EP4554994A1 - Composition polymère qui peut être durcie à température ambiante et qui est constituée de polyaldéhyde et de polycyanoacétate - Google Patents

Composition polymère qui peut être durcie à température ambiante et qui est constituée de polyaldéhyde et de polycyanoacétate

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Publication number
EP4554994A1
EP4554994A1 EP23734252.2A EP23734252A EP4554994A1 EP 4554994 A1 EP4554994 A1 EP 4554994A1 EP 23734252 A EP23734252 A EP 23734252A EP 4554994 A1 EP4554994 A1 EP 4554994A1
Authority
EP
European Patent Office
Prior art keywords
cyanoacetate
mol
groups
aldehyde
molecular weight
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.)
Pending
Application number
EP23734252.2A
Other languages
German (de)
English (en)
Inventor
Andreas Kramer
Hans HÄBERLE
Urs Burckhardt
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
Publication of EP4554994A1 publication Critical patent/EP4554994A1/fr
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G16/00—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00
    • C08G16/06—Block or graft polymers prepared by polycondensation of aldehydes or ketones on to macromolecular compounds
    • 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
    • C08G16/00—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00
    • C08G16/02—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes
    • C08G16/0212—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds
    • C08G16/0218—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds containing atoms other than carbon and hydrogen
    • C08G16/0231—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds containing atoms other than carbon and hydrogen containing nitrogen
    • 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
    • C08G18/28—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
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three 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
    • C08G18/4825—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
    • C08G18/4841—Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end 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
    • C08G18/75—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
    • C08G18/83—Chemically modified polymers
    • C08G18/84—Chemically modified polymers by aldehydes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2150/00—Compositions for coatings
    • 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
    • C08G2170/00—Compositions for adhesives
    • 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
    • C08G2190/00—Compositions for sealing or packing joints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0642—Copolymers containing at least three different monomers

Definitions

  • the invention relates to two-component compositions and their use as room temperature curable adhesives, sealants or coatings.
  • Reactive polymer compositions that are curable at room temperature and can be used as adhesives, sealants or coatings with elastic properties are known.
  • Polyurethane systems that harden through the reaction of isocyanate groups with polyols and/or moisture and form particularly highly elastic polymers are widely used.
  • the formulation, production and use of polyurethane systems presents a number of challenges in practice. They usually contain significant amounts of monomeric diisocyanates, which can irritate the eyes, skin and mucous membranes.
  • the moisture sensitivity of the isocyanate groups can lead to premature crosslinking reactions combined with an increase in viscosity and even gelling and thus impair the shelf life and storage stability.
  • the water required for curing must penetrate from the outside in the form of atmospheric moisture, which makes application in thick layers or between moisture-tight substrates difficult.
  • the problem with two-component systems with a polyol and an isocyanate component is that the isocyanate groups can react not only with the hydroxyl groups of the polyols, but also with any water that may be present. Especially at high ambient humidity, this can trigger the formation of bubbles and cause incomplete polymerization with chain terminations due to only partially reacted polyols, which leads to a more or less severe loss of strength and elasticity.
  • mercury catalysts have not been used for a long time usable.
  • two-component polyurethanes are often catalyzed with tin compounds and/or tertiary amines, but these are significantly less selective, which can cause bubbles to form, especially in high ambient humidity.
  • Bismuth or zirconium catalysts have higher selectivity;
  • these and other alternative metal catalysts are sensitive to hydrolysis, whereby the catalytic activity is largely lost, which in turn can lead to curing problems.
  • Reactive polymer compositions based on silane-functional polymers (SMP/STP) and silicones are also widely used. These polymer systems cure by hydrolysis and condensation of silane groups, releasing alcohols, especially methanol or ethanol, or oximes, which are toxic and cause VOC emissions; In addition, as crosslinkers or drying agents, they usually contain high amounts of low molecular weight silanes, which are also harmful to health. Due to the moisture sensitivity of the silane groups, these polymer systems are also challenging to produce and use and do not always produce the desired results. Also known are water-based polymer systems, which are mostly based on acrylate or polyurethane dispersions. These harden through water evaporation and coalescence and are largely free of chemical reactive groups.
  • the object of the present invention is therefore to provide a new, room temperature-curable polymer composition which is suitable as an elastic adhesive, sealant or coating and overcomes the disadvantages of the known polymer systems.
  • the composition comprises a first component containing aldehyde group-containing compounds and a second component containing cyanoacetate group-containing compounds, the average molecular weight Mn of the first and second components with respect to the aldehyde and cyanoacetate group-containing compounds, respectively, being in the range from 400 to 20 '000 g / mol, and the average functionality of at least one of the two components in relation to the aldehyde or cyanoacetate group-containing compounds is greater than 2.0.
  • This composition has several advantageous and surprising properties over prior art room temperature curable polymer systems.
  • Both the compounds containing aldehyde groups and the compounds containing cyanoacetate groups are substances of little toxicological concern, which do not require any hazard labeling and can be handled without special precautions.
  • the composition according to the invention is not sensitive to moisture and bubbling and allows a high degree of freedom in formulation, since additives commonly used in curable compositions can be used in both components without causing problems with the storage stability of the respective component. This means that the mixing ratio of the two components can be adjusted almost arbitrarily, which allows a great deal of freedom in the processing method.
  • the composition is readily processable under ambient conditions without the need for organic solvents to dissolve or dilute or water to emulsify or disperse components. The composition cures surprisingly quickly and smoothly under ambient conditions, regardless of humidity, without causing emissions.
  • the curing rate can be controlled very well with conventional catalysts, in particular non-metallic bases such as tertiary amines, amidines or guanidines.
  • the hardening process creates is a non-sticky, elastic polymer of high strength and surprisingly high extensibility with good resistance to heat and water.
