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WO2008138855A1 - Compositions à base de polyuréthane, durcissables à basse température et comportant des groupes uretdione, qui contiennent des polymères formés à partir de polyols portant des groupes oh secondaires - Google Patents

Compositions à base de polyuréthane, durcissables à basse température et comportant des groupes uretdione, qui contiennent des polymères formés à partir de polyols portant des groupes oh secondaires Download PDF

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Publication number
WO2008138855A1
WO2008138855A1 PCT/EP2008/055686 EP2008055686W WO2008138855A1 WO 2008138855 A1 WO2008138855 A1 WO 2008138855A1 EP 2008055686 W EP2008055686 W EP 2008055686W WO 2008138855 A1 WO2008138855 A1 WO 2008138855A1
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WIPO (PCT)
Prior art keywords
uretdione
hydroxide
weight
polyurethane compositions
hydroxyl
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Ceased
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PCT/EP2008/055686
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German (de)
English (en)
Inventor
Emmanouil Spyrou
Werner Grenda
Corey King
Christoph Lammers
Rainer LOMÖLDER
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Evonik Operations GmbH
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Evonik Degussa GmbH
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Priority claimed from DE102007022789A external-priority patent/DE102007022789A1/de
Application filed by Evonik Degussa GmbH filed Critical Evonik Degussa GmbH
Publication of WO2008138855A1 publication Critical patent/WO2008138855A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/798—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing urethdione groups
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4219—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from aromatic dicarboxylic acids and dialcohols in combination with polycarboxylic acids and/or polyhydroxy compounds which are at least trifunctional
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C08G2150/00—Compositions for coatings
    • C08G2150/20—Compositions for powder coatings

Definitions

  • the invention relates to uretdione-group-containing polyurethane compositions which cure at low stoving temperatures, processes for the preparation of such compositions and their use for the production of plastics, in particular lacquer coatings and adhesives.
  • DE-OS 27 35 497 PUR coatings with excellent weathering and heat stability The crosslinkers, the preparation of which is described in DE-OS 27 12 931, consist of ⁇ -caprolactam blocked isocyanurate-containing isophorone diisocyanate. There are also known urethane, biuret or urea group-containing polyisocyanates whose isocyanate groups are also blocked.
  • DE-OS 30 30 539 and DE-OS 30 30 572 describe processes for the preparation of uretdione polyaddition compounds whose terminal Isocyanate groups with monoalcohols or monoamines are irreversibly blocked. Disadvantages are, in particular, the chain-breaking constituents of the crosslinkers, which lead to low network densities of the PUR varnish coatings and thus to moderate solvent resistance.
  • Hydroxyl-terminated, polyaddition compounds containing uretdione groups are the subject of EP 669 353. Due to their functionality of two, they have improved resistance to solvents. The compositions based on these uretdione group-containing polyisocyanates have in common that they do not emit volatile compounds in the curing reaction. However, the baking temperatures are at least 180 ° C at a high level.
  • amidines as catalysts in PU coating composition is described in EP 803 524. Although these catalysts lead to a lowering of the curing temperature, but show a considerable yellowing, which is generally undesirable in the coating area. The reason for this yellowing is probably the reactive nitrogen atoms in the amidines. These can react with atmospheric oxygen to N-oxides, which are responsible for the discoloration.
  • EP 803 524 also mentions other catalysts which have hitherto been used for this purpose, but without showing any particular effect on the curing temperature. These include known from polyurethane chemistry organometallic catalysts such. As dibutyltin dilaurate (DBTL), or tertiary amines, such as. B. 1, 4-diazabicyclo [2.2.2] octane (DABCO).
  • DBTL dibutyltin dilaurate
  • DABCO 4-diazabicyclo [2.2.2] octane
  • Quaternary ammonium salts are z. B. in EP 1 334 987 and 1 475 399 described as catalysts for highly reactive uretdione powder coating formulations.
  • the object of the present invention was therefore to find highly reactive uretdione-containing polyurethane compositions which have a more favorable balance between reactivity and storage stability.
