US20040236029A1 - Low molecular weight hydrogenated nitrile rubber - Google Patents
Low molecular weight hydrogenated nitrile rubber Download PDFInfo
- Publication number
- US20040236029A1 US20040236029A1 US10/878,080 US87808004A US2004236029A1 US 20040236029 A1 US20040236029 A1 US 20040236029A1 US 87808004 A US87808004 A US 87808004A US 2004236029 A1 US2004236029 A1 US 2004236029A1
- Authority
- US
- United States
- Prior art keywords
- molecular weight
- nitrile rubber
- range
- hydrogenated nitrile
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 0 *C([1*])=C(*)(C)(C)C Chemical compound *C([1*])=C(*)(C)(C)C 0.000 description 4
Images
Classifications
-
- 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
- C08C19/22—Incorporating nitrogen atoms into the molecule
-
- 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
-
- 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
- C08C19/08—Depolymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
-
- 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 hydrogenated nitrile rubber polymers having lower molecular weights and narrower molecular weight distributions than those known in the art.
- 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.
- HNBR Hydrophilicity-based mechanical property of the rubber
- oil stators, well head seals, valve plates
- electrical cable sheathing
- mechanical engineering wheels, rollers
- shipbuilding pipe seals, couplings
- 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 (MIR) 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%.
- Acyclic diene metathesis (or ADMET) is catalyzed by a great variety of transition metal complexes as well as non-metallic systems.
- Heterogeneous catalyst systems based on metal oxides; sulfides or metal salts were originally used for the metathesis of olefins.
- the limited stability (especially towards hetero-substituents) and the lack of selectivity resulting from the numerous active sites and side reactions are major drawbacks of the heterogeneous systems.
- Rhodium based complexes are effective catalysts for the metathesis of electron-rich olefins.
- this ruthenium carbene catalyst is stable to acids, alcohols, aldehydes and quaternary amine salts and can be used in a variety of solvents (C 6 H 6 , CH 2 Cl 2 , THF, t-BuOH).
- transition-metal catalyzed alkene metathesis has since enjoyed increasing attention as a synthetic method.
- the most commonly used catalysts are based on Mo, W and Ru.
- Research efforts have been mainly focused on the synthesis of small molecules, but the application of olefin metathesis to polymer synthesis has allowed the preparation of new polymeric material with unprecedented properties (such as highly stereoregular poly-norbornadiene).
- the present invention is directed to a hydrogenated nitrile rubber having a molecular weight (MW) in the range of from 30,000 to 250,000 g/mol, a Mooney viscosity (ML 1+4 @100 deg. C) in the range of from 3 to 50, and a MWD (or polydispersity index) of less than 2.5.
- MW molecular weight
- ML 1+4 @100 deg. C Mooney viscosity
- MWD or polydispersity index
- nitrile polymer 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, preferably 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 4 -C 6 conjugated dienes are butadiene, isoprene and mixtures thereof. The most preferred C 4 -C 6 conjugated diene is butadiene.
- the ⁇ , ⁇ -unsaturated nitrile may be any known ⁇ , ⁇ -unsaturated nitrile, preferably 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 -C 5 ⁇ , ⁇ -unsaturated nitrile is acrylonitrile.
- the copolymer contains 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 contains 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.
- the copolymer contains 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 nitrites.
- the copolymer may further contain repeating units derived from one or more copolymerizable monomers, such as unsaturated carboxylic acids.
- suitable unsaturated carboxylic acids include 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 weight percents will have to be adjusted to result in 100 weight percent.
- the nitrile rubber preferably contain 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 monomers include unsaturated mono- or di-carboxylic acids or derivatives thereof (e.g., esters, amides and the like) including mixtures thereof.
- the HNBR of the invention is readily available in a two step synthesis, which may take place in the same reaction set-up or different reactors.
- the metathesis reaction is conducted in the presence of one or more compounds of the general formulas I, II, III or IV;
- M is Os or Ru
- R and R 1 are, independently, hydrogen or a hydrocarbon selected from the group consisting of C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 1 -C 20 alkyl, aryl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, aryloxy, C 2 -C 20 alkoxycarbonyl, C 1 -C 20 alkylthio, C 1 -C 20 alkylsulfonyl and C 1 -C 20 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 imidazolidines or any neutral carbine, optionally, L and L 1 can be linked to one another to from a bidentate neutral ligand;
- M 1 is Os or Ru
- R 2 and R 3 are, independently, hydrogen or a hydrocarbon selected from the group consisting of C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 1 -C 20 alkyl, aryl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, aryloxy, C 2 -C 20 alkoxycarbonyl, C 1 -C 20 alkylthio, C 1 -C 20 alkylsulfonyl and C 1 -C 20 alkylsulfinyl,
- 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-, ammonumalkyl-, 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 C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 1 -C 20 alkyl, aryl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, aryloxy, C 2 -C 20 alkoxycarbonyl, C 1 -C 20 alkylthio, C 1 -C 20 alkylsulfonyl and C 1 -C 20 alkylsulfinyl,
- 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
- L and L 1 are independently any neutral ligand, such as phosphines, amines, thioethers or imidazolidines or any neutral carbine, optionally, L and L 1 can be linked to one another to from a bidentate neutral ligand;
- Compounds of Formula I are preferred.
- Compounds of Formula I wherein L and L 1 are trialkylphosphines, X and X 1 are chloride ions and M is Ruthenium are more preferred.
- the amount of compound 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 16 linear or branched olefin such as ethylene, isobutene, styrene or 1-hexene.
- a co-olefin which is preferably a C 2 to C 16 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 ⁇ 105 Pa to 1 ⁇ 107 Pa, preferably in the range of from 5.2 ⁇ 05 Pa to 4 ⁇ 106 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.
- the concentration of nitrile polymer (NBR) in the reaction mixture is not critical but, should be such that the reaction is not hampered if the mixture is too viscous to be stirred efficiently, for example.
- concentration of NBR is in the range of from 1 to 20% by weight, more preferably in the range of from 6 to 15% by weight.
- the metathesis reaction can carried out at a temperature in the range of from 20 to 140° C.; preferably in the range of from 60 to 120° 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.
- the nitrile polymer must be hydrogenated to result in a partially or fully hydrogenated nitrile polymer (HNBR).
- 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 RhCl ⁇ 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 metathesized 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 RuCl 2 H 2 , which is itself an olefin hydrogenation catalyst.
- a dihydride complex PR 3
- RuCl 2 H 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.
- Hydrogenation in this invention is preferably understood by more than 50% of the residual double bonds (RDB) present in the starting nitrile polymer 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 low Mooney HNBR which forms an object of the invention, can be characterized by standard techniques known in the art.
- 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.
- the Mooney viscosity of the rubber was determined using ASTM test D1646.
- the hydrogenated nitrile rubber of the present invention is 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 or footwear component.
- the reactor was heated to desired temperature and 60 mL of a monochlorobenzene solution containing Grubb's catalyst was added to the reactor.
- the reactor was pressurized to the desired ethylene pressure for Examples 1-3 or to 100 psi of Nitrogen for Example 4.
- the temperature was maintained constant for the duration of the reaction.
- a cooling coil connected to a temperature controller and a thermal sensor was used to regulate the temperature.
