WO2015150408A1 - Isocyanate trimerization catalyst for making polyisocyanurate comprising foams - Google Patents

Isocyanate trimerization catalyst for making polyisocyanurate comprising foams Download PDF

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Publication number
WO2015150408A1
WO2015150408A1 PCT/EP2015/057079 EP2015057079W WO2015150408A1 WO 2015150408 A1 WO2015150408 A1 WO 2015150408A1 EP 2015057079 W EP2015057079 W EP 2015057079W WO 2015150408 A1 WO2015150408 A1 WO 2015150408A1
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WIPO (PCT)
Prior art keywords
isocyanate
polyisocyanurate
polyols
composition
trimerization catalyst
Prior art date
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Ceased
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PCT/EP2015/057079
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English (en)
French (fr)
Inventor
Hugo Verbeke
Anja Anneke VANHALLE
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Huntsman International LLC
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Huntsman International LLC
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Publication date
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Priority to BR112016021581-8A priority Critical patent/BR112016021581B1/pt
Priority to RU2016143070A priority patent/RU2707290C2/ru
Priority to US15/301,411 priority patent/US11548973B2/en
Priority to CA2941348A priority patent/CA2941348C/en
Priority to CN201580018197.4A priority patent/CN106459335B/zh
Priority to EP15741883.1A priority patent/EP3126423B1/en
Priority to PL15741883T priority patent/PL3126423T3/pl
Publication of WO2015150408A1 publication Critical patent/WO2015150408A1/en
Anticipated expiration legal-status Critical
Ceased 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
    • C08G18/28—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
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
    • C08G18/3851—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing three nitrogen atoms in the ring
    • C08G18/3853—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing three nitrogen atoms in the ring containing cyanurate and/or 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/09—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture
    • C08G18/092—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/14—Manufacture of cellular products
    • 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
    • C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
    • C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
    • 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
    • C08G18/1875—Catalysts containing secondary or tertiary amines or salts thereof containing ammonium salts or mixtures of secondary of tertiary amines and acids
    • 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
    • C08G18/48—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
    • C08G18/28—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
    • 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
    • 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
    • C08J9/127—Mixtures of organic and inorganic blowing agents
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus
    • 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
    • C08G2110/0058—≥50 and <150kg/m3
    • 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
    • C08G2330/00—Thermal insulation 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/18—Binary blends of expanding agents
    • C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
    • 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
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
    • 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
    • C08J2375/08—Polyurethanes from polyethers

