EP2838925A1 - Polymères pouvant être obtenus par polymérisation en émulsion de nanoparticules de polyuréthane fonctionnalisées et de monomères durcissables par voie radicalaire, procédé de préparation correspondant et utilisation - Google Patents

Polymères pouvant être obtenus par polymérisation en émulsion de nanoparticules de polyuréthane fonctionnalisées et de monomères durcissables par voie radicalaire, procédé de préparation correspondant et utilisation

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Publication number
EP2838925A1
EP2838925A1 EP13721608.1A EP13721608A EP2838925A1 EP 2838925 A1 EP2838925 A1 EP 2838925A1 EP 13721608 A EP13721608 A EP 13721608A EP 2838925 A1 EP2838925 A1 EP 2838925A1
Authority
EP
European Patent Office
Prior art keywords
radically curable
polyurethane
molecular weight
polymer according
polyol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP13721608.1A
Other languages
German (de)
English (en)
Inventor
Jorge Rodriguez Prieto
Klaus-Uwe Koch
Kirsten Siebertz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LEHMANN & VOSS & CO. KG
Original Assignee
Dritte Patentportfolio Beteiligungs GmbH and Co KG
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 Dritte Patentportfolio Beteiligungs GmbH and Co KG filed Critical Dritte Patentportfolio Beteiligungs GmbH and Co KG
Publication of EP2838925A1 publication Critical patent/EP2838925A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
    • 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
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • 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
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/6715—Unsaturated monofunctional alcohols or amines
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/69—Polymers of conjugated dienes
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to polymers which are obtainable by reacting at least one polyisocyanate with at least one polyol and at least one free-radically curable monomer A with isocyanate-reactive groups in at least one free-radically curable monomer B.
  • Polyurethane particles having an average diameter of less than 40 nm, preferably less than 20 nm and more preferably less than 10 nm and an average number of free-radically curable functionalities in the range of 2 to 4, preferably 2 to 3, and subsequent emulsion polymerization of the product obtained are. These polymers are suitable for
  • EP 1 015 507 A1 describes aqueous polyurethane dispersions which can be used as lacquer for a number of substrates, including wood or metals, glass, Cloth, leather, paper or plastic and can be applied by methods such as dipping, flow coating, spraying or similar methods.
  • the aqueous carrier medium is removed from the coating after application by drying.
  • polyurethane varnishes derived from aqueous dispersions can be modified by incorporating vinyl polymers, especially acrylic polymers, into the dispersions.
  • vinyl polymers especially acrylic polymers
  • acrylic polymers can result in improved hardness of the resulting paint coating.
  • Such dispersions contain the polyurethane and vinyl polymer components as a physical mixture.
  • EP 0 666 275 describes water-based polyurethane / acrylic polymer dispersions which are suitable for films and film laminations as well as flexible packaging materials. These polyurethane / acrylic polymer dispersions are based on polyisocyanates functionalized with carboxylic acid side chains to form anionic water-dispersible prepolymers. These can then be modified by chain extension and converted by polymerization of the acrylate monomers in the mixture to give polyurethane acrylate polymer dispersions.
  • EP 0 309 114 A1 discloses an aqueous polymer dispersion containing a
  • Vinyl polymer and a nonionic water-dispersible polyurethane with polyethylene oxide side chains contains.
  • the vinyl polymer is prepared by radical polymerization of at least one vinyl monomer in the presence of an aqueous dispersion of the polyurethane.
  • US Pat. No. 6,787,596 A1 discloses the stepwise preparation of a polyurethanepredispersion containing a proportion of additional acrylate polymer.
  • Polyurethane polymer prepared in aqueous dispersion, which is then added to an acrylate component and also polymerized in an aqueous phase.
  • nonaqueous polyurethane / acrylate dispersions also referred to as 100% systems or reactive systems
  • Polyurethane particles are dispersed in a reactive solvent which can be cured in a subsequent polymerization step.
  • Such dispersions can be cured, for example by means of UV radiation and show advantageous in applications such as bonding of glass, wood, metal or plastic or in painting in the furniture and parquet area
  • Aqueous dispersions have other important advantages over solvent-borne or 100% solids-containing dispersions (100% non-volatile content) in the application.
  • dispersions based on high molecular weight polymers can be prepared and processed very well, since the viscosity of the dispersion is generally independent of the degree of polymerization. After removal of the water by means of physical drying very dry surfaces are obtained, which is associated with advantages for many coating processes.
  • aqueous dispersions can be reproducibly applied as thin layers.
  • aqueous dispersions are advantageous for applications in which matte surfaces are desired, since "matting" can be accomplished easily and gloss levels of less than 3E (60 ° measurement angle) can be set.
