EP4259684A1 - Production de mousse de polyuréthane - Google Patents

Production de mousse de polyuréthane

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Publication number
EP4259684A1
EP4259684A1 EP21810379.4A EP21810379A EP4259684A1 EP 4259684 A1 EP4259684 A1 EP 4259684A1 EP 21810379 A EP21810379 A EP 21810379A EP 4259684 A1 EP4259684 A1 EP 4259684A1
Authority
EP
European Patent Office
Prior art keywords
foam
polyester
different
radicals
carbon atoms
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
EP21810379.4A
Other languages
German (de)
English (en)
Inventor
Michael SUCHAN
Michael Ferenz
Carsten Schiller
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.)
Evonik Operations GmbH
Original Assignee
Evonik Operations GmbH
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 Evonik Operations GmbH filed Critical Evonik Operations GmbH
Publication of EP4259684A1 publication Critical patent/EP4259684A1/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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • 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
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1808—Catalysts containing secondary or tertiary amines or salts thereof having alkylene polyamine 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
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1816—Catalysts containing secondary or tertiary amines or salts thereof having carbocyclic 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
    • C08G18/225—Catalysts containing metal compounds of alkali or alkaline earth metals
    • 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
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic 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
    • 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
    • C08G18/61—Polysiloxanes
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • 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
    • C08G2115/00—Oligomerisation
    • C08G2115/02—Oligomerisation to isocyanurate 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
    • C08G2350/00—Acoustic or vibration damping material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/10—Rigid foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/10—Block- or graft-copolymers containing polysiloxane sequences

Definitions

  • the present invention is in the field of polyurethanes, particularly polyurethane foams.
  • polyurethane foams particularly polyurethane foams.
  • it relates to the production of polyurethane foams using polyester-polysiloxane block copolymers and also to the use of these foams.
  • These are in particular rigid polyurethane foams.
  • polyurethane is understood to mean in particular a product obtainable by reaction of polyisocyanates and polyols or compounds having isocyanate-reactive groups.
  • other functional groups can also be formed, such as uretdiones, carbodiimides, isocyanurates, allophanates, biurets, ureas and/or uretimines.
  • PU is therefore understood to mean both polyurethane and polyisocyanurate, polyureas and polyisocyanate reaction products containing uretdione, carbodiimide, allophanate, biuret and uretimine groups.
  • polyurethane foam is understood to mean foam which is obtained as a reaction product based on polyisocyanates and polyols or compounds with isocyanate-reactive groups.
  • other functional groups can also be formed, such as allophanates, biurets, ureas, carbodiimides, uretdiones, isocyanurates or uretimines.
  • the specific object of the present invention was to make it possible to provide PU foams, in particular rigid PU foams, with good flame retardant properties.
  • the subject of the invention is a composition for producing PU foam, in particular PU rigid foam, comprising at least one isocyanate component, a polyol component, blowing agent, optionally a catalyst which catalyzes the formation of a urethane or isocyanurate bond, the composition includes polyester-polysiloxane block copolymers.
  • the subject of the invention is associated with a variety of advantages. It enables the provision of PU foams, in particular rigid PU foams, with good flame retardant properties. This is advantageously made possible without impairing the other properties of the foam, in particular its mechanical properties. Especially with a view to the provision of PU rigid foams, particularly fine-celled, uniform and low-defect foam structures are also made possible. This makes it possible to provide corresponding PU foams with particularly good performance properties, and in particular the thermal insulation capacity of rigid PU foams is positively influenced. The invention makes it possible in particular to improve the flame retardant properties of corresponding PU foams in such a way that the amount of conventional flame retardants used in the production of corresponding PU foams can be reduced.
  • the polyester-polysiloxane block copolymers of this invention also act as foam stabilizers.
