WO2004035670A1 - Polymer composites comprising low molecular weight nitrile rubber - Google Patents
Polymer composites comprising low molecular weight nitrile rubber Download PDFInfo
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- WO2004035670A1 WO2004035670A1 PCT/CA2003/001591 CA0301591W WO2004035670A1 WO 2004035670 A1 WO2004035670 A1 WO 2004035670A1 CA 0301591 W CA0301591 W CA 0301591W WO 2004035670 A1 WO2004035670 A1 WO 2004035670A1
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- nitrile rubber
- mooney viscosity
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/04—Antibacterial agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C2019/09—Metathese
Definitions
- the present invention relates to polymer composites comprising at least one nitrile rubber polymer having a Mooney viscosity (ML 1+4 @ 100°C) below 30 at least one filler and optionally at least one cross-linking agent, a process for preparing said polymer composite wherein at least one nitrile rubber polymer having a Mooney viscosity (ML 1+4 @ 100°C) below 30, at least one filler and optionally at least one cross-linking agent are mixed and a process for the manufacture of a shaped article comprising the step of injection molding a polymer composite comprising at least one nitrile rubber polymer having a Mooney viscosity (ML 1 +4 @ 100°C) below 30, at least one filler and at least one cross-linking agent.
- Hydrogenated nitrile rubber prepared by the selective hydrogenation of acrylonitrile-butadiene rubber (nitrile rubber; NBR, a co- polymer comprising at least one conjugated diene, at least one unsaturated nitrile and optionally further comonomers), is a specialty rubber which has very good heat resistance, excellent ozone and chemical resistance, and excellent oil resistance.
- NBR and HNBR have found widespread use in the automotive (seals, hoses, bearing pads) oil (stators, well head seals, valve plates), electrical (cable sheathing), mechanical engineering (wheels, rollers) and shipbuilding (pipe seals, couplings) industries, amongst others.
- HNBR has a Mooney viscosity in the range of from 55 to 105, a molecular weight in the range of from 200,000 to 500,000 g/mol, a polydispersity greater than 3.0 and a residual double bond (RDB) content in the range of from 1 to 18% (by IR spectroscopy).
- HNBR high Mooney Viscosity
- HNBR having a lower molecular weight and lower Mooney viscosity would have better processability.
- Attempts have been made to reduce the molecular weight of the polymer by mastication (mechanical breakdown) and by chemical means (for example, using strong acid), but such methods have the disadvantages that they result in the introduction of functional groups (such as carboxylic acid and ester groups) into the polymer, and the altering of the microstructure of the polymer. This results in disadvantageous changes in the properties of the polymer.
- these types of approaches by their very nature, produce polymers having a broad molecular weight distribution.
- the hydrogenation of NBR to produce HNBR results in an increase in the Mooney viscosity of the raw polymer.
- This Mooney Increase Ratio is generally around 2, depending upon the polymer grade, hydrogenation level and nature of the feedstock.
- Therban® VP KA 8837 available from Bayer, which has a Mooney viscosity of 55 (ML 1 +4 @ 100°C) and a RDB of 18%.
- Co-pending applications CA-2,351 ,961 , CA-2,357,470, CA 2,350,280 and CA 2,357,465 disclose a low-Mooney NBR and HNBR and a method for producing said low-Mooney NBR and HNBR. While the disclosed NBR or HNBR being perfectly suitable for the present invention, said applications are silent about polymer composites comprising said low-Mooney NBR and/or HNBR and methods of producing shaped articles from said low-Mooney NBR and/or HNBR.
- the present invention relates to a polymer composite comprising at least one nitrile rubber polymer ("NBR") having a Mooney viscosity (ML 1+4 @ 100°C) below 30, at least one filler and optionally at least one cross-linking agent. It is preferred that the NBR is fully or partially hydrogenated (“HNBR").
- the invention relates to polymer composites comprising at least one, optionally hydrogenated, nitrile rubber polymer having a Mooney viscosity (ML 1+4 @ 100°C) below 20, preferably below 10.
