EP3833702A1 - Polymère contenant des groupes isocyanate ayant une faible teneur en diisocyanates monomères - Google Patents

Polymère contenant des groupes isocyanate ayant une faible teneur en diisocyanates monomères

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Publication number
EP3833702A1
EP3833702A1 EP19746107.2A EP19746107A EP3833702A1 EP 3833702 A1 EP3833702 A1 EP 3833702A1 EP 19746107 A EP19746107 A EP 19746107A EP 3833702 A1 EP3833702 A1 EP 3833702A1
Authority
EP
European Patent Office
Prior art keywords
composition
polymer
monomeric
weight
range
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
EP19746107.2A
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German (de)
English (en)
Inventor
Michael Schlumpf
Sven Reimann
Berzad DURMIC
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
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Filing date
Publication date
Application filed by Sika Technology AG filed Critical Sika Technology AG
Publication of EP3833702A1 publication Critical patent/EP3833702A1/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
    • 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
    • C08G18/4829—Polyethers containing 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
    • 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
    • C08G18/302—Water
    • C08G18/307—Atmospheric humidity
    • 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
    • C08G18/3225—Polyamines
    • C08G18/325—Polyamines containing secondary or tertiary amino 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3253—Polyamines being in latent form
    • C08G18/3256—Reaction products of polyamines with aldehydes or ketones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • 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
    • C08G18/28—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
    • C08G18/4866—Polyethers having a low unsaturation value
    • 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
    • C08G18/82—Post-polymerisation treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
    • 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
    • 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
    • C09J175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
    • 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • 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
    • C09J2475/00—Presence of polyurethane

Definitions

  • the invention relates to low-monomer polymers for moisture-curing polyurethane compositions and their use as elastic adhesives, sealants and coatings.
  • Polyurethane compositions which crosslink by reaction of isocyanate groups with moisture or water and thereby cure to form elastomers are used in particular as elastic adhesives, sealants or coatings in the construction and manufacturing industry, for example for gluing components in assembly, for filling joints, as floor coating or as roof sealing. Due to their good adhesion and elasticity, they can gently dampen and bridge forces acting on the substrates, for example caused by vibrations or temperature fluctuations.
  • Such polyurethane compositions contain as binders polymers containing isocyanate groups, which are produced by reacting polyols with monomeric diisocyanates.
  • the polymers obtained in this way contain a residual monomeric diisocyanate content, typically in the range from 1 to 3% by weight, due to chain extension reactions.
  • Monomeric diisocyanates are potentially harmful to health.
  • Preparations containing monomeric diisocyanates must contain danger symbols and warnings on the label and in the data sheets, in particular from a concentration of 0.1% by weight, and in some countries they can only be sold and used under certain conditions.
  • Another way is to exchange symmetrical monomeric diiisocyanates for unsymmetrical ones, such as, for example, 4,4'-diphenylmethane diisocyanate for 2,4'-diphenylmethane diisocyanate or 2,4-tolylene diisocyanate, in order to reduce the proportion of chain extension reactions and thus a lower viscosity of the polymer.
  • Polymers containing isocyanate groups produced in this way are, however, significantly less reactive. They lead to slow curing and the mechanical strengths achieved in the products drop significantly compared to those based on symmetrical diisocyanates.
  • Another way is to partially react the isocyanate group-containing polymer with a functional compound, for example a mercaptosilane, aminosilane or hydroxyaldimine.
  • a functional compound for example a mercaptosilane, aminosilane or hydroxyaldimine.
  • the reaction products obtained have a different crosslinking characteristic and a greatly increased viscosity and are only stable and processable to a limited extent.
  • EP 2,439,219 describes the use of silicon dioxide having amino groups on the surface for reducing the content of monomeric diisocyanates.
  • the special silicon dioxide is expensive and also leads to high viscosities.
  • the most attractive route in terms of product properties to polymers containing isocyanate groups with a low content of monomeric diisocyanates is to use the monomeric diisocyanate in excess in the polymer production and then to use the majority of the unreacted monomeric diisocyanate by means of a suitable separation process, in particular - To remove them by distillation. Polymers from this process have a comparatively low viscosity and a low residual content of monomeric diisocyanates. This route is particularly easy to carry out with low molecular weight monomeric diisocyanates such as hexane diisocyanate.
  • Polymers produced in this way also have disadvantages in the products, in particular slower curing, weaknesses in the build-up of adhesion to the substrates and reduced elasticity after curing.
  • Polymers based on aromatic monomeric diisocyanates are particularly suitable for elastic adhesives, sealants and coatings, since these lead to quick curing and high strength with high elasticity and elasticity.
  • 4,4'-diphenylmethane diisocyanate in particular gives particularly good results.
  • due to its low vapor pressure this is particularly difficult to remove by distillation, in particular from polymers with a high molecular weight.
  • EP 1, 237.967 discloses somewhat longer-chain linear, monomer-exempted polymers based on 4,4'-diphenylmethane diisocyanate.
  • Example 7 a polyether diol with an average molecular weight of 3 ⁇ 00 g / mol is reacted with an excess of 4,4'-diphenylmethane diisocyanate, largely monomer-free by distillation and cured in Example 24 with an aromatic diamine at 100 ° C. Cured with moisture, however, this polymer leads to insufficient stretchability and elasticity.
  • EP 1, 746,117 in Table 2 shows a monomer-free polymer with an NCO content of 2.0% by weight based on 4,4'-diphenylmethane diisocyanate and a polyether triol with an OH functionality of 2.7 and an OH number of 28 mg KOH / g.
  • Such a polymer is generally suitable as the basis for one-component elastic polyurethane sealants and adhesives, but it can still be improved with regard to the stretchability and tear resistance of the products obtainable with it.
  • the polymer is based on aromatic monomeric diisocyanates, in particular 4,4'-diphenylmethane diisocyanate, and a polyether triol with a mean OH functionality in the range from 2.2 to 2.6 and an OH number in the range from 25 to 32 mg KOH / g. It has an NCO content in the range from 1.3 to 1.9% by weight and a monomeric diisocyanate content of at most 0.5% by weight.
  • the polymer according to the invention enables moisture-curing polyurethane compositions which have a very low residual content of monomeric diisocyanates and are thus safe to use without any special protective measures and which show surprisingly good usage properties.
  • they can be processed very well, which is evident in the case of pasty compositions in good squeezability, a short thread pull when the application cartridge is set down and good stability, and in the case of liquid compositions in a good course when applied flatly. They have a surprisingly long open time and are therefore easy to process even with large-scale and / or complex applications; nevertheless, they cure surprisingly quickly, which in this combination is extremely advantageous in many applications.
  • Compared to commercial, label-free products they show surprisingly high cold flexibility, better heat stability and better resistance to yellowing.