  • the very high tear resistance of the cured polymer which makes it particularly resistant to strong mechanical stress. Due to the combination of these advantageous properties, the composition according to the invention is particularly easy to handle without special protective measures as well as high robustness and longevity, both in the production and storage of the components, in their use in a wide range of environmental and application conditions, and after Hardening under mechanical, thermal or chemical stress.
  • composition according to the invention is therefore very suitable for use as a high-quality elastic adhesive, sealant or coating. Further aspects of the invention are the subject of further independent claims. Particularly preferred embodiments of the invention are the subject of the dependent claims.
  • the subject matter of the invention is a curable composition
  • a curable composition comprising
  • a second component containing cyanoacetate group-containing compounds comprising at least one compound with two or more cyanoacetate groups, the average molecular weight M n of the first and second components in relation to the aldehyde or cyanoacetate group-containing compounds being in the range from 400 to 20' 000 g/mol, and the average functionality of at least one of the two components in relation to the aldehyde or the cyanoacetate group-containing compounds is greater than 2.0.
  • Aldehyde groups are functional groups of the formula referred to, which are bound via the dashed line.
  • ⁇ O denotes which are bound via the dashed line.
  • Molecular weight is the molar mass (in grams per mole) of a molecule.
  • the “average molecular weight” is the number-average molecular weight (M n ) of a polydisperse mixture of oligomeric or polymeric molecules. It is determined using gel permeation chromatography (GPC) against polystyrene as a standard.
  • composition is described as “storage stable” if it can be stored at room temperature in a suitable container for a long period of time, typically for at least 3 months up to 6 months or more, without its application or usage properties being affected by storage changed to an extent relevant to their use.
  • Substance names beginning with “Poly” such as polycyanoacetate, polyaldehyde or polyol refer to substances that formally contain two or more of the functional groups appearing in their name per molecule.
  • room temperature A temperature of 23 °C is referred to as “room temperature”.
  • Weight percent refers to mass proportions of a component of a composition or a molecule based on the entire composition or the entire molecule, unless otherwise stated.
  • mass percent refers to mass proportions of a component of a composition or a molecule based on the entire composition or the entire molecule, unless otherwise stated.
  • mass refers to mass proportions of a component of a composition or a molecule based on the entire composition or the entire molecule, unless otherwise stated.
  • mass and weight
  • the first and second components of the curable composition are storage stable on their own and are stored in separate containers until they are mixed together shortly before or during application.
  • the curable composition is preferably not water-based. It is preferably largely free of water or contains only a small water content. Such a composition cures quickly regardless of ambient humidity, can be used in thick layers and/or between waterproof substrates, and shows little shrinkage upon curing.
  • the curable composition preferably contains less than 10% by weight, preferably less than 5% by weight, in particular less than 2% by weight, of water based on the total composition.
  • the composition contains a small amount of water.
  • the water acts as an accelerator for hardening.
  • water is preferred in an amount of 0.05 to 5% by weight, in particular 0.1 to 2% by weight, based on the entire composition.
  • the curable composition is preferably free of compounds with aldehyde or cyanoacetate groups, which are present as an emulsion or dispersion.
  • the compounds contained with aldehyde or cyanoacetate groups are preferably largely free of ionic groups or precursors thereof, and largely free of longer poly(oxyethylene) chains, as are common in surfactants.
  • Such a composition has high water resistance.
  • the aldehyde group-containing compounds of the first component and the cyanoacetate group-containing compounds of the second component each have an acid group or ionic group content of less than 0.1% by weight, preferably less than 0.05% by weight, based on the aldehyde group-containing or .
  • the ionic groups are in particular carboxylate groups, ammonium groups or sulfonate groups.
  • the average molecular weight M n of the first and second components is relative to the aldehyde, respectively the compounds containing cyanoacetate groups in the range from 400 to 20,000 g/mol. This enables polymers with high stretchability.
  • At least one of the two components preferably has an average molecular weight M n in relation to the compounds with aldehyde or cyanoacetate groups in the range from 1,000 to 20,000 g/mol, preferably 1,500 to 15,000 g/mol, in particular 2,000 to 10,000 g/mol. This enables a particularly high level of stretch.
  • the average functionality of at least one of the two components with respect to the aldehyde or cyanoacetate groups is greater than 2.0. If the average aldehyde functionality of the first component is 2.0 or less, the average cyanoacetate functionality of the second component must therefore be more than 2.0. And if the average cyanoacetate functionality of the second component is 2.0 or less, then the average aldehyde functionality of the first component must be more than 2.0.
  • Such a composition cures to form an elastic polymer of high strength and durability.
  • the average aldehyde functionality of the first component and the average cyanoacetate functionality of the second component are each greater than 2.0, in particular 2.2 to 3.0. This enables polymers with high strength and durability, which still have good stretchability.
  • the average molecular weight M n of the first component in relation to the aldehyde group-containing compounds is preferably in the range from 1,000 to 20,000 g/mol, preferably 1,500 to 15,000 g/mol, in particular 2,000 to 10 '000 g/mol, measured using gel permeation chromatography (GPC) against polystyrene as a standard.
  • GPC gel permeation chromatography
  • the average aldehyde functionality of the aldehyde group-containing compounds in the first component is preferably in the range from 1.6 to 4, preferably 1.8 to 3.5, particularly preferably 2.0 to 3.0, in particular 2.2 to 3.0. This enables cured compositions with high extensibility, strength and durability.
  • the aldehyde group-containing compounds preferably comprise a polymer with a polymer backbone containing poly(oxyalkylene) units and/or polyester units.
  • Preferred poly(oxyalkylene) is poly(oxyethylene), poly(oxy-1,2-propylene), poly(oxy-1,3-propylene), poly(oxy-1,4-butylene), poly(oxy-1 ,2-butylene) or a mixed form of these poly(oxyalkylenes).