Definitions

  • the present invention is related to a catalyst compound for catalysing the trimerization of a polyisocyanate compound (trimerization catalyst) for making a polyisocyanurate comprising foam, in particular polyisocyanurate comprising rigid foams. Further the present invention is related to a process for preparing said polyisocyanurate comprising (rigid) foam.
  • the present invention is concerned with a polyisocyanurate comprising (rigid) foam suitable for use as insulation foams obtained by using the trimerization catalyst according to the invention.
  • US2011201709 discloses a trimerisation catalyst system comprising an imidazolium or imidazolinium cation, an isocyanate-trimer inducing anion wherein the trimerisation catalyst system has a trimerisation activation temperature in the range of equal to or less than 73 °C.
  • EP 1004607 discloses a method for making a rigid polyurethane/polyisocyanurate foam by reacting a polyisocyanate and a polyol in the presence of a catalyst composition comprising a trimerization catalyst compound of the formula B + O2-C-X-C(0)-NR-R 1 where X is the residue of an organic acid anhydride; R is hydrogen or a C1-C4 alkyl group; R 1 is a C1-C4 alkyl or a phenyl group or Y-NR 2 R 3 , where Y is a C2-C6 alkylene group which may contain heteroatoms and R 2 and R 3 are C1-C20 alkyl groups which may contain oxygen atoms or which together with the tertiary nitrogen form a 5 or 6 member ring which may contain oxygen atoms; and B is an alkali metal ion or a quaternary ammonium ion.
  • the present invention relates to trimerization catalysts selected from one or more organic salts from alkoxides, preferably said organic salt is selected from alkali metal, earth alkali metal, a transition metal such as Ti and/or quaternary ammonium organic salts from alkoxides such as potassium ethoxide, sodium ethoxide, potassium methoxide, sodium methoxide, potassium tert-butoxide, titanium isopropoxide and mixtures thereof suitable for making a polyisocyanurate comprising rigid foam.
  • organic salt is selected from alkali metal, earth alkali metal, a transition metal such as Ti and/or quaternary ammonium organic salts from alkoxides such as potassium ethoxide, sodium ethoxide, potassium methoxide, sodium methoxide, potassium tert-butoxide, titanium isopropoxide and mixtures thereof suitable for making a polyisocyanurate comprising rigid foam.
  • the present invention is concerned with a process to prepare a polyisocyanurate comprising rigid foam, said polyisocyanurate comprising rigid foam obtained using the trimerization catalyst of the invention and the use of said polyisocyanurate comprising rigid foam as/in insulation panels.
  • the present invention relates to a trimerization catalyst which is suitable for making a polyisocyanurate- polyurethane comprising rigid insulation foam (PIR-PUR) having a density ⁇ 60 kg/m 3 and a process for making said foam.
  • PIR-PUR rigid insulation foam
  • the trimerization catalyst composition of the present invention comprises at least a trimerization catalyst compound selected from one or more organic alkoxides wherein said organic salt is selected from an alkali metal, an earth alkali metal, a transition metal such as Ti and/or a quaternary ammonium organic alkoxide.
  • the trimerization catalyst composition of the present invention comprises at least a trimerization catalyst compound wherein the trimerization catalyst compound corresponds to the general formula (I): (R-0 ) x M +x (I)
  • ⁇ x is a number being defined by the oxidation state of M
  • ⁇ M is selected from an alkali metal ion, an earth alkali metal ion, a transition metal ion such as Ti or a quaternary ammonium ion
  • the organic groups R in the trimerization catalyst compound according to formula I are identical.
  • the organic groups may be identical and for example selected from isopropyl groups (see formula II).
  • Titanium (IV) isopropoxide also commonly referred to as titanium tetraisopropoxide or TTIP, is a chemical compound with the formula Ti[OCH(CH 3 ) 2 ]4.
  • the trimerization catalyst composition of the present invention comprises further a monool/polyol composition wherein the polyol/monool composition is an isocyanate reactive agent which comprises polyester and/or poly ether polyols having an average molecular weight of preferably 32-6000 and an average nominal functionality of preferably 1-8.
  • the polyol/monool composition is an isocyanate reactive agent which comprises polyester and/or poly ether polyols having an average molecular weight of preferably 32-6000 and an average nominal functionality of preferably 1-8.
  • the trimerization catalyst composition of the present invention comprises further one or more surfactants and/or one or more flame retardants and/or one or more antioxidants and/or one or more auxiliary blowing agents (not being water) and/or one or more urethane catalysts and/or one or more auxiliary trimerisation catalysts (other than the trimerisation catalyst compound according to the invention).
  • the present invention further relates to a process for making a polyisocyanurate- polyurethane comprising foam (PIR-PUR), said process comprising combining and mixing at an isocyanate index of at least more than 100, preferably 180 or higher, more preferably higher than 250:
  • a polyisocyanate composition comprising polyisocyanate compounds
  • R is an organic group which is selected from an hydrocarbyl group which hydrocarbyl groups having 1-4 carbon atoms
  • the trimerisation catalyst compound used in the process for making a PIR-PUR foam according to the invention is present in an amount such that the number of catalyst equivalents over the number of isocyanate equivalents ranges from 0.001 to 0.4, preferably in an amount from 0.01 to 0.26, or from 0.01 to 0.24, or from 0.02 to 0.2.
