EP1328586A1 - Polymeres ayant des groupes uree et des groupes silyle, leur production et leur utilisation - Google Patents

Polymeres ayant des groupes uree et des groupes silyle, leur production et leur utilisation

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Publication number
EP1328586A1
EP1328586A1 EP01978452A EP01978452A EP1328586A1 EP 1328586 A1 EP1328586 A1 EP 1328586A1 EP 01978452 A EP01978452 A EP 01978452A EP 01978452 A EP01978452 A EP 01978452A EP 1328586 A1 EP1328586 A1 EP 1328586A1
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EP
European Patent Office
Prior art keywords
carbamate
group
groups
polymer
compounds
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.)
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Application number
EP01978452A
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German (de)
English (en)
Inventor
Johann Klein
Wilfried Hübner
Wolfgang Klauck
Hermann Kluth
Thomas Bachon
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1328586A1 publication Critical patent/EP1328586A1/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Withdrawn legal-status Critical Current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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
    • C08G71/04—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
    • C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
    • C08G71/02—Polyureas
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249982—With component specified as adhesive or bonding agent
    • Y10T428/249985—Composition of adhesive or bonding component specified

Definitions

  • the present invention relates to a process for the preparation of compounds having at least one urea group and at least one silyl group, in which a compound having at least one amino group is reacted with a carbamate, either the compound having at least one amino group or the carbamate having a silyl group, according to this Processed compounds, their use, and surface coating agents, foams and adhesives containing such compounds.
  • Organic compounds in particular polymers, which carry both a silyl group and a urea group are used in many branches of industry, for example in coating or adhesive technology.
  • the advantages of such compounds, in particular of such polymers lie in particular in their ability to develop a binding effect both to hydrophobic and to hydrophilic substrates and to crosslink them with one another in the event of moisture.
  • Adhesives that contain such polymers are able, for example, to permanently bond both hydrophilic and hydrophobic substrates, as well as substrates of different polarities.
  • Chemical Abstracts 123: 171406 (abstract of JP 93-185 595) describes a process for the preparation of polyethers which have both a urea group and an alkoxysilyl group. To prepare such compounds, an amino group-containing polyether is reacted with a silyl compound having an isocyanate group.
  • US Pat. No. 5,886,205 relates to a process for the preparation of isocyanate compounds containing silyl groups, which comprises the thermal decomposition of carbamic acid esters containing silyl groups in the presence of a catalyst.
  • the publication does not describe the reaction of a carbamate with a compound having at least one amino group.
  • US-A 5218133 relates to a process for the preparation of silyl carbamates or silyl isocyanurates in which an aminosilane is reacted with a dialkyl carbonate, diaryl carbonates or a mixture thereof in the presence of a basic catalyst to obtain a silyl organocarbannate.
  • the basic catalyst is then optionally neutralized and the remaining aminosilane is neutralized.
  • a silyl isocyanurate is obtained.
  • the publication does not describe how silyl compounds with urea structural elements can be obtained by reacting carbamates with amino compounds, where either the amino compound or the carbamate or both carry a silyl group.
  • EP-A 1 006 132 relates to paint preparations containing alkoxysilane, which are prepared using 4,4'-diisocyanatodicyclohexylmethane polyisocyanates.
  • the publication describes, for example, the implementation of Polyisocyanates, as can be obtained by trimerization of 4,4'-diisocyanatodicyclohexylmethane, with alkoxysilanes carrying amino groups.
  • the reaction described has the disadvantage that isocyanurates are used, which generally have a proportion of low molecular weight diisocyanates.
  • such low molecular weight isocyanates have a considerable toxic potential.
  • urethane groups also leads to a reduced thermal stability of these compounds, since urethane groups split at about 140-160 ° C. However, this behavior prevents the use of such connections in heat-resistant applications.
  • isocyanurate-containing isocyanurates are difficult to prepare.
  • the trimerization of isocyanates to isocyanurates can only be carried out to a certain degree, which is below a corresponding crosslinking point, because of the increasing risk of crosslinking the batch as the conversion increases.
  • the original for networking The isocyanate used and the isocyanurate containing isocyanate groups obtained as the product must then be separated in complex distillation processes. The distilled isocyanate is returned to the trimerization process after the distillation.
  • the space / time yields in such a process are poor due to the complex separation steps.
  • the object on which the invention is based is achieved by processes for the preparation of compounds having at least one urea group and at least one silyl group, compounds prepared by this process, by polymers which have at least one isocyanurate group and at least one silyl group, by processes for preparing such polymers and by using the the compounds produced according to the invention and the compounds according to the invention dissolved in surface coating agents foams or adhesives.
  • a first object of the present invention is therefore a process for the preparation of compounds having at least one urea group and at least one silyl group, in which a compound having at least one amino group is reacted with a carbamate as the reactant, at least one of the reactants carrying a silyl group.
  • urea group is a structural element of the general formula I
  • radical R 8 is hydrogen and the radical R 9 is hydrogen is a linear or branched alkyl group having 1 to 24 carbon atoms, an optionally substituted aryl group having 6 to 24 carbon atoms, an alkyl or arylsilyl group.
  • the radical R 9 can also contain one or more substituents such as ester groups, keto groups, amino groups or hydroxyl groups.
  • the radical R 9 is preferably hydrogen or a linear or branched alkyl group having 1 to 12 carbon atoms, in particular hydrogen.
  • a “silyl group” is understood to mean a compound of the general formula II
  • a compound which carries a silyl group according to the general formula II is used as at least one reaction partner.
  • Suitable compounds are in particular compounds of the general formula
  • R 1 to R 6 , a, b, c, n, m and j have the meaning given above
  • suitable substituents are functional groups such as thioether, mercapto, amino, ester, amido, nitro or ether groups or mixtures of two or more thereof.
  • a “carbamate group” is understood to mean a structural element of the general formula IV
  • radical R 10 is a linear or branched, saturated or unsaturated alkyl radical with 1 to about 10 C atoms, a saturated or unsaturated cycloalkyl radical with about 6 to about 24 C atoms, or an arlyl radical with 6 to about 24 C atoms stands.
  • compounds of the general formula III in which Z represents an amino group are used as at least one reaction partner.
  • compounds are also referred to as aminosilanes.
  • Suitable aminosilanes are, for example, N- ( ⁇ -methyldimethoxysilylmethyl) amine, N- ( ⁇ -trimethoxysilylmethyl) amine, N- ( ⁇ -diethylmethoxysilylmethyl) amine, N- ( ⁇ -ethyldimethoxysilylmethyl) amine, N- ( ⁇ -methyldiethoxysilylmethyl) amine, N- ( ⁇ -triethoxysilylmethyl) amine, N- ( ⁇ -ethyldiethoxysilylmethyl) amine, N- (ß-
  • Methyldimethoxysilylethyl) amine N- (ß-trimethoxysilylethyl) amine, N- (ß-ethyldimethoxysilylethyl) amine, N- (ß-methyldiethoxysilylethyl) amine, N- (ß-)
  • Triethoxysilylethyl) amine N- (ß-ethyldiethoxysilylethyl) amine, N- ( ⁇ -methyldimethoxysilylpropyl) amine, N- ( ⁇ -trimethoxysilylpropyl) amine, N- ( ⁇ -ethyldimethoxysilylpropyl) amine, N- (methyl) amine, N- ) amine, N- ( ⁇ -triethoxysilylpropyl) amine, N- ( ⁇ - ethyldiethoxysilylpropyl) amine, N- (4-methyldimethoxysilylbutyl) amine, N- (4-trimethoxysilylbutyl) amine, N- (4-triethyl) silylbutyl) N- (4-diethylmethoxysilylbutyl) amine, N- (4-ethyldimethoxysilylbutyl) amine, N- (4
  • Diethylethoxysilylpentyl) amine N- (5-ethyldiethoxysilylpentyl) amine, N- (6-methyldimethoxysilylhexyl) amine, N- (6-trimethoxysilylhexyl) amine, N- (6-ethyldimethoxysilylhexyl) amine, N- (6-methyldiethyl) ) amine, N- (6-triethoxysilylhexyl) amine, N- (6-ethyldiethoxysilylhexyl) amine, N- [ ⁇ -tris- (trimethoxysiloxy) silylpropyl] amine, N- [ ⁇ -tris (trimethoxysiloxy) silylpropyl] amine, N- ( ⁇ -trimethoxysiloxy) silylpropyl] amine, N- ( ⁇ -trimethoxysiloxydimethylsilylpropyl)
  • aminosilanes of the general formula III can be used in which the repeat unit identified by the parameter c for a repeat unit of the general formula V
  • carbamatosilanes of the general formula III where Z in this case represents a carbamate group according to the general formula IV.