  • poly(oxy-1,2-propylene), poly(oxy-1,3-propylene) or poly(oxy-1,4-butylene), in particular poly(oxy-1,2-propylene) are preferred may contain a content of 0 to 25% by weight of poly(oxyethylene) units based on the poly(oxyalkylene) backbone, particularly at the chain ends.
  • Aldehyde-functional polymers with such a backbone are low-viscosity and therefore particularly easy to handle and particularly hydrophobic. They enable compositions with particularly good processability, high elasticity and good water resistance.
  • polyesters are esters of dicarboxylic acids and di- or trioien, triglycerides or polyesters based on dimer or trimer fatty acids. Particularly Preferred are polyesters of dimer fatty acids or derived from castor oil, derivatives of castor oil or vegetable oils. Aldehyde-functional polymers with such a backbone are particularly hydrophobic and enable compositions with particularly good resistance to heat and water. They are also based on renewable raw materials and are therefore particularly sustainable.
  • the compound with two or more aldehyde groups preferably additionally contains urethane groups. This results in compositions with particularly high extensibility and particularly high tear resistance.
  • the compounds containing aldehyde groups preferably comprise a polymer containing urethane groups which is liquid at room temperature and has an average molecular weight M n of 1,000 to 20,000 g/mol, preferably 1,500 to 15,000 g/mol, in particular 2,000 to 10,000 g/mol, and an average aldehyde functionality of 1.8 to 3.5, particularly preferably 2.0 to 3.0, in particular 2.2 to 3.0.
  • the compound with two or more aldehyde groups is preferably obtained from the reaction of at least one hydroxyaldehyde with at least one polymer containing isocyanate groups or at least one polyisocyanate.
  • alkoxylated preferably stands for (single or multiple) "ethoxylated” or "propoxylated”, as well as 4,4'-(2-hydroxypropane-1,3-diyl) -bis(oxy)-bis(benzaldehyde) or 4,4'-(2-hydroxypropane-1,3-diyl)-bis(oxy)-bis(3-methoxybenzaldehyde).
  • ethoxylated salicylaldehyde in particular 2-(2-hydroxyethoxy)-benzaldehyde, ethoxylated vanillin, in particular 4-(2-hydroxyethoxy)-3-methoxy- benzaldehyde, or 5-hydroxymethylfurfural.
  • hydroxyaldehydes are accessible in simple processes and enable aldehyde group-containing compounds with low viscosity and thus good handling and compositions with good processability and high strength with very high extensibility.
  • Particularly preferred hydroxyaldehyde is 5-hydroxymethylfurfural.
  • This hydroxyaldehyde is available from renewable starting materials and surprisingly enables particularly low-viscosity compounds with aldehyde groups and curable compositions with particularly good processability and high strength, extensibility, tear resistance and resistance to heat and water.
  • Suitable polymers containing isocyanate groups for the production of compounds with two or more aldehyde groups are, in particular, reaction products of polyols with diisocyanates, in particular in a molar NCO / OH ratio of 1.5/1 to 10/1, with unreacted monomeric diisocyanates optionally from the polymer were removed.
  • the polymer containing isocyanate groups preferably has a content of free isocyanate groups in the range from 0.5 to 15% by weight, particularly preferably 1 to 10% by weight, in particular 1.5 to 6% by weight, based on the polymer.
  • Very particularly preferred polymer containing isocyanate groups is a reaction product from the reaction of at least one diisocyanate and at least one polyol in an NCO/OH ratio of at least 3/1, preferably 3/1 to 10/1, in particular 4/1 to 8 /1, and subsequent removal of a large part of the monomeric diisocyanate by means of a suitable separation process, so that the polymer containing isocyanate groups ultimately has a monomeric diisocyanate content of at most 0.2% by weight based on the polymer.
  • Such a polymer containing isocyanate groups enables aldehyde-functional polymers with a particularly low content of reaction products from monomeric diisocyanate and hydroxyaldehyde, in particular less than 0.5% by weight. % of these reaction products based on the aldehyde-functional polymer. This enables curable compositions with particularly easy processing with a long open time and quick curing and particularly good flexibility.
  • diisocyanates are 1,6-hexane diisocyanate (HDI), 2, 2(4), 4-trimethyl-1,6-hexane diisocyanate (TMDI), 1-methyl-2,4(6)-diisocyanatocyclohexane (HeTDI) , isophorone diisocyanate (IPDI), 4,4'-diisocyanatodicyclohexylmethane (H12MDI), 4(2),4'-diphenylmethane diisocyanate (MDI) or 2,4(6)-toluene diisocyanate.
  • HDI, IPDI, TDI or MDI are preferred.
  • IPDI is particularly preferred. This results in compositions that are particularly easy to process and which harden to form polymers with high strength and extensibility.
  • Particularly suitable polyols are:
  • Polyether polyols in particular polyoxyalkylene diols or polyoxyalkylene triols, 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, with the aid of a starter molecule with two or more active hydrogen atoms can be polymerized, in particular a starter molecule such as water, ammonia or a compound with several OH or NH groups such as 1,2-ethanediol, 1,2- or 1,3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols or tripropylene glycols, the isomeric butanediols, pentanediols, hexanediols, heptanediols, octanediols, non
  • Preferred polyether polyols are polyoxypropylene diols or polyoxypropylene triols, or so-called ethylene oxide-terminated (EO-endcapped or EO-tipped) polyoxypropylene diols or triols.
  • the latter are polyoxyethylene-polyoxypropylene mixed polyols, which are obtained in particular by adding polyoxypropylene diols or triols after completion of the polypropoxylation reaction are further alkoxylated with ethylene oxide and thus ultimately have primary hydroxyl groups.
  • Preferred polyether polyols have a degree of unsaturation of less than 0.02 mEq/g, in particular less than 0.01 mEq/g.
  • Polyester polyols in particular those from the polycondensation of hydroxycarboxylic acids or lactones or the polycondensation of aliphatic and/or aromatic polycarboxylic acids with di- or polyhydric alcohols.
