CA2825164A1 - Rubber material with barrier material made of cycloolefin copolymers - Google Patents
Rubber material with barrier material made of cycloolefin copolymers Download PDFInfo
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- CA2825164A1 CA2825164A1 CA2825164A CA2825164A CA2825164A1 CA 2825164 A1 CA2825164 A1 CA 2825164A1 CA 2825164 A CA2825164 A CA 2825164A CA 2825164 A CA2825164 A CA 2825164A CA 2825164 A1 CA2825164 A1 CA 2825164A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0008—Compositions of the inner liner
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0041—Compositions of the carcass layers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
- C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
- C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
- C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
- C08G2261/3322—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from cyclooctene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
- C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
- C08G2261/3325—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from other polycyclic systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/418—Ring opening metathesis polymerisation [ROMP]
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Laminated Bodies (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
A rubber material is described, provided with a barrier material in the form of a copolymer preparable by ring-opening metathesis polymerization of a) at least one olefin monomer selected from the group consisting of monocyclic olefin monomers having one or two endocyclic C-C double bonds and bicyclic olefin monomers having one endocyclic C-C double bond, and b) at least one polycyclic olefin monomer having at least two C-C double bonds. The barrier material can be used to reduce the gas permeability of the rubber material.
Description
:A 02825164 2013 07 18 RUBBER MATERIAL WITH BARRIER MATERIAL MADE OF CYCLOOLEFIN
COPOLYMERS
The invention relates to a rubber material modified with a barrier material in the form of a copolymer which can be produced via ring-opening metathesis polymerization (ROMP) of a) olefin monomers selected from monocyclic olefin monomers having one or two endocyclic C-C double bonds and bicyclic olefin monomers having one endocyclic C-C double bond and b) polycyclic olefin monomers having at least two C-C double bonds.
An important factor in pneumatic tires is to ensure that the compressed air or the filler gas has the required pressure value and the necessary gas volume to maintain tire operation with functional capability for a maximum period. For this reason, the interior of conventional pneumatic tires usually has a gas-impermeable rubber layer or a rubber layer with minimum gas permeability. Said inner layer of a tire serves to seal the gas-filled interior and in tubeless tires acts as replacement for the tube. An example of a material that can be used is halobutyl-containing, vulcanizable rubber mixture, or butyl rubber.
Ring-opening metathesis polymerization reactions are described in EP 1847558 Al and in the US patent application 61/257063. Homopolymers produced via ring-opening metathesis polymerization from cycloolefins, starting from cyclooctene or from cyclopentadiene, are often brittle, thermoset, or non-film-forming materials which are not suitable for forming flexible coatings or which have poor barrier properties, or the glass transition temperature of which cannot be adjusted to the desired value.
It was an object of the present invention to provide alternative barrier materials for rubber products, in particular for pneumatic tires, where these can be used simply, efficiently and at low cost and/or have good or improved gas-barrier properties.
The invention provides a rubber material modified with a barrier material in the form of a copolymer which can be produced via ring-opening metathesis polymerization of :A 02825164 2013 07 18 . .
COPOLYMERS
The invention relates to a rubber material modified with a barrier material in the form of a copolymer which can be produced via ring-opening metathesis polymerization (ROMP) of a) olefin monomers selected from monocyclic olefin monomers having one or two endocyclic C-C double bonds and bicyclic olefin monomers having one endocyclic C-C double bond and b) polycyclic olefin monomers having at least two C-C double bonds.
An important factor in pneumatic tires is to ensure that the compressed air or the filler gas has the required pressure value and the necessary gas volume to maintain tire operation with functional capability for a maximum period. For this reason, the interior of conventional pneumatic tires usually has a gas-impermeable rubber layer or a rubber layer with minimum gas permeability. Said inner layer of a tire serves to seal the gas-filled interior and in tubeless tires acts as replacement for the tube. An example of a material that can be used is halobutyl-containing, vulcanizable rubber mixture, or butyl rubber.
Ring-opening metathesis polymerization reactions are described in EP 1847558 Al and in the US patent application 61/257063. Homopolymers produced via ring-opening metathesis polymerization from cycloolefins, starting from cyclooctene or from cyclopentadiene, are often brittle, thermoset, or non-film-forming materials which are not suitable for forming flexible coatings or which have poor barrier properties, or the glass transition temperature of which cannot be adjusted to the desired value.
It was an object of the present invention to provide alternative barrier materials for rubber products, in particular for pneumatic tires, where these can be used simply, efficiently and at low cost and/or have good or improved gas-barrier properties.
The invention provides a rubber material modified with a barrier material in the form of a copolymer which can be produced via ring-opening metathesis polymerization of :A 02825164 2013 07 18 . .
a) at least one olefin monomer selected from the group consisting of monocyclic olefin monomers having one or two endocyclic C-C double bonds and bicyclic olefin monomers having one endocyclic C-C double bond and b) at least one polycyclic olefin monomer having at least two C-C double bonds.
It is preferable to use the copolymer in the form of a polymer layer of thickness at least 1 m. It is preferable that the molar ratio of olefin monomers a) to polycyclic olefin monomers b) is from 99:1 to 15:85 or from 80:20 to 15:85.
The invention also provides a pneumatic tire comprising a rubber material of the invention.
The invention also provides a process for modifying a rubber material with gas-barrier properties, where at least one of the abovementioned copolymers, described in more detail below, is applied to the rubber material or is introduced into the rubber material.
The invention also provides the use of the abovementioned copolymers, described in more detail below, for reducing the gas permeability of rubber material.
The rubber material provided with the copolymer in the invention exhibits a gas-barrier property (e.g. with respect to air, oxygen, nitrogen, argon, carbon dioxide, etc.), and this barrier property is generated or amplified via the use of the copolymer in the invention. The expression "barrier property" means, in comparison with uncoated backing substrate, reduced transmission or permeability with respect to certain substances.
Oxygen- or gas-barrier properties can by way of example be measured by the permeability test described in the examples. It is preferable that the oxygen transmission rate for substrates coated in the invention is less than 30% of the value for the untreated substrates, in particular less than 15% or less than 5%, e.g. from 0.1% to 3% (measured at 23 C and 85% relative humidity).