  • the one or more isocyanate reactive compounds used in the process for making a PIR-PUR foam according to the invention is selected from monools selected from methanol, ethanol, propanol, butanol, phenol, cyclohexanol and hydrocarbon monools having an average molecular weight of 200-5000 like aliphatic and polyether monools and/or polyols selected from ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, trimethylol propane, sorbitol, sucrose, glycerol, ethanediol, propanediol, butanediol, pentanediol, hexanediol, aromatic and/or aliphatic polyols having a molecular weight of up to 8000, preferably 200-6000 polyester polyols having an average molecular weight of 200-8000,
  • trimerization catalyst composition comprising at least one trimerization catalyst compound selected from one or more organic alkoxides corresponding to the formula (I):
  • - M is selected from an alkali metal ion, an earth alkali metal ion, a transition metal ion such as Ti or a quaternary ammonium ion c) optionally one or more surfactants, one or more flame retardants, water, one or more antioxidants, one or more auxiliary blowing agents, one or more urethane catalysts, one or more auxiliary trimerisation catalysts, or combinations thereof
  • isocyanate-reactive compounds and "isocyanate-reactive hydrogen atoms" as used herein for the purpose of calculating the isocyanate index refers to the total of active hydrogen atoms in hydroxyl and amine groups present in the isocyanate reactive compounds; this means that for the purpose of calculating the isocyanate index at the actual polymerisation process one hydroxyl group is considered to comprise one reactive hydrogen, one primary amine group is considered to comprise one reactive hydrogen and one water molecule is considered to comprise two active hydrogens.
  • Reaction system a combination of compounds wherein the polyisocyanates are kept in one or more containers separate from the isocyanate-reactive components.
  • Polyisocyanurate comprising material refers to a material composition comprising urethane and isocyanurate structures (PIR-PUR) made at an isocyanate index 180 or higher, more preferably at an isocyanate index higher than 250.
  • Open cell content of a foam is measured using a pycno meter according to ISO 4590
  • the trimerization catalyst compound may be selected from potassium ethoxide, sodium ethoxide, potassium methoxide, sodium methoxide, potassium tert-butoxide, titanium isopropoxide and mixtures thereof suitable for making a polyisocyanurate comprising rigid foam.
  • the trimerization catalyst composition according to the invention may further comprise a solvent. According to embodiments the trimerization catalyst composition according to the invention may further comprise a monool/polyol composition.
  • polyol/monool composition is suitable for use as isocyanate reactive agent and preferably comprises polyester and/or polyether polyols having an average molecular weight of preferably 32-6000 and an average nominal functionality of preferably 1-8.
  • the trimerization catalyst composition according to the invention may further comprise optionally one or more surfactants, one or more flame retardants, water, one or more antioxidants, one or more auxiliary blowing agents, one or more urethane catalysts, one or more auxiliary trimerisation catalysts (other than the trimerisation catalyst compound according to the invention), or combinations thereof.
  • trimerization catalyst composition comprising at least a trimerization catalyst compound
  • an isocyanate-reactive composition comprising one or more isocyanate reactive compounds
  • trimerization catalyst compound is selected from compounds which comprise an alkoxy group and correspond to the formula (I)
  • ⁇ R is an organic group which is selected from an hydrocarbyl group which hydrocarbyl groups having less than 5 carbon atoms, preferably 1-4 carbon atoms,
  • ⁇ x is a number being defined by the oxidation state of M ⁇ M is selected from an alkali metal ion, an earth alkali metal ion, a transition metal ion such as Ti and/or a quaternary ammonium ion
  • the trimerisation catalyst compound should be present in the foam formulation in a catalytically effective amount, preferably the trimerisation catalyst compound is present in amounts the trimerisation catalyst compound is present in an amount such that the number of catalyst equivalents over the number of isocyanate equivalents ranges from 0.001 to 0.4, preferably in an amount from 0.01 to 0.26, or from 0.01 to 024, or from 0.02 to 0.2.
  • the trimerisation catalyst compound is present in an amount such that the number of catalyst equivalents over the number of isocyanate equivalents ranges from 0.001 to 0.4, preferably in an amount from 0.01 to 0.26, or from 0.01 to 024, or from 0.02 to 0.2.
  • the polyisocyanate compounds used in the process for making a PIR-PUR foam according to the invention are selected from organic isocyanates containing a plurality of isocyanate groups including aliphatic isocyanates such as hexamethylene diisocyanate and more preferably aromatic isocyanates such as m- and p-phenylene diisocyanate, tolylene-2,4- and 2,6-diisocyanates, diphenylmethane-4,4'- diisocyanate, chlorophenylene-2,4-diisocyanate, naphthylene-l ,5-diisocyanate, diphenylene-4,4'-diisocyanate, 4,4'-diisocyanate-3,3'-dimethyldiphenyl, 3- methyldiphenylmethane-4,4'-diisocyanate and diphenyl ether diisocyanate, cycloaliphatic diisocyanates such as
  • Preferred polyisocyanate compositions of the present invention are those wherein the polyisocyanate is an aromatic diisocyanate or polyisocyanate of higher functionality in particular crude mixtures of methylene bridged polyphenyl polyisocyanates containing diisocyanates, triisocyanate and higher functionality polyisocyanates.
  • Methylene bridged polyphenyl polyisocyanates e.g. Methylene diphenyl diisocyanate, abbreviated as MDI
  • MDI Methylene diphenyl diisocyanate
  • suitable polyisocyanate compositions may include isocyanate ended prepolymers made by reaction of an excess of a diisocyanate or higher functionality polyisocyanate with a hydroxyl ended polyester or hydroxyl ended polyether and products obtained by reacting an excess of diisocyanate or higher functionality polyisocyanate with a monomeric polyol or mixture of monomeric polyols such as ethylene glycol, trimethylol propane or butane-diol.