  • Carbamatosilanes of the general formula III can be obtained, for example, by reacting an aminosilane with a dialkyl or diaryl carbonate or pyrocarbonate, or a mixture of two or more thereof. Such a reaction is usually carried out in the presence of a basic catalyst. In principle, however, all other processes known to those skilled in the art are also suitable for the preparation of carbamates, provided they are suitable for the preparation of carbamatosilanes, for example the reaction of the aminosilanes with chloroformic acid esters or the reaction of isocyanatosilanes with alcohols.
  • Suitable carbonates are, for example, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, diisobutyl carbonate, di-tert-butyl carbonate, diisopentyl carbonate, diisopropyl carbonate, ethyl methyl carbonate, ethyl 2-butoxyethyl carbonate, bis (2-chloroethyl) carbonate, diphenyl carbonate, bis (o, m-chlorophenyl) carbonate, Bis (o, p-chlorophenyl) carbonate, bis (dichlorophenyl) carbonate, bis (trichlorophenyl) carbonate or bis (o-, m-, p-tolyl) carbonate or mixtures of two or more thereof.
  • carbamatosilanes which have been prepared using dimethyl carbonate, diethyl carbonate or dipropyl carbonate or pyrocarbonate or mixtures of two or more thereof.
  • Suitable dialkyl pyrocarbonates are, for example, dimethyl pyrocarbonate, diethyl pyrocarbonate or ditert-butyl pyrocarbonate.
  • the reaction between the aminosilane and the organic carbonate can take place, for example, using stoichiometric amounts of the reactants. However, it is also possible and often preferred to use an excess of organic carbonate from about 0.05 to about 1 mole per mole of aminosilane. Good results can be achieved, for example, with an excess of carbonate of about 0.1 to about 0.4 moles per mole of aminosilane. With higher molecular weight aminosilanes, for example a molecular weight of more than about 200 or more than about 500 or with aminosilanes with a sterically hindered amino group, it may be necessary to use a higher excess of carbonate.
  • Suitable basic catalysts are, for example, alkali metal alkoxides, as can be obtained by reacting monohydric alcohols with alkali metals.
  • Suitable alkali metals are for example lithium, sodium or potassium
  • suitable monohydric alcohols are for example methanol, ethanol, propanol or butanol.
  • Suitable strong basic In particular, catalysts are sodium methoxide, sodium ethanolate, sodium propanolate, sodium tert-butoxide, potassium methoxide, potassium ethanolate, potassium propanolate or potassium tert-butoxide and the like.
  • the amount of catalyst during the reaction is about 0.01 to about 2% by weight, based on the carbonate and aminosilane used.
  • the reaction between aminosilane and organic carbonate is slightly exothermic.
  • Aminosilane and organic carbonate are usually reacted with one another in the presence of the basic catalyst such that the reaction temperature remains within a range from about 10 to about 120 ° C., for example about 20 to about 80 ° C. or about 25 to about 60 ° C.
  • the constancy of the temperature within this range can be achieved, for example, by conventional cooling methods such as cold water, ice bath, dry ice bath or by controlling the rate of addition of the reactants.
  • the reaction is usually carried out at ambient pressure under a protective gas atmosphere.
  • Suitable neutralizing agents are, for example, inorganic acids such as anhydrous hydrochloric acid, anhydrous phosphoric acid or organic acids such as glacial acetic acid, propionic acid, butyric acid, hexanoic acid, oleic acid, maleic acid, fumaric acid, succinic acid and the like.
  • Weak organic acids such as glacial acetic acid or inorganic acids such as anhydrous phosphoric acids, for example superphosphoric acid or polyphosphoric acid or, if present, their anhydrides are preferably used for the neutralization.
  • the use of anhydrides of the corresponding acids is particularly suitable since both catalyst and excess amine are bound.
  • reaction product can be separated off using customary methods known to the person skilled in the art.
  • separation of precipitated salts by filtration for example over silica gel or a suitable filter paper, and subsequent ones is particularly suitable Removal of volatile components through reduced pressure or temperature increase, or both.
  • Particularly suitable carbamatosilanes of the general formula III are, for example, methyl N- ( ⁇ -methyldimethoxysilylmethyl) carbamate, methyl N- ( ⁇ -trimethoxysilylmethyl) carbamate, methyl N- ( ⁇ -ethyldimethoxysilylmethyl) carbamate, methyl-N- ( ⁇ -Methyldiethoxysilylmethyl) carbamate, methyl-N- ( ⁇ -triethoxysilyl-methyl) carbamate, methyl-N- (ß-methyldimethoxysilylethyl) carbamate, methyl-N- (ß-trimethoxysilylethyl) carbamate, methyl-N- (ß-diethylmethoxy-silylethyl ) carbamate, methyl-N- (ß-ethyldimethoxysilylethyl) carbamate, methyl-N- (ß-diethoxysilylethyl) carb
  • a compound which has at least one amino group and a compound which has at least one carbamine group, at least one of the compounds carrying a silyl group are reacted with one another.
  • the abovementioned compounds of the general formula III fulfill the corresponding requirements in the variants shown, ie if Z represents an amino group or Z represents a carbamate group. It is therefore within the scope of the method according to the invention For example, it is possible to prepare compounds which have a urea group and two silyl groups if two compounds of the general formula III are reacted with one another, one of the compounds mentioned having an amino group and one of the compounds mentioned having a carbamate group. However, it is also possible and contemplated within the scope of the present invention that one of the reactants has no silyl group.
  • Suitable reactants have, for example, a structure according to the general formula VI
  • p for a rational number from 1 to about 1000 and R 11 for a linear or branched, saturated or unsaturated, optionally substituted alkyl radical having 2 to about 44 carbon atoms, a saturated or unsaturated, optionally substituted cycloalkyl with 6 to about 44 carbon atoms, an optionally substituted aryl with 6 to about 44 carbon atoms, an isocyanurate ring or a polymer with a molecular weight of at least about 150.
  • a compound of the general formula VI in which Z represents an amino group is used as at least one reaction partner in the process according to the invention. If, in the case of a compound of the general formula VI, Z represents an amino group, then at least one further reaction partner according to the general formula III must be present in the reaction mixture, in which Z represents a carbamate group.
  • the radical R 11 can be , for example, a linear or branched, saturated or unsaturated, optionally substituted alkyl group having 1 to about 44 carbon atoms. atoms stand. Suitable alkyl groups have a length of 3 to about 20 carbon atoms, for example. If the alkyl group is unsubstituted, the compounds according to general formula VI are monoalkylamines.
  • Suitable monoalkylamines are, for example, ethylamine, propylamine, butylamine, pentylamine, hexylamine and their linear or branched higher homologues with up to about 100 carbon atoms, the position of the amino group being able to be arranged at the end or at any point within the alkyl group.