The copolymers used in the invention can be produced via ring-opening metathesis polymerization. A metathesis reaction is very generally a chemical reaction between two :A 02825164 2013 07 18 compounds where a group is exchanged between two reactants. If this is an organic metathesis reaction, it can be formally represented as exchange of the substituents at a double bond. However, a particularly important reaction is the metal-complex-catalyzed ring-opening metathesis reaction of organic cycloolefin compounds ("ring opening metathesis polymerization", abbreviated to ROMP), where this provides access to polymeric polyolefins. Catalytic metal complexes used are in particular metal carbene complexes of the general structure Met=CR2, where R is an organic moiety. The metal carbene complexes are very susceptible to hydrolysis, and the metathesis reactions can therefore be carried out in anhydrous organic solvents or in the olefins themselves (see by way of example US-A 2008234451, EP-A 0824125). It is also possible to carry out the metathesis reaction of olefins in an aqueous medium in order to avoid complicated purification steps for the removal of large amounts of solvents or unreacted olefins (DE 19859191; US patent application 61/257063).
The copolymers used in the invention are formed from a) at least one olefin monomer selected from the group consisting of monocyclic olefin monomers having one or two endocyclic C-C double bonds and bicyclic olefin monomers having one endocyclic C-C double bond and b) at least one polycyclic olefin monomer having at least two C-C double bonds.
The molar ratio of olefin monomers a) to polycyclic olefin monomers b) is preferably from 80:20 to 15:85, preferably from 65:35 to 20:80.
The ring strain of the olefin monomers a) is preferably at least 2 kcal/mol.
The ring strain of the polycyclic olefin monomers b) is preferably at least 15 kcal/mol, based on the ring with the highest strain.
Examples of olefin monomers a) are cyclobutene, cyclopentene, 2-methylcyclo-pentene-1, 3-methylcyclopentene-1, 4-methylcyclopentene-1, 3-butylcyclopentene-1, cyclohexene, 2-methylcyclohexene-1, 3-methylcyclohexene-1, 4-methylcyclohexene-1, 1,4-dimethylcyclohexene-1, 3,3,5-trimethylcyclohexene-1, cycloheptene, 1,2-dimethylcycloheptene-1, cis-cyclooctene, trans-cyclooctene, 2-methylcyclooctene-1, 3-methylcyclooctene-1, 4-methylcyclooctene-1, 5-methylcyclooctene-1, cyclononene, :A 02825164 2013 07 18 cyclodecene, cycloundecene, cyclododecene, cyclooctadiene, cyclopentadiene, cyclohexadiene and norbornene, and particular preference is given here to monocyclic olefins having one C-C double bond, in particular cis-cyclooctene.
Preferred polycyclic olefin monomers b) are bicyclic dienes, e.g.
norbornadiene, dicyclopentadiene (3a,4,7,7a-tetrahydro-1H-4,7-methanoindene), bicyclo[2.2.2]octa-2,5-diene, bicyclo[3.3.0]octa-2,6-diene, and cyclopentadiene oligomers, e.g.
tricyclopentadiene. Particular preference is given to dicyclopentadiene.
In one preferred embodiment, the copolymer has been formed via ring-opening metathesis polymerization of cis-cyclooctene and dicyclopentadiene.
The copolymers used in the invention are preferably produced in an aqueous medium. The ring-opening metathesis reaction here can be carried out by using water and dispersing agent as initial charge in a polymerization vessel, dissolving an organometallic carbene complex used as catalyst in the cycloolefin, introducing the cycloolefin/metal complex solution into the aqueous dispersing agent solution, converting the resultant cycloolefin/metal complex macroemulsion to a cyclocolefin/metal complex miniemulsion, and converting this at room temperature to an aqueous polyolefin dispersion.
In a preferred method for carrying out the ring-opening metathesis reaction, at least one portion of the water, at least one portion of dispersing agent, and at least one portion of the monomers in the form of an aqueous monomer macroemulsion with an average droplet diameter? 2 pm are used as initial charge, and then the monomer macroemulsion is converted to a monomer miniemulsion with an average droplet diameter < 1500 nm, with introduction of energy, and then the optionally remaining residual amount of the water, the optionally remaining residual amount of the dispersing agent, the optionally remaining residual amount of the monomers, and the entire amount of an organometallic carbene complex used as catalyst are added to the resulting monomer miniemulsion at polymerization temperature.
Organometallic carbene complexes can be used as metathesis catalysts. Examples of metals are transition metals of the 6th, 7th, or 8th transition group, preferably :A 02825164 2013 07 18 molybdenum, tungsten, osmium, rhenium, or ruthenium, of which osmium and ruthenium are preferred. It is particularly preferable to use ruthenium alkylidene complexes. These metathesis catalysts are known from the prior art and are described by way of example in R.H. Grubbs (Ed.) "Handbook of Metathesis", 2003, Wiley-VCH, Weinheim, WO
93/20111, WO 96/04289, WO 97/03096, WO 97/06185, J. Am. Soc. 1996, pp. 784-790, Dalton Trans. 2008, pp.5791-5799, and in Coordination Chemistry Reviews, 2007, 251, pp. 726-764.
The concentration of the copolymers in the aqueous dispersions or solutions used for the coating process is preferably at least 1% by weight, in particular at least 5% by weight, and up to 50% by weight, or up to 70% by weight. The content of the copolymers in the aqueous dispersion is mostly from 10 to 60% by weight, or from 15 to 55% by weight, in particular from 20 to 50% by weight.
The viscosity of preferred aqueous dispersions of the copolymers at pH 4 and at a temperature of 20 C is from 10 to 150 000 mPas, or from 200 to 5000 mPas (measured by a Brookfield viscosimeter at 20 C, 20 rpm, spindle 4). The average particle size of the copolymer particles dispersed in the aqueous dispersion is by way of example from 0.02 to 100 m, preferably from 0.05 to 10 Jim. It can be determined by way of example with the aid of optical microscopy, light scattering, hydrodynamic chromatography, or freeze-fracture electron microscopy.
The rubber constituents of the rubber material can by way of example have been selected from diene rubber, natural rubber, butyl rubber, synthetic polyisoprene, polybutadiene, styrene-butadiene copolymer, isoprene-butadiene rubber, styrene-isoprene-butadiene rubber, acrylonitrile-butadiene rubber, ethylene-propylene rubber, and chloroprene rubber.
The rubber material is preferably a constituent of a pneumatic tire, in particular being an inner layer of a pneumatic tire, or being a carcass of a pneumatic tire.
:A 02825164 2013 07 18 =
In one embodiment, the rubber materials themselves are modified with a solution or aqueous dispersion of at least one of the copolymers described above. In another embodiment, constituents of a rubber-containing article, in particular of pneumatic tires, are modified with the barrier material and are introduced into the rubber-containing article, preferably pneumatic tire. By way of example, the textile cord insert of pneumatic tires can be modified with the copolymers to be used in the invention.