- the present invention relates to a process for the manufacture of a shaped article comprising the step of injection molding a polymer composite comprising at least one, optionally hydrogenated, nitrile rubber polymer having a Mooney viscosity (ML 1+4 @ 100°C) below 30, at least one filler and at least one cross-linking agent.
- a shaped article such as a seal, hose, bearing pad, stator, well head seal, valve plate, cable sheathing, wheel, roller, pipe seal or footwear component prepared by injection molding and subsequent curing of a polymer composite comprising at least one, optionally hydrogenated, nitrile rubber polymer having a Mooney viscosity (ML 1+4 @ 100°C) below 30, at least one filler and optionally at least one cross-linking agent.
- a polymer composite comprising at least one, optionally hydrogenated, nitrile rubber polymer having a Mooney viscosity (ML 1+4 @ 100°C) below 30, at least one filler and optionally at least one cross-linking agent.
- nitrile polymer or NBR is intended to have a broad meaning and is meant to encompass a copolymer having repeating units derived from at least one conjugated diene, at least one ⁇ , ⁇ -unsaturated nitrile and optionally further one or more copolymerizable monomers.
- the conjugated diene may be any known conjugated diene, in particular a C 4 -C 6 conjugated diene.
- Preferred conjugated dienes are butadiene, isoprene, piperylene, 2,3-dimethyl butadiene and mixtures thereof. Even more preferred C -C6 conjugated dienes are butadiene, isoprene and mixtures thereof. The most preferred C -C6 conjugated diene is butadiene.
- the ⁇ , ⁇ -unsaturated nitrile may be any known ⁇ , ⁇ -unsaturated nitrile, in particular a C 3 -C 5 ⁇ , ⁇ -unsaturated nitrile.
- Preferred C 3 -C 5 ⁇ , ⁇ -unsaturated nitriles are acrylonitrile, methacrylonitrile, ethacrylonitrile and mixtures thereof.
- the most preferred C 3 -C5 ⁇ , ⁇ -unsatu rated nitrile is acrylonitrile.
- the copolymer comprises in the range of from 40 to 85 weight percent of repeating units derived from one or more conjugated dienes and in the range of from 15 to 60 weight percent of repeating units derived from one or more unsaturated nitriles. More preferably, the copolymer comprises in the range of from 60 to 75 weight percent of repeating units derived from one or more conjugated dienes and in the range of from 25 to 40 weight percent of repeating units derived from one or more unsaturated nitriles. Most preferably, the copolymer comprises in the range of from 60 to 70 weight percent of repeating units derived from one or more conjugated dienes and in the range of from 30 to 40 weight percent of repeating units derived from one or more unsaturated nitriles.
- the copolymer may further comprise repeating units derived from one or more copolymerizable monomers, such as unsaturated carboxylic acids.
- suitable unsaturated carboxylic acids are fumaric acid, maleic acid, acrylic acid, methacrylic acid and mixtures thereof.
- Repeating units derived from one or more copolymerizable monomers will replace either the nitrile or the diene portion of the nitrile rubber and it will be apparent to the skilled in the art that the above mentioned figures will have to be adjusted to result in 100 weight percent.
- the nitrile rubber preferably comprises repeating units derived from one or more unsaturated carboxylic acids in the range of from 1 to 10 weight percent of the rubber, with this amount displacing a corresponding amount of the conjugated diolefin.
- Other preferred optionally further monomers are unsaturated mono- or di-carboxylic acids or derivatives thereof (e.g., esters, amides and the like) including mixtures thereof.
- Hydrogenated in this invention is preferably understood by more than 50 % of the residual double bonds (RDB) present in the starting nitrile polymer/NBR being hydrogenated, preferably more than 90 % of the RDB are hydrogenated, more preferably more than 95 % of the RDB are hydrogenated and most preferably more than 99 % of the RDB are hydrogenated.
- RDB residual double bonds
- the Mooney viscosity of the rubber was determined using ASTM test D1646.
