WO2001077185A1 - Process for hydrogenating carboxylated nitrile rubber, the hydrogenated rubber and its uses - Google Patents
Process for hydrogenating carboxylated nitrile rubber, the hydrogenated rubber and its uses Download PDFInfo
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- WO2001077185A1 WO2001077185A1 PCT/CA2001/000485 CA0100485W WO0177185A1 WO 2001077185 A1 WO2001077185 A1 WO 2001077185A1 CA 0100485 W CA0100485 W CA 0100485W WO 0177185 A1 WO0177185 A1 WO 0177185A1
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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
- C08C19/02—Hydrogenation
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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
- C08L13/00—Compositions of rubbers containing carboxyl groups
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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
- C08L15/00—Compositions of rubber derivatives
- C08L15/005—Hydrogenated nitrile rubber
Definitions
- the present invention relates to novel polymers to processes for preparing them, and to their uses .
- Hydrogenation of the nitrile moieties is to be avoided, as any reduction of the nitrile groups has an undesired and deleterious effect on the properties of the nitrile rubber; in particular it reduces the oil resistance of the nitrile rubber.
- copolymerisable monomers in nitrile rubbers.
- copolymerisable monomers ⁇ , ⁇ -unsaturated mono- and dicarboxylic acids. These can be incorporated into the polymer backbone, but difficulty has been encountered when polymers containing carboxyl groups have been hydrogenated.
- the carboxyl groups have undergone reduction or other side reactions, which has resulted in an unsatisfactory product.
- polymerisation of conjugated diene and nitrile results in a polymer that has some carbon-carbon double bonds in a vinyl side chain, from 1, 2-polymerisation of butadiene, and some carbon-carbon double bonds in the main polymer backbone, from 1, 4-polymerisation of butadiene.
- These double bonds in the main polymer backbone may be in the cis or in the trans configuration.
- the vinyl groups undergo hydrogenation first, followed by the double bonds in the cis configuration.
- the partially hydrogenated polymer to which the ⁇ , ⁇ -unsaturated acid is added contains mostly or entirely double bonds in the main polymer backbone and in the trans configuration.
- the chemical structure of a polymer made in this latter way differs from the chemical structure of the statistical polymers that is formed by the terpolymerisation of a conjugated diene, an unsaturated nitrile and an unsaturated acid, where the monomers are statistically or randomly distributed throughout the polymer chain.
- European Patent Application No. 933381 is concerned with carboxylated nitrile-group-containing highly saturated copolymer rubber, and in the Background Art discusses three processes for adding aleic anhydride to a nitrile-group- containing highly saturated copolymer rubber.
- the European application refers to "a highly saturated copolymer rubber", but it is believed that some degree of unsaturation in the rubber is required, to serve as reaction sites for addition of the maleic anhydride. Disadvantages of all three processes for adding maleic anhydride are mentioned, and it is said that no satisfactory industrial process has been found.
- the product of the addition i.e., the maleic anhydride- nitrile-group-containing polymer is said to be unsatisfactory in various properties, including "abrasion resistance and tensile strength which are required for belts and hoses.”
- Preparing a carboxylated, hydrogenated nitrile rubber by first preparing a nitrile rubber, then hydrogenating and thereafter adding an unsaturated acid results in an expensive production process. Furthermore, it is difficult to control the amount of acid that adds to the polymer so the quality of the product is uncertain. A product made in this way was introduced commercially but has since been withdrawn from the market .
- a process has now been discovered that permits the selective hydrogenation of a polymer whose backbone is composed of a conjugated diene, an unsaturated nitrile and an unsaturated carboxylic acid, and does not result in any detectable hydrogenation of nitrile or carboxyl moieties.
- This permits the preparation of a novel polymeric material that is a hydrogenated polymer of a conjugated diene, an unsaturated nitrile and an unsaturated acid. It has also been found that this novel polymeric material has unexpected and valuable properties .
- the present invention provides a polymer of a conjugated diene, an unsaturated nitrile and an unsaturated carboxylic acid that has been selectively hydrogenated to reduce carbon-carbon double bonds without hydrogenating nitrile groups and carboxyl groups .