  • the invention relates to an isocyanate group-containing polyether urethane polymer, characterized in that it
  • “Monomeric diisocyanate” is an organic compound with two isocyanate groups separated by a divalent hydrocarbon residue with 4 to 15 carbon atoms.
  • An “isocyanate group” is referred to as “aromatic”, which is bonded directly to an aromatic carbon atom.
  • Isocyanates with exclusively aromatic isocyanate groups are accordingly referred to as “aromatic isocyanates”.
  • isocyanate group is referred to as “aliphatic” which is bonded directly to an aliphatic or cycloaliphatic carbon atom. Isocyanates with exclusively aliphatic isocyanate groups are accordingly referred to as “aliphatic isocyanates”.
  • a “monomeric aromatic diisocyanate” is a monomeric diisocyanate with aromatic isocyanate groups.
  • a “polyether urethane polymer” is a polymer that contains ether groups as repeating units and also contains urethane groups.
  • the “NCO content” is the content of isocyanate groups in% by weight.
  • the “molecular weight” is the molar mass (in grams per mole) of a molecule or a molecule residue.
  • the “average molecular weight” is the number average molecular weight (M n ) of a polydisperse mixture of oligomeric or polymeric molecules or molecule residues. It is determined by means of gel permeation chromatography (GPC) against polystyrene as the standard, in particular with tetrahydrofuran as the mobile phase, refractive index detector and evaluation from 200 g / mol.
  • a substance or a composition is said to be “stable in storage” or “storable” if it can be stored at room temperature in a suitable container for a longer period of time, typically for at least 3 months to 6 months and more, without it it changes in its application or use properties due to storage to an extent relevant to its use.
  • room temperature A temperature of 23 ° C is referred to as "room temperature”.
  • the polymer according to the invention can also be referred to as a polyurethane prepolymer.
  • the polymer according to the invention preferably has an average molecular weight M n in the range from 5 ⁇ 00 to 15 ⁇ 00 g / mol, determined by means of gel permeation chromatography (GPC) against polystyrene as the standard with tetrahydrofuran as the mobile phase, refractive index detector and evaluation from 200 g / mol.
  • M n average molecular weight in the range from 5 ⁇ 00 to 15 ⁇ 00 g / mol
  • the average molecular weight is particularly preferably in the range from 5,500 to 12 ⁇ 00 g / mol, in particular in the range from 6 ⁇ 00 to 10 ⁇ 00 g / mol.
  • Such a polymer enables moisture-curing polyurethane compositions with a particularly attractive combination of low viscosity, long open time with fast curing and high elasticity and strength.
  • the polymer according to the invention preferably has a monomeric diisocyanate content of at most 0.3% by weight, in particular at most 0.2% by weight.
  • a polymer is particularly suitable for the production of elastic adhesives, sealants and coatings which have a monomeric diisocyanate content of less than 0.1% by weight; these are safe to use even without special protective measures and can therefore be sold in many countries without hazard labeling.
  • 4,4'-diphenylmethane diisocyanate optionally with proportions of 2,4'- and / or 2,2'-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate or mixtures thereof with 2 , 6-tolylene diisocyanate (TDI), 1,4-phenylene diisocyanate (PDI), 2,3,5,6-tetramethyl-1,4-diisocyanatobenzene, naphthalene-1,5-diisocyanate (NDI) or 3,3 '-Dimethyl-4,4'-diisocyanatodiphenyl (TODI).
  • TDI 6-tolylene diisocyanate
  • PDI 1,4-phenylene diisocyanate
  • NDI naphthalene-1,5-diisocyanate
  • TODI 3,3 '-Dimethyl-4,4'-diisocyanatodiphenyl
  • 4,4'-Diphenylmethane diisocyanate (4,4'-MDI) is particularly preferred as the monomeric aromatic diisocyanate.
  • the 4,4'-MDI is of a quality which only contains small amounts of 2,4'- and / or 2,2'-diphenylmethane diisocyanate and is solid at room temperature. It enables moisture-curing polyurethane compositions with particularly fast curing and particularly high strength with high ductility and elasticity.
  • the 4,4'-MDI is preferably distilled and has a purity of at least 95%, in particular at least 97.5%.
  • a commercially available 4,4'-diphenylmethane diisocyanate of this quality is, for example, Desmodur ® 44 MC (from Covestro) or Lupranat ® MRSS or ME (from BASF) or Suprasec ® 1400 (from Fluntsman).
  • the polyether triol has an average OH functionality in the range from 2.2 to 2.6. Due to the manufacturing process, commercial polyether triols contain a certain amount of monols, which means that their average OH functionality is typically somewhat below 3. They typically contain trifunctional and monofunctional components.
  • the polyether triol preferably has 1,2-ethyleneoxy, 1,2-propyleneoxy, 1,3-propyleneoxy, 1,2-butyleneoxy or 1,4-butyleneoxy groups as repeating units. 1,2-Ethyleneoxy and / or 1,2-propyleneoxy groups are preferred.
  • the polyether triol has repeating units for the majority or exclusively of 1,2-propyleneoxy groups.
  • the polyether triol has 80 to 100% by weight of 1,2-propyleneoxy groups and 0 to 20% by weight of 1,2-ethyleneoxy groups, based on all repeating units.
  • the polyether triol has 80 to 90% by weight of 1,2-propyleneoxy groups and 10 to 20% by weight of 1,2-ethyleneoxy groups, based on all repeating units.
  • the 1,2-propyleneoxy groups and the 1, 2-ethyleneoxy groups in particular in each case homogeneous blocks and the poly (1, 2-ethyleneoxy) blocks are located at the chain ends.
  • Such a polyether triol enables moisture-curing polyurethane compositions with particularly rapid curing and particularly good heat stability.
  • the polyether triol preferably has an OH number in the range from 25 to 32 mg KOH / g and, based on all repeating units, 80 to 90% by weight of 1,2-propyleneoxy groups and 10 to 20% by weight of 1,2 -Ethyleneoxy groups.
  • Such a polymer enables moisture-curing polyurethane compositions with a particularly attractive combination of low viscosity, long open time with fast curing and high elasticity and strength.
  • the polyether triol preferably has an average molecular weight M n in the range from 4,000 to 8,500 g / mol, in particular 5,200 to 7,500 g / mol.
  • the polyether triol is preferably started using trimethylolpropane or, in particular, glycerol.
  • polyether triols are commercially available, for example as Desmo- phen ® 5031 BT (of Covestro), Voranol ® 5815 (from Dow) ® or Caradol ET28- 03 (from Shell).
  • the polymer according to the invention is obtained from the reaction of at least one monomeric aromatic diisocyanate and the polyether triol in an NCO / OH ratio of at least 3/1.