- the inventive polymer composite comprises at least one, optionally hydrogenated, NBR having a Mooney viscosity (ML 1+4 @ 100°C according to ASTM test D1646) of less than 30, in particular less than 20, preferably less than 15 and even more preferably less than 10. It is preferred that the low-Mooney, optionally hydrogenated NBR of this invention has a polydispersity index of less than 3, more preferred less than 2.9, even more preferred less than 2.8, even more preferred less than 2.7, even more preferred less than 2.6, even more preferred less than 2.5, even more preferred less than 2.4, even more preferred less than 2.3, and even more preferred less than 2.2.
- the present invention is not restricted to a special process for preparing the optionally hydrogenated NBR.
- the NBR/HNBR of the invention is readily available in a two step synthesis as disclosed in CA-2,351 ,961 , CA- 2,357,470, CA 2,350,280 and CA 2,357,465, which may take place in the same reaction set-up or different reactors.
- CA-2,351 , 961 , CA-2,357,470, CA 2,350,280 and CA 2,357,465 are incorporated herein by reference.
- Step 1 Metathesis The metathesis reaction is conducted in the presence of one or more compounds of the general formulas I, II, III or IV;
- R and R 1 are, independently, hydrogen or a hydrocarbon selected from the group consisting of C 2 -C 2 o alkenyl, C 2 -C 2 o alkynyl, CrC 2 o alkyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, aryloxy, C 2 - C 2 o alkoxycarbonyl, C1-C20 alkylthio, C1-C20 alkylsulfonyl and C1-C20 alkylsulfinyl,
- X and X 1 are independently any anionic ligand
- L and L 1 are independently any neutral ligand, such as phosphines, amines, thioethers or imidazolidinylidenes or any neutral carbene, optionally, L and L 1 can be linked to one another to from a bidentate neutral ligand;
- M is Os or Ru
- R 2 and R 3 are, independently, hydrogen or a hydrocarbon selected from the group consisting of C2-C20 alkenyl, C2-C20 alkynyl, C1-C20 alkyl. a
- X 2 is a anionic ligand
- L 2 is a neutral ⁇ -bonded ligand, independent of whether they are mono- or polycyclic
- L 3 is a ligand selected from the group consisting of phosphines, sulfonated phosphines, fluorinated phosphines, functionalized phosphines bearing up to three aminoalkyl-, ammoniumalkyl-, alkoxyalkyl-, alkoxylcarbonylalkyl-, hydrocycarbonylalkyl-, hydroxyalkyl- or ketoalkyl- groups, phosphites, phosphinites, phosphonites, phosphinamines, arsines, stibenes, ethers, amines, amides, imines, sulfoxides, thioethers and pyridines,
- Y " is a non-coordinating anion, n is an integer in the range of from 0 to 5;
- M 2 is Mo or W
- R 4 and R 5 are, independently, hydrogen or a hydrocarbon selected from the group consisting of C2-C20 alkenyl, C2-C20 alkynyl, C1-C20 alkyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, aryloxy, C2-
- R 6 and R 7 are independently selected from any unsubstituted or halo- substituted alkyl, aryl, aralkyl groups or silicon-containing analogs thereof,
- M is Os or Ru
- R and R 1 are independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, and substituted or unsubstituted alkyl,
- X and X 1 are independently any anionic ligand, and L and L 1 are independently any neutral ligand, such as phosphines, amines, thioethers or imidazolidinylidenes or any neutral carbene, optionally, L and L 1 can be linked to one another to from a bidentate neutral ligand;
- the amount of compounds will depend upon the nature and catalytic activity of the compound(s) in question.
- the ratio of compound(s)to NBR is in the range of from 0.005 to 5, preferably in the range of from 0.025 to 1 and, more preferably, in the range of from 0.1 to 0.5.
- the metathesis reaction is carried out in the presence of a co-olefin which is preferably a C 2 to C ⁇ 6 linear or branched olefin such as ethylene, isobutene, styrene or 1-hexene.
- a co-olefin which is preferably a C 2 to C ⁇ 6 linear or branched olefin such as ethylene, isobutene, styrene or 1-hexene.