  • Emulsion polymers which show advantageous properties in applications, for example in the adhesive sector, in the paint sector or for coatings.
  • Embodiments of the polymer according to claim 1 specified.
  • a process for the preparation of the polymer according to the invention is specified in claims 10 to 17.
  • Claims 17 to 19 relate to uses for which the polymer according to the invention is suitable. In claim 1, only the
  • Monomer A but not to consider the monomer B as an optional component.
  • the polymers in the form of adhesives, lacquers or coatings have an advantageous transparency.
  • point adhesives prepared from the polymers according to the invention have a high impact strength, are easily controllable with regard to their elasticity and have a very high adhesive strength and resistance. Accordingly, in these applications, the polyurethane particles fulfill the function of an impact modifier.
  • paints prepared from the polymers according to the invention have a high resistance to micro-scratches.
  • the polymer according to the invention is characterized in that in him, based on the total weight of
  • a higher proportion of polyurethane particles may be contained, as in solutions of polyurethanes in a curable solvent (reactive diluent).
  • a curable solvent reactive diluent
  • the proportion of polyurethane is limited by the strong increase in viscosity at high levels.
  • polymers according to the invention a high proportion of polyurethane than
  • polyurethane particles are functionalized with monomers with isocyanate-reactive
  • the polyurethane particles consist of polyurethanes which are prepared by reaction of polyisocyanates with polyols and optionally monomers A with isocyanate-functional groups.
  • Polyisocyanates denote in the context of the invention, low molecular weight compounds which contain two or more isocyanate groups in the molecule. Preference is given to using diisocyanates in the present invention. However, polyisocyanates having three or more isocyanate groups may additionally be added in order to set a suitable property spectrum of elongation at break and tear resistance. The higher the proportion of compounds having three or more functionalities, the higher the tensile strength becomes.
  • the proportion of polyisocyanates having three or more isocyanate groups should not be greater than about 10% by weight, preferably not greater than 5% by weight, based on the total weight of polyisocyanates.
  • the polyisocyanates which can be used in the present invention include, in particular, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate (4,4'-methylene diphenylene diisocyanate, MDI), 4,4'-dicyclohexyl diisocyanate, 2, 4'-methylenedicyclohexyl diisocyanate, 4,4'-methylenedicyclohexyl diisocyanate, meta- and para-tetramethylxylenediisocyanate, 3-isocyanatemethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), hexamethylene isocyanate, 1,5-naphthylene diisocyanate, dianisyl diisocyanate, di ( 2-is
  • Suitable polyisocyanates can also be obtained, for example, by the reaction of polyhydric alcohols with diisocyanates or by the polymerization of diisocyanates (e.g., isocyanurate structure)
  • Polyisocyanates can be used, which can be represented by reacting hexamethylene diisocyanate with small amounts of water. These polyisocyanates contain urea groups.
  • polyisocyanates can in the implementation of the polyols with the
  • Polyisocyanates are also used small amounts of monoisocyanates, which act as a chain regulator for the polyisocyanate.
  • the amount of the additional monoisocyanates is not more than 10 Mol .-%, in particular not more than 5 mol .-%, based on the total amount of the Isocyanatfunktionön is.
  • the polyol is preferably a high molecular weight polyol having a statistical molecular weight distribution.
  • high molecular weight polyol means a polyol having two or more hydroxy groups wherein the weight average molecular weight of the high molecular weight polyol is in the range of> 500 to about 20,000 g / mole. It is preferably in the range of> 500 to 15,000 g / mol,
  • Exemplary of high molecular weight polyols are the polyether polyols.
  • Polyether polyols are polyalkylene ether polyols of the structural formula
  • substituent R is hydrogen or an alkyl group having 1-5
  • high molecular weight polyols can medium molecular weight
  • Copolyester diols or linear copolyesters with terminal primary
  • Hydroxyl groups are used. Your weight-average molecular weight is preferably at 3000-5000 g / mol. Such polyols are available by
  • Polycarboxylic acids and polyols aliphatic or aromatic dibasic acids and diols Polycarboxylic acids and polyols aliphatic or aromatic dibasic acids and diols.
  • alkylglycols such as
  • Ethylene glycol neopentyl glycol, or glycols such as bisphenol A,
  • Polyols of higher functionality can also be used. They include, for example, trimethylolpropane, trimethylolethane, pentaerythritol, and also higher molecular weight polyols, such as those made by oxyalkylation of low molecular weight polyols.
  • the acid component in the copolyester diol it is preferable to use monomeric carboxylic acids or anhydrides having 2 to 36 carbon atoms per molecule.