  • the radical R 11 can likewise stand for a substituted alkyl radical.
  • Suitable substituents are, for example, hydroxyl groups, ester groups, carboxylic acid groups, sulfonic acid groups,
  • R Reesstt FR 11 has two or more substituents Z, ie, p stands for a number of 2 or more.
  • a compound of the general formula VI for example, which has two or more amino groups, can therefore be present as the reactant in the reaction mixture.
  • Suitable compounds of this type are, for example, ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, 2,4,4-
  • R 11 can represent a saturated or unsaturated, optionally substituted cycloalkyl radical having 6 to about 24 carbon atoms.
  • a corresponding cycloalkyl radical can carry the substituents already mentioned as substituents.
  • the cycloalkyl radical can have one or more further amino groups.
  • Suitable cycloalkyl compounds are, for example Cyclohexylamine, Dicyclohexylamine, 1, 4-Cyclohexyldiamin, 4,4'-
  • amines in which the radical R 11 is optionally substituted aryl groups having 6 to about 24 carbon atoms can be used as compounds of the general formula VI.
  • Suitable substituents are in particular the substituents already mentioned above.
  • Particularly suitable aryl compounds of the general formula VI are, for example, aniline, 1,4-diaminobenzene, aminotoluene, m- or p-phenylenediamine, diaminobiphenyl, p-methoxyaniline, p-chloroaniline, o-, m- or p-toluidine, 2,4-xylidine , 2,4-, and 2,6-toluenediamine and corresponding mixtures, 4,4'-diphenylenediamine, methylenebis (aniline) including 4,4'-methylenebis (aniline), 2,4'-methylenebis (aniline), 4, 4'-oxybis (aniline), 4,4'-carbonylbis (aniline), 4,4'-sulfonylbis (aniline) or naphthyldiamines or mixtures of two or more of the compounds mentioned.
  • aniline 1,4-diaminobenzene, aminotoluene, m- or
  • amines in which the radical R11 is optionally substituted isocyanurates can be used as compounds of the general formula VI.
  • Particularly suitable compounds are 1,3,5-trisaminoalkyl, cycloalkyl and aryl isocyanurates. Examples include: 1,3,5-tris (6-aminohexyl) isocyanurate, 1,3,5-tris (6-aminopropy) isocyanurate, 1,3,5-tris (6-aminoethyl) isocyanurate, 1,3 , 5-tris (3-aminophenyl) isocyanurate and 1, 3,5-tris (4-methyl-3-aminophenyl) isocyanurate. Mixtures of two or more of the compounds mentioned can also be used.
  • compounds of the general formula VI are used in which R 11 represents one of the radicals mentioned above, but which have at least one carbamate group as functional group Z.
  • Such compounds can be obtained by reacting the above-mentioned amino compounds with organic carbonates or pyrocarbonates, as already described in the context of this text.
  • compounds which have only one carbmate group are suitable.
  • compounds which have two or more carbamate groups can also be used in the process according to the invention. If a compound having one or more carbamate groups is used as a compound of the general formula VI in the context of the present invention, then at least one compound of the general formula III in which Z represents an amino group must be present as a further reaction partner in the process according to the invention.
  • compounds of the general formula VI which have both an amino group and a carbamate group.
  • Such compounds can be obtained, for example, by reacting compounds of the type described above with more than one amino compound with organic carbonates in a corresponding stoichiometric ratio, for example in a molar ratio of 1: 1 or less.
  • radical R 11 in the formula VI is a polymer.
  • a polymer selected from the group consisting of polyacrylates, polymethacrylates, polystyrenes, polyesters, polyethers, polyamides, polyurethanes, polycarbonates, polylactones, polyethyleneimine, polyureas, polyolefins and polyoxazolidones is used as the polymer.
  • a “polymer” is understood to mean a compound which has a molecular weight of at least about 150, but preferably an overlying molecular weight, for example at least about 500, 800 or at least about 1,000.
  • the polymers which can be used in the context of the present invention as compounds of the general formula VI can have, for example, only one functional group Z. However, it is equally possible and preferred within the scope of the present invention if the number of functional groups Z is more than 1, for example at least about 2, 3, 4, 5 or more.
  • the number p in the general formula VI in the context of the present invention stands for a rational number between 1 and about 1,000.
  • the number p of functional groups Z in a polymer of the general formula VI can then assume a value deviating from an integer if the number of functional groups Z is taken as the average value in a mixture of molecules of the general formula VI, the number of functional groups per molecule, as often found in polymer chemistry, fluctuates. Such fluctuations can arise, for example, due to the functionalization of a polymer in the context of a polymer-analogous reaction.
  • the number p stands for a value of approximately 1.5 to approximately 10, in particular for a value of approximately 1.8 to approximately 5 and particularly preferably for a value of approximately 1.9 to approximately 3 ,
  • a functional group Z can be arranged terminally or laterally to the polymer chain R 11 in the process according to the invention. If the number of functional groups Z> 1, then two or more functional groups on a polymer chain can be arranged exclusively at the end, as well as exclusively at the side or at the end and at the side.
  • Suitable polymeric radicals R 11 in the context of the present invention are, for example, polymers such as can be obtained by polymerizing compounds having at least one olefinically unsaturated double bond.
  • Suitable polymers are, for example, polyacrylates, polymethacrylates, polyvinyl esters, polyvinyl ethers, polyolefins or polystyrenes.
  • the molecular weight (M n ) of polymers suitable as radical R 11 is preferably between approximately 300 and approximately 1,000,000, particularly preferably between approximately 500 and approximately 300,000 and particularly preferably between approximately 1,000 and approximately 30,000.
  • the molecular weight distribution of the polymers as can be determined, for example, by gel permeation chromatography, based on the polystyrene standard, under measurement conditions usually used for polymers, need not be monomodal. If appropriate, a suitable polymer can also have a bimodal or higher-modal distribution.
  • polyacrylate or “polyacrylates” as used in the context of the present text refer below to both polymers or copolymers of acrylic acid and / or their derivatives and to polymers or copolymers of methacrylic acid and / or their derivatives, unless otherwise stated in the text.
  • Polyacrylates can be produced by acrylic acid and / or methacrylic acid and / or derivatives of acrylic acid and / or methacrylic acid, for example their esters with mono- or polyfunctional alcohols, in each case alone or as a mixture of two or more thereof, in a known manner, for example by radical means, ionic or metal catalyzed, polymerized.
  • both homopolymers and copolymers can be used as polyacrylates.
  • suitable copolymers can also contain, for example, styrene, acrylonitrile, vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride and / or butadiene.
  • the monomers used in the preparation of the polyacrylates are, in particular, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate or lauryl acrylate and the corresponding esters of methacrylic acid in question. If necessary, small amounts of acrylic acid, methacrylic acid, acrylamide or methacrylamide can be added as further monomers during the polymerization.
  • acrylates and / or methacrylates with one or more functional groups can be present in the polymerization.
  • examples include maleic acid, itaconic acid, butanediol diacrylate, hexanediol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, 2-hydroxyethyl methacrylate,
  • suitable functionalized monomers having amino groups are suitable, for example, which are copolymerized into the monomers forming the radical R 11 as part of a copolymerization.
  • suitable functionalized monomers having amino groups are suitable, for example, which are copolymerized into the monomers forming the radical R 11 as part of a copolymerization.
  • Monomers suitable for introducing amino groups into the polymers are, for example, 2-aminoethyl acrylamide, 2-aminoethyl methacrylamide, 3-aminopropylacrylamide, 3-aminopropyl methacrylamide and allylamine.
  • Such amino groups as polymers bearing functional groups Z can then be converted in a polymer-analogous reaction into compounds of the general formula VI which carry a carbamate group as functional groups Z.
