EP3394134A1 - Hydroxyaldimine et composition de polyuréthane durcissable ayant une teneur faible en isocyanates monomères - Google Patents

Hydroxyaldimine et composition de polyuréthane durcissable ayant une teneur faible en isocyanates monomères

Info

Publication number
EP3394134A1
EP3394134A1 EP16820246.3A EP16820246A EP3394134A1 EP 3394134 A1 EP3394134 A1 EP 3394134A1 EP 16820246 A EP16820246 A EP 16820246A EP 3394134 A1 EP3394134 A1 EP 3394134A1
Authority
EP
European Patent Office
Prior art keywords
formula
hydroxyaldimine
reaction
reaction product
composition
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Withdrawn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
EP16820246.3A
Other languages
German (de)
English (en)
Inventor
Urs Burckhardt
Andreas Kramer
Martin Schmider
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.)
Sika Technology AG
Original Assignee
Sika Technology AG
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 Sika Technology AG filed Critical Sika Technology AG
Priority to EP23181909.5A priority Critical patent/EP4253499A3/fr
Publication of EP3394134A1 publication Critical patent/EP3394134A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271—Hydroxyamines
    • C08G18/3296—Hydroxyamines being in latent form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/24—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/227—Catalysts containing metal compounds of antimony, bismuth or arsenic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • 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
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • 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
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
    • C08G18/8041—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3271
    • 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
    • C09J175/08—Polyurethanes from polyethers