- the progress of the reaction was monitored using solution viscosity measurements for the 6% cements. At higher cement concentration, the reaction was assumed to be complete after 18 hours.
- the cement from the metathesis reaction was degassed 3 times with H2 (100 psi) under full agitation.
- the temperature of the reactor was raised to 130° C. and a 60 mL 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.
- the Ruthenium metathesis catalyst could be used to hydrogenate the polymer.
- the Mn is 27 kg/mol (compared to 85 kg/mol for the starting polymer) while he Mw is 54 kg/mol (compared to 296 kg/mol for the starting polymer).
- the molecular weight distribution falls from 3.4 for the starting substrate feedstock to 2.0 for the metathesized product. This is consistent with a more homogeneous range of polymer chain lengths and molecular weights.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Sealing Material Composition (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The present invention relates to hydrogenated nitrile rubber polymers having lower molecular weights and narrower molecular weight distributions than those known in the art. The present invention is also related to shaped articles containing hydrogenated nitrile rubber polymers having lower molecular weights and narrower molecular weight distributions than those known in the art.
Description
- The present invention relates to hydrogenated nitrile rubber polymers having lower molecular weights and narrower molecular weight distributions than those known in the art.
- Hydrogenated nitrile rubber (HNBR), 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. Coupled with the high level of mechanical properties of the rubber (in particular the high resistance to abrasion) it is not surprising that HNBR has 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.
- Commercially available 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).
- One limitation in processing HNBR is the relatively high Mooney Viscosity. In principle, 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. In addition, these types of approaches, by their very nature, produce polymers having a broad molecular weight distribution.
- A hydrogenated nitrile rubber having a low Mooney (<55) and improved processability, but which has the same microstructure as those rubbers which are currently available, is difficult to manufacture using current technologies. The hydrogenation of NBR to produce HNBR results in an increase in the Mooney viscosity of the raw polymer. This Mooney Increase Ratio (MIR) is generally around 2, depending upon the polymer grade, hydrogenation level and nature of the feedstock. Furthermore, limitations associated with the production of NBR itself dictate the low viscosity range for the HNBR feedstock. Currently, one of the lowest Mooney viscosity products available is Therban® VP KA 8837 (available from Bayer), which has a Mooney viscosity of 55 (ML 1+4 @ 100° C.) and a RDB of 18%.
- Karl Ziegler's discovery of the high effectiveness of certain metal salts, in combination with main group alkylating agents, to promote olefin polymerization under mild conditions has had a significant impact on chemical research and production to date. It was discovered early on that some “Ziegler-type” catalysts not only promote the proposed coordination-insertion mechanism but also effect an entirely different chemical process, that is the mutual exchange (or metathesis) reaction of alkenes according to a scheme as shown in FIG. 1.
- Acyclic diene metathesis (or ADMET) is catalyzed by a great variety of transition metal complexes as well as non-metallic systems. Heterogeneous catalyst systems based on metal oxides; sulfides or metal salts were originally used for the metathesis of olefins. However, the limited stability (especially towards hetero-substituents) and the lack of selectivity resulting from the numerous active sites and side reactions are major drawbacks of the heterogeneous systems.
- Homogeneous systems have also been devised and used to effect olefin metathesis. These systems offer significant activity and control advantages over the heterogeneous catalyst systems. For example, certain Rhodium based complexes are effective catalysts for the metathesis of electron-rich olefins.
- The discovery that certain metal-alkylidene complexes are capable of catalyzing the metathesis of olefins triggered the development of a new generation of well-defined, highly active, single-site catalysts. Amongst these, Bis-(tricyclohexylphosphine)-benzylidene ruthenium dichloride (commonly know as Grubb's catalyst) has been widely used, due to its remarkable insensitivity to air and moisture and high tolerance towards various functional groups. Unlike the molybdenum-based metathesis catalysts, this ruthenium carbene catalyst is stable to acids, alcohols, aldehydes and quaternary amine salts and can be used in a variety of solvents (C6H6, CH2Cl2, THF, t-BuOH).
- The use of transition-metal catalyzed alkene metathesis has since enjoyed increasing attention as a synthetic method. The most commonly used catalysts are based on Mo, W and Ru. Research efforts have been mainly focused on the synthesis of small molecules, but the application of olefin metathesis to polymer synthesis has allowed the preparation of new polymeric material with unprecedented properties (such as highly stereoregular poly-norbornadiene).
- The utilization of olefin metathesis as a means to produce low molecular weight compounds from unsaturated elastomers has received growing interest. The principle for the molecular weight reduction of unsaturated polymers is shown in FIG. 2. The use of an appropriate catalyst allows the cross-metathesis of the unsaturation of the polymer with the co-olefin. The end result is the cleavage of the polymer chain at the unsaturation sites and the generation of polymer fragments having lower molecular weights. In addition, another effect of this process is the “homogenizing” of the polymer chain lengths, resulting in a reduction of the polydispersity. From an application and processing stand point, a narrow molecular weight distribution of the raw polymer results in improved physical properties of the vulcanized rubber, whilst the lower molecular weight provides good processing behavior.
- The so-called “depolymerization” of copolymers of 1,3-butadiene with a variety of co-monomers (styrene, propene, divinylbenzene and ethylvinylbenzene, acrylonitrile, vinyltrimethylsilane and divinyidimethylsilane) in the presence of classical Mo and W catalyst system has been investigated. Similarly, the degradation of a nitrile rubber using WCl6 and SnMe4 or PhC≡CH co-catalyst was reported in 1988. However, the focus of such research was to produce only low molecular fragments, which could be characterized by conventional chemical means and contains no teaching with respect to the preparation of low molecular weight nitrile rubber polymers. Furthermore, such processes are non-controlled and produce a wide range of products.
- The catalytic depolymerization of 1,4-polybutadiene in the presence of substituted olefins or ethylene (as chain transfer agents) in the presence of well-defined Grubb's or Schrock's catalysts is also possible. The use of Molybdenum or Tungsten compounds of the general structural formula {M(═NR1)(OR2)2(═CHR); M=Mo, W} to produce low molecular weight polymers or oligomers from gelled polymers containing internal unsaturation along the polymer backbone was claimed in U.S. Pat. No. 5,446,102. Again, however, the process disclosed is non-controlled, and there is no teaching with respect to the preparation of low molecular weight nitrile rubber polymers.
- We have now discovered that hydrogenated nitrile rubber having lower molecular weights and narrower molecular weight distributions than those known in the art can be prepared by the olefin metathesis of nitrile butadiene rubber, followed by hydrogenation of the resulting metathesized NBR.
- Thus, the present invention is directed to a hydrogenated nitrile rubber having a molecular weight (MW) in the range of from 30,000 to 250,000 g/mol, a Mooney viscosity (ML 1+4 @100 deg. C) in the range of from 3 to 50, and a MWD (or polydispersity index) of less than 2.5.
- The present invention is also directed to the use of low molecular weight hydrogenated nitrile rubber 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 or footwear component.
- As used throughout this specification, the term “nitrile polymer” 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 α,β-unsaturated nitrile and optionally further one or more copolymerizable monomers.