  • Usable acids are e.g. Phthalic acid, isophthalic acid,
  • Terephthalic acid Terephthalic acid, tetrahydrophthalic acid, decanedioic acid, dodecanedioic acid.
  • the polyesters may contain minor amounts of monobasic acids, e.g. Benzoic acid, stearic acid, acetic acid and oleic acid. Also usable are higher polycarboxylic acids, such as trimellitic acid.
  • lactone-type polyesters are formed by the reaction of a lactone, e.g. epsilon-caprolactone, with a polyol.
  • a lactone e.g. epsilon-caprolactone
  • the product of a lactone with an acidic polyol can also be used.
  • the polyol for the polyurethane (meth) acrylate particles consists of a mixture of at least one high molecular weight polyol and at least one low molecular weight polyol.
  • a low molecular weight polyol is understood according to the invention to mean a compound which has two or more hydroxyl functionalities and has a molar mass of from 50 to 500 g / mol and preferably 50 to 250 g / mol.
  • the molecular weight may be uniform (single compound), or it may be randomly distributed (oligomer), in the latter case below the
  • Molecular weight is the weight average molecular weight to understand.
  • Preferred as a low molecular weight polyol is one having a uniform molecular weight, wherein the aliphatic diols having 2 to 18 carbon atoms, such as. Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,2-hexanediol and 1,6-hexanediol, and the cycloaliphatic polyols, such as 1,2-cyclohexanediol and Cyclohexanedimethanol are particularly preferred.
  • polyols with ether groups such as diethylene glycol
  • Triethylene glycol and dipropylene glycol Triethylene glycol and dipropylene glycol.
  • exemplary of low molecular weight polyols having more than two hydroxyl groups are trimethylolmethane,
  • Trimethylolethane Trimethyloipropane, glycerol and pentaerythritol.
  • the low molecular weight polyol used is 1,4-butanediol and 1,3-propanediol.
  • the low molecular weight polyol used 1,4-butanediol or 1,3-propanediol.
  • the molar ratio of the OH groups of the low molecular weight polyol to the OH groups of the high molecular weight polyol is suitably in the range of 0.3 to 1.2.
  • Polyisocyanates are also used small amounts of monohydric alcohols, which act as monoisocyanates as a chain regulator for the polyisocyanate. However, it is preferred if the amount of additional monoalcohol is not more than 10 mol%, in particular not more than 5 mol%, calculated on the total amount of OH functionalities based on polyols and monoalcohol.
  • polythiols polyamines or alkanolamines in addition to the polyols.
  • Aliphatic, alkene or alkynediols which have at least two or more -SH groups in particular polythiols such as the 2,2'-oxytris (ethanethiol) and di- and tri-groups, are particularly preferably aliphatic thiols.
  • Mercaptoproprionate ester of Poly (oxyethylene) diol thiodigiycols and trioenes are particularly preferably aliphatic thiols.
  • Mercaptoproprionate ester of Poly (oxyethylene) diol thiodigiycols and trioenes As polyamines, a wide range of compounds can also be used. Examples of suitable linear diamides include, in particular, Jeffami TM as the
  • Polyoxypropylene diamines commercially available as Jeffamine TM D230, Jeffamine TM D400 and Jeffamine TM D2000, and as Jeffamine TM EDR-148 (a
  • Triethylene glycol diamine are available.
  • alkyl-substituted branched diamines are the 2-methyl-l, 5-pentanediamine, 2,2,4-trimethyl-l, 6-hexanediamine and the 2,4,4-trimethyl-l, 6-hexanediamine.
  • Cyclic diamines may also be used, such as isophoronediamine, for example.
  • Alkanolamines are compounds that have amine functionalities and hydroxyl functionalities. Further examples of alkanolamines are 2- (methylamino) ethanol and N-methyldiethanolamine. Suitable examples of compounds that have a
  • Amino group and another group selected from amino and hydroxyl are diamines, Akanoiamine and amine-terminated polyamides or polyethers. Likewise, mixtures of such compounds can be used. It is preferred if the amount of the polyamines, polythiols and alkanolamines is not more than 50 mol%, in particular not more than 20 mol% and particularly preferably not more than 10 mol%, based on the total amount of the OH, NH and SH functionalities in the isocyanate-reactive compounds.
  • urethane particles having particularly advantageous properties are obtained when the molar ratio of the isocyanate groups of the polyisocyanate to the hydroxy groups of the polyol is in the range of 1.03 to 1.7.
