WO2017085158A1 - Polyols de polyester ayant une solubilité améliorée - Google Patents

Polyols de polyester ayant une solubilité améliorée Download PDF

Info

Publication number
WO2017085158A1
WO2017085158A1 PCT/EP2016/077931 EP2016077931W WO2017085158A1 WO 2017085158 A1 WO2017085158 A1 WO 2017085158A1 EP 2016077931 W EP2016077931 W EP 2016077931W WO 2017085158 A1 WO2017085158 A1 WO 2017085158A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
polyester polyol
methanol
tetrahydrofuran
component
Prior art date
Application number
PCT/EP2016/077931
Other languages
English (en)
Inventor
Kathrin COHEN
David TUERP
Christina HAAF-KLEINHUBBERT
Original Assignee
Basf Se
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Basf Se filed Critical Basf Se
Publication of WO2017085158A1 publication Critical patent/WO2017085158A1/fr

Links

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
    • C08G18/28—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
    • 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
    • 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
    • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
    • C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
    • 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
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • 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

Definitions

  • polyester polyols with enhanced solubility Description The present invention relates to a polyester polyol based on a carboxylic acid component (A) which comprises at least one carboxylic acid having at least 2 carboxyl groups and an alcohol component (B) which comprises at least [5-(hydroxymethyl)tetrahydrofuran-2-yl]methanol, to processes for preparing such polyester polyols, to the use of these polyester polyols in coatings, and to PU and HMMM varnishes comprising these polyester polyols.
  • A carboxylic acid component
  • B which comprises at least [5-(hydroxymethyl)tetrahydrofuran-2-yl]methanol
  • Polyester polyols and their use for producing coatings are known per se.
  • WO 2012/005647 A1 discloses a branched polyester based on a dicarboxylic acid component (A) comprising at least one furandicarboxylic acid or its ester or halide, on a diol component (B), and on a branching component (C) comprising at least one component having at least three or more reactive groups, for esterification and/or transesterification reaction(s).
  • This polyester is used for producing protective and/or decorative coatings, such as in powder coatings or 2-component PU coatings, for example.
  • WO 2012/005648 A1 describes an unsaturated oligoester or polyester based on at least one carboxylic acid component (A), comprising at least one mono-, di-, tri-, or polybasic carboxylic acid, and on an alcohol component (B), comprising at least one mono-, di-, tri-, or polyhydric alcohol, for one or more esterification and/or transesterification reaction(s), characterized in that the carboxylic acid component (A) comprises at least one furandicarboxylic acid or the ester or halide thereof and in that the carboxylic acid component (A) and/or the alcohol component (B) comprise(s) at least one component having at least one carbon-carbon double or triple bond.
  • oligoesters or polyesters prepared according to WO 2012/005648 A1 are used for producing decorative and/or protective, solvent-borne or waterborne varnishes, inks, enamels, gelcoats, adhesives, or putties, such as in the production of fiber materials and plastics constructions.
  • polyesters disclosed in WO 2012/005647 A1 and WO2012/005648 A1 are disadvantages of the polyesters disclosed in WO 2012/005647 A1 and WO2012/005648 A1.
  • the furandicarboxylic acid(s) present significantly lower the solubility of the polyesters in the majority of solvents.
  • Polyesters of low solubility have only limited usefulness in varnishes, since they have to be diluted with substantial amounts of solvents.
  • the use of polyesters based on furandicarboxylic acids in varnishes and inks leads to disadvantages, therefore, because high solubility of the polyester in solvents is an advantage.
  • polyester polyol based on a) a carboxylic acid component (A) which comprises at least one carboxylic acid having at least 2 carboxyl groups, and
  • an alcohol component (B) which comprises at least [5-(hydroxymethyl)tetrahydrofuran-2- yl]methanol.
  • polyester polyols based on [5-(hydroxymethyl)- tetrahydrofuran-2-yl]methanol are used in polyurethane (PU) or hexamethoxymethylmelamine (HMMM) varnishes
  • PU polyurethane
  • HMMM hexamethoxymethylmelamine
  • carboxylic acid component (A) Used in accordance with the invention as carboxylic acid component (A) are carboxylic acids having at least two carboxyl groups, i.e., di-, tri-, or polycarboxylic acids, preferably di- or tricarboxylic acids, and more preferably dicarboxylic acids.
  • Suitable dicarboxylic acids are generally aliphatic, cycloaliphatic, aromatic, heteroaromatic, or heterocyclic dicarboxylic acids or their alkyl esters or halides. In general the dicarboxylic acids have 2 to 20 carbon atoms, preferably 4 to 12 carbon atoms, more preferably 6 to 10 carbon atoms.
  • alkanedioic acids alkenedioic acids, cyclohexanedioic acids, cyclopentanedioic acids, benzenedicarboxylic acids, or furandicarboxylic acids, or their esters or halides.
  • dicarboxylic acids examples include adipic acid, glutaric acid, succinic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedioic acid, octadecanedioic acid, maleic acid, fumaric acid, itaconic acid, 1 ,2-cyclohexanedicarboxylic acid, 1 ,3-cyclohexane- dicarboxylic acid, 1 ,4-cyclohexanedicarboxylic acid, furandicarboxylic acid, isophthalic acid, phthalic acid, or terephthalic acid.
  • alkyl esters and/or dialkyl esters of these carboxylic acids which may be esterified with alcohols based on 1 to 4 carbon atoms, or the halides thereof, such as chloride, bromide and/or iodide, for example.
  • the stated dicarboxylic acids may be used individually or in a mixture of several dicarboxylic acids.
  • Preferred dicarboxylic acids of the carboxylic acid component (A) are adipic acid
  • the carboxylic acid component (A) comprises adipic acid.
  • Suitable tricarboxylic acids are linear or branched aliphatic, cycloaliphatic, aromatic, heteroaromatic, or heterocyclic tricarboxylic acids or their alkyl esters or halides. In general tricarboxylic acids have 4 to 20 carbon atoms. Preference is given to using benzenetricarboxylic acids.
  • trimellitic acid can be used. Preference is given to using trimellitic acid or its alkyl esters, such as methyl or ethyl esters, for example, or halides, such as chlorides, bromides and/or iodides, for example. A particularly preferred embodiment is the use of trimellitic acid.
  • the stated tricarboxylic acids can be used individually or in a mixture of several tricarboxylic acids.
  • Polycarboxylic acids in the sense of the invention are organic compounds having at least four carboxyl groups.
  • suitable polycarboxylic acids are linear or branched aliphatic, cycloaliphatic, aromatic, heteroaromatic, or heterocyclic polycarboxylic acids or their alkyl esters or halides. In general the polycarboxylic acids have 5 to 20 carbon atoms.