Definitions

  • the invention relates to Aid im ine and polyurethanes, as well as adhesives, sealants and coatings.
  • Curable polyurethane compositions which crosslink by reaction of isocyanate groups with hydroxyl groups and / or moisture or water are used in many industrial applications, for example as adhesives, sealants or coatings in the construction and manufacturing industry.
  • the usual products have a considerable content of monomeric isocyanates. This applies in particular to two-component systems in which the isocyanate component to a large extent consists of monomeric diisocyanates.
  • one-component systems based on so-called prepolymers which are addition products of monomeric diisocyanates with polyols, typically also contain an undesirably high content of monomeric diisocyanates. Since the addition proceeds relatively unselectively and chain extension occurs, unreacted monomeric diisocyanates remain in such products.
  • Monomeric diisocyanates are harmful compounds which escape from the products under certain conditions of use and can pose a danger to the user due to their respiratory irritant or sensitizing effect and are therefore increasingly undesirable from the point of view of occupational safety. This is especially true for spray applications as well as for hot-to-process compositions, such as hot melt adhesives.
  • WO 2007/036575 describes a polyurethane hotmelt adhesive with a low isocyanate monomer content and a process for reducing the content of monomeric diisocyanates by reacting them with special long-chain ester aldimines which contain a reactive group with active hydrogen.
  • the disclosed aldimines and their reaction products are temperature sensitive, and the hotmelt adhesives obtained therewith have limited durability when heated. In the typical application of such hotmelt adhesives on open rolls, thickening and hardening on the roll therefore soon occur, which lead to an abutment in the plant and may require expensive cleaning.
  • WO 2008/1 16927 also describes a process for preparing a low isocyanate monomer content polyurethane composition by reacting the composition with a blocked amine containing an active hydrogen reactive group.
  • the aldimines carried out cause intense odor emissions by the released volatile blocking agents and sometimes lead to low storage stability and undesirably short open times of the compositions formulated therewith.
  • hot-melt adhesives which are typically processed at high temperature over open, air-exposed rolls, they are totally unsuitable. Presentation of the invention
  • the object of the present invention is therefore to provide a route to curable polyurethanes with a low content of monomeric diisocyanates, which overcomes the disadvantages of the prior art.
  • a hydroxyaldimine of the formula (I) as described in claim 1 solves this problem.
  • the hydroxyaldimine of the formula (I) is odorless, pH neutral, liquid at room temperature and low viscosity and less sensitive to heat and moisture. It can thus be easily stored, transported, dosed and processed.
  • the hydroxyaldimine of the formula (I) is suitable for the preparation of aldimino-containing reaction products, in particular by reacting it with the exclusion of moisture with polyisocyanates. It can very effectively reduce the content of monomeric diisocyanates of isocyanate-containing polyurethane polymers, which is very advantageous for toxicological reasons.
  • the resulting reaction products are very stable on their own and in isocyanate-containing compositions. Under the influence of moisture, their aldimino groups react relatively slowly, but nevertheless completely and without any disturbance, whereby the reaction can also be quickly adjusted by means of suitable catalysts. This allows a wide range of open times.
  • the released in the hydrolysis aldehyde is non-volatile, odorless and colorless and thus causes neither emissions or odor emissions nor discoloration. It is well tolerated in polyurethanes and hardly prone to plasticizer migration. This is surprising. Aldimines, whose splitters have a high molecular weight, are naturally particularly critical in terms of plasticizer migration after curing, since the amount used is correspondingly high due to the high equivalent weight and thus a high amount of released aldehyde remains in the cured material. In addition, Nesse the long-chain hydrophobic alkyl or alkoxy substituent, especially in a branched structure, expected in the hydrophilic, hydrogen-containing polymer backbone of polyurethanes rather poor compatibility.
  • hydroxyaldimine of the formula (I) or its reaction products for use in reactive polyurethane hot-melt adhesives. It reduces their content of monomeric diisocyanates and allows particularly good thermal stability. Particularly surprising is the excellent stability of hot melt adhesives prepared with hydroxyaldimine of the formula (I) in the hot molten state, where no appreciable viscosity increase is observed during the processing of such hot melt adhesives on open rotating rolls for many hours.
  • the hydroxyaldimine of the formula (I) or its reaction products enable polyurethane compositions with a low content of monomeric diisocyanates, good storage stability and easily manageable processing times, which crosslink rapidly and completely and without blistering or odor immissions. The result is a bubble-free material with non-sticky surface and good strength, ductility and resistance, which does not tend to problems with plasticizer migration such as bleeding, substrate discoloration or stress cracking in the substrate.
  • the invention relates to a hydroxyaldimine of the formula (I)
  • Z is an aryl radical having a total of 12 to 26 C atoms substituted by an alkyl or alkoxy group
  • A is a divalent aliphatic or cycloaliphatic or arylaliphatic, optionally ether-oxygen-containing hydrocarbon radical having a molecular weight in the range from 28 to 500 g / mol.
  • a dashed line in the formulas in each case represents the bond between a substituent and the associated molecular residue.
  • primary amino group is meant an amino group attached to a single organic radical bearing two hydrogen atoms;
  • Secondary amino group is an amino group which is bonded to two organic radicals, which may also be part of a ring together, and carries a hydrogen atom, and as “tertiary amino group” is an amino group attached to three organic radicals which also in twos or threes part of one or more rings, is bonded and bears no hydrogen atom.
  • primary polyamine is meant a compound having at least two primary amino groups.
  • aromatic isocyanate refers to an isocyanate whose isocyanate groups are bonded directly to an aromatic carbon atom, and accordingly such isocyanate groups are referred to as “aromatic isocyanate groups”.
  • molecular weight is meant the molar mass (in grams per mole) of a molecule or molecular residue.
  • Average molecular weight refers to the number average molecular weight (M n ) of a polydisperse mixture of oligomeric or polymeric molecules or molecular moieties , It is usually determined by gel permeation chromatography (GPC) against polystyrene as standard.
  • viscosity denotes the dynamic viscosity or shear viscosity, which is defined by the ratio between the shear stress and the shear rate (velocity gradient) and determined as described in DIN EN ISO 3219.
  • a “storage stable” or “shelf stable” is a substance or composition when it can be stored at room temperature in a suitable container for extended periods of time, typically for at least 3 months to 6 months or more, without being concentrated in its own Application or use properties changed by storage in a relevant for their use to the extent.
  • a Zusannnnener is referred to, in which all components of Zusannnnener in the same container and which is stable as such.
  • Tron-component refers to a composition in which the constituents of the composition are present in two different components, which are stored in separate containers and mixed together only shortly before or during the application of the composition.
  • “Curing” or “crosslinking” refers to the chemical setting of a curable composition.
  • room temperature refers to a temperature of 23 ° C.
  • Z is preferably a radical of the formula (II)
  • R is a linear or branched alkyl or alkoxy radical having 6 to 20, preferably 8 to 16, carbon atoms.
  • R is preferably a linear or branched alkyl radical having 10 to 14 C atoms or a linear or branched alkoxy radical having 8 to 12 C atoms.
  • R is in particular a linear or branched alkyl radical having 10 to 14 C atoms. Such a hydroxyaldimine is particularly reactive.
  • R is particularly preferably a branched alkyl radical.
  • hydroxyaldimine is typically liquid at room temperature and comparatively low viscosity, which is advantageous for its handling.
  • R is a branched alkyl radical having 10 to 14 carbon atoms.
  • R very particularly preferably represents a branched alkyl radical having 10 to 14 C atoms.
  • Such a hydroxyaldimine is particularly reactive, usually liquid at room temperature and comparatively low viscosity.
  • R is preferably in the meta or para position, in particular in the para position. Such a hydroxyaldimine is particularly accessible.
  • R is a radical of the formula - ⁇ R 2 , where R 1 and R 2 are each an alkyl radical and together have 9 to 13 C atoms.
  • R 1 and R 2 are each linear.
  • Z is thus a radical of the formula (IIa)
  • R 1 and R 2 have the meanings mentioned.
  • the preferred radicals Z are particularly readily accessible and allow particularly low-odor hydroxyaldimines which are particularly liquid and particularly low-viscosity at room temperature.
  • A preferably has a molecular weight in the range of 28 to 250 g / mol.
  • 3-oxa-1, 5-pentylene Particularly preferred is 3-oxa-1, 5-pentylene. These hydroxyaldimines are not prone to cyclization and allow isocyanate group-containing compounds to be cyclized. Compositions with a particularly low content of monomeric diisocyanates and hot melt adhesives with particularly good stability during processing in the molten state.
  • the preferred hydroxyaldimines of the formula (I) are particularly readily available and allow particularly good properties in the use according to the invention.
  • the hydroxyaldimine of the formula (I) is optionally in equilibrium with a cyclic compound of the formula (II)
  • the hydroxyaldimine of the formula (I) is preferably obtained from the reaction of at least one amine of the formula (III) with at least one aldehyde of the formula (IV) in a condensation reaction with liberation of water.
  • the aldehyde of the formula (IV) is preferably used stoichiometrically or in a stoichiometric excess with respect to the primary amino groups. puts. In this way, the reaction product is largely or completely free of primary amino groups.
  • a further subject of the invention is thus a reaction product comprising at least one hydroxyaldimine of the formula (I) obtained from the reaction of at least one amine of the formula (III) with at least one aldehyde of the formula (IV) in a condensation reaction with liberation of water wherein the aldehyde was present stoichiometrically or in stoichiometric excess with respect to the primary amino groups.
  • the reaction is advantageously carried out at a temperature in the range of 15 to 120 ° C, preferably at 20 to 100 ° C, optionally in
  • the condensation water is preferably removed from the reaction mixture, either as an azeotrope with a suitable solvent or preferably directly by distillation, optionally under vacuum.
  • a catalyst is used in the reaction, in particular an acid catalyst.
  • Such a reaction product can be used without further workup as hydroxyaldimine of the formula (I).
  • the amine of formula (III) is combined with the aldehyde of formula (IV) to form a reaction mixture wherein the aldehyde is stoichiometric or in stoichiometric excess relative to the primary amino groups and the condensation water is removed from the reaction mixture by a suitable method is, optionally with heating of the reaction mixture.
  • Suitable amines of the formula (III) are primary hydroxyamines, in particular 2-aminoethanol, 2-methylaminoethanol (2-amino-1-propanol), 1-amino-2-propanol panol, 3-amino-1-propanol, 4-amino-1-butanol, 4-amino-2-butanol, 2-amino-2-methylpropanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 7 -Amino-1-heptanol 8-amino-1-octanol, 10-amino-1-decanol, 12-amino-1-dodecanol, 4- (2-aminoethyl) -2-hydroxyethylbenzene, 3-aminoethyl-3, 5,5-trinethylcyclohexanol, a derivative of glycols such as diethylene glycol, di-propylene glycol, dibutylene glyco