  • the proportion of the polyurethane particles, based on the total weight of the organic components in the polymers it is expedient if the proportion of the polyurethane particles, based on the total weight of the organic components in the
  • Polymer is about 5 to 70 wt .-%, preferably 20 to 60 wt .-% and particularly preferably 30 to 50 wt .-% is.
  • the polyurethane particles can be functionalized with free-radically curable, in particular with vinylic monomers A. These are preferably (meth) acrylates. These polyurethane particles are available by reacting at least one polyisocyanate with at least one polyoi and at least one nukieophii functionalized monomer A, in particular a nukieophii functionalized (meth) acrylic acid ester.
  • nucleophilic functional group which can be reacted wholly or partly with free isocyanate groups. This is preferably a hydroxy, amine or mercapto functionality, more preferably a hydroxy functionality.
  • nucleophil-functionalized (meth) acrylic esters are also referred to as "hydroxyfunctional (meth) acrylic acid esters”.
  • Polyurethane particles are obtained which carry on their surface acrylate functionalities, and thus enter into an interaction with the radically curable monomers in the dispersion. Such particles are also referred to as polyurethane (meth) acrylates.
  • polyurethane (meth) acrylate in the context of this invention means a polyurethane whose free terminal isocyanate groups have been completely or partially reacted with a nukieophii functionalized (meth) acrylic acid ester.
  • the isocyanate groups react with the nucleophilic group of the nukieophii functionalized (meth) acrylic ester, e.g. Hydroxy, amino or mercapto, and there are formed terminal ethylenically unsaturated functionalities derived from (meth) acrylates.
  • (meth) acrylic acid e.g. Hydroxy, amino or mercapto
  • Isocyanate groups of the polyurethane react ie they "cap" are also referred to as “capping reagents” or “capping reagents”.
  • nukieophii functionalized (meth) acrylic esters are hydroxy-functional (meth) acrylic esters.
  • a "hydroxy-functional (meth) acrylic acid ester” is understood according to the invention to mean a (meth) acrylic acid ester which, after esterification with (meth) acrylic acid, still carries at least one hydroxyl functionality in the residue derived from the alcohol. Different said, it is the ester of a (meth) acrylic acid and a diol or polyol, wherein the diols are preferred.
  • Hydroxyalkyl (meth) acrylates which can be used according to the invention are monoesters of (meth) acrylic acid with dihydric, aliphatic alcohols.
  • the proportion of nucleophilically functionalized (meth) acrylic acid esters there are no relevant restrictions within the scope of the present invention. However, it should be ensured that the polyurethane nanoparticles have on average at least one vinyl functionality.
  • the average functionality of free-radically curable groups per nanoparticle is preferably in the range from about 2 to 4, in particular in the range from 2 to 3. In a preferred
  • the proportion of nucleophilic groups in the vinylic monomer to be incorporated into the particles is based on the total amount of all the functional groups in the precursors of the polyurethane, i. in particular the OH groups from the polyols, in the range of about 0.1 to 70%, in particular about 25 to 50%.
  • the proportion of the functional groups, based on the total amount of all functional groups in the precursors of the polyurethane is about 0.1 to 10%, in particular 0.5 to 7%.
  • nano-centers that are integrated (ie, polymerized in) during the polymerization of the free-radically curable monomers into classical acrylic / polyurethane dispersions are usually considered physical
  • the particles are integrated at least proportionately in the acrylate matrix.
  • the mechanical technological properties compared to non-covalently linked polyacrylate / polyurethane hybrids significantly improved.
  • excess isocyanate functionalities in the polyurethane particles can also be reacted with monohydric alcohols, such as methanol, ethanol, n- or iso-propanol, butanol, etc., so that the resulting polyurethane particles do not react with respect to the radically curable monomer B groups exhibit.
  • monohydric alcohols such as methanol, ethanol, n- or iso-propanol, butanol, etc.
  • the functionalized polyurethanes which are then subjected to emulsion polymerization with free-radically curable monomers B, have an average molecular weight Mn of about 3,000 g / mol to 800,000 g / mol and preferably from 3,000 g / mol to 600,000 g / mol.
  • the functionalized polyurethanes preferably have high average molecular weights, since this is advantageous for the chemical resistance of the particles.
  • high molecular weight functionalized polyurethanes also have better mechanical and technological properties, such as improved adhesion, adhesiveness, tensile and tear strength, and excellent ductility. For this reason, the average molecular weight of the functionalized polyurethanes is preferably in the range from 100,000 to 800,000 g / mol,
  • the polymers according to the invention are by emulsion polymerization of the polyurethane particles described above, the free-radically curable
  • the polyurethane particles have an average diameter of less than 40 nm, preferably a mean diameter of less than 20 nm and in particular a mean diameter of less than 10 nm. While the Applicant does not invoke any particular theory, the small particle size that the resulting polymer has a favorable transparency.