  • One preferred class of isocyanate-ended prepolymers are the isocyanate ended prepolymers of the crude mixtures of methylene bridged polyphenyl polyisocyanates containing diisocyanates, triisocyanates and higher functionality polyisocyanates.
  • the polyisocyanate compounds in the polyisocyanate composition are selected from a toluene diisocyanate, a methylene diphenyl diisocyanate or a polyisocyanate composition comprising a methylene diphenyl diisocyanate or a mixture of such polyisocyanates.
  • the one or more isocyanate reactive compounds are selected from monools and/or polyols such as glycols, high molecular weight poly ether polyols and polyester polyols, mercaptans, carboxylic acids such as polybasic acids, amines, polyamines, components comprising at least one alcohol group and at least one amine group such as polyaminepolyols, urea and amides.
  • monools and/or polyols such as glycols, high molecular weight poly ether polyols and polyester polyols, mercaptans, carboxylic acids such as polybasic acids, amines, polyamines, components comprising at least one alcohol group and at least one amine group such as polyaminepolyols, urea and amides.
  • the isocyanate reactive component is selected from monools or polyols which have an average nominal hydroxy functionality of 1-8 and an average molecular weight of 32-8000 and mixtures of said monools and/or polyols.
  • the isocyanate reactive component is selected from monools selected from methanol, ethanol, propanol, butanol, phenol, cyclohexanol and hydrocarbon monools having an average molecular weight of 200-5000 like aliphatic and polyether monools and/or polyols selected from ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, trimethylol propane, sorbitol, sucrose, glycerol, ethanediol, propanediol, butanediol, pentanediol, hexanediol, aromatic and/or aliphatic polyols having a molecular weight of up to 8000, preferably 200-6000 polyester polyols having an average molecular weight of 200-8000, preferably 200-6000, polyether polyester polyols having an average molecular weight of 200-
  • the isocyanate index ranges from at least more than 100, preferably an isocyanate index of 180 or higher, more preferably at an isocyanate index higher than 250.
  • the isocyanate index may range from 150 to 650, from 150 to 600, or from 180 to 500.
  • the blowing agent may be selected from isobutene, dimethyl ether, water, methylene chloride, acetone, chlorofluorocarbons (CFCs), hydrofluorocarbons (HFCs), hydrochlorofluorocarbons (HCFCs), and hydrocarbons such as pentane.
  • the amount of blowing agent used can vary based on, for example, the intended use and application of the foam product and the desired foam stiffness and density.
  • the blowing agent may be present in amounts from 1 to 80 parts by weight (pbw) per hundred weight parts isocyanate reactive compounds (polyol) including the weight contribution of the catalyst diluent, more preferably from 5 to 60 pbw.
  • one or more urethane catalyst compounds may be added if needed although the catalyst according to the invention is suitable for both polyurethane formation and polyisocyanurate formation.
  • Said urethane catalyst compound may be added to the formulation in an amount such that the number of urethane catalyst equivalents over the number of isocyanate equivalents ranges from 0 to 0.2, preferably in an amount from 0 to 0.04, or from 0 to 0.026, or from 0 to 0.01
  • the present invention further relates to a polyisocyanurate comprising foam made using the process according to the invention and making use of the trimerization catalyst disclosed in the present invention (see formula I) and the use of said foam as (thermal) insulating (rigid) foam.
  • the polyisocyanurate comprising material according to the invention has a free rise density in the range between 25 kg/m 3 up to 60 kg/m 3 , preferably in the range 30 kg/m 3 up to 55 kg/m 3 (however it may have a free rise density up to 100 kg/m 3 and higher for some applications), a thermal conductivity in the range 20 up to 30 mW/mK, preferably 20 up to 25 mW/mK and having a closed cell content higher than 75% calculated on the total amount of closed and open cells being present in the material.
  • the polyisocyanurate comprising material according to the invention has a compression hardness at 10% strain between 80 and 300 kPa, measured in three dimensions (thickness, length and width according to IS0844).
  • Figure 2 illustrates the PIR/PUR ratio in the skin for a polyisocyanurate comprising insulation foam fabricated according to the present invention and for a polyisocyanurate comprising insulation foam not fabricated according to the invention (comparative) using an isocyanate index of 265 and 300.
  • Example 1 Fabrication of a polyisocyanurate comprising insulation foam using isocyanate index 265
  • Table 1 Figure 1 illustrates the PIR/PUR ratio in the core for example 1 and for the comparative example fabricated using an isocyanate index of 265. The increase in PIR conversion for example 1 compared to the comparative example 1 is significant.
  • Figure 1 illustrates the PIR/PUR ratio in the core for example 2 and for the comparative example fabricated using an isocyanate index of 300. The increase in PIR conversion for example 2 compared to the comparative example 2 is significant.
  • Figure 3 illustrates the increase in PIR conversion in the core and the skin for a polyisocyanurate comprising insulation foam fabricated using an isocyanate index of respectively 300 (example 1) according the according to the present invention compared to a polyisocyanurate comprising insulation foam not according to the invention fabricated using an isocyanate index of 300 (wherein the comparative foam is taken as 100%).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
PCT/EP2015/057079 2014-04-03 2015-03-31 Isocyanate trimerization catalyst for making polyisocyanurate comprising foams Ceased WO2015150408A1 (en)

