EP3374413A1 - Wässrige zusammensetzungen auf basis von polyalkenameren - Google Patents
Wässrige zusammensetzungen auf basis von polyalkenamerenInfo
- Publication number
- EP3374413A1 EP3374413A1 EP16795024.5A EP16795024A EP3374413A1 EP 3374413 A1 EP3374413 A1 EP 3374413A1 EP 16795024 A EP16795024 A EP 16795024A EP 3374413 A1 EP3374413 A1 EP 3374413A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polymer
- palk
- composition according
- aqueous
- range
- 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.)
- Withdrawn
Links
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0828—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing sulfonate groups or groups forming them
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3234—Polyamines cycloaliphatic
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- 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
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D131/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
- C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C09D131/04—Homopolymers or copolymers of vinyl acetate
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
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- 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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- 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
- C08G2261/3324—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 norbornene
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- 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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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/60—Glass transition temperature
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/61—Permeability
- C08G2261/612—Permeability for gases
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- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/08—Homopolymers or copolymers of acrylic acid esters
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/06—Polyurethanes from polyesters
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- C08J2445/00—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers
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- C08L2201/54—Aqueous solutions or dispersions
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
Definitions
- the present invention relates to aqueous compositions based on polyalkenamers and their use as barrier coatings.
- a pneumatic vehicle tire In the case of pneumatic vehicle tires, it is important to ensure that the compressed air or gas, with the required pressure and gas volume, will allow the operation of the tire to function for as long as possible.
- conventional pneumatic tires in the tire interior are provided with a gas-impermeable rubber layer.
- This tire inner layer is used to seal the gas-filled interior and replaced in tubeless tires the hose.
- a pneumatic vehicle tire is usually constructed of several materials and also contains metallic components, for example as carcass material. These materials and tire ingredients are partially sensitive to oxidation. Therefore, the tire innerliner also serves to protect the tire materials and ingredients from oxidation. Due to the high mechanical stresses to which vehicle tires are exposed, the materials used must have corresponding mechanical properties, in particular a good elasticity.
- halide butyl rubbers and blends with butyl rubbers have been used as barrier coatings in vehicle tires. These have the disadvantage that sufficient gas barrier properties can only be achieved by a thick coating, which is unfavorable to the weight of the tire. In addition, the materials are expensive and limited in the market.
- EP 1932688 A1, US 8,541, 527 B2, and US 3,778,420 describe the use of polyalkenamers in rubber materials.
- the polyalkeneamines used are unoxidized.
- EP 1932688 describes run-fiat tires having elastomeric layers containing polyalkenamers.
- WO 2012/028530, WO2012 / 107418 and WO 2014/0268865 describe the use of aqueous dispersions of polyalkenamers for the preparation of barrier coatings on rubber materials
- EP 1664183 B1 describes mixtures of polyurethane dispersions and latex dispersions.
- the films made from these blends are called Gas barrier used, wherein the barrier is generated by the polyurethane.
- the best latex / polyurethane blend has a permeation of 1.5 * 10 -5 (cm 3 mm) / (m 2 h Pa), which corresponds to 36 (cm 3 mm) / (m 2 day bar) invention
- the present invention is based on the object to provide compositions which are suitable for the production of coatings or films with good barrier properties, in particular with a low permeability to non-polar gases such as oxygen.
- the compositions should be stable.
- the compositions should be suitable for the production of films or films and coatings.
- the production should be simple, inexpensive and insensitive.
- the films or films and coatings produced from the compositions should have advantageous mechanical properties, in particular good elasticity and low brittleness.
- the films and coatings produced from the compositions should have an advantageous barrier effect against gases, preferably a good oxygen barrier effect, with simultaneously advantageous mechanical properties, preferably low brittleness and high elongation at break.
- the invention relates to aqueous compositions containing
- the aqueous compositions are particularly suitable for the production of films and barrier coatings which have a very good barrier to gases, such as air, oxygen, nitrogen, argon, carbon dioxide, and in particular to oxygen and oxygen-containing gases, such as air.
- the films and coatings have very good mechanical properties, in particular a high elongation at break with good tear strength.
- the invention also relates to the use of the aqueous composition according to the invention for the production of barrier films and barrier coatings, in particular on rubber materials.
- the invention also relates to coatings obtainable by a process comprising (a) applying an aqueous composition of the invention to the surface of a sheet carrier, and (b) removing the volatile components of the composition to obtain a coating.
- the invention furthermore relates to polymer films which are produced using an aqueous composition according to the invention and which can be prepared, in particular, by drying a film of the aqueous polymer composition comprising at least one polymer PALK and at least one polymer P2.
- Another object of the invention is a polymer powder obtainable by drying an aqueous composition according to the invention.
- the invention further provides a process for the preparation of the aqueous compositions according to the invention which comprises mixing at least one aqueous dispersion PALK-D comprising at least one polymer PALK with at least one aqueous dispersion P2-D comprising at least one polymer P2.
- polymer encompasses both homopolymers and copolymers and terpolymers.
- polymer dispersion denotes an aqueous dispersion of similar or different polymer particles in a liquid phase in which the polymer is insoluble.
- a polymer dispersion may have further constituents, for example surface-active compounds, emulsifiers, stabilizers or other compounds.
- the liquid phase usable besides water also mixtures of water which contain one or more water-miscible organic solvents, but wherein water is the main constituent of the mixture and preferably at least 80 wt .-%, in particular at least 90 wt .-%, based on the total amount of the solvent.
- a water-miscible organic solvent typically, tel has a solubility in water of at least 100 g / L at 25 ° C and 1 bar.
- water-miscible organic solvents are especially alkanols having 1 to 6 carbon atoms such as methanol, ethanol, propanol, isopropanol, n-butanol, 2-butanol and tert-butanol and polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol and glycerol.
- polymer particles designates particles of one or more polymers, wherein in the case that the polymer particle is composed of a plurality of polymers, these may be identical or different.
- Barrier coatings are coatings on a surface of a support which imparts to the support an improved barrier effect, in particular to gases, such as air, oxygen, nitrogen, argon, carbon dioxide, and in particular to oxygen and oxygen-containing gas mixtures, such as air.
- Barrier films are understood as meaning films which have at least one layer which gives the film an improved barrier effect, in particular to gases, such as air, oxygen, nitrogen, argon, carbon dioxide, and in particular to oxygen and oxygen-containing gases, such as air.
- the aqueous compositions according to the invention contain as a first constituent at least one polymer PALK. This is present in the aqueous composition in the form of polymer particles.
- the polymer particles of the polymer PALK preferably have a volume-average particle size, determined by analytical ultracentrifuge (AUC), in the range from 200 to 1000 nm, preferably from 200 to 500 nm.
- the polymer PALK has a density in the range of 0.75 to 0.97 g / cm 3 , more preferably in the range of 0.85 to 0.97 g / cm 3 , determined by means of a H 2 0-D 2 0 Sedimentation analysis (HDA).
- HDA H 2 0-D 2 0 Sedimentation analysis
- the density and the mean particle diameter of the particles can be determined, for example, by means of turbidity optics using an analytical ultracentrifuge (AUC) as described in "Analytical Ultracentrifugation of polymers and nanoparticles" (Springer Laboratory 2006, W. Gurchtie and L. Börger)
- AUC analytical ultracentrifuge
- the density is determined by measuring sedimentation rates under otherwise identical conditions in three solvents of different densities (H2O, H2O / D2O (1: 1) and D2O) .
- the particle size can be determined from the sedimentation rate.
- the particle size can also be determined as described in ISO 13318.
- the evaluation of the sedimentation in H2O and D2O can be carried out with the same centrifuge and the same optics. The expert can adjust the evaluation to determine the density.
- the polymer PALK has a glass transition temperature Tg determined by differential scanning calorimetry, DSC, in the range of -100 to -20 ° C, more preferably in the range of -90 to -30 ° C.
- Tg glass transition temperature
- the glass transition temperature (Tg) was determined using a differential scanning calorimeter DSC Q2000 V24.4 Build 1 16 from TA Instruments. The heating rate was 20 K / min. The measurement can be carried out according to the standard DIN N ISO 1 1352-2 or modified from it.
- the polymer PALK is at least partially oxidized in the barrier film or barrier coating.
- oxidized means that the polymer PALK carries at least one oxygen-containing group.