  • the NCO / OH ratio is preferably in the range from 3/1 to 10/1, particularly preferably in the range from 3/1 to 8/1, in particular in the range from 4/1 to 7/1.
  • the reaction is preferably carried out with exclusion of moisture at a temperature in the range from 20 to 160 ° C., in particular 40 to 140 ° C., if appropriate in the presence of suitable catalysts.
  • the monomeric diisocyanate remaining in the reaction mixture is removed by means of a suitable separation process except for the residual content described.
  • a preferred method of separation is a distillation process, in particular thin-film distillation or short-path distillation, preferably with the application of a vacuum.
  • a multi-stage process is particularly preferred, in which the monomeric aromatic diisocyanate is removed in a short-path evaporator at a jacket temperature in the range from 120 to 200 ° C. and a pressure of 0.001 to 0.5 mbar.
  • the removal by distillation is particularly demanding. For example, care must be taken to ensure that the condensate does not become solid and clog the system.
  • the process is preferably carried out at a jacket temperature in the range from 160 to 200 ° C. at 0.001 to 0.5 mbar and the removed monomer is condensed at a temperature in the range from 40 to 60 ° C.
  • the monomeric aromatic diisocyanate is preferably reacted with the polyether triol and the subsequent removal of the majority of the monomeric diisocyanate remaining in the reaction mixture without the use of solvents or entraining agents.
  • the aromatic monomeric diisocyanate removed after the reaction is subsequently reused, i.e. used again for the production of polyether urethane polymer containing isocyanate groups.
  • the isocyanate group-containing polyether urethane polymer very particularly preferably has an NCO content in the range from 1.3 to 1.9% by weight and a monomeric diisocyanate content of at most 0.3% by weight and is obtained from the reaction of 4,4 ' Diphenylmethane diisocyanate with a polyether triol with an average OH functionality in the range from 2.2 to 2.6, an OH number in the range from 25 to 32 mg KOH / g and a content of 80 to 90% by weight of 1,2-propyleneoxy Groups and 10 to 20% by weight of 1,2-ethyleneoxy groups based on all repeating units in the polyether segment.
  • Such an isocyanate group-containing polyether urethane polymer preferably has an average molecular weight M n in the range from 6 ⁇ 00 to 10 ⁇ 00 g / mol.
  • Such a polymer enables moisture-curing polyurethane compositions with a particularly attractive combination of low viscosity, long open time with fast curing and high elasticity and strength.
  • the polymer according to the invention preferably has a viscosity at 20 ° C. of at most 50 Pa s, in particular at most 40 Pa s, particularly preferably at most 30 Pa s.
  • the viscosity is determined using a cone-plate viscometer with a cone diameter of 25 mm, cone angle 1 °, cone-tip-plate distance 0.05 mm at a shear rate of 10 s 1 .
  • the OH groups of the polyether triol react with the isocyanate groups of the monomeric aromatic diisocyanate.
  • chain extension reactions also occur in that OH groups and / or isocyanate groups of reaction products react between polyol and monomeric diisocyanate.
  • a measure of the chain extension reaction is the average molecular weight of the polymer or the width and distribution of the peaks in the GPC analysis. Another measure is the effective NCO content of the monomer-exempted polymer in relation to the theoretical NCO content calculated from the reaction of each OH group with a monomeric aromatic diisocyanate.
  • the NCO content in the polymer according to the invention is preferably at least 80%, in particular at least 85%, of the theoretical NCO content, which is calculated from the addition of one mole of monomeric diisocyanate per mole of OH groups of the polyether triol.
  • Such a polyether urethane polymer is particularly suitable for use in moisture-curing polyurethane compositions.
  • the polymer according to the invention is of low viscosity, contains a low content of monomeric diisocyanates and is very stable in storage with the exclusion of moisture. It is particularly suitable for the production of moisture-curing polyurethane compositions with excellent usage properties.
  • Another object of the invention is a moisture-curing polyurethane composition with a monomeric diisocyanate content of less than 0.1% by weight, based on the total composition, containing the isocyanate group-containing polyether urethane polymer.
  • the moisture-curing polyurethane composition preferably has a content of polymer according to the invention in the range from 10 to 80% by weight, in particular 15 to 70% by weight, particularly preferably 20 to 60% by weight.
  • the moisture-curing polyurethane composition can contain at least one additional polymer containing isocyanate groups.
  • a preferred additional polymer containing isocyanate groups is a conventionally produced polyurethane polymer containing isocyanate groups from the reaction of polyester or polycarbonate diols and monomeric diisocyanates in an NCO / OH ratio in the range from 1.5 / 1 to 2.5 / 1 and an NCO content in the range of 2 to 8% by weight.
  • Preferred monomeric diisocyanates are MDI, TDI, IPDI or HDI.
  • Preferred polyester diols are OH-functional polyesters of adipic acid or sebacic acid or dodecanedicarboxylic acid with 1,4-butanediol or 1,4-hexanediol or neopentyl glycol.
  • Preferred polycarbonate diols are OH-functional polycarbonates of 1,6-hexanediol.
  • Such a polymer is typically solid at room temperature and is at least partially crystalline in character. Its use in the composition immediately after application can result in increased stability and / or increased initial adhesive strength when used as an adhesive.
  • Another preferred additional isocyanate group-containing polymer is an isocyanate group-containing polyether urethane polymer with an NCO content in the range from 1 to 2.5% by weight, in particular 1 .1 to 2.1% by weight, and a content of monomeric diisocyanates of at most 0.5% by weight, in particular at most 0.3% by weight, obtained from the reaction of IPDI with the above-described polyether triol suitable for producing the polyether urethane polymer according to the invention in an NCO / OH ratio of at least 3/1 and subsequent removal of a large part of the unconverted IPDI using short path distillation.
  • It preferably has an average molecular weight M n in the range from 5 ⁇ 00 to 15 ⁇ 00 g / mol, in particular 6 ⁇ 00 to 10 ⁇ 00 g / mol.
  • M n average molecular weight in the range from 5 ⁇ 00 to 15 ⁇ 00 g / mol, in particular 6 ⁇ 00 to 10 ⁇ 00 g / mol.
  • Another preferred additional isocyanate group-containing polymer is a linear isocyanate group-containing polyether urethane polymer with an NCO content in the range from 0.8 to 2.4% by weight, in particular 1 .2 to 2.1% by weight, and a maximum content of monomeric diisocyanates 0.3% by weight, obtained from the reaction of 4,4'-MDI with a polyoxypropylene diol with an OH number in the range from 13 to 38 mg KOH / g, in particular 22 to 32 mg KOH / g, in an NCO / OH ratio of at least 3/1 and subsequent removal of a large part of the unreacted 4,4'-MDI, as previously described.