  • a corresponding polymer-analogous reaction for example with organic carbonates, can be carried out according to the scheme already described above.
  • polyester can be used as polymeric radicals R 11 in the context of the present invention.
  • Suitable polyesters can be obtained in a manner known to the person skilled in the art by polycondensation of acid and alcohol components, in particular by polycondensation of a polycarboxylic acid or a mixture of two or more polycarboxylic acids and a polyol or a mixture of two or more polyols.
  • polycarboxylic acids suitable for the preparation of the polyester which can be used as R 11 can be based on an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic base body and, if appropriate, in addition to the at least two carboxylic acid groups, one or more substituents which are non-reactive in the context of polycondensation, for example halogen atoms or olefinically unsaturated double bonds.
  • substituents which are non-reactive in the context of polycondensation for example halogen atoms or olefinically unsaturated double bonds.
  • their acid anhydrides (if any) or their esters with C 5 -C 5 -monoalcohols, or mixtures of two or more thereof, can be used for the polycondensation.
  • Suitable polycarboxylic acids are, for example succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, glutaric acid, glutaric anhydride, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetra- chlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dimer fatty acids or trimer fatty acids or Mixtures of two or more of the polycarboxylic acids mentioned. If necessary, minor amounts of monofunctional fatty acids can be present in the reaction mixture.
  • polyols can be used as diols for the preparation of a polyester or polycarbonate which can be used as R 11 in a compound of the general formula VI.
  • these are aliphatic polyols with 2 to 4 OH groups per molecule.
  • the OH groups can be either primary or secondary be bound.
  • Suitable aliphatic polyols include, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3, 2,3-butanediol, 1,4-butenediol, 1,4-butynediol , Pentanediol-1, 5, and the isomeric pentanediols, pentenediols or pentindiols or mixtures of two or more thereof, hexanediol-1, 6, and the isomeric hexanediols, hexenediols or hexindiols or mixtures of two or more thereof, heptanediol-1, 7 and the isomeric heptane, heptene or heptinediols, octanediol-1, 8 and the is
  • Highly functional alcohols such as glycerol, trimethylolpropane, pentaerythritol or sugar alcohols such as sorbitol or glucose, as well as oligomeric ethers of the substances mentioned with themselves or in a mixture of two or more of the compounds mentioned, for example polyglycerol with a degree of polymerization of about 2, are also suitable to about 4.
  • one or more OH groups can be esterified with monofunctional carboxylic acids having 1 to about 20 C atoms, with the proviso that on average at least two OH groups are retained.
  • the higher-functionality alcohols mentioned can be used in pure form or, if possible, as the technical mixtures obtainable in the course of their synthesis.
  • polyether polyols which are to be used for the production of polyesters suitable as radicals R 11 are preferably obtained by reacting polyols with alkylene oxides.
  • the alkylene oxides preferably have two to about four carbon atoms.
  • the reaction products of ethylene glycol, propylene glycol, the isomeric butanediols or hexanediols, as mentioned above, are suitable. or mixtures of two or more thereof, with ethylene oxide, propylene oxide or butylene oxide or mixtures of two or more thereof.
  • polyether polyols with a molecular weight (M n ) of about 100 to about 3,000, preferably of about 200 to about 2,000, obtainable from the reactions mentioned are particularly suitable.
  • M n molecular weight
  • the polyether polyols mentioned can be reacted with the abovementioned polycarboxylic acids in a polycondensation reaction to give the polyesters which can be used as radicals R 11 .
  • the radicals R 11 can be functionalized with corresponding functional groups Z in a conventional manner known to the person skilled in the art.
  • Polyesters which have a carboxylic acid group as end groups are particularly suitable for functionalization. Such polyesters can, for example, be reacted with polyamines in a polymer-analogous reaction so that the polyester has amino end groups.
  • Such amino groups as polyesters bearing functional groups Z can then be converted in a polymer-analogous reaction into compounds of the general formula VI which carry a carbamate group as functional groups Z.
  • a corresponding polymer-analogous reaction for example with organic carbonates, can be carried out according to the scheme already described above.
  • Polyether polyols are also suitable as R 11 radicals. Suitable polyether polyols are usually obtained by reacting a starter compound having at least two reactive hydrogen atoms with alkylene or arylene oxides, for example Ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran or epichlorohydrin or mixtures of two or more thereof.
  • a starter compound having at least two reactive hydrogen atoms with alkylene or arylene oxides, for example Ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran or epichlorohydrin or mixtures of two or more thereof.
  • Suitable starting compounds are, for example, water, ethylene glycol, propylene glycol-1, 2 or -1, 3, butylene glycol-1,4, or -1, 3, hexanediol-1,6, octanediol-1, 8, neopentylglycol, 1, 4-hydroxymethylcyclohexane , 2-methyl-1, 3-propanediol, glycerol, trimethylolpropane, hexanetriol-1, 2,6, butanetriol-1, 2,4, trimethylolethane, pentaerythritol, mannitol, sorbitol, methylglycosides, sugar, phenol, isononylphenol, resorcinol, hydroquinone , 1, 2,2- or 1, 1, 2-tris (hydroxyphenyl) ethane, ammonia, methylamine, ethylenediamine, tetra- or hexamethyleneamine, triethanolamine, aniline, pheny
  • R 11 radicals are also suitable for use as R 11 radicals.
  • polyether polyols which have been modified by vinyl polymers.
  • Such products are available, for example, in which styrene or acrylonitrile or a mixture thereof is polymerized in the presence of polyethers.
  • polyether polyols are functionalized in a manner known to the person skilled in the art.
  • conventional polyether polyols can be converted into the corresponding polyether amines by reaction of the terminal OH groups with ammonia or primary amines by processes known from the literature.
  • Corresponding polyether polyols are commercially available, for example, under the trade name JEFFAMIN® in different compositions. Examples include the Jeffamin types D 230, D 400 and D 2000 based on difunctional polypropylene glycols, types T 403, T 3000 and T 5000 based on trifunctional polypropylene glycols, types ED 600, ED 900, ED 2001 and ED 6000 based on difunctional polyethylene glycols and the types M 300, M 600, M 1000 and M 2070 based on monofunctional polypropylene glycols. Suitable polyethers containing amino groups can be converted in the course of a polymer-analogous functionalization to polymers which have a carbamate group as functional group Z.
  • Polyacetals are also suitable as R 11 radicals.
  • Polyacetals are understood to mean compounds as can be obtained by reacting glycols, for example diethylene glycol or hexanediol, with formaldehyde.
  • Polyacetals which can be used in the context of the invention can also be obtained by the polymerization of cyclic acetals.
  • functionalization of the polyacetals with functional groups Z what has already been said in the context of the description of the polyester applies.
  • polycarbonates are also suitable as radicals R 11 .
  • Polycarbonates can, for example, by the reaction of the above-mentioned polyols, in particular diols such as propylene glycol, 1,4-butanediol or 1,6-hexanediol, diethylene glycol, triethylene glycol or tetraethylene glycol or mixtures of two or more thereof, with diaryl carbonates, for example diphenyl carbonate or phosgene, be preserved.
  • diols such as propylene glycol, 1,4-butanediol or 1,6-hexanediol
  • diethylene glycol triethylene glycol or tetraethylene glycol or mixtures of two or more thereof
  • diaryl carbonates for example diphenyl carbonate or phosgene
  • Suitable polylactones are preferably those which are derived from compounds of the general formula HO- (CH 2 ) z -COOH, where z is a number from 1 to about 20. Examples are ⁇ -caprolactone, ß-propiolactone, ⁇ -butyrolactone or methyl- ⁇ -caprolactone or mixtures of two or more thereof.
  • functional groups Z what has already been said in the description of the polyesters applies.
  • Polyethyleneimines are also suitable as polymeric radical R 11 .