- the oxidation of the polymer PALK can be carried out, for example, by storage in an oxygen-containing environment, preferably using radiation energy, thermal energy or oxidation accelerators or a combination thereof.
- the oxidation of the polymer PALK can be done, for example, in air under daylight and at room temperature (about 20-25 ° C).
- the oxidation can be accelerated by radiation energy, thermal energy or oxidation accelerators.
- Oxidation accelerators which can be used are, for example, chemical oxidation accelerators, such as transition metals and transition metal compounds known therefor, in particular those of iron, zirconium, manganese, zinc or cobalt.
- the aqueous polymer composition containing at least one polymer PALK and at least one polymer P2 comprises at least one oxidation accelerator.
- This oxidation accelerator is preferably selected from transition metal compounds, in particular from Zr-containing compounds, Zn-containing compounds and Co-containing compounds and mixtures thereof, such as Octa-Soligen® 144 aqua and Octa-Soligen® 141 Z from OMG Borchers.
- the polymers PALK, their aqueous dispersions and processes for the preparation of the dispersions are known, for. From WO 201 1/051374, WO 2012/028530,
- aqueous dispersions of the polymers PALK used according to the invention can be prepared by ring-opening metathesis polymerization of cyclic olefins by the methods described therein.
- a metathesis reaction Under a metathesis reaction is generally understood a chemical reaction between two compounds in which a group is exchanged between the two reactants. If this is an organic metathesis reaction, the substituents on a double bond are formally exchanged. Of particular importance, however, is the metal complex-catalyzed ring-opening metathesis reaction of organic cycloolefin compounds, or ROMP (ring opening metathesis polymerization), which makes polyalkeneamers accessible.
- ROMP ring opening metathesis polymerization
- the metathesis reactions can be carried out in anhydrous organic solvents or the olefins themselves (see for example US-A 2008234451, EP-A 0824125).
- the metathesis reaction of olefins can also be carried out in aqueous medium (DE 19859191, US Patent Application 61/257063, WO 201 1/051374, WO 2012 / 028530, WO 2012/076426, WO2012 / 107418 and
- the polyalkene esters PALK are generally obtainable by ring-opening metathesis polymerization of at least one cyclic olefin monomer O which has at least one endocylic double bond.
- the cyclic olefin monomer O has at least one 5- to
- the carbon ring of the olefin monomer O can be replaced by one or more, for. B. 1, 2, 3, 4, 5 or 6, Ci-C6-alkyl groups or C3-C6-cycloalkyl groups, for. B. be substituted by methyl or ethyl groups.
- the cyclic olefin monomer may also contain one or more, e.g. B. 1, 2, or 3, further carbon rings, which in turn may have an endocyclic double bond and / or by one or more, for. B. 1, 2, 3, 4, 5 or 6, Ci-C4-alkyl groups, for. B.
- the olefin monomer O is preferably pure hydrocarbons, which are preferably not substituted with heteroatoms.
- Olefin monomers O are z.
- cyclopentene 1, 3-cyclopentadiene, dicyclopentadiene
- the olefin monomers comprise O
- At least one first olefin monomer 01 selected from the group consisting of monocyclic olefin monomers having at least one endocyclic CC double bond, wherein in the position alpha to the double bond no tertiary carbon atom carrying hydrogen atom is present, and b) optionally one or a plurality of further olefin monomers 02 selected from the group consisting of
- monocyclic olefin monomers 02.1 having an endocyclic double bond, wherein a tertiary carbon atom carrying a hydrogen atom is present in at least one alpha position relative to the double bond; bicyclic olefin monomers 02.2 having at least one endocyclic double bond and two hydrocarbon rings,
- polycyclic olefin monomers 02.3 having at least one endocyclic double bond and at least 3, e.g. B. 3 or 4 hydrocarbon rings.
- the olefin monomer 01 is at least 20% by weight, especially at least 50% by weight, based on the total amount of the olefin monomers O.
- the at least one olefin monomer 01 may be the sole monomer.
- the olefin monomer O comprises at least one olefin monomer O1 and at least one olefin monomer O2.
- the molar ratio of olefin monomers 01 to olefin monomers 02 is generally in the range of 99: 1 to 1:99; preferably in the range of 90:10 to 10:90; more preferably in the range of 50:50 to 80:20.
- Olefin monomers 01 are e.g.
- Preferred monomers 02.1 are 3-alkyl-cycloalk-1-enes having preferably 1 to 10 or 1 to 4 C atoms in the alkyl group and preferably 5 to 8 C atoms in the cycloalkene ring. Suitable z. B. 3-methylcyclopent-1-ene, 3-butylcyclopent-1-ene, 3-methylcyclohex-1-ene, 3-methylcyclooct-1-ene, 3-propylcyclopent-1-ene, 3-methyl-cyclooct-1 - and 3,3,5-trimethylcyclohex-1-ene.
- Preferred olefin 02.2 is norbornene.
- Example of a polycyclic olefin 02.3 is dicyclopentadiene
- no polycyclic dienes 02.3 are used as the olefin monomer b).
- the polymers are PALK formed by ring-opening metathesis polymerization of cis-cyclooctene or a mixture of cis-cyclooctene and norbornene or a mixture of cis-cyclooctene and dicyclopentadiene.
- the preparation of the polymers PALK is preferably carried out as emulsion polymerization or miniemulsion polymerization in an aqueous medium in the presence of an organometallic carbene complex suitable for the metathesis polymerization by a process of the prior art, for. B. according to the in WO 201 1/051374,
- the ring-opening metathesis reaction of the olefin monomers can be carried out by initially introducing water and optionally dispersing agent into a polymerization vessel, dissolving an organometallic carbene complex in the polymerizable olefin or olefin mixture or in a mixture of olefin and an organic solvent, introducing the olefin / carbene complex solution into the aqueous dispersant solution, optionally converting the resulting olefin / carbene complex macroemulsion into a miniemulsion and converting the macroemulsion or miniemulsion at the polymerization temperature to an aqueous polyolefin dispersion.
- an organometallic carbene complex suitable for metathesis polymerization for example in the form of an aqueous solution of a water-soluble carbene complex, to which macro- or miniemulsion gives and converts these into an aqueous polyolefin dispersion.
- the ring-opening metathesis reaction is preferably carried out by initially introducing at least a subset of the water, at least a subset of dispersant, at least a portion of the monomers in the form of an aqueous monomer macro emulsion having an average droplet diameter> 2000 nm, then applying energy, for example by means of ultrasound or by Hochlichhomogenisa- tion, the monomer macroemulsion in a Monomerminiemulsion having a mean droplet diameter ⁇ 1500 nm, in particular ⁇ 1000 nm transferred, and then the resulting Monomerenminiemulsion at polymerization temperature, the remaining amount of water remaining if desired, the remaining amount of dispersant remaining if any, remaining amount the monomers and the total amount of an organometallic carbene complex used as a catalyst, preferably in the form of an aqueous solution.
- organometallic carbene complexes can be used.
- Metals are z.
- Such metathesis catalysts are known from the prior art and are z. In RH Grubbs (Ed.) "Handbook of Metathesis", 2003, Wiley-VCH, Weinheim, WO 93/20111, WO96 / 04289, WO97 / 03096, WO97 / 06185, J. Am.
- Suitable dispersants are, for example, those in WO 201 1/051374 and
- Suitable dispersants are both the neutral, anionic or cationic protective colloids customarily used for carrying out free-radical aqueous emulsion polymerizations, as well as anionic or nonionic emulsifiers.
- Preferred dispersants comprise at least one nonionic emulsifier.
- nonionic emulsifiers are ethoxylated mono-, di- and tri-alkylphenols (EO degree: 3 to 50, alkyl radical: C 4 to C 12) and ethoxylated fatty alcohols (EO degree: 3 to 80, alkyl radical: Cs to C36).
- Lutensol ® A grades C 2 C 4 fatty alcohol ethoxylates, EO units: 3 to 8
- Lutensol ® AO brands C 2 C 4 fatty alcohol ethoxylates, EO units: 3 to 8
- the organic solvents can serve to dissolve the monomers and thus to lower their concentration in the macro- or miniemulsion droplets and, on the other hand, to ensure the stability of the thermodynamically unstable miniemulsion droplets (by preventing the so-called Ostwald ripening).