Priority Applications (7)

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BR112016021581-8A BR112016021581B1 (pt) 2014-04-03 2015-03-31 Processo para produzir um poli-isocianuratopoliuretano compreendendo espuma rígida, composição reativa com isocianato, sistema reativo, poliisocianurato compreendendo material, e, uso de um poli-isocianurato compreendendo material
RU2016143070A RU2707290C2 (ru) 2014-04-03 2015-03-31 Катализатор тримеризации изоцианата для изготовления полиизоцианурат-содержащих пеноматериалов
US15/301,411 US11548973B2 (en) 2014-04-03 2015-03-31 Isocyanate trimerization catalyst for making polyisocyanurate comprising foams
CA2941348A CA2941348C (en) 2014-04-03 2015-03-31 Process for preparing polyisocyanurate-polyurethane foams
CN201580018197.4A CN106459335B (zh) 2014-04-03 2015-03-31 用于制造含聚异氰脲酸酯泡沫体的异氰酸酯三聚催化剂
EP15741883.1A EP3126423B1 (en) 2014-04-03 2015-03-31 Process for preparing polyurethane-polyisocyanurate foams
PL15741883T PL3126423T3 (pl) 2014-04-03 2015-03-31 Sposób wytwarzania pianek poliuretanowo-poliizocyjanuranowych

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024133871A1 (en) 2022-12-23 2024-06-27 Recticel Pir chemical recycling by alkaline cleavage

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107627527B (zh) * 2017-09-30 2019-09-13 中国科学院长春应用化学研究所 带有亲水性单元的共聚聚合物泡沫的制备方法
BR112020022108A2 (pt) * 2018-05-14 2021-01-26 Huntsman International Llc composição reativa, método para reduzir a viscosidade de uma composição reativa, processo para produzir uma espuma rígida, espuma rígida, e, uso da espuma rígida.
KR102065251B1 (ko) 2018-06-07 2020-01-10 대한폴리텍(주) 준불연 단열재의 제조방법
JP2022517512A (ja) 2019-01-22 2022-03-09 コベストロ・インテレクチュアル・プロパティ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング・アンド・コー・カーゲー 二重硬化ウレタンポリマーおよび二重硬化イソシアヌレートポリマーに基づく複合材料
EP3997146A1 (en) * 2019-07-12 2022-05-18 Dow Global Technologies LLC Transition metal chelating polyol blend for use in a polyurethane polymer

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1498506A (en) * 1975-04-14 1978-01-18 Eurane Europ Polyurethan Flexible cellular polyurethane foam compositions having increased flame retardance
US4256841A (en) * 1978-06-10 1981-03-17 Basf Aktiengesellschaft Manufacture of light-stable polyurethane integral foams
US4568703A (en) * 1984-07-27 1986-02-04 Bp Chemicals Limited Process for the production of polymers containing isocyanurate and or oxazolidone linkages
EP1004607A1 (en) 1998-11-23 2000-05-31 Air Products And Chemicals, Inc. Trimerization catalysts for making polyisocyanurate foams
US20050245629A1 (en) 2002-07-18 2005-11-03 Grigsby Robert A Jr Catalyst combinations for increasing trimer content in foam
US20110124756A1 (en) * 2009-05-21 2011-05-26 Huntsman International Llc Rigid polyurethane foam and system and method for making the same
US20110201709A1 (en) 2008-11-10 2011-08-18 Dow Global Technologies Llc Isocyanate trimerisation catalyst system, a precursor formulation, a process for trimerising isocyanates, rigid polyisocyanurate/polyurethane foams made therefrom, and a process for making such foams
US20110201708A1 (en) 2008-11-10 2011-08-18 Dow Global Technologies Llc Isocyanate trimerisation catalyst system, a precursor formulation, a process for trimerising isocyanates, rigid polyisocyanurate/polyurethane foams made therefrom, and a process for making such foams
US20110201707A1 (en) 2008-11-10 2011-08-18 Dow Global Technologies Llc Isocyanate trimerisation catalyst system, a precursor formulation, a process for trimerising isocyanates, rigid polyisocyanurate/polyurethane foams made therefrom, and a process for making such foams