The invention also provides a process for modifying a rubber material, where at least one of the copolymers described herein is applied to the rubber material or is incorporated into the rubber material. The modification can by way of example use one or more of the following methods: impregnation, spraying, spreading, coating, calendering.
The dispersions or solutions used for the coating process can comprise further additives or auxiliaries, e.g. thickeners to adjust rheology, wetting aids, organic or inorganic fillers, or binders.
It is preferable that the copolymer is applied in the form of an aqueous dispersion of the copolymer, and a film is formed via drying of the dispersion on the backing substrate.
The invention also provides a pneumatic tire comprising a rubber material of the invention. The copolymer here can have been applied by one or more of the following methods:
- application on at least one portion of the surface or on the entire surface of the inner layer of the tire;
- introduction into the material of the inner layer of the tire;
- in the form of film, in the form of unsupported foil, or in the form of coating of a foil backing, where the films or foils can have been introduced in addition to a rubber-based inner layer of a tire or as replacement form for an inner layer of a tire, into the interior of a tire;
- in the form of binder or coating of a fiber cord insert of the pneumatic tire;
- in the form of laminate between two or more backing foils, where the laminate has been introduced into the interior of the tire.
:A 02825164 2013 07 18 A film applied can take the form of spray film or of spread film, for example through roll-, doctor-, airbrush-, or cast-spreading processes. The material applied can also take the form of a foil which serves as backing and then is crosslinked (vulcanized) or adhesive-bonded to the carcass. Examples of suitable foil backings are those made of rubber, of polyolefin, of polyester, of polyamide, or of polyurethane.
As an alternative, it is also possible to use the copolymer in the form of a laminate between two backing foils, where the laminate is then crosslinked or adhesive-bonded to the carcass.
The copolymers can also be used in the form of self-supporting film.
The application process can by way of example be undertaken on coating machines, by applying the coating composition to a backing foil made of a plastic. If materials are used in the form of webs, the polymer dispersions is usually applied from a trough by way of an applicator roll, and rendered uniform by an airbrush.
Examples of other successful methods of applying the coating use the reverse gravure process, or use spray processes, or use a metering bar, or use other coating processes known to the person skilled in the art. The backing substrate here has a coating on at least one side, i.e. can have a coating on one or both sides.
In order to achieve a further improvement in adhesion on a foil, the backing foil can be subjected in advance to a corona treatment or, as an alternative, adhesion promoters, such as polyethyleneimines, can be used. The amounts applied to the sheet materials are preferably by way of example from Ito 800 g (of polymer, solid) per m2, preferably from 1 to 400 g/m2, or from 5 to 200 g/m2. Once the coating compositions have been applied to the backing substrates, the solvent or dispersion medium is evaporated. To this end, it is possible by way of example in the case of continuous operation to pass the material through a drying tunnel which can have an infrared irradiation apparatus. The coated and dried material is then passed over a cooling roll and finally is wound up. The thickness of the dried coating is at least 1 [im preferably from 1 to 400 1.1m, particularly :A 02825164 2013 07 18 . .
preferably from 5 to 200 gm. The thickness of the backing foils is generally in the range from 10 gm to 1 cm.
The substrates coated in the invention exhibit excellent gas-barrier effect.
Examples The following copolymer dispersions were used (monomer ratios are based on molar ratios):
Dispersion Dl:
30% strength aqueous poly(dicyclopentadiene-co-octenamer) dispersion, produced via ring-opening metathesis polymerization (ROMP) starting from dicyclopentadiene and cis-cyclooctene (50:50) with use of a ruthenium-alkylidene catalyst.
Number-average particle size: 270 nm Dispersion D2:
30% strength aqueous poly(dicyclopentadiene-co-octenamer) dispersion, produced via ring-opening metathesis polymerization (ROMP) starting from dicyclopentadiene and cis-cyclooctene (60:40) with use of a ruthenium-alkylidene catalyst.
Dispersion D3:
30% strength aqueous poly(dicyclopentadiene-co-octenamer) dispersion, produced via ring-opening metathesis polymerization (ROMP) starting from dicyclopentadiene and cis-cyclooctene (70:30) with use of a ruthenium-alkylidene catalyst.
Dispersion D4:
40% strength aqueous poly(dicyclopentadiene-co-octenamer) dispersion, produced via ring-opening metathesis polymerization (ROMP) with use of a ruthenium-alkylidene catalyst starting from dicyclopentadiene and cis-cyclooctadiene (50:50).
Number-average particle size of dispersed latex particles: 265 nm :A 02825164 2013 07 18 Dispersion D5:
30% strength aqueous poly(dicyclopentadiene-co-octenamer) dispersion, produced via ring-opening metathesis polymerization (ROMP) with use of a ruthenium-alkylidene catalyst starting from dicyclopentadiene and cis-cyclooctene (2:98).
Number-average particle size of dispersed latex particles: 419 nm Determination of oxygen permeability of a self-supporting polyalkenamer foil:
The foil was produced by casting a polyalkenamer dispersion into a silicone mold of dimensions 15 cm x 10 cm x 0.5 cm (length x width x height). The cast dispersion film was dried at 25 C for 48 h and then heat-conditioned at a temperature of 65 C
for minutes.
Dry and moist oxygen permeabilities were measured with a MOCON OXTRAN
2/21, the measurement principle of which is based on the carrier-gas method (ASTM
D3985). In the carrier-gas method, the masked specimen films (without supportive material) with a surface area which in this case is 5 cm' are incorporated into an airtight cell with a cavity on both sides. A carrier gas (95% of N2 and 5% of H2) is passed over one side of the specimen and the measurement gas (100% of 02) is passed over the other side of the specimen, in both cases at atmospheric pressure. The measurement gas that diffuses through the specimen is absorbed by the carrier gas and conducted to a coulometric sensor.
Oxygen concentration can thus be determined as a function of time. All measurements were carried out at 23 Celsius and at a defined relative humidity (RH). Both sides of the specimen were exposed to the defined humidity. Conditioning of the equipment and of the specimen took about half an hour. The machine running time for the measurements was from 1 to 4 days. Two determinations were carried out on each specimen. For the purposes of the tests, the transmission rate (cm3/(m2*day)) of the specimen was standardized to 1 pm and 1 bar, using the average thickness of the foil, which was measured at 5 different points. This standardization gave the permeation rate [cm3 m/(m2*day*bar)].