  • Another preferred additional polymer containing isocyanate groups is a conventionally produced polyether urethane polymer containing isocyanate groups with an NCO content in the range from 1.7 to 2.2% by weight, obtained from the reaction of IPDI with a mixture of polyoxypropylene diol and polyoxypropylene -Triol, which may contain 1, 2-ethyleneoxy groups, in an NCO / OH ratio in the range from 1.5 / 1 to 2.2 / 1.
  • the use of such a polymer can bring about advantages in terms of the adhesive properties.
  • Another preferred additional isocyanate group-containing polymer is a conventionally produced isocyanate group-containing polyether urethane polymer with an NCO content in the range from 1.2 to 2.5% by weight, obtained from the reaction of TDI, preferably a mixture of 80% by weight. 2,4-TDI and 20% by weight 2,6-TDI, with a mixture of polyoxypropylene
  • Diol and polyoxypropylene triol which optionally contain fractions of 1,2-ethylenoxy groups, in an NCO / OH ratio in the range from 1.5 / 1 to 2/1.
  • NCO / OH ratio in the range from 1.5 / 1 to 2/1.
  • the moisture-curing polyurethane composition preferably additionally contains at least one blocked amine.
  • a suitable blocked amine preferably has at least one aldimino group or oxazolidino group. When it comes into contact with moisture, it reacts with hydrolysis and release of the amino group with existing isocyanate groups and can promote rapid, bubble-free curing, a particularly non-sticky surface and / or particularly good mechanical properties.
  • Preferred oxazolidines are bis-oxazolidines, in particular those derived from isobutyraldehyde, benzaldehyde or substituted benzaldehyde, in particular benzaldehyde, which is substituted in the para position with an optionally branched alkyl group having 10 to 14 carbon atoms.
  • Bis-oxazolidines from the reaction of OH-functional mono-oxazolidines with diisocyanates, in particular 1,6-hexamethylene diisocyanate, are preferred.
  • Sweet mono-oxazolidines are obtained in particular from the reaction of diethanolamine and an aldehyde with the liberation and removal of water.
  • Suitable aldimines are, in particular, di- or trialdimines from the reaction of commercially available primary di- or triamines with aldehydes which cannot be enolized. These are aldehydes which have no hydrogen atom in the alpha position to the carbon atom of the aldehyde group.
  • Preferred blocked amines are selected from aldimines of the formula (I) and (II).
  • n 2 or 3
  • A represents an n-valent hydrocarbon radical, optionally having ether-oxygen, with a molecular weight in the range from 28 to 6 ⁇ 00 g / mol,
  • R 1 and R 2 independently of one another each for a monovalent hydrocarbon radical with 1 to 12 C atoms or together for a divalent hydrocarbon radical with 4 to 12 C atoms, which is part of an optionally substituted, carbocyclic ring having 5 to 8, preferably 6, carbon atoms,
  • R 3 represents a hydrogen radical or a linear or branched alkyl, arylalkyl or alkoxycarbonyl radical having 1 to 12 carbon atoms,
  • R 4 represents a hydrogen radical or a monovalent hydrocarbon radical having 1 to 20 carbon atoms
  • R 5 represents an alkyl or alkoxy radical having 6 to 20 carbon atoms.
  • A is preferably an aliphatic, cycloaliphatic or arylaliphatic radical, in particular with a molecular weight in the range from 28 to 500 g / mol, in particular for a radical selected from the group consisting of 1,6-hexylene (1,5,5 Trimethylcyclohexane-1 -yl) methane-1, 3, 4 (2) -methyl-1, 3-cyclohexylene, 1, 3-cyclohexylene-bis (methylene), 1, 4-cyclohexylene-bis (methylene), 1, 3-phenylene-bis (methylene), 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, methylene-bis (2-methylcyclohexan-4-yl), (bicyclo [2.2.1] heptane -2.5 (2.6) - diyl) dimethylene, (tricyclo [5.2.1 .0 2 ' 6 ] decane-3 (4), 8 (9) -diyl) dim
  • R 1 and R 2 each preferably represent methyl.
  • R 3 preferably represents a hydrogen radical.
  • R 4 is preferably methyl or undecyl.
  • R 5 is preferably a para, optionally branched alkyl radical having 10 to 14 carbon atoms.
  • Particularly preferred blocked amines are selected from the group consisting of N, N'-bis (2,2-dimethyl-3-lauroyloxypropylidene) hexylene-1,6-diamine, N, N'-bis (2,2-dimethyl -3-acetoxypropylidene) -3-aminomethyl-3,5,5-trimethylcyclohexylamine, N, N'-bis (2,2-dimethyl-3-lauroyloxypropylidene) -3-aminomethyl-3,5,5-trimethylcyclohexylamine, N, N'-bis (4-Cio-14-alkylbenzylidene) -3-aminomethyl-3,5,5-trimethylcyclohexylamine, N, N'-bis (2,2-dimethyl-3-acetoxypropylidene) polyoxypropylene diamine with a average molecular weight M n in the range from 450 to 880 g / mol, N, N'-bis (2
  • the moisture-curing polyurethane composition preferably additionally contains at least one further constituent selected from oligomeric isocyanates, catalysts, fillers and plasticizers.
  • Suitable oligomers isocyanates are particularly HDI biurets such as Desmodur ® N 100 N or 3200 (from Covestro), Tolonate ® HDB or HDB-LV (from Venco- rex), or Duranate 24A-100 ® (by Asahi Kasei); HDI isocyanurates such as Desmo- dur ® 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 asa- hi Kasei) or Coronate HX ® (from Nippon Polyurethane); HDI uretdiones as Desmodur ® N 3400 (from Covestro); HDI Iminooxadiazindiones as Desmodur ® XP 2410 (of Covestro); HDI-allophanates such as Desmodur ® VP LS 2102
  • Suitable catalysts are catalysts for accelerating the reaction of isocyanate groups tion, especially organotin (IV) compounds such as in particular dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, di butylzinndiacetylacetonat, dimethyltin diacetate, dioctyltin diacetate, dioctyltin dilaurate or Dioctylzinndiacetylacetonat, 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 compounds containing tertiary amino groups, such as in particular 2,2'-dimorpholinodiethyl ether (DMDEE).