  • Amorphous, di- or trimer fatty acid-based polyester polyols such as those commercially available, for example from Croda, are preferred.
  • Polycarbonate polyols obtainable for example by reacting diols with dialkyl carbonates, diaryl carbonates or phosgene.
  • Block copolymers containing at least two hydroxyl groups in particular polyetherpolyester polyols.
  • Polyhydrocarbon polyols such as in particular polyhydroxy-functional polyolefins, polyisobutylenes, polyisoprenes; polyhydroxy-functional ethylene-propylene, ethylene-butylene or ethylene-propylene-diene copolymers, such as those produced, for example, by Kraton Polymers; polyhydroxy-functional polymers of dienes, in particular of 1,3-butadiene, which can in particular also be produced from anionic polymerization; polyhydroxy-functional copolymers made from 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 those made from epoxides or amino alcohols and carboxyl-terminated acrylonitrile/butadiene.
  • Copolymers for example commercially
  • Polyols that are liquid at room temperature are preferred.
  • Polyols with an OH number in the range from 9 to 115 mg KOH/g, preferably 14 to 60 mg KOH/g, in particular 18 to 40 mg KOH/g are preferred.
  • Polyether polyols di- or trimer fatty acid-based polyester polyols, castor oil, derivatives of castor oil or hydroxylated vegetable oils are particularly preferred. Polyether polyols are most preferred.
  • reaction products of at least one polyisocyanate with at least one hydroxyaldehyde in particular the aforementioned hydroxyaldehydes.
  • Suitable polyisocyanates are in particular oligomeric diisocyanates, in particular HDI biurets such as Desmodur® N 100 or N 3200 (from Covestro), Tolonate® HDB or HDB-LV (from Vencorex) or Duranate® 24A-100 (from Asahi Kasei); HDI isocyanurates such as Desmodur® N 3300, N 3600 or N 3790 BA (all from Covestro), Tolonate® HDT, HDT-LV or HDT-LV2 (from Vencorex), Duranate® TPA-100 or THA-100 (from Asahi Kasei ) or Coronate® HX (from Nippon Polyurethane); HDI uretdione such as Desmodur® N 3400 (from Covestro); HDI-iminooxadiazinediones such as Desmodur® XP 2410 (from Covestro); HDI allophanates such as Desmodur® VP LS 2102 (
  • Oligomers derived from HDI are preferred.
  • the polymer containing isocyanate groups or the polyisocyanate and the hydroxyaldehyde are preferably reacted in an OH/NCO ratio of 1/1 to 1.2/1 at a temperature of 40 to 140 ° C, preferably 60 to 120 ° C, if necessary in the presence a suitable catalyst.
  • the curable composition comprises, as part of the second component, at least one compound with two or more cyanoacetate groups.
  • the compound with two or more cyanoacetate groups is liquid at room temperature.
  • it has a viscosity at 20 ° C of 0.1 to 100 Pa s, preferably 0.2 to 50 Pa s, in particular 0.5 to 20 Pa s, measured using cone-plate viscometers with cone diameter 10 mm, cone angle 1 °, cone tip plates -Distance 0.05 mm, shear rate 10 s -1 , for viscosities of less than 1 Pa s with cone diameter 50 mm.
  • Such a compound can be easily handled at ambient temperatures even without the addition of solvents or thinners and enables easy-to-process compositions.
  • the average functionality of the second component in relation to the compounds containing cyanoacetate groups is preferably in the range from 1.6 to 4, preferably 1.8 to 3.5, particularly preferably 2.0 to 3.0, in particular 2.3 to 3.0. This enables cured compositions with high extensibility, strength and durability.
  • the average molecular weight M n of the second component in relation to the compounds containing cyanoacetate groups is preferably in the range from 400 to 10,000 g/mol, preferably 500 to 2,000 g/mol.
  • the average molecular weight M n of the second component is in the range from 500 to 2,000 g/mol.
  • Such a second component enables compositions that are particularly easy to process and have high strength.
  • the average molecular weight M n of the second component is in the range from 2,000 to 10,000 g/mol in relation to the cyanoacetate group-containing compounds.
  • such a second component In combination with a first component with a similarly high average molecular weight M n in relation to the aldehyde group-containing compounds, such a second component enables compositions with a mixing ratio of the two components in the range of 1:1 in a particularly simple manner, which is particularly important in certain applications is particularly advantageous when processing using static mixers.
  • the second component particularly preferably contains at least one cyanoacetate-functional polymer with an average molecular weight M n of 400 to 10,000 g/mol, preferably 500 to 2,000 g/mol, and an average cyanoacetate functionality of 1.8 to 3.5, particularly preferably 2.0 to 3.0, in particular 2.5 to 3.0.
  • the compound with at least two cyanoacetate groups is preferably obtained from the transesterification of at least one cyanoacetate of the formula (I)
  • R preferably represents methyl, ethyl or tert. Butyl, especially for ethyl.
  • the reaction preferably takes place at a temperature in the range from 50 to 150 ° C with the released alcohol R—OH being removed by distillation, if necessary under vacuum and if necessary in the presence of catalysts.
  • Suitable polyfunctional alcohols are commercially available compounds or polymers with two or more OH groups, such as in particular 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1 ,6-Hexanediol, 1,3- Cyclohexanedimethanol, 1,4-cyclohexanedimethanol, diethylene glycol, dipropylene glycol, 1,1,1-trimethylolpropane, glycerin, ethoxylated or in particular propoxylated glycerin, ethoxylated or in particular propoxylated 1,1,1-trimethylolpropane, castor oil, ethoxylated or in particular propoxylated castor oil, Ketone resin-modified castor oil, hydroxylated vegetable oils, dimer fatty acid trio or trimer fatty acid trio, dimer or trimer fatty acid-
  • Propoxylated 1,1,1-trimethylolpropane with an average molecular weight M n of 300 to 1,700 g/mol is particularly preferred as a polyfunctional alcohol.