  • Polyester-polysiloxane block copolymers and their preparation have long been known to those skilled in the art. They can be prepared, for example, by reacting organofunctional siloxanes with cyclic esters with the addition of catalysts, e.g. by reacting hydroxy-alkylsiloxanes with s-caprolactone in the opposite direction of an organotin compound as a catalyst.
  • catalysts e.g. by reacting hydroxy-alkylsiloxanes with s-caprolactone in the opposite direction of an organotin compound as a catalyst.
  • the synthesis of block copolymers that can be used according to the invention is described by means of 4 examples.
  • R 1 identical or different aliphatic or aromatic hydrocarbon radicals having 1 to 16 carbon atoms, preferably aliphatic or aromatic hydrocarbon radicals having 1 to 8 carbon atoms, in particular methyl or phenyl,
  • R 2 identical or different radicals from the group R 1 , R 3 or R 4 , preferably R 1 ,
  • R 3 identical or different polyester radicals, preferably polyester radicals of the formula 2,
  • R 5 identical or different divalent alkyl radicals which are optionally interrupted by one or more oxygen atoms, preferably -(CH2)3-, -(CH2)B-, -(CH2)3OCH2CH2- or -(CH2)3OCH2CH(CH3)-
  • R e O or NH or NMe, preferably O
  • R 7 identical or different divalent alkyl radicals having 1 to 20 carbon atoms, preferably alkyl radicals of the general formula -[CR 9 2]e-,
  • R 9 identical or different alkyl radicals having 1 to 8 carbon atoms or H, preferably methyl or H,
  • R 8 identical or different radicals of the general formula -C(O)R 10 or H, preferably H,
  • R 10 identical or different alkyl radicals having 1 to 16 carbon atoms, preferably methyl,
  • R 4 identical or different polyether radicals, preferably identical or different polyether radicals of the formula 3
  • R 11 identical or different divalent alkyl radicals having 2 to 12 carbon atoms, preferably divalent alkyl radicals having 3 to 6 carbon atoms, in particular -(CFhh-,
  • R 12 identical or different alkyl radicals having 1 to 12 carbon atoms, preferably methyl, ethyl or phenyl,
  • compositions show particularly advantageous results with regard to the advantages according to the invention described above, such as in particular flame retardancy and foam stabilization.
  • polyester-polysiloxane block copolymers according to the invention are produced by reacting cyclic esters, their cyclic dimers or higher analogues with alcohol and/or amino functional siloxanes, preferably derived from formulas 1 and 2, are obtained.
  • At least two or more different cyclic esters are used to produce the polyester-polysiloxane block copolymers according to the invention. This corresponds to a further particularly preferred embodiment of the invention.
  • polyester-polysiloxane block copolymers are used in a total amount of 0.01 to 15 parts, preferably 0.1 to 10 parts, particularly preferably 0.1 to 5 parts, based on 100 parts of polyols, this corresponds to a further particularly preferred one embodiment of the invention.
  • polyester-polysiloxane block copolymers according to the invention with certain blowing agents gives particularly advantageous results with regard to the advantages according to the invention mentioned above, such as in particular flame retardancy and foam stabilization.
  • the composition according to the invention contains water, hydrocarbons having 3, 4 or 5 carbon atoms, preferably cyclo-, iso- and/or n-pentane, fluorocarbons, preferably HFC 245fa, HFC 134a and /or HFC 365mfc, chlorofluorocarbons, preferably HCFC 141 b, hydrofluoroolefins (HFO) or hydrohaloolefins such as 1234ze, 1234yf, 1224yd, 1233zd(E) and/or 1336mzz, oxygen-containing compounds such as methyl formate, acetone and/or dimethoxymethane, or chlorinated hydrocarbons , preferably dichloromethane and/or 1,2-dichloroethane, water, cyclopentane, isopentane and/or n-pentane, 1233zd(E) or 1236mzz being used in particular.
  • polyester-polysiloxane block copolymers according to the invention may also contain polyether side chains in addition to the polyester side chains. This corresponds to a further preferred embodiment of the present invention.