- the present invention provides a process for selectively hydrogenating a polymer of a conjugated diene, an unsaturated nitrile and an unsaturated carboxylic acid which comprises subjecting the polymer to hydrogenation in the presence of a rhodium-containing compound as catalyst and a co-catalyst ligand. wherein the weight ratio of the rhodium- containing compound to the co-catalyst ligand is from 1:3 to 1:55.
- conjugated dienes are used in nitrile rubbers and these may all be used in the present invention. Mention is made of 1, 3 -but diene, isoprene, 2 , 3-dimethyl-l, 3 -butadiene, 1, 3-pentadiene and piperylene, of which 1 , 3 -butadiene is preferred.
- the nitrile is normally acrylonitrile or ethacrylonitrile or ⁇ -chloroacrylonitrile, of which acrylonitrile is preferred.
- the , ⁇ -unsaturated acid can be, for example, acrylic, methacrylic, ethacrylic, crotonic, maleic (possibly in the form of its anhydride) , fumaric or itaconic acid, of which acrylic and methacrylic are preferred.
- the conjugated diene usually constitutes about 50 to about 85% of the polymer, the nitrile usually constitutes about 15 to 50% of the polymer and the acid about 0.1 to about 10%, preferably 0.5 to 7%, these percentages being by weight.
- the polymer may also contain an amount, usually not exceeding about 10%, of another copolymerisable monomer, for example, an ester of an unsaturated acid, say ethyl, propyl or butyl acrylate or methacrylate, or a vinyl compound, for example, styrene, - methylstyrene or a corresponding compound bearing an alkyl substitutent on the phenyl ring, for instance, a p-alkylstyrene such as p-methylstyrene .
- the polymer preferably is a solid that has a molecular weight in excess of about 60,000, most preferably in excess of about 100,000.
- the polymer that is to be hydrogenated can be made in known manner, by emulsion or solution polymerisation, resulting in a statistical polymer.
- the polymer will have a backbone composed entirely of carbon atoms. It will have some vinyl side-chains, caused by 1,2-addition of the conjugated diene during the polymerisation. It will also have double bonds in the backbone from 1,4-addition of the diene. Some of these double bonds will be in the cis and some in the trans orientation. These carbon-carbon double bonds are selectively hydrogenated by the process of the invention, without concomitant hydrogenation of the nitrile and carboxyl groups present in the polymer.
- the selective hydrogenation can be achieved by means of a rhodium-containing catalyst.
- the preferred catalyst is of the formula:
- each R is a group, a C 4 -C 8 -cycloalkyl group a Cg-C*]_5-aryl group or a C7 ⁇ C*_5-aralkyl group
- X is hydrogen or an anion, preferably a halide and more preferably a chloride or bromide ion
- 1 is 2, 3 or 4
- m is 2 or 3
- n is 1, 2 or 3 , preferably 1 or 3.
- Preferred catalysts are tris- (triphenylphosphine) -rhodium (I) -chloride, tris (triphenylphosphine) -rhodium(III) -chloride and tris- (dimethylsulphoxide) -rhodium(III) -chloride, and tetrakis-
- the catalyst can be used in small quantities. An amount in the range of 0.01 to 1.0% preferably 0.03% to 0.5%, most preferably
- the catalyst is used with a co-catalyst that is a ligand of formula R m B, where R, m and B are as defined above, and m is preferably 3.
- R m B is phosphorus
- the R groups can be the same or different.
- co-catalyst ligands examples are given in US Patent No 4,631,315, the disclosure of which is incorporated by reference.
- the preferred co-catalyst ligand is triphenylphosphine.
- the co-catalyst ligand is preferably used in an amount in the range 0.3 to 5%, more preferably 0.5 to 4% by weight, based on the weight of the terpolymer.
- the weight ratio of the rhodium-containing catalyst compound to co-catalyst is in the range 1:3 to 1:55, more preferably in the range 1:5 to 1:45.
- the weight of the co- catalyst, based on the weight of one hundred parts of rubber, is suitably in the range 0.1 to 33, more suitably 0.5 to 20 and preferably 1 to 5, most preferably greater than 2 to less than 5.