A first measurement determined oxygen permeability under dry conditions. A
second measurement determined oxygen permeability under moist conditions (85%
relative humidity). Table 1 lists the results. The thickness of the foils was 386.8 m.
:A 02825164 2013 07 18 Table 1: Oxygen permeability of a self-supporting polyalkenamer foil Specimen Transmission Permeation rate, Transmission Permeation rate, rate, 23 C, dry rate, 23 C, 85% RH
23 C, dry [cm3i.tm/(m2*day*bar)] 23 C, 85% RH
[cm31.1m/(m2*day*bar)]
[cm3/(m 2* day)] [cm3/(m2*day)]
D1 0.272 104.8 0.254 98.247 Determination of water-vapor permeability of a self-supporting polyalkenamer foil:
The foil was produced as described above. Water-vapor permeabilities were measured at 85% relative humidity by a MOCON PERMATRAN-W 3/33, the measurement principle of which is likewise based on the carrier-gas method.
The equipment operates in accordance with ASTM F1249. In the carrier-gas method, the masked specimen films (without supportive material) with a surface area which in this case is 5 cm2 are incorporated into an airtight cell with a cavity on both sides. A carrier gas (dry N2) is passed over one side of the specimen and the measurement gas (N2 +
water vapor) is passed over the other side of the specimen, in both cases at atmospheric pressure.
The measurement gas that diffuses through the specimen is absorbed by the carrier gas and conducted to a selective sensor. In the case of water-vapor-measurement equipment, an IR
sensor is used. This permits determination of water-vapor concentration as a function of time. The measurements were carried out at 23 Celsius. Conditioning of the equipment took about 30 minutes. Machine running time for all of the measurements was from 1 to 4 days. The transmission rate of the specimen was measured with relative humidity adjusted with maximum precision to 85%, and the small metrological error in humidity adjustment was then computer-corrected. It was assumed here that there is a linear correlation between the transmission rate and the relative humidity within the range of measurement.
For the purposes of the tests, the transmission rate (g/(m2*day)) of the specimen was standardized, using the average thickness of the foil, which was determined at 5 different :A 02825164 2013 07 18 points. This standardization gave the permeation rate (g*Rm/(m2*day)). Table 2 lists the results. The thickness of the foils was 320 ii.m.
Table 2: Water-vapor permeability of a self-supporting polyalkenamer foil Specimen Transmission Permeation rate, rate, 23 C, 85% RH
23 C, 85% RH [g*[trn/(m2*day)]
[g/(m2*day)]
D1 3.76 1203 Determination of oxygen permeability of a polyalkenamer-coated rubber foil The effect of the oxygen barrier was measured via determination of oxygen transmission of a poly(dicyclopentadiene-co-octenamer)-coated natural rubber substrate. The oxygen barrier was measured with a MOCON OXTRAN 2/21, the measurement principle of which is based on the carrier-gas method (ASTM D3985). The measurement was made at 23 C, using synthetic air (21% of oxygen). Two determinations were carried out on each specimen. Oxygen-barrier effect was measured at relative humidity of 0% and 85%.
Specimen 1:
Uncoated natural rubber (Erwin Telle GmbH, Nuremberg), Substrate thickness: 346 1,tm Specimen 2:
A natural rubber substrate (Erwin Telle GmbH, Nuremberg) of thickness 346 m was cleaned with ethanol and coated with poly(dicyclopentadiene-co-octenamer) of dispersion D1, dried at 50 C for 10 min, and then stored at room temperature for 7 days.
The thickness of the poly(dicyclopentadiene-co-octenamer) coating on the natural rubber substrate was 8 p.m.
:A 02825164 2013 07 18 , .
Table 1 collates the results for oxygen-barrier effect:
Table 1:
Specimen Transmission rate Transmission rate [cm3/(m2*day)], [cm3/(m2*day)], 0% relative humidity 85%
relative humidity Specimen 1 5010 5080 Specimen 2 66.1 93.5
It is preferable to use the copolymer in the form of a polymer layer of thickness at least 1 m. It is preferable that the molar ratio of olefin monomers a) to polycyclic olefin monomers b) is from 99:1 to 15:85 or from 80:20 to 15:85.
The invention also provides a pneumatic tire comprising a rubber material of the invention.
The invention also provides a process for modifying a rubber material with gas-barrier properties, where at least one of the abovementioned copolymers, described in more detail below, is applied to the rubber material or is introduced into the rubber material.
The invention also provides the use of the abovementioned copolymers, described in more detail below, for reducing the gas permeability of rubber material.
The rubber material provided with the copolymer in the invention exhibits a gas-barrier property (e.g. with respect to air, oxygen, nitrogen, argon, carbon dioxide, etc.), and this barrier property is generated or amplified via the use of the copolymer in the invention. The expression "barrier property" means, in comparison with uncoated backing substrate, reduced transmission or permeability with respect to certain substances.
Oxygen- or gas-barrier properties can by way of example be measured by the permeability test described in the examples. It is preferable that the oxygen transmission rate for substrates coated in the invention is less than 30% of the value for the untreated substrates, in particular less than 15% or less than 5%, e.g. from 0.1% to 3% (measured at 23 C and 85% relative humidity).
The copolymers used in the invention can be produced via ring-opening metathesis polymerization. A metathesis reaction is very generally a chemical reaction between two :A 02825164 2013 07 18 compounds where a group is exchanged between two reactants. If this is an organic metathesis reaction, it can be formally represented as exchange of the substituents at a double bond. However, a particularly important reaction is the metal-complex-catalyzed ring-opening metathesis reaction of organic cycloolefin compounds ("ring opening metathesis polymerization", abbreviated to ROMP), where this provides access to polymeric polyolefins. Catalytic metal complexes used are in particular metal carbene complexes of the general structure Met=CR2, where R is an organic moiety. The metal carbene complexes are very susceptible to hydrolysis, and the metathesis reactions can therefore be carried out in anhydrous organic solvents or in the olefins themselves (see by way of example US-A 2008234451, EP-A 0824125). It is also possible to carry out the metathesis reaction of olefins in an aqueous medium in order to avoid complicated purification steps for the removal of large amounts of solvents or unreacted olefins (DE 19859191; US patent application 61/257063).
The copolymers used in the invention are formed from a) at least one olefin monomer selected from the group consisting of monocyclic olefin monomers having one or two endocyclic C-C double bonds and bicyclic olefin monomers having one endocyclic C-C double bond and b) at least one polycyclic olefin monomer having at least two C-C double bonds.