  • 2-aminoethanol 2-methylaminoethanol (2-amino-1-propanol), 1-amino-2-propanol, 3-amino-1-propanol, 5-amino-1-pentanol, 6-amino-1-hexa - nol, 3-aminomethyl-3,5,5-trimethylcyclohexanol or 2- (2-aminoethoxy) ethanolene.
  • 3-aminomethyl-3,5,5-trimethylcyclohexanol or 2- (2-aminoethoxy) ethanol is particularly preferred.
  • a preferred aldehyde of the formula (IV) is an aldehyde of the formula (IVa), where R has the meanings already described.
  • a particularly preferred aldehyde of the formula (IV) is an aldehyde of the formula (IVb), where R 1 and R 2 have the meanings already described.
  • aldehydes of the formula (IV) are 4-decylbenzaldehyde, 4-undecylbenzaldehyde, 4-dodecylbenzaldehydes, 4-tridecylbenzaldehydes or 4-tetradecylbenzaldehydes, in which the alkyl radicals are linear or branched, in particular branched.
  • aldehyde of the formula (IV) is a mixture containing 4-decylbenzaldehydes, 4-undecylbenzaldehydes, 4-dodecylbenzaldehydes, 4-tridecylbenzaldehydes and 4-tetradecylbenzaldehydes, the alkyl radicals of which are mostly selected.
  • the aldehyde of formula (IV) is especially obtainable from the formylation of at least one alkyl- and / or alkoxy-substituted aromatic hydrocarbon with carbon monoxide under the action of an acid catalyst.
  • an acid catalyst for example, the system HCI-AICI3 (Gattermann-Koch reaction) is suitable.
  • the formylation is carried out with HF-BF 3 as the acid catalyst.
  • HF-BF 3 as the acid catalyst.
  • the hydroxyaldimine of the formula (I) is preferably selected from the group consisting of N- (4-alkylbenzylidene) -2-aminoethanol, N- (4-alkylbenzylidene) -2-methylaminoethanol, N- (4-alkylbenzylidene) -1-amino 2-propanol, N- (4-alkylbenzylidene) -3-amino-1-propanol, N- (4-alkylbenzylidene) -5-amino-1-pentanol, N- (4-alkylbenzylidene) -6-amino 1-hexanol, N- (4-alkylbenzylidene) -3-aminomethyl-3,5,5-trimethylcyclohexanol and N- (4-alkylbenzylidene) -2- (2-aminoethoxy) ethanol, wherein each alkyl is a linear or in particular branched decyl,
  • the hydroxyaldimine of the formula (I) preferably represents a mixture of hydroxyaldimines of the formula (I) in which Z in each case represents a radical of the formula (II) and R is here selected from alkyl radicals having 6 to 20 C atoms. R is particularly preferably selected from linear or in particular branched decyl, undecyl, dodecyl, tridecyl and tetradecyl radicals.
  • Another object of the invention is thus a mixture of hydroxyaldehydes of the formula (I) in which Z is in each case a radical of the formula (II) and R is here selected from linear or in particular branched decyl, undecyl, dodecyl , Tridecyl and tetradecyl radicals.
  • Such a mixture is technically particularly easily accessible.
  • the hydroxyaldimine of the formula (I) can be used as a hardener for isocyanate group-containing compositions.
  • the hydroxyaldimine of the formula (I) is particularly advantageously used for the preparation of aldimino-containing reaction products, where at least one hydroxyaldimine of the formula (I) is reacted with at least one compound which has hydroxyl-reactive groups.
  • the compound is multifunctional with respect to these reactive groups.
  • These are particularly preferably at least one polyisocyanate or at least one polyfunctional ester, in particular at least one polyisocyanate.
  • Such aldimino-containing reaction products can be used to advantage as latent hardeners for isocyanate group-containing compositions.
  • the use according to the invention is characterized in that the hydroxyaldimine of the formula (I) or its reaction products are excellently compatible with isocyanate group-containing compositions.
  • they allow a good storage stability with exclusion of moisture together with isocyanate groups and on contact with moisture with a long open time with a rapid and complete curing, without causing odor emissions, with mechanically high quality and stable polymers that are not prone to plasticizer migration problems.
  • Another object of the invention is a reaction product with
  • a and Z have the meanings already mentioned.
  • at least one hydroxyaldimine of the formula (I) is mixed with at least one polyisocyanate in the absence of moisture, whereupon the hydroxyl groups react with the isocyanate groups present.
  • the reaction can be carried out at ambient temperature or at an elevated temperature. Preference is given to a temperature in the range from 0 to 180.degree. C., preferably from 10 to 180.degree. C., in particular from 20 to 180.degree.
  • a catalyst may be present, in particular a bismuth (III), zinc (II), zirconium (IV) or tin (II) compound or an organotin (IV) compound.
  • further constituents of substances commonly used in polyurethane compositions may be present, for example fillers, plasticizers or solvents.
  • the reaction can be carried out substoichiometrically, ie at an OH / NCO ratio of less than 1.
  • a reaction product is obtained, which in addition to aldimino groups also has isocyanate groups.
  • Such a reaction product is storage-stable in the absence of moisture. It is particularly suitable as a latent hardener for isocyanate-containing compositions or as a binder in moisture-curing polyurethane compositions.
  • the OH / NCO ratio in the reaction in the range of 0.05 / 1 to 0.5 / 1, in particular 0.1 / to 0.5 / 1, preferably 0.2 / 1 to 0.5 / 1.
  • Such a reaction product crosslinks on contact with moisture to a solid material.
  • the hydrolyzing aldimino groups react with existing isocyanate groups and excess isocyanate groups react directly with moisture.
  • the polyisocyanate is an isocyanate-group-containing polyurethane polymer
  • an advantage of the reaction product is that its content of monomeric diisocyanates is greatly reduced compared to the polyurethane polymer used.
  • the reaction product remains usable in the same way as the polyurethane polymer used for the reaction, in particular as a binder in one-component moisture curable polyurethanes without significant disadvantages in terms of storage stability, reactivity, odor or mechanical properties.
  • the reaction may further be stoichiometric or superstoichiometric, i. at an OH / NCO ratio of 1 or above.
  • a reaction product is obtained which is free of isocyanate groups.
  • Such a reaction product is storage stable even in the presence of moisture. It is particularly suitable as a latent hardener in one- or two-component isocyanate group-containing compositions.
  • the OH / NCO ratio in the reaction in the range of 1/1 to 1 .5 / 1, in particular 1/1 to 1 .2 / 1, preferably 1/1 to 1 .1 / 1.
  • Hydroxyaldimines of the formula (I) which are suitable for the preparation of reaction products having aldimino groups of the formula (V) are those mentioned above, in particular the preferred embodiments.
  • Polyisocyanates which are suitable for the preparation of reaction products having aldimino groups of the formula (V) are in particular aliphatic, cycloaliphatic or arylaliphatic di- or triisocyanates, preferably 1,4-tetramethylene diisocyanate, 2-methylpentamethylene-1,5-diisocyanate, 1,6-hexamethylene diisocyanate (HDI), 2,2,4- and / or 2,4 , 4-trimethyl-1,6-hexamethylene diisocyanate (TMDI), 1,10-decamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, lysine or lysine ester diisocyanate, cyclohexane-1, 3- or -1,4-diisocyanate, 1 -Methyl-2,4- and / or 2,6-diisocyanato-cyclohexane (H 6 TDI), 1-isocyanato-3,3,5
  • aromatic di- or triisocyanates preferably 4,4'- or 2,4'- or 2,2'-di-phenylmethane diisocyanate or any mixtures of these isomers (MDI), 2,4- or 2,6-toluene diisocyanate or any mixtures thereof Isomers (TDI), mixtures of MDI and MDI homologs (polymeric MDI or PMDI), 1, 3 or 1, 4-phenylene diisocyanate, 2,3,5,6-tetramethyl-1,4-diisocyanatobenzene, naphthalene 1,5-diisocyanate (NDI), 3,3'-dimethyl-4,4'-diisocyanatodiphenyl (TODI), dianisidine diisocyanate (DADI), tris (4-isocyanatophenyl) methane or tris (4-isocyanatophenyl ) thiophosphate; in particular MDI or TDI;
  • MDI 4,4'-
  • Oligomers or derivatives of said di- or triisocyanates in particular derived from HDI, IPDI, MDI or TDI, in particular oligomers containing uretdione or isocyanurate or iminooxadiazinedione groups or various of these groups; or di- or polyvalent derivatives containing ester or urea or urethane or biuret or allophanate or carbodiimide or uretonimine or oxadiazinetrione groups or various of these groups.
  • Such polyisocyanates are in practice usually mixtures of substances with different degrees of oligomerization and / or chemical structures. In particular, they have an average NCO functionality of 2.1 to 4.0.
  • Isocyanate group-containing polyurethane polymers from the reaction of polyols with the aforementioned polyisocyanates, as described below.
  • a suitable isocyanate group-containing polyurethane polymer is obtained, in particular, from the reaction of at least one polyol with a superstoichiometric amount of at least one diisocyanate.
  • the reaction is preferably carried out with exclusion of moisture at a temperature in the range of 50 to 160 ° C, optionally in the presence of suitable catalysts.
  • the NCO / OH ratio is preferably in the range of 1 .3 / 1 to 2.5 / 1.
  • the monomeric diisocyanate remaining in the reaction mixture after reaction of the OH groups can for the most part be removed, in particular by means of distillation, which is preferred in the case of a high NCO / OH ratio.
  • the polyurethane polymer obtained preferably has a content of free isocyanate groups in the range of 0.5 to 10% by weight, in particular 1 to 5% by weight, particularly preferably 1 to 3% by weight. It preferably has a residual content of monomeric diisocyanates in the range from 0.5 to 5% by weight, in particular from 1 to 3% by weight.
  • the polyurethane polymer may be prepared using plasticizers or solvents, with the plasticizers or solvents used containing no isocyanate-reactive groups.
  • the isocyanate group-containing polyurethane polymer preferably has an average molecular weight in the range of 500 to 20 ⁇ 00 g / mol, in particular 1 ⁇ 00 to 15 ⁇ 00 g / mol, preferably 1'500 to 10 ⁇ 00 g / mol.
  • Preferred polyisocyanates for preparing an isocyanate group-containing polyurethane polymer are diisocyanates, in particular MDI, TDI, IPDI, HDI or H 2 MDI.
  • polyol are suitable for the preparation of an isocyanate group-containing polyurethane polymer
  • Polyetherpolyols in particular polyoxyalkylenediols and / or polyoxyalkylenetriols, in particular polymerization products of ethylene oxide or 1,2-propylene oxide or 1,2- or 2,3-butylene oxide or oxetane or tetrahydrofuran or mixtures thereof, these with the aid of a starter molecule having two or more active hydrogen atoms may be polymerized, in particular a starter molecule such as water, ammonia or a compound having several OH or NH groups such as 1, 2-ethanediol, 1, 2- or 1, 3-propanediol, neopentyl glycol, diethylene glycol, tri ethylene glycol, the isomeric dipropylene glycols or tripropylene glycols, the isomeric butanediols, pentanediols, hexanedi
  • Preferred polyether polyols are polyoxypropylene diols or polyoxypropylene triols, or so-called ethylene oxide-terminated (EO-endcapped) polyoxypropylene diols or triols.
  • the latter are polyoxyethylene-polyoxypropylene mixed polyols, which are obtained, in particular, in that polyoxypropylene diols or triols are further alkoxylated after completion of the polypropoxylation reaction with ethylene oxide and thus ultimately have primary hydroxyl groups.
  • Preferred polyether polyols have an unsaturation degree of less than 0.02 meq / g, especially less than 0.01 meq / g.
  • Polyesterpolyols also called oligoesterols, prepared by known processes, in particular the polycondensation of hydroxycarboxylic acids or lactones or the polycondensation of aliphatic and / or aromatic polycarboxylic acids with dihydric or polyhydric alcohols.
  • polyester diols from the reaction of dihydric alcohols such as in particular 1, 2-ethanediol, diethylene glycol, 1, 2-propanediol, dipropylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, glycerol , 1, 1, 1 -Trimethylolpropan or mixtures of the aforementioned alcohols, with organic dicarboxylic acids or their anhydrides or esters, in particular succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid or hexahydrophthalic acid or mixtures of the abovementioned acids, or polyesterpolyols of lactones, in particular ⁇ -caprolactone , Particular preference is given