- Suitable organic solvents are, in particular, liquid aliphatic and aromatic hydrocarbons having 5 to 30 C atoms, such as, for example, n-pentane and isomers, cyclopentane, n-hexane and isomers, cyclohexane, n-heptane and isomers, n-octane and isomers.
- Nonane and isomers Nonane and isomers, n-decane and isomers, n-dodecane and isomers, n-tetradecane and isomers, n-hexadecane and isomers, n-octadecane and isomers, benzene, toluene, ethylbenzene, cumene, o-, m- or p- Xylene, and generally hydrocarbon mixtures in the boiling range of 30 to 250 ° C.
- esters such as fatty acid esters having 10 to 28 carbon atoms in the acid moiety and 1 to 10 carbon atoms in the alcohol moiety or esters of carboxylic acids and fatty alcohols having 1 to 10 carbon atoms in the carboxylic acid moiety and 10 to 28 carbon atoms in the alcohol moiety ,
- the organic solvent is selected from the group comprising n-hexane, n-octane, n-decane, n-tetradecane, n-hexadecane and their isomeric compounds, benzene, toluene and / or ethylbenzene.
- non-water-soluble oligomers or polymers for preventing Ostwald ripening can be used, which even under polymerization conditions (given pressure and given temperature) have a low water solubility, ie a solubility ⁇ 10 g, advantageously ⁇ 1 g and in particular advantageously ⁇ 0.2 g per liter of deionized water.
- Suitable substances here are, for example, polystyrene, polystearyl acrylate, polybutadiene, polyisobutylene, polynorbornene, polyoctenamer, polydicyclopentadiene or styrene-butadiene rubber.
- the aqueous compositions according to the invention also contain at least one polymer P2 which has at least one polar group in the repeat units and no unsaturated C-C bond.
- the polymer P2 is also present in the aqueous composition in the form of polymer particles.
- the polymer P2 is preferably present in the form of polymer particles having an average particle size, determined by analytical ultracentrifuge (AUC), in the range from 20 to 500 nm, particularly preferably from 30 to 250 nm.
- AUC analytical ultracentrifuge
- the polymer P2 has a density in the range of 1, 0 to 1, 5 g / cm 3 , particularly preferably in the range of 1, 05 to 1, 20 g / cm 3 , determined by H20-D20 sedimentation analysis.
- the polymer P2 has at least one glass transition temperature Tg, determined by differential scanning calorimetry, DSC, in the range from -70 to 30 ° C, more preferably in the range from -50 to 0 ° C.
- the polymers P2 In contrast to the polymers PALK, the polymers P2 have no olefinically unsaturated C-C bonds.
- An olefinically unsaturated C-C bond is understood to mean C-C double bonds which are not part of an aromatic ⁇ -electron system.
- the polar groups are preferably groups which contain a carbonyl group, for example ester, amide, carbonate, urea or urethane groups.
- the polar groups can also be carboxyl groups, phosphonic acid groups, sulfonic acid groups, ammonium groups, hydroxy-C 2 -C 4 -alkyl groups or poly-C 2 -C 4 -alkylene oxide groups, eg.
- the polymer P2 is selected from polyurethanes, i. H. the polymer P2 contains urethane groups.
- the polyurethane may be aliphatic or aromatic.
- the polyurethane can be unmodified or modified for better dispersibility in water with nonionic or ionic polar groups.
- nonionic polar groups are especially poly-C 2 -C 4 -alkylene oxide groups, eg. As polyethylene oxide, polypropylene oxide or poly (ethylene oxide-co-propylene oxide) groups, in particular polyethylene oxide groups, wherein the poly-C 2 -C 4 -alkylene oxide groups may be part of the polyurethane backbone or in the form of side chains and preferably a number average molecular weight ranging from 200 to 10,000 g / mol.
- ionic polar groups are especially anionic groups, eg.
- Sulfonic acid groups, sulfate groups, phosphate groups, phosphonate groups and carboxylate groups which are in the acid form or especially in the salt form, as well as basic polar groups, eg. As di-Ci-C4-alkylamino or morpholino.
- the polyurethanes are obtainable by copolymerization
- Suitable isocyanate-reactive groups are especially OH groups, primary amino groups and mercapto groups.
- the polyurethane is very particularly preferably selected from polyesterurethanes; in particular, the polymer P2 is selected from anionically modified, aliphatic polyesterurethanes.
- the isocyanate component generally comprises at least one diisocyanate and optionally a polyisocyanate having an isocyanate functionality> 2, z. In the range of 2.5 to 5.
- the isocyanate component may be aliphatic, cycloaliphatic, araliphatic or aromatic.
- Preferred diisocyanates are aliphatic or cycloaliphatic.
- tetramethylene diisocyanate hexamethylene diisocyanate (HDI)
- dodecamethylene diisocyanate 1,4-diisocyanatocyclohexane
- 1-isocyanato-3,5,5-trimethyl-5-isocyanatomethylcyclohexane IPDI
- 2,2-bis (4-isocyanatocyclohexyl) propane 1,2-bis (4-isocyanatocyclohexyl) propane
- Trimethylhexandiisocyanat the isomers of bis (4-isocyanatocyclo- hexyl) methane (HMDI) as the trans / trans, the cis / cis and the cis / trans isomers and mixtures consisting of these compounds.
- HMDI bis (4-isocyanatocyclo- hexyl) methane
- aromatic and araliphatic diisocyanates are 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 4,4'-diisocyanatodiphenylmethane, 2,4'-diisocyanatodiphenylmethane and p-xylylene diisocyanate, tetramethylxylylene diisocyanate (TMXDI ).
- mixtures of these isocyanates for example, the mixtures of the respective structural isomers of diisocyanatotoluene and diisocyanatodiphenylmethane, z.
- Example a mixture of 80 mol% of 2,4-diisocyanatotoluene and 20 mol% of 2,6 diisocyanatotoluene, mixtures of aromatic isocyanates such as 2,4-diisocyanatotoluene and / or 2,6-diisocyanatotoluene with aliphatic or cycloaliphatic isocyanates such as He- xamethylenediisocyanate or IPDI.
- polyisocyanates are the biurets and cyanurates of the aforementioned diisocyanates and oligomeric products of these diisocyanates, which in addition to the free isocyanate groups further blocked isocyanate groups, eg. B.
- diisocyanates are 1-isocyanato-3,5,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), hexamethylene diisocyanate (HDI) and
- Suitable polyol component b) are compounds having at least two hydroxyl groups. These include low molecular weight diols or polyols as well as polymeric polyols such as polyester diols, polycarbonate diols, polyacrylate polyols and polyether diols and mixtures thereof. With regard to good film formation and elasticity, the polyol component b) preferably comprises at least one polymeric diol, which preferably has a number-average molecular weight of from about 500 to 10,000 g / mol, preferably from about 1,000 to 5,000 g / mol.
- the polyurethane is at least 40 wt .-%, more preferably at least 60 wt .-% and most preferably at least 80 wt .-% of diisocyanates, polyether diols, polycarbonate diols and / or polyester diols constructed.
- the polyurethane contains at least one polyester diol, in particular in an amount of at least 10% by weight, particularly preferably at least 30% by weight. %, in particular at least 40% by weight or at least 50% by weight, based on that of component B.
- polyesterdiols are used as synthesis components. If polyesterdiols are used in admixture with polyetherdiols or polycarbonatediols, they are preferably at least 50 mol%, particularly preferably at least 80 mol%, very particularly preferably 100 mol% of the mixture of polyester and polyetherdiols, polyesterdiols.
- polyester polyols examples include the z. B. from Ullmann's Encyclopedia of Industrial Chemistry, 4th Edition, Volume 19, pages 62 to 65 known polyester polyols. Preference is given to using polyesterpolyols which are obtained by reacting dihydric alcohols with dibasic carboxylic acids. Instead of the free polycarboxylic acids, it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof to prepare the polyesterpolyols.
- the polycarboxylic acids may be aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic and optionally, for. B. by halogen atoms, substituted and / or unsaturated.
- Examples of these are: suberic acid, azelaic acid, phthalic acid, isophthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, Tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, alkenylsuccinic acid, fumaric acid, dimer fatty acids.
- dicarboxylic acids of the general formula HOOC- (CH 2) y COOH, where y is a number from 1 to 20, preferably an even number from 2 to 20, z. Succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid.