  • Suitable polyethyleneimines can be obtained by polymerizing ethyleneimine and have a molecular weight of about 300 to about 100,000.
  • Polyamides are also suitable as polymeric radical R 11 in the context of the present invention.
  • Suitable polyamides can be, for example Produce implementation of the above dicarboxylic acids with appropriate diamines.
  • Suitable diamines are, for example, those which have a molecular weight of about 32 to about 200 g / mol and have at least two primary, 2 secondary or one primary and one secondary amino groups.
  • Examples include diaminoethane, diaminopropane, diaminobutane, diaminohexane, piperazine, 2,5-dimethylpiperazine, amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophorone diamine, IPDA), 4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane , Aminoethylethanolamine, hydrazine, hydrazine hydrate or, optionally in small amounts, diamines such as the diethylenetriamine or 1, 8-diamino-4-aminomethyloctane. Synthesis from lactams such as ⁇ -caprolactam or aminocarboxylic acids such as 11-aminoundecanoic acid is also possible.
  • lactams such as ⁇ -caprolactam
  • aminocarboxylic acids such as 11-aminoundecanoic acid
  • the molecular weights of the compounds of the general formula VI which can be used in the process according to the invention are preferably in a range from about 300 to about 1,000,000. If a polymer is to be used as the compound of the general formula VI, a polymer having a molecular weight of about 500 to about 300,000, in particular about 1,000 to about 30,000, is preferably used.
  • a polyester is used as the compound of the general formula VI, it preferably has a molecular weight of about 300 to about 100,000, for example about 500 to about 50,000 or about 1,000 to about 30,000.
  • a polyether is used as the polymer of the general formula VI, it preferably has a molecular weight of about 300 to about 100,000, in particular about 500 to about 50,000 or about 1,000 to about 30,000, for example about 3,000 to about 20,000 or about 4,000 to about 8,000 or about 12,000.
  • Suitable molecular weights for polycarbonates, polylactones, polyethyleneimines or polyamides which can be used as polymers of the general formula VI in the context of the present invention are preferably from about 300 to about 50,000, in particular from about 1,000 to about 30,000.
  • the compounds of the general formula VI can also have one or more silyl groups of the general formula II as functional groups in addition to the functional groups Z.
  • a compound having at least one amino group is reacted with a carbamate in the context of the present invention, at least one of the reactants carrying a silyl group. It is therefore possible and envisaged within the scope of the present invention that, for example, two compounds of the general formula III, one of which carries an amino group and the other carries a carbamate group, are reacted with one another. It is also provided according to the invention that, for example, a compound of the general formula III is reacted with a compound of the general formula VI or two compounds of the general formula VI if one of the reactants has an amino group and the other reactant has a carbamate group.
  • the reaction according to the process of the invention takes place in the presence of a catalyst.
  • Suitable catalysts are, for example, compounds of the general formula VII
  • M (OR 12 ), (VII) where M is a metal selected from the group consisting of aluminum, titanium, magnesium or zirconium and R 12 is identical or different linear or branched hydrocarbon radicals having 1 to 8 carbon atoms and x is 2, 3 or 4.
  • Suitable catalysts are, for example, aluminum alkoxides, titanium alkoxides, magnesium alkoxides and zirconium alkoxides.
  • Tin compounds in particular organotin carboxylates such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin bis (2-ethylhexanorate) or other organotin compounds such as dibutyltin oxide, dibutyltin dimethoxide, dibutyltin dibromide, butyldidylchloride, dibutyltin chloride, dibutyltin chloride, dibutyltin chloride,
  • Dimethyltin dibromide, dimethyltin dichloride, diphenyltin dichloride or tin octoate are preferred.
  • dibutyltin dilaurate, dibutyltin oxide and dibutyltin diacetate are preferred.
  • catalysts are compounds which have at least one of the metals selected from the group consisting of antimony, iron, cobalt, nickel, copper, chromium, manganese, molybdenum, tungsten or lead.
  • the oxides, halides, carboxylates, phosphates or organometallic compounds of the metals mentioned are particularly suitable.
  • iron acetate, iron benzoate, iron naphthenates are particularly suitable;
  • the amount of catalyst used in the process according to the invention is in a range from about 0.01 to about 0.5% by weight, in particular from 0.05 to about 0.2% by weight, based on the total amount of carbamate.
  • the process according to the invention is preferably carried out at a pH of about 2 to about 12, in particular about 5 to about 9, for example about 5.5 to about 8.5.
  • Suitable organic solvents have a boiling point of at least about 100 ° C., but preferably a boiling point above that.
  • Suitable solvents are, for example, dioctyl phthalate, didecyl phthalate, didodecyl phthalate or other homologous esters of polybasic carboxylic acids.
  • Phosphoric acid esters for example chlorinated phosphoric acid esters, are also suitable.
  • Dibenzyltoluene, triphenylmethane, phenylnaphthalene, biphenyl, diethylbiphenyl or ethylbiphenyl are also suitable.
  • all solvents with a sufficiently high boiling point can be used, provided they are inert to the reactants.
  • the solvent used is a solvent which is used in a later formulation using the compounds according to the invention, for example as a plasticizer, and can therefore remain in the prepolymer.
  • the reaction is preferably carried out at a temperature of about 50 to about 300, in particular about 50 to about 250 ° C. Suitable reaction temperatures are in particular in a range from about 80 to about 220 or to about 190 ° C.
  • the reaction time is about 0.1 to about 10 hours.
  • the reaction conditions are chosen so that the reaction time is about 0.5 to about 1.5 hours.
  • the progress of the reaction can be recognized, for example, by monitoring the amine number in the reaction mixture.
  • the reaction is preferably continued until the amine number has dropped to a value of about 5 or less, for example to a value of 1 or less, in particular to a value of 0.5 or less.
  • the reaction mixture Upon completion of the reaction, i.e. after reaching the desired amine number, the reaction mixture is cooled. Depending on the desired reaction procedure, the pressure can be reduced, for example, during cooling, so that optionally volatile constituents such as low molecular weight alcohols or an optionally used solvent are removed in vacuo.
  • the above-mentioned reactants can be used in different molar ratios in the process according to the invention.
  • any ratios of amino groups to carbamate groups can be used.
  • the ratio of amino groups to carbamate groups is selected so that it is at most about 1: 1. This ensures that essentially every amino group reacts with a carbamate group.
  • a further embodiment of the present invention relates to a reaction procedure in which the reactant carrying the carbamate groups has at least two carbamate groups.
  • the present invention provides as a further embodiment that the ratio of carbamate groups to amino groups is 1 or less than 1, for example about 0.1 to about 0.99 or about 0.3 to about 0.9 or about 0 , 4 to about 0.8.
  • any reaction partner carrying at least two carbamate groups is suitable as the reaction partner which has at least two carbamate groups of the general formula VI.
  • Suitable compounds can be prepared in the manner already described, for example, starting from the compounds which have already been described and carry at least two amino groups.
  • a polymer is used as the reactant having at least two carbamate groups.
  • Suitable polymers having at least two carbamate groups can be prepared in the manner already described from the polymers having at least two amino groups already described above.
  • a polymer which has at least one ether group is used as the polymer having at least two carbamate groups.
  • a polyether or a polyamide or a polyurea or a mixture of two or more thereof is used as the polymer carrying at least two carbamate groups.
  • a compound having an amino group or a compound having two or more amino groups can be used as reactant for the compound having at least two carbamate groups or the mixture of two or more such compounds. In a preferred embodiment, however, a compound is used which has only one amino group.
  • the reactant carrying the amino group or the amino groups has one or more silyl groups.