  • Polycarbonate polyols as they are accessible by reacting, for example, the above-mentioned - used to build the polyester polyols - alcohols with dialkyl carbonates, diaryl carbonates or phosgene.
  • At least two hydroxyl-bearing block copolymers which have at least two different blocks having a polyether, polyester and / or polycarbonate structure of the type described above, in particular polyetherpolyesterpolyols.
  • Polyhydroxy-functional fats and oils for example natural fats and oils, especially castor oil; or obtained by chemical modification of natural fats and oils - so-called oleochemical - polyols, for example, the Epoxypolyesters obtained by epoxidation of unsaturated oils and subsequent ring opening with carboxylic acids or alcohols or Epoxypolyether, or by hydroformylation and hydrogenation of unsaturated oils obtained polyols; or from natural fats and oils by degradation processes such as alcoholysis or ozonolysis and subsequent chemical linkage, for example by transesterification or dimerization, the resulting degradation products or derivatives thereof obtained polyols.
  • oleochemical - polyols for example, the Epoxypolyesters obtained by epoxidation of unsaturated oils and subsequent ring opening with carboxylic acids or alcohols or Epoxypolyether, or by hydroformylation and hydrogenation of unsaturated oils obtained polyols; or from natural fats and oils by degradation processes such as alcoholys
  • Suitable degradation products of natural fats and oils are in particular fatty acids and fatty alcohols and fatty acid esters, in particular the methyl esters (FAME), which can be derivatized for example by hydroformylation and hydrogenation to hydroxy fatty acid esters.
  • FAME methyl esters
  • Polyhydrocarbyl polyols also called oligohydrocarbonols, such as, for example, polyhydroxy-functional polyolefins, polyisobutylenes, polyisoprenes; polyhydroxy-functional ethylene-propylene, ethylene-butylene or Ethylene-propylene-diene copolymers, such as those manufactured by Kraton Polymers; polyhydroxy-functional polymers of dienes, in particular of 1, 3-butadiene, which may in particular also be prepared from anionic polymerization; polyhydroxy-functional copolymers of dienes such as 1,3-butadiene or diene mixtures and vinyl monomers such as styrene, acrylonitrile, vinyl chloride, vinyl acetate, vinyl alcohol, isobutylene and isoprene, for example polyhydroxy-functional acrylonitrile / butadiene copolymers, such as, for example, from epoxides or amino alcohols and carboxyl-terminated Acrylonitrile /
  • CTBNX or ETBN from Emerald Performance Materials CTBNX or ETBN from Emerald Performance Materials
  • hydrogenated polyhydroxy-functional polymers or copolymers of dienes
  • polyether polyols Preference is given to polyether polyols, polyester polyols, polycarbonate polyols, poly (meth) acrylate polyols or polybutadiene polyols.
  • polyether polyols particularly preference is given to polyether polyols, polyester polyols, in particular aliphatic polyester polyols, or polycarbonate polyols, in particular aliphatic polycarbonate polyols.
  • polyols having an average OH functionality in the range from 1 .6 to 4, in particular 1 .6 to 3.
  • fractions of difunctional or polyfunctional alcohols in particular 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1 , 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 3-pentanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, neopentyl glycol, dibromoneopentyl glycol, 1, 2-hexanediol, 1 , 6-hexanediol, 1, 7-heptanediol, 1, 2-octanediol, 1, 8-octanediol, 2-ethyl-1, 3-hexanediol, diethylene glycol,
  • Preferred polyisocyanates for the preparation of reaction products having aldimino groups of the formula (V) are HDI, IPDI, H 2 MDI, TDI, MDI or oligomers or isocyanate group-containing polyurethane polymers of these isocyanates or mixtures thereof.
  • liquid at room temperature or solid at room temperature isocyanate-containing polyurethane polymers wherein the content of monomeric diisocyanates is greatly reduced in the reaction.
  • a room temperature solid isocyanate group-containing polyurethane polymer may be crystalline, partially crystalline or amorphous at room temperature.
  • a partially crystalline or amorphous polyurethane polymer it is true that it is not or only slightly fluid at room temperature. This means in particular that it has a viscosity of more than 5 ⁇ 00 Pa s at 20 ° C.
  • reaction of a hydroxyaldimine of the formula (I) with an isocyanate group-containing polyurethane polymer which is solid at room temperature is preferably carried out at a temperature at which the polymer is molten, in particular at a temperature in the range from 80 to 180.degree.
  • reaction product with aldimino groups of the formula (V) has, in particular, the formula (VI)
  • u is 0 or an integer in the range of 1 to 5 and v is an integer in the range of 1 to 6, where (u + v) is an integer in the range of 2 to 6,
  • G is a (u + v) -valent hydrocarbon radical having an average molecular weight in the range from 56 to 20 ⁇ 00 g / mol, which optionally has heteroatoms,
  • u is 0 or 1 or 2 and v is 1 or 2 or 3 and (u + v) is 2 or 3.
  • G is preferably the radical of one of the preferred polyisocyanates, in particular HDI, IPDI, H-
  • reaction product G is the radical of an isocyanate group-containing polyurethane polymer after removal of the isocyanate groups and has an average molecular weight in the range from 500 to 20 ⁇ 00 g / mol, in particular 1 ⁇ 00 to 15 ⁇ 00 g / mol, preferably 1'500 to 10 ⁇ 00 g / mol, on, and (u + v) stands on average for a value in the range of 1 .8 to 3, where the mean value of u is greater than or equal to the mean value of v.
  • Such a reaction product has on average at least as many isocyanate groups as aldimino groups. It is obtained in particular from the reaction of at least one hydroxyaldimine of the formula (V) with at least one isocyanate group-containing polyurethane polymer in one
  • OH / NCO ratio in the range of 0.05 / 1 to 0.5 / 1, in particular 0.1 / 1 to 0.5 / 1, preferably 0.2 / 1 to 0.5 / 1, as previously described.
  • Such a reaction product may also contain portions of unreacted isocyanate group-containing polyurethane polymer.
  • v on average in particular for a value in the range of 0.1 to 0.95.
  • reaction product G is the radical of an isocyanate group-containing polyurethane polymer after removal of the isocyanate groups and has an average molecular weight in the range of 500 to 20 ⁇ 00 g / mol, in particular 1 ⁇ 00 to 15 ⁇ 00 g / mol, preferably 1 '500 to 10 ⁇ 00 g / mol, on, u is 0 and v is on the average a value in the range of 1 .8 to 3.
  • Such a reaction product is free of isocyanate groups.
  • reaction products described are particularly suitable for use in compositions containing isocyanate groups, either themselves having some or all of the isocyanate groups contained therein or being able to be combined with other polyisocyanates. Both one-component and multi-component, in particular two-component, compositions are possible.
  • the reaction products allow the already mentioned advantageous properties such as reduced content of monomeric diisocyanates, good storage stability, no odor, long open time, good mechanical properties and little tendency to plasticizer migration.
  • Another object of the invention is an isocyanate-containing composition containing at least one reaction product with aldimino groups of the formula (V), as described above.
  • the composition contains a reaction product which itself has at least as many isocyanate groups as aldimino groups.
  • a reaction product which has been obtained from the reaction of at least one hydroxyaldimine of the formula (I) with at least one isocyanate-containing polyurethane polymer in the OH / NCO ratio in the range from 0.05 / 1 to 0.5 / 1, in particular 0.1 / 1 to 0.5 / 1, preferably 0.2 / 1 to 0.5 / 1.
  • Such a composition has the advantage that the content of monomeric diisocyanates is particularly low, since in the reaction with the hydroxyaldimine a disproportionately large proportion of monomeric diisocyanate was reacted.
  • Such a composition may additionally contain other polyisocyanates. However, it preferably contains no further polyisocyanates. It is particularly suitable as a one-component moisture-curing composition.
  • the reaction product is based on an isocyanate group-containing polyurethane polymer
  • the composition contains a particularly low content of monomeric diisocyanates. In particular, it contains a content of monomeric diisocyanates below 1% by weight, preferably below 0.5% by weight, in particular below 0.3% by weight. Most preferably, it contains less than 0.1% by weight of monomeric diisocyanates.
  • the composition contains a reaction product which itself is free of isocyanate groups.
  • the isocyanate-free reaction product is liquid at room temperature and has an average molecular weight in the range of 56 to 20 ⁇ 00 g / mol, in particular 500 to 10 ⁇ 00 g / mol.
  • the composition additionally contains at least one polyisocyanate, the same polyisocyanates being suitable as those already mentioned, in particular a liquid form of MDI or PMDI or an oligomer of HDI or IPDI or TDI or an isocyanate group-containing polyurethane polymer of HDI , IPDI, H 2 MDI, TDI or MDI, or a mixture of said polyisocyanates.
  • a composition is suitable as a one-component or as a two-component composition.
  • a one-component composition has the advantage that it is easier to process.
  • the reaction product having aldimino groups of the formula (V) and the polyisocyanate may be present in the same or in separate components. Preferably, they are present in separate components.
  • the reaction product is preferably based on a polyurethane polymer and the polyisocyanate is a liquid at room temperature form of MDI or PMDI or an oligomer of HDI or IPDI or TDI.
  • a form of MDI which is liquid at room temperature represents liquefied 4,4'-MDI either by partial chemical modification-in particular carbodiimidization or uretonimine formation or adduct formation with polyols-or it is a deliberately brought about by mixing or conditioned by the preparation process Mixture of 4,4'-MDI with other MDI isomers (2,4'-MDI and / or 2, 2'-MDI), and / or MDI oligomers and / or MDI homologs (PMDI).
  • Such a two-component composition has the advantage that the component based on the polyurethane polymer is only aldimino-functional and thus not sensitive to contact with moisture, as long as it does not come into contact with isocyanate groups. It can therefore be easily formulated and filled with other ingredients. It may be advantageous if some water is added to such an aldimino-functional component, in particular in such an amount that the component contains up to 2% by weight, in particular up to 1% by weight, of water. This accelerates the curing process.
  • the component separated from the polyisocyanate optionally contains further isocyanate-reactive compounds, in particular difunctional or polyfunctional alcohols or polyols or amino alcohols or polyamines or further latent hardeners such as in particular ketimines, enamines, oxazolidines or not of the formula (I) corresponding aldimines.
  • further isocyanate-reactive compounds in particular difunctional or polyfunctional alcohols or polyols or amino alcohols or polyamines or further latent hardeners such as in particular ketimines, enamines, oxazolidines or not of the formula (I) corresponding aldimines.
  • the two-component composition preferably contains a polyol, in particular with an average molecular weight in the range from 400 to
  • a polyether polyol polymer particles dispersed in it, in particular styrene-acrylonitrile particles (SAN) or acrylonitrile-methyl methacrylate particles, can also be present in particular.
  • SAN styrene-acrylonitrile particles
  • acrylonitrile-methyl methacrylate particles can also be present in particular.
  • the two-component composition preferably contains at least one difunctional or polyhydric alcohol, in particular 1,4-butanediol.
  • the composition containing isocyanate groups preferably additionally comprises one or more further constituents, which are selected in particular from catalysts, fillers, plasticizers and solvents. In the case of a two-component composition, such ingredients may be present in only one or both components.