- the co-olefin is a liquid (such as 1 - hexene)
- the amount of co-olefin employed is preferably in the range of from 1 to 200 weight %.
- the co-olefin is a gas (such as ethylene) the amount of co-olefin employed is such that it results in a pressure in the reaction vessel in the range of from 1 * 10 5 Pa to 1 * 10 7 Pa, preferably in the range of from 5.2 * 10 5 Pa to 4 * 10 6 Pa.
- the metathesis reaction can be carried out in any suitable solvent which does not inactivate the catalyst or otherwise interfere with the reaction.
- Preferred solvents include, but are not limited to, dichloromethane, benzene, toluene, tetrahydrofuran, cylcohexane and the like.
- the most preferred solvent is monochlorobenzene (MCB).
- MMB monochlorobenzene
- the co-olefin can itself act as a solvent (for example, 1 -hexene), in which case no other solvent is necessary.
- concentration of nitrile polymer (NBR) in the reaction mixture is not critical but, obviously, should be such that the reaction is not hampered if the mixture is too viscous to be stirred efficiently, for example.
- the concentration of NBR is in the range of from 1 to 20% by weight, most preferably in the range of from 6 to 15% by weight.
- the metathesis reaction is carried out at a temperature in the range of from 20 to 140 Q C; preferably in the range of from 60 to 120 S C.
- the reaction time will depend upon a number of factors, including cement concentration, amount of catalyst used and the temperature at which the reaction is performed.
- the metathesis is usually complete within the first two hours under typical conditions.
- the progress of the metathesis reaction may be monitored by standard analytical techniques, for example using GPC or solution viscosity.
- GPC gel permeation chromatography
- the molecular weight distribution of the polymer was determined by gel permeation chromatography (GPC) using a Waters 2690 Separation Module and a Waters 410 Differential Refractometer running Waters Millenium software version 3.05.01. Samples were dissolved in tetrahydrofuran (THF) stabilized with 0.025% BHT. The columns used for the determination were three sequential mixed-B gel columns from Polymer Labs. Reference Standards used were polystyrene standards from American Polymer Standards Corp.
- HNBR partially or fully hydrogenated nitrile polymer
- Reduction of the product from the metathesis reaction can be effected using standard reduction techniques known in the art.
- homogeneous hydrogenation catalysts known to those of skill in the art such as Wilkinson's catalyst ⁇ (PPh 3 ) 3 RhCI ⁇ and the like can be used.
- the hydrogenation may be performed in situ i.e. in the same reaction vessel in which the metathesis step is carried out, without the need to first isolate the metathesised product.
- the hydrogenation catalyst is simply added to the vessel, which is then treated with hydrogen to produce the HNBR.
- Grubb's catalyst in the presence of hydrogen, is converted to a dihydride complex (PR 3 ) 2 RuCl2H 2 , which is itself an olefin hydrogenation catalyst.
- PR 3 dihydride complex
- RuCl2H 2 which is itself an olefin hydrogenation catalyst.
- the reaction mixture was then treated with hydrogen, converting the Grubb's complex to the dihydride species which then hydrogenated the metathesis product to produce the HNBR of the invention.
- the rate of hydrogenation was lower in this case than in the case where Wilkinson's catalyst was used for the hydrogenation step, but it is clear that such an approach is indeed a viable one.
- the low Mooney NBR as well as the low Mooney HNBR which forms a preferred component of the polymer composite of the invention can be characterized by standard techniques known in the art. For example, the molecular weight distribution of the polymer was determined by gel permeation chromatography (GPC) using a Waters 2690 Separation Module and a Waters 410 Differential Refractometer running Waters Millennium software version 3.05.01.
- Samples were dissolved in tetrahydrofuran (THF) stabilized with 0.025% BHT.
- THF tetrahydrofuran
- the columns used for the determination were three sequential mixed-B gel columns from Polymer Labs.
- Reference Standards used were polystyrene standards from American Polymer Standards Corp.
- the inventive polymer composite further comprises at least one filler.
- the filler may be an active or an inactive filler or a mixture thereof.