- a co-catalyst ligand is beneficial for the selective hydrogenation reaction. There should be used no more than is necessary to obtain this benefit, however, as the ligand will be present in the hydrogenated product . For instance triphenylphosphine is difficult to separate from the hydrogenated product, and if it is present in any significant quantity may create some difficulties in processing of the product .
- the hydrogenation reaction can be carried out in solution.
- the solvent must be one that will dissolve carboxylated nitrile rubber. This limitation excludes use of unsubstituted aliphatic hydrocarbons.
- Suitable organic solvents are aromatic compounds including halogenated aryl compounds of 6 to 12 carbon atoms. The preferred halogen is chlorine and the preferred solvent is a chlorobenzene, especially monochlorobenzene .
- Other solvents that can be used include toluene, halogenated aliphatic compounds, especially chlorinated aliphatic compounds, ketones such as methyl ethyl ketone and methyl isobutyl ketone, tetrahydrofuran and dimethylformamide.
- the concentration of polymer in the solvent is not particularly critical but is suitably in the range from 1 to 30% by weight, preferably from 2.5 to 20% by weight, more preferably 10 to 15% by weight.
- the concentration of the solution may depend upon the molecular weight of the carboxylated nitrile rubber that is to be hydrogenated. Rubbers of higher molecular weight are more difficult to dissolve, and so are used at lower concentration.
- the reaction can be carried out in a wide range of pressures, from 10 to 250 atm and preferably from 50 to 100 atm.
- the temperature range can also be wide. Temperatures from 60 to 160°, preferably 100 to 160°C, are suitable and from 110 to 140°C are preferred. Under these conditions, the hydrogenation is usually completed in about 3 to 7 hours.
- reaction is carried out, with agitation, in an autoclave .
- Hydrogenation of carbon-carbon double bonds improves various properties of the polymer, particularly resistance to oxidation. It is preferred to hydrogenate at least 80% of the carbon-carbon double bonds present. For some purposes it is desired to eliminate all carbon-carbon double bonds, and hydrogenation is carried out until all, or at least 99%, of the double bonds are eliminated. For some other purposes, however, some residual carbon-carbon double bonds may be required and reaction may be carried out only until, say, 90% or 95% of the bonds are hydrogenated. The degree of hydrogenation can be determined by infrared spectroscopy or 1 H-NMR analysis of the polyrner .
- the degree of hydrogenation can be determined by measuring iodine value. This is not a particularly accurate method, and it cannot be used in the presence of triphenyl phosphine, so use of iodine value is not preferred.
- the hydrogenation of carbon-carbon double bonds is not accompanied by reduction of carboxyl groups.
- 95% of the carbon-carbon double bonds of a carboxylated nitrile rubber were reduced with no reduction of carboxyl and nitrile groups detectable by infrared analysis.
- reduction of carboxyl and nitrile groups may occur to an insignificant extent, and the invention is considered to extend to encompass any process or production in which insignificant reduction of carboxyl groups has occurred.
- insignificant is meant that less than 0.5%, preferably less than 0.1%, of the carboxyl or nitrile groups originally present have undergone reduction.
- the mixture can be worked up by any suitable method. One method is to distil off the solvent. Another method is to inject steam, followed by drying the polymer. Another method is to add alcohol, which causes the polymer to coagulate.
- the catalyst can be recovered by means of a resin column that absorbs rhodium, as described in US Patent No 4,985,540, the disclosure of which is incorporated herein by reference .
- the hydrogenated carboxylated nitrile rubber (HXNBR) of the invention can be crosslinked.
- HXNBR hydrogenated carboxylated nitrile rubber
- it can be vulcanized using sulphur or sulphur-containing vulcanizing agents, in known manner.
- Sulphur vulcanization requires that there be some unsaturated carbon-carbon double bonds in the polymer, to serve as reactions sites for addition of sulphur atoms to serve as crosslinks.
- the degree of hydrogenation is controlled to obtain a product having a desired number of residual double bonds.
- a degree of hydrogenation that results in about 3 or 4% residual double bonds (RDB) based on the number of double bonds initially present, is suitable.