  • the polyurethane particles may also function as an emulsifier for free-radically curable monomers in emulsion polymerization of these monomers without the need for modification of the pendant anionic polyurethane.
  • the present invention is not subject to any relevant restrictions. However, it is preferred if, as the radically curable monomer B, a vinyl monomer,
  • styrene and substituted styrenes such as substituted styrenes having an alkyl substituent in the side chain, e.g. alpha-methylstyrene and alpha-ethylstyrene, substituted styrenes having an alkyl substituent on the ring, such as vinyltoluene, halogenated styrenes, such as
  • Monochlorostyrenes Monochlorostyrenes, dichlorostyrenes, tribromostyrenes or tetrabromostyrenes.
  • a preferred free-radically curable monomer is vinylidene chloride (1,1-dichloroethylene).
  • the radically curable monomer B comprises dienes, in particular isoprene, butadiene or a mixture thereof.
  • the free-radically curable monomer B is (meth) acrylate.
  • the (meth) acrylates may have one or more double bonds.
  • (Meth) acrylates which have two or more double bonds are referred to in the context of the invention as polyvalent (meth) acrylates and serve above all to establish a desirable degree of crosslinking.
  • the alcohol-derived residue of the (meth) acrylates may contain heteroatoms, for example in the form of ethers, alcohols, carboxylic acids, esters or urethane groups.
  • the radical curable monomer B may be used in the form of a single compound or two or more radical curable monomers.
  • Particularly preferred free-radically curable monomers B in the context of the invention include alkyl (meth) acrylates which are derived from saturated
  • Alcohols such as methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acryiate, n-propyl (meth) acrylate, n-, iso- or tert-butyl (meth) acrylate, pentyl (meth) acrylate , n-hexyl (meth) acrylate, n-octyl (meth) acrylate, n-decyl (meth) acrylate, isooctyl (meth) acrylate, tetra-decyl (meth) acrylate, phenoxyethyl (meth) acrylate, allyl (meth ) acrylate, glycidyl (meth) acrylate, neopentyl (meth) acrylate, isobornyl (meth) acrylate, hexanedioic diacrylate (HD
  • Most preferred free-radically curable monomers B are methyl acrylate (MMA), 2-phenoxyethyl methacrylate (POEMA), isobornyl acrylate (IBOA), 2-ethylhexyl acrylate (2-EHA), and tetrahydrofurfuryl methacrylate (THFMA).
  • MMA methyl acrylate
  • POEMA 2-phenoxyethyl methacrylate
  • IBOA isobornyl acrylate
  • 2-EHA 2-ethylhexyl acrylate
  • THFMA tetrahydrofurfuryl methacrylate
  • vinyl ethers may also be copolymerized in, e.g. 2-ethylhexyl vinyl ether, 4-hydroxybutyl vinyl ether, butanediol divinyl ether, cyclohexyl vinyl ether, diethylene glycol divinyl ether, dodecyl vinyl ether, isobutyl vinyl ether (bar 0.1% DEA), N-butyl vinyl ether, octadecyl vinyl ether, triethylene glycol divinyl ether and tert-butyl vinyl ether.
  • 2-ethylhexyl vinyl ether 4-hydroxybutyl vinyl ether
  • butanediol divinyl ether butanediol divinyl ether
  • cyclohexyl vinyl ether diethylene glycol divinyl ether
  • dodecyl vinyl ether dodecyl vinyl ether
  • alkyl sulfate salts such as sodium dodecyl sulfate, alkyldiphenyl oxide disulfonates, ethoxylates of secondary alcohols, ethylene oxide /
  • Propylene oxide copolymers diphenol ethoxylates or polyether phosphate esters.
  • polymerizable emulsifiers such as e.g. Sodium vinyl sulfonate can be used.
  • the addition of an emuigator is not mandatory.
  • suitable polyols for example, long-chain polyoxyalkylene polyols
  • the polymerization can be carried out in the absence of additional emulsifiers be carried out as an emulsifying effect is ensured on the one hand by the nano-structure of the polyurethane particles and on the other by the interaction of the polyol chains with water.
  • additional emulsifiers can be reduced compared to conventional emulsion polymerizations.
  • the polymerization is conveniently started by conventional polymerization initiators, which are preferably water-soluble and after
  • Ammonium persulfate or corresponding peroxodisulfates and tert-butyl hydroperoxide wherein the catalyst is useful in amounts ranging from 0.01 wt .-% to 3 wt .-%, preferably 0.01 to 1 wt .-%, based on the total solids content the emulsion is to be used.