  • Suitable catalysts are, in particular, catalysts for the hydrolysis of the aldimino groups, in particular organic acids, especially carboxylic acids such as 2-ethylhexanoic acid, lauric acid, stearic acid, isostearic acid, oleic acid, neodecanoic acid, benzoic acid, salicylic acid or 2-nitrobenzoic acid, organic carboxylic anhydrides such as phthalic anhydride, hexahydrophthalic anhydride or hexahydromethylphthalic anhydride Silyl esters of carboxylic acids, organic sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid or 4-dodecylbenzenesulfonic acid, sulfonic acid esters, other organic or inorganic acids, or mixtures of the abovementioned acids and acid esters. Particular preference is given to carboxylic acids, in particular aromatic carboxylic acids, such as benzoic
  • catalysts for accelerating the reaction of isocyanate groups in particular organotin (IV) compounds such as, in particular, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dilauride, dibutyltin diacetylacetonate, dimethyltin dilaurate, dioctyltin diacetate, dioctyltin dilaurate or dioctyltin diacetylacetonate, complex compounds of bismuth (III) or zirconium (IV), in particular with ligands selected from Alcoholates, carboxylates, 1, 3-diketonates, oxinate, 1, 3-ketoesterates and 1, 3-ketoamidates, or tertiary amino-containing compounds such as in particular 2,2'-Dimorpholinodiethylether (DMDEE).
  • organotin (IV) compounds such as, in particular, dibutyltin diacetate, dibut
  • Suitable fillers are in particular ground or precipitated calcium carbonates which are optionally coated with fatty acids, in particular stearates, barytes, quartz flours, quartz sands, dolomites, wollastonites, kaolins, calcined kaolins, phyllosilicates such as mica or talc, zeolites, aluminum hydroxides, magnesium hydroxides, Silicas including finely divided silicas from pyrolysis processes, cements, gypsum, fly ash, industrially produced Russian, graphite, metal powder, for example of aluminum, copper, iron, silver or steel, PVC powder or hollow spheres.
  • fatty acids in particular stearates, barytes, quartz flours, quartz sands, dolomites, wollastonites, kaolins, calcined kaolins, phyllosilicates such as mica or talc, zeolites, aluminum hydroxides, magnesium hydroxides, Silicas including finely divided sili
  • Suitable plasticizers are, in particular, carboxylic esters, such as phthalates, in particular diisononyl phthalate (DINP), diisodecyl phthalate (DIDP) or di (2-propylheptyl) phthalate (DPHP), hydrogenated phthalates, in particular hydrogenated diisononyl phthalate (DINCH), terephthalates, in particular dioctyl terephthalate, trimellitates, adipates , in particular dioctyl adipate, azelates, sebacates, benzoates, glycol ethers, glycol esters, organic phosphoric or sulfonic acid esters, polybutenes, polyisobutenes or plasticizers derived from natural fats or oils, in particular epoxidized soybean or linseed oil.
  • carboxylic esters such as phthalates, in particular diisononyl phthalate (DINP), diisodec
  • Suitable solvents are in particular acetone, methyl ethyl ketone, methyl n-propyl ketone, diisobutyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, methyl isoamyl ketone, acetylacetone, mesityl oxide, cyclohexanone, methylcyclohexanone, ethyl acetate, propyl acetate, butyl acetate, n-butyl propionate, diethyl malonate, 1 -Methoxy-2-propyl acetate, ethyl 3-ethoxypropionate, diisopropyl ether, diethyl ether, dibutyl ether, diethylene glycol diethyl ether, ethylene glycol diethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono-2-ethylhexyl ether, tolu
  • composition may contain other additives useful in polyurethane compositions.
  • auxiliaries and additives may be present:
  • Non-reactive thermoplastic polymers in particular homo- or copolymers of unsaturated monomers, in particular from the group comprising ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate and alkyl (meth) acrylate, in particular polyethylene (PE), polypropylene (PP), polyisobutylene, ethylene-vinyl acetate copolymers (EVA) and atactic poly- ⁇ -olefins (APAO); furthermore polyesters, polyacrylates, polymethacrylates, polyacrylamides, polyacrylonitriles, polyimides, polyamides, polyvinyl chlorides, polysiloxanes, polyurethanes, polystyrenes, and combinations thereof, in particular polyetheramide copolymers, styrene-butadiene-styrene copolymers, styrene-isoprene-styrene copolymers, styrene E
  • Tackifier resins in particular a hydrocarbon resin, in particular coumarone-indene resins, terpene resins, phenol-modified terpene resins, natural, optionally modified, resins, in particular rosin, wood rosin or tall oil resin, furthermore a-methyl-styrene resins and polymeric lactic acid;
  • inorganic or organic pigments in particular titanium dioxide, chromium oxides or iron oxides;
  • Fibers in particular glass fibers, carbon fibers, metal fibers, ceramic fibers, synthetic fibers such as polyamide fibers or polyethylene fibers or natural fibers such as wool, cellulose, hemp or sisal;
  • - dyes - drying means, particularly molecular sieve, calcium oxide, highly reactive isocyanates such as p-tosyl isocyanate, monomeric diisocyanates, mono- oxazolidines such as Incozol ® 2 (of Incorez) or Orthoameisen yarnester;
  • Adhesion promoters in particular organoalkoxysilanes, in particular epoxysilanes, in particular 3-glycidoxypropyltrimethoxysilane or 3-glycidoxypropyltriethoxysilane, (meth) acrylosilanes, anhydridosilanes, carbamatosilanes, alkylsilanes or iminosilanes, or oligomeric forms of these silanes, or titanates;
  • latent hardeners or crosslinkers in particular aldimines, ketimines, enamines or oxazolidines;
  • catalysts which accelerate the reaction of the isocyanate groups in particular salts, soaps or complexes of tin, zinc, bismuth, iron, aluminum, molybdenum, dioxomolybdenum, titanium, zirconium or potassium, in particular tin (II) 2-ethylhexanoate, tin ( II) -neodecanoate, zinc (II) acetate, zinc (II) 2-ethylhexanoate, zinc (II) -aurate, zinc (II) acetylacetonate, aluminum lactate, aluminum oleate, diisopropoxytitanium bis (ethylacetoacetate) or potassium - acetate; tertiary amino group-containing compounds, in particular N-ethyldiisopropylamine, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylalkylenediamines, pentamethylalkenetriamines and higher
  • Rheology modifiers in particular thickeners, in particular
  • Phyllosilicates such as bentonites, derivatives of castor oil, hydrogenated castor oil, polyamides, polyamide waxes, polyurethanes, urea compounds, pyrogenic silicas, cellulose ethers or hydrophobically modified polyoxyethylenes;
  • flame-retardant substances in particular the already mentioned fillers aluminum hydroxide or magnesium hydroxide, and in particular organic phosphoric acid esters such as, in particular, triethyl phosphate, tricresyl phosphate, triphenyl phosphate, diphenyl cresyl phosphate, isodecyldiphenyl phosphate, tris (1,3-dichloro-2-propyl) phosphate, tris (2-chloroethyl) phosphate, tris (2-ethylhexyl) phosphate, tris ( chloroisopropyl) phosphate, tris (chloropropyl) phosphate, isopropylated triphenyl phosphate, mono-, bis- or tris (isopropylphenyl) phosphates of varying degrees of isopropylation, resorcinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate) or ammoni
  • Additives in particular wetting agents, leveling agents, defoamers, deaerators, stabilizers against oxidation, heat, light or UV radiation or biocides;
  • the preparation of the reaction product having aldimino groups of the formula (V) which is contained in the composition can also be carried out in situ in an otherwise fully formulated isocyanate group-containing composition in which at least one hydroxyaldimine of the formula (I) is admixed with the exclusion of moisture and the React hydroxyl groups with existing isocyanate groups.
  • the ratio between the isocyanate-reactive groups including aldimino groups and the isocyanate groups is preferably in the range from 0.2 to 1 .2, particularly preferably in the range from 0.4 to 1 .0, in particular in the range from 0.5 to 0.95.
  • the ratio between aldimino groups and isocyanate groups is preferably in the range from 0.05 to 1 .1, particularly preferably in the range from 0.1 to 1 .0, in particular in the range from 0.2 to 0.9.
  • the composition is prepared in the absence of moisture, the constituents of the composition becoming macroscopic. homogeneous mass and stored at ambient temperature in moisture-proof containers.
  • a suitable moisture-proof container consists in particular of an optionally coated metal and / or plastic and represents in particular a barrel, a container, a pretzel, a bucket, a canister, a can, a bag, a tubular bag, a cartridge or a tube ,
  • composition can be present in the form of a one-component or a multi-component, in particular two-component, composition.
  • the process of crosslinking begins.
  • the cured crosslinked composition is formed.
  • a one-component composition is applied as such and begins to cure or crosslink under the influence of moisture or water.
  • the composition can be admixed with an accelerator component which contains or releases water and / or a catalyst during application, or the composition can be brought into contact with such an accelerator component after its application.
  • a two-component composition is applied after mixing the two components and begins to crosslink by internal reaction, wherein the crosslinking is optionally completed by the action of external moisture.
  • the isocyanate groups react under the influence of moisture with the aldimino groups and any further blocked amino groups present.
  • Some of the isocyanate groups in particular those which are excessively active with respect to the aldimino groups, react with one another under the influence of moisture and / or with further reactive groups optionally present in the composition, in particular hydroxyl groups or free amino groups.
  • the entirety of these reactions of the isocyanate groups leading to the curing of the composition is also referred to as crosslinking.
  • the moisture required to cure a one-component composition preferably passes from the air (atmospheric moisture) by diffusion into the composition.
  • a solid layer of cured composition (“skin”) forms on the air contacting surfaces of the composition, curing continues from the outside to the inside along the direction of diffusion, the skin becoming progressively thicker and eventually embracing the entire applied composition
  • the moisture may additionally or completely also originate from one or more substrate (s) to which the composition has been applied, and / or originate from an accelerator component which admixes the composition during application or after the application is brought into contact with this, for example by brushing or spraying.
  • the external moisture optionally required to complete the curing of a two-part composition is preferably from the air and / or from the substrates.
  • Open time refers to the time during which the composition can be processed or post-processed after the curing process has begun.
  • skin-forming time or "tack-free time”
  • tack-free time represents a measure of the open time
  • an aldehyde of formula (IV) Upon crosslinking, an aldehyde of formula (IV) is liberated. This is largely non-volatile and odorless and remains for the most part in the cured composition. There he behaves or acts as a plasticizer. As such, he can basically migrate himself and / or influence the migration of plasticizers.
  • the aldehyde of formula (IV) is with the cured composition is very well tolerated, hardly migrates itself and also triggers no increased migration of plasticizers.
  • the composition is an adhesive or a sealant or a coating.
  • the adhesive or sealant or coating is elastic and is typically applied at ambient temperature, especially in the range of about 0 to 50 ° C, preferably in the range of 5 to 40 ° C.
  • Such an adhesive and / or sealant may have a pasty consistency with pseudoplastic properties and be applied by means of a suitable device, for example from commercially available cartridges or barrels or hobbocks, for example in the form of a bead, which may have a substantially round or triangular cross-sectional area , But it can also be liquid or only slightly thixotropic and self-leveling.