  • the present invention relates to polyurethane compositions containing highly reactive uretdione groups
  • At least one uretdione hardener based on aromatic, aliphatic, (cyclo) aliphatic or cycloaliphatic polyisocyanates and hydroxyl-containing compounds, having a free NCO content of less than 5 wt .-% and a Uretdiongehalt 1-25 wt.
  • C) at least one catalyst which leads to an increased reactivity of uretdione groups, such that the proportion of the catalyst under C) is 0.001-5% by weight based on the total formulation
  • D) if appropriate at least one acid group-reactive compound having a weight fraction, based on the total formulation, from 0.1 to 10%
  • E) optionally at least one acid in monomeric or polymeric form in a proportion by weight, based on the total formulation, of from 0.01 to 20%
  • Another object of the invention is also a process for the preparation of the polyurethane compositions.
  • the invention also provides the use of the polyurethane compositions according to the invention for the production of powdered coating compositions on metal, plastic, glass, wood, MDF (Middle Density Fiber Boards) or leather substrates or other heat-resistant substrates.
  • MDF Middle Density Fiber Boards
  • the invention also provides the use of the polyurethane compositions according to the invention as adhesive compositions for bonding metal, plastic, glass, wood, MDF or leather substrates or other heat-resistant substrates.
  • the invention also relates to metal coating compositions, in particular for automobile bodies, motorcycles and bicycles, building parts and household appliances, wood coating compositions, MDF coatings, glass coating compositions, leather coating compositions and plastic coating compositions.
  • the polyurethane compositions according to the invention are highly reactive. This means that the polyurethane compositions cure already at 120 to 160 ° C within 5 to 30 minutes.
  • polyurethane compositions of the invention have a much better balance between reactivity and storage stability compared to non-inventive polyurethane compositions.
  • High reactivity leads to an increased in polyurethane compositions Turnover of reactive groups, which in turn results in a denser polymer network. This network leads in powder coatings to increased mechanical strength, eg. B. to higher ball impact values.
  • powder coatings based on polyurethane compositions according to the invention before and / or after storage at 40 ° C. have at least 30% better ball impact (ASTM D 2794-93, direct and / or indirect) and / or a better course, which is according to PCI scale is at least 2 units higher than non-inventive polyurethane compositions under otherwise comparable conditions (in particular comparable catalysis, acidity, glass transition point of the components).
  • Hardeners A) containing uretdione groups are obtained from uretdione-containing polyisocyanates and hydroxyl-containing monomers or polymers.
  • the reaction - optionally carried out in solvents, but preferably in the absence of solvents - Is stopped when a desired conversion by addition of catalyst poisons. Excess monomeric isocyanate is subsequently separated by short path evaporation. If the catalyst is volatile enough, the reaction mixture can be freed from the catalyst in the course of the monomer separation. The addition of catalyst poisons can be dispensed with in this case.
  • isocyanates is suitable for the preparation of polyisocyanates containing uretdione groups.
  • IPDI isophorone diisocyanate
  • HDI hexamethylene diisocyanate
  • MPDI 2-methylpentanediisocyanate
  • TMDI 2,2, 4-trimethylhexamethylene diisocyanate / 2,4,4-trimethylhexamethylene diisocyanate (TMDI), norbornane diisocyanate (NBDI)
  • MDI methylene diphenyl diisocyanate
  • TDI toluidine diisocyanate
  • TMXDI tetramethylxylylene diisocyanate
  • uretdione group-bearing polyisocyanates to uretdione groups having curing agents A) includes the reaction of the free NCO groups with hydroxyl-containing monomers or polymers, such as.
  • polyesters polythioethers, polyethers, polycaprolactones, polyepoxides, polyester amides, polyurethanes or low molecular weight di-, tri- and / or tetra alcohols as chain extenders and optionally monoamines and / or monoalcohols as chain terminators and has been frequently described (EP 669 353, EP 669 354 DE 30 30 572, EP 639 598 or EP 803 524).