- RDB residual double bonds
- the HXNBR can be crosslinked with peroxide crosslinking agents, again in known manner.
- Peroxide crosslinking does not require the presence of double bonds in the polymer, and results in carbon-containing crosslinks rather than sulphur-containing crosslinks.
- peroxide crosslinking agents there are mentioned dicumyl peroxide, di-t-butyl peroxide, benzoyl peroxide, 2, 5-dimethyl-2 , 5-di (t-butylperoxy) - hexyne-3 and 2, 5-dimethyl-2 , 5-di (benzoylperoxy) hexane and the like. They are suitably used in amounts of about 0.2 to 20 parts by weight, preferably 1 to 10 parts by weight, per 100 parts of rubber.
- the HXNBR can also be crosslinked via the carboxyl groups, by .
- a multivalent ion especially a metal ion, that is ionically bound to carboxyl groups on two different polymer chains. This may be done, for example, with zinc, magnesium, calcium or aluminum salts.
- the carboxyl groups can also be crosslinked by means of amines, especially diamines, that react with the carboxyl group. Mention is made of ⁇ , ⁇ - alkylenediamines, such as 1,2-ethylene diamine, 1 , 3-propylene diamine, and 1,4-butylene diamine, and also 1, 2-propylene diamine .
- the HXNBR of the inventioned can be compounded with any of the usual compounding agents, for example fillers such as carbon black or silica, heat stabilisers, antioxidants, activators such as zinc oxide or zinc peroxide, curing agents co-agents, processing oils and extenders.
- compounding agents for example fillers such as carbon black or silica, heat stabilisers, antioxidants, activators such as zinc oxide or zinc peroxide, curing agents co-agents, processing oils and extenders.
- fillers such as carbon black or silica
- heat stabilisers such as carbon black or silica
- antioxidants antioxidants
- activators such as zinc oxide or zinc peroxide
- curing agents co-agents processing oils and extenders.
- the hydrogenated carboxylated nitrile rubbers of the invention display excellent adhesive properties and, especially, excellent hot tear strength that is much better than that of non-carboxylated nitrile rubber.
- the rubbers of the invention also display better heat ageing resistance and better low temperature flexibility than non-hydrogenated carboxylated nitrile rubber. They also display excellent abrasion resistance, and good adhesion at both low and high temperature. These properties render them valuable for many specialised applications, but particular mention is made of use as seals in situations where severe stress is encountered, high stiffness automative belts, roll covers, and hoses.
- the HXNBR of the invention displays good adhesion to materials, including fabrics, woven and non-woven, metals and plastics, especially plastics with polar groups.
- the HXNBR will adhere to fabrics of natural fibers, for example wood, cotton, hemp, silk, to synthetic fibers, for example polyamides, polyesters, polyolefins such as polyethylene and polypropylene, poly (meth) acrylonitriles and ara id fibers. It will also adhere well to glass fibers and steel cords.
- the HXNBR displays particularly good adhesion when the substrate to which it is applied also bears polar groups.
- HXNBR hydrogenated nitrile rubber
- XNBR carboxylated nitrile rubber
- Hydrogenated nitrile rubber are used in many specialised applications where difficult conditions are encountered. Hydrogenated carboxylated nitrile rubbers of this invention have physical properties that are superior in some respects to those of commercially available hydrogenated nitrile rubbers and hence are useful in many applications where hydrogenated nitrile rubbers are of proven utility. Mention is made of seals, especially in automotive systems and heavy equipment and any other environment in which there may be encountered high or low temperatures, oil and grease. Examples include wheel bearing seals, shock absorber seals, camshaft seals, power steering assembly seals, 0-rings, water pump seals, gearbox shaft seals, and air conditioning system seals.
- HXNBR high modulus and high abrasion resistance of HXNBR renders it useful for high-hardness roll applications in, for instance, metal- working rolls, paper industry rolls, printing rolls, elastomer components for looms and textile rolls.
- the good abrasion resistance and good adhesion to metals of HXNBR renders it suitable for use in bearing pads attached to tracks of tracked vehicles such as bulldozers and other large items of earth moving equipment, military tanks, and the like.