  • a polymer having at least two carbamate groups or a mixture of two or more such polymers and an aminosilane or a mixture of two or more aminosilanes are used as reactants. If the reaction according to the invention is carried out between a compound having at least two carbamate groups or a mixture of two or more thereof and a compound having one or more amino groups such that the ratio of amino groups to carbamate groups is ⁇ 1, the process according to the invention is preferably carried out in the presence carried out a trimerization catalyst. In the reaction according to the process of the invention, isocyanurate groups are formed in the presence of a trimerization catalyst.
  • the reaction according to the invention can, for example, be carried out in the context of the present invention until the reaction mixture no longer has any carbamate groups.
  • the implementation is carried out only incompletely.
  • an “incomplete reaction” is understood to mean a reaction in which not all carbamate groups present in the reaction mixture are reacted, ie in which carbamate groups still remain in the reaction product.
  • This variant of the process according to the invention is suitable in principle for all combinations of reactants in which at least one reactant carries at least one carbamate group, but this variant is particularly advantageous if one of the reactants has at least two carbamate groups.
  • the present invention therefore also relates to a polymer which has at least one urea group, at least one alkoxysilyl group and at least one carbamate group.
  • a polymer which has at least one urea group, at least one alkoxysilyl group and at least one carbamate group.
  • such a polymer can, for example, also have one or more isocyanurate groups.
  • the reaction can easily be terminated by methods known to those skilled in the art, such as adding a catalyst poison or lowering the temperature.
  • the remaining carbamate groups have the effect that the reaction product has a lower viscosity than the fully converted product and thus simplifies use as a binder for adhesives and sealants.
  • the remaining carbamate groups can also be used to formulate heat-activated adhesives and sealants, since the carbamate groups can split into isocyanate at temperatures above 150 ° C and can further crosslink via trimerization or allophanate formation.
  • Trimerization catalysts are known to the person skilled in the art from the relevant literature, e.g. Laas et al., J. Prakt. Chem. 336 (1994), pages 192 to 196 and various patent publications such as US 5218133 (Union Carbide), US 4412073 (Rhone-Poulenc), US 5260436 (Iowa), US 5837796 (Bayer) and US 4124545 (Bayer).
  • Suitable trimerization catalysts are, for example, the catalysts already described above in the course of the reaction of carbamate groups and amino groups. Are also suitable as
  • Trimerization catalysts the alkali metal salts of organic acids or alkali metal salts of phosphoric acid and amines that do not react with the carbamate groups.
  • alkali metal salts of organic acids include the sodium, potassium, lithium or cesium salts of acetic acid, propionic acid, butyric acid, hexanoic acid, oleic acid, maleic acid, fumaric acid, succinic acid and the like.
  • alkali metal salts of phosphoric acid include, for example, alkali orthophosphates such as trisodium orthophosphate, tripotassium orthophosphate or dialkali orthophosphates such as disodium orthophosphate or dipotassium orthophosphate.
  • Amines suitable as trimerization catalysts are, for example, tertiary amines such as N, N-dimethyldodecylamine, 1,4-diazabicyclo [2.2.2.] Octane (DABCO). Mixtures of two or more of the compounds mentioned are also suitable.
  • the process according to the invention can be used to produce polymers which, in contrast to polymers with isocyanurate structures, each have only one isocyanurate group and three urea groups and three silyl groups, or, if the ratio of carbamate groups to amino groups is selected appropriately, several triisocyanurate groups and a corresponding number of urea groups and silyl groups exhibit.
  • polymers which have more than one isocyanurate group there is no further structural element between two isocyanurate groups which can be obtained by reacting isocyanate groups with a compound which is reactive toward isocyanates.
  • the present invention therefore also relates to the fact that at least one isocyanurate structural element and at least one alkoxysilyl group have, where, provided that the polymer has more than one isocyanurate structural element, there is no structural element between at least two isocyanurate structural elements in polymers that by reaction of an isocyanate group can arise with a functional group reactive towards isocyanate groups or the structure lying between two isocyanurate groups has a molecular weight of at least 300.
  • a “structure lying between two isocyanurate groups” is understood to mean a chain of covalently bonded atoms.
  • the polymers according to the invention provide that they either have only one isocyanurate structural element, at least one urine group and at least one alkoxysilyl group or more as an isocyanurate structural element, at least one urea group and at least one alkoxysilyl group. If a polymer according to the invention has more than one isocyanurate structural element, then various requirements apply to a polymer according to the invention.
  • Such polymers according to the invention can be obtained, for example, if compounds of at least two carbamate groups are used as compounds of the general formula VI which have no structural elements in the radical R 11 which can result from the reaction of an isocyanate group with a compound which is reactive toward isocyanates. Essentially all of the polymers already mentioned are suitable
  • molecular weight refers to the molecular weight with respect to a polystyrene standard determined by GPC under conditions customary for the respective polymer.
  • the polymers according to the invention can be prepared by reacting a prepolymer having at least two carbamate groups or a mixture of two or more such prepolymers with an alkoxysilane having at least one amino group, the molar ratio of carbamate group to amino groups being less than 1.
  • the present invention therefore also provides a polymer which can be obtained by reacting a prepolymer containing at least two carbamate groups or a mixture of two or more such prepolymers with an alkoxysilane having at least one amino group, the molar ratio of carbamate groups to amino groups being less than 1.
  • a “prepolymer” is understood to mean a compound of the general formula VI which has at least two functional groups Z, at least two of the functional groups Groups Z represent a carbamate group.
  • a prepolymer according to the present invention has a molecular weight of at least about 150 and at most about 1,000,000, preferably at least about 500 to about 500,000, for example about 1,000 to 50,000.
  • the compounds produced by the process according to the invention and the polymers according to the invention are suitable, for example, for use in surface coating compositions such as lacquers or similar coating systems and for use in adhesives, sealants and foams.
  • the present invention therefore also relates to the use of a compound produced by a process according to the invention or a polymer according to the invention for the production of
  • Another object of the present invention is a
  • surface coating compositions or adhesives according to the invention contain a crosslinking catalyst which catalyzes the crosslinking of the silyl groups, or a mixture of two or more such catalysts.
  • Suitable crosslinking catalysts are, for example, amino compounds such as triethylenediamine, trimethylaminoethylpiperazine, pentamethyldiethylenetriamine, tetramethyliminoisopropylamine or bis (dimethylaminopropyl) -N-isopropanolamine or dimorpholinodiethyl ether.
  • Other suitable catalysts are those based on organic or inorganic heavy metal compounds such as cobalt naphthenate, dibutyltin dilaurate, tin mercaptide, tin dichloride, zirconium tetractate, antimony dioctoate, lead dioctoate, metal, especially iron acetylacetonate.
  • all catalysts known for the acceleration of the silanol condensation can be used.
  • these are organotin, organotitanium, organozirconium or organoaluminium compounds.
  • organotin, organotitanium, organozirconium or organoaluminium compounds examples of such compounds are dibutyltin dilaurate, dibutyltin dimaleate, tin octoate, isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate,
  • Dibutyltin alkyl esters such as dibutyltin alkyl maleate or dialkyltin laurate are particularly suitable, in particular dibutyltin bisethyl maleate, dibutyltin bisbutyl maleate, di-butyltin bisoctyl maleate, dibutyltin bisoleyl dibutyl dibutyl dibutyl dibutyl dibutyl dibutyl dibutyl dibutyl dibutyl dibutyl dibutyl dibutyl dibutyl dibutyl dibutyl dibutyl dibutyl dibutyl dibutyl dibutyl dibutyl dibutyl dibutyl dibutyl dibutyl dibutyl dibutyl dibutyl dibutyl dibutyldibutyl dibutyl dibutyl dibutyl dibutyldibutyl dibutyl dibutyl dibutyldibuty
  • a crosslinking catalyst can be used, for example, in an amount of 0.01% up to about 2%, preferably 0.05% up to about 0.5%, based on the weight of the silyl groups.