  • Preferred uretdione curing agents A) have a free NCO content of less than 5% by weight and a content of uretdione groups of from 1 to 25% by weight, preferably from 6 to 25% by weight (calculated as C 2 N 2 O) 2 , molecular weight 84). Preference is given to polyesters having an OH number of 30 to 150 mg KOH / g and an average molecular weight of 500 to 6000 g / mol or monomeric dialcohols, such as.
  • the hardeners A) may also have isocyanurate, biuret, allophanate, urethane and / or urea structures.
  • hydroxyl-containing polymers B) are polymers having an OH number of 20 - 500 mg KOH / gram, preferably 30 to 120 mg KOH / g, wherein the polymer is based on at least one di- or polyol with at least one secondary OH group and the Share is at least 2 mol% based on the alcohols used, used.
  • At least one di- or polyol with at least one secondary alcohol group is mandatory in the polymers B).
  • 1, 2-propylene glycol, 2,3-butylene glycol, glycerol, hexane triol-1, 2,6 and butane triol-1, 2,4 are listed as examples. Glycerol is particularly preferred, alone or in mixtures.
  • the proportion of required alcohol with secondary OH groups must be at least 2 mol% based on the alcohols used. The proportion can also be 100 mol%. Preferably, 2 to 20 mol%, particularly preferably 3 to 10 mol%, of these alcohols are contained in the polymers B).
  • polyesters are suitable.
  • the preferred carboxylic acids for the preparation of these polyesters may be aliphatic, cycloaliphatic, aromatic and / or heterocyclic in nature and optionally substituted by halogen atoms and / or unsaturated. Examples which may be mentioned are: succinic, adipic, cork, azelaic, sebacic, phthalic, terephthalic, isophthalic, trimellitic, pyromellitic, tetrahydrophthalic, hexahydrophthalic, hexahydroterephthalic, di- and tetrachlorophthalic .
  • polyhydric alcohols come z.
  • ethylene glycol 1, 2- and 1, 3-propylene glycol, 1, 4- and 2,3-butylene glycol, di-ß-hydroxyethylbutandiol, 1, 6-hexanediol, 1, 8-octanediol, neopentyl glycol, cyclohexanediol, bis- (hydroxymethyl) propane,
  • 2-methylpropanediol-1 3. 2-Methylpentanediol-1, 5, 2,2,4 (2,4,4) -trimethylhexanediol-1, 6, glycerol, trimethylolpropane, trimethylolethane, hexanetriol-1, 2,6, butanetriol-1, 2,4, tris - (ß-hydroxyethyl) isocyanurate, pentaerythritol, mannitol and sorbitol and diethylene glycol, ethylene glycol, tetraethylene glycol, dipropylene glycol, polypropylene glycol, polybutylene glycol, xylylene glycol and
  • mono- and polyesters from lactones eg. B.
  • ⁇ -caprolactone or hydroxycarboxylic acids eg. As hydroxypivalic, ⁇ -hydroxydecanoic, ⁇ -hydroxycaproic, thioglycolic, can be used as starting materials for the preparation of the polymers B.
  • Polyesters of the above-mentioned p.
  • polycarboxylic acids or their derivatives and polyphenols such as hydroquinone, bisphenol-A, 4,4'-dihydroxybiphenyl or bis (4-hydroxyphenyl) - sulfone;
  • Polyester of carbonic acid which consists of hydroquinone, diphenylolpropane, p-xylylene glycol, ethylene glycol, butanediol or hexanediol-1, 6 and other polyols by conventional condensation reactions, eg. B.
  • polyesters B) are z.
  • reaction products of polycarboxylic acids and glycidic compounds as z. B. in DE-OS 24 10 513 are described.
  • glycidyl compounds which can be used are esters of 2,3-epoxy-1-propanol with monobasic acids having 4 to 18 carbon atoms, such as glycidyl palmitate, glycidyl laurate and glycidyl stearate, alkylene oxides of 4 to 18 carbon atoms, such as butylene oxide, and Glycidyl ethers, such as octyl glycidyl ether.