- polyester polyols For the preparation of the polyester polyols come as diols z.
- ethylene glycol propane-1, 2-diol, propane-1, 3-diol, butane-1, 3-diol, butane-1, 4-diol, butene-1, 4-diol, butyne-1, 4- diol, pentane-1, 5-diol, neopentyl glycol, bis (hydroxymethyl) cyclohexanes
- ethylene glycol propane-1, 2-diol, propane-1, 3-diol, butane-1, 3-diol, butane-1, 4-diol, butene-1, 4-diol, butyne-1, 4- diol, pentane-1, 5-diol, neopentyl glycol, bis (hydroxymethyl) cyclohexanes
- Examples of these are ethylene glycol, butane-1, 4-diol, hexane-1, 6-diol, octane-1, 8-diol and dodecane-1, 12-diol. Further preferred are neopentyl glycol and pentane-1, 5-diol. These diols can also be used as diols directly for the synthesis of the polyurethanes.
- lactone-based polyesterdiols which are homopolymers or copolymers of lactones, preferably terminal hydroxyl-containing addition products of lactones onto suitable difunctional starter molecules.
- Preferred lactones are those which are derived from compounds of the general formula HO- (CH 2) z -COOH, where z is a number from 1 to 20 and an H atom of a methylene unit is also denoted by a d- to C 4 - Alkyl radical may be substituted. Examples are ⁇ -caprolactone, ⁇ -propiolactone, ⁇ -butyrolactone and / or methyl-s-caprolactone and mixtures thereof.
- Suitable starter components are for.
- polyester polyols low molecular weight dihydric alcohols.
- the corresponding polymers of ⁇ -caprolactone are particularly preferred.
- Lower polyester diols or polyether diols can also be used as starters for the preparation of the lactone polymers.
- the polymers of lactones it is also possible to use the corresponding, chemically equivalent polycondensates of the hydroxycarboxylic acids corresponding to the lactones.
- polyol component b) are polycarbonate diols, as described, for example, in US Pat. B. can be obtained by reacting phosgene with an excess of the mentioned as synthesis components for the polyester polyols low molecular weight alcohols.
- polyether diols are also suitable as polyol component b).
- polyether diols which are obtained by polymerization of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with themselves, eg. B. in the presence of BF3 or by addition of these compounds, optionally in admixture or in succession, to starting components with reactive hydrogen atoms, such as alcohols or amines, for.
- reactive hydrogen atoms such as alcohols or amines
- water ethylene glycol, propane-1, 2-diol, propane-1, 3-diol, 1, 1 -Bis- (4-hydroxyphenyl) propane or aniline available.
- polytetrahydrofuran having a molecular weight of 240 to 5000 g / mol, and especially 500 to 4500 g / mol.
- polyether diols it is also possible to use mixtures of polyester diols and polyether diols as monomers.
- polyol component b) are also polyhydroxypolyolefins and comparable polyhydroxypolymere based on monoethylenically unsaturated monomers suitable, preferably those having 2 terminal hydroxyl groups, eg. B. ⁇ - ⁇ -Dihydroxypolybutadien, ⁇ - ⁇ -Dihydroxypolymethacrylester or ⁇ - ⁇ -Dihydroxypolyacrylester. Such compounds are known, for example, from EP-A 622 378. Further suitable polyols are polyacetals, polysiloxanes and alkyd resins.
- the polyol component b) in addition to the at least one polymeric diol also comprises one or more low molecular weight diols.
- the low molecular weight diols typically have a number average molecular weight of about 60 to 500 g / mol, preferably from 62 to 200 g / mol.
- the proportion of low molecular weight diols, if present, is generally not more than 90% by weight, in particular not more than 70% by weight and especially not more than
- 50 wt .-% and is often in the range of 1 to 90 wt .-%, in particular in the range of 5 to 70 wt .-% or 10 to 50 wt .-%, each based on the total weight of the polyol component.
- the low molecular weight diols used are in particular the synthesis components of the short-chain alkanediols mentioned for the preparation of polyester polyols, where the diols having 2 to 12 C atoms, such as ethylene glycol, propane-1, 2-diol, propane-1,3-diol, Butane-1,3-diol, butane-1,4-diol, butene-1, 4-diol, butyne-1, 4-diol, pentane-1,5-diol, neopentyl glycol, bis (hydroxymethyl) cyclohexanes as in 1 , 4-bis (hydroxymethyl) cyclohexane, 2-methylpropane-1, 3-diol, methylpentanediols, diethylene glycol, triethylene glycol and dipropylene glycol are preferred.
- the diols having 2 to 12 C atoms such as ethylene glycol, propane-1, 2-
- the polyurethanes preferably contain, in copolymerized form, one or more hydrophilic compounds of component c) which have at least one isocyanate-reactive group and, in addition, at least one hydrophilic group or a group which is present in carry a hydrophilic group, carry.
- the (potentially) hydrophilic groups may be nonionic groups such as polyethylene oxide groups, or preferably (potentially) ionic hydrophilic groups, e.g. Sulfonate groups, sulfate groups, phosphate groups, phosphonate groups or carboxylate groups.
- the proportion of component c) will generally not exceed 20 wt .-%, based on the total amount of the polyurethane-forming constituents, and is often in the range of 0.1 to 20 wt .-%, in particular in the range of 0, 5 to 10 wt .-%.
- hydrophilic compounds of component c) are examples of hydrophilic compounds
- nonionic compounds such as methyl polyethylene glycols, in particular those having a molecular weight in the range from 150 to 1500 daltons,
- Mono- and dicarboxylic acids having two hydroxyl groups e.g. B. Dimethylolpropionic acid.
- These include compounds which have at least two isocyanate-reactive groups selected from OH and NH 2 groups, and at least one sulfonic acid group and their salts, for.
- Particularly suitable components d) are compounds which carry one, two, three, or more than three primary amino groups.
- Examples of preferred compounds of this type are hydrazine, hydrazine hydrate, ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, 1,2-bis (3-aminoproplyamino) ethane, isophoronediamine, 1,4-cyclohexyldiamine, N- (2-aminoethyl) -ethanolamine, N, N-diethylethanolamine, morpholine, piperazine or hydroxyethylpiperazine.
- the polymer P2 is anionic polyurethanes which are composed of the following constituents a) to c) and optionally d):
- At least one further component selected from isophoronediamine, diethylenetriamine, ⁇ , ⁇ -dimethylethanolamine and mixtures thereof.
- the polymer P2 is selected from polymers of ethylenically unsaturated monomers M which comprise as main constituent at least one monomer M1 which is C 1 -C 20 -alkyl esters of acrylic acid, C 1 -C 20 -alkyl esters of methacrylic acid and Vinyl esters of aliphatic C1-C20 carboxylic acids is selected.
- the monomers M1 at least 30 wt .-%, in particular 50 wt .-%, based on the total amount of the monomers M from.
- C 1 -C 20 -alkyl esters in particular C 1 -C 10 -alkyl esters of acrylic acid, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-butyl acrylate, tert-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, 2-propylheptyl acrylate, decyl acrylate and stearyl acrylate;
- C 1 -C 20 -alkyl esters in particular C 1 -C 10 -alkyl esters of methacrylic acid, such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-butyl methacrylate, tert-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate,
- methacrylic acid such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-butyl methacrylate, tert-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate,
- Preferred main monomers M1 are C 1 -C 10 -alkyl acrylates, their mixtures with
- C 1 -C 10 -alkyl methacrylates pure acrylates
- mixtures of C 1 -C 10 -alkyl acrylates with vinyl esters of aliphatic carboxylic acids, in particular with vinyl acetate are particularly preferred.
- the polymers P2 can also contain various monomers in copolymerized form. Their proportion will usually not exceed 70% by weight, in particular 50% by weight.
- monoethylenically unsaturated monomers M2 having limited water solubility such as, for example
- vinylaromatic compounds such as styrene, vinyltoluene, ⁇ - and p-methylstyrene, ⁇ -butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and in particular styrene;
- monoethylenically unsaturated nitriles such as acrylonitrile and methacrylonitrile
- Vinyl halides ie, chloro, fluoro or bromo substituted ethylenically unsaturated compounds, especially vinyl chloride and vinylidene chloride
- Vinyl ethers e.g. As vinyl methyl ether or vinyl isobutyl ether. Preference is given to vinyl ethers of alcohols containing from 1 to 4 carbon atoms;
- Olefinic hydrocarbons having 2 to 8 C atoms and one or two olefinic double bonds are ethylene, propylene, butadiene, isoprene and chloroprene.