  • organotin (IV) compounds such as in particular dibutyltin diacetate
  • suitable catalysts are furthermore catalysts for the flydrolysis of the blocked amino groups, in particular organic acids, in particular 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 acid anhydrides such as phthalic anhydride, hexahydrophthalic anhydride or hexahydromethyl phthalic anhydride, silyl esters of carboxylic acids, organic sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid or 4-dulfonic acid, inorganic sulfonic acid, organic sulfonic acid, or 4-dulfonic acid, organic sulfonic acid, inorganic or other 4-dode
  • Suitable fillers are in particular ground or precipitated calcium carbonates, which are optionally coated with fatty acids, in particular stearates, barites (heavy spades), quartz flours, quartz sands, dolomites, wollastonites, calcined kaolins, layered silicates such as mica or talc, zeolites, Aluminum hydroxides, magnesium hydroxides, silicas including highly disperse silicas from pyrolysis processes, cements, gypsum, fly ash, industrially produced russet, graphite, metal powder, for example of aluminum, copper, iron, silver or steel, PVC powder or hollow spheres ,
  • Suitable plasticizers are, in particular, carboxylic acid 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 or diisononyl-1,2-cyclohexanedicarboxylate (DINCH) , Terephthalates, especially bis (2-ethylhexyl) terephthalate or diisononyl terephthalate, hydrogenated terephthalates, especially hydrogenated bis (2-ethylhexyl) terephthalate or diisononyl terephthalate or bis (2-ethylhexyl) -1, 4-cyclohex
  • the moisture-curing polyurethane composition can contain other additives, in particular
  • inorganic or organic pigments in particular titanium dioxide, chromium oxides or iron oxides;
  • Fibers in particular glass fibers, carbon fibers, metal fibers, ceramic fibers, plastic fibers such as polyamide fibers or polyethylene fibers, or natural fibers such as wool, cellulose, hemp or sisal;
  • nanofillers such as graphene or carbon nanotubes
  • Drying agents in particular molecular sieve powder, calcium oxide, highly reactive isocyanates such as p-tosyl isocyanate, mono-oxazolidines such as Incozol ® 2 (from Incorez) or orthoformic acid esters;
  • Adhesion promoters in particular organoalkoxysilanes, in particular epoxysilanes such as in particular 3-glycidoxypropyltrimethoxysilane or 3-glycidoxypropyltriethoxysilane, (meth) acrylosilanes, anhydridosilanes, carbamatosilanes, alkylsilanes or iminosilanes, or oligomeric forms of these silanes, or oligomeric forms;
  • 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 (ll) neodecanoate, zinc (ll) acetate, Zinc (II) -2-ethylhexanoate, zinc (II) laurate, zinc (II) acetylacetonate, aluminum lactate, aluminum oleate, diisopropoxytitanium bis (ethyl acetoacetate) or potassium acetate; Compounds containing tertiary amino groups, in particular N-ethyldiisopropylamine, N, N, N ', N'-tetramethylalkylenediamines, pentamethylalkylenetriamines and higher homolog
  • DABCO 1, 8-diazabicyclo [5.4.0] undec-7-ene
  • DBN 1, 5-diazabicyclo [4.3.0] - non-5-ene
  • N-alkylmorpholines N, N '-Dimethylpiperazin
  • nitrogen-aromatic compounds such as 4-dimethylaminopyridine, N-methylimidazole, N-vinylimidazole or 1,2-dimethylimidazole
  • organic ammonium compounds such as benzyltrimethylammonium hydroxide or alkoxylated tertiary amines; so-called “delayed action” catalysts, which represent modifications of known metal or amine catalysts;
  • Layered silicates such as bentonites, derivatives of castor oil, hydrogenated castor oil, polyamides, polyamide waxes, polyurethanes, urea compounds, pyrogenic silicas, cellulose ethers or hydrophobically modified polyoxyethylene;
  • - Solvents especially acetone, methyl acetate, tert-butyl acetate, 1-methoxy-2-propyl acetate, ethyl 3-ethoxypropionate, diisopropyl ether, diethylene glycol diethyl ether, ethylene glycol diethyl ether, ethylene glycol monobutyl ether, ethylene glycol mono-2-ethylhexyl ether, acetals such as propylal, butyl 2-ethylhexylal, dioxolane, glycerol formal or 2, 5,7,10-tetraoxaundecane (TOU), toluene,
  • TOU 5,7,10-tetraoxaundecane
  • non-reactive polymers in particular homo- or copolymers of unsaturated monomers, in particular from the group comprising ethylene, propylene, oil, butylene, isobutylene, isoprene, vinyl acetate or alkyl (meth) acrylates, in particular polyethylenes (PE), polypropylenes (PP), polyisobutylenes, ethylene-vinyl acetate copolymers (EVA) or atactic poly-a-olefins (APAO);
  • PE polyethylenes
  • PP polypropylenes
  • EVA ethylene-vinyl acetate copolymers
  • APAO atactic poly-a-olefins
  • flame-retardant substances in particular the fillers already mentioned, aluminum hydroxide or magnesium hydroxide, and in particular organic phosphoric acid esters, such as, in particular, triethyl phosphate, tricresyl phosphate, triphenyl phosphate, diphenylcresyl phosphate, isodecyl diphenyl phosphate, tris (1, 3-dichloro-2-propyl) phosphate -chloroethyl) phosphate, tris (2-ethylhexyl) phosphate, tris (chloroisopropyl) phosphate, tris (chloropropyl) phosphate, isopropylated triphenyl phosphate, mono-, bis- or tris (isopropylphenyl) phosphates of different degrees of isopropylation, resorcinol bis ( diphenyl phosphate), bisphenol A bis (diphenyl phosphate) or ammonium poly
  • Additives in particular wetting agents, leveling agents, defoamers, deaerators, stabilizers against oxidation, heat, light or UV radiation or biocides; or other substances commonly used in moisture-curing polyurethane compositions.
  • the content of monomeric diisocyanates is optionally further reduced by reaction with the moisture present.
  • the moisture-curing polyurethane composition preferably contains
  • plasticizer 0 to 35% by weight plasticizer
  • oligomeric isocyanates optionally further constituents, in particular oligomeric isocyanates, blocked amines, catalysts or further polymers.
  • the moisture-curing polyurethane composition is produced in particular in the absence of moisture and in at ambient temperature moisture-proof containers.
  • a suitable moisture-tight container consists in particular of an optionally coated metal and / or plastic and in particular represents a barrel, a container, a hobbock, a bucket, a canister, a can, a bag, a tubular bag, a cartridge or a tube ,
  • the moisture-curing polyurethane composition can be in the form of a one-component or in the form of a multi-component, in particular two-component, composition.
  • a “one-component” is a composition in which all components of the composition are in the same container and which as such is stable in storage.
  • a “two-component” is a composition in which the components of the composition are in two different components, which are stored in separate containers and are only mixed with one another shortly before or during application of the composition.
  • the moisture-curing polyurethane composition is preferably a one-component. With suitable packaging and storage, it is stable in storage, typically for several months to a year or longer.
  • the process of curing begins with the application of the moisture-curing polyurethane composition.
  • the result of this is the cured composition.
  • a one-component composition it is applied as such and then begins to cure under the influence of moisture or water.