- the filler may be in particular:
- silicas prepared e.g. by the precipitation of silicate solutions or the flame hydrolysis of silicon halides, with specific surface areas of in the range of from 5 to 1000 m 2 /g, and with primary particle sizes of in the range of from 10 to 400 nm;
- the silicas can optionally also be present as mixed oxides with other metal oxides such as those of Al, Mg, Ca, Ba, Zn, Zr and Ti;
- - synthetic silicates such as aluminum silicate and alkaline earth metal silicate like magnesium silicate or calcium silicate, with BET specific surface areas in the range of from 20 to 400 m 2 /g and primary particle diameters in the range of from 10 to 400 nm;
- - natural silicates such as kaolin and other naturally occurring silica
- - glass fibers and glass fiber products matting, extrudates or glass microspheres
- metal oxides such as zinc oxide, calcium oxide, magnesium oxide and aluminum oxide
- - metal carbonates such as magnesium carbonate, calcium carbonate and zinc carbonate
- - metal hydroxides e.g. aluminum hydroxide and magnesium hydroxide
- - carbon blacks the carbon blacks to be used here are prepared by the lamp black, furnace black or gas black process and have preferably BET (DIN 66 131) specific surface areas in the range of from 20 to 200 m 2 /g, e.g. SAF, ISAF, HAF, FEF or GPF carbon blacks;
- - rubber gels especially those based on polybutadiene, butadiene/styrene copolymers, butadiene/acrylonitrile copolymers and polychloroprene; or mixtures thereof.
- preferred mineral fillers include silica, silicates, clay such as bentonite, gypsum, alumina, titanium dioxide, talc, mixtures of these, and the like. These mineral particles have hydroxyl groups on their surface, rendering them hydrophilic and oleophobic. This exacerbates the difficulty of achieving good interaction between the filler particles and the rubber.
- the preferred mineral is silica, especially silica made by carbon dioxide precipitation of sodium silicate.
- Dried amorphous silica particles suitable for use in accordance with the invention may have a mean agglomerate particle size in the range of from 1 to 100 microns, preferably between 10 and 50 microns and most preferably between 10 and 25 microns. It is preferred that less than 10 percent by volume of the agglomerate particles are below 5 microns or over 50 microns in size.
- a suitable amorphous dried silica moreover usually has a BET sur ace area, measured in accordance with DIN (Deutsche Industrie Norm) 66131 , of in the range of from 50 and 450 square meters per gram and a DBP absorption, as measured in accordance with DIN 53601 , of in the range of from 150 and 400 grams per 100 grams of silica, and a drying loss, as measured according to DIN ISO 787/11, of in the range of from 0 to 10 percent by weight.
- Suitable silica fillers are available under the trademarks HiSil® 210, HiSil® 233 and HiSil® 243 from PPG Industries Inc. Also suitable are Vulkasil® S and Vulkasil® N, from Bayer AG.
- carbon black is present in the polymer composite in an amount of in the range of from 20 to 200 parts by weight, preferably 30 to 150 parts by weight, more preferably 40 to 100 parts by weight.
- carbon black and mineral filler it might be advantageous to use a combination of carbon black and mineral filler in the inventive polymer composite. In this combination the ratio of mineral fillers to carbon black is usually in the range of from 0.05 to 20, preferably 0.1 to 10.
- the polymer composite may advantageously further comprise other natural or synthetic rubbers such as BR (polybutadiene), ABR
- polyisoprene polyisoprene
- SBR styrene/butadiene-copolymers
- NBR butadiene/acrylonitrile-copolymers with acrylonitrile contents of 5 to 60 wt%
- the polymer composite furthermore optionally comprises one or more cross-linking agents or curing systems.
- the invention is not limited to a special curing system, however, peroxide curing system are preferred. Furthermore, the invention is not limited to a special peroxide curing system. For example, inorganic or organic peroxides are suitable.