- the monomers other than the monomers M1 also include monoethylenically unsaturated monomers M3 having increased water solubility of generally at least 80 g / L at 25 ° C. and 1 bar, such as, for example
- monoethylenically unsaturated monomers having at least one acid group such as carboxylic acid, sulfonic acid or phosphonic acid groups and the salts of these monomers, in particular the alkali metal, alkaline earth metal and ammonium salts.
- hydrophilic acidic monomers such as carboxylic acid, sulfonic acid or phosphonic acid groups and the salts of these monomers, in particular the alkali metal, alkaline earth metal and ammonium salts.
- acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid and aconitic acid The content of hydrophilic acidic monomers in the polymer P2 is generally not more than 10% by weight. If desired, the amount of hydrophilic acidic monomers is usually in the range from 0.1 to 10% by weight, in particular in the range from 0.2 to 5% by weight, based on the total amount
- Neutral monoethylenically unsaturated monomers having an increased water solubility include, for example, hydroxyl-containing monomers, in particular C 2 -C 4 -hydroxyalkyl (meth) acrylates, esters of (meth) acrylic acid with poly-C 2 -C 3 -alkylene glycols, monoethylenically unsaturated amides, such as
- the content of neutral hydrophilic monomers in polymer P2 is generally not more than 20% by weight. If desired, the amount of neutral hydrophilic monomers is usually in the range from 0.1 to 20% by weight, in particular in the range from 0.2 to 10% by weight, based on the total amount of monomers M copolymerized in polymer P2 ,
- the concentration of the polymer PALK in the aqueous composition is typically in the range of 2 to 35% by weight, especially 5 to 25% by weight, based on the total weight of the aqueous composition.
- the concentration of the polymer P2 in the aqueous composition is typically in the range of 7 to 58 wt .-%, in particular 15 to 50 wt .-%, based on the total weight of aqueous composition.
- the total content of polymer PALK and polymer P2 in the aqueous composition is preferably in the range from 10 to 60% by weight, in particular in the range from 20 to 55% by weight, based on the total weight of the aqueous composition.
- the composition contains 5 to 60 wt .-%, preferably 10 to 40 wt .-%, based on the total content of polymers PALK and P2, at least one polymer PALK. Accordingly, the composition preferably contains 40 to 95 wt .-%, in particular 60 to 90 wt .-%, based on the total content of polymers PALK and P2, at least one polymer P2.
- the polymers PALK and P2 constitute at least 50% by weight, in particular at least 70% by weight, based on the total weight of all non-volatile constituents in the aqueous compositions according to the invention. Accordingly, not more than 50% by weight, in particular not more than
- the aqueous compositions according to the invention usually comprise one or more surface-active substances for stabilizing the polymer particles.
- These can originate from the aqueous polymer dispersions of the polymers PALK or P2 used for the preparation of the aqueous compositions or can be added during dispersion of the polymers PALK and P2.
- Suitable surface-active substances basically include cationic, anionic and nonionic emulsifiers as well as cationic, nonionic and anionic protective colloids. Such substances are known in the art and can be found, for. In H.
- emulsifiers whose number-average molecular weights, in contrast to the protective colloids, usually do not exceed 1500 g / mol.
- emulsifiers and / or protective colloids can be used from emulsifiers and / or protective colloids.
- the individual components must be compatible with each other, which can be checked in case of doubt by hand on fewer preliminary tests.
- the surface-active substances include nonionic emulsifiers, anionic emulsifiers and mixtures thereof and mixtures of at least one nonionic emulsifier with at least one protective colloid from the group of anionic or nonionic protective colloids and mixtures of at least one anionic emulsifier with at least one protective colloid from the group of anionic or nonionic Protective colloids preferred.
- the surface-active substance comprises at least one nonionic emulsifier or a mixture of at least one nonionic emulsifier with at least one further surface-active substance from the group of anionic emulsifiers, anionic protective colloids and nonionic protective colloids.
- the total concentration of surface-active substances is typically in the range of 0.1 to 10 wt .-%, and in particular in the range of 0.2 to 5 wt .-%, based on the total weight of the aqueous composition.
- emulsifiers are z.
- B ethoxylated mono-, di- and tri-alkylphenols (EO degree: 2 to 50, alkyl radical: C 4 to C 12) and ethoxylated fatty alcohols (EO degree: 2 to 80, alkyl radical: Cs to C36).
- Examples are the Eumulgin ®
- Usual anionic emulsifiers are z.
- B Alkali metal and ammonium salts of alkyl sulfates (alkyl radical: Cs to C12), of sulfuric monoesters of ethoxylated alkanols (EO degree: 4 to 30, alkyl radical: C12 to Ci 8 ) and ethoxylated alkylphenols (EO degree: 3 to 50, alkyl radical: C 4 to C 12), of alkylsulfonic acids (alkyl radical: C 12 to Cie) and of alkylarylsulfonic acids (alkyl radical: C9 to Cis).
- R a and R b hydrogen atoms or C 4 - to C2 4 alkyl, and simultaneously hydrogen atoms are not, and ⁇ ⁇ and alkali metal ions and / or may be ammonium ions.
- R a and R b are preferably linear or branched alkyl radicals having 6 to 18 C atoms, in particular having 6, 12 and 16 C atoms or -H, wherein R a and R b are not both simultaneously H Atoms are.
- ⁇ and ⁇ are sodium, potassium or ammonium, with sodium being particularly preferred.
- Particularly advantageous compounds (II) are those in which ⁇ and ⁇ are sodium, R a is a branched alkyl radical having 12 C atoms and R b is an H atom or R a .
- technical mixtures are used which have a proportion of 50 to 90 wt .-% of the monoalkylated product, such as Dowfax ® 2A1 (trademark of Dow Chemical Corp.).
- the compounds (II) are well known, for. Example, from US-A 4269749, and commercially available.
- Suitable cationic emulsifiers are generally primary, secondary, tertiary or quaternary ammonium salts having C 6 -C 18 -alkyl, aralkyl or heterocyclic radicals, alkanolammonium salts, pyridinium salts, imidazolinium salts, oxazolinium salts, morpholinium salts, thiazolinium salts and salts of amine. oxides, quinolinium salts, isoquinolinium salts, tropylium salts, sulfonium salts and phosphonium salts. Examples include dodecylammonium acetate or the corresponding hydrochloride, the chlorides or acetates of the various
- N, N '- (lauryl) ethylendiamindibromid Numerous other examples can be found in H. Stumblee, Tensid-Taschenbuch, Carl-Hanser-Verlag, Kunststoff, Vienna, 1981, and McCutcheon's, Emulsifiers & Detergents, MC Publishing Company, Glen Rock, 1989.
- Suitable neutral protective colloids are, for example, polyvinyl alcohols, polyalkylene glycols, polyvinylpyrrolidones, cellulose, starch and gelatin derivatives.
- anionic protective colloids d. H.
- Protective colloids whose dispersing component has at least one negative electrical charge include, for example, polyacrylic acids and polymethacrylic acids and their alkali metal salts, acrylic acid, methacrylic acid, itaconic acid, 2-acrylamido-2-methylpropanesulfonic acid, 4-styrenesulfonic acid and / or maleic anhydride-containing copolymers and their alkali metal salts and alkali metal salts of sulfonic acids of high molecular weight compounds, such as polystyrene, into consideration.
- Protective colloids whose dispersing component has at least one positive electrical charge are, for example, the nitrogen protonated and / or alkylated derivatives of
- N-vinylpyrrolidone N-vinylcaprolactam
- N-vinylformamide N-vinylacetamide
- N-vinylcarbazole 1-vinylimidazole, 2-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine, acrylamide, methacrylamide, acrylates containing amine groups, methacrylates, homopolymers and copolymers containing acrylamides and / or methacrylamides.
- the aqueous compositions according to the invention may contain one or more further constituents, as are customarily used for the purpose of compounding.
- further constituents are rheology modifiers, wetting aids, organic fillers, inorganic fillers, stabilizers and colorants, eg. B. coloring pigments.
- the content of these additives is known to the person skilled in the art.