  • the polyesters B) can be obtained in a conventional manner by condensation in an inert gas atmosphere at temperatures of 100 to 260 ° C, preferably 130 to 220 ° C, in the melt or in azeotropic procedure, as described, for.
  • in methods of organic chemistry Houben-Weyl; Vol. 14/2, pages 1 to 5, 21 to 23, 40 to 44, Georg Thieme Verlag, Stuttgart, 1963, or by C.R. Martens, Alkyd Resins, pages 51 to 59, Reinhold Plastics Appl. Series, Reinhold Publishing Comp., New York, 1961.
  • polymers B) are also hydroxy-functional polyethers and polycarbonates into consideration.
  • Preferred polyethers may, for. Example by polyaddition of epoxides such as ethylene oxide, propylene oxide, butylene oxide, trimethylene oxide, 3,3-bis (chloromethyl) -oxabicyclobutane, tetrahydrofuran, styrene oxide or the bis (2,3) - epoxypropylether of diphenylolpropane, by cationic polymerization in the presence of Lewis acids, such as. B.
  • epoxides such as ethylene oxide, propylene oxide, butylene oxide, trimethylene oxide, 3,3-bis (chloromethyl) -oxabicyclobutane, tetrahydrofuran, styrene oxide or the bis (2,3) - epoxypropylether of diphenylolpropane
  • boron trifluoride or by anionic polymerization with alkali metal hydroxides or alkali metal or by addition of these epoxides, optionally in admixture or sequentially, to starting components with reactive hydrogen atoms, such as alcohols or amines, for.
  • reactive hydrogen atoms such as alcohols or amines
  • di- ( ⁇ -hydroxyethoxy) -resorcinol examples mentioned polymers B) having carbonate groups can be known by reacting the exemplified dihydric or trihydric alcohols of molecular weight range 62 to 300 with diaryl carbonates, such as. As diphenyl carbonate, phosgene or preferably cyclic carbonates, such as. B. trimethylene carbonate or 2,2-dimethyl-trimethylene carbonate (NPC) or mixtures of such cyclic carbonates.
  • Particularly preferred carbonate diols are those which can be prepared from the dihydric alcohols mentioned as starter molecules and NPC with ring opening.
  • polymers B) are also z. B. in polyurethane chemistry known polythioethers, polyacetals, polyepoxides, polyester amides or polyurethanes in the molecular weight range 250 to 8500 g / mol, which have isocyanate-reactive hydroxyl groups suitable.
  • mixtures of the aforementioned polymers B) can be used.
  • polymers B) containing secondary alcohols are more pronounced in the polyurethane compositions according to the invention, the higher the Tg of these polymers. Therefore, polymers B) are preferred based on secondary alcohols having a Tg of at least 45 0 C. Even more preferred are such polymers B) having a Tg of at least 55 ° C. and most preferred are those polymers B) having a Tg of at least 60 ° C.
  • the ratio of A) to B), expressed by the NCO: OH ratio of these components varies from 0.5: 1 to 5: 1 NCO: OH, preferably from 1: 1 to 2.5: 1 NCO: OH.
  • the invention also provides the use of at least one catalyst C), which leads to an increased reactivity of uretdione groups.
  • catalysts are preferably selected from the group of the quaternary ammonium or phosphonium salts with carboxylates, hydroxides or halides as the counterion, or the metal hydroxides. Examples of such catalysts are: tetramethylammonium formate, tetramethylammonium acetate, tetramethylammonium propionate, tetramethylammonium butyrate,
  • Tetramethyl ammonium benzoate Tetramethyl ammonium benzoate, tetraethyl ammonium formate, tetraethyl ammonium acetate, tetraethyl ammonium propionate, tetraethyl ammonium butyrate, tetraethyl ammonium benzoate, tetrapropyl ammonium formate, tetrapropyl ammonium acetate, tetrapropyl ammonium propionate, tetrapropyl ammonium butyrate,
  • Tetrapropylammonium benzoate Tetrapropylammonium benzoate, tetrabutylammonium formate, tetrabutylammonium acetate, tetrabutylammonium propionate, tetrabutylammonium butyrate and tetrabutylammonium benzoate.
