary skill in the art for crosslinlcing 3o and curing polymer blends. In any event, the blend is heated sufficiently to obtain crosslinlang, i.e., cure of the blend.
Although the invention has been illustrated by typical examples, it is not limited thereto. Changes and modifications of the examples of the invention herein chosen for purposes of disclosure can be made which do not constitute departure from the spirit and scope of the invention.
Claims (20)
1. A method for the preparation of coated targetable fillers which are customed designed to locate in specific polymer components of a polymer blend of at least two polymers, said method comprising:
coating or adsorbing the filler with a minor amount of at least a first polymer. and thereafter, coating or adsorbing said coated car adsorbed filler with a minor amount of s second polymer having a greater affinity for the solid than said first polymer.
coating or adsorbing the filler with a minor amount of at least a first polymer. and thereafter, coating or adsorbing said coated car adsorbed filler with a minor amount of s second polymer having a greater affinity for the solid than said first polymer.
2. The method of claim 1 wherein the filler is selected from the group.
consisting of silica, bentonite, clay, titanium oxide, calcium carbonate, lignin, talc and resins.
consisting of silica, bentonite, clay, titanium oxide, calcium carbonate, lignin, talc and resins.
3. The method of claim 3 wherein the filler is pre-coated or pre-adsorbed with a curative.
4. The method of claim 1 wherein the polymers are selected from the group consisting of thermoplastic and thermoset polymers, and mixtures thereof.
5. The method of claim 1 wherein the polymers are polybutadiene and a halogenated copolymer of isobutene and 4-methylstyrene.
6. A solid targetable filler produced according to the method of claim 1.
7. A solid targetable curative produced according to the method of claim 1.
8. A method for the preparation of a polymer blend comprising a filler which is customed designed to locate in specific polymer components of the blend, and two or more polymers, wherein said filler is dispersed throughout at least one polymer blend component, said method comprising:
coating or adsorbing said filler with a minor amount of at least a first polymer having affinity for said filler, and thereafter, coating or adsorbing said coated or adsorbed filler with a minor amount of a second polymer having a greater affinity for said filler than said first polymer, and mixing the coated or adsorbed filler with the two or more polymer components to form a polymer blend.
coating or adsorbing said filler with a minor amount of at least a first polymer having affinity for said filler, and thereafter, coating or adsorbing said coated or adsorbed filler with a minor amount of a second polymer having a greater affinity for said filler than said first polymer, and mixing the coated or adsorbed filler with the two or more polymer components to form a polymer blend.
9. The method of claim 8 wherein the filler is selected from the group consisting of clay, silica, bentonite, talc, calcium carbonate, lignin, resins, and titanium oxide.
10. The method of claim 8 wherein the polymer blend components are selected from the group consisting of thermoplastic and thermoset polymers, and mixtures thereof.
11. The method of claim 8 wherein the filler is coated or adsorbed with polybutadiene and a brominated copolymer of isobutene and methylstyrene.
12. The method of claim 11 wherein the filler is pre-coated or pre-adsorbed with a curative.
13. A blend produced according to claim 8.
14. A polymer blend comprising:
a fires polymer blend component and at least a second polymer blend component and a filler prepared in accordance with claim 1.
a fires polymer blend component and at least a second polymer blend component and a filler prepared in accordance with claim 1.
15. The blend of claim 14 wherein the polymer blend components comprise polybutadiene and a brominated copolymer of isobutene and methylstyrene.
16. The blend of claim 14 wherein the filler is coated or adsorbed with at least one of the polymer blend components.
17. The blend of claim 14 wherein the filler is coated or adsorbed with two of the polymer blend components.
18. The blend of claim 14 wherein the filler is pre-coated or pre-adsorbed with a curative.
19. A method of curing a polymer blend of at least two polymers, said method comprising:
subjecting the blend of claim 18 to curing conditions.
subjecting the blend of claim 18 to curing conditions.