  • polyester-polysiloxane block copolymers according to the invention not only improve the flame retardant properties of the PU foam, but also act as a foam stabilizer. It even allows the complete substitution of conventional foam stabilizers, which are usually polyether siloxanes, which in turn do not contain any polyester side chains.
  • Si-containing foam stabilizers based on the total amount of foam stabilizers, are more than 10% by weight, in particular more than 20% by weight and particularly preferably more than 50% by weight. are contained in the composition according to the invention.
  • Another subject of the invention is a process for the production of PU foams, in particular PU rigid foams, based on foamable reaction mixtures containing polyisocyanates, compounds with reactive hydrogen atoms, blowing agents, and optionally other additives, with polyester-polysiloxane block copolymers being used, preferably as previously described in more detail, in particular as previously described in more detail in the preferred embodiments.
  • the process according to the invention for the production of PU foams can be carried out according to the known methods, e.g. by hand mixing or preferably with the aid of foaming machines. If the process is carried out using foaming machines, high-pressure or low-pressure machines can be used.
  • the process according to the invention can be carried out either batchwise or continuously.
  • a preferred rigid PU foam formulation for the purposes of this invention has a density of 5 to 900 kg/m 3 and has the composition given in Table 1.
  • a further object of the present invention is a PU foam, in particular a rigid PU foam, produced by the aforementioned method according to the invention, in particular using a composition according to the invention.
  • the PU foam according to the invention in particular PU rigid foam, has a density of 5 to 900 kg/m 3 , preferably 5 to 350 kg/m 3 , in particular 10 to 200 kg/m 3 , this is a preferred embodiment of the invention .
  • Another object of the present invention relates to the use of PU foam according to the invention, in particular PU rigid foam, as mentioned above, as insulating material and/or as a construction material, in particular in construction applications, in particular in spray foam or in the cooling area, as acoustic foam for sound absorption, as packaging foam, as headliners for automobiles or pipe coatings for tubes.
  • PU foam according to the invention in particular PU rigid foam, as mentioned above, as insulating material and/or as a construction material, in particular in construction applications, in particular in spray foam or in the cooling area, as acoustic foam for sound absorption, as packaging foam, as headliners for automobiles or pipe coatings for tubes.
  • polyester-polysiloxane block copolymers according to the invention in particular as defined in one of the claims, in the production of PU foams, preferably rigid PU foams, in particular using a composition according to the invention, in particular as defined in one of the claims of the invention, the polyester-polysiloxane block copolymers being used in particular as foam-stabilizing components in the production of PU foams, preferably PU rigid foams.
  • a preferred composition according to the invention contains the following components: a) polyester-polysiloxane block copolymers according to the invention b) isocyanate-reactive components, in particular polyols c) at least one polyisocyanate and/or polyisocyanate prepolymer d) a catalyst which promotes the reaction of polyols b) with the isocyanates c) accelerates or controls e) optionally another silicon-containing compound as surfactant f) one or more blowing agents g) optionally further additives, fillers, flame retardants, etc.
  • a component having at least 2 isocyanate-reactive groups preferably a polyol component, a catalyst and a polyisocyanate and/or a polyisocyanate prepolymer are used to produce the PU foams.
  • the catalyst is in particular via the polyol component brought in.
  • Suitable polyol components, catalysts and polyisocyanates and/or polyisocyanate prepolymers are known per se, but are also described further below.
  • Polyols suitable as the isocyanate-reactive component or polyol component b) for the purposes of the present invention are all organic substances having one or more groups which are reactive toward isocyanates, preferably OH groups, and preparations thereof.
  • Preferred polyols are all for the production of polyurethane systems, in particular polyurethane coatings, polyurethane elastomers or foams; commonly used polyetherpolyols and/or polyesterpolyols and/or hydroxyl-containing aliphatic polycarbonates, in particular polyetherpolycarbonatepolyols and/or polyols of natural origin, so-called “natural oil-based polyols” (NOPs).