  • particularly preferred polyfunctional alcohols are poly(oxy-1,2-propylene) di- or triols with an average molecular weight M n of 2,000 to 10,000 g/mol, whereby these are optionally endcapped with ethylene oxide.
  • particularly preferred polyfunctional alcohols are dimer fatty acid-based amorphous polyester triols or trimer fatty acid-based amorphous polyester triols with an average molecular weight M n of 800 to 4,000 g/mol.
  • the compounds containing cyanoacetate groups particularly preferably comprise at least one cyanoacetate-functional polymer selected from propoxylated 1,1,1-trimethylolpropane-tris(cyanoacetate) with an average molecular weight M n of 500 to 2,000 g/mol, poly(oxy-1, 2-propylene)diol-bis(cyanoacetate) with an average molecular weight M n of 2,000 to 10,000 g/mol, poly(oxy-1,2-propylene)triol-tris(cyanoacetate) with an average molecular weight M n of 2 '000 to 10,000 g/mol, poly(oxy-1,2-propylene)diol-bis(cyanoacetate) containing ethylene oxide units with an average molecular weight Mn of 2,000 to 10,000 g/mol, containing ethylene oxide units Poly(oxy-1,2-propylene)triol-tris(cyanoacetate) with an average molecular weight M n of 2,000 to 10,000 g/mol, dimer
  • the average functionality of the entire composition in relation to the aldehyde and cyanoacetate group-containing compounds is preferably at least 2.2.
  • a composition with an average aldehyde functionality in the first component of, for example, 1.8 is preferably combined with a second component with an average cyanoacetate functionality of at least 2.4 in order to achieve an overall average reactive group functionality of 2.2.
  • the curable composition contains, as part of the first component, at least one polymer containing urethane groups that is liquid at room temperature and has an average molecular weight M n of 1,000 to 20,000 g/mol, preferably 1,500 to 15,000 g/mol.
  • the second component at least one polymer containing cyanoacetate groups with a average molecular weight M n of 400 to 10,000 g/mol, preferably 500 to 2,000 g/mol, and an average cyanoacetate functionality of 1.8 to 3.5, preferably 2.0 to 3.0, in particular 2.5 to 3.0, the average reactive group being Functionality is preferably at least 2.2 overall.
  • the first component of the curable composition can contain proportions of low molecular weight polyaldehydes, such as in particular 1,6-hexanedialdehyde, 1,7-heptanedialdehyde, 1,8-octanedialdehyde, 1,9-nonanedialdehyde, 2-methyl-1,8- octanedialdehyde, 1,10-decanedialdehyde, 1,11-undecanedialdehyde, 1,12-dodecanedialdehyde, hexahydrophthalaldehyde, hexahydroisophthalaldehyde, hexahydroterephthalaldehyde, octahydro-4,7-methano-1 H-indenedicarbaldehyde, 3,6,9-trioxaundecane-1,11 -dial, 1,3-bis-(2,2-dimethyl-3-oxopropyl)imidazo
  • the second component of the curable composition can contain proportions of low molecular weight polycyanoacetates, such as in particular 1,2-ethanediol-bis(cyanoacetate), 1,2-propanediol-bis(cyanoacetate), 1,3-propanediol-bis(cyanoacetate), 1 ,4-butanediol-bis(cyanoacetate), 1,6-hexanediol-bis(cyanoacetate), 1,4-cyclohexanedimethanol-bis(cyanoacetate), dipropylene glycol-bis(cyanoacetate), 1, 1, 1-trimethylolpropane-tris(cyanoacetate) or glycerin tris(cyanoacetate).
  • polycyanoacetates such as in particular 1,2-ethanediol-bis(cyanoacetate), 1,2-propanediol-bis(cyanoacetate), 1,3-propanediol-bis(cyanoacetate), 1 ,
  • the curable composition may additionally contain further components, in particular the following:
  • - Fillers in particular ground or precipitated calcium carbonates, which are optionally coated with fatty acids, in particular stearates, barite (barite), quartz powder, quartz sand, dolomite, wollastonite, kaolin, calcined kaolin, layered silicates such as mica or talc, zeolites, aluminum hydroxides, magnesium hydroxides, Silicas including highly disperse silicas from pyrolysis processes, industrially produced carbon black, graphite, metal powder, for example aluminum, copper, iron, silver or steel, PVC powder or hollow spheres;
  • fatty acids in particular stearates, barite (barite), quartz powder, quartz sand, dolomite, wollastonite, kaolin, calcined kaolin, layered silicates such as mica or talc, zeolites, aluminum hydroxides, magnesium hydroxides, Silicas including highly disperse silicas from pyrolysis processes, industrially produced carbon black
  • Fibers in particular glass fibers, carbon fibers, metal fibers, ceramic fibers, hemp fibers, cellulose fibers or plastic fibers such as polyamide fibers or polyethylene fibers;
  • Nanofillers such as graphene or carbon nanotubes
  • Pigments in particular titanium dioxide, chromium oxide, iron oxides or organic pigments;
  • Plasticizers in particular phthalates, in particular diisononyl phthalate (DINP), diisodecyl phthalate (DIDP) or di(2-propylheptyl) phthalate (DPHP), hydrogenated phthalates, in particular diisononyl-1,2-cyclohexanedicarboxylate (DINCH), terephthalates, in particular bis(2- ethylhexyl) terephthalate or diisononyl terephthalate (DINT), hydrogenated terephthalates, in particular bis(2-ethylhexyl)-1,4-cyclohexanedicarboxylate or diisononyl-1,4-cyclohexanedicarboxylate, isophthalates, trimellitates, adipates, in particular dioctyl adipate (DOA), azelates, Sebacates, benzoates, glycol ethers, glycol esters, plasticizers,
  • - Rheology modifiers in particular urea compounds, layered silicates such as bentonites, derivatives of castor oil, hydrogenated castor oil, polyamides, polyurethanes, fumed silicas or hydrophobically modified polyoxyethylenes;
  • - Drying agents in particular molecular sieves, calcium oxide, mono-oxazolidines such as Incozol® 2 (from Incorez) or orthoformate;
  • Adhesion promoters in particular titanates or organoalkoxysilanes such as aminosilanes, mercaptosilanes, epoxysilanes, vinylsilanes, (meth)acrylsilanes, carbamatosilanes, alkylsilanes, S-(alkylcarbonyl)mercaptosilanes or oligomeric forms of these silanes;
  • - Catalysts in particular non-metallic bases such as tertiary amines, in particular 2-dimethylaminoethyl ether, 2,2'-dimorpholinodiethyl ether (DMDEE) or 1,4-diazabicyclo[2.2.2]octane (DABCO), amidines, in particular 1,8-diaza - bicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) or 1-(2-hydroxy-3-(3-trimethoxysilylpropoxy)prop -1-yl)-2-methyl-1,4,5,6-tetrahydropyrimidine, or guanidines, in particular 1,1,3,3-tetramethylguanidine, 1-hexyl-2,3-diisopropylguanidine or 1,1 ' -(a,®-polyoxypropylene)bis(2,3-diiso
  • - flame-retardant substances in particular the fillers already mentioned, aluminum hydroxide or magnesium hydroxide, organic phosphoric acid esters, ammonium polyphosphates, melamine or derivatives thereof, boron compounds or antimony compounds;
  • Additives in particular wetting agents, leveling agents, defoamers, deaerators, stabilizers against oxidation, heat, light or UV radiation or biocides; and other substances commonly used in curable compositions.