  • Elastic bonding in vehicle construction for example, the adhesion of parts such as plastic covers, moldings, flanges, bumpers, cabs or other attachments, to the painted body of a vehicle, or the gluing of windows in the body, the vehicles especially automobiles, trucks, buses, Represent rail vehicles or ships.
  • the composition is particularly suitable for the elastic sealing of joints, seams or cavities of all kinds, in particular joints in construction such as dilation joints or connecting joints between components.
  • An elastic coating can have a liquid consistency and can be self-leveling applied to predominantly flat surfaces, or it can have a certain intrinsic viscosity so that it does not run off on inclined surfaces when applied.
  • the composition is particularly suitable for a coating.
  • the composition is a reactive hot-melt adhesive (PUR-RHM).
  • the composition is in particular one-component and contains in particular at least one isocyanate-group-containing polyurethane polymer which is solid at room temperature and which is reacted with at least one hydroxyaldimine of the formula (I ) in an OH / NCO ratio in the range of 0.05 / 1 to 0.5 / 1, in particular 0.1 / 1 to 0.5 / 1, preferably 0.2 / 1 to 0.5 / 1, to a solid at room temperature reaction product with aldimino groups of the formula (V) implemented.
  • PUR-RHM reactive hot-melt adhesive
  • Such a reactive hotmelt adhesive contains a particularly low content of monomeric diisocyanates. This is particularly advantageous for toxicological reasons, since when processed in a hot state, the monomeric diisocyanates increasingly enter the environment and thus load the processor particularly heavily.
  • the reactive hot-melt adhesive preferably has a content of room-temperature solid polyurethane polymer including reaction product in the range of 5 to 100% by weight, in particular 15 to 95% by weight, more preferably 30 to 90% by weight, most preferably 50 to 80% by weight -%, on.
  • It preferably contains at least one further polymer selected from the group consisting of non-reactive thermoplastic polymers and tackifier resins.
  • It preferably has a content of polymers, including the polyurethane polymer which is solid at room temperature, including the reaction product in the range from 70 to 100% by weight, particularly preferably 80 to 100% by weight, in particular 90 to 100% by weight.
  • the reactive hot-melt adhesive is melted for the application and processed and applied in the molten state.
  • the processing is typically carried out at a temperature in the range of 80 to 180 ° C, in particular 100 to 180 ° C.
  • the molten uncrosslinked adhesive for some time, especially for a few hours remain stable on a rotating roller as a low-viscosity liquid in contact with the ambient humidity, so in particular show no strong increase in viscosity and no hardening or precipitation. This is achieved surprisingly well with the hot-melt adhesive according to the invention.
  • the adhesive solidifies on cooling very quickly, which he virtually immediately hardens and builds adhesion, but in the uncrosslinked state is still thermoplastic and can be re-deformed or liquefied by reheating.
  • the existing aldimino and isocyanate groups crosslink as described above, as a result of which the adhesive additionally chemically crosslinks.
  • a cured crosslinked adhesive is obtained, which can not be remelted by re-heating to the application temperature.
  • the composition is particularly suitable for construction and industrial applications, in particular as laminating adhesive, laminate adhesive, packaging adhesive, textile adhesive or wood adhesive. It is particularly suitable for bonds in which the bonding site is visible, in particular for the bonding of glass, for example in vehicle and window construction, or for the gluing of transparent packaging.
  • Suitable substrates which can be glued or sealed or coated with the composition are, in particular
  • PCC polymer-modified cement mortar
  • ECC epoxy resin-modified cement mortar
  • metals or alloys such as aluminum, copper, iron, steel, non-ferrous metals, including surface-refined metals or alloys such as galvanized or chromium-plated metals;
  • Plastics such as hard and soft PVC, polycarbonate, polystyrene, polyester, polyamide, PMMA, ABS, SAN, epoxy resins, phenolic resins, PUR, POM, TPO, PE, PP, EPM or EPDM, each untreated or surface-treated, for example by means of plasma , Corona or flames;
  • CFRP Carbon Fiber Reinforced Plastics
  • GRP Glass Fiber Reinforced Plastics
  • SMC Sheet Molding Compounds
  • insulating foams in particular of EPS, XPS, PUR, PIR, rock wool, glass wool or foamed glass (foam glass);
  • coated or painted substrates in particular painted tiles, painted concrete, powder-coated metals or alloys or painted sheets;
  • the substrates can be pretreated prior to application, in particular by physical and / or chemical cleaning methods or the application of an activator or a primer. It is possible to bond and / or seal two identical or two different substrates.
  • Preferred for bonding with the reactive hot-melt adhesive are plastics, textiles, leather, wood, wood-based materials, polymer composites, paper, metals, paints or lacquers, in particular two different substrates being bonded.
  • This article is obtained which is glued or sealed or coated with the composition.
  • This article may be a building or a part thereof, in particular a civil engineering structure, a bridge, a roof, a stairwell or a façade, or it may be an industrial good or a consumer good, in particular a wood fiber material from the showers.
  • composition described is characterized in that it is particularly stable on storage and optionally has a particularly low content of monomeric diisocyanates.
  • the composition in the molten state in contact with the ambient air has a particularly good stability, as a result of which the adhesive can be rotated for a few hours on an open roll in the hot state without a noticeable increase in viscosity occurring.
  • the crosslinking of the composition proceeds bubble-free, completely and without odor immissions.
  • the composition When cured, the composition has good strengths and ductility and does not have problems with plasticizer migration.
  • Another object of the invention is a method for reducing the content of monomeric diisocyanates of an isocyanate group-containing polyurethane polymer by this is reacted in a substoichiometric OH / NCO ratio with exclusion of moisture with at least one hydroxy aldimine of the formula (I), optionally in the presence of catalysts, plasticizers, fillers and / or solvents.
  • the OH / NCO ratio is preferably in the range from 0.05 / 1 to 0.5 / 1, in particular 0.1 / 1 to 0.5 / 1, preferably 0.2 / 1 to 0.5 / 1.
  • the isocyanate-group-containing polyurethane polymer is solid, especially at room temperature, and is suitable as a constituent of a reactive hotmelt adhesive.
  • the products of this process have odor-free curing, good storage stability, long open time with rapid curing and are not prone to problems with plasticizer migration such as bleeding, substrate discoloration or stress cracking in the substrate.
  • Aldehyde-1 is a mixture of aldehydes of the formula (IV). 2,2-Dimethyl-3-lauroyloxypropanal serves as a comparison.
  • the amine number (including aldimino groups) was determined by titration (with 0.1 N HCl in acetic acid against crystal violet).
  • the viscosity was measured using a thermostatically controlled Rheotec RC30 cone-plate viscometer (cone diameter 50 mm, cone angle 1 °, cone tip-to-plate distance 0.05 mm, shear rate 10 s -1 ).
  • the hydroxyaldimines A1 and A2 represent hydroxyaldimines of the formula (I) and are examples according to the invention.
  • the hydroxyaldimines R1 and R2 are comparative examples.
  • reaction product U8 60.00 g (about 1 15 mmoles NCO) polymer P3, 15.82 g (ca. 40.4 mmol) hydroxy aldimine A1 and 0.05g Coscat ® 83 were mixed in a honey jar under argon and then for 16 hours in a convection oven at 60 ° C react. There was obtained a clear, liquid at room temperature, aldimino and isocyanate groups containing reaction product.
  • reaction product Q1 60.00 g (about 1 15 mmoles NCO) polymer P3, 18:51 g (ca. 40.4 mmol) hydroxy aldimine A2 and 0.05g Coscat ® 83 were mixed in a honey jar under argon and then for 16 hours in a convection oven at 60 ° C react. There was obtained a clear, liquid at room temperature, aldimino and isocyanate groups containing reaction product.
  • reaction product Q3 227.30 g (ca. 100 mmol NCO) polymer P1, 10.84 g (ca. 24 mmol) imine Hydroxyald- R2 and 0.13g Coscat ® 83 were stirred in a planetary mixer under vacuum at 70 ° C for 90 minutes. There was obtained a clear, liquid at room temperature, aldimino and isocyanate groups containing reaction product.
  • Reaction product Q3 227.30 g (ca. 100 mmol NCO) polymer P1, 10.84 g (ca. 24 mmol) imine Hydroxyald- R2 and 0.13g Coscat ® 83 were stirred in a planetary mixer under vacuum at 70 ° C for 90 minutes. There was obtained a clear, liquid at room temperature, aldimino and isocyanate groups containing reaction product.
  • Reaction product Q3 227.30 g (ca. 100 mmol NCO) polymer P1, 10.84 g (ca. 24 mmol) imine Hydroxy
  • the reaction products U1 to U8 are reaction products with aldimino groups of the formula (V) and are examples according to the invention.
  • the reaction products Q1 to Q7 are comparative examples.
  • the viscosity (1d RT) on the following day of the preparation and the viscosity (7d 60 ° C) were determined after storage in a sealed container for 7 days in a 60 ° C convection oven. Viscosity was measured in each case at a temperature of 20 ° C. using a Rheostec RC30 thermostated cone-plate viscometer (cone diameter 50 mm, cone angle 1 °, cone tip-to-plate distance 0.05 mm, shear rate 10 s -1 ).
  • the skin formation time (tack-free time) was determined.
  • tack-free time a few grams of the composition in a layer thickness of about 2 mm were applied to cardboard and determined in the standard climate, the time until lightly tapping the surface of the assembly Setting by means of a pipette made of LDPE for the first time left no residues on the pipette more.
  • dumbbells with a length of 75 mm with a web length of 30 mm and a web width of 4 mm punched out of the film and these according to DIN EN 53504 at a tensile strength of 200 mm / min on tensile strength (breaking strength), elongation at break, modulus of elasticity 5% (at 0.5-5% elongation) and modulus of elasticity 50% (at 0.5 - 50% elongation) tested.
  • compositions Z1 to Z3 are examples according to the invention.
  • Compositions Ref1 to Ref3 are comparative examples.
  • Table 2 Composition (in parts by weight) and properties of Z1 to
  • compositions Z4 and Z5 and Ref4 Compositions Z4 and Z5 and Ref4
  • each composition was applied to a cardboard backing to have a circular base area of 12 mm diameter and a height of 20 mm and stored for 7 days in the NK. Around each composition there was a dark oval spot on the cardboard. Its dimensions (height and width) were measured and reported in Table 3 as a migration.
  • compositions Z4 and Z5 are examples according to the invention.
  • Composition Ref4 is a comparative example.
  • Salicylic acid 4 5.0 5.0 5.0 5.0
  • composition Z1 the two components of each composition were processed to a homogeneous liquid by centrifugal mixer and tested immediately as described for composition Z1.
  • compositions Z6 and Z7 are examples according to the invention.
  • Compositions Ref5 and Ref6 are comparative examples.
  • Adhesives H1 and HR1 and HR2 Adhesives H1 and HR1 and HR2:
  • the content of 4,4'-MDI was determined by means of HPLC (detection over photodiode array, 0.04 M sodium acetate / acetonitrile as mobile phase).
  • viscosity was measured on the following day of preparation with Brookfield Thermosel at 5 rpm with spindle 27 at the indicated temperature and referred to as "viscosity (fresh)".
  • the adhesive was allowed to rotate in a standard atmosphere on an open roll tempered at 140 ° C. At regular intervals, the viscosity (Brookfield Thermosel, 5 rpm, spindle 27) was measured. The results are shown in Table 5.
  • Adhesive H1 is an example according to the invention.
  • Adhesives HR1 and HR2 are comparative examples.
  • Adhesive H1 HR1 HR2 added hydroxyaldynin A1 R1 -
  • N.m stands for “immeasurable” (too viscous / gelled).
  • N.d stands for "not measured”.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