- The conjugated diene may be any known conjugated diene, preferably a C4-C6 conjugated diene. Preferred conjugated dienes are butadiene, isoprene, piperylene, 2,3-dimethyl butadiene and mixtures thereof. Even more preferred C4-C6 conjugated dienes are butadiene, isoprene and mixtures thereof. The most preferred C4-C6 conjugated diene is butadiene.
- The α,β-unsaturated nitrile may be any known α,β-unsaturated nitrile, preferably a C3-C5 α,β-unsaturated nitrile. Preferred C3-C5 α,β-unsaturated nitriles are acrylonitrile, methacrylonitrile, ethacrylonitrile and mixtures thereof. The most preferred C3-C5 α,β-unsaturated nitrile is acrylonitrile.
- Preferably, the copolymer contains 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 contains 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 contains 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 nitrites.
- Optionally, the copolymer may further contain repeating units derived from one or more copolymerizable monomers, such as unsaturated carboxylic acids. Non-limiting examples of suitable unsaturated carboxylic acids include 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 weight percents will have to be adjusted to result in 100 weight percent. In case of the mentioned unsaturated carboxylic acids, the nitrile rubber preferably contain 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 monomers include unsaturated mono- or di-carboxylic acids or derivatives thereof (e.g., esters, amides and the like) including mixtures thereof.
- The HNBR of the invention is readily available in a two step synthesis, which may take place in the same reaction set-up or different reactors.
-
- wherein:
- M is Os or Ru,
- R and R1 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-C20 alkoxycarbonyl, C1-C20 alkylthio, C1-C20 alkylsulfonyl and C1-C20 alkylsulfinyl,
- X and X1 are independently any anionic ligand, and
-
- wherein
- M1 is Os or Ru;
- R2 and R3 are, independently, hydrogen or a hydrocarbon selected from the group consisting of C2-C20 alkenyl, C2-C20 alkynyl, C1-C20alkyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, aryloxy, C2-C20 alkoxycarbonyl, C1-C20 alkylthio, C1-C20 alkylsulfonyl and C1-C20 alkylsulfinyl,
- X2 is a anionic ligand, and
- L2 is a neutral π-bonded ligand, independent of whether they are mono- or polycyclic,
- L3 is a ligand selected from the group consisting of phosphines, sulfonated phosphines, fluorinated phosphines, functionalized phosphines bearing up to three aminoalkyl-, ammonumalkyl-, 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,
-
- wherein
- M2 is Mo or W,
- R4 and R5 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-C20 alkoxycarbonyl, C1-C20 alkylthio, C1-C20 alkylsulfonyl and C1-C20 alkylsulfinyl,
-
- wherein
- M is Os or Ru,
- R and R1 are independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, and substituted or unsubstituted alkyl,
- X and X1 are independently any anionic ligand, and
- L and L1 are independently any neutral ligand, such as phosphines, amines, thioethers or imidazolidines or any neutral carbine, optionally, L and L1 can be linked to one another to from a bidentate neutral ligand;
- Compounds of Formula I are preferred. Compounds of Formula I wherein L and L1 are trialkylphosphines, X and X1 are chloride ions and M is Ruthenium are more preferred.
- The amount of compound will depend upon the nature and catalytic activity of the compound(s) in question. Typically, 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 C2 to C16 linear or branched olefin such as ethylene, isobutene, styrene or 1-hexene. Where 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 %. Where 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 1×105 Pa to 1×107 Pa, preferably in the range of from 5.2×05 Pa to 4×106 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). In certain cases the co-olefin can itself act as a solvent (for example, 1-hexene), in which case no other solvent is necessary.
- The concentration of nitrile polymer (NBR) in the reaction mixture is not critical but, should be such that the reaction is not hampered if the mixture is too viscous to be stirred efficiently, for example. Preferably, the concentration of NBR is in the range of from 1 to 20% by weight, more preferably in the range of from 6 to 15% by weight.
- The metathesis reaction can carried out at a temperature in the range of from 20 to 140° C.; preferably in the range of from 60 to 120° 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. Whenever referenced throughout the specification 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.
- After the metathesis reaction, the nitrile polymer must be hydrogenated to result in a partially or fully hydrogenated nitrile polymer (HNBR). Reduction of the product from the metathesis reaction can be effected using standard reduction techniques known in the art. For example, homogeneous hydrogenation catalysts known to those of skill in the art, such as Wilkinson's catalyst {(PPh3)3RhCl} 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 metathesized 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 (PR3)2RuCl2H2, which is itself an olefin hydrogenation catalyst. Thus, in a favorable one-pot reaction, Grubb's catalyst was used to reduce the molecular weight of NBR in the presence of co-olefin. 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.
- Hydrogenation in this invention is preferably understood by more than 50% of the residual double bonds (RDB) present in the starting nitrile polymer 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.
- The low Mooney HNBR, which forms an object 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 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.
- The Mooney viscosity of the rubber was determined using ASTM test D1646.
- The hydrogenated nitrile rubber of the present invention is 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 or footwear component.
- Bis(tricyclohexylphosphine)benzylidene ruthenium dichloride (Grubb's metathesis catalyst), 1-hexene and monochlorobenzene (MCB) were purchased from Alfa, Aldrich Chemicals, and PPG respectively and used as received. Perbunan was obtained from Bayer Inc.
- The metathesis reactions were carried out in a Parr high-pressure reactor under the following conditions:
Cement Concentration 6 or 15% by weight Co-Olefin Ethylene or 1-Hexene Co-Olefin Concentration see Table 1 Agitator Speed 600 rpm Reactor Temperature see Table 1 Catalyst Loading see Table 1 Solvent Monochlorobenzene Substrate statistical Butadiene- acrylonitrilecopolymer with a acrylonitrile content of 34 mol % and a Mooney- Viscosity ML (1 + 4) @ 100 deg. C. of 35 - The reactor was heated to desired temperature and 60 mL of a monochlorobenzene solution containing Grubb's catalyst was added to the reactor. The reactor was pressurized to the desired ethylene pressure for Examples 1-3 or to 100 psi of Nitrogen for Example 4. The temperature was maintained constant for the duration of the reaction. A cooling coil connected to a temperature controller and a thermal sensor was used to regulate the temperature. The progress of the reaction was monitored using solution viscosity measurements for the 6% cements. At higher cement concentration, the reaction was assumed to be complete after 18 hours.
- The hydrogenation reactions were carried out in the same reactor as the metathesis under the following conditions:
Cement solid concentration 12% H2(g) pressure 1200 psi Agitator Speed 600 rpm Reactor Temperature 138° C. Catalyst Loading (Wilkinson's) 0.08 phr Triphenylphosphine 1 phr Solvent Monochlorobenzene - The cement from the metathesis reaction was degassed 3 times with H2 (100 psi) under full agitation. The temperature of the reactor was raised to 130° C. and a 60 mL 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.
- Alternatively, the Ruthenium metathesis catalyst could be used to hydrogenate the polymer.
- 200 g of rubber was dissolved in 1133 g of MCB (15 wt.-% solid). The cement was then charged to the reactor and degassed 3 times with C2H4 (6.9×105 Pa) under full agitation.
- 200 g of rubber was dissolved in 1133 g of MCB (15 wt.-% solid). The cement was then charged to the reactor and degassed 3 times with C2H4 (6.9×105 Pa) under full agitation.