- the material to which the polymer of the invention is to adhere may be subjected to treatment to enhance bonding before being contacted with the polymer.
- cotton rayon or nylon may be dipped in a mixture that is composed of an aqueous solution of an initial condensate of resorcinal and formaldehyde (referred to as RF) and a rubber latex, this mixture being referred to as RFL.
- RF initial condensate of resorcinal and formaldehyde
- RFL rubber latex
- the rubber latex is not particularly limited but may be an acrylonitrile/butadiene copolymer latex, and acrylonitrile/butadiene/methacrylic acid copolymer latex, an acrylonitrile/butadiene/acrylic acid copolymer latex or an acrylonitrile/butadiene/vinylpyridine copolymer latex.
- the HXNBR rubber of this invention can be used in a latex to serve as the rubber latex for this purpose.
- Polyester and aromatic polyamide fibers may be treated- with a dip containing an isocyanate, ethylenethiourea or epoxy, heat-treated, and then subjected to treatment with RFL .
- the HXNBR rubber can be used in the form of a latex. Formation of a latex can be carried out by milling the HXNBR rubber in the presence of water containing appropriate emulsifiers until the required latex is formed.
- Suitable emulsifiers for this purpose include amino emulsifiers such as fatty acid soaps, i.e., sodium and potassium salts of fatty acids, rosin acid salts, alkyl and aryl sulfonic acid salts and the like. Oleate salts are mentioned by way of example.
- the rubber latex may be in solution in an organic solvent, or in admixture with an organic solvent, when added to the water, to form an oil-in-water emulsion. The organic solvent is then removed from the emulsion to yield the required latex.
- Organic solvents that can be used include the solvents that can be used for the hydrogenation reaction.
- Figure 1 is a graph showing the infrared spectrum of the polymer prior to and subsequent to hydrogenation.
- Figure 2 is a graph showing the degree of hydrogenation achieved with different amounts of ligand co- catalyst
- Figure 3 is a graph showing the degree of hydrogenation of a polymer with time using various different amounts of catalyst loading
- Figure 4 is a bar chart showing die B tear strength of HNBR, XNBR and HXNBR compounds at different temperatures
- Figure 5 is a bar chart showing die C tear strength of HNBR, XNBR and HXNBR compounds at different temperatures
- Figure 6 is a bar chart showing the adhesion to nylon of HNBR, XNBR and HXNBR compounds at room temperature and at 125°C;
- Figure 7 is a bar chart showing results obtained with HNBR, XNBR and HXNBR in the Pico abrasion test; and Figure 8 is a graph of storage tensile modulus E' versus temperature for HNBR, XNBR and HXNBR.
- the temperature of the reactor was raised to 130°C and a solution of 0.139g (0.076 phr) of tris- (triphenylphosphine) -rhodium- (I) chloride catalyst and 2.32g of co-catalyst triphenylphosphine (TPP) in 60 ml of monochlorobenzene having an oxygen content less than 5 ppm was then charged to the reactor under hydrogen.
- the temperature was raised to 138°C and the pressure of the reactor was set at 1200 psi (83 atm) .
- the reaction temperature and hydrogen pressures of the reactor were maintained constant throughout the whole reaction.
- the degree of hydrogenation was monitored by sampling after a certain reaction time followed by Fourier Transfer Infra Red Spectroscopy (FTIR) analysis of the sample.
- FTIR Fourier Transfer Infra Red Spectroscopy
- the properties of the HXNBR of the invention were investigated in the following examples. All non-polymer raw materials used in the examples are commercially available. Preparative Examples 1 to 5 above were carried out in the laboratory. The process was then transferred to a pilot plant. The HXNBR that was subjected to testing for physical properties was made in the pilot plant but generally in accordance with the conditions used in the laboratory. In particular, the amount of catalyst used was 0.076 phr, the weight ratio of triphenylphosphine co-catalyst to rhodium-containing catalyst was 16.7:1, the XNBR subjected to hydrogenation was Krynac X 7.40 the solvent was monochlorobenzene and the solution was either 6% or 12% strength.