  • Methyltributylammonium hydroxide methyltriethylammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide,
  • Tetrapentylammonium hydroxide Tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, tetradecylammonium hydroxide, tetradecyltrihexylammonium hydroxide, tetraoctadecylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, trimethylvinylammonium hydroxide, tetramethylammonium fluoride,
  • Tetraethylammonium fluoride, tetrabutylammonium fluoride, tetraoctylammonium fluoride and benzyltrimethylammonium fluoride lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, aluminum hydroxide, zinc hydroxide, tetrabutylammonium chloride,
  • Examples include lithium acetoacetate and zinc acetylacetonate. Particularly preferred is zinc acetylacetonate.
  • catalysts C) can be used. They are in an amount of 0.001 to 5 wt .-%, preferably 0.01 to 3 wt .-%, particularly preferably from 0.5 to 1, 5 wt .-%, based on the total formulation of the components A) - F. ) contain.
  • the catalysts C) may be surrounded with an inner shell and encapsulated therewith.
  • the catalysts may contain water of crystallization, which is not taken into account in the calculation of the amount of catalyst used, d. H. the amount of water is deducted.
  • a variant according to the invention includes the polymeric attachment of such catalysts C) to the hardener A) or to the hydroxyl-containing polymers B). So z. B. free alcohol, thio or amino groups of the ammonium salts
  • Acid, isocyanate, or glycidyl groups of the hardener A) or hydroxyl-containing polymers B) are reacted to the catalysts C) in the polymeric composite to integrate.
  • uretdione-containing curing agents include hydroxyl-containing polyesters. Due to the method of preparation of polyesters, they sometimes carry acid groups to a small extent. In the presence of such acid-group-bearing polyesters, it makes sense to use the catalysts mentioned either in excess relative to the acid groups, or to add reactive compounds which are capable of intercepting acid groups. Both monofunctional and polyfunctional compounds can be used for this purpose.
  • Reactive acid-scavenging compounds D are well known in paint chemistry.
  • basic salts such as hydroxides, bicarbonates or carbonates with acid groups at elevated temperatures.
  • Triglycidyl ether isocyanurate (TGIC) EPIKOTE 828 (diglycidyl ether based on bisphenol A, Schell), glycidyl versatate, ethylhexyl glycidyl ether, butyl glycidyl ether, POLYPOX R 16
  • These reactive compounds can be used in proportions by weight of from 0.1 to 10%, preferably from 0.5 to 3%, based on the total formulation.
  • Acids which are mentioned under E) are all substances, solid or liquid, organic or inorganic, monomeric or polymeric, which have the properties of a Bronsted or a Lewis acid. Examples are: sulfuric acid, Acetic acid, benzoic acid, malonic acid, succinic acid, terephthalic acid, but also copolyesters or copolyamides having an acid number of at least 20. If present, the proportion of these acids in the overall formulation may be between 0.01% and 20%, preferably between 0.1 and 5%. ,
  • auxiliaries and additives F may be used, such as leveling agents, eg. As polysilicone or acrylates, light stabilizers z. As sterically hindered amines, or other auxiliaries, such as. As described in EP 669 353, be added in a total amount of 0.05 to 5 wt .-%. Fillers and pigments such. Titanium dioxide may be added in an amount of up to 50% by weight of the total composition.
  • additional catalysts such as are already known in polyurethane chemistry may be included.
  • organometallic catalysts such as. As dibutyltin dilaurate, or tertiary amines, such as. B. 1, 4-diazabicyclo [2.2.2,] octane, in amounts of 0.001 -1 wt .-%.
  • the homogenization of all constituents for the preparation of the polyurethane composition according to the invention can be carried out in suitable aggregates, such. As heated stirred tanks, kneaders, or extruders, take place
  • Terephthalic acid (688 g, 4.1 mol), adipic acid (12.5 g, 0.1 mol), 2,2 '-dimethyl-1, 3- propanediol (302 g, 2.9 mol), ethylene glycol (93 g , 1, 5 mol) and glycerol (42 g, 0.5 mol) are melted in a 2 l flask with distillation head in a stream of nitrogen. When reaching a temperature of 160 ° C, water begins to distill off. Within one hour, the temperature is gradually increased to 220 ° C. After four more hours at this temperature, the dehydration slows down.