  • reducing agents such as sodium formaldehydesulfoxylate, iron salts,
  • the polymerization is usually carried out at a pH of between 2 and 7, preferably 3 to 5.
  • a buffer system such as alkali metal acetates, alkali metal carbonates or alkali metal phosphates.
  • regulators such as mercaptans, aldehydes, chloroform,
  • the polymer can with regard to its proportion of free-radically curable
  • Monomers B have functional groups, in particular hydroxyl or carboxyl groups, which are available for subsequent crosslinking.
  • Such crosslinking can be achieved by self-crosslinking or by adding external crosslinking agents such as melamine resins, polyaziridines, polycarbodiimides, hydrophobized and / or hydrophilic polyisocyanates.
  • the present invention also relates to a process for preparing a polymer as described above, comprising a) the reaction of at least one polyisocyanate with at least one polyol and optionally at least one free-radically curable monomer A with isocyanate-reactive groups in at least one free-radically curable monomer B to polyurethane particles with an average diameter of less than 40 nm, preferably less than 20 nm and more preferably less than 10 nm, and an average number of radically curable functionalities in the range of 2 to 4, preferably 2 to 3, and b) emulsion polymerization of the under a ) obtained product.
  • the reaction a) is carried out in a stirred tank at a Rrockercons Kunststoffs Kunststoff of at least 5 m / s, wherein the ratio of stirrer diameter to vessel diameter 0.3 to 0.80 and the distance of the stirrer from the bottom of the vessel from 0.25 to 0.5 times the stirrer diameter.
  • the geometry of the stirrer and its speed can be expertly designed by the person skilled in the art on the basis of the above information. However, it has been found to be expedient for the stirrer peripheral speed to be in the range of 100 to 500 rpm, preferably 150 to 300 rpm.
  • the method according to the present invention can be advantageously designed by the stirrer peripheral speed being at least 12 m / s.
  • a dispersing disk eg Unidrive X 1000 D CAT, Zipperer GmbH Co. with G20 20 mm V shank
  • a KPG stirrer is used as the stirrer.
  • reaction of the polyisocyanate with the polyol in step a) of the process is carried out in the presence of a catalyst which may be selected from tertiary organic amines and / or organic tin compounds.
  • a catalyst which may be selected from tertiary organic amines and / or organic tin compounds.
  • Dibutyltin laurate as a catalyst particularly useful.
  • the emulsion polymers according to the invention preferably have a particle size of the secondary particles obtainable from the emulsion polymerization in the range from about 50 to about 150 nm, more preferably from about 70 to about 120 nm. In these secondary particles, the polyurethane nanoparticles are involved in the form of inclusions.
  • Polymers obtainable by emulsion polymerization have a very high market importance and are especially established for use in adhesives, textiles and coatings. According to the process of the present invention, such polymers can be prepared much easier, less expensive and more targeted, in particular the use of organic
  • Solvents such as acetone is dispensable. Therefore, another aspect of the method described above is that the use of organic solvents, in particular acetone is dispensed with. Due to the adhesive strength, the polymers of the invention are particularly suitable as an adhesive. Accordingly, a further aspect of the present invention relates to the use of a polymer as described above as an adhesive, in particular as a dispersion adhesive. to
  • the polymer can be used in pure form (i.e., as described above), or with other reactive adhesives on an aqueous basis or with reactive adhesives on reactive adhesive base, in particular (meth) acrylate-based added.
  • a use of the polymers as adhesive layer on adhesive tapes is the subject of the present invention.
  • Another aspect of the present invention relates to the use of the above-described polymers as a lacquer or constituent of a lacquer.
  • Furniture coating can be used as a primer and / or topcoats (TopCoats).
  • TopCoats topcoats
  • the highest level of transparency is required for clearcoat systems (ie.
  • Color depression referred to which occurs during the wetting of the wood surface through the coating material and permanently emphasizes the wood grain.
  • turbidity is often visible from an effective concentration.
  • plastics such as. ABS, AMMA, ASA, CA, CAB, EP, UF, CF, MF, MPF, PF, PAN, PA, PC, PE, HDPE, LOPE, LLDPE, UHMWPE, PET, PMMA, PP, PS, SB, PUR, PVC, RF, SAN, PBT, PPE, POM, PUR-RIM, SMC, BMC, PP-EPDM and UP (curve designations according to DIN 7728 Tl) are coated.
  • the coating of plastics serves one
  • the paint systems must have a certain elasticity to remain crack-free at high and low temperatures at impact stress (eg bumpers).