- 75 g of rubber was dissolved in 1175 g of MCB (6 wt.-% solid). The cement was then charged to the reactor and degassed 3 times with C2H4 (6.9×105 Pa) under full agitation.
- 75 g of rubber was dissolved in 1175 g of MCB (6 wt.-% solid). The cement was then charged to the reactor. 150 g of 1-hexene was added to the reactor and the mixture was degassed 3 times with dry N2 under full agitation.
TABLE 1 Experimental Details Example 1 Example 2 Example 3 Example 4 Cement 15% 15% 6% 6% Concentration Co-olefin C2H4 C2H4 C2H4 1-hexene Co-olefin 500 psi 500 psi 500 psi 150 g Concentration Reactor 80° C. 80° C. 80° C. 80° C. Temperature Catalyst Load 0.05 phr 0.10 phr 0.25 phr 0.25 phr - For a typical product the Mn is 27 kg/mol (compared to 85 kg/mol for the starting polymer) while he Mw is 54 kg/mol (compared to 296 kg/mol for the starting polymer). As expected, the molecular weight distribution falls from 3.4 for the starting substrate feedstock to 2.0 for the metathesized product. This is consistent with a more homogeneous range of polymer chain lengths and molecular weights.
- A summary of the polymer properties for selected samples is shown in Table 2. The GPC results show up to a fivefold reduction in Mw and a narrowing of the polydispersity index to a minimum of 1.90.
TABLE 2 Summary of Polymer Properties: Mooney Viscosity (ML 1 + 4 @ 100 MN MW MZ PDI deg C.) Therban ® A3407 98000 320000 945000 3.27 73 (Comp.) Substrate 85000 296000 939000 3.50 Experiment 1 73000 189000 441000 2.59 43 Experiment 260000 136000 277000 2.27 28 Experiment 3 31000 59000 98000 1.90 3 Experiment 4 55000 111000 1197000 2.02 31 - Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Claims (7)
1. A hydrogenated nitrile rubber having a molecular weight (MW) in the range of from 30,000 to 250,000, a Mooney viscosity (ML 1+4 @ 100 deg. C) in the range of from 3 to 50, and a MWD (or polydispersity index) of less than 2.5.
2. A hydrogenated nitrile rubber according to claim 1 wherein the molecular weight (Mw) is in the range of from 40,000 to 220,000.
3. A hydrogenated nitrile rubber according to claim 1 wherein the polydispersity index is less than 2.3.
4. A hydrogenated nitrile rubber according to claim 1 wherein the rubber has a Mooney viscosity (ML 1+4 @ 100 deg. C) of less than 35.
5. (Cancelled).
6. A shaped article comprising a hydrogenated nitrile rubber having a molecular weight (MW) in the range of from 30,000 to 250,000, a Mooney viscosity (ML 1+4 @100 deg. C) in the range of from 3 to 50, and a MWD (or polydispersity index) of less than 2.5.
7. A shaped article according to claim 6 , wherein the shaped article is a seal, a hose, a bearing pad, a stator, a well head seal, a valve plate, a cable sheathing, a wheel, a roller or a pipe seal.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/878,080 US20040236029A1 (en) | 2001-06-12 | 2004-06-28 | Low molecular weight hydrogenated nitrile rubber |
US11/973,064 US7772328B2 (en) | 2001-06-12 | 2007-10-05 | Low molecular weight hydrogenated nitrile rubber |
US12/791,088 US7951875B2 (en) | 2001-06-12 | 2010-06-01 | Low molecular weight hydrogenated nitrile rubber |
US12/791,048 US7919563B2 (en) | 2001-06-12 | 2010-06-01 | Low molecular weight hydrogenated nitrile rubber |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA2,350,280 | 2001-06-12 | ||
CA002350280A CA2350280A1 (en) | 2001-06-12 | 2001-06-12 | Low molecular weight hydrogenated nitrile rubber |
US10/167,289 US6780939B2 (en) | 2001-06-12 | 2002-06-10 | Low molecular weight hydrogenated nitrile rubber |
US10/878,080 US20040236029A1 (en) | 2001-06-12 | 2004-06-28 | Low molecular weight hydrogenated nitrile rubber |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/167,289 Continuation US6780939B2 (en) | 2001-06-12 | 2002-06-10 | Low molecular weight hydrogenated nitrile rubber |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/973,064 Continuation US7772328B2 (en) | 2001-06-12 | 2007-10-05 | Low molecular weight hydrogenated nitrile rubber |
Publications (1)
Publication Number | Publication Date |
---|---|
US20040236029A1 true US20040236029A1 (en) | 2004-11-25 |
Family
ID=4169260
Family Applications (5)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/167,289 Expired - Fee Related US6780939B2 (en) | 2001-06-12 | 2002-06-10 | Low molecular weight hydrogenated nitrile rubber |
US10/878,080 Abandoned US20040236029A1 (en) | 2001-06-12 | 2004-06-28 | Low molecular weight hydrogenated nitrile rubber |
US11/973,064 Expired - Fee Related US7772328B2 (en) | 2001-06-12 | 2007-10-05 | Low molecular weight hydrogenated nitrile rubber |
US12/791,088 Expired - Fee Related US7951875B2 (en) | 2001-06-12 | 2010-06-01 | Low molecular weight hydrogenated nitrile rubber |
US12/791,048 Expired - Fee Related US7919563B2 (en) | 2001-06-12 | 2010-06-01 | Low molecular weight hydrogenated nitrile rubber |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/167,289 Expired - Fee Related US6780939B2 (en) | 2001-06-12 | 2002-06-10 | Low molecular weight hydrogenated nitrile rubber |
Family Applications After (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/973,064 Expired - Fee Related US7772328B2 (en) | 2001-06-12 | 2007-10-05 | Low molecular weight hydrogenated nitrile rubber |
US12/791,088 Expired - Fee Related US7951875B2 (en) | 2001-06-12 | 2010-06-01 | Low molecular weight hydrogenated nitrile rubber |
US12/791,048 Expired - Fee Related US7919563B2 (en) | 2001-06-12 | 2010-06-01 | Low molecular weight hydrogenated nitrile rubber |
Country Status (13)
Country | Link |
---|---|
US (5) | US6780939B2 (en) |
EP (2) | EP1754720A3 (en) |
JP (2) | JP4753535B2 (en) |
KR (1) | KR100825592B1 (en) |
CN (1) | CN1318493C (en) |
BR (1) | BR0210349B1 (en) |
CA (1) | CA2350280A1 (en) |
DE (1) | DE60219011T3 (en) |
HK (1) | HK1068362A1 (en) |
MX (1) | MXPA03011205A (en) |
RU (1) | RU2004100531A (en) |
TW (1) | TWI250167B (en) |