  • the polyols usually have a functionality of 1.8 to 8 and number-average molecular weights in the range from 500 to 15,000.
  • the polyols with OH numbers in the range from 10 to 1200 mg KOH/g are usually used.
  • Polyols or mixtures thereof are preferably used to produce PU rigid foams, with the proviso that at least 90 parts by weight of the polyols present, based on 100 parts by weight of polyol component, have an OH number greater than 100, preferably greater than 150, in particular greater than 200 exhibit.
  • the basic difference between flexible foam and rigid foam is that flexible foam shows elastic behavior and can be reversibly deformed. If the flexible foam is deformed by the application of force, it returns to its original shape as soon as the application of force is removed. Hard foam, on the other hand, is permanently deformed.
  • Polyether polyols can be prepared by known processes, for example by anionic polymerization of alkylene oxides in the presence of alkali metal hydroxides, alkali metal alcoholates or amines as catalysts and with the addition of at least one starter molecule that preferably contains 2 or 3 reactive hydrogen atoms or by cationic polymerization of alkylene oxides in the presence of Lewis -Acids such as antimony pentachloride or boron trifluoride etherate or by double metal cyanide catalysis.
  • Suitable alkylene oxides contain 2 to 4 carbon atoms in the alkylene radical.
  • Examples are tetrahydrofuran, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide; ethylene oxide and 1,2-propylene oxide are preferably used.
  • the alkylene oxides can be used individually, cumulatively, in blocks, alternately one after the other, or as mixtures.
  • compounds with at least 2, preferably 2 to 8, hydroxyl groups or with at least two primary amino groups in the molecule are used as starter molecules.
  • starter molecules examples include water, di-, tri- or tetrahydric alcohols such as ethylene glycol, 1,2- and 1,3-propanediol, diethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, pentaerythritol, castor oil, etc., higher polyfunctional polyols, in particular sugar compounds such as glucose, sorbitol, mannitol and sucrose, polyhydric phenols, resols such as oligomeric condensation products of phenol and formaldehyde and Mannich condensates of phenols, formaldehyde and dialkanolamines and melamine, or amines such as aniline, EDA, TDA, MDA and PMDA , particularly preferably TDA and PMDA. Choosing the right one Starter molecule depends on the particular area of application of the resulting polyether polyol in polyurethane production.
  • Polyester polyols are based on esters of polybasic aliphatic or aromatic carboxylic acids, preferably having 2 to 12 carbon atoms.
  • aliphatic carboxylic acids are succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedioic acid, maleic acid and fumaric acid.
  • aromatic carboxylic acids are phthalic acid, isophthalic acid, terephthalic acid and the isomeric naphthalenedicarboxylic acids.
  • polyester polyols are obtained by condensing these polybasic carboxylic acids with polyhydric alcohols, preferably diols or triols having 2 to 12, particularly preferably 2 to 6, carbon atoms, preferably trimethylolpropane and glycerol.
  • Polyether polycarbonate polyols are polyols containing carbon dioxide bound as a carbonate. Since carbon dioxide is produced in large quantities as a by-product in many processes in the chemical industry, the use of carbon dioxide as a comonomer in alkylene oxide polymerizations is of particular commercial interest. Partial replacement of alkylene oxides in polyols with carbon dioxide has the potential to significantly reduce the cost of polyol production. In addition, the use of CO2 as a comonomer is ecologically very advantageous, since this reaction represents the conversion of a greenhouse gas into a polymer. The production of polyether polycarbonate polyols by addition of alkylene oxides and carbon dioxide onto H-functional starter substances using catalysts has been known for a long time.
  • the first generation represented heterogeneous zinc or aluminum salts, as described, for example, in US Pat. No. 3,900,424 or US Pat. No. 3,953,383.