  • pyromellitic acid or its alkyl esters such as methyl or ethyl esters, for example, or halides, such as chlorides, bromides and/or iodides, for example.
  • halides such as chlorides, bromides and/or iodides
  • Particularly preferred is the use of pyromellitic acid.
  • the stated polycarboxylic acids can be used individually or in a mixture of several polycarboxylic acids. Also suitable in accordance with the invention are mixtures of the stated dicarboxylic, tricarboxylic, or polycarboxylic acids.
  • the stated dicarboxylic, tricarboxylic, and polycarboxylic acids are available commercially. They may also be obtained from natural raw materials. Natural raw materials is a term used in particular for substances obtained by processing from plants, or from parts of plants (or animals). Furthermore, the stated dicarboxylic, tricarboxylic, and polycarboxylic acids may be produced by microbiological methods. These are common knowledge to the skilled person or, for example, are described by F. Koopman, N. Wierckx, J.H. de Winde, and H.J. Ruijssenaars. Bioresource Technology 2010, volume 101 , No. 16, pages 6291 to 6296.
  • the carboxylic acid component (A) preferably comprises at least adipic acid, octadecanedioic acid, isophthalic acid and/or furandicarboxylic acid. With particular preference the carboxylic acid component (A) comprises at least adipic acid.
  • the alcohol component (B) of the invention comprises at least [5-(hydroxymethyl)tetrahydro- furan-2-yl]methanol.
  • Suitable additional alcohols are generally alcohols having at least two hydroxyl groups, i.e., diols, triols, or polyols. Preference is given to using diols or triols and more preferably diols.
  • Suitable in accordance with the invention are, for example, C2 to C12 alcohols, i.e., alcohols having 2 to 12 carbon atoms, preferably C2 to C10 alcohols, and very preferably C2 to C8 alcohols.
  • Diols suitable in accordance with the invention are generally aliphatic, cycloaliphatic, or aromatic diols, polyester diols or polyether diols, preferably aliphatic diols.
  • Suitable aliphatic diols are common knowledge to the skilled person and comprise, for example, 2,2-dimethyl-1 ,3- propanediol, ethylene glycol, diethylene glycol, 3-oxapentane-1 ,5-diol, 1 ,3-propanediol, 1 ,2- propanediol, dipropylene glycol, 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, 2-methyl-1 ,3- propanediol and 3-methyl-1 ,5-pentanediol, 2-butyl-2-ethyl-1 ,3-propanediol, cyclohexan
  • Suitable triols are generally aliphatic, cycloaliphatic, or aromatic triols, polyester triols or polyether triols, such as glycerol, trimethylolpropane, 1 ,2,3-trihydroxybenzene, 1 ,2,4- trihydroxybenzene, or 1 ,3,5-trihydroxybenzene, for example. Preference is given to using trimethylolpropane and/or glycerol.
  • Polyols as a constituent of component B are, for the purposes of the invention, organic compounds having at least four hydroxyl groups.
  • Suitable polyols are generally aliphatic, cycloaliphatic, or aromatic polyols, such as pentaerythritol, for example, and also polyester polyols or polyether polyols (polyetherols) having molecular weights of between 200 and 6000 g/mol. Preference is given to using polyetherols with a molecular weight of 200 to
  • the stated di-, tri-, or polyols are available commercially. They may also be obtained from natural raw materials. Natural raw materials is a term used in particular for substances obtained by processing from plants, or from parts of plants (or animals). Furthermore, the stated di-, tri-, and polyols may be produced by microbiological methods. These are common knowledge to the skilled person or, for example, are described by F. Koopman, N. Wierckx, J.H. de Winde, and H.J. Ruijssenaars. Bioresource Technology 2010, volume 101 , No. 16, pages 6291 to 6296.
  • the alcohol component (B) comprises, apart from
  • [5-(hydroxymethyl)tetrahydrofuran-2-yl]methanol at least one further C2 to C8 diol, preferably at least 2,2-dimethyl-1 ,3-propanediol, 2-butyl-2-ethyl-1 ,3-propanediol, cyclohexanedimethanol and/or 2-ethyl-1 ,3-hexanediol, more preferably at least 2, 2-dimethyl-1 ,3-propanediol, very preferably 2,2-dimethyl-1 ,3-propanediol.
  • Component B comprises in general at least 10 wt% of [5-(hydroxymethyl)tetrahydrofuran-2-yl]- methanol, preferably 10 to 100 wt% of [5-(hydroxymethyl)tetrahydrofuran-2-yl]methanol, more preferably 50 to 100 wt% of [5-(hydroxymethyl)tetrahydrofuran-2-yl]methanol, and especially preferably 75 to 100 wt% of [5-(hydroxymethyl)tetrahydrofuran-2-yl]methanol, based on the total weight of component B.
  • the alcohol component (B) consists of [5-(hydroxy- methyl)tetrahydrofuran-2-yl]methanol.
  • polyester polyols examples include polycondensation reactions, i.e., polycondensation of the functional carboxylic acid groups with the hydroxyl groups, e.g., condensation in the presence of or without addition of solvents, preferably polycondensation without addition of solvents.
  • catalysts examples include iron, cadmium, cobalt, lead, zinc, zirconium, hafnium, aluminum, antimony, magnesium, titanium, or tin catalysts in the form of metals, metal oxides, or metal salts, or acids such as, for example, sulfuric acid, p-toluenesulfonic acid, or bases such as, for example, potassium hydroxide or sodium methoxide. Also suitable are mixtures of these catalysts.
  • polyester polyols are, for example, high- temperature polycondensation or enzymatically catalyzed polycondensation, or
  • polyester polyol of the invention comprising a carboxylic acid component (A) which comprises at least one carboxylic acid having at least 2 carboxyl groups and an alcohol component (B) which comprises at least [5-(hydroxymethyl)tetrahydrofuran-2-yl]methanol is polymerized by polycondensation reaction.
  • the polyester polyol of the invention comprising a carboxylic acid component (A) which comprises at least one carboxylic acid having at least 2 carboxyl groups and an alcohol component (B) which comprises at least [5-(hydroxymethyl)tetrahydrofuran-2-yl]- methanol is prepared by means of condensation, without addition of solvents, catalyzed by iron, cadmium, cobalt, lead, zinc, zirconium, hafnium, aluminum, antimony, magnesium, titanium, or tin catalysts in the form of metals, metal oxides, or metal salts, or acids such as, for example, sulfuric acid, p-toluenesulfonic acid, or bases such as, for example, potassium hydroxide or sodium methoxide.
  • A carboxylic acid component
  • B which comprises at least [5-(hydroxymethyl)tetrahydrofuran-2-yl]- methanol
  • a suitable molar mixing ratio of the carboxylic acid component (A) to the alcohol component (B) is generally 1 :0.5 to 1 :2. Preferably this mixing ratio is 1 :0.67 to 1 :1.5, and more preferably 1 :0.8 to 1 :1.2.
  • the polyester polyols of the invention generally have a linear or branched molecular structure.
  • Linear means that the polyester polyol molecules each consist only of one polymer chain and possess no branches.
  • a branched polyester polyol is characterized by branches with side chains being attached to the main polymer chain.