- organic peroxides such as diaikylperoxides, ketalperoxides, aralkylperoxides, peroxide ethers, peroxide esters, such as di-tert.-butylperoxide, bis-(tert.-butylperoxyisopropyl)- benzene, dicumylperoxide, 2,5-dimethyl-2,5-di(tert.-butylperoxy)-hexane, 2,5- dimethyl-2,5-di(tert.-butylperoxy)-hexene-(3), 1 ,1 -bis-(tert.-butylperoxy)-3,3,5- trimethyl-cyclohexane, benzoylperoxide, tert.-butylcumylperoxide and tert.- butylperbenzoate.
- diaikylperoxides such as diaikylperoxides, ketalperoxides
- the rubber composition according to the invention can contain further auxiliary products for rubbers, such as reaction accelerators, vulcanizing accelerators, vulcanizing acceleration auxiliaries, antioxidants, foaming agents, anti-aging agents, heat stabilizers, light stabilizers, ozone stabilizers, processing aids, plasticizers, tackifiers, blowing agents, dyestuffs, pigments, waxes, extenders, organic acids, inhibitors, metal oxides, and activators such as triethanolamine, polyethylene glycol, hexanetriol, etc., which are known to the rubber industry.
- the rubber aids are used in conventional amounts, which depend inter alia on the intended use. Conventional amounts are e.g. from 0.1 to 50 wt.%, based on rubber.
- the composition comprises in the range of 0.1 to 20 phr of an organic fatty acid as an auxiliary product, preferably a unsaturated fatty acid having one, two or more carbon double bonds in the molecule which more preferably includes 10% by weight or more of a conjugated diene acid having at least one conjugated carbon-carbon double bond in its molecule.
- those fatty acids have in the range of from 8-22 carbon atoms, more preferably 12-18. Examples include stearic acid, palmitic acid and oleic acid and their calcium-, zinc-, magnesium-, potassium- and ammonium salts.
- the composition comprises in the range of 5 to 50 phr of an acrylate as an auxiliary product.
- Suitable acrylates are known from EP-A1-0 319 320, in particular p. 3, I. 16 to 35, from US- 5 208 294, in particular Col. 2, I. 25 to 40, and from US-4 983 678, in particular Col. 2, 1. 45 to 62.
- Particular reference is made to zinc acrylate, zinc diacrylate or zinc dimethacrylate or a liquid acrylate, such as trimethylolpropanetrimethacrylate (TRIM), butanedioldimethacrylate (BDMA) and ethylenglycoldimethacrylate (EDMA). It might be advantageous to use a combination of different acrylates and/or metal salts thereof.
- TAM trimethylolpropanetrimethacrylate
- BDMA butanedioldimethacrylate
- EDMA ethylenglycoldimethacrylate
- metal acrylates in combination with a Scorch-retarder such as sterically hindered phenols (e.g. methyl-substituted aminoalkylphenols, in particular 2,6-di-tert.-butyl-4-dimethylaminomethylphenol).
- a Scorch-retarder such as sterically hindered phenols (e.g. methyl-substituted aminoalkylphenols, in particular 2,6-di-tert.-butyl-4-dimethylaminomethylphenol).
- the ingredients of the final polymer composite are mixed together, suitably at an elevated temperature that may range from 25 °C to 200 °C. Normally the mixing time does not exceed one hour and a time in the range from 2 to 30 minutes is usually adequate.
- the mixing is suitably carried out in an internal mixer such as a Banbury mixer, or a Haake or Brabender miniature internal mixer.
- a two roll mill mixer also provides a good dispersion of the additives within the elastomer.
- An extruder also provides good mixing, and permits shorter mixing times. It is possible to carry out the mixing in two or more stages, and the mixing can be done in different apparatus, for example one stage in an internal mixer and one stage in an extruder.
- the polymer composite Due to the low viscosity of the polymer composite, the polymer composite is ideally suited to be processed by but not limited to molding injection technology.
- the polymer composite can also be useful to transfer molding, to compression molding, to liquid injection molding.
- the polymer composite comprising a cross-linking system is usually introduced in a conventional injection molding and injected into hot (about 160-230°C) forms where the cross-linking/vulcanization takes place depending on the polymer composite composition and temperature of the mold.