  • mono- and binuclear metal complexes have been used successfully for the copolymerization of CO2 and alkylene oxides (WO 2010/028362, WO 2009/130470, WO 2013/022932 or WO 2011/163133).
  • the most important class of catalyst systems for the copolymerization of carbon dioxide and alkylene oxides are the double metal cyanide catalysts, also referred to as DMC catalysts (US-A 4500704, WO 2008/058913).
  • Suitable alkylene oxides and H-functional starter substances are those which are also used for the preparation of carbonate-free polyether polyols, as described above.
  • Polyols based on renewable raw materials "Natural oil-based polyols” (NOPs) for the production of PU foams are of increasing interest and are already widely used in view of the long-term limited availability of fossil resources, namely oil, coal and gas, and against the background of rising crude oil prices described in such applications (WO 2005/033167; US 2006/0293400, WO 2006/094227, WO 2004/096882, US 2002/0103091, WO 2006/116456 and EP 1678232).
  • a number of these polyols from various manufacturers are now available on the market (WO 2004/020497, US 2006/0229375, WO 2009/058367).
  • the basic raw material e.g.
  • soybean oil, palm oil or castor oil and the subsequent processing, polyols with different properties result.
  • two groups can be distinguished: a) polyols based on renewable raw materials, which are modified to such an extent that they can be used 100% for the production of polyurethanes (WO 2004/020497, US 2006/0229375); b) polyols based on renewable raw materials which, due to their processing and properties, can only replace the petrochemical-based polyol to a certain extent (WO 2009/058367).
  • the so-called packed polyols represent a further class of usable polyols. These are characterized in that they contain solid organic fillers up to a solids content of 40% or more in disperse distribution.
  • SAN, PHD and PIPA polyols can be used.
  • SAN polyols are highly reactive polyols containing a dispersed styrene/acrylonitrile (SAN)-based copolymer.
  • PHD polyols are highly reactive polyols which also contain polyurea in dispersed form.
  • PIPA polyols are highly reactive polyols containing a polyurethane in dispersed form, e.g., formed by the in situ reaction of an isocyanate with an alkanolamine in a conventional polyol.
  • a further class of polyols which can be used are those which are obtained as prepolymers by reacting polyol with isocyanate in a molar ratio of preferably 100:1 to 5:1, preferably 50:1 to 10:1.
  • prepolymers are preferably prepared as a solution in the polymer, with the polyol preferably corresponding to the polyol used to produce the prepolymers.
  • recycling polyols Another class of polyols that can be used are so-called recycling polyols, ie polyols that are obtained from the recycling of polyurethanes. Recycling polyols are known per se. In this way, polyurethanes can be split by solvolysis and thus brought into a soluble form. Almost all chemical recycling processes for polyurethanes use such reactions, e.g. B. glycolysis, hydrolysis, acidolysis or aminolysis, with a variety of process variants are known in the art. The use of recycling polyols represents a preferred embodiment of the invention.
  • a preferred ratio of isocyanate and polyol, expressed as the formulation index, i.e. as the stoichiometric ratio of isocyanate groups to isocyanate-reactive groups (e.g. OH groups, NH groups) multiplied by 100, is in the range of 10 to 1000, preferred 40 to 400.
  • An index of 100 represents a 1 to 1 molar ratio of the reactive groups.
  • One or more organic polyisocyanates having two or more isocyanate functions are preferably used as isocyanate components or polyisocyanate c).
  • One or more polyols having two or more isocyanate-reactive groups are preferably used as polyol components.
  • Isocyanates suitable as isocyanate components for the purposes of this invention are all isocyanates which contain at least two isocyanate groups.
  • Isocyanates are particularly preferably used in a range from 40 to 400 mol % relative to the sum of the isocyanate-consuming components.