  • a surface coating agent according to the invention or an adhesive according to the invention can also contain further additives.
  • Suitable additives are, for example, tackifiers, plasticizers, rheological additives, antioxidants, UV stabilizers, dyes, pigments, adhesion promoters, drying agents, flame retardants, cell regulations, propellant gases or fillers.
  • reactive silanes are suitable for increasing the storage stability of the compounds according to the invention or of the compositions produced therefrom.
  • Suitable reactive silanes are, for example, tetramethoxysilane, trimethoxymethylsilane or trimethoxyvinylsilane, which are suitable for trapping water. The amount of such compounds should not exceed 3% by weight, based on the total mixture containing the reactive silane or the mixture of two or more reactive silanes.
  • suitable flame retardants are conventional phosphorus-containing compounds, in particular elemental phosphorus, phosphates or phosphonates, for example triethyl phosphate or trichloropropyl phosphate. Such compounds can have plasticizing and viscosity-regulating properties at the same time.
  • Suitable flame retardants are, for example, diphenyl cresyl phosphate, triphenyl phosphate, dimethyl methane phosphonate and the like. Chlorine paraffins can also be used as flame retardants.
  • Halogenated polyester or polyether polyols are likewise suitable, for example commercially available brominated polyether polyol. Such halogenated polyester or polyether polyols can, for example, be incorporated into the polymers according to the invention.
  • compositions which are used to produce foams can contain, for example, cell regulators or blowing agents or both.
  • Silicon-based compounds are usually used as cell regulators.
  • liquid, crosslinkable polybutadiene, silicone oils or paraffin oils are used in particular as cell regulators.
  • commercially available silicone stabilizers are used as stabilizers.
  • a composition which contains a compound according to the invention also contains at least one propellant.
  • Suitable blowing agents are, for example, low-boiling fluorocarbons, hydrocarbons or ethers or mixtures of two or more thereof.
  • CO 2 , N 2 O or N 2 can also be present as blowing agents. Any combination of these gases is possible.
  • propellant gas contents of 5 to 40% by weight, in particular 5 to 20% by weight, based on the overall composition, are preferred.
  • the content of gases that cannot be condensed under the prevailing pressure conditions should be such that the volume based on the empty space of the pressure vessel results in a pressure of approximately 8 to 10 bar, depending on the relevant national regulations for aerosol cans or pressure vessels (if such regulations exist). , Since no CO 2 is released during the crosslinking of the compounds according to the invention, sufficient propellant gas must be available both for the application and for the foaming.
  • hydrocarbon resins are used as tackifiers, in particular C5 or C9 resins or C9 resins modified with C5 resins.
  • Resins based on pure hydrocarbon monomers for example resins such as are obtainable from the polymerization of mixtures of styrene, ⁇ -methylstyrene and vinyltoluene, are also suitable for use as tackifiers.
  • the hydrocarbon resins mentioned can be partially hydrogenated or fully hydrogenated.
  • tackifiers such as balsam resin, such as that obtained from trees, or tall resin, which is produced in paper production.
  • the natural resins can be used in the form mentioned above as tackifiers, but it is also possible to use the resins mentioned after esterification with corresponding polyfunctional alcohols as pentaerythritol esters, glycerol esters, diethylene glycol esters, triethylene glycol esters or methyl esters.
  • the polyterpene resins are also suitable as tackifiers.
  • Terpenes are obtained when resin acids are separated from their natural solvents and can be polymerized to polyterpene resins.
  • the adhesive according to the invention can contain stabilizers or antioxidants as additives. These generally include the phenols, the sterically hindered high molecular weight, polyfunctional phenols, sulfur- and phosphorus-containing phenols or amines. Suitable stabilizers are, for example, hydroquinone, hydroquinone methyl ether, 2,3- (di-tert-butyl) hydroquinone, 1 ) 3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) )benzene; Pentaerythritol tetrakis-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate; n-octadecyl-3,5-di-tert-butyl-4-hydroxyphenyl) propionate; 4,4-methylenebis (2,6-di-tert-butyl-phenol); 4,4-thiobis (6-tert-phenol
  • the surface coating agent according to the invention or the adhesive according to the invention can further contain plasticizers such as benzoate plasticizers, phosphate plasticizers, liquid resin derivatives or vegetable and animal oils. Suitable are, for example, sucrose benzoate, diethylene glycol dibenzoate and / or diethylene glycol benzoate, in which about 50 to about 95% of all hydroxyl groups have been esterified, phosphate plasticizers, for example t-butylphenyldiphenylphosphate, polyethylene glycols and their derivatives, for example diphenyl ether of poly (ethylene glycol), liquid resin for example the methyl ester of hydrogenated resin, vegetable and animal oils, for example glycerol esters of fatty acids and their polymerization products.
  • plasticizers such as benzoate plasticizers, phosphate plasticizers, liquid resin derivatives or vegetable and animal oils.
  • Plasticizers based on phthalic acid are also suitable, especially the alkyl phthalates.
  • the surface coating agent according to the invention or the adhesive according to the invention can furthermore contain dyes such as titanium dioxide, fillers such as gypsum, talc, clay and the like as well as pigments.
  • the additives can be present individually or as a mixture of two or more of the substances mentioned.
  • the amount of additives should not exceed about 20% by weight (based on the total surface coating agent or the total adhesive).
  • amounts of about 0.1 to about 15% by weight are suitable, or about 1 to about 10% by weight in a preferred embodiment of the invention, for example about 2, 3, 4, 5, 7 or 9% by weight.
  • Suitable surface coating agents or adhesives have, for example, the following approximate composition:
  • plasticizer or flame retardant 10 - 25% by weight plasticizer or flame retardant
  • the liquid was mixed with 0.2% dibutyltin diacetonate and stored in a rectangular shape in a layer thickness of 2 mm at 50% RH / 23 ° C. for 1 week until it had completely hardened.
  • the liquid was mixed with 0.2% dibutyltin diacetonate and stored in a rectangular shape in a layer thickness of 2 mm at 50% RH / 23 ° C. for 1 week until it had completely hardened.
  • the cured film (catalyst 0.1% by weight of dibutyltin bis (2,4-pentanedionate)) was somewhat sticky on the surface 24 hours after application.
  • a clear, yellow liquid with a viscosity of 9,000 mPas (Brookfield RVT, spindle 6/20 rpm) was obtained.
  • the cured film (catalyst 0.1% by weight of dibutyltin bis (2,4-pentanedionate)) was soft, elastic and tack-free 24 hours after application.
  • Macromelt TPX22-405 polyamide with terminal amino groups
  • 0.15 g of dibutyltin dilaurate and 4.4 g of N- (trimethoxysilylpropyl) methyl carbamate were stirred into the melt.
  • the mixture was then heated to 180 to 190 ° C. for about 2 hours. After cooling to ⁇ 150 ° C., the mixture was slowly cooled to room temperature under vacuum (approx. 20 mbar).

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Abstract

La présente invention concerne un procédé de production de composés comprenant au moins un groupe urée et au moins un groupe silyle. Selon ce procédé, on fait réagir un composé ayant au moins un groupe amino avec un carbamate, sachant que le composé présente au moins un groupe amino ou bien le carbamate présente un groupe silyle. L'invention concerne également les composés produits selon le procédé, leur utilisation ainsi que des produits de revêtement de surface, des matières d'étanchéité, des colles, des mousses d'assemblage et d'isolation contenant de tels composés.