  • Such additives may be present as part of the first or second component.
  • Substances reactive with cyanoacetate groups are preferably a component of the first component.
  • Substances reactive with aldehyde groups are preferably a component of the second component.
  • the curable composition preferably additionally contains at least one further component selected from plasticizers, fillers and catalysts.
  • the curable composition preferably contains several such additional components.
  • the curable composition preferably contains at least one basic catalyst with a pKa of at least 8, preferably at least 8.5, in particular a nitrogen-containing compound or an aqueous solution of a basic salt. Such a composition shows particularly rapid curing.
  • the curable composition contains 10 to 95% by weight, preferably 20 to 90% by weight, in particular 30 to 80% by weight, of fillers, based on the entire composition.
  • Fillers are preferably selected from calcium carbonates, barite, quartz powder, Quartz sand, kaolin, aluminum hydroxide, titanium dioxide and soot.
  • Such a composition is particularly suitable for applications in layer thicknesses of at least 1 mm, preferably 1 to 50 mm. in particular 1.5 to 25 mm.
  • the cured composition shows pronounced elastic properties.
  • the curable composition contains 5 to 80% by weight, in particular 10 to 60% by weight, of plasticizers, based on the entire composition.
  • Plasticizers are preferably selected from DINP, DIDP, DPHP, DINCH, bis(2-ethylhexyl) terephthalate, DINT, bis(2-ethylhexyl)-1,4-cyclohexanedicarboxylate, diisononyl-1,4-cyclohexanedicarboxylate, DOA, polypropylene oxide monols, polypropylene oxide diols , polypropylene oxide triols, polypropylene oxide monolacetates, polypropylene oxide diol diacetates, polypropylene oxide triol triacetates and DPK.
  • the curable composition contains fillers and plasticizers, in particular 20 to 90% by weight, in particular 30 to 80% by weight, of fillers and 5 to 60% by weight of plasticizers, based on the entire composition.
  • the curable composition preferably contains less than 10% by weight, particularly preferably less than 5% by weight, in particular less than 1% by weight, of volatile organic solvents with a boiling point at normal pressure of less than 250 ° C, based on the entire composition. Such a composition causes particularly few emissions.
  • the first component of the curable composition is preferably free of aldimine groups or contains only a low content of aldimine groups of less than 0.2 mol, in particular less than 0.1 mol, of aldimine groups per mol of cyanoacetate groups in the second component.
  • This means that the first component is largely free of primary amines.
  • Primary amino groups react with aldehydes to form aldimines. It is not within the scope of the present invention to convert the aldehyde groups in the first component to aldimine groups.
  • the composition according to the invention is cured mainly by reaction of cyanoacetate groups with free aldehyde groups.
  • the curable composition comprises the whole
  • the ratio of the number of cyanoacetate groups to the number of aldehyde groups is preferably in the range from 0.7 to 1.5, particularly preferably 0.8 to 1.2, in particular 0.9 to 1.1. Such a ratio enables rapid, trouble-free curing.
  • the ratio of the number of cyanoacetate groups to the number of aldehyde groups is particularly preferably in the range from 0.9 to 1.5. Such a ratio enables compositions with particularly high strength.
  • the consistency of the first and second components of the curable composition is suitably such that the components can be well mixed together under ambient conditions using simple methods. Liquid or pasty components are particularly suitable for this.
  • the first and second components of the curable composition are prepared separately.
  • the components of the respective component are mixed together so that a macroscopically homogeneous mass is created.
  • Each component is stored in a separate container. Suitable containers are in particular a barrel, a container, a hobbock, a bucket, a canister, a can, a bag, a tubular bag, a cartridge or a tube.
  • the components are storage stable.
  • the mixing ratio is chosen so that the ratio of the number of cyanoacetate groups to the number of aldehyde groups is in a suitable range, in particular around 0.9 to 1.1. In parts by weight, the mixing ratio between the first and second components is typically in the range of approximately 100:1 to 1:10, preferably 50:1 to 1:5.
  • the “open time” is the period of time between the mixing of the components and the end of the composition being in a suitable state for processing.
  • the mixing is preferably carried out at ambient temperature, in particular at a temperature in the range from -5 to 50°C, in particular 0 to 40°C.