  • an accelerator component which contains or releases water and / or a catalyst and / or a hardener can be added to the composition during application, or the composition can be mixed with such an accelerator component after application Be brought in contact.
  • the isocyanate groups react with one another under the influence of moisture.
  • the moisture-curing polyurethane composition contains a blocked amine
  • the isocyanate groups also react with the hydrolyzing blocked amino groups.
  • the entirety of these reactions of the isocyanate groups which lead to curing of the composition is also referred to as crosslinking.
  • the moisture required to cure the moisture-curing polyurethane composition is preferably diffused into the composition from the air (air humidity).
  • a solid layer of hardened composition (“skin”) forms on the surfaces of the composition that are in contact with air. Curing continues from the outside inwards along the direction of diffusion, the skin becoming increasingly thicker and finally comprising the entire composition applied.
  • the moisture can additionally or completely also get into the composition from one or more substrate (s) to which the composition has been applied and / or originate from an accelerator component which is added to the composition during application or after Application is brought into contact with this, for example by brushing or spraying.
  • the moisture-curing polyurethane composition is preferably applied at ambient temperature, in particular in the range from approximately -10 to 50 ° C., preferably in the range from -5 to 45 ° C., in particular 0 to 40 ° C.
  • the moisture-curing polyurethane composition is also preferably cured at ambient temperature.
  • the moisture-curing polyurethane composition has a long processing time (open time) and quick curing.
  • the “open time” is the period of time during which the composition can be processed or reworked without loss of functionality after application.
  • the open time refers in particular to the time span within which a bond must be added after its application in order to build up sufficient liability. With a one-component composition, the open time is exceeded at the latest when skin formation has occurred.
  • the degree of polymer formation in the composition within a given period of time after application is referred to as the "curing rate", in particular by determining the thickness of the skin formed. If the moisture-curing polyurethane composition contains a blocked amine, the aldehyde used to block the amino groups is released during crosslinking. In the event that this is largely volatile, it largely remains in the hardened composition and acts as a plasticizer.
  • the moisture-curing polyurethane composition is preferably used as an elastic adhesive or elastic sealant or elastic coating.
  • the moisture-curing polyurethane composition is particularly suitable for adhesive and sealing applications in the construction and manufacturing industry or in vehicle construction, in particular for parquet gluing, assembly, attachment part gluing, module gluing, window gluing, joint sealing, Body sealing, seam sealing or cavity sealing.
  • Elastic bonds in vehicle construction are, for example, the gluing of parts such as plastic covers, decorative strips, flanges, bumpers, driver's cabins or other add-on parts to the painted body of a vehicle, or the gluing of windows into the body, the vehicles in particular automobiles, trucks , Buses, rail vehicles or ships.
  • the moisture-curing polyurethane composition is particularly suitable for the elastic sealing of joints, seams or cavities of all kinds, in particular of construction joints such as dilatation joints or connecting joints between components, or floor joints in civil engineering.
  • a sealant with soft elastic properties and high cold flexibility is particularly suitable for sealing dilatation joints on buildings.
  • the moisture-curing polyurethane composition is particularly suitable for protecting and / or sealing buildings or parts thereof, in particular for building icons, terraces, roofs, in particular flat roofs or slightly inclined roof areas or roof gardens, or inside buildings under tiles or ceramic tiles in Wet rooms or kitchens, or in drip pans, channels, shafts, silos, dances or wastewater treatment plants.
  • It can also be used for repair purposes as a seal or coating, for example of leaky roof membranes or floor coverings that are no longer suitable, or as a repair compound for highly reactive spray seals.
  • the moisture-curing polyurethane composition can be formulated in such a way that it has a pasty consistency with pseudoplastic properties.
  • a composition is applied by means of a suitable device, for example from commercially available cartridges or barrels or flobbocks, for example in the form of a caterpillar, which can have an essentially round or triangular cross-sectional area.
  • the moisture-curing polyurethane composition can also be formulated so that it is liquid and so-called self-leveling or only slightly thixotropic and can be poured out for application. As a coating, for example, it can then be distributed over the entire area up to the desired layer thickness, for example by means of a roller, a slide, a trowel or a spatula. A layer thickness in the range from 0.5 to 3 mm, in particular 1 to 2.5 mm, is typically applied in one operation. Suitable substrates, which can be glued or sealed or coated with the moisture-curing polyurethane 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-coated metals or alloys such as galvanized or chromed 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 made of EPS, XPS, PUR, PIR, rock wool, glass wool or foamed glass (foam glass);
  • lacquered substrates in particular lacquered tiles, painted concrete, powder-coated metals or alloys or lacquered sheets;
  • the substrates can be pretreated before application, in particular by physical and / or chemical cleaning processes or by applying an activator or a primer.
  • Two identical or two different substrates can be glued and / or sealed.
  • Another object of the invention is a method for gluing or sealing, comprising the steps
  • Another object of the invention is a method for coating or sealing, comprising the steps
  • an article is obtained which is glued or sealed or coated with the composition.
  • This article can be a building or a part thereof, in particular a building of the underground or civil engineering, a bridge, a roof, a staircase or a facade, or it can be an industrial good or a consumer good, in particular a window, a pipe, a rotor blade of a wind power plant, a holding machine or a means of transport such as, in particular, an automobile, a bus, a truck, a rail vehicle, a ship, an aircraft or a helicopter, or an attachment part thereof.
  • Another object of the invention is therefore an article obtained from the described method for gluing or sealing or from the described method for coating or sealing.
  • the moisture-curing polyurethane composition has advantageous properties. Due to the low content of monomeric diisocyanates, it is safe to use, even without special protective measures, and does not require hazard labeling due to the monomeric diisocyanates. In the absence of moisture, it is very stable in storage, very easy to apply and has a long processing time (open time) with fast curing. The result is an elastic material with high elasticity and high strength, high tear resistance, good low-temperature flexibility, good rafting properties and high resistance, in particular to lightning and UV radiation.
  • NK standard climate
  • Desmophen ® 5031 BT Glycerin-started ethylene oxide-terminated polyoxypropylene triol, OH number 28 mg KOH / g, OH functionality approx. 2.3 (from Covestro);
  • the viscosity was measured with a thermostatted Rheotec RC30 cone-plate viscometer (cone diameter 25 mm, cone angle 1 °, cone tip-plate distance 0.05 mm, shear rate 10 s _1 ).
  • the average molecular weight was determined by means of gel permeation chromatography (GPC) against polystyrene (474 to 2,520,000 g / mol) as a standard with tetrahydrofuran as the mobile phase, refractive index detector and evaluation from 200 g / mol.
  • the monomeric diisocyanate content was determined by HPLC (detection via photodiode array; 0.04 M sodium acetate / acetonitrile as mobile phase) after prior derivatization using N-propyl-4-nitrobenzylamine.