EP01978452A 2000-10-27 2001-10-24 Polymeres ayant des groupes uree et des groupes silyle, leur production et leur utilisation Withdrawn EP1328586A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10053545A DE10053545A1 (de) 2000-10-27 2000-10-27 Polymere mit Harnstoffgruppen und Silylgruppen, deren Herstellung und Verwendung
DE10053545 2000-10-27
PCT/EP2001/012291 WO2002034838A1 (fr) 2000-10-27 2001-10-24 Polymeres ayant des groupes uree et des groupes silyle, leur production et leur utilisation

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Publication Number Publication Date
EP1328586A1 true EP1328586A1 (fr) 2003-07-23

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Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7045588B2 (en) * 2004-02-12 2006-05-16 Basf Corporation Polyester resin composition for use in a coating composition and method of preparing the same
WO2005077321A1 (fr) * 2004-02-13 2005-08-25 Kettenbach Gmbh & Co. Kg Produit dentaire a base de polyethers a fonction alcoxysilyle
DE102005031201A1 (de) * 2005-07-01 2007-01-25 Kettenbach Gmbh & Co. Kg Zu formstabilen Formkörpern aushärtendes kondensationsvernetzendes Dentalmaterial
JP5498697B2 (ja) 2005-07-15 2014-05-21 ダウ コーニング コーポレーション 疎水化鉱物及び充填剤物質
DE102005051921A1 (de) * 2005-10-29 2007-05-03 Henkel Kgaa α-Ethoxysilan modifizierte Polymere, deren Herstellung und Verwendung
DE102006054155A1 (de) * 2006-11-16 2008-05-21 Wacker Chemie Ag Schäumbare Mischungen enthaltend alkoxysilanterminierte Prepolymere
DE102006059473A1 (de) 2006-12-14 2008-06-19 Henkel Kgaa Silylgruppen enthaltende Mischung von Prepolymeren und deren Verwendung
DE102007011511A1 (de) 2007-03-09 2008-09-11 Henkel Ag & Co. Kgaa Ein-Komponenten-Montageklebstoff mit hoher Anfangshaftung
US8378037B2 (en) * 2007-12-26 2013-02-19 Momentive Performance Materials Inc. Moisture-curable silylated polyurea and adhesive, sealant and coating compositions containing same
DE102008043218A1 (de) 2008-09-24 2010-04-01 Evonik Goldschmidt Gmbh Polymere Werkstoffe sowie daraus bestehende Kleber- und Beschichtungsmittel auf Basis multialkoxysilylfunktioneller Präpolymerer
DE102009022628A1 (de) 2008-12-05 2010-06-10 Evonik Goldschmidt Gmbh Verfahren zur Modifizierung von Oberflächen
DE102009022631A1 (de) 2009-05-25 2010-12-16 Evonik Goldschmidt Gmbh Härtbare Silylgruppen enthaltende Zusammensetzungen und deren Verwendung
HUE036462T2 (hu) * 2011-05-09 2018-07-30 Saudi Aramco Tech Co Polimer készítmények és eljárások
EP2626317A1 (fr) 2012-02-13 2013-08-14 de Schrijver, Aster Systèmes d'emballage sous pression pour des adhésifs mono-composants et produits d'étanchéité
US20140024795A1 (en) * 2012-04-25 2014-01-23 Novomer, Inc. Aliphatic polycarbonate polyols containing silyl groups
JP6072493B2 (ja) * 2012-10-10 2017-02-01 株式会社カネカ 活性エネルギー線硬化性コーティング用樹脂組成物
DE102013216787A1 (de) 2013-08-23 2015-02-26 Evonik Degussa Gmbh Guanidingruppen aufweisende semi-organische Siliciumgruppen enthaltende Verbindungen
EP3707220B1 (fr) 2017-11-07 2024-01-03 Henkel AG & Co. KGaA Polymères modifiés par silane et leur utilisation dans des compositions adhésives
TWI649349B (zh) * 2017-12-20 2019-02-01 財團法人工業技術研究院 聚氨酯脲組成物與其製備方法
JP7535508B2 (ja) * 2018-11-07 2024-08-16 メルツ＋ベンテリ アクチェンゲゼルシャフト シラン変性ポリマーを製造する方法
CN109721734B (zh) * 2018-12-20 2021-08-03 上海东大化学有限公司 一种双端烷氧基硅酮树脂及其制备方法
KR102626818B1 (ko) * 2021-08-30 2024-01-18 (주)에프티씨코리아 안정성이 향상된 수분산 블록이소시아네이트 조성물

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1207594A (en) * 1967-03-16 1970-10-07 Union Carbide Corp One component room temperature vulcanizable silicon terminated polymers
US3671562A (en) * 1968-09-12 1972-06-20 Union Carbide Corp Urea silicon product and the preparation thereof
US4124545A (en) 1973-05-22 1978-11-07 Bayer Aktiengesellschaft Carbamic acid esters as catalysts for trimerization of isocyanates
SU606863A1 (ru) * 1974-07-08 1978-05-15 Предприятие П/Я Г-4302 Способ получени полимочевин
US4232133A (en) * 1978-07-27 1980-11-04 Ici Americas Inc. Polyisocyanurate containing molding compositions
PL141806B1 (en) 1981-02-03 1987-08-31 Rhone Poulenc Spec Chim Method of obtaining compounds with isocyanure groups
US4345053A (en) * 1981-07-17 1982-08-17 Essex Chemical Corp. Silicon-terminated polyurethane polymer
DE3821465A1 (de) 1988-06-25 1989-12-28 Degussa Verfahren zur herstellung ein- oder mehrfach substituierter organyloxysilylfunktioneller thioharnstoffe und diese verbindungen
CA2052842C (fr) * 1990-10-09 1999-08-24 Hideyuki Ohnari Resine durcissable et composition contenant cette resine
JPH05185595A (ja) 1992-01-16 1993-07-27 Seiko Epson Corp インクジェット記録装置およびその製造方法
US5218133A (en) * 1992-08-20 1993-06-08 Union Carbide Chemicals & Plastics Technology Corporation Process for making a silylisocyanurate
US5260436A (en) 1992-09-21 1993-11-09 Iowa State University Research Foundation, Inc. Method for synthesis of triarylisocyanurates from aryl isocyanates using triazaprophosphatrane catalysts
US5423735A (en) 1993-04-16 1995-06-13 Minnesota Mining And Manufacturing Company Orthopedic cast composed of an alkoxysilane terminated resin
JP4171530B2 (ja) 1996-04-15 2008-10-22 三井化学ポリウレタン株式会社 ケイ素含有イソシアネート化合物の製造方法
US5770672A (en) * 1997-04-03 1998-06-23 Elf Atochem North America, Inc. Catalyst for low temperature cure of blocked isocyanates
DE19627825A1 (de) 1996-07-10 1998-01-15 Bayer Ag Verfahren zur Herstellung von Isocyanuratgruppen aufweisenden Polyisocyanaten, die nach diesem Verfahren erhältlichen Verbindungen und ihre Verwendung zur Herstellung von Polyisocyanat-Additionsprodukten
US6008396A (en) 1997-04-11 1999-12-28 Osi Specialties, Inc. Hot oil process for producing isocyanato organosilanes
DE19855999A1 (de) 1998-12-04 2000-06-15 Bayer Ag Alkoxysilanhaltige Lackzubereitung
JP4462679B2 (ja) * 1999-03-30 2010-05-12 旭化成イーマテリアルズ株式会社 シリコン系カップリング剤及びその用途
US6451930B1 (en) * 2000-03-14 2002-09-17 Ppg Industries Ohio, Inc. Topcoat with improved adhesive qualities

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0234838A1 *

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CA2426620A1 (fr) 2002-05-02
WO2002034838A1 (fr) 2002-05-02
US7057001B2 (en) 2006-06-06
US20050260401A1 (en) 2005-11-24
DE10152505A1 (de) 2002-07-04
DE10053545A1 (de) 2002-05-08
JP2004512414A (ja) 2004-04-22
US20060247407A1 (en) 2006-11-02

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