La présente invention concerne des hydroxyaldimines de formule (I), leur produits réactionnels, notamment avec des polyisocyanates, ainsi que des compositions présentant des groupes isocyanate contenant ces produits réactionnels. L'hydroxyaldimine permet l'obtention de compositions se caractérisant par une bonne stabilité au stockage, un temps ouvert supérieur, une faible odeur, un durcissement sans bulle et rapide et de bonnes propriétés mécaniques, ne posant pas de problème lié à la migration du plastifiant et présentant une teneur particulièrement faible en diisocyanates monomères. L'invention permet notamment d'obtenir des adhésifs thermofusibles réactifs ayant une particulièrement bonne ouvrabilité.
EP16820246.3A 2015-12-21 2016-12-20 Hydroxyaldimine et composition de polyuréthane durcissable ayant une teneur faible en isocyanates monomères Withdrawn EP3394134A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP23181909.5A EP4253499A3 (fr) 2015-12-21 2016-12-20 Hydroxyaldimine et composition de polyurethane durcissable a faible teneur en isocyanates monomeres

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP15201650 2015-12-21
PCT/EP2016/081983 WO2017108829A1 (fr) 2015-12-21 2016-12-20 Hydroxyaldimine et composition de polyuréthane durcissable ayant une teneur faible en isocyanates monomères