- Another object of the invention is a process for the preparation of the aqueous compositions of the invention. For this purpose, it is usual to mix an aqueous dispersion of the polymer PALK with an aqueous dispersion of the polymer P2.
- aqueous dispersions of the polymers PALK and P2 are known to the person skilled in the art.
- the polymers P2 and their aqueous dispersions are also known to the person skilled in the art.
- the polymers P2 and their aqueous dispersions are also commercially available.
- the polymer P2 is a polyurethane
- this is typically prepared by reacting the aforementioned components a) to c) and optionally d), wherein the proportions are typically selected so that the molar ratio of the isocyanate groups of the component a) to the number of isocyanate-reactive groups in the components b), c) and optionally d) in the range of 1: 1, 1 to 1, 1: 1.
- the preparation is carried out in an aprotic organic solvent, for example a ketone having 3 to 6 carbon atoms, such as acetone, methyl ethyl ketone, diethyl ketone or cyclohexanone, an aliphatic carboxylic acid ester, eg.
- Ci-C6-alkyl ester or Ci-C3-alkoxy-C2-C4-alkyl esters of acetic acid such as methyl acetate, ethyl acetate, methoxyethyl acetate, etc.
- the resulting polymer solution can then be emulsified in a conventional manner in water and the organic solvent remove, for. B. by azeotropic distillation. If the polymer P2 is composed of polymerized, ethylenically unsaturated monomers M, the aqueous dispersion of the polymer P2 is generally an emulsion polymer.
- Emulsion polymers are familiar to the person skilled in the art and are prepared, for example, in the form of an aqueous polymer dispersion by free-radically initiated aqueous emulsion polymerization of ethylenically unsaturated monomers. This method has been described many times and is therefore sufficiently known to the person skilled in the art [cf. z. Encyclopedia of Polymer Science and Engineering, Vol. 8, pp. 659-677, John Wiley & Sons, Inc., 1987; DC Blackley, Emulsion Polymerization, pp. 155-465, Applied Science Publishers, Ltd., Essex, 1975; DC Blackley, Polymer Latices, 2nd Edition, Vol. 1, pp. 33-415, Chapman & Hall, 1997; H.
- the free-radically initiated aqueous emulsion polymerization is usually carried out by dispersing the ethylenically unsaturated monomers, generally with the concomitant use of dispersing aids, such as emulsifiers and / or protective colloids, in aqueous medium and polymerizing them by means of at least one water-soluble free-radical polymerization initiator.
- dispersing aids such as emulsifiers and / or protective colloids
- the polymer solids content Dilution or concentration adjusted to a desired value or the aqueous polymer dispersion further conventional additives, such as bactericidal, foam or viscosity modifying additives added.
- bactericidal, foam or viscosity modifying additives examples of commercially available aqueous dispersions of polymers P2 synthesized from ethylenically unsaturated monomers M are the Acronal types from BASF SE, for example US Pat.
- Acronal 500 D and Acronal S 504 the Mowilith types of Fa.
- Examples of commercially available aqueous dispersions of polyurethanes P2 are the astacine types and some Joncryl dispersions of BASF SE, z. B. Astacin- Finish PE or Joncryl FLX 5200, the Impranil types of Fa. Bayer MaterialScience, z. B. Impranil DLV / 1 and Impranil DL 1380 and the NeoRez types of the company. DSM, z. NeoRez 1013.
- the invention also relates to polymer powders obtainable by drying an aqueous composition.
- the drying can be carried out in analogy to known methods for the preparation of polymer powders from aqueous polymer dispersions, for. B. by spray drying or freeze drying.
- drying aids e.g. As the aforementioned protective colloids, and / or flow aids and Antiagglomiati- onsstoff be added.
- the aqueous compositions according to the invention film on drying, ie the polymer particles in the aqueous compositions coalesce on drying and form a polymer film having advantageous mechanical properties, e.g. B. a high elasticity with high strength, especially breaking or breaking strength.
- the polymer films are characterized by a good barrier effect, in particular to gases and especially to oxygen or oxygen-containing gas mixtures such as air. They are therefore suitable for the production of coating or films with barrier effect.
- Another object of the invention is a polymer film, which is obtainable using an aqueous composition according to the invention.
- the aqueous composition is applied as a wet film on a support and dried.
- a layer is formed on the support, which contains the polymers PALK and P2. This layer can be left as a coating on the carrier or detached from the carrier as a self-supporting film.
- the polyalkenamer may be partially oxidized.
- the oxidation of the polymer film can be carried out, for example, by storage in an oxygen-containing environment, preferably using radiation energy, thermal energy or oxidation accelerators or a combination thereof.
- the oxidation of the polymer PALK can be done, for example, in air under daylight and at room temperature (about 20-25 ° C).
- the oxidation can be accelerated by radiation energy, thermal energy or oxidation accelerator.
- the oxidation accelerator for example, chemical oxidation accelerators, such as known transition metals and transition metal compounds, in particular those of iron, zirconium, manganese, zinc or cobalt, can be used.
- the aqueous composition can be applied to a carrier film made of a plastic.
- the aqueous composition is usually applied from a trough over an applicator roll and leveled using an air brush.
- Other ways to apply the aqueous composition succeed z.
- the carrier substrate is coated on at least one side, ie it may be coated on one side or on both sides.
- the carrier film may be subjected to a corona treatment or alternatively adhesion promoter, such as.
- polyethyleneimines are used.
- the applied to the sheet materials amounts are z. B.
- the coating compositions preferably 1 to 800 g (polymer, solid) per m 2 , preferably 1 to 400 g / m 2 or 5 to 200 g / m 2 .
- volatiles are evaporated. This can be done, for example, during continuous work passing the material through a dryer channel that may be equipped with an infrared radiation device. Thereafter, the coated and dried material is passed over a cooling roll and finally wound up.
- the application rate of the aqueous composition to the film is generally selected such that the thickness of the dried coating is at least 1 ⁇ m, in particular at least 5 ⁇ m, and preferably 1 to 400 ⁇ m, particularly preferably 5 to 200 ⁇ m.
- the thickness of the carrier films depends on the desired application and is generally in the range of 10 ⁇ m to 1 cm.
- the polymer PALK at the surface of the layer is preferably at least partially oxidized.
- the core of the coating may contain non-oxidized polymer PALK.
- Another object of the invention is the use of the aqueous compositions according to the invention for the preparation of barrier coatings.
- Another object of the invention is a coating obtainable by a method comprising
- the polymer PALK is at least partially oxidized in the barrier film or barrier coating.
- oxidized means that the polymer PALK carries at least one oxygen-containing group.
- the application of the aqueous composition according to the invention can be carried out as a spray or coating film, for. B. by roller, doctor blade, air brushing or casting.
- the application rate of the aqueous composition to the support is generally selected so that the thickness of the dried coating is at least 1 ⁇ m, in particular at least 5 ⁇ m, and preferably 1 to 400 ⁇ m, particularly preferably 1 to 200 ⁇ m.
- Preferred is a coating obtainable by a process comprising:
- composition can be applied in one or more steps, and a2) where appropriate, the composition can be selected by one or more methods selected from soaking, impregnation, spraying, brushing, coating and calendering;
- Energy, oxidation accelerator or a combination thereof, can take place.
- steps a), b) and optionally c) can be run once or several times, wherein the steps can each be carried out with identical or different variants.
- the oxidation in step c) can, as described above, be carried out, for example, by storage in an oxygen-containing environment, preferably using radiation energy, thermal energy or oxidation accelerators or a combination thereof.
- aqueous compositions according to the invention are also suitable for the following applications: For the production of adhesives, sealants, plastic plasters, paper coating slips, nonwoven fabrics, paints and impact modifiers and for the consolidation of sand, textile finishing, leather finishing and for the modification of mineral binders and plastics.
- an aqueous composition according to the invention which contains at least one polymer PALK and at least one polymer P2 for finishing rubber materials and for producing barrier coatings on rubber substrates.
- the rubber components of the rubber material may be selected from, for example, 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 a component of a pneumatic tire, in particular, a tire inner layer of a pneumatic tire or a tire carcass of a pneumatic tire.
- the rubber materials themselves are equipped with one of the aqueous compositions according to the invention.
- components of a rubber-containing article, in particular of pneumatic tires are equipped with the barrier material and introduced into the rubber-containing article, preferably pneumatic tires.