  • Branched polyester polyols differ in their degree of branching. Suitable degrees of branching for the polyester polyols of the invention, determined by the method from D. Holter, A. Burgath, H. Frey. Acta Polymer 1997, volume 48, pages 30 to 35, are from 1 to 100, for example, preferably from 1.5 to 10, more preferably from 2 to 5.
  • the number-average molecular weight of the polyester polyols is determined by means of gel permeation chromatography based on four styrene-divinylbenzene (SDV) columns. Calibration is carried out using polymethyl methacrylate (PMMA) or polyethylene glycol (PEG) standards. The injected sample volume is 100 ⁇ having a concentration of 2 mg/ml. Elution is carried out with tetrahydrofuran (THF) at a flow rate of 1 ⁇ /min. Suitable molecular weight ranges for the polyester polyols obtained in accordance with the invention are common knowledge to the skilled person.
  • the number-average molecular weight of the polyester polyol is generally in the range from 200 to 8000 g/mol, preferably in the range from 350 to 5000 g/mol, more preferably in the range from 500 to 3000 g/mol.
  • Polyester polyols of the invention generally have a viscosity of 20 to 6000 mPas, preferably 50 to 4500 mPas, and more preferably 80 to 3000 mPas.
  • the polyester polyols of the invention have an acid number of 0.1 to 30 mg KOH/g, preferably 0.3 to 25 mg KOH/g, and very preferably 0.5 to 20 mg KOH/g.
  • Polyester polyols suitable in accordance with the invention generally have a hydroxyl number in the range from 25 to 230 mg KOH/g, preferably in the range from 35 to 140 mg KOH/g, more preferably in the range from 40 to 1 15 mg KOH/g, and very preferably in the range from 70 to 1 10 mg KOH/g.
  • Suitable solvents for dissolving the polyester polyols of the invention are the solvents known to the skilled person for the dissolution of polyester polyols that are used in order to produce coatings. Encompassed here among others are aprotic-polar or protic solvents or aliphatic hydrocarbon mixtures.
  • Suitable aprotic-polar solvents are ketones.
  • MEK methyl ethyl ketone
  • MAK methyl amyl ketone
  • acetone or mixtures thereof.
  • Suitable protic solvents are linear or branched carboxylic acids or alcohols.
  • aliphatic hydrocarbon mixtures suitable as solvents are alkanes or isoalkanes or mixtures thereof.
  • One particularly preferred embodiment uses methyl ethyl ketone or butyl acetate as solvent. With very particular preference, methyl ethyl ketone is the solvent used.
  • the concentrations of the polyester polyol of the invention that are used in the solvent are likewise common knowledge to the skilled person.
  • the polyester polyol of the invention is soluble in concentrations of at least 55 wt% in a solvent for polyester polyols, with preference being given to the use of 55 to 85 wt% of polyester polyol, more preferably 60 to 85 wt% of polyester polyol, and very preferably 70 to 85 wt% of polyester polyol, based on the solvent and on the polyester polyol.
  • the polyester polyols of the invention can be used for producing coatings, such as varnishes, for example. Preference is given to using the polyester polyols of the invention for producing polyurethane (PU) varnish or hexamethoxymethylmelamine (HMMM) varnish.
  • PU polyurethane
  • HMMM hexamethoxymethylmelamine
  • PU varnish Processes for producing polyurethane (PU) varnish are common knowledge to the skilled person or are described in WO 2014/191503 A9, for example.
  • the polyester polyol is generally dissolved in solvent. Examples of such solvents have already been described above and are already common knowledge to the skilled person. The concentrations used are also common knowledge to the skilled person.
  • the polyester polyol is soluble in general in concentrations of at least 55 wt% in a solvent for polyester polyols, preferably 55 to 85 wt% of polyester polyol, more preferably 60 to 85 wt% of polyester polyol, and very preferably 70 to 85 wt% of polyester polyol are used, based on the solvent and on the polyester polyol.
  • isocyanate component (C) which comprises at least one isocyanate having at least one isocyanate group.
  • Suitable as isocyanate component (C) are in general compounds having at least one isocyanate group, i.e., monoisocyanates, or polyisocyanates, or isocyanurate, biuret, or allophanate compounds.
  • Polyisocyanates in the sense of the invention are organic compounds having at least two isocyanate groups. Polyisocyanates are used with preference. With particular preference, diisocyanates are used.
  • Suitable diisocyanates are generally linear or branched aliphatic, araliphatic, cycloaliphatic and/or aromatid diisocyanates, examples being 2,2'-, 2,4'-, and/or 4,4'-diphenylmethane diisocyanate (MDI), 1 ,5-naphthylene diisocyanate (NDI), 2,4- and/or 2, 6-tolylene diisocyanate (TDI), diphenylmethane diisocyanate, 3,3'-dimethylbiphenyl diisocyanate, 1 ,2-diphenylethane diisocyanate and/or phenylene diisocyanate, tri-, tetra-, penta-, hexa-, hepta- and/or octa- methylene diisocyanate, 2-methylpentamethylene 1 ,5-diisocyanate, 2-ethylbutylene 1 ,4- di
  • the isocyanate component (C) comprises at least hexamethylene diisocyanate.
  • the isocyanate component (C) consists of
  • polyisocyanurates of aliphatic polyisocyanates more preferably polyisocyanurates of aliphatic diisocyanates, and very preferably polyisocyanurates of hexamethylene diisocyanate, such as Basonat H1100 ® , for example.
  • the stated isocyanates and polyisocyanates are available commercially or can be obtained from natural raw materials. Natural raw materials are more particularly substances obtained by processing from plants, or parts of plants (or animals).
  • Suitable catalysts are the catalysts that are common knowledge to the skilled person for the synthesis of polyurethanes, and are described in, for example, WO 2014/191053 A9 or WO 201 1/083000 A1 , such as tertiary amines or organic metal compounds, for example.
  • tertiary amines examples include triethylamine, dimethylcyclohexylamine, N-methyl- morpholine, ⁇ , ⁇ '-dimethylpiperazine, 2-(dimethylaminoethoxy)ethanol, and
  • Suitable organic metal compounds are, for example, Lewis-acidic organic metal compounds.
  • Lewis acids are understood to be compounds with the ability to form a covalent bond by acceptance of an electron pair (electron pair acceptors).
  • suitable Lewis-acidic organic metal compounds are tin compounds or zinc salts, or tin-free and zinc-free catalysts, such as titanic esters or iron compounds, for example.
  • Suitable tin-free and zinc-free catalysts include organic metal salts of bismuth, zirconium, titanium, aluminum, iron, manganese, nickel, and cobalt, and also cerium salts and cesium salts.
  • Suitable iron compounds are, for example, iron(lll) acetylacetonate or the like.
  • Suitable titanic esters are, for example, titanium tetrabutoxide or titanium tetraisopropoxide.
  • suitable zirconium compounds are zirconium acetylacetonate and zirconium 2,2,6,6-tetramethyl- 3,5-heptanedionate.