  • the composition begins to harden as a result of the chemical reaction that occurs.
  • the cyanoacetate groups react with the aldehyde groups, causing the composition to gradually harden into a solid, polymeric material. It can be assumed that the curing reaction causes structural units of the
  • Curing preferably takes place at ambient temperature, in particular at a temperature in the range from -5 to 50 ° C, in particular 0 to 40 ° C.
  • Another subject of the invention is the cured composition obtained from the curable composition after mixing the two components.
  • the cured composition is preferably elastic and has high strength with high extensibility and tear resistance.
  • the cured composition preferably has a tensile strength, determined according to DIN EN 53504 as described in the examples, of at least 1 MPa, preferably at least 1.5 MPa, more preferably at least 2 MPa, more preferably at least 2.5 MPa, in particular at least 3 MPa.
  • the cured composition preferably has an elongation at break, determined according to DIN EN 53504 as described in the examples, of at least 100%, preferably at least 150%, more preferably at least 200%, more preferably at least 250%, in particular at least 300%.
  • the cured composition preferably has a tear strength, determined according to DIN ISO 34-1, method B as described in the examples, of at least 3 N/mm, preferably at least 5 N/mm, more preferably at least 7 N/mm, in particular at least 10 N /mm, on.
  • the cured composition preferably has a Shore A hardness, determined according to DIN 53505 as described in the examples, in the range from 10 to 90, in particular 20 to 80.
  • the cured composition has good resistance to heat and water.
  • the cured composition preferably shows high strength, extensibility and hardness even after storage for 7 days at 100 ° C or at 70 ° C and 100% relative humidity.
  • the curable composition is suitable for a variety of uses. It can be used in particular as an adhesive, sealant, coating, casting resin or filler.
  • a further subject of the invention is the use of the curable composition as an elastic adhesive, elastic sealant or elastic coating, whereby the first and second and any further components present are mixed with one another and the mixed composition is applied in the liquid state to at least one substrate.
  • the layer thickness of the cured composition is preferably at least 1 mm, preferably 1 to 50 mm, in particular 1.5 to 25 mm.
  • Suitable substrates are in particular:
  • PCC polymer-modified cement mortar
  • ECO epoxy resin-modified cement mortar
  • Metals or alloys such as aluminum, iron, steel, copper, other non-ferrous metals, including surface-refined metals or alloys such as galvanized or chrome-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 using plasma , corona or flames;
  • Fiber-reinforced plastics such as carbon fiber-reinforced plastics (CFRP), glass fiber-reinforced plastics (GRP), natural fiber-reinforced plastics (NFK) and sheet molding compounds (SMC);
  • CFRP carbon fiber-reinforced plastics
  • GRP glass fiber-reinforced plastics
  • NFK natural fiber-reinforced plastics
  • SMC sheet molding compounds
  • - Insulating foams in particular made of EPS, XPS, PUR, PIR, rock wool, glass wool, airgel 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 before application, in particular by physical and/or chemical cleaning processes or the application of an activator or a primer.
  • Two similar or two different substrates can be glued and/or sealed.
  • An article is obtained from the use of the curable composition.
  • the article is in particular glued, sealed or coated with the composition.
  • This article may be a structure or part thereof, in particular a civil engineering structure, a bridge, a roof, a stairwell or a facade, or it may be an industrial good or a consumer good, in particular a window, a pipe, a rotor blade of a wind turbine, a household machine or a means of transport such as, in particular, an automobile, a bus, a truck, a rail vehicle, a ship, an airplane or a helicopter or an attachment thereof.
  • NK standard climate
  • the viscosity was measured on a thermostated cone-plate viscometer
  • Rheotec RC30 (cone diameter 10 mm, cone angle 1 °, cone tip plate Distance 0.05 mm, shear rate 10 s -1 ) measured. Viscosities of less than 1 Pa s were measured with a cone diameter of 50 mm.
  • FT-IR Infrared spectra
  • the volatile components in particular unreacted isophorone diisocyanate, were then removed by distillation in a short-path evaporator (jacket temperature 160 ° C, pressure 0.1 to 0.005 mbar), producing a polymer with an NCO content of 1.84% by weight and a monomeric isophorone diisocyanate content of 0.02 Weight % was obtained.
  • polyoxypropylene diol (Acclaim® 4200, OH number 28 mg KOH/g, from Covestro), 1180 g of ethylene oxide-terminated polyoxypropylene triol (Caradol® MD34-02, OH number 35 mg KOH/g, from Shell) and 230 g of isophorone diisocyanate (Vestanat® IPDI, from Evonik) were converted at 80 °C using a known process to give a polymer with an NCO content of 2.1% by weight.
  • Table 1 Preparation and properties of the compounds A-1 to A-8.
  • the average molecular weight M n of compound A-1 was additionally determined using gel permeation chromatography (GPC) against polystyrene (474 to 2,520,000 g/mol) as a standard with tetrahydrofuran as mobile phase and refractive index detector.
  • the average molecular weight M n was 6,100 g/mol.
  • Trimethylolpropane-launched polyoxypropylene triol (Desmophen® 4011 T, OH number 550 mg KOH/g, from Covestro)
  • Trimethylolpropane started polyoxypropylene triol (Desmophen® 1381 BT, OH number 385 mg KOH/g, from Covestro)
  • the ingredients of the first component (K1) specified in Tables 3 to 8 were mixed together in the specified amounts (in parts by weight) using a centrifugal mixer (SpeedMixerTM DAC 150, FlackTek Inc.) and stored in a sealed container.
  • a centrifugal mixer SpeedMixerTM DAC 150, FlackTek Inc.
  • Socal® U1S2 (from Imerys), a precipitated calcium carbonate coated with stearate, was used as “CaCOs precipitated”.
  • component K2 consisting of compound C-9 was warmed or melted to 60 °C before mixing.
  • the gelling time was determined by stirring a freshly mixed amount of approx. 3 g in a standard climate with a spatula at regular intervals until this was no longer possible due to the gelling of the mass.