  • Polymer P1 (according to the invention)
  • the volatile constituents in particular a large part of the monomeric 4,4'-diphenylmethane diisocyanate, were then removed by distillation in a short path evaporator (jacket temperature 180 ° C., pressure 0.1 to 0.005 mbar, condensation temperature 47 ° C.).
  • the polyether urethane polymer thus obtained had an NCO content of 1.7% by weight and a viscosity of 19 Pa-s 20 ° C, a content of monomeric 4,4'-diphenylmethane diisocyanate of 0.04% by weight and an average molecular weight M n of about 6,900 g / mol.
  • Polymer P2 (not according to the invention)
  • the volatile constituents in particular a large part of the monomeric 4,4'-diphenylmethane diisocyanate, were then removed by distillation in a short path evaporator (jacket temperature 180 ° C., pressure 0.1 to 0.005 mbar, condensation temperature 47 ° C.).
  • the polyether urethane polymer thus obtained had an NCO content of 1.7% by weight, a viscosity of 34.7 Pa-s at 20 ° C, a content of monomeric 4,4'-diphenylmethane diisocyanate of 0.06% by weight and an average molecular weight M n of approximately 9,300 g / mol.
  • the volatile constituents in particular a large part of the monomeric 4,4'-diphenylmethane diisocyanate, were then removed by distillation in a short path evaporator (jacket temperature 180 ° C., pressure 0.1 to 0.005 mbar, condensation temperature 47 ° C.).
  • the polyether urethane polymer thus obtained had an NCO content of 2.0% by weight, a viscosity of 16.8 Pa-s at 20 ° C, a content of monomeric 4,4'-diphenylmethane diisocyanate of 0.05% by weight and an average molecular weight M n from approx. 5,700 g / mol.
  • Polymer P4 (not according to the invention)
  • the volatile constituents in particular a large part of the monomeric 4,4'-diphenylmethane diisocyanate, were then removed by distillation in a short path evaporator (jacket temperature 180 ° C., pressure 0.1 to 0.005 mbar, condensation temperature 47 ° C.).
  • the polyether urethane polymer thus obtained had an NCO content of 1.8% by weight, a viscosity of 15.2 Pa-s at 20 ° C and a content of monomeric 4,4'-diphenylmethane diisocyanate of 0.08% by weight.
  • Polymer P5 (not according to the invention)
  • polyester diol Dynacoll 7360 ® and 142 g of 4,4'-diphenylmethane diisocyanate (Desmodur ® 44 MC L, of Covestro) were according to a known method at 80 ° C to a room temperature solid polymer having a NCO content of 2.0 % By weight and a content of monomeric 4,4'-diphenylmethane diisocyanate of 2.3% by weight.
  • the polymer P5 is a conventionally produced polymer which is solid at room temperature and which can be used to improve the initial adhesive strength of an adhesive.
  • Aldimine A1 N, N'-bis (2,2-dimethyl-3-lauroyloxypropylidene) -3-aminomethyl-3,5,5-trimethylcyclohexylamine
  • Moisture-curing polyurethane compositions are:
  • compositions Z1 to Z4 are Compositions Z1 to Z4:
  • the thickeners aste was prepared by mixing in a vacuum mixer, 300 g of diisodecyl phthalate and 48 g of 4,4'-diphenylmethane diisocyanate; submitted, and then gently heated with vigorous stirring, 27 g monobutyl amine were slowly added dropwise (Desmodur ® 44 MC L of Covestro). The resulting paste was further stirred for one hour under vacuum and cooling.
  • the squeezing force of the composition after storage was determined by storing a closed cartridge for 7 days at room temperature or for 7 days in a convection oven at 60 ° C and then the squeezing force using a squeezer
  • the skin formation time was determined as a measure of the processing time (open time). For this purpose, a few grams of the composition were applied in a layer thickness of approx. 2 mm to cardboard and in the standard climate the time Duration determined until, for the first time, no residues remained on the pipette when the surface of the composition was lightly tapped using an LDPE pipette.
  • the curing rate was determined by applying the composition as a free-standing cone with a diameter of 3 cm, allowing it to stand in a standard atmosphere or at 10 ° C / 50% relative humidity, cutting it open transversely after 24 h and measuring the layer thickness of the cured polymer ring formed. These results are shown in Table 2 as “after 24h” with the addition “(NK)” or “(10 ° C / 50%)", depending on the climate during curing. Additional cones were cut open after a few days and the thicker hardened layer was determined until it was at least 10 mm. In Table 2 the time for reaching a hardened layer of at least 10 mm layer thickness is given as "for 10mm".
  • each composition was pressed between two wax-coated transfer printing papers to a film of 2 mm thickness and stored in a standard atmosphere for 14 days. After the wax papers had been removed, some test specimens were punched out and tested as follows:
  • dumbbells For the determination of tensile strength ("tensile"), elongation at break and modulus of elasticity at 0.5-50% elongation (“modulus of elasticity 50%”), dumbbells with a length of 75 mm with a web length of 30 mm and a web width of 4 were used mm punched out of the film and tested according to DIN EN 53504 at a train speed of 200 mm / min. These results are marked with the addition "14d NK”. As a measure of the heat stability, further punched dumbbells were stored in a circulating air oven at 90 ° C. for 7 days, cooled in a standard atmosphere and tested in the same way. These results are provided with the addition "7d 90 ° C”.
  • the tensile shear strength (ZSF) on glass was determined to determine the strength of an adhesive connection.
  • Composite bodies were produced by degreasing two with isopropanol and two with Sika ® Aktivator-100 (from Sika Switzerland) pretreated glass plates were glued 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 protruded at the head ends. After the composite bodies had been stored for 14 days in a standard climate, the tensile shear strength was tested in accordance with DIN EN 1465 at a tensile speed of 20 mm / min. As a measure of the heat and hydrolysis stability of the bond, additional test specimens were additionally placed in a convection oven at 90 ° C for 7 days, or 7 days at
  • the Shore A hardness was determined according to DIN 53505 during 1 d, 2d, and 7d in
  • the 60% yield stress and the 100% yield stress were determined with concrete test specimens (pretreated with Sika ® Primer-3N, from Sika Switzerland) at 23 ° C and at -20 ° C according to DIN EN 28339, method A.
  • a low value at -20 ° C and a slight increase in the value between 23 and -20 ° C show a high degree of flexibility in the cold.
  • the color change of a film hardened in the standard climate was also after the time and storage in the standard climate "NK" on the window sill specified in table 2 or after exposure in a QUV device "QUV” or after exposure in a weathering tester Type Q-Sun Xenon Xe-1 with optical filter Q-SUN Daylight-Q and a xenon lamp with a light intensity of 0.51 W / m 2 at 340 nm at a temperature of 65 ° C ("Q-Sun” ).