- the HXNBR had a Mooney of 114 (ML 1+4 100°C) .
- the commercially available XNBR was Krynac X 7.40.
- Also used for comparison purposes was a hydrogenated nitrile rubber (HNBR) commercially available from Bayer under the trade-mark Therban C 3446, composed of 34% acrylontrile, 66% butadiene, hydrogenated to about 3.5 - 4.5% RDB.
- Therban C 3446 has a
- the HXNBR, HNBR and XNBR compounds were mixed in a 1.6 liter model BR 82, Farrel Banbury mixer at 53 rpm. For better mixing, an 80% fill factor was used when sizing the batch.
- the polymer was added first with carbon black filler and mixed for about 1 minute followed by the addition of all other dry fillers, stearic acid, non zinc containing antioxidants and plasticizer.
- the batch was dumped at a mixing time of 6 minutes and the dump temperatures were recorded. In general the dump temperature for HXNBR based compounds ranged between 140 - 155°C. For the other two polymer-based compounds, the dump temperature was below 140°C. Standard laboratory mill mixing procedures were used to incorporate the curatives and zinc containing ingredients in a separate mixing step.
- both XNBR and HXNBR showed a higher modulus and higher tensile strength than those of HNBR.
- HXNBR based compound had a much better elongation at break than the XNBR based compound.
- HXNBR based compound also showed the best tensile strength and ultimate elongation at high testing temperature.
- HXNBR shows excellent tear strength at all temperatures in both die B and die C tear tests. For example, when tested at 100 to 170°C, the die B tear strength of HXNBR remains in the range of 30 to 40 kN/m, while the die B tear for
- XNBR and HNBR are only in the range of 10-20 kN/m ( Figure 4, and Table 7) .
- HXNBR shows the same tear strength as that of HNBR at room temperature, its tear strength is two or three times that of HNBR at higher testing temperatures .
- the die C tear strength of the HXNBR based compound is also much higher than that of the XNBR based compound in the temperature range 23 to 170°C.
- HXNBR Hexadiene styrene-maleic anhydride
- HXNBR superior abrasion resistance of HXNBR is not observed in the DIN abrasion test as shown in Table 9. This is probably due to its rather different abrasion mechanism from the Pico abrasion test. In this test, both HNBR and HXNBR show better resistance to abrasion than the XNBR based compound.
- HXNBR based compounds The low temperature flexibility of HXNBR based compounds is compared with those of HNBR and XNBR based compound in both Gehman and TR tests. The results of these tests are summarized in Tables 10 and 11 Due to the presence of 7% carboxylic acid groups, the low temperature flexibility of HXNBR polymer is not as good as that of HNBR, as shown in both TR and Gehman testing. The lower temperature properties of the HXNBR compounds are better to these of the XNBR compounds .
- the low temperature flexibility of these three compounds was determined by using a Rheometrics Solid analyzer (RSA-II) .
- RSA-II Rheometrics Solid analyzer
- a small sinusoidal tensile deformation is imposed on the specimen at a given frequency.
- the resulting force, as well as the phase difference between the imposed deformation and the response, are measured at various temperatures.
- the storage tensile modulus (E 1 ), loss tensile modulus (E") and tan ⁇ can be calculated.
- E 1 storage tensile modulus
- E loss tensile modulus
- tan ⁇ the storage tensile modulus
- Figure 8 presents the E'- temperature plots for these three compounds.
- the HXNBR showed a higher glass transition temperature than that of HNBR. It has surprisingly been found that the glass transition temperature of HXNBR is lower than that of the XNBR.