20. The method of claim 19 wherein the blend polymers comprise polybutadiene and a brominated copolymer of isobutene and methylstyrene.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US3302696P | 1996-12-17 | 1996-12-17 | |
| US60/033,026 | 1996-12-17 | ||
| PCT/US1997/022504 WO1998027143A1 (en) | 1996-12-17 | 1997-11-24 | New targetable solids for polymer blends and methods of manufacturing the solids and blends containing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2271128A1 true CA2271128A1 (en) | 1998-06-25 |
Family
ID=21868160
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002271128A Abandoned CA2271128A1 (en) | 1996-12-17 | 1997-11-24 | New targetable solids for polymer blends and methods of manufacturing the solids and blends containing the same |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0946627A1 (en) |
| JP (1) | JP2001506306A (en) |
| KR (1) | KR20000057591A (en) |
| BR (1) | BR9713077A (en) |
| CA (1) | CA2271128A1 (en) |
| EA (1) | EA199900514A1 (en) |
| HU (1) | HUP9904187A3 (en) |
| PL (1) | PL333930A1 (en) |
| TW (1) | TW400352B (en) |
| WO (1) | WO1998027143A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6472042B1 (en) | 1994-02-10 | 2002-10-29 | Dow Global Technologies Inc. | Highly filled thermoplastic compositions |
| US20030211280A1 (en) | 1997-02-28 | 2003-11-13 | Shaw Industries, Inc. | Carpet, carpet backings and methods |
| EP0963402A1 (en) | 1997-02-28 | 1999-12-15 | The Dow Chemical Company | Filled polyethylene compositions |
| US7338698B1 (en) | 1997-02-28 | 2008-03-04 | Columbia Insurance Company | Homogeneously branched ethylene polymer carpet, carpet backing and method for making same |
| KR20000063679A (en) * | 2000-07-28 | 2000-11-06 | 최재영 | The elastic fillers and compositions |
| JP4485191B2 (en) * | 2001-06-08 | 2010-06-16 | エクソンモービル・ケミカル・パテンツ・インク | Low permeability nanocomposite |
| JP5018664B2 (en) * | 2008-06-17 | 2012-09-05 | 横浜ゴム株式会社 | Method for producing elastomer composition and pneumatic tire using the same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1090972A (en) * | 1964-02-12 | 1967-11-15 | Dunlop Rubber Co | Improvements in or relating to polymeric compositions |
| DE1806118A1 (en) * | 1968-10-30 | 1970-05-21 | Amicon Corp | Polymeric substance reinforced by fillers |
| JPS58103556A (en) * | 1981-12-15 | 1983-06-20 | Mitsubishi Petrochem Co Ltd | Impact resistant polyphenylene ether composition |
| US5135971A (en) * | 1989-02-18 | 1992-08-04 | Basf Aktiengesellschaft | Flameproofed thermoplastic molding compositions based on phlegmatized red phosphorus |
-
1997
- 1997-11-24 CA CA002271128A patent/CA2271128A1/en not_active Abandoned
- 1997-11-24 KR KR1019990705365A patent/KR20000057591A/en not_active Application Discontinuation
- 1997-11-24 HU HU9904187A patent/HUP9904187A3/en unknown
- 1997-11-24 EA EA199900514A patent/EA199900514A1/en unknown
- 1997-11-24 JP JP52778798A patent/JP2001506306A/en active Pending
- 1997-11-24 WO PCT/US1997/022504 patent/WO1998027143A1/en not_active Application Discontinuation
- 1997-11-24 PL PL97333930A patent/PL333930A1/en unknown
- 1997-11-24 EP EP97948623A patent/EP0946627A1/en not_active Withdrawn
- 1997-11-24 BR BR9713077-0A patent/BR9713077A/en not_active Application Discontinuation
- 1997-12-10 TW TW086118617A patent/TW400352B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| EP0946627A1 (en) | 1999-10-06 |
| HUP9904187A2 (en) | 2000-04-28 |
| EA199900514A1 (en) | 2000-02-28 |
| JP2001506306A (en) | 2001-05-15 |
| TW400352B (en) | 2000-08-01 |
| KR20000057591A (en) | 2000-09-25 |
| PL333930A1 (en) | 2000-01-31 |
| BR9713077A (en) | 2000-04-11 |
| WO1998027143A1 (en) | 1998-06-25 |
| HUP9904187A3 (en) | 2000-05-29 |
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