  • the mixed composition was applied to a silicone-coated release paper to form a film 2 mm thick, this was allowed to harden for 7 days in a standard climate, some dumbbell-shaped test specimens 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 this tested according to DIN EN 53504 at a tensile speed of 200 mm/min for tensile strength, elongation at break, modulus of elasticity 5% (at 0.5-5% elongation) and modulus of elasticity 50% (at 0.5-50% elongation).
  • test specimens were punched out to determine the tear strength and tested according to DIN ISO 34-1, method B (angular test specimen) at a tensile speed of 500 mm/min.
  • the tensile shear strength of some compositions on glass was determined as a measure of the strength of an adhesive bond.
  • composite bodies were produced by bonding two glass plates degreased with isopropanol and pretreated with Sika® Activator-205 (from Sika Switzerland) in such a way that the overlapping adhesive connection had a dimension of 12 x 25 mm and a thickness of 4 mm and the glass plates protruding from the headboards.
  • the tensile shear strength was tested according to DIN EN 1465 at a tensile speed of 20 mm/min. The fracture pattern was then assessed for AF (adhesive fracture or adhesive failure) or CF (cohesive failure). Without further information, the fracture pattern given in the table was observed on 90 to 100% of the fracture surface.
  • the Shore A hardness was determined according to DIN 53505 on test specimens hardened for 7 days in a standard climate. These results are marked with the addition “7d NK”. To determine the resistance to heat and water, further Shore A test specimens were either stored additionally for 7 days in a circulating air oven at 100 ° C after 7 days of curing in a standard climate or additionally stored for 7 days at 70 ° C and 100% relative humidity and then Cool to room temperature and determine the Shore A hardness as described. These results are marked with the addition “+7d 100°C” or “+7d 70/100”.
  • Table 3 Composition and properties of E-1 to E-8.
  • Example E-1 shows that the compound C-1 with cyanoacetate groups enables significantly better mechanical values than the compound R-1 with acetoacetate groups, in particular in terms of high tensile strength, high elongation and high tear resistance.
  • DBU was used as a catalyst in order to achieve a similarly fast gel time.
  • Table 4 Composition and properties of E-1 and E-9 to E-15.
  • Table 5 Composition and properties of E-10 and E-16 to E-20.
  • Table 6 Composition and properties of E-1 and E-21 to E-27.
  • Table 7 Composition and properties of E-28 to E-30.
  • Examples E-32 (Ref.) and E-33 (Ref.) are comparative examples in which the first and second components each only have an average functionality of 2.0 with respect to the compounds with aldehyde groups or cyanoacetate groups. Such a composition based only on linear reactive compounds did not cure into a solid, elastic material, whereas Example E-31 according to the invention with a second component with an average cyanoacetate functionality of 3.0 cured into an elastic material.

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Abstract

La présente invention concerne une composition durcissable comprenant - un premier composant contenant des composés contenant des groupes aldéhyde qui comprennent au moins un composé comportant au moins eux groupes aldéhyde et - un second composant contenant des composés contenant des groupes cyanoacétate qui comprennent au moins un composé comportant au moins deux groupes cyanoacétate, le poids moléculaire moyen Mn des premier et second composants, par rapport aux composés contenant des groupes aldéhyde ou cyanoacétate, étant compris entre 400 et 20 000 g/mol, et la fonctionnalité moyenne d'au moins l'un des deux composants, par rapport aux composés contenant des groupes aldéhyde ou des groupes cyanoacétate, étant supérieure à 2,0. La composition est largement exempte d'ingrédients toxiques et durcit dans des conditions ambiantes à l'aide de catalyseurs classiques rapidement et sans problème afin de former un polymère élastique non collant présentant un haut degré de résistance, un haut degré d'élasticité et un haut degré de résistance à la propagation des déchirures. La composition est particulièrement appropriée pour être utilisée en tant qu'adhésif élastique, agent d'étanchéité ou revêtement présentant un haut degré de robustesse pendant la production, le stockage et le traitement ainsi qu'un haut degré de résistance après durcissement.
EP23734252.2A 2022-07-13 2023-06-21 Composition polymère qui peut être durcie à température ambiante et qui est constituée de polyaldéhyde et de polycyanoacétate Pending EP4554994A1 (fr)

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EP22184828 2022-07-13
PCT/EP2023/066813 WO2024012827A1 (fr) 2022-07-13 2023-06-21 Composition polymère qui peut être durcie à température ambiante et qui est constituée de polyaldéhyde et de polycyanoacétate

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JP (1) JP2025522707A (fr)
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EP4103633A1 (fr) * 2020-02-10 2022-12-21 Sika Technology AG Polymère contenant des groupes silane
EP4585629A1 (fr) * 2024-01-12 2025-07-16 Sika Technology AG Composition durcissable comprenant un polymère newtonien aldéhyde, composés comprenant du méthylènegrupène activé, et accélérateur comprenant un groupe amine secondaire
EP4585628A1 (fr) * 2024-01-12 2025-07-16 Sika Technology AG Composition polymère durcissable contenant des aldéhydes, des composés ayant des groupes méthylène activés et un composant accélérateur

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DE69224987T2 (de) * 1991-06-10 1998-07-30 Eastman Chem Co Licht absorbierende polymere
WO2002014399A1 (fr) * 2000-08-11 2002-02-21 Akzo Nobel N.V. Composition aqueuse de liant reticulable et son utilisation dans la production de revetements a base de vernis-laque
US12360455B2 (en) 2019-02-08 2025-07-15 Brewer Science, Inc. Poly(cyanocinnamate)s for structural and optical applications

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CN119546665A (zh) 2025-02-28
JP2025522707A (ja) 2025-07-17
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KR20250036055A (ko) 2025-03-13
WO2024012827A1 (fr) 2024-01-18

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