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Priority Applications (13)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/258,245 US7265185B2 (en) | 2000-04-10 | 2001-04-09 | Process for hydrogenating carboxylated nitrile rubber, the hydrogenated rubber and its uses |
CA2404295A CA2404295C (en) | 2000-04-10 | 2001-04-09 | Process for hydrogenating carboxylated nitrile rubber, the hydrogenated rubber and its uses |
SK1448-2002A SK14482002A3 (en) | 2000-04-10 | 2001-04-09 | Process for hydrogenating carboxylated nitrile rubber, the hydrogenated rubber and its uses |
HU0300336A HUP0300336A3 (en) | 2000-04-10 | 2001-04-09 | Process for hydrogenating carboxylated nitrile rubber, the hydrogenated rubber and its uses |
MXPA02009754A MXPA02009754A (en) | 2000-04-10 | 2001-04-09 | Process for hydrogenating carboxylated nitrile rubber, the hydrogenated rubber and its uses. |
AT01925236T ATE454406T1 (en) | 2000-04-10 | 2001-04-09 | METHOD FOR HYDRATING CARBOXYLATED NITRILE RUBBER AND USE THEREOF |
EP01925236A EP1276773B1 (en) | 2000-04-10 | 2001-04-09 | Process for hydrogenating carboxylated nitrile rubber, the hydrogenated rubber and its uses |
AU2001252059A AU2001252059A1 (en) | 2000-04-10 | 2001-04-09 | Process for hydrogenating carboxylated nitrile rubber, the hydrogenated rubber and its uses |
PL01358059A PL358059A1 (en) | 2000-04-10 | 2001-04-09 | Process for hydrogenating carboxylated nitrile rubber, the hydrogenated rubber and its uses |
DE60141007T DE60141007D1 (en) | 2000-04-10 | 2001-04-09 | METHOD FOR HYDROGENATION OF CARBOXYLATED NITRIL RUBBER AND ITS USE |
BRPI0109933-7A BR0109933B1 (en) | 2000-04-10 | 2001-04-09 | "Process for hydrogenating a conjugated diene polymer, unsaturated nitrile and unsaturated carboxylic acid". |
JP2001575655A JP4694082B2 (en) | 2000-04-10 | 2001-04-09 | Hydrogenation method of carboxylated nitrile rubber |
HK03106862.9A HK1054558A1 (en) | 2000-04-10 | 2003-09-24 | Process for hydrogenating carboxylated nitrile rubber, the hydrogenated rubber and its uses |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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CA2,304,501 | 2000-04-10 | ||
CA002304501A CA2304501A1 (en) | 2000-04-10 | 2000-04-10 | Process for hydrogenating carboxylated nitrile rubber, the hydrogenated rubber and its uses |
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WO2001077185A1 true WO2001077185A1 (en) | 2001-10-18 |
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US (1) | US7265185B2 (en) |
EP (1) | EP1276773B1 (en) |
JP (1) | JP4694082B2 (en) |
KR (1) | KR20030007512A (en) |
CN (1) | CN100523013C (en) |
AT (1) | ATE454406T1 (en) |
AU (1) | AU2001252059A1 (en) |
BR (1) | BR0109933B1 (en) |
CA (1) | CA2304501A1 (en) |
DE (1) | DE60141007D1 (en) |
HK (1) | HK1054558A1 (en) |
HU (1) | HUP0300336A3 (en) |
MX (1) | MXPA02009754A (en) |
PL (1) | PL358059A1 (en) |
RU (1) | RU2002129931A (en) |
SK (1) | SK14482002A3 (en) |
WO (1) | WO2001077185A1 (en) |
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US6794452B2 (en) | 2001-07-31 | 2004-09-21 | Bayer Inc. | Covulcanization of polymers |
WO2004101671A1 (en) | 2003-05-15 | 2004-11-25 | Lanxess Deutschland Gmbh | Hxnbr rubber as a cross-linking agent |
US6905319B2 (en) | 2002-01-29 | 2005-06-14 | Halliburton Energy Services, Inc. | Stator for down hole drilling motor |
EP1544242A1 (en) * | 2003-08-14 | 2005-06-22 | Bayer Inc. | Butyl compositions comprising nitrile polymers |