WO (1) | WO2002100941A1 (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050027075A1 (en) * | 2001-06-29 | 2005-02-03 | Frederic Guerin | Low molecular weight nitrile rubber |
US20090076227A1 (en) * | 2007-08-21 | 2009-03-19 | Lanxess Deutschland Gmbh | Process for the metathetic degradation of nitrile rubber |
EP1760093A3 (en) * | 2005-08-30 | 2009-11-04 | Lanxess Deutschland GmbH | Use of catalysts for the metathesis degradation of nitrile rubber |
US20110059279A1 (en) * | 2008-01-29 | 2011-03-10 | Lanxess Deutschland Gmbh | Nitrile rubbers which optionally contain alkylthio terminal groups and which are optionally hydrogenated |
US20110123748A1 (en) * | 2008-01-29 | 2011-05-26 | Lanxess Deutschland Gmbh | Nitrile rubbers which optionally contain alkylthio terminal groups and which are optionally hydrogenated |
US20110190441A1 (en) * | 2009-11-03 | 2011-08-04 | Lanxess Deutschland Gmbh | Nitrile rubbers |
US20140024784A1 (en) * | 2010-03-25 | 2014-01-23 | Lanxess Deutschland Gmbh | Process for the production of water and solvent-free hydrogenated nitrile rubbers |
US10280244B2 (en) | 2014-03-27 | 2019-05-07 | Zeon Corporation | Nitrile group-containing copolymer rubber, cross-linkable rubber composition, and cross-linked rubber |
Families Citing this family (89)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2350280A1 (en) * | 2001-06-12 | 2002-12-12 | Bayer Inc. | Low molecular weight hydrogenated nitrile rubber |
CA2409429A1 (en) * | 2002-10-17 | 2004-04-17 | Bayer Inc. | Hydrogenated nitrile rubber composites with improved proccesability |
CA2409436A1 (en) | 2002-10-17 | 2004-04-17 | Bayer Inc. | Polymer composites comprising low molecular weight nitrile rubber |
CA2409434A1 (en) | 2002-10-17 | 2004-04-17 | Bayer Inc. | Polymer blends comprising low molecular weight nitrile rubber |
CA2413636A1 (en) | 2002-12-05 | 2004-06-05 | Bayer Inc. | Adhesive compositions |
CA2413607A1 (en) * | 2002-12-05 | 2004-06-05 | Bayer Inc. | Process for the preparation of low molecular weight hydrogenated nitrile rubber |
CA2462011A1 (en) * | 2004-02-23 | 2005-08-23 | Bayer Inc. | Process for the preparation of low molecular weight nitrile rubber |
CA2462005A1 (en) | 2004-02-23 | 2005-08-23 | Bayer Inc. | Process for the preparation of low molecular weight hydrogenated nitrile rubber |
US20050129890A1 (en) * | 2004-08-05 | 2005-06-16 | Wang Shen-Ling A. | Automotive driveline components manufactured of hydrogenated nitrile butadiene rubber material |
JP5132060B2 (en) * | 2005-02-08 | 2013-01-30 | 株式会社クラレ | Method for producing ring-opening metathesis polymer |
US8058351B2 (en) * | 2005-05-20 | 2011-11-15 | Bridgestone Corporation | Method for preparing low molecular weight polymers |
EP1757623A1 (en) * | 2005-07-14 | 2007-02-28 | Lanxess Inc. | Process for the preparation of low mooney nitrile terpolymers |
EP1743918B1 (en) * | 2005-07-14 | 2008-05-14 | Lanxess Deutschland GmbH | Low mooney nitrile rubber thermoplastic elastomer composition with improved processability |
DE102005061628A1 (en) * | 2005-12-21 | 2007-06-28 | Lanxess Deutschland Gmbh | Hydrogenated nitrile rubber with narrow molecular weight distribution, a process for its preparation and its use |
DE102005061627A1 (en) * | 2005-12-21 | 2007-06-28 | Lanxess Deutschland Gmbh | Synthetic rubber with narrow molecular weight distribution, a process for its preparation and its use |
DE102006008520A1 (en) | 2006-02-22 | 2007-08-23 | Lanxess Deutschland Gmbh | New catalyst system comprising a metathesis catalyst and a salt of a mono-, di- or tri-valent cation other than copper, used for metathesis reactions, e.g. for the degradation of nitrile rubber |
DE102006008521A1 (en) | 2006-02-22 | 2007-08-23 | Lanxess Deutschland Gmbh | Use of a specified ruthenium or osmium catalyst in the metathesis of nitrile rubbers results in improvements in activity and in gel prevention |
US7666950B2 (en) * | 2006-06-01 | 2010-02-23 | Lanxess Deutschland Gmbh | Process for preparing hydrogenated nitrile rubbers |
DE102006040569A1 (en) | 2006-08-30 | 2008-03-06 | Lanxess Deutschland Gmbh | Process for the metathesis degradation of nitrile rubbers |
DE102007024010A1 (en) * | 2007-05-22 | 2008-11-27 | Lanxess Deutschland Gmbh | nitrile rubbers |
DE102007024011A1 (en) | 2007-05-22 | 2008-11-27 | Lanxess Deutschland Gmbh | nitrile rubbers |
DE102007039526A1 (en) | 2007-08-21 | 2009-02-26 | Lanxess Deutschland Gmbh | Catalyst systems and their use for metathesis reactions |
EP2028194B1 (en) * | 2007-08-21 | 2010-05-12 | Lanxess Deutschland GmbH | Metathesis of nitrile rubbers in the presence of transition metal complex catalysts |
EP2075262A1 (en) | 2007-12-17 | 2009-07-01 | Lanxess Inc. | Hydrogenation of diene-based polymers |
EP2072535A1 (en) | 2007-12-17 | 2009-06-24 | Lanxess Inc. | Hydrogenation of diene-based polymer latex |
EP2075263A1 (en) | 2007-12-17 | 2009-07-01 | Lanxess Inc. | Hydrogenation of a diene-based polymer latex |
EP2072536A1 (en) | 2007-12-17 | 2009-06-24 | Lanxess Inc. | Hydrogenation of diene-based polymers |
EP2072532A1 (en) | 2007-12-21 | 2009-06-24 | Lanxess Deutschland GmbH | A process for removing iron-residues, rhodium- and ruthenium-containing catalyst residues from optionally hydrogenated nitrile rubber |
CA2646056A1 (en) | 2007-12-21 | 2009-06-21 | Lanxess Deutschland Gmbh | A process for removing ruthenium-containing catalyst residues from optionally hydrogenated nitrile rubber |
TW200934662A (en) * | 2007-12-28 | 2009-08-16 | Du Pont | Method for reworking adhesively bonded liquid crystal displays |
US8623981B2 (en) * | 2008-01-29 | 2014-01-07 | Lanxess Deutschland Gmbh | Nitrile rubbers which optionally contain alkylthio terminal groups and which are optionally hydrogenated |
EP2147721A1 (en) | 2008-07-08 | 2010-01-27 | Lanxess Deutschland GmbH | Catalyst systems and their use in metathesis reactions |