- the inventive polymer composite is very well suited for the manufacture of a shaped article, such as a seal, hose, bearing pad, stator, well head seal, valve plate, cable sheathing, wheel, roller, pipe seal, in place gaskets or footwear component prepared by injection molding technology.
- the cement from the metathesis reaction was degassed 3 times with H 2 (100 psi) under full agitation.
- the temperature of the reactor was raised to 130°C and a 1L monochlorobenzene solution containing Wilkinson's catalyst and triphenylphosphine was added to the reactor.
- the temperature was allowed to increase to 138°C and maintained constant for the duration of the reaction.
- the hydrogenation reaction was monitored by measuring the residual double bond (RDB) level at various intervals using IR spectroscopy.
- RDB residual double bond
- the Ruthenium metathesis catalyst could be used to hydrogenate the polymer.
- Polymer composites were mixed on an open mill.
- the curatives were added on a cold open mill in a separate mixing step.
- the formulations used in this assessment are based on a simplified peroxide recipe according to Table 1.
- Carbon black N 660 Sterling-V available from Cabot Tire Blacks Maglite® D is a MgO available from C.P. Hall.
- Naugard® 445 is a diphenylamine available from Uniroyal Chemical.
- Plasthall TOTM is a Trioctyl trimellitate available from C.P. Hall.
- Vulkanox® ZMB-2/C5 is a Zinc salt of 4- and 5-methyl-mercapto benzimidazole available from Bayer AG
- DIAK #7 is a Triallylisocyanurate available from DuPont Dow Elastomers
- Vulcup 40KE is 2,2'-bis (tert-butylperoxy di-isopropylbenzene) available from Harwick Standard.
- Table 1 Compounding Recipe
- Zinc Oxide (Kadox® 920) Grade PC 3 3 3 3 3 3 3
- the molecular weight (Mw) of the Polymer of Example 1 is 14 that of regular Therban® A3407 while the narrow polydispersity (PDI) is 2.1 compared to 3.2 for the regular grade.
- Table 3 shows a summary of the properties of polymer composites of Exp. 2-6. Examples 2 and 6 are for comparison.
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Abstract
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Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BRPI0315361-4A BR0315361B1 (en) | 2002-10-17 | 2003-10-17 | POLYMERIC COMPOSITE, PROCESS FOR PREPARING A POLYMERIC COMPOSITE AND PROCESS FOR MANUFACTURING A MOLDED ARTICLE |
EP03769114.4A EP1554335B1 (en) | 2002-10-17 | 2003-10-17 | Polymer composites comprising low molecular weight nitrile rubber |
AU2003278031A AU2003278031A1 (en) | 2002-10-17 | 2003-10-17 | Polymer composites comprising low molecular weight nitrile rubber |
KR1020057006532A KR101194089B1 (en) | 2002-10-17 | 2003-10-17 | Polymer composites comprising low molecular weight nitrile rubber |
JP2004543874A JP4509792B2 (en) | 2002-10-17 | 2003-10-17 | Low molecular weight nitrile rubber containing polymer composite |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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CA2,409,436 | 2002-10-17 | ||
CA002409436A CA2409436A1 (en) | 2002-10-17 | 2002-10-17 | Polymer composites comprising low molecular weight nitrile rubber |
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WO2004035670A1 true WO2004035670A1 (en) | 2004-04-29 |
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PCT/CA2003/001591 WO2004035670A1 (en) | 2002-10-17 | 2003-10-17 | Polymer composites comprising low molecular weight nitrile rubber |
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US (1) | US7262244B2 (en) |
EP (1) | EP1554335B1 (en) |
JP (1) | JP4509792B2 (en) |
KR (1) | KR101194089B1 (en) |
CN (1) | CN1325546C (en) |
AU (1) | AU2003278031A1 (en) |
BR (1) | BR0315361B1 (en) |
CA (1) | CA2409436A1 (en) |
TW (1) | TWI319414B (en) |
WO (1) | WO2004035670A1 (en) |