Related Child Applications (1)

Application Number Title Priority Date Filing Date
EP23181909.5A Division EP4253499A3 (fr) 2015-12-21 2016-12-20 Hydroxyaldimine et composition de polyurethane durcissable a faible teneur en isocyanates monomeres

Publications (1)

Publication Number Publication Date
EP3394134A1 true EP3394134A1 (fr) 2018-10-31

Family

ID=54850532

Family Applications (2)

Application Number Title Priority Date Filing Date
EP16820246.3A Withdrawn EP3394134A1 (fr) 2015-12-21 2016-12-20 Hydroxyaldimine et composition de polyuréthane durcissable ayant une teneur faible en isocyanates monomères
EP23181909.5A Pending EP4253499A3 (fr) 2015-12-21 2016-12-20 Hydroxyaldimine et composition de polyurethane durcissable a faible teneur en isocyanates monomeres

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP23181909.5A Pending EP4253499A3 (fr) 2015-12-21 2016-12-20 Hydroxyaldimine et composition de polyurethane durcissable a faible teneur en isocyanates monomeres

Country Status (4)

Country Link
US (1) US11242428B2 (fr)
EP (2) EP3394134A1 (fr)
CN (1) CN108431067B (fr)
WO (1) WO2017108829A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6880062B2 (ja) * 2015-12-21 2021-06-02 シーカ テクノロジー アクチェンゲゼルシャフト 二剤ポリウレタン組成物
PE20210643A1 (es) * 2018-08-08 2021-03-23 Sika Tech Ag Polimero que contiene grupos isocianato con un bajo contenido de diisocianatos monomericos
CA3055748C (fr) * 2018-09-20 2024-03-19 Seal Bond, Inc. Composition adhesive pour l'utilisation dans des materiaux de couverture
WO2020126841A1 (fr) * 2018-12-17 2020-06-25 Sika Technology Ag Composition de polyuréthane durcissant à l'humidité contenant de l'oxazolidine
EP4279521A1 (fr) * 2022-05-16 2023-11-22 Soprema Prépolymères de polyuréthane

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2546536A1 (de) * 1975-10-17 1977-04-28 Bayer Ag Hochmolekulare polyamine und verfahren zu ihrer herstellung
IL129583A (en) 1999-04-25 2005-05-17 Kenneth I Sawyer Diesters of oligobutyleneglycol and amidine benzoic acid and their use for preparation of moisture-curable, storage-stable, one-part polyurethane/urea compositions
DE10229519A1 (de) 2001-07-10 2003-01-30 Henkel Kgaa Reaktive Polyurethane mit einem geringen Gehalt an monomeren Diisocyanaten
EP1770107A1 (fr) 2005-09-30 2007-04-04 Sika Technology AG Composition de polyuréthanne durcissant par l'humidité
EP1975186A1 (fr) * 2007-03-27 2008-10-01 Sika Technology AG Composition munie de groupes d'isocyanat et d'aldimine contenant une teneur en isocyanat monomère moindre
EP1975187A1 (fr) * 2007-03-28 2008-10-01 Sika Technology AG Procédé de fabrication de composition de polyuréthane ayant une teneur en isocyanat monomère moindre
ES2613861T3 (es) * 2012-05-29 2017-05-26 Mitsubishi Gas Chemical Company, Inc. Aldehído aromático, agente de curado de resina epoxi que comprende aldehído aromático, y composición de resina epoxi que comprende el mismo

Also Published As

Publication number Publication date
WO2017108829A1 (fr) 2017-06-29
US20180327535A1 (en) 2018-11-15
CN108431067B (zh) 2021-11-23
US11242428B2 (en) 2022-02-08
EP4253499A2 (fr) 2023-10-04
EP4253499A3 (fr) 2023-12-13
CN108431067A (zh) 2018-08-21

Similar Documents

Publication Publication Date Title
EP3394136B1 (fr) Polyaldimine et composition de polyurethane durcissable
EP3394139B1 (fr) Composition de polyurethane a migration de plastifiant reduite
EP3642252B1 (fr) Durcisseur latent et composition de polyuréthane durcissable
EP3394134A1 (fr) Hydroxyaldimine et composition de polyuréthane durcissable ayant une teneur faible en isocyanates monomères
EP3830203B1 (fr) Composition de polyuréthane à temps de transformation élevé et à résistance élevée
EP3833702A1 (fr) Polymère contenant des groupes isocyanate ayant une faible teneur en diisocyanates monomères
WO2020030607A1 (fr) Composition de polyuréthane ayant une faible teneur en diisocyanates monomères
EP3833700A1 (fr) Composition de polyuréthane comprenant un plastifiant polymère et ayant une faible teneur en diisocyanates monomères
EP3947507A1 (fr) Polymère renfermant des groupes isocyanate, fondé sur un polyester diol à base d'acide dimère
EP3394132B1 (fr) Composition de polyurethane bi-composants
EP3642253B1 (fr) Moyen de blocage pour amine, durcisseur latent et compositions de polyuréthane
EP3642211B1 (fr) Aldiminosilanes
EP4100455B1 (fr) Polymère linéaire contenant des groupes isocyanate
EP3898619B1 (fr) Composition de polyuréthane durcissant à l'humidité contenant de l'oxazolidine
EP3947509A1 (fr) Composition durcissant à l'humidité présentant de bonnes propriétés adhésives
EP3880730B1 (fr) Solvant pour acides carboxyliques ou sulfoniques aromatiques
EP4100451B1 (fr) Composition de polyuréthane à bonne adhérence à des matières plastiques
WO2024012829A1 (fr) Composition polymère qui peut être durcie à température ambiante et qui est constituée de polyaldéhyde et de polymalonate

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20180723

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20200513

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

GRAJ Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

INTG Intention to grant announced

Effective date: 20221129

INTC Intention to grant announced (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20230714