CN102257049B (en) | 2008-09-12 | 2014-09-10 | 朗盛公司 | Novel elastomeric compositions with improved heat resistance, compression set, and processability |
EP2267037B1 (en) | 2009-06-26 | 2012-11-14 | LANXESS Deutschland GmbH | Use of wholly or partially hydrated nitrile rubbers |
EP2289622A1 (en) | 2009-08-31 | 2011-03-02 | LANXESS Deutschland GmbH | Ruthenium based catalysts for the metathesis of nitrile rubbers |
EP2289621A1 (en) * | 2009-08-31 | 2011-03-02 | LANXESS Deutschland GmbH | Process for the preparation of low molecular weight hydrogenated nitrile rubber |
EP2289620A1 (en) * | 2009-08-31 | 2011-03-02 | LANXESS Deutschland GmbH | Process for the preparation of hydrogenated nitrile rubber |
EP2289623A1 (en) * | 2009-08-31 | 2011-03-02 | LANXESS Deutschland GmbH | Metathesis of nitrile rubbers in the presence of transition metal catalysts |
EP2473279B1 (en) | 2009-08-31 | 2014-04-02 | LANXESS Deutschland GmbH | Metathesis of a nitrile rubber in the presence of a transition metal catalyst |
TWI503330B (en) | 2009-09-17 | 2015-10-11 | Lanxess Deutschland Gmbh | Nitrile rubbers and their preparation in organic solvents |
EP2298824A1 (en) | 2009-09-17 | 2011-03-23 | LANXESS Deutschland GmbH | Nitrile rubbers and production of same in organic solvents |
EP2385074A1 (en) | 2010-05-07 | 2011-11-09 | LANXESS Deutschland GmbH | Nitrile rubbers and production of same in organic solvents |
EP2386600B1 (en) | 2010-04-15 | 2013-06-19 | LANXESS Deutschland GmbH | Cross-linking agent for nitrile rubbers containing isocyanate groups |
EP2598537B1 (en) | 2010-07-28 | 2017-05-03 | ARLANXEO Deutschland GmbH | Hydrogenation of diene-based polymers |
EP2418225A1 (en) | 2010-08-09 | 2012-02-15 | LANXESS Deutschland GmbH | Partially hydrated nitrile rubbers |
EP2423234A1 (en) | 2010-08-31 | 2012-02-29 | LANXESS Deutschland GmbH | Rubber blends from different nitrile rubbers |
EP2423238A1 (en) | 2010-08-31 | 2012-02-29 | LANXESS Deutschland GmbH | Method for producing nitrile rubbers in organic solvents |
EP2423235A1 (en) | 2010-08-31 | 2012-02-29 | LANXESS Deutschland GmbH | Method for producing nitrile rubbers in organic solvents |
EP2471852A1 (en) | 2010-12-29 | 2012-07-04 | Lanxess Deutschland GmbH | Vulcanisable compounds based on nitrile rubbers containing epoxy groups |
EP2471851A1 (en) | 2010-12-29 | 2012-07-04 | LANXESS Deutschland GmbH | Vulcanisable compounds based on nitrile rubbers containing epoxy groups |
CN102603928B (en) * | 2011-01-11 | 2015-07-15 | 赞南科技(上海)有限公司 | Preparation method of hydrogenated nitrile rubber and degradation and hydrogenation method of butadiene type rubber |
EP2484700B1 (en) | 2011-02-04 | 2013-10-09 | LANXESS Deutschland GmbH | Functionalised nitrile rubbers and their manufacture |
US8633280B2 (en) * | 2011-03-30 | 2014-01-21 | Zannan Scitech Co., Ltd | Methods of modifying polymers with highly active and selective metathesis catalysts |
EP2554558A1 (en) | 2011-08-02 | 2013-02-06 | Lanxess Deutschland GmbH | Method for producing nitrile rubbers in organic solvents |
EP2565229A1 (en) | 2011-09-02 | 2013-03-06 | LANXESS Deutschland GmbH | Vulcanisable compounds on the basis of ethylene vinyl acetate copolymerisates containing epoxy groups |
EP2581409A1 (en) | 2011-10-11 | 2013-04-17 | Lanxess Deutschland GmbH | Vulcanisable compounds on the basis of nitrile rubbers containing epoxy groups |
EP2581407A1 (en) | 2011-10-11 | 2013-04-17 | Lanxess Deutschland GmbH | Vulcanisable compounds on the basis of nitrile rubbers containing epoxy groups |
WO2013056461A1 (en) | 2011-10-21 | 2013-04-25 | Lanxess Deutschland Gmbh | Catalyst compositions and their use for hydrogenation of nitrile rubber |
WO2013056400A1 (en) | 2011-10-21 | 2013-04-25 | Lanxess Deutschland Gmbh | Catalyst compositions and their use for hydrogenation of nitrile rubber |
WO2013056459A1 (en) | 2011-10-21 | 2013-04-25 | Lanxess Deutschland Gmbh | Catalyst compositions and their use for hydrogenation of nitrile rubber |
WO2013056463A1 (en) | 2011-10-21 | 2013-04-25 | Lanxess Deutschland Gmbh | Catalyst compositions and their use for hydrogenation of nitrile rubber |
WO2013098052A2 (en) | 2011-12-28 | 2013-07-04 | Lanxess Deutschland Gmbh | Metathesis of nitrile rubbers in the presence of transition metal complex catalysts |
WO2013098056A1 (en) | 2011-12-28 | 2013-07-04 | Lanxess Deutschland Gmbh | Purification of optionally hydrogenated nitrile rubber |
EP2676969B1 (en) * | 2012-06-22 | 2016-06-01 | University Of Waterloo | Tandem metathesis and hydrogenation of diene-based polymers in latex |
EP2676971B1 (en) | 2012-06-22 | 2015-04-08 | University Of Waterloo | Hydrogenation of a diene-based polymer latex |
US9683067B2 (en) * | 2013-03-22 | 2017-06-20 | Zeon Corporation | Nitrile group-containing copolymer rubber, cross-linkable rubber composition, and cross-linked rubber |
WO2014187830A1 (en) | 2013-05-24 | 2014-11-27 | Lanxess Deutschland Gmbh | Ruthenium-based complexes, their preparation and use as catalysts |
JP2015017168A (en) * | 2013-07-10 | 2015-01-29 | 日本ゼオン株式会社 | Highly saturated nitrile rubber composition for hose and hose |
EP2868677A1 (en) | 2013-10-30 | 2015-05-06 | LANXESS Deutschland GmbH | Copolymer rubber containing nitrile groups |
EP2868676A1 (en) | 2013-10-30 | 2015-05-06 | LANXESS Deutschland GmbH | Functionalised copolymer rubber containing nitrile groups |
CN106459484B (en) | 2014-02-03 | 2019-10-15 | 阿朗新科德国有限责任公司 | Stabilized rubber |
PL3034518T3 (en) | 2014-12-19 | 2017-10-31 | Arlanxeo Deutschland Gmbh | Color stable nitrile rubbers |
TWI566835B (en) | 2014-12-25 | 2017-01-21 | 財團法人工業技術研究院 | Olefin-metathesis catalysts and method for preparing low-molecular-weight nitrile butadiene rubber |
EP3196240B1 (en) | 2016-01-25 | 2020-06-10 | ARLANXEO Deutschland GmbH | Hydrogenated nitrile butadiene peg acrylate copolymers |
EP3333196B1 (en) | 2016-12-09 | 2020-05-13 | ARLANXEO Deutschland GmbH | Hydrogenated nitrile diene carboxylic acid ester copolymers |