  • Lewis-acidic organic metal compounds are tin compounds, such as tin dialkyl salts of aliphatic carboxylic acids, or zinc salts, such as tin diacetate, tin dioctoate, tin dilaurate, dimethyltin diacetate, dibutyltin dibutyrate, dibutyltin bis(2-ethylhexanoate), dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, zinc(ll) diacetate or zinc(ll) dioctoate, for example.
  • tin compounds such as tin dialkyl salts of aliphatic carboxylic acids, or zinc salts, such as tin diacetate, tin dioctoate, tin dilaurate, dimethyltin diacetate, dibutyltin dibutyrate, dibutyltin bis(2-ethylhexano
  • Preferred Lewis-acidic organic metal compounds are tin compounds or the tin dialkyl salts of aliphatic carboxylic acids, such as, for example, tin diacetate, tin dioctoate, tin dilaurate, dimethyltin diacetate, dibutyltin dibutyrate, dibutyltin bis(2-ethylhexanoate), dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, or zinc salts, such as zinc(ll) diacetate, zinc(ll) dioctoate, or zirconium compounds, such as, for example, zirconium acetylacetonate or zirconium 2,2,6,6- tetramethyl-3,5-heptanedionate, or bismuth compounds, or titanic esters.
  • tin diacetate, tin dioctoate, tin dilaurate
  • catalysts are also suitable in accordance with the invention.
  • suitable catalyst amounts are from 0.00001 to 0.1 part by weight per 100 parts by weight of polyhydroxyl compound.
  • typical varnish components and/or additives may be added to the varnish.
  • Suitable in accordance with the invention are, for example, antioxidants, UV stabilizers such as UV absorbers and suitable radical scavengers (especially HALS compounds, hindered amine light stabilizers), activators (accelerators), dryers, fillers, pigments, dyes, antistatic agents, flame retardants, thickeners, thixotropic agents, surface-active agents, viscosity modifiers, plasticizers, or chelating agents.
  • suitable typical varnish components and/or additives are also suitable in accordance with the invention. Further details regarding suitable typical varnish components and/or additives and also concerning the amounts used are common knowledge to the skilled person or are described in WO 2014/191503 A9, for example.
  • a suitable mixing ratio of the isocyanate component (C) to the polyester polyol composed of the carboxylic acid component (A) and the alcohol component (B) is, for example, a molar ratio of isocyanate groups to isocyanate-reactive hydroxyl groups of in general 0.2:1 to 5:1 , preferably 0.75:1 to 2.5:1 , more preferably 0.8:1 to 2:1 , and very preferably 0.8:1 to 1.5:1 .
  • Methods for applying the coating composition to substrates, for the curing of the coating composition, and for the optional removal of solvents are known in general to the skilled person or are described in WO 2014/191503 A9, for example.
  • Methods for the coating of substrates encompass, for example, the application of the coating composition to a substrate to be coated, in the desired thickness, and also the removal of volatile constituents optionally present in the coating composition, by means of heating, for example.
  • the isocyanate component (C) is first mixed with the polyester polyol of the invention and optionally with further components and then applied to a substrate.
  • Application may take place, for example, by spraying, troweling, coating with a doctor knife, brushing, rolling, roller coating, pouring, laminating, injection backmolding, or coextruding.
  • Further method constituents and methods are known to the skilled person or are described in WO 2014/191503 A9, for example.
  • Suitable substrates for the varnish formulations of the invention are likewise common knowledge to the skilled person or are described in WO 2014/191503 A9, for example.
  • the coating mixture can be subsequently be cured at an ambient temperature of 20 to 150°C, preferably of 25 to 80°C, and more preferably of 30 to 60°C (e.g., for refinish applications or large objects which are difficult to place in an oven).
  • the varnish mixture is cured generally at 1 10 to 150°C, preferably at 120 to 140°C.
  • the thickness of a layer of this kind for curing may be from 0.1 ⁇ up to several mm, preferably from 1 to 2000 ⁇ , more preferably 5 to 200 ⁇ , very preferably from 5 to 60 ⁇ (based on the varnish in the state in which the solvent is removed from the varnish).
  • the coating compositions and varnish formulations of the invention are suitable for interior and exterior coatings and also for daylight exposure. They can be used as clearcoat, basecoat, and topcoat materials and also as primers and fillers, and they are also suitable for the coating of plastic and/or rubber articles. Further and more detailed possibilities for use are known to the skilled person or are described in WO 2014/191503 A9, for example. Processes for the preparation of hexamethoxymethylmelamine (HMMM) varnish are common knowledge to the skilled person or are described in WO 201 1/101301 A1 , for example.
  • HMMM hexamethoxymethylmelamine
  • the polyester polyol of the invention may be used, for example, as binder.
  • the polyester polyol of the invention is generally dissolved in solvent.
  • concentrations and solvents employed here correspond to those already described above, to those used, as already described, for the preparation of PU varnishes, or else are common knowledge to the skilled person. Examples of solvents are also found in WO 201 1/101301 A1.
  • Preferred solvents for the preparation of HMMM varnishes are methyl ethyl ketones, ethyl acetates, cyclohexanone, methyl isobutyl ketone, isopropanol, n-butanol, methoxypropyl acetate, or xylene, and also mixtures of these solvents. Particular preference is given to using methyl ethyl ketone.
  • Concentrations suitable in accordance with the invention are generally at least 55 wt% of polyester polyol, with preference being given to use of 55 to 85 wt% of polyester polyol, more preferably 60 to 85 wt% of polyester polyol, and very preferably 70 to 85 wt% of polyester polyol, based on the solvent and on the polyester polyol.
  • Amino resins which can be used are all of the compounds known to the skilled person, as described in WO 201 1/101301 A1 , for example, examples being melamine-formaldehyde resins, benzoguanamine/formaldehyde resins, or urea/formaldehyde resins, preferably melamine-formaldehyde resins. Mixtures of the stated amino resins are also suitable in accordance with the invention. These resins may optionally have been at least partly etherified, and preferably are at least partly etherified, via an ether bond, for example, with alcohols such as methanol, ethanol, isobutanol, and n-butanol, and mixtures thereof, for example.
  • a preferred embodiment is the use of at least partially etherified melamine-formaldehyde resins.
  • Particularly preferred is the use of methanol ethers of melamine-formaldehyde resins such as, for example, Luwipal 066 LF ® .
  • Methods and compositions, such as molar incorporation ratios, for example, for the preparation of the amino resins of the invention are known to the skilled person or are described in WO 201 1/101301 A1 , for example.