The molar ratio of olefin monomers a) to polycyclic olefin monomers b) is preferably from 80:20 to 15:85, preferably from 65:35 to 20:80.
The ring strain of the olefin monomers a) is preferably at least 2 kcal/mol.
The ring strain of the polycyclic olefin monomers b) is preferably at least 15 kcal/mol, based on the ring with the highest strain.
Examples of olefin monomers a) are cyclobutene, cyclopentene, 2-methylcyclo-pentene-1, 3-methylcyclopentene-1, 4-methylcyclopentene-1, 3-butylcyclopentene-1, cyclohexene, 2-methylcyclohexene-1, 3-methylcyclohexene-1, 4-methylcyclohexene-1, 1,4-dimethylcyclohexene-1, 3,3,5-trimethylcyclohexene-1, cycloheptene, 1,2-dimethylcycloheptene-1, cis-cyclooctene, trans-cyclooctene, 2-methylcyclooctene-1, 3-methylcyclooctene-1, 4-methylcyclooctene-1, 5-methylcyclooctene-1, cyclononene, :A 02825164 2013 07 18 cyclodecene, cycloundecene, cyclododecene, cyclooctadiene, cyclopentadiene, cyclohexadiene and norbornene, and particular preference is given here to monocyclic olefins having one C-C double bond, in particular cis-cyclooctene.
Preferred polycyclic olefin monomers b) are bicyclic dienes, e.g.
norbornadiene, dicyclopentadiene (3a,4,7,7a-tetrahydro-1H-4,7-methanoindene), bicyclo[2.2.2]octa-2,5-diene, bicyclo[3.3.0]octa-2,6-diene, and cyclopentadiene oligomers, e.g.
tricyclopentadiene. Particular preference is given to dicyclopentadiene.
In one preferred embodiment, the copolymer has been formed via ring-opening metathesis polymerization of cis-cyclooctene and dicyclopentadiene.
The copolymers used in the invention are preferably produced in an aqueous medium. The ring-opening metathesis reaction here can be carried out by using water and dispersing agent as initial charge in a polymerization vessel, dissolving an organometallic carbene complex used as catalyst in the cycloolefin, introducing the cycloolefin/metal complex solution into the aqueous dispersing agent solution, converting the resultant cycloolefin/metal complex macroemulsion to a cyclocolefin/metal complex miniemulsion, and converting this at room temperature to an aqueous polyolefin dispersion.
In a preferred method for carrying out the ring-opening metathesis reaction, at least one portion of the water, at least one portion of dispersing agent, and at least one portion of the monomers in the form of an aqueous monomer macroemulsion with an average droplet diameter? 2 pm are used as initial charge, and then the monomer macroemulsion is converted to a monomer miniemulsion with an average droplet diameter < 1500 nm, with introduction of energy, and then the optionally remaining residual amount of the water, the optionally remaining residual amount of the dispersing agent, the optionally remaining residual amount of the monomers, and the entire amount of an organometallic carbene complex used as catalyst are added to the resulting monomer miniemulsion at polymerization temperature.
Organometallic carbene complexes can be used as metathesis catalysts. Examples of metals are transition metals of the 6th, 7th, or 8th transition group, preferably :A 02825164 2013 07 18 molybdenum, tungsten, osmium, rhenium, or ruthenium, of which osmium and ruthenium are preferred. It is particularly preferable to use ruthenium alkylidene complexes. These metathesis catalysts are known from the prior art and are described by way of example in R.H. Grubbs (Ed.) "Handbook of Metathesis", 2003, Wiley-VCH, Weinheim, WO
93/20111, WO 96/04289, WO 97/03096, WO 97/06185, J. Am. Soc. 1996, pp. 784-790, Dalton Trans. 2008, pp.5791-5799, and in Coordination Chemistry Reviews, 2007, 251, pp. 726-764.
The concentration of the copolymers in the aqueous dispersions or solutions used for the coating process is preferably at least 1% by weight, in particular at least 5% by weight, and up to 50% by weight, or up to 70% by weight. The content of the copolymers in the aqueous dispersion is mostly from 10 to 60% by weight, or from 15 to 55% by weight, in particular from 20 to 50% by weight.
The viscosity of preferred aqueous dispersions of the copolymers at pH 4 and at a temperature of 20 C is from 10 to 150 000 mPas, or from 200 to 5000 mPas (measured by a Brookfield viscosimeter at 20 C, 20 rpm, spindle 4). The average particle size of the copolymer particles dispersed in the aqueous dispersion is by way of example from 0.02 to 100 m, preferably from 0.05 to 10 Jim. It can be determined by way of example with the aid of optical microscopy, light scattering, hydrodynamic chromatography, or freeze-fracture electron microscopy.
The rubber constituents of the rubber material can by way of example have been selected from diene rubber, natural rubber, butyl rubber, synthetic polyisoprene, polybutadiene, styrene-butadiene copolymer, isoprene-butadiene rubber, styrene-isoprene-butadiene rubber, acrylonitrile-butadiene rubber, ethylene-propylene rubber, and chloroprene rubber.
The rubber material is preferably a constituent of a pneumatic tire, in particular being an inner layer of a pneumatic tire, or being a carcass of a pneumatic tire.
:A 02825164 2013 07 18 =
In one embodiment, the rubber materials themselves are modified with a solution or aqueous dispersion of at least one of the copolymers described above. In another embodiment, constituents of a rubber-containing article, in particular of pneumatic tires, are modified with the barrier material and are introduced into the rubber-containing article, preferably pneumatic tire. By way of example, the textile cord insert of pneumatic tires can be modified with the copolymers to be used in the invention.
The invention also provides a process for modifying a rubber material, where at least one of the copolymers described herein is applied to the rubber material or is incorporated into the rubber material. The modification can by way of example use one or more of the following methods: impregnation, spraying, spreading, coating, calendering.
The dispersions or solutions used for the coating process can comprise further additives or auxiliaries, e.g. thickeners to adjust rheology, wetting aids, organic or inorganic fillers, or binders.
It is preferable that the copolymer is applied in the form of an aqueous dispersion of the copolymer, and a film is formed via drying of the dispersion on the backing substrate.