- the textile cords of pneumatic tires can be equipped with the aqueous compositions according to the invention.
- the invention also provides a process for finishing a rubber material, wherein at least one of the aqueous compositions described herein is applied to the rubber material or incorporated into the rubber material.
- the equipment can z. B. by one or more of the following methods: Impregnation by impregnation, by spraying or by brushing, coating, calendering.
- the compositions used for the coating may contain further additives or auxiliaries, for. As thickeners for adjusting the rheology, wetting aids, organic or inorganic fillers or binders.
- At least one aqueous composition according to the invention is applied to a carrier substrate.
- a film then forms on the carrier substrate.
- the invention also relates to pneumatic tires comprising a rubber material finished or coated with a composition according to the invention.
- composition can be applied to or incorporated into the rubber material in one or more of the following methods:
- films or films may be incorporated in addition to a rubber-based inner tire layer or as a substitute for a tire inner layer in the tire interior;
- the application as a film can be done as a spray or coating film, z. B. by roller, doctor blade, Lucasbürsten- or Gußstreichbacter.
- the application can also be carried out as a film, which serves as a carrier and then glued to the carcass or crosslinked (vulcanized) is.
- Suitable film carriers are z. B. rubber, polyolefin, polyester, polyamide or polyurethane film support.
- the aqueous composition can also be used for producing a laminate between two carrier films, the laminate then being bonded or crosslinked to the carcass.
- the substrates coated according to the invention exhibit an outstanding gas barrier effect, in particular with respect to oxygen and oxygen-containing gas mixtures such as air.
- the solids contents of the aqueous dispersions were generally determined by drying a defined amount of the aqueous polymer dispersion (about 0.8 g) with the aid of moisture meter HR73 from Mettler Toledo at a temperature of 130 ° C. to constant weight. In each case two measurements were carried out. The values given represent the mean values of these measurements.
- the density and the mean particle diameter of the polymer particles were determined as described in "Analytical Ultracentrifugation of polymers and nanoparticles" (Springer Laboratory 2006, W. Gurchtie and L. Börger) using Turbid Optic Analytical Ultracentrifuge (AUC) on an Optima XL-A I instrument
- AUC Turbid Optic Analytical Ultracentrifuge
- sedimentation rates are measured under otherwise identical conditions in three solvents of different densities (H2O, H2O / D2O (1: 1) and D2O) .
- the particle size can be determined from the sedimentation rate.
- the glass transition temperature (Tg) was determined using a differential scanning calorimeter DSC Q2000 V24.4 Build 1 16 from TA Instruments. The heating rate was 20 K / min.
- Tensile elongation values were determined by tensile tests on a Z050 testing machine from Zwick GmbH & Co in compliance with the following conditions and parameters: Standard ISO 527-2, geometry DIN 53504 S3A, temperature 23 ° C, relative humidity 50%, force sensor 50 N, test speed 200 mm / min, clamping length 25 mm, measuring length 25 mm.
- the oxygen permeabilities were measured according to ASTM D 3985 (for measurements at 0% relative humidity) and ASTM F 1927 (for measurements at 85% relative humidity) using a MOCON OXTRAN® 2/21, which is based on the carrier gas method.
- the carrier gas method the masked sample films (without support material) are installed in an airtight cell with cavity on both sides.
- On one side of the sample is a carrier gas (95% N2 and 5% H2) and on the other side the sample gas (100%). O2) bypassed without pressure.
- the sample gas diffusing through the sample is taken up by the carrier gas and passed to a coulometric sensor.
- the oxygen concentration can be determined as a function of time.
- the metal carbene complex dichloro-1,3-bis (2,6-dimethyl-4-dimethylaminophenyl) imidazolidin-2-ylidene bis (4-dimethylaminopyridine) - (phenylthio) methylene ruthenium (II) (metal carbene complex 1) used.
- the preparation of this catalyst is described in WO 2012/076426.
- a mixture consisting of 107.3 g of deionized water, 13.8 g of an aqueous solution (20% by weight) of a C16 / C18 fatty alcohol polyethoxylate (Lutensol® AT 18 from BASF SE), 2.6 g of n-hexadecane, 8.9 g of norbornene and 43.4 g of cis-cyclooctene were weighed at 20 to 25 ° C (room temperature) under nitrogen atmosphere in a 250 ml glass bottle with magnetic stirring and the mixture stirred vigorously for one hour to form a homogeneous monomer macroemulsion.
- a C16 / C18 fatty alcohol polyethoxylate Litensol® AT 18 from BASF SE
- the resulting monomer macroemulsion was processed by an ultrasonic processor Homogenized UP 400s (Sonotrode H7, 100% power) for a period of 10 minutes. Subsequently, the resulting aqueous Monomerenminiemulsion was transferred under a nitrogen atmosphere in a temperature-controlled, equipped with stirrer, thermometer, reflux condenser and feed vessels 500 ml glass flask and heated to 75 ° C with stirring.
- Example 2 The procedure of Example 2 was carried out analogously to Example 1, but with the difference that instead of 8.9 g of norbornene and 43.4 g of cis-cyclooctene, 1 1, 9 g of dicyclopentadiene and 40.5 g of cis-cyclooctene were used ,
- the resulting aqueous polymer dispersion had a solids content of 29.9% by weight.
- the average particle size was determined to be 401 nm, the glass transition temperature of the resulting polymer to -59 ° C and the density determined to be 0.895 g / cm 3 .
- Example 3 was carried out analogously to Example 1, but with the difference that instead of 8.9 g of norbornene and 43.4 g of cis-cyclooctene, 22.9 g of dicyclopentadiene and 29.2 g of cis-cyclooctene were used.
- the aqueous polymer dispersion obtained had a solids content of 29.7% by weight.
- the average particle size was determined to be 385 nm, the glass transition temperature of the resulting polymer to -40 ° C. and the density determined to be 0.940 g / cm 3 .
- Example 4 Preparation of Polyalkenamer Dispersion 4 (PALK-D4)
- the procedure of Example 4 was carried out analogously to Example 1, but with the difference that instead of 8.9 g of norbornene and 43.4 g of cis-cyclooctene, 52.6 g of cis - Cyclooctene was used.
- the aqueous polymer dispersion obtained had a solids content of 29.7% by weight.
- the mean particle size was 339 nm, the Glass transition temperature of the resulting polymer determined to -85 ° C and determines the density to 0.866 g / cm 3 .
- Polymer dispersions and polymer dispersion blends were used to make the polymer films.
- the polyalkenamer dispersion was adjusted to a pH of between 7 and 8 prior to mixing with a 25% aqueous ammonia solution.
- Oxidation accelerator (7 wt .-% based on the solids content of the polyalkenamer dispersion) was emulsified in water.
- the emulsion of the oxidation accelerator and the polymer dispersion or the mixture of the polymer dispersions were combined.
- the solids content of the entire mixture was between 15 and 20%.
- the mixture was then filtered through 125 ⁇ .
- the polymer film was produced by pouring the mixture into a silicone mold.
- the cast film was dried at 25 ° C for 48 hours and then annealed for 12 hours at a temperature of 100 ° C.
- the composition of the films produced is shown in Table 1.
- PU-D1 is an aqueous anionic polyester-polyurethane dispersion prepared from an amorphous polyester diol, 1,4-butanediol, hexamethylene diisocyanate, isophorone diisocyanate, sodium 2 - [(2-aminoethyl) amino] ethanesulfonate, isophoronediamine and diethylenetriamine ,
- the aqueous polymer dispersion had a solids content of 40.0% by weight.
- the mean particle size was determined to be 84 nm, the density to be 1.1.19 g / cm 3 and the glass transition temperature of the soft phase of the resulting polymer to -45 ° C.
- PU-D2 is an aqueous, anionic aliphatic polyurethane dispersion which has been prepared from an amorphous polyester diol, 1,4-butanediol, isophorone diisocyanate, dimethylolpropionic acid, isophoronediamine, ⁇ , ⁇ -diethylethanolamine and diethylenetriamine.
- the aqueous polymer dispersion had a solids content of 36.5% by weight.
- the mean particle size was determined to be 38 nm, the density to 1.154 g / cm 3 and the glass transition temperature of the soft phase of the resulting polymer to -21 ° C.