  • the processes for reacting the amino resin used with the polyester polyol are common knowledge to the skilled person or are described in WO 201 1/101301 A1 , for example.
  • the reaction of the polyester polyol with the amino resin may take place by transetherification, in which, in the case of hydroxyl groups already etherified in the amino resin, the ether group is eliminated and is replaced by a free hydroxyl group of the polyester polyol; or by etherification, in which a free hydroxyl group of the amino resin is converted into an ether by a free hydroxyl group of the polyester polyol.
  • the two reactions may take place simultaneously, insofar as free hydroxyl groups are present.
  • the reaction may take place both with and without catalysis, and with or without addition of an entrainer, such as toluene, for example.
  • an entrainer such as toluene, for example.
  • Catalysts contemplated for the crosslinking of the coating compositions are the catalysts which are common knowledge to the skilled person for the synthesis of HMMM varnishes, such as weak and strong acids, for example. Examples are known, moreover, from WO 201 1/101301 A1 .
  • Weak acids for the purposes of the present invention are mono- or polybasic, organic or inorganic, acids, preferably organic acids, having a pK a value of between 1 .6 and 5.2, preferably between 1 .6 and 3.8.
  • Examples thereof are carbonic acid, phosphoric acid, formic acid, acetic acid, maleic acid, glyoxylic acid, bromoacetic acid, chloroacetic acid, thioglycolic acid, glycine, cyanoacetic acid, acrylic acid, malonic acid, hydroxypropanedioic acid, propionic acid, lactic acid, 3-hydroxypropionic acid, glyceric acid, alanine, sarcosine, fumaric acid, acetoacetic acid, succinic acid, isobutyric acid, valeric acid, ascorbic acid, citric acid, nitrilotriacetic acid, cyclopentanecarboxylic acid, 3-methylglutaric acid, adipic acid, hexanoic acid, benzoic acid, cyclohexanecarboxylic acid, heptanedioic acid, heptanoic acid, phthalic acid, isophthalic acid, terephthalic
  • Strong acids for the purposes of the present invention are mono- or polybasic, organic or inorganic, acids, preferably organic acids, having a pK a value of less than 1 .6, preferably less than 1 .
  • organic acids having a pK a value of less than 1 .6, preferably less than 1 .
  • organic acids preferably organic sulfonic acids.
  • methanesulfonic acid para-toluenesulfonic acid
  • benzenesulfonic acid dodecylbenzenesulfonic acid
  • cyclododecanesulfonic acid or camphorsulfonic acid.
  • One particularly preferred embodiment in accordance with the invention is the use as catalyst of p-toluenesulfonic acid neutralized with amines, such as in Nacure® 2500, for example.
  • Acids can be used as free acids or in blocked form. "Blocking" of the acid means that an acid is present in the form, for example, of a salt of the acid with primary, secondary, and tertiary amines.
  • the acids are used generally in amounts of up to 10 wt%, preferably of 0.1 to 8 wt%, more preferably of 0.3 to 6 wt%, very preferably of 0.5 to 5 wt%, and especially preferably of 1 to 3 wt%, based on the amino resin used.
  • the coating compositions may be admixed additionally, as described in WO 201 1/101301 A1 , with cocrosslinkers, examples being trisalkylcarbamoyltriazines (TACT), preferably
  • trismethylcarbamoyltriazines tris-n-butylcarbamoyltriazines and/or mixed methylated/ n-butylated trisalkylcarbamoyltriazines.
  • the varnish mixtures may further be admixed with typical varnish components and/or additives.
  • typical varnish components and/or additives include antioxidants, stabilizers, activators (accelerators), fillers, pigments, dyes, antistatic agents, flame retardants, thickeners, thixotropic agents, surface-active agents, viscosity modifiers, plasticizers, or chelating agents. Examples can be found in WO 201 1/101301 A1 . Mixtures of the stated typical varnish components and/or additives as well are suitable in accordance with the invention.
  • At least one varnish formulation of the invention is applied in the desired thickness to the substrate that is to be coated, and the volatile constituents of the coating composition are removed (drying), optionally with heating. Coating may take place by spraying, troweling, coating with a doctor knife, brushing, rolling, roller coating, or pouring, under the conditions specified in WO 201 1/101301 A1 , for example.
  • the coating thickness may be in a range from 3 to 1000 g/m 2 and preferably 10 to 200 g/m 2 .
  • solvent substantially present is removed; furthermore, there may also already be a reaction with the binder, whereas the curing encompasses essentially the reaction with the binder.
  • Varnish curing takes place by the methods known to the skilled person, as are described in WO 201 1/101301 A1 , for example, generally depending on the amount of coating material applied and on the crosslinking energy introduced by way of high-energy radiation, by transfer of heat from heated surfaces, or via convection of gaseous media, for example.
  • curing may also take place by means of IR and NIR radiation.
  • Suitable substrates for the varnish formulations of the invention are general knowledge to the skilled person and are described in WO 201 1/101301 A1 , for example, examples being thermoplastic polymers, metals or alloys, wood, paper, textile, leather, nonwoven, surfaces of plastic, glass, ceramic, or mineral building materials.
  • the coating composition of the invention or the HMMM varnish of the invention is suitable, for example, for the coating of the above-described substrates and is in general suitable, moreover, for use as an exterior coating.
  • Other fields of use may be the coating of containers (can coating) and metal strips (coil coatings), and also use as primer, filler, topcoat, or clearcoat. Further details of this are described in WO 201 1/101301 A1 , for example.
  • the present specification further provides a PU varnish comprising at least one polyester polyol based on a carboxylic acid component (A) which comprises at least one carboxylic acid having at least 2 carboxyl groups, and on an alcohol component (B) which comprises at least [5- (hydroxymethyl)tetrahydrofuran-2-yl]methanol.
  • A carboxylic acid component
  • B alcohol component
  • the present specification further provides an HMMM varnish comprising at least one polyester polyol based on a carboxylic acid component (A) which comprises at least one carboxylic acid having at least 2 carboxyl groups, and on an alcohol component (B) which comprises at least [5-(hydroxymethyl)tetrahydrofuran-2-yl]methanol.
  • A carboxylic acid component
  • B alcohol component
  • the viscosity of the polyols is determined unless otherwise specified at 25°C according to DIN EN ISO 3219 (October 1 , 1994 edition) with a Rheotec RC 20 rotational viscometer using spindle CC 25 DIN (spindle diameter: 12.5 mm; measuring cylinder internal diameter:
  • hydroxyl numbers are determined by the phthalic anhydride method of DIN 53240
  • the acid number is determined according to DIN EN 1241 (May 1 , 1998 edition) and is reported in mg KOH/g.