EP3387931B1 (en) | 2017-04-10 | 2020-07-15 | ARLANXEO Deutschland GmbH | Vulcanizable composition comprising hxnbr latex and polyfunctional epoxide |
US20200140595A1 (en) | 2017-07-25 | 2020-05-07 | Arlanxeo Deutschland Gmbh | Vulcanizable Compositions Comprising Hydrogenated Nitrile-Diene-Carboxylic Ester Copolymer and Silica |
US20200392316A1 (en) | 2017-12-21 | 2020-12-17 | Arlanxeo Deutschland Gmbh | Vulcanized hnbr product with improved hot air |
EP3728355B1 (en) | 2017-12-21 | 2022-04-20 | ARLANXEO Deutschland GmbH | Nitrile diene carboxylic acid ester copolymers |
US11713361B2 (en) | 2018-04-20 | 2023-08-01 | Arlanxeo Deutschland Gmbh | Hydrogenation catalyst compositions and their use for hydrogenation of nitrile rubber |
KR20210035088A (en) | 2018-07-23 | 2021-03-31 | 아란세오 도이치란드 게엠베하 | Method for producing hydrogenated nitrile rubber and HNBR composition thereof |
US11673130B2 (en) | 2018-12-12 | 2023-06-13 | Arlanxeo Deutschland Gmbh | Catalyst system containing a metathesis catalyst and at least one phenolic compound and a process for metathesis of nitrile-butadiene rubber (NBR) using the catalyst system |
EP3898706A1 (en) | 2018-12-17 | 2021-10-27 | ARLANXEO Deutschland GmbH | Process for preparing hnbr solutions with alternative solvents |
WO2020126343A1 (en) | 2018-12-19 | 2020-06-25 | Arlanxeo Deutschland Gmbh | Electrode composition for a cathode of a cell of a lithium-ion battery, a cathode slurry composition, a cathode and the battery incorporating it |
CN110283454A (en) * | 2019-05-29 | 2019-09-27 | 周宁东 | A kind of Low-smoke flame retardant cable material and preparation method thereof |
JP2022538058A (en) | 2019-07-02 | 2022-08-31 | アランセオ・ドイチュランド・ゲーエムベーハー | HNBR vulcanizates containing polycyclic aromatic hydrocarbons |
WO2021001357A1 (en) | 2019-07-02 | 2021-01-07 | Arlanxeo Deutschland Gmbh | Use of vulcanisates comprising peg acrylate-hnbr copolymer in contact with pah |
CN114262394B (en) * | 2020-09-16 | 2023-08-18 | 浙江赞昇新材料有限公司 | Liquid hydrogenated nitrile rubber and preparation method and application thereof |
WO2024046966A1 (en) | 2022-08-30 | 2024-03-07 | Arlanxeo Deutschland Gmbh | HNBR CATHODE BINDERS FOR BATTERY CELLS USING γ-VALEROLACTONE AS PROCESSING SOLVENT |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3995095A (en) * | 1973-07-17 | 1976-11-30 | Phillips Petroleum Company | Modification of polymers by treatment with olefins |
US4647627A (en) * | 1984-09-08 | 1987-03-03 | Bayer Aktiengesellschaft | Low molecular weight copolymers and covulcanisates produced therefrom |
US5208296A (en) * | 1992-09-02 | 1993-05-04 | Polysar Rubber Corporation | Nitrile rubber hydrogenation |
US5446102A (en) * | 1994-08-10 | 1995-08-29 | Bridgeston, Corporation | Olefin metathesis catalysts for degelling polymerization reactors |
US6084033A (en) * | 1997-05-08 | 2000-07-04 | Nantex Industry Co., Ltd. | Bimetallic complex catalyst systems, their preparations and application in the hydrogenation of unsaturated copolymers |
US6780939B2 (en) * | 2001-06-12 | 2004-08-24 | Bayer Inc. | Low molecular weight hydrogenated nitrile rubber |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3329974A1 (en) * | 1983-08-19 | 1985-02-28 | Bayer Ag, 5090 Leverkusen | MANUFACTURE OF HYDRATED NITRILE RUBBER |
DE3433392A1 (en) * | 1984-09-12 | 1986-03-20 | Bayer Ag, 5090 Leverkusen | HYDROGENATION OF UNSATURATED POLYMER WITH NITRILE GROUPS |
DE3921264A1 (en) * | 1989-06-29 | 1991-01-03 | Bayer Ag | HYDROGENATION OF UNSATURED POLYMER WITH NITRILE GROUPS |
DE3932019C1 (en) * | 1989-09-26 | 1991-05-08 | Bayer Ag, 5090 Leverkusen, De | |
US5312940A (en) | 1992-04-03 | 1994-05-17 | California Institute Of Technology | Ruthenium and osmium metal carbene complexes for olefin metathesis polymerization |
EP0773948A4 (en) | 1992-04-03 | 1998-09-02 | California Inst Of Techn | High activity ruthenium or osmium metal carbene complexes for olefin metathesis reactions and synthesis thereof |
US5241013A (en) * | 1992-09-02 | 1993-08-31 | Polysar Rubber Corporation | Catalytic hydrogenation of nitrile rubber |
US5210151A (en) * | 1992-09-02 | 1993-05-11 | Polysar Rubber Corporation | Hydrogenation of nitrile rubber |
US5258467A (en) * | 1992-09-02 | 1993-11-02 | Polysar Rubber Corporation | Catalytic solution hydrogenation of nitrile rubber |
JP3445615B2 (en) * | 1993-03-30 | 2003-09-08 | 日本ゼオン株式会社 | Unsaturated nitrile-conjugated diene copolymer, method for producing the same, and rubber composition |
JP3477849B2 (en) * | 1994-09-30 | 2003-12-10 | 日本ゼオン株式会社 | Rubber composition comprising a nitrile group-containing highly saturated copolymer rubber and an ethylene-based saturated copolymer rubber |
US5831108A (en) | 1995-08-03 | 1998-11-03 | California Institute Of Technology | High metathesis activity ruthenium and osmium metal carbene complexes |
US6281293B1 (en) | 1997-03-31 | 2001-08-28 | Nippon Zeon Co., Ltd. | Mixture composition of synthetic resin and rubber |
CN1058974C (en) * | 1997-04-22 | 2000-11-29 | 中国石油化工集团公司 | Process for hydrogenation of NBR |
CA2462005A1 (en) | 2004-02-23 | 2005-08-23 | Bayer Inc. | Process for the preparation of low molecular weight hydrogenated nitrile rubber |
-
2001
- 2001-06-12 CA CA002350280A patent/CA2350280A1/en not_active Abandoned
-
2002
- 2002-06-10 US US10/167,289 patent/US6780939B2/en not_active Expired - Fee Related
- 2002-06-10 TW TW091112467A patent/TWI250167B/en not_active IP Right Cessation
- 2002-06-11 EP EP06025383A patent/EP1754720A3/en not_active Withdrawn
- 2002-06-11 DE DE60219011T patent/DE60219011T3/en not_active Expired - Lifetime
- 2002-06-11 JP JP2003503704A patent/JP4753535B2/en not_active Expired - Fee Related
- 2002-06-11 KR KR1020037016188A patent/KR100825592B1/en not_active IP Right Cessation
- 2002-06-11 CN CNB028117344A patent/CN1318493C/en not_active Expired - Fee Related
- 2002-06-11 MX MXPA03011205A patent/MXPA03011205A/en active IP Right Grant