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EP2028194A1 (en) * | 2007-08-21 | 2009-02-25 | Lanxess Deutschland GmbH | Metathesis of nitrile rubbers in the presence of transition metal complex catalysts |
EP3324468A4 (en) * | 2015-07-14 | 2019-03-06 | Zeon Corporation | Binder composition for secondary battery electrodes, conductive material paste composition for secondary battery electrodes, slurry composition for secondary battery electrodes, electrode for secondary batteries, and secondary battery |
WO2020020677A1 (en) | 2018-07-23 | 2020-01-30 | Arlanxeo Deutschland Gmbh | Method for producing hydrogenated nitrile rubber and hnbr compositions thereof |
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CA2409429A1 (en) * | 2002-10-17 | 2004-04-17 | Bayer Inc. | Hydrogenated nitrile rubber composites with improved proccesability |
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- 2003-10-16 TW TW092128647A patent/TWI319414B/en not_active IP Right Cessation
- 2003-10-17 KR KR1020057006532A patent/KR101194089B1/en active IP Right Grant
- 2003-10-17 CN CNB2003801014463A patent/CN1325546C/en not_active Expired - Fee Related
- 2003-10-17 WO PCT/CA2003/001591 patent/WO2004035670A1/en active Application Filing
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Cited By (9)
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EP2009050A1 (en) * | 2006-04-17 | 2008-12-31 | Zeon Corporation | Crosslinkable nitrile rubber composition and crosslinked rubber product |
EP2009050A4 (en) * | 2006-04-17 | 2010-07-21 | Zeon Corp | Crosslinkable nitrile rubber composition and crosslinked rubber product |
US8742006B2 (en) | 2006-04-17 | 2014-06-03 | Zeon Corporation | Cross-linkable nitrile rubber composition and cross-linked rubber |
EP2028194A1 (en) * | 2007-08-21 | 2009-02-25 | Lanxess Deutschland GmbH | Metathesis of nitrile rubbers in the presence of transition metal complex catalysts |
EP2028195A1 (en) * | 2007-08-21 | 2009-02-25 | Lanxess Deutschland GmbH | Metathesis of nitrile rubbers in the presence of transition metal complex catalysts |
EP3324468A4 (en) * | 2015-07-14 | 2019-03-06 | Zeon Corporation | Binder composition for secondary battery electrodes, conductive material paste composition for secondary battery electrodes, slurry composition for secondary battery electrodes, electrode for secondary batteries, and secondary battery |
US10388961B2 (en) | 2015-07-14 | 2019-08-20 | Zeon Corporation | Binder composition for secondary battery electrode, conductive material paste composition for secondary battery electrode, slurry composition for secondary battery electrode, electrode for secondary battery, and secondary battery |
EP3920285A1 (en) * | 2015-07-14 | 2021-12-08 | Zeon Corporation | Binder composition for secondary battery electrode, conductive material paste composition for secondary battery electrode, slurry composition for secondary battery electrode, electrode for secondary battery, and secondary battery |
WO2020020677A1 (en) | 2018-07-23 | 2020-01-30 | Arlanxeo Deutschland Gmbh | Method for producing hydrogenated nitrile rubber and hnbr compositions thereof |
Also Published As
Publication number | Publication date |
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US7262244B2 (en) | 2007-08-28 |
BR0315361B1 (en) | 2014-05-27 |
US20040113320A1 (en) | 2004-06-17 |
EP1554335B1 (en) | 2013-07-17 |
BR0315361A (en) | 2005-08-23 |
KR101194089B1 (en) | 2012-10-24 |
EP1554335A1 (en) | 2005-07-20 |
CN1705707A (en) | 2005-12-07 |
KR20050053768A (en) | 2005-06-08 |
AU2003278031A1 (en) | 2004-05-04 |
TWI319414B (en) | 2010-01-11 |
CA2409436A1 (en) | 2004-04-17 |
TW200416247A (en) | 2004-09-01 |
JP4509792B2 (en) | 2010-07-21 |
JP2006503128A (en) | 2006-01-26 |
CN1325546C (en) | 2007-07-11 |
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