  • a 3000 ml round-neck flask equipped with thermometer, nitrogen inlet, stirrer, and heating jacket is charged initially with 413.7 g of isophthalic acid, 496.8 g of 2,2-dimethyl-1 ,3- propanediol, 121 .3 g of adipic acid, and 1 17.7 g of trimellitic acid.
  • the temperature is raised to 160°C, with distillation of water beginning from 154°C.
  • the temperature is raised further and, when the reaction temperature reaches 175°C, the batch becomes clear.
  • the temperature is raised further to 220°C and held at this temperature for 4.5 hours.
  • the resulting polymer is cooled and discharged when it has reached an acid number of less than 25 mg KOH/g.
  • the resulting polymer has the following properties:
  • a 500 ml round-neck flask equipped with thermometer, nitrogen inlet, stirrer, and heating jacket is charged with 189.6 g of adipic acid, 71 .8 g of isophthalic acid, and 300.9 g of 1 ,4-cyclo- hexanedimethanol.
  • the mixture is heated to 170°C, with distillation beginning when a temperature of 154°C is reached.
  • the temperature is raised further to 220°C and held for 4 hours. After reaching an acid number of less than 2 mg KOH/g, the product is cooled and discharged.
  • the resulting polymer has the following properties:
  • Comparative example 3 A 500 ml round-neck flask equipped with thermometer, nitrogen inlet, stirrer, and heating jacket is charged with 189.6 g of adipic acid and 297.5 g of cyclohexanedimethanol. The mixture is heated to 180°C, with distillation of water beginning at 164°C. The mixture is heated further at 180°C until 42 g of the distillate have been removed. Then the batch is cooled to 100°C and 67.5 g of furandicarboxylic acid are added. The mixture is in turn heated to a temperature of 200°C, which is maintained for 6 hours. After reaching an acid number of less than 2 mg KOH/g, the product is cooled and discharged.
  • the resulting polymer has the following properties: Acid number: 0.1 mg KOH/g
  • a 1000 ml round-neck flask equipped with thermometer, nitrogen inlet, stirrer, and heating jacket is charged with 163.6 g of adipic acid, 349.0 g of 2,2-dimethyl-1 ,3-propanediol, and 58.4 g of trimellitic acid.
  • the mixture is heated to 180°C, with distillation of water beginning at 164°C.
  • the mixture is heated further at 180°C until 40 g of the distillate have been removed.
  • the batch is cooled to 100°C and 174.7 g of furandicarboxylic acid are added.
  • the mixture is in turn heated to a temperature of 200°C, which is maintained for 14 hours. After reaching an acid number of less than 10 mg KOH/g, the product is cooled and discharged.
  • the resulting polymer has the following properties:
  • Inventive example 5 A 3000 ml round-neck flask equipped with thermometer, nitrogen inlet, stirrer, and heating jacket is charged initially with 1309.9 g of adipic acid and 1513.2 g of [5-(hydroxymethyl)- tetrahydrofuran-2-yl]methanol. The mixture is heated to 180°C, during which, at 167°C, the distillation of water begins. The temperature is raised further to 220°C and held for 8 hours. After reaching an acid number of less than 2 mg KOH/g, the product is discharged.
  • the resulting polymer has the following properties:
  • a 500 ml round-neck flask equipped with thermometer, nitrogen inlet, stirrer, and heating jacket is charged with 202.9 g of adipic acid and 291 .6 g of [5-(hydroxymethyl)tetrahydrofuran-2-yl]- methanol and this initial charge is heated to 180°C.
  • the quantity of distillate has reached 41 g, the mixture is cooled to 100°C and 72.2 g of furandicarboxylic acid are added. This is followed by reheating to 200°C. After a further reaction time of 6 hours, the batch becomes clear. After an acid number of less than 10 mg KOH/g has been reached, the product is discharged.
  • the resulting polymer has the following properties:
  • Inventive example 7 A 1000 ml round-neck flask equipped with thermometer, nitrogen inlet, stirrer, and heating jacket is charged with 413.7 g of isophthalic acid, 247.9 g of 2,2-dimethyl-1 ,3-propanediol, 314.2 g of [5-(hydroxymethyl)tetrahydrofuran-2-yl]methanol, 121 .3 g of adipic acid, and 1 17.7 g of trimellitic acid. The mixture is heated to 200°C and the temperature is maintained for 12 hours. When an acid number of less than 20 mg KOH/g has been reached, the product is discharged.
  • the resulting polymer has the following properties: Acid number: 17.5 mg KOH/g
  • a 500 ml round-neck flask equipped with thermometer, nitrogen inlet, stirrer, and heating jacket is charged with 200.8 g of adipic acid, 76.1 g of isophthalic acid, and 289.1 g of
  • the resulting polymer has the following properties:
  • the polymers obtained are investigated for their solubility in butyl acetate and methyl ethyl ketone. This is done by dissolving the samples at 55%, 70%, and 85% in the two solvents.
  • the pendulum damping PD is determined in analogy to DIN EN ISO 1522:2006.
  • the pendulum damping is a measure of the hardness of the coating. High values in this case denote high hardness.
  • the Erichsen cupping EC is determined in analogy to DIN EN ISO 1520:2006.
  • the Erichsen cupping is a measure of the flexibility and elasticity. It is reported in millimeters (mm). High values denote high flexibility.
  • the adhesion is determined via the cross-cut test (DIN EN ISO 2409:2013) on Bonder® panel. G in the table denotes the score for cut, T denotes the score for adhesive tape.
  • Application example 10 varnish 1a (PU varnish)
  • a formulation of 60 wt% polyol in methyl ethyl ketone, Basonat HI 100®, and 1 drop of DBTL (dibutyltin dilaurate) are mixed with one another. Subsequently a wet film 200-300 ⁇ thick is applied to the Bonder® panel and glass substrates.
  • the film After flashing off the solvent (15 minutes, room temperature), the film is cured at 120°C for 30 minutes.
  • varnish 1 b (HMMM varnish)
  • a formulation of 60 wt% polyol in methyl ethyl ketone, Luwipal 066 LF®, and Nacure 2500 (Kings Industries) are mixed with one another. Subsequently a wet film 200-300 ⁇ thick is applied to the Bonder® panel and glass substrates. After flashing off the solvent (15 minutes, room temperature), the film is cured at 140°C for 30 minutes.
  • Table 3 Hardness, flexibility, and elasticity and also adhesion of inventive PU and HMMM varnishes in comparison to noninventive PU and HMMM varnishes.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Paints Or Removers (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne un polyol de polyester à base d'un composant acide carboxylique (A) qui comprend au moins un acide carboxylique ayant au moins deux groupes carboxyle et d'un composant alcool (B) comprenant au moins du [5-(hydroxyméthyl)tétrahydrofuran-2-yl]méthanol, des procédés de préparation de ces polyols de polyester, l'utilisation de ces polyols de polyester dans des revêtements, et des vernis PU et HMMM contenant ces polyols de polyester.
PCT/EP2016/077931 2015-11-18 2016-11-17 Polyols de polyester ayant une solubilité améliorée WO2017085158A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP15195106 2015-11-18
EP15195106.8 2015-11-18

Publications (1)

Publication Number Publication Date
WO2017085158A1 true WO2017085158A1 (fr) 2017-05-26

Family

ID=54704981

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2016/077931 WO2017085158A1 (fr) 2015-11-18 2016-11-17 Polyols de polyester ayant une solubilité améliorée

Country Status (1)

Country Link
WO (1) WO2017085158A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10844229B2 (en) 2016-10-13 2020-11-24 Basf Se Radiation-curable compounds containing polyester acrylate
WO2021252080A1 (fr) * 2020-06-10 2021-12-16 Dow Global Technologies Llc Composition comprenant un polyol et un isocyanate
WO2022065997A1 (fr) * 2020-09-22 2022-03-31 코오롱인더스트리 주식회사 Polyester comprenant un composant issu de la biomasse et son procédé de préparation
CN114763408A (zh) * 2021-01-15 2022-07-19 万华化学集团股份有限公司 一种高透明度高硬度低双折射聚碳酸酯和制备方法及应用

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011083000A1 (fr) 2009-12-16 2011-07-14 Basf Se Procédé de préparation de polyols de polyester, polyols de polyester préparés à l'aide de ces derniers et polyuréthanes obtenus à partir de ces derniers
WO2011101301A1 (fr) 2010-02-16 2011-08-25 Basf Se Résines aminoplastes silylées
WO2012005647A1 (fr) 2010-07-07 2012-01-12 Perstorp Ab Polyester ramifié
EP2431352A2 (fr) 2010-09-17 2012-03-21 Evonik Degussa GmbH Systèmes de catalyseurs pour la fabrication de biodiesel
EP2467414B1 (fr) 2009-08-20 2014-04-16 Basf Se Procédé de préparation de polyesterpolyol
WO2014191053A1 (fr) 2013-05-31 2014-12-04 Telefonaktiebolaget L M Ericsson (Publ) Signalement de commande averti d'une commande de couche de service dans un réseau de communication
WO2014191503A9 (fr) 2013-05-28 2015-01-29 Basf Se Revêtements anti-microbiens en polyuréthane

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2467414B1 (fr) 2009-08-20 2014-04-16 Basf Se Procédé de préparation de polyesterpolyol
WO2011083000A1 (fr) 2009-12-16 2011-07-14 Basf Se Procédé de préparation de polyols de polyester, polyols de polyester préparés à l'aide de ces derniers et polyuréthanes obtenus à partir de ces derniers
WO2011101301A1 (fr) 2010-02-16 2011-08-25 Basf Se Résines aminoplastes silylées
WO2012005647A1 (fr) 2010-07-07 2012-01-12 Perstorp Ab Polyester ramifié
WO2012005648A1 (fr) 2010-07-07 2012-01-12 Perstorp Ab Oligo ou polyester insaturé
EP2431352A2 (fr) 2010-09-17 2012-03-21 Evonik Degussa GmbH Systèmes de catalyseurs pour la fabrication de biodiesel
WO2014191503A9 (fr) 2013-05-28 2015-01-29 Basf Se Revêtements anti-microbiens en polyuréthane
WO2014191053A1 (fr) 2013-05-31 2014-12-04 Telefonaktiebolaget L M Ericsson (Publ) Signalement de commande averti d'une commande de couche de service dans un réseau de communication

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
D. HOLTER; A. BURGATH; H. FREY, ACTA POLYMER, vol. 48, 1997, pages 30 - 35
F. KOOPMAN; N. WIERCKX; J.H. DE WINDE; H.J. RUIJSSENAARS, BIORESOURCE TECHNOLOGY, vol. 101, no. 16, 2010, pages 3291 - 6296
F. KOOPMAN; N. WIERCKX; J.H. DE WINDE; H.J. RUIJSSENAARS, BIORESOURCE TECHNOLOGY, vol. 101, no. 16, 2010, pages 6291 - 6296
LONESCU, MIHAIL, CHEMISTRY AND TECHNOLOGY OF POLYOLS FOR POLYURETHANES, 2005, pages 264 - 279
MOORE J A ET AL: "Polyesters derived from Furan and Tetrahydrofuran Nuclei", MACROMOLECULES, AMERICAN CHEMICAL SOCIETY, US, vol. 11, no. 3, 1 January 1978 (1978-01-01), pages 568 - 573, XP002413093, ISSN: 0024-9297, DOI: 10.1021/MA60063A028 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10844229B2 (en) 2016-10-13 2020-11-24 Basf Se Radiation-curable compounds containing polyester acrylate
WO2021252080A1 (fr) * 2020-06-10 2021-12-16 Dow Global Technologies Llc Composition comprenant un polyol et un isocyanate
CN115551912A (zh) * 2020-06-10 2022-12-30 陶氏环球技术有限责任公司 具有多元醇和异氰酸酯的组合物
WO2022065997A1 (fr) * 2020-09-22 2022-03-31 코오롱인더스트리 주식회사 Polyester comprenant un composant issu de la biomasse et son procédé de préparation
CN114763408A (zh) * 2021-01-15 2022-07-19 万华化学集团股份有限公司 一种高透明度高硬度低双折射聚碳酸酯和制备方法及应用
CN114763408B (zh) * 2021-01-15 2023-10-24 万华化学集团股份有限公司 一种高透明度高硬度低双折射聚碳酸酯和制备方法及应用

Similar Documents

Publication Publication Date Title
EP2393893B1 (fr) Compositions de revêtement en polyester thermodurcissable contenant du tétraméthyl-cyclobutanediol
EP2150566B1 (fr) Revêtements, adhésifs et liants peu volatiles obtenus à partir d'une huile renouvelable
WO2017085158A1 (fr) Polyols de polyester ayant une solubilité améliorée
CN107278212B (zh) 具有低voc和雾化值的粘合剂
JP2006111878A (ja) 柔軟性超耐久性粉末被覆組成物
Gubbels et al. Bio-based semi-aromatic polyesters for coating applications
EP1545875B1 (fr) Revetement en polyester durable
JP7253544B2 (ja) イソソルビド及びペンタメチレンジイソシアネートを含む、生物由来モノマーの含有量が高いポリウレタンコーティング
US9650541B2 (en) Crosslinkable coating composition and method of producing the same
JP2016518466A (ja) 接着剤および封止剤における、内在の難燃性を有するポリエステルの使用。
CN108884214B (zh) 生产呋喃基聚酯的方法
KR20160101917A (ko) 실리콘-개질된 폴리에스테르 코팅
EP3638706A1 (fr) Compositions durcissables à basse température
US9822280B2 (en) Crosslinkable coating composition and method of producing the same
KR20200074123A (ko) 이소소르비드를 포함하는 폴리우레탄 코팅
CA3068822A1 (fr) Polyols de faible viscosite destines a des applications de polyurethane
TWI719998B (zh) 共聚酯及利用此共聚酯之金屬底漆塗料
EP2949687B1 (fr) Procédés d'alimentation en eau pour la distribution de commande de poids moléculaire et sous-produits de la carbamylation de l'urée
EP0932649B1 (fr) Liant filmogene destine a des compositions de revetement et compositions de revetement comprenant celui-ci
CA3089052A1 (fr) Polyols pour des applications de polyurethane a faible teneur en cov
EP3350241B1 (fr) Compositions de revêtement durcissable employant l'acide succinique
US20220073763A1 (en) Novel biobased polyester
KR20120076149A (ko) 유연성과 탄성이 우수한 자가 복원 가능 폴리에스터수지 및 그의 제조방법
CA1245670A (fr) Enduit a base de polyester a forte teneur de solides
EP2586839B1 (fr) Procédé de revêtement d'une bobine métallique

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16797888

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16797888

Country of ref document: EP

Kind code of ref document: A1