- 2002-06-11 EP EP02737701A patent/EP1401950B2/en not_active Expired - Fee Related
- 2002-06-11 BR BRPI0210349-4B1A patent/BR0210349B1/en not_active IP Right Cessation
- 2002-06-11 RU RU2004100531/04A patent/RU2004100531A/en not_active Application Discontinuation
- 2002-06-11 WO PCT/CA2002/000967 patent/WO2002100941A1/en active IP Right Grant
-
2004
- 2004-05-06 JP JP2004137595A patent/JP4468063B2/en not_active Expired - Fee Related
- 2004-06-28 US US10/878,080 patent/US20040236029A1/en not_active Abandoned
-
2005
- 2005-01-14 HK HK05100393A patent/HK1068362A1/en not_active IP Right Cessation
-
2007
- 2007-10-05 US US11/973,064 patent/US7772328B2/en not_active Expired - Fee Related
-
2010
- 2010-06-01 US US12/791,088 patent/US7951875B2/en not_active Expired - Fee Related
- 2010-06-01 US US12/791,048 patent/US7919563B2/en not_active Expired - Fee Related
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3995095A (en) * | 1973-07-17 | 1976-11-30 | Phillips Petroleum Company | Modification of polymers by treatment with olefins |
US4647627A (en) * | 1984-09-08 | 1987-03-03 | Bayer Aktiengesellschaft | Low molecular weight copolymers and covulcanisates produced therefrom |
US5208296A (en) * | 1992-09-02 | 1993-05-04 | Polysar Rubber Corporation | Nitrile rubber hydrogenation |
US5446102A (en) * | 1994-08-10 | 1995-08-29 | Bridgeston, Corporation | Olefin metathesis catalysts for degelling polymerization reactors |
US6084033A (en) * | 1997-05-08 | 2000-07-04 | Nantex Industry Co., Ltd. | Bimetallic complex catalyst systems, their preparations and application in the hydrogenation of unsaturated copolymers |
US6780939B2 (en) * | 2001-06-12 | 2004-08-24 | Bayer Inc. | Low molecular weight hydrogenated nitrile rubber |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050027075A1 (en) * | 2001-06-29 | 2005-02-03 | Frederic Guerin | Low molecular weight nitrile rubber |
US7745539B2 (en) * | 2001-06-29 | 2010-06-29 | Lanxess Inc. | Low molecular weight nitrite rubber |
EP1760093A3 (en) * | 2005-08-30 | 2009-11-04 | Lanxess Deutschland GmbH | Use of catalysts for the metathesis degradation of nitrile rubber |
CN102850471A (en) * | 2005-08-30 | 2013-01-02 | 朗盛德国有限责任公司 | Use of catalysts for the metathesis degradation of nitrile rubber |
US20090076227A1 (en) * | 2007-08-21 | 2009-03-19 | Lanxess Deutschland Gmbh | Process for the metathetic degradation of nitrile rubber |
US7875683B2 (en) * | 2007-08-21 | 2011-01-25 | Lanxess Deutschland Gmbh | Process for the metathetic degradation of nitrile rubber |
US20110123748A1 (en) * | 2008-01-29 | 2011-05-26 | Lanxess Deutschland Gmbh | Nitrile rubbers which optionally contain alkylthio terminal groups and which are optionally hydrogenated |
US20110059279A1 (en) * | 2008-01-29 | 2011-03-10 | Lanxess Deutschland Gmbh | Nitrile rubbers which optionally contain alkylthio terminal groups and which are optionally hydrogenated |
US8664315B2 (en) | 2008-01-29 | 2014-03-04 | Lanxess Deutschland Gmbh | Nitrile rubbers which optionally contain alkylthio terminal groups and which are optionally hydrogenated |
US20110190441A1 (en) * | 2009-11-03 | 2011-08-04 | Lanxess Deutschland Gmbh | Nitrile rubbers |
US8436091B2 (en) | 2009-11-03 | 2013-05-07 | Lanxess Deutschland Gmbh | Nitrile rubbers |
US20140024784A1 (en) * | 2010-03-25 | 2014-01-23 | Lanxess Deutschland Gmbh | Process for the production of water and solvent-free hydrogenated nitrile rubbers |
US9249236B2 (en) * | 2010-03-25 | 2016-02-02 | Lanxess Deutschland Gmbh | Process for the production of water and solvent-free hydrogenated nitrile rubbers |
US10280244B2 (en) | 2014-03-27 | 2019-05-07 | Zeon Corporation | Nitrile group-containing copolymer rubber, cross-linkable rubber composition, and cross-linked rubber |
Also Published As
Publication number | Publication date |
---|---|
US20100240838A1 (en) | 2010-09-23 |
DE60219011T3 (en) | 2011-07-21 |
EP1754720A3 (en) | 2008-02-27 |
CA2350280A1 (en) | 2002-12-12 |
US7951875B2 (en) | 2011-05-31 |
EP1401950B1 (en) | 2007-03-21 |
JP2004300444A (en) | 2004-10-28 |
KR20040027517A (en) | 2004-04-01 |
US20100240848A1 (en) | 2010-09-23 |
US20030088035A1 (en) | 2003-05-08 |
CN1514852A (en) | 2004-07-21 |
US7919563B2 (en) | 2011-04-05 |
CN1318493C (en) | 2007-05-30 |
RU2004100531A (en) | 2005-06-20 |
BR0210349B1 (en) | 2013-10-01 |
JP2004529256A (en) | 2004-09-24 |
WO2002100941A1 (en) | 2002-12-19 |
EP1401950B2 (en) | 2010-12-29 |
BR0210349A (en) | 2004-07-20 |
DE60219011D1 (en) | 2007-05-03 |
US6780939B2 (en) | 2004-08-24 |
HK1068362A1 (en) | 2005-04-29 |
EP1401950A1 (en) | 2004-03-31 |
US7772328B2 (en) | 2010-08-10 |
KR100825592B1 (en) | 2008-04-25 |
US20080090970A1 (en) | 2008-04-17 |
MXPA03011205A (en) | 2004-02-26 |
JP4468063B2 (en) | 2010-05-26 |
TWI250167B (en) | 2006-03-01 |
DE60219011T2 (en) | 2007-12-06 |
JP4753535B2 (en) | 2011-08-24 |
EP1754720A2 (en) | 2007-02-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6780939B2 (en) | Low molecular weight hydrogenated nitrile rubber | |
US6673881B2 (en) | Process for the preparation of low molecular weight hydrogenated nitrile rubber | |
US6841623B2 (en) | Low molecular weight nitrile rubber | |
US7579410B2 (en) | Process for the preparation of low molecular weight nitrile rubber | |
US7585920B2 (en) | Process for the preparation of low molecular weight hydrogenated nitrile rubber | |
CA2413607A1 (en) | Process for the preparation of low molecular weight hydrogenated nitrile rubber | |
US20070049699A1 (en) | Process for the preparation of low mooney nitrile terpolymers | |
CA2357470A1 (en) | Process for the metathesis of functionalized polymers | |
CA2357465A1 (en) | Process for the preparation of low molecular weight hydrogenated nitrile rubber | |
KR101162394B1 (en) | Process for the preparation of low molecular weight nitrile rubber |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |