EP2321242A1 - Utilisation de 1,1-diméthylolcycloalcanes ou de 1,1-diméthylolcycloalcènes pour produire des polymères - Google Patents

Utilisation de 1,1-diméthylolcycloalcanes ou de 1,1-diméthylolcycloalcènes pour produire des polymères

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Publication number
EP2321242A1
EP2321242A1 EP09781833A EP09781833A EP2321242A1 EP 2321242 A1 EP2321242 A1 EP 2321242A1 EP 09781833 A EP09781833 A EP 09781833A EP 09781833 A EP09781833 A EP 09781833A EP 2321242 A1 EP2321242 A1 EP 2321242A1
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EP
European Patent Office
Prior art keywords
formula
polymer according
compounds
preparation
polymer
Prior art date
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Application number
EP09781833A
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German (de)
English (en)
Inventor
Darijo Mijolovic
Sebastien Garnier
Qiang MIAO
Maria Guixa Guardia
Gerd-Dieter Tebben
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BASF SE
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BASF SE
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Priority to EP09781833A priority Critical patent/EP2321242A1/fr
Publication of EP2321242A1 publication Critical patent/EP2321242A1/fr
Withdrawn legal-status Critical Current

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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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxo-reaction combined with reduction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/27—Polyhydroxylic alcohols containing saturated rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/27—Polyhydroxylic alcohols containing saturated rings
    • C07C31/272—Monocyclic
    • 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
    • C08G18/4263—Polycondensates having carboxylic or carbonic ester groups in the main chain containing carboxylic acid 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
    • 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
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/553—Acids or hydroxy compounds containing cycloaliphatic rings, e.g. Diels-Alder adducts
    • 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/02—Aliphatic polycarbonates
    • C08G64/0208—Aliphatic polycarbonates saturated
    • 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/02—Aliphatic polycarbonates
    • C08G64/0291—Aliphatic polycarbonates unsaturated
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
    • 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
    • C09D169/00—Coating compositions based on polycarbonates; Coating compositions based on derivatives of polycarbonates
    • 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
    • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D177/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
    • C09J177/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
    • C07C2601/20—Systems containing only non-condensed rings with a ring being at least seven-membered the ring being twelve-membered
    • 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 a polymer which is obtainable by polycondensation or polyadduct formation of monomeric compounds, wherein as a monomeric compound
  • DE-A 922648 describes a process for the preparation of cycloalkane-1, 1-dicarboxylic acids, during which time the 1, 1-dimethylolcycloalkanes are also formed during the preparation. The use of these 1, 1-dimethylolcycloalkanes for the preparation of polymers is not disclosed.
  • DE-A 1468065 describes a process for preparing a mixture of cyclododecane derivatives containing mainly monoxymethylcyclododecane.
  • the starting point is cyclododecatriene, which is subjected to hydroformylation by the addition of carbon monoxide and hydrogen. Subsequently, the resulting aldehyde is subjected to a further hydrogenation to the corresponding alcohol.
  • this production method however, only one methylol group is introduced per double bond. A preparation of a dimethylol derivative with both methylol groups on the same carbon atom is not described. 1, 1-Dimethylolcyclodecan and its use for the preparation of polymers is not described.
  • the viscosity is important, be it as melt viscosity (100% systems) or as solution viscosity (polymer solutions).
  • the coatings produced are said to have good mechanical properties for coating applications, such as impact resistance and elasticity, high scratch and impact resistance, good resistance to water, solvents, grease and chemicals and environmental influences, and to have a high gloss.
  • the polymers should have a high weather stability and a lower tendency to yellowing.
  • the object of the present invention was to provide such polymers.
  • This object is achieved by a polymer obtainable by polycondensation or polyadduct formation of monomeric compounds, characterized in that as a monomeric compound
  • n, X and R are the same as above, are obtainable in a Cannizzaro reaction with formaldehyde.
  • the polymer according to the invention is characterized in that it is a polyester.
  • the polymer according to the invention is characterized in that it is a polycarbonate diol (obtainable by reaction of dialkyl carbonates or cyclic carbonates with diols with elimination of alcohol).
  • the polymer according to the invention is advantageously characterized in that it is a polyurethane.
  • Another object of the invention is the use of the polymer according to the invention for the preparation of a thermoplastic composition.
  • thermoplastic composition comprising a polymer according to the invention and / or repeat units of a polymer according to the invention.
  • Another object of the invention is the use of the thermoplastic compositions according to the invention for the production of moldings.
  • Another object of the invention is the use of the polymer according to the invention for the preparation of coating compositions, sealants or adhesives.
  • Another object of the invention are coating compositions, sealants or adhesives containing repeating units of a polymer according to the invention.
  • the coating compositions, sealants or adhesives of the invention characterized in that they are aqueous compositions.
  • Another object of the invention is the use of the polymer according to the invention for the preparation of powder coatings.
  • Another object of the invention are powder coating, containing repeating units of a polymer of the invention.
  • Another object of the invention is the use of the polymer according to the invention for the preparation of radiation-curable coating compositions.
  • Another object of the invention are radiation-curable coating compositions containing repeating units of a polymer of the invention.
  • Another object of the invention is 1, 1-dimethylolcyclododecane.
  • Another object of the invention is a process for the preparation of 1, 1-dimethylolcyclododecane, wherein cyclododecene is subjected to hydroformylation with hydrogen and carbon monoxide, the resulting aldehyde is reacted by means of formaldehyde to 1, 1 -dimethylolcyclododecane.
  • Another object of the invention is a mixture containing 1, 1-dimethylol-cyclooct-3-ene, 1, 1-dimethylolcyclooct-2-ene and 1, 1-dimethylolocycloct-4-ene.
  • the invention further provides a process for preparing the mixture comprising 1, 1-dimethylolcyclooct-3-ene, 1, 1-dimethylolcyclooct-2-ene and 1, 1-dimethylolcyclooct-4-ene, where 1, 5 Cyclooctadiene is subjected to a hydroformylation with hydrogen and carbon monoxide, the resulting aldehydes is reacted by means of formaldehyde to the mixture according to the invention.
  • compounds of the formula I or of the formula Ia or the alkoxylated derivatives of the formula I or of the formula Ia are used in which n is a whole natural number selected from the group of 1, 2, 4 to 9.
  • the alkoxylated derivatives of the compound of the general formula I or of the formula Ia are products of the reaction with one or a mixture of alkylene oxides.
  • alkylene oxides are ethylene, propylene, n-butylene, isobutylene, styrene or cyclohexene oxide.
  • the above diols are ethoxylated and propoxylated.
  • the alkoxylation products are obtainable in a known manner by reacting the above alcohols with alkylene oxides, in particular ethylene oxide or propylene oxide.
  • the degree of alkoxylation per hydroxyl group is 0 to 20, especially 0 to 10, i. 1 mol of hydroxyl group may preferably be alkoxylated with up to 20 mol, in particular 10 mol of alkylene oxides.
  • the compounds of the formula I or of the formula Ia are not alkoxylated.
  • the compounds of the formula I or of the formula Ia are obtained by a Cannizzaro reaction of the corresponding aldehydes of the formula II or of the formula IIa with formaldehyde.
  • the process for the preparation of 1, 1-dimethylolcycloalkanes is already known and described in US 2993912 or DE 922648.
  • compounds of the formal I or formal Ia can be obtained by aldol reaction of the corresponding aldehydes of the formula II or of the formula IIa with formaldehyde followed by hydrogenation.
  • the aldol reaction is described, for example, in WO 01/51438, WO 97/17313 or WO 98/29374.
  • the hydrogenation can be carried out analogously to the disclosure of EP-A 44412 or EP-A 44444.
  • the polymers are obtainable by polycondensation or polyadduct formation of monomeric compounds with concomitant use of one or more compounds of formula I or formula Ia; the polymers may, if desired, be chemically modified by other or further reactions, e.g. functionalized or networked.
  • Preferred polycondensates are polyesters, which are obtainable by reacting di- or polyols with di- or polycarboxylic acids, which can also be used in the form of reactive derivatives, such as anhydrides or esters.
  • polyester is to be understood below as meaning a polymer which contains more than 50% by weight, more preferably more than 70% by weight and in particular more than 90% by weight, of synthesis components selected from among diols, polyols , Dicarboxylic acids and polycarboxylic acids.
  • polycarbonate diols which are obtainable by reacting dialkyl carbonates or cyclic carbonates with diols with elimination of alcohols.
  • polyurethane is to be understood in the following to mean a polymer which contains more than 50% by weight, more preferably more than 70% by weight, in particular more than 90% by weight, of synthesis components selected from diisocyanates , Polyisocyanates, diols and polyols.
  • All these polymers have in common that they are composed essentially of diols and compounds reactive with these diols, such as di- or polycarboxylic acids (polyesters) or di- or polyisocyanates (polyurethanes).
  • Preferred polymers are polyesters and polyurethanes, particularly preferred are polyesters.
  • the polymers according to the invention preferably have the following content of the monomer building blocks of the compounds of the formula I or of the formula Ia or its alkoxylated derivatives.
  • the following weights for the content of the compounds of the formula I or of the formula Ia or its alkoxylated derivatives in the polymer refer to the units of the polymer which are derived from compounds of the formula I or the formula Ia or their alkoxylated compounds.
  • the weight of these units corresponds unchanged to the compound of the formula I or of the formula Ia or their alkoxylated derivatives, in the case of polycondensates the weight of these units is reduced by the hydrogen atoms of the hydroxyl groups.
  • Preferred polymers are at least 0.5, particularly preferably at least 2, very preferably at least 5 and in particular at least 10% by weight and in a particular embodiment at least 20% by weight of compounds of the formula I or of the formula Ia or their alkoxylated derivatives. Since the concomitant use of other reactive with the diols compounds is mandatory, the polymers are generally not more than 90 wt .-%, in particular not more than 60 wt .-% or not more than 50 wt .-% of the compounds of the formula I or the formula Ia or their alkoxylated derivatives.
  • the polymers may also contain other diols or polyols as synthesis components. In a preferred embodiment, it is at least 10 wt .-%, more preferably at least 25 wt .-% and most preferably at least 50 wt .-% of the diols and polyols, of which the polymers are made to the compounds of Formula I or Formula Ia or their alkoxylated derivatives.
  • At least 70% by weight or at least 90% by weight of the diols and polyols of which the polymers consist can be the compounds of the formula I or of the formula Ia or their alkoxylated derivatives.
  • it may be at 100 wt .-% of all diols and polyols that make up the polymers to a single compound of formula I or formula Ia or a mixture of compounds of formula I or formula Ia or their alkoxylated derivatives.
  • polyesters may contain further diols or polyols as synthesis components.
  • further diols are ethylene glycol, propylene glycol and their more highly condensed representatives, for example diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, etc., 2-methyl-1,3-propanediol, butanediol, pentanediol, hexanediol, neopentyl glycol, alkoxylated phenolic acid Compounds, such as ethoxylated or propoxylated bisphenols, called cyclohexanedimethanol.
  • polystyrene resin examples include glycerol, trimethylolpropane, butanetriol, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol.
  • glycerol trimethylolpropane
  • butanetriol trimethylolethane
  • pentaerythritol ditrimethylolpropane
  • dipentaerythritol dipentaerythritol
  • sorbitol mannitol
  • Preferred mixtures of the compounds of formula I or formula Ia with a diol and a triol are mixtures of the unsubstituted and bearing as X CH 2 group 5-, 8-, 10- and 12-rings with neopentyl glycol and trimethylolpropane.
  • the above diols or polyols may be alkoxylated, in particular ethoxy- and propoxylated.
  • the alkoxylation products can be obtained in a known manner by reacting the above alcohols with alkylene oxides, in particular ethylene oxide or propylene oxide.
  • the degree of alkoxylation per hydroxyl group is 0 to 20, i. 1 mol of hydroxyl group may preferably be alkoxylated with up to 20 mol of alkylene oxides.
  • the polyesters also contain dicarboxylic acids or polycarboxylic acids as synthesis components.
  • Dicarboxylic acids or polycarboxylic acids may also be used in the preparation of the polyesters in the form of their reactive derivatives, e.g. be used as anhydrides or esters.
  • Suitable dicarboxylic acids are succinic acid, glutaric acid, adipic acid, sebacic acid, isophthalic acid, terephthalic acid, their isomers and hydrogenation products, such as tetrahydrophthalic acid.
  • maleic acid and fumaric acid for unsaturated polyesters.
  • Polyesters may also contain monoalcohols or monocarboxylic acids as a constituent; By concomitant use of such compounds, the molecular weight can be adjusted or limited.
  • the polyesters may contain special functional groups.
  • Water-soluble or water-dispersible polyesters contain the necessary amount of hydrophilic groups, for example carboxyl groups or carboxylate groups, in order to achieve water solubility or water dispersibility.
  • Crosslinkable polyesters for example for powder coatings, contain functional groups which undergo a crosslinking reaction with the crosslinking agent used. These may likewise be carboxylic acid groups if it is intended to crosslink with hydroxyl-containing compounds, for example hydroxyalkylamides.
  • the functional groups may also be ethylenically unsaturated groups, for example by modification of the polyester with unsaturated dicarboxylic acids (maleic acid). or reaction with (meth) acrylic acid.
  • Such polyesters are thermally or chemically crosslinkable or radiation-curable.
  • Unsaturated polyesters can be 0 alkyl acrylates, Dialkylacrylaten, z with simple or multi-ethylenically un- saturated, free-radically polymerizable compounds such as styrene, C r Ci. B. the diacrylate of ethanediol or butanediol are copolymerized.
  • the unsaturated polyester may be used in admixture with the ethylenically unsaturated monomers, such as. As described in WO 00/23495 and EP 1 131372.
  • the above ethylenically unsaturated compounds simultaneously serve as solvents (reactive diluents), so that the mixture is preferably present as a solution of the polyesters in these compounds.
  • the mixture may, for. B. as a coating or impregnating agent, in particular for the production of laminates.
  • the curing can be effected thermally or photochemically, in both cases optionally also with the addition of an initiator.
  • Such compounds which can be hardened chemically, thermally or by UV irradiation, are special thermoplastics, which are also called thermosets.
  • unsaturated compounds of the formula I or of the formula Ia are suitable for UPR (unsaturated polyester resins).
  • Polyurethanes contain diisocyanates or polyisocyanates as essential constituent components.
  • diisocyanates Y (NCO) 2 wherein Y is an aliphatic hydrocarbon radical having 4 to 15 carbon atoms, a cycloaliphatic or aromatic hydrocarbon radical having 6 to 15 carbon atoms or an arabiphatic hydrocarbon radical having 7 to 15 carbon atoms.
  • diisocyanates examples include tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 1-isocyanato-3,5,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,2-bis (4-isocyanatocyclohexyl) propane , Trimethylhexane diisocyanate, 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 4,4'-diisocyanatodiphenylmethane, 2,4'-diisocyanatodiphenylmethane, p-xylylene diisocyanate, tetramethylxylylene diisocyanate (TMXDI ), the isomers of bis (4-isocyanatocyclo
  • Such diisocyanates are available commercially.
  • mixtures of these isocyanates especially the mixtures of the respective structural isomers of diisocyanatotoluene and diisocyanatodiphenylmethane are of importance, in particular the mixture of 80 mol% 2,4-diisocyanatotoluene and 20 mol% 2,6- Diisocyanatotoluol suitable.
  • mixtures of aromatic isocyanates such as 2,4-diisocyanatotoluene and / or 2,6-diisocyanatotoluene with aliphatic or cycloaliphatic isocyanates such as hexamethylene diisocyanate or IPDI are particularly advantageous, the preferred mixing ratio of the aliphatic to aromatic isocyanates 4: 1 to 1: 4.
  • compounds of the general formula I or of the formula Ia are used as pure substances or as mixtures of compounds of the general formula I or of the formula Ia or mixed with other diols. or polyols used.
  • polymers of the invention it is also possible to use polymers of the invention as diols or polyols.
  • polyester diols or polyols are preferably also used as diols or polyols.
  • polyesterols are obtained beforehand by reacting di- or polyols with di- or polycarboxylic acids (see above description of the polyesters).
  • the compounds of the general formula I or of the formula Ia or mixtures of compounds of the general formula I or of the formula Ia can be contained in the polyurethanes in the form of such polyesterols.
  • diols, polyols the above genierenden come into consideration, either as structural components which are reacted directly with the di- or polyisocyanates, either as part of the polyesterols.
  • Suitable dicarboxylic acids or polycarboxylic acids for the polyesterols are also those mentioned above.
  • the polyurethanes may also contain monoalcohols or monoisocyanates as constituents; By concomitant use of such compounds, the molecular weight can be adjusted or limited.
  • the polyurethanes may contain special functional groups.
  • Water-soluble or water-dispersible polyurethanes contain the necessary amount of hydrophilic groups, e.g. Carboxyl groups or carboxylate groups to achieve a water solubility or water dispersibility.
  • As a suitable building component e.g. Called dimethylolpropionic acid.
  • Crosslinkable polyurethanes contain functional groups which undergo a crosslinking reaction with the crosslinking agent used.
  • the polyurethanes may also contain other functional groups, e.g. Contain urea groups, which are formed by reaction of the di- or polyisocyanates with amino compounds.
  • the polymers may also be chemically modified, for example functionalized or crosslinked, at or in particular at a later time, for example during use, by other or further reactions.
  • the polymers can contain crosslinking groups which, as soon as the necessary conditions are present, undergo a crosslinking reaction and thus act as a thermoset.
  • the polymers can also be used in particular in admixture with crosslinkers which undergo a crosslinking reaction with the polymer at the desired time under the necessary conditions (in particular at elevated temperature).
  • the crosslinker is added just before the later use
  • the crosslinker can be added to the system early (latent crosslinker), the crosslinking occurs only at the later set conditions, e.g. in the removal of solvent and / or temperature increase.
  • Typical crosslinkers are e.g. Isocyanates, epoxides, acid anhydrides or in the case of polymers having free-radically polymerizable ethylenically unsaturated groups, also ethylenically unsaturated monomers such as styrene.
  • the polymers are useful as a component of thermoplastic compositions.
  • the polymers e.g. Polyesters or polyurethanes preferably have a sufficiently high molecular weight to have thermoplastic properties.
  • Thermoplastic compositions are generally used to make molded articles using conventional methods such as injection molding, extrusion or blow molding.
  • the polymers are suitable as a constituent of coating compositions, sealants or adhesives.
  • the coating compositions, sealants or adhesives preferably contain the polymers according to the invention as binders. They may contain other binders and other additives, e.g. Antioxidants, stabilizers, dyes, pigments, flow control agents, thickeners or wetting aids.
  • the coating compositions, sealants or adhesives may be aqueous or solvent-containing compositions. Preference is given to aqueous compositions.
  • Such compositions preferably contain the binders according to the invention in the form of solutions or dispersions in water or organic solvents or mixtures thereof. If necessary, the polymers contain additional functional groups. which cause solubility or dispersibility in water or organic solvents, preferably in water (see above).
  • the coating compositions, sealants or adhesives may also be masses which are substantially free of water or organic solvents (so-called 100% systems).
  • Such compositions generally contain less than 10 parts by weight of water or other organic solvents (boiling point less than 150 0 C, at 1 bar), per 100 parts by weight of the masses. More preferably, they contain less than 2 parts by weight, most preferably less than 1 part by weight, or less than 0.5 parts by weight of water or other organic solvents (boiling point less than 150 0 C, at 1 bar), to 100 parts by weight of the masses.
  • These may be masses which are still free-flowing at room temperature or masses containing e.g. present as a powder and are processed only at elevated temperatures.
  • compositions in particular coating compositions, may be radiation-curable or used as radiation-curable compositions or coating compositions, which are referred to as thermosets.
  • they preferably contain a radiation-curable polymer according to the invention, in particular a radiation-curable polyester (see above).
  • Radiation curing can be performed with high energy radiation, e.g. Electron radiation or UV light; when using UV light, a photoinitiator may preferably be added to the polymers.
  • a preferred use in the context of the present invention is the use of the polymers according to the invention as or in powder coatings.
  • polyesters are used as powder coating, which are crosslinkable.
  • the powder coating is prepared by mixing and melting the polyester, crosslinking agent and other additives, e.g. Pigments and dispersants produced at high temperatures. The mixture can be powdered by subsequent extrusion and processing of the extrudate.
  • the powder coating may be in the usual manner, e.g. also electrostatically, on the desired substrates; e.g. be coated with metal, plastic or wood surfaces.
  • the polymers according to the invention When used in coating compositions, sealants and adhesives, the polymers according to the invention have good mechanical properties; in particular the coating compositions, e.g. Powder Coatings; have a high impact resistance, good elasticity and a good shine.
  • the coating compositions e.g. Powder Coatings
  • ADS adipic acid
  • D polydispersity index (Mw / Mn)
  • M n number average molecular weight in [g / mol]
  • M w weight average molecular weight in [g / mol]
  • nFA non-volatile components
  • NPG neopentyl glycol
  • the acid number of the polyester is determined according to the DIN standard method 53169.
  • the determination of the melt viscosity ⁇ i of the polyester is carried out with a cone and plate viscometer at 160 0 C in the oscillatory mode and at an angular velocity of 0.1 rad / s.
  • the determination of the solution viscosity r 2 of the polyesters is carried out with a cone-plate viscometer at room temperature in a rotary mode.
  • the solutions consist of 70% polyester and 30% solvent (mixture SoIvesso 100 TM / Solvenon PM TM 5/1).
  • the Tg of the polyester is determined by DSC according to ASTM D3418.
  • the reaction mixture is gradually heated to 230 0 C within 3 to 5 h with stirring and nitrogen flow, and stirred at 230 0 C until the oligomer has an SZ of 10 to 15 mg KOH / g.
  • the SZ of the oligomer is 10 mg KOH / g.
  • Step II Preparation of COOH Group-Containing Polymer P1
  • the oligomer synthesized above is cooled to 180 ° C before adding 187.7 g of IPS (1.13 mol).
  • the temperature is raised to 230 ° C, and it is further condensed under these conditions until the polymer has an SZ of 50 ⁇ 2 mg KOH / g.
  • the water resulting from the polymerization can be drawn at the end of the reaction by a slight vacuum to reach the desired SZ. This gives a branched COOH-containing powder polyester P1 whose SZ is 49 mg KOH / g.
  • P1 has a glass transition temperature T 9 of 74 ° C and a melt viscosity ⁇ i of 41, 9 Pa * s at 160 0 C.
  • Polyester P2 to P4
  • the polymers P2 and P3 according to the invention have a significantly higher glass transition temperature than the corresponding comparative polymer P4, which represents an advantage for powder coating.
  • Step I Preparation of OH group-containing oligomer 181, 7 g DMCP (1.40 mol), 327.0 g NPG (3.14 mol), 435.0 g IPS (2.6 mol), and 0.6 Catalyst DBZO are placed in a 2L four-necked flask equipped with thermometer, inert gas inlet, stirrer and reflux condenser. By passing a nitrogen stream and under reflux, the reactant mixture is heated to 160 0 C quickly. Water is distilled off continuously. Subsequently, the reaction mixture is gradually heated to 220 0 C within 3 to 5 h with stirring and nitrogen flow, and stirred at 220 0 C until the reaction mixture has an SZ of 10 to 15 mg KOH / g. The SZ of the oligomer is 11 mg KOH / g.
  • the reference binder (REF) used is the polyester resin Uralac® P-862 (T 9 .70 0 C, SZ 35 mg KOH / g) from DSM Resins BV.
  • the powder coatings PL1, PL4 and PLR 570.0 g of powder polyester P1, P4 or REF are each treated with 30.0 g of commercial primer Primid® XL-552 (hydroxylalkylamide from EMS), 300.0 g of Kronos® 2160 titanium dioxide pigment (Kronos Co.), 9.0 g of leveling agent Resiflow® PV5 (Worlee Chemie GmbH) and 2.5 g of benzoin are mixed in a laboratory universal mixer (MIT MIT Mischtechnik GmbH), melted and then dried in a twin-screw extruder ( MP 19, Fa. APV) at 80 - 100 0 C extruded. The resulting extrudate is then roughly crushed, ground and sieved.
  • the powder coatings PL1, PL4 and PLR thus obtained are subject
  • the powder coatings are applied to Gradientenofenbleche and in a gradient oven (BYK-Gardner GmbH) 10 min. baked at 160 0 C.
  • the cured coatings are examined for their visual properties (yellowing). The yellow value is determined with the help of the colorimeter spectrocolor (from Hach Lange GmbH).
  • the powder coatings are applied electrostatically to steel test panels (Q-Panel R-36) and at 160 0 C for 10 min. long burned. In this case, layer thicknesses of 60 microns to 80 microns are desired.
  • the resulting coatings are subjected to the following tests:
  • the DMCP paint system has a very low tendency to yellowing, which is a great advantage compared to the reference (PLR) which contains phosphite additives against yellowing (PL1 not according to the invention).
  • the high-solids paints 1K-PL5 and 1K-PL6 according to the invention have very good mechanical properties and high hydrolysis resistance.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Paints Or Removers (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un polymère pouvant être produit par polycondensation ou polyaddition de composés monomères. Cette invention est caractérisée en ce que les composés monomères utilisés sont des 1,1-diméthylolcycloalcanes de formule (I) ou des 1,1-diméthylolcycloalcènes de formule (Ia) ou leurs dérivés alcoxylés.
EP09781833A 2008-08-26 2009-08-14 Utilisation de 1,1-diméthylolcycloalcanes ou de 1,1-diméthylolcycloalcènes pour produire des polymères Withdrawn EP2321242A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP09781833A EP2321242A1 (fr) 2008-08-26 2009-08-14 Utilisation de 1,1-diméthylolcycloalcanes ou de 1,1-diméthylolcycloalcènes pour produire des polymères

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP08162960 2008-08-26
EP08163024 2008-08-27
EP09781833A EP2321242A1 (fr) 2008-08-26 2009-08-14 Utilisation de 1,1-diméthylolcycloalcanes ou de 1,1-diméthylolcycloalcènes pour produire des polymères
PCT/EP2009/060529 WO2010026030A1 (fr) 2008-08-26 2009-08-14 Utilisation de 1,1-diméthylolcycloalcanes ou de 1,1-diméthylolcycloalcènes pour produire des polymères

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EP2321242A1 true EP2321242A1 (fr) 2011-05-18

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EP (1) EP2321242A1 (fr)
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WO (1) WO2010026030A1 (fr)

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9394212B2 (en) 2010-06-15 2016-07-19 Basf Se Process for the cooligomerization of olefins
EP2978740B1 (fr) 2013-03-28 2020-05-13 Basf Se Polyétheramines sur la base de 1,3-dialcohols
HUE043499T2 (hu) 2013-03-28 2019-09-30 Procter & Gamble Poliéteramin-tartalmú tiszítószerek
KR101903977B1 (ko) 2014-03-27 2018-10-04 바스프 에스이 디알코올 기반 에테르아민
JP6275864B2 (ja) 2014-03-27 2018-02-07 ザ プロクター アンド ギャンブル カンパニー ポリエーテルアミンを含有する洗浄組成物
KR101903976B1 (ko) 2014-03-27 2018-10-04 바스프 에스이 1,2-디알코올 기재의 에테르아민
US20150275143A1 (en) 2014-03-27 2015-10-01 The Procter & Gamble Company Cleaning compositions containing a polyetheramine
EP2940117B1 (fr) 2014-04-30 2020-08-19 The Procter and Gamble Company Composition de nettoyage contenant un polyéthéramine
EP2940116B1 (fr) 2014-04-30 2018-10-17 The Procter and Gamble Company Composition détergente
US9974985B2 (en) 2014-05-15 2018-05-22 Basf Se Etheramines based on 1,2-dialcohols
US9617502B2 (en) 2014-09-15 2017-04-11 The Procter & Gamble Company Detergent compositions containing salts of polyetheramines and polymeric acid
RU2017113008A (ru) 2014-09-15 2018-10-17 Басф Се Соли простых эфираминов и полимерной кислоты
EP3197862B1 (fr) 2014-09-25 2020-06-10 Basf Se Polyétheramines sur la base de 1,3-dialcohols
JP6396583B2 (ja) 2014-09-25 2018-09-26 ザ プロクター アンド ギャンブル カンパニー ポリエーテルアミンを含有する洗浄組成物
US9631163B2 (en) 2014-09-25 2017-04-25 The Procter & Gamble Company Liquid laundry detergent composition
CA2959431C (fr) 2014-09-25 2019-10-22 The Procter & Gamble Company Compositions d'entretien de tissus contenant une polyetheramine
JP2016150909A (ja) * 2015-02-17 2016-08-22 株式会社クラレ ジオールの製造方法
EP3162880A1 (fr) 2015-10-29 2017-05-03 The Procter and Gamble Company Composition de détergent liquide
ES2689048T3 (es) 2015-10-29 2018-11-08 The Procter & Gamble Company Composición detergente líquida
US20170275565A1 (en) 2016-03-24 2017-09-28 The Procter & Gamble Company Compositions containing an etheramine
EP3257924A1 (fr) 2016-06-17 2017-12-20 The Procter and Gamble Company Composition de détergent liquide
EP3279301A1 (fr) 2016-08-04 2018-02-07 The Procter & Gamble Company Article de dose unitaire soluble dans l'eau comprenant un amine de nettoyage

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2993912A (en) * 1961-07-25 Process for the production of
DE1059904B (de) * 1957-10-24 1959-06-25 Studiengesellschaft Kohle Mbh Verfahren zur Herstellung von Cyclododecanderivaten
US3067240A (en) * 1960-02-18 1962-12-04 Cassenne Lab Sa New dicarbamate and process of preparing same
US3236774A (en) * 1962-08-10 1966-02-22 Eastman Kodak Co Antioxidant composition and synthetic lubricant containing it
JPS51113850A (en) * 1975-03-29 1976-10-07 Toho Iyaku Kenkyusho:Kk A process for preparing dicarbamate derivatives
US4659747A (en) * 1986-05-15 1987-04-21 The Dow Chemical Company Cyclohexanedimethanol/diamine mixtures as RIM extenders
DE19538061C2 (de) * 1995-10-13 2001-01-04 Basf Coatings Ag Wasserverdünnbarer Polyester
JP3763310B2 (ja) * 1998-06-25 2006-04-05 富士ゼロックス株式会社 高分子量ポリカーボネートおよびその製造方法
US6454965B1 (en) * 1999-03-24 2002-09-24 Chevron Phillips Chemical Company Lp Oxygen scavenging polymers in rigid polyethylene terephthalate beverage and food containers
JP2001048967A (ja) * 1999-08-11 2001-02-20 Fuji Xerox Co Ltd ポリエステル重合体、及びその製造方法
US8318890B2 (en) * 2005-02-18 2012-11-27 Asahi Kasei Chemicals Corporation Polycarbonate diol
SE528590C2 (sv) * 2005-10-14 2006-12-27 Perstorp Specialty Chem Ab Polyurethane elastomer
US7868090B2 (en) * 2006-12-28 2011-01-11 Sabic Innovative Plastics Ip B.V. Polyester molding compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2010026030A1 *

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CN102131755A (zh) 2011-07-20
JP2012500874A (ja) 2012-01-12
US20110144259A1 (en) 2011-06-16
KR20110069026A (ko) 2011-06-22

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