  • alkylene diisocyanates having 4 to 12 carbon atoms in the alkylene radical such as 1,12-dodecane diisocyanate, 2-ethyltetramethylene 1,4-diisocyanate, 2-methylpentamethylene 1,5-diisocyanate, tetramethylene 1,4-diisocyanate and preferably hexamethylene diisocyanate -1,6 (HMDI), cycloaliphatic diisocyanates such as cyclohexane-1,3- and 1-4-diisocyanate and any mixtures of these isomers, 1-isocyanato-3,35-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate or IPDI for short ), 2,4- and 2,6-hexahydrotoluylene diisocyanate and the corresponding isomer mixtures, and preferably aromatic di- and polyisocyanates, such as 2,4
  • the organic di- and polyisocyanates can be used individually or in the form of their mixtures.
  • Corresponding “oligomers” of the diisocyanates can also be used (IPDI trimer based on isocyanurate, biurete-urethdione.) It is also possible to use prepolymers based on the isocyanates mentioned above.
  • modified isocyanates which have been modified by the incorporation of urethane, uretdione, isocyanurate, allophanate and other groups.
  • Particularly suitable organic polyisocyanates and therefore particularly preferably used are various isomers of toluene diisocyanate (2,4- and 2,6-toluene diisocyanate (TDI), in pure form or as isomer mixtures of different composition), 4,4'-diphenylmethane diisocyanate (MDI), that so-called “crude MDI” or “polymeric MDI” (contains not only the 4,4'- but also the 2,4'- and 2,2'-isomers of MDI and polynuclear products) as well as the binuclear product referred to as "pure MDI". from predominantly 2,4'- and 4,4'-isomer mixtures or their prepolymers.
  • TDI 2,4- and 2,6-toluene diisocyanate
  • MDI 4,4'-diphenylmethane diisocyanate
  • Suitable catalysts d) for the purposes of the present invention are all compounds which are able to accelerate the reaction of isocyanates with OH functions, NH functions or other isocyanate-reactive groups.
  • the usual catalysts known from the prior art can be used here, including, for example, amines (cyclic, acyclic; monoamines, diamines, oligomers with one or more amino groups), ammonium compounds, organometallic compounds and metal salts, preferably those of tin, iron , bismuth, potassium and zinc.
  • amines cyclic, acyclic; monoamines, diamines, oligomers with one or more amino groups
  • ammonium compounds preferably those of tin, iron , bismuth, potassium and zinc.
  • mixtures of several components can be used as catalysts.
  • Optional component e) can be further surface-active silicon-containing compounds that serve as an additive in order to optimize the desired cell structure and the foaming process. Therefore, such additives are also called foam stabilizers.
  • foam stabilizers are also called foam stabilizers.
  • all Si-containing compounds that support foam production stabilization, cell regulation, cell opening, etc. can be used here. These compounds are well known from the prior art.
  • All known compounds which are suitable for the production of PU foam can be used as further surface-active Si-containing compounds.
  • siloxane structures that can be used within the meaning of this invention are described, for example, in the following patent specifications, although the use there is only described in classic PU foams, as molded foam, mattresses, insulation material, construction foam, etc.:
  • blowing agents f are basically optional, depending on which foaming process is used. Chemical and physical blowing agents can be used. The choice of propellant depends heavily on the type of system.
  • a high or low density foam is produced.
  • foams with densities of 5 kg/m 3 to 900 kg/m 3 can be produced.
  • Preferred densities are 5 to 350, particularly preferably 10 to 200 kg/m 3 , in particular 20 to 150 kg/m 3 .
  • Corresponding compounds with suitable boiling points can be used as physical blowing agents.
  • Chemical blowing agents that react with NCO groups and release gases, such as water or formic acid, can also be used.
  • Particularly preferred blowing agents for the purposes of this invention include hydrocarbons having 3, 4 or 5 carbon atoms, hydrofluoroolefins (HFO), hydrohaloolefins and/or water.