  • the color difference DE of the film so loaded compared to the corresponding unloaded film was then equipped with a NH310 colorimeter from Shenzen 3NH Technology Co. LTD with Silicon Photoelectric Diode Detector, Light Source A, Color Space Measurement Interface CIE L * a * b * C * H *.
  • a high DE value stands for a large color difference.
  • Sikaflex ® As a comparative example (Ref.) Sikaflex ® was examined -11 FC + (Sika) in the same manner.
  • Sikaflex ® -11 FC + is a commercial elastic moisture-curing polyurethane sealant / adhesive with a monomeric diisocyanate content of less than 0.1% by weight based on polyether urethane polymers containing isocyanate groups, which is conventional without removing the excess monomeric diisocyanates were produced.
  • compositions designated with “(Ref.)” are comparative examples.
  • Table 1 Composition (in parts by weight) from Z1 to ZA.
  • Table 2 Properties of Sikaflex ® -11 FC + (comparison) and Z1 to Z4. Table 2 shows the properties of labeling-free one-component polyurethane compositions.
  • the comparison of the composition of the invention Z1 with the commercial product Sikaflex ® -11 FC + is a massively improved resistance to heat and yellowing in faster curing.
  • compositions Z1 and Z2 based on the polymer P1 according to the invention show a longer open time (skin formation time) with somewhat faster Curing, a massively higher elongation at break with significantly higher strength and a higher tear resistance, which are in each case on the level of the commercial product Sikaflex ® -11FC + .
  • compositions Z5 and Z6 are Compositions Z5 and Z6:
  • the squeezing force was tested as for composition Z1, but using a nozzle with an inner diameter of 5 mm and determining an additional value after 14 days of storage at 60 ° C.
  • composition Z1 The skin formation time and the tear resistance were tested as for composition Z1.
  • dumbbells were stored in a convection oven at 100 ° C for 7 days or at 70 ° C / 100% relative humidity for 7 days, cooled in a standard atmosphere and tested in the same way. These results are marked with the addition "7d 100 ° C” or "7d 70/100".
  • the tensile shear strength (ZFS) was tested as for composition Z1.
  • ZFS tensile shear strength
  • the adhesion was checked after waiting by degreasing several 40x100 mm glass plates with isopropanol, pretreating with Sika ® Activator-100 (from Sika Switzerland) and then at 35 ° C / 80% relative humidity the composition was applied in the longitudinal direction in the form of a triangular bead (10x10x10mm).
  • test specimens were then stored at 35 ° C./80% relative humidity for the waiting time given in Table 3 (3 min to 12 min), then coated with Teflon paper, the triangular bead pressed to a thickness of 4.5 mm and thus kept for 7 days , whereby the applied composition hardened.
  • Teflon paper was then removed and the adhesion of the pressed bead to the glass plate was tested by cutting the hardened composition at the narrow end just above the adhesive surface, holding the cut end of the composition with a pair of pliers and trying to pull the composition away from the surface. Then the composition was cut again down to the base, the cut-out part being rolled up with the round nose pliers and an attempt was again made to pull the composition off the base. For example, the composition was cut away from the substrate over a length of 80 mm. The adhesion was then assessed on the basis of the fracture pattern on the following scale:
  • compositions designated with “(Ref.)” are comparative examples.
  • composition Z5 based on the polymer P1 according to the invention compared to the composition Z6 based on the polymer P3 not according to the invention with a somewhat shorter chain length (higher NCO value and higher OH number of the underlying triol) has a higher elongation with higher tensile strength, a higher tear resistance and a longer open time when bonding glass in a warm, humid climate.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Sealing Material Composition (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

La présente invention concerne un polymère de polyétheruréthanne contenant des groupes isocyanate ayant une teneur en NCO comprise dans la plage de 1,3 à 1,9% en poids et une teneur en diisocyanates monomères d'au maximum 0,5% en poids, obtenu par la réaction d'au moins un diisocyanate aromatique monomère avec un polyéther-triol ayant une fonctionnalité OH dans la plage de 2,2 à 2,6 et un indice OH dans la plage de 25 à 32 mg KOH/g en un rapport NCO/OH d'au moins 3/1 et l'élimination ultérieure d'une grande partie des diisocyanates monomères au moyen d'un procédé de séparation approprié, ainsi que des compositions de polyuréthane durcissant à l'humidité ayant une teneur en diisocyanates monomères inférieure à 0,1% en poids contenant ce polymère. Le polymère selon l'invention rend possible des compositions de polyuréthane durcissant à l'humidité très stables au stockage, lesquelles sont sûres dans leur manipulation, même sans mesures de protection spéciales, possèdent une bonne aptitude à la transformation, ont un long temps d'ouverture et durcissent rapidement en un matériau élastique ayant une élasticité et une ductilité élevée avec une grande solidité, une haute résistance à l'allongement d'une déchirure, une bonne flexibilité à froid, de bonne propriétés d'adhésion et une haute résistance, en particulier contre la chaleur et le rayonnement UV. De telles compositions de polyuréthane sont particulièrement adaptées comme adhésifs, enduits d'étanchéité et revêtements élastiques.
EP19746107.2A 2018-08-08 2019-08-05 Polymère contenant des groupes isocyanate ayant une faible teneur en diisocyanates monomères Pending EP3833702A1 (fr)

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PCT/EP2019/071051 WO2020030608A1 (fr) 2018-08-08 2019-08-05 Polymère contenant des groupes isocyanate ayant une faible teneur en diisocyanates monomères

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EP4355838A1 (fr) * 2021-06-16 2024-04-24 DDP Specialty Electronic Materials US, LLC Adhésif de polyuréthane à un composant
CN113956436B (zh) * 2021-11-09 2023-05-30 万华化学（宁波）有限公司 一种浅色且存储过程中色号稳定的二苯基甲烷二异氰酸酯组合物
WO2023180217A1 (fr) 2022-03-25 2023-09-28 Sika Technology Ag Adhésif de pare-brise durcissant à l'humidité à base de polyuréthane

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CO2021001259A2 (es) 2021-02-26
ZA202101444B (en) 2022-07-27
CL2021000108A1 (es) 2021-07-23
BR112021001534A2 (pt) 2021-04-20
JP2022511239A (ja) 2022-01-31
CN112543779B (zh) 2024-04-05
PE20210643A1 (es) 2021-03-23
CN112543779A (zh) 2021-03-23
CN117887023A (zh) 2024-04-16
US12104005B2 (en) 2024-10-01
US20210309786A1 (en) 2021-10-07
AU2019319596A1 (en) 2021-03-18
MX2021001499A (es) 2021-04-28
KR20210041555A (ko) 2021-04-15
JP7261287B2 (ja) 2023-04-19

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