  • Terephthalic acid (688 g, 4.1 mol), adipic acid (12.5 g, 0.1 mol), 2,2 '-dimethyl-1, 3- propanediol (302 g, 2.9 mol), ethylene glycol (93 g , 1, 5 mol) and trimethylolpropane (67 g, 0.5 mol) are melted in a 2 l flask with distillation head in a stream of nitrogen.
  • ethylene glycol 93 g , 1, 5 mol
  • trimethylolpropane 67 g, 0.5 mol
  • Polyesters A and B are comparable because of their similar composition.
  • Terephthalic acid (688 g, 4.1 mol), adipic acid (12.5 g, 0.1 mol), 2,2 '-dimethyl-1, 3- propanediol (453 g, 4.4 mol), and Glycehn (34 g, 0.4 mol) are melted in a 2 l flask with distillation head in a stream of nitrogen. Upon reaching a
  • Temperature of 160 ° C begins to distill water. Within one hour, the temperature is gradually increased to 220 ° C. After four more hours at this temperature, the dehydration slows down. 200 mg of titanium tetrabutoxide are stirred in and further worked in vacuo, which is adjusted in the course of the reaction so that still distillate is obtained. After reaching a hydroxyl number of 41 mg KOH / g (method DIN 53240-2) and an acid number of 6.0 mg KOH / g (method DIN EN ISO 2114) is turned off. The Glass transition temperature of the polyester is 60 ° C (DSC method, 2 heating). Viscosity (120 0 C): 910 mPas.
  • Terephthalic acid (688 g, 4.1 mol), adipic acid (12.5 g, 0.1 mol), 2,2 '-dimethyl-1, 3- propanediol (453 g, 4.4 mol) and trimethylolpropane (54 g, 0.4 mol) are melted in a 2 l flask with distillation head in a stream of nitrogen.
  • a temperature of 160 ° C water begins to distill off.
  • the temperature is gradually increased to 240 ° C.
  • the dehydration slows down.
  • 200 mg of titanium tetrabutoxide are stirred in and further worked in vacuo, which is adjusted in the course of the reaction so that still distillate is obtained.
  • Polyester C and D are comparable due to their similar composition.
  • the comminuted feedstocks from Table 2 are intimately mixed in a premixer and then homogenized in the extruder to a maximum of 130 ° C. After cooling, the extrudate is broken and ground with a pin mill to a particle size ⁇ 63 microns. Thereafter, the electrostatic spraying was carried out on normal steel sheets (layer thickness 70-90 microns) and curing in an oven within 30 min and 150 0 C. The examination of the cured films gave the following results, in Table 3:

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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  • Engineering & Computer Science (AREA)
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  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne des compositions à base de polyuréthane, durcissables à basse température et comportant des groupes d'uréthanedione, qui contiennent des polymères formés à partir de polyols portant des groupes OH secondaires.