- PAc-DI Polyacrylate Dispersion 1
- PAc-DI is an aqueous dispersion of an acrylic ester copolymer with concomitant use of vinyl acetate prepared from n-butyl acrylate and vinyl acetate.
- the aqueous polymer dispersion had a solids content of 50.0% by weight.
- the average particle size was determined to 175 nm, the density to 1, 1 19 g / cm 3 and the glass transition temperature of the resulting polymer to -6 ° C.
- Octa-Soligen® 144 aqua from OMG Borchers was used as an oxidation accelerator.
- Table 1 shows that films of polyalkenamer dispersions on the one hand have a very good barrier effect for oxygen, but have a very low extensibility (elongation at break ⁇ 50%). Table 1 further shows that films which contain formulations containing up to 20% by weight of polyalkenamer dispersions surprisingly have both low permeability and good flexibility (elongation at break> 150%).
- the polyalkenamer dispersions were adjusted to pH 7-8 before mixing with ammonia (25% in water). Polymer dispersions were mixed before the film preparation with an aqueous emulsion of the oxidation accelerator (7 wt .-% oxidation accelerator, based on the solids content of the polyalkylene dispersion).
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Abstract
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EP3666835A1 (de) * | 2018-12-14 | 2020-06-17 | Henkel AG & Co. KGaA | Wasserbasierte dispersion zur herstellung von beschichtungen mit erhöhten mvtr-barriereeigenschaften daraus |
CN111808248B (zh) * | 2019-04-10 | 2023-09-15 | 罗门哈斯公司 | 乙酸乙烯酯和环状烯酮缩醛单体的共聚物粒子的水性分散液 |
Family Cites Families (34)
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 |
US4025708A (en) | 1975-03-24 | 1977-05-24 | The B. F. Goodrich Company | Process for polymerizing cyclopentene |
US4269749A (en) | 1979-04-30 | 1981-05-26 | The Dow Chemical Company | Method of imparting salt and/or mechanical stability to aqueous polymer microsuspensions |
DE4003422A1 (de) | 1990-02-06 | 1991-08-08 | Basf Ag | Waessrige polyurethanzubereitungen |
WO1996004289A1 (en) | 1992-04-03 | 1996-02-15 | California Institute Of Technology | High activity ruthenium or osmium metal carbene complexes for olefin metathesis reactions and synthesis thereof |
US5312940A (en) | 1992-04-03 | 1994-05-17 | California Institute Of Technology | Ruthenium and osmium metal carbene complexes for olefin metathesis polymerization |
DE4314111A1 (de) | 1993-04-29 | 1994-11-03 | Goldschmidt Ag Th | alpha,omega-Polymethacrylatdiole, Verfahren zu ihrer Herstellung und deren Verwendung zur Herstellung von Polymeren, insbesondere Polyurethanen und Polyestern |
CN1120180C (zh) | 1994-06-03 | 2003-09-03 | 巴斯福股份公司 | 聚合物水分散液的制备 |
DE19624299A1 (de) | 1995-06-30 | 1997-01-02 | Basf Ag | Verfahren zur Entfernung organischer Verbindungen aus Dispersionen und Vorrichtung zu dessen Durchführung |
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 |
DE19621027A1 (de) | 1996-05-24 | 1997-11-27 | Basf Ag | Verfahren zur Abtrennung flüchtiger organischer Komponenten aus Suspensionen oder Dispersionen |
EP0824125A1 (de) | 1996-08-13 | 1998-02-18 | Ciba SC Holding AG | Umhüllungsmassen auf Basis von Dicyclopentadienderivaten |
DE19741184A1 (de) | 1997-09-18 | 1999-03-25 | Basf Ag | Verfahren zur Verminderung von Restmonomeren in Flüssigsystemen unter Zugabe eines Redoxinitiatorsystems |
DE19741187A1 (de) | 1997-09-18 | 1999-03-25 | Basf Ag | Verfahren zur Verminderung des Restmonomerengehalts in wässrigen Polymerdispersionen |
DE19805122A1 (de) | 1998-02-09 | 1999-04-22 | Basf Ag | Verfahren zur Herstellung wässriger Polymerisatdispersionen mit geringem Restmonomerengehalt |
DE19828183A1 (de) | 1998-06-24 | 1999-12-30 | Basf Ag | Verfahren zur Entfernung von restflüchtigen Komponenten aus Polymerdispersionen |
DE19839199A1 (de) | 1998-08-28 | 2000-03-02 | Basf Ag | Verfahren zur Verminderung der Restmonomerenmenge in wässrigen Polymerdispersionen |
DE19840586A1 (de) | 1998-09-05 | 2000-03-09 | Basf Ag | Verfahren zur Verminderung der Restmonomerenmenge in wässrigen Polymerdispersionen |
DE19847115C1 (de) | 1998-10-13 | 2000-05-04 | Basf Ag | Gegenstrom-Stripprohr |
DE19859191A1 (de) | 1998-12-21 | 2000-06-29 | Basf Ag | Verfahren zur Herstellung einer wässrigen Polyalkenamer-Dispersion durch ringöffnende Metathese-Emulsionspolymerisation |
EP1371685A3 (de) * | 2002-06-14 | 2004-01-07 | Rohm And Haas Company | Wässrige Polymerzusammensetzung enthaltend Polymernanopartikel und hieraus hergestellte Beschichtungsmittel |
MY139350A (en) | 2003-09-26 | 2009-09-30 | Invista Tech Sarl | Alloy blends of polyurethane and latex rubber |
GB0428172D0 (en) | 2004-12-23 | 2005-01-26 | Ici Plc | Olefin metathesis polymerisation |
WO2008048536A2 (en) | 2006-10-17 | 2008-04-24 | Firestone Polymers, Llc | Elastomers, process for preparation, and uses thereof |
US20080142142A1 (en) | 2006-12-15 | 2008-06-19 | Giorgio Agostini | Pneumatic run-flat tire |
EP2496628A1 (de) | 2009-11-02 | 2012-09-12 | Basf Se | Verfahren zur herstellung einer wässrigen polymerisatdispersion |
WO2012028530A1 (de) | 2010-09-03 | 2012-03-08 | Basf Se | Barrierebeschichtung aus cycloolefincopolymeren |
US20120058332A1 (en) * | 2010-09-03 | 2012-03-08 | Basf Se | Barrier coating made of cycloolefin copolymers |
EP2461613A1 (de) | 2010-12-06 | 2012-06-06 | Gemalto SA | Verfahren und System zur Handhabung von UICC-Daten |
WO2012076426A1 (de) | 2010-12-08 | 2012-06-14 | Basf Se | Verfahren zur herstellung einer wässrigen polymerisatdispersion |
US8790753B2 (en) * | 2011-02-11 | 2014-07-29 | Basf Se | Rubber material with barrier material made of cycloolefin copolymers |
BR112013019826A2 (pt) | 2011-02-11 | 2020-11-17 | Basf Se | material de borracha, pneumático processo para modificar o material de borracha, e, uso de um copolímero |
BR112015003100A2 (pt) * | 2012-08-13 | 2017-07-04 | Basf Se | uso de um copolímero, material de borracha modificada, pneumático, e, processo para modificar um material de borracha. |
-
2016
- 2016-11-11 US US15/775,140 patent/US20180319974A1/en not_active Abandoned
- 2016-11-11 JP JP2018524317A patent/JP2019508508A/ja active Pending
- 2016-11-11 WO PCT/EP2016/077403 patent/WO2017081233A1/de active Application Filing
- 2016-11-11 CN CN201680078806.XA patent/CN108541257A/zh active Pending
- 2016-11-11 MX MX2018005943A patent/MX2018005943A/es unknown
- 2016-11-11 BR BR112018009370A patent/BR112018009370A8/pt not_active Application Discontinuation
- 2016-11-11 EP EP16795024.5A patent/EP3374413A1/de not_active Withdrawn
- 2016-11-11 CA CA3005068A patent/CA3005068A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
US20180319974A1 (en) | 2018-11-08 |
MX2018005943A (es) | 2018-08-14 |
JP2019508508A (ja) | 2019-03-28 |
BR112018009370A8 (pt) | 2019-02-26 |
CN108541257A (zh) | 2018-09-14 |
WO2017081233A1 (de) | 2017-05-18 |
BR112018009370A2 (pt) | 2018-11-13 |
CA3005068A1 (en) | 2017-05-18 |
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