  • Another area of application is, for example, PVC and linoleum floors.
  • embossable linoleum floors the prior art is UV-curing
  • the polymers according to the invention are used to improve the abrasion resistance or service life.
  • Automotive paints are mainly applied by spraying. As a rule, such paints are shiny. Such high quality surfaces are expected to have a clear, brilliant appearance.
  • the use of inorganic and nanoscale fillers or nanoparticles in clearcoats leads to slightly milky / cloudy phenomena. This effect is referred to as a haze or "haze.” The haze only occurs in high-gloss surfaces
  • Polymers are used to prevent such haze and, moreover, for improvements, "scrub brush resistance" to micro-scratching.
  • Polyisocyanates 2K-polyisocyanate, 1K self-crosslinking, 1K physically
  • Polymers according to the invention can be functionalized in such a way that the above-mentioned crosslinking processes are possible. They are therefore compatible with appropriate formulation with melamine resins, blocked and unblocked polyisocyanates.
  • dispersions of the invention can be further processed on films.
  • films based on polyvinylidene chloride as barrier films for food and
  • compositions can be used.
  • Another field of application for the polymers according to the invention are corrosion protection applications.
  • the varnishes and adhesives described above may be formulated with conventional additives depending on their use.
  • additives are coalescing agents such as ethylene glycol, defoamers, for example based on polyether siloxane copolymers, wetting agents, for example based on polyether-modified siloxanes and thickeners, for example based on polyurethanes.
  • a suitable pH in the context of the present invention is in the range of 7 to 9.
  • Another aspect of the present invention relates to the application of a polymer according to the invention to a textile.
  • polymers according to the invention for the production of films and cast films, wherein the polymers can be used either alone or as a mixture with other components.
  • the uses described above may include applying the polymers of the invention to a corresponding substrate and optionally curing the dispersion by physical drying. This can be done for example by applying a vacuum or by heating.
  • physical drying may include applying the polymers of the invention to a corresponding substrate and optionally curing the dispersion by physical drying. This can be done for example by applying a vacuum or by heating.
  • the person skilled in the art is familiar with further alternatives for physical drying, which require no further explanation here.
  • the polymers according to the invention described above are characterized in many applications by advantageous properties, in particular a desirable transparency, high impact strength and elongation at break and good adhesion to materials such as PVC, glass, wood and metal.
  • the degree of crosslinking can be advantageously adjusted within the scope of the invention, so that sufficient flowability is ensured.
  • TM DI diisocyanate
  • MMA methyl methacrylate
  • VCD vinylidene chloride
  • capping an equimolar amount of capping reagent (hydroxyethyl methacrylate (HEMA), methanol, or to the determined isocyanate content
  • HSA Hydroxyethyl acrylate
  • the emulsion of the monomers is generated by stirring. 97.44 g of water, 13.33 g of sodium dodecyl sulfate (15%) and 200 g of the respective starting material are weighed in (emulsion feed).
  • the initiator is dissolved in water. 39.00 g of water and 1.0 g of sodium peroxodisulfate are weighed in (initiator).
  • the nitrogen-purged reactor now 55.90 g of water, 15.54 g
  • Paint formulations were formulated from the aqueous dispersions of the comparative sample and the inventive samples 8 and 9, and corresponding paint films were produced. Table 3 lists the formulations used (parts by weight, 100%). To the stability and compatibility of the used
  • coalescing agent for the filming of the dispersions 1 coalescing agent for the filming of the dispersions, 2 antifoams in the form of a polyethersiloxane copolymer, silicic acid containing silicic acid, 3 substrate wetting agents in the form of a solution of a polyether-modified siloxane, 4 polyurethane thickeners.
  • Formulations were applied to black PVC film, glass and wood (beech veneer) with a box wiper (200 ⁇ m wet application). After the order, the formulations filmed foam-free. Thereafter, the coated substrates at 40 ° C (circulating air temperature) in the laboratory oven for 8
  • wood firing refers to the color deepening which occurs when the wood surface wets through the coating material and permanently emphasizes the wood grain (Prieto / Kiene: frabuch “Holzbe harshung”, Coatings Compendien, Curt Vincentz-Verlag Hannover, 2007)
  • the aqueous dispersions paint 2 and paint 3 compared to the comparative sample paint 1 to improve the adhesion to glass and PVC film.
  • the coated surfaces with Lacquer 2 and Lacquer 3 also tend to perform better than the Comparative Sample Lacquer 1.
  • the best chemical resistance water, alcohol
  • this dispersion also shows the lowest pendulum attenuation values (softer than varnish 1 and varnish 2, the aqueous dispersions varnish 1 and varnish 2 show very similar oscillation damping values).