EP1659150A1 (en) | 2004-11-18 | 2006-05-24 | Lanxess Inc. | Peroxide curable rubber composition comprising HNBR |
JP2006316278A (en) * | 2006-06-12 | 2006-11-24 | Mitsubishi Cable Ind Ltd | Rubber composition for sealant and sealant using the same |
JP2006527777A (en) * | 2003-06-18 | 2006-12-07 | ランクセス・ドイチュランド・ゲーエムベーハー | adhesive |
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US6794452B2 (en) | 2001-07-31 | 2004-09-21 | Bayer Inc. | Covulcanization of polymers |
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JP2006527777A (en) * | 2003-06-18 | 2006-12-07 | ランクセス・ドイチュランド・ゲーエムベーハー | adhesive |
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KR101361943B1 (en) | 2005-09-30 | 2014-02-12 | 란세스 도이치란트 게엠베하 | Crosslinkable compositions, processes for the preparation thereof and the use thereof |
JP2006316278A (en) * | 2006-06-12 | 2006-11-24 | Mitsubishi Cable Ind Ltd | Rubber composition for sealant and sealant using the same |
JP4669443B2 (en) * | 2006-06-12 | 2011-04-13 | 三菱電線工業株式会社 | Rubber composition for sealing material and sealing material using the same |
US8709603B2 (en) | 2007-07-30 | 2014-04-29 | Michel Oulie | Article based on a composition containing a crosslinked blend of elastomers |
EP2138535A1 (en) | 2008-06-23 | 2009-12-30 | Lanxess Deutschland GmbH | Carbon nanotube containing rubber compositions |
US9484123B2 (en) | 2011-09-16 | 2016-11-01 | Prc-Desoto International, Inc. | Conductive sealant compositions |
EP2868676A1 (en) | 2013-10-30 | 2015-05-06 | LANXESS Deutschland GmbH | Functionalised copolymer rubber containing nitrile groups |
EP3196239A1 (en) | 2016-01-25 | 2017-07-26 | ARLANXEO Deutschland GmbH | Vulcanisable compounds on the basis of hydrogenated nitrile rubber, method for their preparation and their use |
WO2017129494A1 (en) | 2016-01-25 | 2017-08-03 | Arlanxeo Deutschland Gmbh | Vulcanizable compositions based on hydrogenated nitrile rubber, method for producing same, and use thereof |
EP3255088A1 (en) | 2016-06-07 | 2017-12-13 | ARLANXEO Deutschland GmbH | Use of vulcanizable compositions and vulcanizates in contact with silane-coated wollastonite containing coolant |
WO2017211645A1 (en) | 2016-06-07 | 2017-12-14 | Arlanxeo Deutschland Gmbh | Use of vulcanizable compositions and vulcanizates in contact with coolant, comprising silane-coated wollastonite |
WO2019034572A1 (en) | 2017-08-16 | 2019-02-21 | Arlanxeo Deutschland Gmbh | Vulcanizable compositions containing hydrogenated nitrile rubber, vulcanizates produced therefrom and use thereof |
WO2019057703A1 (en) | 2017-09-20 | 2019-03-28 | Arlanxeo Deutschland Gmbh | Vulcanizable hnbr composition having high thermal conductivity |
Also Published As
Publication number | Publication date |
---|---|
DE60141007D1 (en) | 2010-02-25 |
ATE454406T1 (en) | 2010-01-15 |
KR20030007512A (en) | 2003-01-23 |
US20030171500A1 (en) | 2003-09-11 |
HUP0300336A2 (en) | 2003-06-28 |
HK1054558A1 (en) | 2003-12-05 |
EP1276773B1 (en) | 2010-01-06 |
RU2002129931A (en) | 2004-03-27 |
BR0109933A (en) | 2003-05-27 |
US7265185B2 (en) | 2007-09-04 |
CN100523013C (en) | 2009-08-05 |
CN1422284A (en) | 2003-06-04 |
MXPA02009754A (en) | 2003-03-27 |
SK14482002A3 (en) | 2003-04-01 |
AU2001252059A1 (en) | 2001-10-23 |
HUP0300336A3 (en) | 2005-06-28 |
BR0109933B1 (en) | 2011-05-03 |
PL358059A1 (en) | 2004-08-09 |
JP2003530467A (en) | 2003-10-14 |
CA2304501A1 (en) | 2001-10-10 |
JP4694082B2 (en) | 2011-06-01 |
EP1276773A1 (en) | 2003-01-22 |
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