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8712363D0 (en) * 1987-05-26 1987-07-01 Ici Plc Polyisocyanurate rigid foams
US5151216A (en) * 1991-11-12 1992-09-29 Martin Marietta Corporation High temperature ablative foam
RU2010808C1 (ru) * 1992-03-18 1994-04-15 Научно-исследовательский институт механики и физики при Саратовском государственном университете Композиция для получения жесткого пенополиуретана
UA80927C2 (en) * 2006-08-04 2007-11-12 Composition for the preparation of rigid polyurethane foam
ITMI20081867A1 (it) * 2008-10-22 2010-04-22 Dow Global Technologies Inc Processo per lapreparazione di schiume poliuretaniche rigide a celle chiuse
ES2561042T3 (es) 2008-11-10 2016-02-24 Dow Global Technologies Llc Un sistema catalítico de trimerización de isocianato, una formulación precursora, un procedimiento para trimerizar isocianatos, espumas rígidas de poliisocianurato/poliuretano preparadas a partir del mismo y un procedimiento para preparar dichas espumas
JP2014520909A (ja) * 2011-06-29 2014-08-25 ダウ グローバル テクノロジーズ エルエルシー ポリイソシアヌレート硬質フォームの生強度を改善させるためのポリオール配合物

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1498506A (en) * 1975-04-14 1978-01-18 Eurane Europ Polyurethan Flexible cellular polyurethane foam compositions having increased flame retardance
US4256841A (en) * 1978-06-10 1981-03-17 Basf Aktiengesellschaft Manufacture of light-stable polyurethane integral foams
US4568703A (en) * 1984-07-27 1986-02-04 Bp Chemicals Limited Process for the production of polymers containing isocyanurate and or oxazolidone linkages
EP1004607A1 (en) 1998-11-23 2000-05-31 Air Products And Chemicals, Inc. Trimerization catalysts for making polyisocyanurate foams
US20050245629A1 (en) 2002-07-18 2005-11-03 Grigsby Robert A Jr Catalyst combinations for increasing trimer content in foam
US20110201709A1 (en) 2008-11-10 2011-08-18 Dow Global Technologies Llc Isocyanate trimerisation catalyst system, a precursor formulation, a process for trimerising isocyanates, rigid polyisocyanurate/polyurethane foams made therefrom, and a process for making such foams
US20110201708A1 (en) 2008-11-10 2011-08-18 Dow Global Technologies Llc Isocyanate trimerisation catalyst system, a precursor formulation, a process for trimerising isocyanates, rigid polyisocyanurate/polyurethane foams made therefrom, and a process for making such foams
US20110201707A1 (en) 2008-11-10 2011-08-18 Dow Global Technologies Llc Isocyanate trimerisation catalyst system, a precursor formulation, a process for trimerising isocyanates, rigid polyisocyanurate/polyurethane foams made therefrom, and a process for making such foams
US20110124756A1 (en) * 2009-05-21 2011-05-26 Huntsman International Llc Rigid polyurethane foam and system and method for making the same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024133871A1 (en) 2022-12-23 2024-06-27 Recticel Pir chemical recycling by alkaline cleavage

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BR112016021581A2 (https=) 2017-08-15
EP3126423A1 (en) 2017-02-08
EP3126423B1 (en) 2017-12-20
US11548973B2 (en) 2023-01-10
RU2016143070A (ru) 2018-05-04
CN106459335A (zh) 2017-02-22
CA2941348C (en) 2019-02-05
US20170198082A1 (en) 2017-07-13
CA2941348A1 (en) 2015-10-08
PL3126423T3 (pl) 2018-04-30
RU2707290C2 (ru) 2019-11-26
CN106459335B (zh) 2020-02-14
RU2016143070A3 (https=) 2018-10-17

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