  • additives g All substances known from the prior art that are used in the production of polyurethanes, in particular PU foams, such as crosslinkers and chain extenders, stabilizers against oxidative degradation (so-called antioxidants), flame retardants can be used as additives g). , surfactants, biocides, cell refining additives, cell openers, solid fillers, antistatic additives, nucleating agents, thickeners, dyes, pigments, color pastes, fragrances, emulsifiers, etc.
  • the composition according to the invention can contain all known flame retardants suitable for the production of polyurethane foams.
  • Suitable flame retardants for the purposes of this invention are preferably liquid organic phosphorus compounds, such as halogen-free organic phosphates, e.g. triethyl phosphate (TEP), halogenated phosphates, e.g. tris(1-chloro-2-propyl) phosphate (TCPP) and tris(2-chloroethyl) phosphate (TCEP) and organic phosphonates, e.g. dimethyl methane phosphonate (DMMP), dimethyl propane phosphonate (DMPP), or solids such as ammonium polyphosphate (APP) and red phosphorus.
  • halogenated compounds e.g. halogenated polyols, and solids, such as expandable graphite, aluminum oxides, antimony compounds and melamine.
  • polyester-polysiloxane block copolymers according to the invention enables the reduction of flame retardants, which leads to unsatisfactory results with conventional foam stabilizers.
  • Block copolymer A is a block copolymer A
  • Block copolymer B is a block copolymer
  • Block copolymer C is a block copolymer
  • Block copolymer D is a block copolymer
  • the comparative foamings were carried out using the hand mixing method.
  • polyol, catalysts, water, surfactant and blowing agent were weighed into a beaker and mixed with a plate stirrer (6 cm diameter) at 1000 rpm for 30 s.
  • the amount of propellant evaporated during the mixing process was determined by weighing again and replenished.
  • the MDI was then added, the reaction mixture was stirred with the stirrer described for 7 s at 2500 rpm and immediately transferred into an open mold measuring 27.5 ⁇ 14 ⁇ 14 cm (W ⁇ H ⁇ D).
  • the comparative foamings were carried out using the hand mixing method.
  • polyol, catalysts, water, surfactant, flame retardant and blowing agent were weighed into a beaker and mixed with a plate stirrer (6 cm diameter) at 1000 rpm for 30 s.
  • the amount of propellant evaporated during the mixing process was determined by weighing again and replenished.
  • the MDI was added, the reaction mixture with that described Stirred with stirrer for 7 s at 2500 rpm and immediately transferred into an open mold measuring 27.5 ⁇ 14 ⁇ 14 cm (W ⁇ H ⁇ D).
  • the comparative foamings were carried out using the hand mixing method.
  • polyol, catalysts, water, surfactant, flame retardant and blowing agent were weighed into a beaker and mixed with a plate stirrer (6 cm diameter) at 1000 rpm for 30 s.
  • the amount of propellant evaporated during the mixing process was determined by weighing again and replenished.
  • the MDI was then added, the reaction mixture was stirred with the stirrer described for 5 s at 3000 rpm and immediately transferred into an open mold measuring 27.5 ⁇ 14 ⁇ 14 cm (W ⁇ H ⁇ D).
  • the foams were removed from the mold.
  • the foams were subjected to a cone calorimeter test according to ISO 5660-1 AMD 1:2019-08, and the burning time, defined as the time between the ignition of the foam and the flame going out, was determined at a heating rate of 25 kW/m 2 .

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)

Abstract

L'invention concerne une composition pour la production de mousse de polyuréthane, en particulier une mousse de polyuréthane rigide, comprenant au moins un composant isocyanate, un composant polyol, éventuellement un catalyseur qui catalyse la formation d'une liaison uréthane ou isocyanurate, et un agent gonflant, la composition comprenant des copolymères séquencés de polyester-polysiloxane.
EP21810379.4A 2020-12-08 2021-11-22 Production de mousse de polyuréthane Pending EP4259684A1 (fr)

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JP2023553096A (ja) 2023-12-20
CA3201374A1 (fr) 2022-06-16

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