PCT/EP2008/055686 2007-05-11 2008-05-08 Compositions à base de polyuréthane, durcissables à basse température et comportant des groupes uretdione, qui contiennent des polymères formés à partir de polyols portant des groupes oh secondaires Ceased WO2008138855A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007022789.4 2007-05-11
DE102007022789A DE102007022789A1 (de) 2007-04-26 2007-05-11 Bei niedriger Temperatur härtbare, Uretdiongruppen aufweisende Polyurethanzusammensetzungen enthaltend Polymere auf der Basis von sekundären OH-Gruppen tragenden Polyolen

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WO2008138855A1 true WO2008138855A1 (fr) 2008-11-20

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009095117A1 (fr) * 2008-02-01 2009-08-06 Evonik Degussa Gmbh Procédé de production de compositions polyuréthanne contenant des groupes uretdione hautement actifs dans un mélange à sec
WO2010108701A1 (fr) * 2009-03-24 2010-09-30 Evonik Degussa Gmbh Préimprégnés et corps moulés réalisés à partir desdits préimprégnés
WO2013139704A1 (fr) * 2012-03-20 2013-09-26 Bayer Intellectual Property Gmbh Préimprégnés polyuréthane stables au stockage et éléments composites renforcés par fibres produits à partir desdits préimprégnés
EP2698393A1 (fr) * 2007-07-26 2014-02-19 Ajinomoto Co., Inc. Composition de résine
CN105246952A (zh) * 2013-04-19 2016-01-13 科思创德国股份公司 聚氨酯预浸料和由其制造的纤维复合元件
US9593135B2 (en) 2012-10-23 2017-03-14 Evonik Degussa Gmbh Compositions comprising alkoxysilane-containing isocyanates and acid stabilisers
US10093826B2 (en) 2016-06-27 2018-10-09 Evonik Degussa Gmbh Alkoxysilane-functionalized allophanate-containing coating compositions

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WO2005085314A1 (fr) * 2004-03-06 2005-09-15 Degussa Ag Procede de production de compositions de polyurethanne solides hautement reactives contenant des groupes uretdione

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EP1522548A1 (fr) * 2003-10-09 2005-04-13 Degussa AG Compositions de polyuréthane contenant des groupes urétidinedione réticulables à basse temperature
WO2005085314A1 (fr) * 2004-03-06 2005-09-15 Degussa Ag Procede de production de compositions de polyurethanne solides hautement reactives contenant des groupes uretdione

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US9018321B2 (en) 2007-07-26 2015-04-28 Ajinomoto Co., Inc. Resin composition
EP2698393A1 (fr) * 2007-07-26 2014-02-19 Ajinomoto Co., Inc. Composition de résine
US8702899B2 (en) 2008-02-01 2014-04-22 Evonik Degussa Gmbh Dryblend process for preparing high-reactivity polyurethane compositions containing uretdione groups
WO2009095117A1 (fr) * 2008-02-01 2009-08-06 Evonik Degussa Gmbh Procédé de production de compositions polyuréthanne contenant des groupes uretdione hautement actifs dans un mélange à sec
RU2540078C2 (ru) * 2009-03-24 2015-01-27 Эвоник Дегусса Гмбх Препреги и получаемые из них формованные изделия
WO2010108701A1 (fr) * 2009-03-24 2010-09-30 Evonik Degussa Gmbh Préimprégnés et corps moulés réalisés à partir desdits préimprégnés
CN104185649A (zh) * 2012-03-20 2014-12-03 拜耳知识产权有限责任公司 储存稳定的聚氨酯-预浸料坯和由其生产的纤维复合材料组件
WO2013139704A1 (fr) * 2012-03-20 2013-09-26 Bayer Intellectual Property Gmbh Préimprégnés polyuréthane stables au stockage et éléments composites renforcés par fibres produits à partir desdits préimprégnés
US9399705B2 (en) 2012-03-20 2016-07-26 Bayer Intellectual Property Gmbh Storage-stable polyurethane-prepregs and fibre composite components produced therefrom
RU2616696C2 (ru) * 2012-03-20 2017-04-18 Байер Интеллектуэль Проперти Гмбх Устойчивые при хранении полиуретановые препреги и полученные из них волокнистые композиционные конструктивные элементы
CN104185649B (zh) * 2012-03-20 2017-04-26 科思创德国股份有限公司 储存稳定的聚氨酯‑预浸料坯和由其生产的纤维复合材料组件
US9593135B2 (en) 2012-10-23 2017-03-14 Evonik Degussa Gmbh Compositions comprising alkoxysilane-containing isocyanates and acid stabilisers
CN105246952A (zh) * 2013-04-19 2016-01-13 科思创德国股份公司 聚氨酯预浸料和由其制造的纤维复合元件
US10093826B2 (en) 2016-06-27 2018-10-09 Evonik Degussa Gmbh Alkoxysilane-functionalized allophanate-containing coating compositions

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