The invention also provides a pneumatic tire comprising a rubber material of the invention. The copolymer here can have been applied by one or more of the following methods:
- application on at least one portion of the surface or on the entire surface of the inner layer of the tire;
- introduction into the material of the inner layer of the tire;
- in the form of film, in the form of unsupported foil, or in the form of coating of a foil backing, where the films or foils can have been introduced in addition to a rubber-based inner layer of a tire or as replacement form for an inner layer of a tire, into the interior of a tire;
- in the form of binder or coating of a fiber cord insert of the pneumatic tire;
- in the form of laminate between two or more backing foils, where the laminate has been introduced into the interior of the tire.
:A 02825164 2013 07 18 A film applied can take the form of spray film or of spread film, for example through roll-, doctor-, airbrush-, or cast-spreading processes. The material applied can also take the form of a foil which serves as backing and then is crosslinked (vulcanized) or adhesive-bonded to the carcass. Examples of suitable foil backings are those made of rubber, of polyolefin, of polyester, of polyamide, or of polyurethane.
As an alternative, it is also possible to use the copolymer in the form of a laminate between two backing foils, where the laminate is then crosslinked or adhesive-bonded to the carcass.
The copolymers can also be used in the form of self-supporting film.
The application process can by way of example be undertaken on coating machines, by applying the coating composition to a backing foil made of a plastic. If materials are used in the form of webs, the polymer dispersions is usually applied from a trough by way of an applicator roll, and rendered uniform by an airbrush.
Examples of other successful methods of applying the coating use the reverse gravure process, or use spray processes, or use a metering bar, or use other coating processes known to the person skilled in the art. The backing substrate here has a coating on at least one side, i.e. can have a coating on one or both sides.
In order to achieve a further improvement in adhesion on a foil, the backing foil can be subjected in advance to a corona treatment or, as an alternative, adhesion promoters, such as polyethyleneimines, can be used. The amounts applied to the sheet materials are preferably by way of example from Ito 800 g (of polymer, solid) per m2, preferably from 1 to 400 g/m2, or from 5 to 200 g/m2. Once the coating compositions have been applied to the backing substrates, the solvent or dispersion medium is evaporated. To this end, it is possible by way of example in the case of continuous operation to pass the material through a drying tunnel which can have an infrared irradiation apparatus. The coated and dried material is then passed over a cooling roll and finally is wound up. The thickness of the dried coating is at least 1 [im preferably from 1 to 400 1.1m, particularly :A 02825164 2013 07 18 . .
preferably from 5 to 200 gm. The thickness of the backing foils is generally in the range from 10 gm to 1 cm.
The substrates coated in the invention exhibit excellent gas-barrier effect.
Examples The following copolymer dispersions were used (monomer ratios are based on molar ratios):
Dispersion Dl:
30% strength aqueous poly(dicyclopentadiene-co-octenamer) dispersion, produced via ring-opening metathesis polymerization (ROMP) starting from dicyclopentadiene and cis-cyclooctene (50:50) with use of a ruthenium-alkylidene catalyst.
Number-average particle size: 270 nm Dispersion D2:
30% strength aqueous poly(dicyclopentadiene-co-octenamer) dispersion, produced via ring-opening metathesis polymerization (ROMP) starting from dicyclopentadiene and cis-cyclooctene (60:40) with use of a ruthenium-alkylidene catalyst.
Dispersion D3:
30% strength aqueous poly(dicyclopentadiene-co-octenamer) dispersion, produced via ring-opening metathesis polymerization (ROMP) starting from dicyclopentadiene and cis-cyclooctene (70:30) with use of a ruthenium-alkylidene catalyst.
Dispersion D4:
40% strength aqueous poly(dicyclopentadiene-co-octenamer) dispersion, produced via ring-opening metathesis polymerization (ROMP) with use of a ruthenium-alkylidene catalyst starting from dicyclopentadiene and cis-cyclooctadiene (50:50).
Number-average particle size of dispersed latex particles: 265 nm :A 02825164 2013 07 18 Dispersion D5:
30% strength aqueous poly(dicyclopentadiene-co-octenamer) dispersion, produced via ring-opening metathesis polymerization (ROMP) with use of a ruthenium-alkylidene catalyst starting from dicyclopentadiene and cis-cyclooctene (2:98).
Number-average particle size of dispersed latex particles: 419 nm Determination of oxygen permeability of a self-supporting polyalkenamer foil:
The foil was produced by casting a polyalkenamer dispersion into a silicone mold of dimensions 15 cm x 10 cm x 0.5 cm (length x width x height). The cast dispersion film was dried at 25 C for 48 h and then heat-conditioned at a temperature of 65 C
for minutes.
Dry and moist oxygen permeabilities were measured with a MOCON OXTRAN
2/21, the measurement principle of which is based on the carrier-gas method (ASTM
D3985). In the carrier-gas method, the masked specimen films (without supportive material) with a surface area which in this case is 5 cm' are incorporated into an airtight cell with a cavity on both sides. A carrier gas (95% of N2 and 5% of H2) is passed over one side of the specimen and the measurement gas (100% of 02) is passed over the other side of the specimen, in both cases at atmospheric pressure. The measurement gas that diffuses through the specimen is absorbed by the carrier gas and conducted to a coulometric sensor.
Oxygen concentration can thus be determined as a function of time. All measurements were carried out at 23 Celsius and at a defined relative humidity (RH). Both sides of the specimen were exposed to the defined humidity. Conditioning of the equipment and of the specimen took about half an hour. The machine running time for the measurements was from 1 to 4 days. Two determinations were carried out on each specimen. For the purposes of the tests, the transmission rate (cm3/(m2*day)) of the specimen was standardized to 1 pm and 1 bar, using the average thickness of the foil, which was measured at 5 different points. This standardization gave the permeation rate [cm3 m/(m2*day*bar)].
A first measurement determined oxygen permeability under dry conditions. A
second measurement determined oxygen permeability under moist conditions (85%
relative humidity). Table 1 lists the results. The thickness of the foils was 386.8 m.
:A 02825164 2013 07 18 Table 1: Oxygen permeability of a self-supporting polyalkenamer foil Specimen Transmission Permeation rate, Transmission Permeation rate, rate, 23 C, dry rate, 23 C, 85% RH
23 C, dry [cm3i.tm/(m2*day*bar)] 23 C, 85% RH
[cm31.1m/(m2*day*bar)]
[cm3/(m 2* day)] [cm3/(m2*day)]
D1 0.272 104.8 0.254 98.247 Determination of water-vapor permeability of a self-supporting polyalkenamer foil:
The foil was produced as described above. Water-vapor permeabilities were measured at 85% relative humidity by a MOCON PERMATRAN-W 3/33, the measurement principle of which is likewise based on the carrier-gas method.