  • the highest gloss level based on DIN EN ISO 1522 is shown by the formulations according to paint 1 (38) and paint 2 (46).
  • the dispersion varnish 3 a particularly good "start-up", which exceeds the current level of the known aqueous polyacrylate.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Graft Or Block Polymers (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Adhesive Tapes (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

La présente invention concerne des polymères qui peuvent être obtenus par a) transformation d'au moins un polyisocyanate avec au moins un polyol et, éventuellement, au moins un monomère A, durcissable par voie radicalaire et comprenant des groupes réactifs par rapport à l'isocyanate, dans au moins un monomère B durcissable par voie radicalaire pour former des particules de polyuréthane possédant un diamètre moyen inférieur à 40 nm, de préférence inférieur à 20 nm et de manière particulièrement préférée inférieur à 10 nm, et un nombre moyen de fonctionnalités durcissables par voie radicalaire de l'ordre de 2 à 4, de préférence de 2 à 3, et b) polymérisation en émulsion du produit obtenu sous a). La polymérisation en émulsion permet d'obtenir des quantités importantes de dispersions hybrides polyuréthane/polymère réticulées, dans lesquelles les nanoparticules fonctionnent comme un élément de liaison entre les zones polymères et les constituants de polyuréthane. Cette structure se traduit par une meilleure stabilité chimique et des propriétés mécaniques nettement améliorées par rapport aux dispersions classiques de polyuréthane dans lesquelles les nanoparticules de polyuréthane peuvent être dispersées ultérieurement dans des polyacrylates par un procédé à l'acétone, par exemple. Ce mode de production permet également de mieux ajuster le taux de polyuréthane dans le polymère. La présente invention concerne en outre un procédé de production de tels polymères ainsi que l'utilisation de tels polymères en tant qu'adhésifs ou revêtements, notamment pour des textiles, ou en tant que peintures et vernis, ou pour des films et des feuilles.
EP13721608.1A 2012-04-16 2013-04-16 Polymères pouvant être obtenus par polymérisation en émulsion de nanoparticules de polyuréthane fonctionnalisées et de monomères durcissables par voie radicalaire, procédé de préparation correspondant et utilisation Withdrawn EP2838925A1 (fr)

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Application Number Priority Date Filing Date Title
DE102012007823A DE102012007823A1 (de) 2012-04-16 2012-04-16 Polymerisate, die durch emulsionspolymerisation von funktionalisierten polyurethan-nanopartikeln und radikalisch härtbaren monomeren herstellbar sind, ein verfahren zu deren herstellung sowie deren verwendung
PCT/EP2013/057925 WO2013156486A1 (fr) 2012-04-16 2013-04-16 Polymères pouvant être obtenus par polymérisation en émulsion de nanoparticules de polyuréthane fonctionnalisées et de monomères durcissables par voie radicalaire, procédé de préparation correspondant et utilisation

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WO (1) WO2013156486A1 (fr)

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KR20140104268A (ko) * 2013-02-20 2014-08-28 삼성에스디아이 주식회사 전지용 바인더, 이를 채용한 음극과 리튬전지
KR101739298B1 (ko) 2013-02-20 2017-05-24 삼성에스디아이 주식회사 전지용 바인더, 이를 채용한 음극과 리튬전지
JP2017508015A (ja) * 2013-12-12 2017-03-23 ドリッテ パテントポルトフォーリオ ベタイリグングスゲゼルシャフト エムベーハー ウント コー．カーゲー 非水性透明分散系形態のコーティング組成物
JP2015209538A (ja) * 2014-04-30 2015-11-24 バンドー化学株式会社 光学透明粘着シート
PL3579302T3 (pl) * 2017-12-11 2022-04-19 Lg Energy Solution Ltd. Separator i zawierające go urządzenie elektrochemiczne
US20210009874A1 (en) * 2017-12-27 2021-01-14 Dow Global Technologies Llc Two-component solventless adhesive compositions for adhesion to metal and/or metallized substrates
RU2020120892A (ru) * 2017-12-27 2021-12-24 Дау Глоубл Текнолоджиз Ллк Двухкомпонентные клеевые композиции, не содержащие растворитель, для склеивания с полимерными барьерными подложками
WO2023085387A1 (fr) * 2021-11-12 2023-05-19 東ソー株式会社 Composition de formation de résine d'uréthane et agent adhésif de type à deux parties
CN115873203A (zh) * 2022-12-12 2023-03-31 大连理工大学 高耐磨单组分水性聚氨酯及其乳液或分散体、涂层的制备方法及应用

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