The equipment operates in accordance with ASTM F1249. In the carrier-gas method, the masked specimen films (without supportive material) with a surface area which in this case is 5 cm2 are incorporated into an airtight cell with a cavity on both sides. A carrier gas (dry N2) is passed over one side of the specimen and the measurement gas (N2 +
water vapor) is passed over the other side of the specimen, in both cases at atmospheric pressure.
The measurement gas that diffuses through the specimen is absorbed by the carrier gas and conducted to a selective sensor. In the case of water-vapor-measurement equipment, an IR
sensor is used. This permits determination of water-vapor concentration as a function of time. The measurements were carried out at 23 Celsius. Conditioning of the equipment took about 30 minutes. Machine running time for all of the measurements was from 1 to 4 days. The transmission rate of the specimen was measured with relative humidity adjusted with maximum precision to 85%, and the small metrological error in humidity adjustment was then computer-corrected. It was assumed here that there is a linear correlation between the transmission rate and the relative humidity within the range of measurement.
For the purposes of the tests, the transmission rate (g/(m2*day)) of the specimen was standardized, using the average thickness of the foil, which was determined at 5 different :A 02825164 2013 07 18 points. This standardization gave the permeation rate (g*Rm/(m2*day)). Table 2 lists the results. The thickness of the foils was 320 ii.m.
Table 2: Water-vapor permeability of a self-supporting polyalkenamer foil Specimen Transmission Permeation rate, rate, 23 C, 85% RH
23 C, 85% RH [g*[trn/(m2*day)]
[g/(m2*day)]
D1 3.76 1203 Determination of oxygen permeability of a polyalkenamer-coated rubber foil The effect of the oxygen barrier was measured via determination of oxygen transmission of a poly(dicyclopentadiene-co-octenamer)-coated natural rubber substrate. The oxygen barrier was measured with a MOCON OXTRAN 2/21, the measurement principle of which is based on the carrier-gas method (ASTM D3985). The measurement was made at 23 C, using synthetic air (21% of oxygen). Two determinations were carried out on each specimen. Oxygen-barrier effect was measured at relative humidity of 0% and 85%.
Specimen 1:
Uncoated natural rubber (Erwin Telle GmbH, Nuremberg), Substrate thickness: 346 1,tm Specimen 2:
A natural rubber substrate (Erwin Telle GmbH, Nuremberg) of thickness 346 m was cleaned with ethanol and coated with poly(dicyclopentadiene-co-octenamer) of dispersion D1, dried at 50 C for 10 min, and then stored at room temperature for 7 days.
The thickness of the poly(dicyclopentadiene-co-octenamer) coating on the natural rubber substrate was 8 p.m.
:A 02825164 2013 07 18 , .
Table 1 collates the results for oxygen-barrier effect:
Table 1:
Specimen Transmission rate Transmission rate [cm3/(m2*day)], [cm3/(m2*day)], 0% relative humidity 85%
relative humidity Specimen 1 5010 5080 Specimen 2 66.1 93.5
Claims (15)
1. A rubber material modified with a barrier material in the form of a copolymer which can be produced via ring-opening metathesis polymerization of a) at least one olefin monomer selected from the group consisting of monocyclic olefin monomers having one or two endocyclic C-C double bonds and bicyclic olefin monomers having one endocyclic C-C double bond and b) at least one polycyclic olefin monomer having at least two C-C double bonds.
2. The rubber material according to the preceding claim, wherein the molar ratio of olefin monomers a) to polycyclic olefin monomers b) is from 99:1 to 15:85, preferably from 80:20 to 15:85.
3. The rubber material according to any of the preceding claims, wherein the ring strain of the olefin monomers a) is at least 2 kcal/mol and the polycyclic olefin monomers b) have been selected from bicyclic dienes having ring strain of at least 15 kcal/mol.
4. The rubber material according to any of the preceding claims, wherein the copolymer can be produced via ring-opening metathesis polymerization of cis-cyclooctene and dicyclopentadiene.
5. The rubber material according to any of the preceding claims, wherein the rubber constituents of the rubber material have been selected from diene rubber, natural rubber, butyl rubber, synthetic polyisoprene, polybutadiene, styrene-butadiene copolymer, isoprene-butadiene rubber, styrene-isoprene-butadiene rubber, acrylonitrile-butadiene rubber, ethylene-propylene rubber, and chloroprene rubber.
6. The rubber material according to any of the preceding claims, which is a constituent of a pneumatic tire.
7. The rubber material according to the preceding claim, which is an inner layer of a pneumatic tire or is a carcass of a pneumatic tire.
8. A pneumatic tire comprising rubber material according to any of the preceding claims.
9. The pneumatic tire according to the preceding claim, wherein the copolymer has been applied by one or more of the following methods:
- application on at least one portion of the surface or on the entire surface of the inner layer of the tire;
- introduction into the material of the inner layer of the tire;
- in the form of film, in the form of unsupported foil, or in the form of coating of a foil backing, where the films or foils can have been introduced in addition to a rubber-based inner layer of a tire or as replacement form for an inner layer of a tire, into the interior of a tire;
- in the form of binder or coating of a fiber cord insert of the pneumatic tire;
- in the form of laminate between two or more backing foils, where the laminate has been introduced into the interior of the tire.
- application on at least one portion of the surface or on the entire surface of the inner layer of the tire;
- introduction into the material of the inner layer of the tire;
- in the form of film, in the form of unsupported foil, or in the form of coating of a foil backing, where the films or foils can have been introduced in addition to a rubber-based inner layer of a tire or as replacement form for an inner layer of a tire, into the interior of a tire;
- in the form of binder or coating of a fiber cord insert of the pneumatic tire;
- in the form of laminate between two or more backing foils, where the laminate has been introduced into the interior of the tire.
10. A process for modifying a rubber material, where at least one copolymer is applied to the rubber material or is introduced into the rubber material, and the copolymer can be produced via ring-opening metathesis polymerization of a) at least one olefin monomer selected from the group consisting of monocyclic olefin monomers having one or two endocyclic C-C double bonds and bicyclic olefin monomers having one endocyclic C-C double bond and b) at least one polycyclic olefin monomer having at least two C-C double bonds.
11. The process according to the preceding claim, wherein the modification uses one or more of the following methods: impregnation, spraying, spreading, coating, calendering.
12. The process according to any of the preceding process claims, wherein the copolymer is applied in the form of an aqueous dispersion of the copolymer and a film is formed via drying of the dispersion on the backing substrate.
13. The use of a copolymer for reducing the gas permeability of rubber material, where the copolymer can be produced via ring-opening metathesis polymerization of a) at least one olefin monomer selected from the group consisting of monocyclic olefin monomers having one or two endocyclic C-C double bonds and bicyclic olefin monomers having one endocyclic C-C double bond and b) at least one polycyclic olefin monomer having at least two C-C double bonds.
14. The use according to the preceding claim, wherein the copolymer is used in the form of an aqueous dispersion of the copolymer for producing a barrier film.
15. The use according to any of the preceding use claims, wherein the molar ratio of olefin monomers a) to polycyclic olefin monomers b) is from 80:20 to 15:85, and/or the layer thickness used of the copolymer is at least 1 µm.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP11154240.3 | 2011-02-11 | ||
| EP11154240 | 2011-02-11 | ||
| PCT/EP2012/051992 WO2012107418A1 (en) | 2011-02-11 | 2012-02-07 | Rubber material with barrier material formed from cycloolefin copolymers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2825164A1 true CA2825164A1 (en) | 2012-08-16 |
Family
ID=45592370
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2825164A Abandoned CA2825164A1 (en) | 2011-02-11 | 2012-02-07 | Rubber material with barrier material made of cycloolefin copolymers |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP2673304B1 (en) |
| JP (1) | JP5907995B2 (en) |
| CN (1) | CN103370343B (en) |
| BR (1) | BR112013019826A2 (en) |
| CA (1) | CA2825164A1 (en) |
| ES (1) | ES2566173T3 (en) |
| MX (1) | MX351535B (en) |
| WO (1) | WO2012107418A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2880775A1 (en) | 2012-08-13 | 2014-02-20 | Basf Se | Rubber material with barrier material made of cycloolefin copolymers |
| MX2018005943A (en) | 2015-11-13 | 2018-08-14 | Basf Se | Aqueous compositions based on polyalkenamers. |
Family Cites Families (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3778420A (en) * | 1970-07-27 | 1973-12-11 | Phillips Petroleum Co | Copolymers of cyclic monoolefins and cyclic polyolefin compounds |
| JPS5647124B2 (en) * | 1973-06-26 | 1981-11-07 | ||
| US4025708A (en) * | 1975-03-24 | 1977-05-24 | The B. F. Goodrich Company | Process for polymerizing cyclopentene |
| IN168456B (en) * | 1985-12-16 | 1991-04-06 | Goodrich Co B F | |
| JPH04198317A (en) * | 1990-11-28 | 1992-07-17 | Nippon Zeon Co Ltd | Production of norbornene polymer |
| US5312940A (en) | 1992-04-03 | 1994-05-17 | California Institute Of Technology | Ruthenium and osmium metal carbene complexes for olefin metathesis polymerization |
| AU691645B2 (en) | 1992-04-03 | 1998-05-21 | California Institute Of Technology | High activity ruthenium or osmium metal carbene complexes for olefin metathesis reactions and synthesis thereof |
| US5728785A (en) | 1995-07-07 | 1998-03-17 | California Institute Of Technology | Romp polymerization in the presence of peroxide crosslinking agents to form high-density crosslinked polymers |
| US5831108A (en) | 1995-08-03 | 1998-11-03 | California Institute Of Technology | High metathesis activity ruthenium and osmium metal carbene complexes |
| US6586082B1 (en) * | 1995-11-15 | 2003-07-01 | 3M Innovative Properties Company | Polymer-saturated paper articles |
| EP0824125A1 (en) | 1996-08-13 | 1998-02-18 | Ciba SC Holding AG | Covering composition based on dicyclopentadiene derivatives |
| US7025851B2 (en) * | 1998-12-11 | 2006-04-11 | Lord Corporation | Contact metathesis polymerization |
| DE19859191A1 (en) | 1998-12-21 | 2000-06-29 | Basf Ag | Aqueous polyalkylene dispersion useful for production of coatings, adhesives and binders is prepared by ring opening metathesis polymerization of poorly water soluble cyclic olefin |
| BR0008022A (en) * | 1999-02-05 | 2001-11-06 | Materia Inc | Polyolefin compositions with variable density and processes for their production and use |
| CA2318711A1 (en) * | 2000-09-13 | 2002-03-13 | Lord Corporation | Contact metathesis polymerization |
| WO2005028402A2 (en) * | 2003-09-25 | 2005-03-31 | Ciba Specialty Chemicals Holding Inc. | Romp with fluorinated groups |
| GB0428172D0 (en) | 2004-12-23 | 2005-01-26 | Ici Plc | Olefin metathesis polymerisation |
| CA2597143C (en) | 2005-02-08 | 2013-05-07 | Kuraray Co., Ltd. | Process for producing ring-opening metathesis polymer |
| WO2009154849A1 (en) * | 2008-06-20 | 2009-12-23 | 3M Innovative Properties Company | Molded microstructured articles and method of making same |
| CN103210013A (en) * | 2010-09-03 | 2013-07-17 | 巴斯夫欧洲公司 | Barrier coating composed of cycloolefin copolymers |
-
2012
- 2012-02-07 ES ES12703771.1T patent/ES2566173T3/en active Active
- 2012-02-07 BR BR112013019826-5A patent/BR112013019826A2/en not_active Application Discontinuation
- 2012-02-07 MX MX2013008516A patent/MX351535B/en active IP Right Grant
- 2012-02-07 EP EP12703771.1A patent/EP2673304B1/en not_active Not-in-force
- 2012-02-07 WO PCT/EP2012/051992 patent/WO2012107418A1/en active Application Filing
- 2012-02-07 CN CN201280008616.2A patent/CN103370343B/en not_active Expired - Fee Related
- 2012-02-07 CA CA2825164A patent/CA2825164A1/en not_active Abandoned
- 2012-02-07 JP JP2013552931A patent/JP5907995B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP2673304A1 (en) | 2013-12-18 |
| MX351535B (en) | 2017-10-18 |
| EP2673304B1 (en) | 2016-02-03 |
| WO2012107418A1 (en) | 2012-08-16 |
| BR112013019826A2 (en) | 2020-11-17 |
| JP2014506610A (en) | 2014-03-17 |
| CN103370343B (en) | 2016-11-09 |
| MX2013008516A (en) | 2013-08-12 |
| JP5907995B2 (en) | 2016-04-26 |
| CN103370343A (en) | 2013-10-23 |
| ES2566173T3 (en) | 2016-04-11 |
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| AU773449B2 (en) | Contact metathesis polymerization |
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