WO2024022832A1 - Composition d'amino-amide tertiaire utile dans la fabrication de polymères de polyuréthane - Google Patents

Composition d'amino-amide tertiaire utile dans la fabrication de polymères de polyuréthane Download PDF

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WO2024022832A1
WO2024022832A1 PCT/EP2023/069424 EP2023069424W WO2024022832A1 WO 2024022832 A1 WO2024022832 A1 WO 2024022832A1 EP 2023069424 W EP2023069424 W EP 2023069424W WO 2024022832 A1 WO2024022832 A1 WO 2024022832A1
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acid
acetamide
ethoxy
methyl
ethyl
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PCT/EP2023/069424
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English (en)
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Juan Jesus Burdeniuc
Janine DUBBERT
David ZUGELL
Renee Jo Keller
James Douglas Tobias
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Evonik Operations Gmbh
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Publication of WO2024022832A1 publication Critical patent/WO2024022832A1/fr

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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
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • 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
    • C08G18/1841—Catalysts containing secondary or tertiary amines or salts thereof having carbonyl groups which may be linked to one or more nitrogen or oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271—Hydroxyamines
    • C08G18/3275—Hydroxyamines 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
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4072—Mixtures of compounds of group C08G18/63 with other macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
    • C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201—Oxygen-containing compounds
    • B01J31/0204—Ethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0237—Amines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
    • B01J31/0247—Imides, amides or imidates (R-C=NR(OR))
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
    • 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
    • C08G2110/005—< 50kg/m3

Definitions

  • the field of invention is a composition and the use of new tertiary amino-amides as catalysts useful for the production of polyurethane foam.
  • Polyurethane foam compositions are typically prepared by reacting an isocyanate and a premix which consists of isocyanate-reactive components such as a polyol.
  • the premix optionally also contains other components such as water, flame retardants, blowing agents, foam-stabilizing surfactants, and catalysts to promote the reactions of isocyanate with polyol to make urethane, with water to make CO 2 and urea, and with excess isocyanate to make isocyanurate (trimer).
  • the blowing agent in the premix is usually classified as chemical blowing agents or physical blowing agents.
  • a chemical blowing agent is typically a substance that can produce gas when all the reactive components are mixed to produce a polyurethane foam.
  • Examples of chemical blowing agents include water and formic acid. Water is the most common chemical blowing agent that can react with the isocyanate functionality to produce carbon dioxide. Water is commonly used in many types of polyurethane materials including rigid, semi-rigid and flexible polyurethane foam. Formic acid can also be used as blowing agent producing a mixture of carbon dioxide and carbon monoxide.
  • Physical blowing agents on the other hand are liquids or gases with a boiling point sufficiently low to be vaporized by the heat released during the polymerization reaction.
  • blowing agents useful in the production of insulating polyurethane foam include but are not limited to hydrofluorocarbons, hydrofluoroolefins, hydrofluorochloroolefins, hydrochlorofluorocarbons, formates, ketones such as acetone and hydrocarbons such as pentane and cyclopentane.
  • halogen containing molecules such as chrolofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs) are far less flammable and safer to use in foam production. However, they either harm the ozone layer or contribute in other ways to global warming.
  • CFCs chrolofluorocarbons
  • HCFCs hydrochlorofluorocarbons
  • HFCs hydrofluorocarbons
  • HFCs hydrofluorofluoroolefins
  • HCFOs hydrochlorofluoroolefins
  • polyurethane foam that are either flexible, semi-flexible or rigid.
  • Polyurethane foam materials of various characteristics can be useful in multiple applications including flexible molded foam useful in car interior applications, flexible slabstock foam useful in furniture, bedding, carpeting, transportation equipment interior, rigid-spray applied, poured in place, and used in applications such as refrigerators, freezers, hot water heaters, insulation panels, garage doors, entry doors, and other various applications where insulation is desired.
  • US3816339 discloses a polyurethane catalyst consisting of a mixture of N,N- dimethylcyclohexylamine and N-methyl-dicyclohexylamine that has unique characteristics.
  • N,N-dimethylcyclohexylamine is a typical tertiary amine polyurethane catalyst used in large scale for the production of various types of polyurethane foam grade and in particular rigid closed cell polyurethane polymers.
  • US7169823 discloses a method for preparing a polyurethane foam which comprises reacting an organic polyisocyanate and a polyol in the presence of water as a blowing agent, a cell stabilizer, and a tertiary amine amide catalyst composition represented by formula below wherein A, R 1 -R 6 , and n are defined herein and wherein the tertiary amino amide catalyst of formula I is acid-blocked.
  • the ability of the tertiary amine catalyst to selectively promote either blowing or gelling is an important consideration in selecting a catalyst for preparing a particular polyurethane foam. If a catalyst promotes the blowing reaction too quickly, a substantial portion of the CO 2 will be evolved and will bubble out of the formulation before sufficient reaction of the isocyanate with the polyol has occurred, resulting in collapse of the foam and the production of a poor quality foam. On the other hand, if a catalyst promotes the gelling reaction too quickly, a substantial portion of the polymerization will have occurred before sufficient CO 2 has been evolved, resulting in insufficient blowing action and the production of a poor quality foam.
  • Tertiary amine catalysts are generally malodorous and offensive and many are highly volatile due to their low molecular weight.
  • the release of tertiary amine during foam processing may present significant safety and toxicity problems and the release of residual amine during customer handling is undesirable.
  • low vapor pressure-high molecular weight amine catalysts are expected to require very high catalyst usage due to their low N/C ratio making the manufacturing cost very high.
  • the present invention relates to a method for preparing a polyurethane foam which comprises reacting an organic polyisocyanate and a polyol in the presence of polyurethane additives comprising blowing agent, a cell stabilizer, cross-linkers, and a catalyst composition comprising at least one compound represented by formula (I): where Ri, R 2 and R 3 are a C1-C3 alkyl or C 2 -C 6 alkenyl group linear or branched and R 4 is either hydrogen or Ci-C 6 alkyl or C 2 -C 6 alkenyl group linear or branched.
  • R1, R 2 , and R 3 are each independently methyl groups and R 4 is hydrogen.
  • the instant invention can solve problems associated with conventional foam precursors by allowing the use of the inventive catalysts thereby improving and reducing the odor of the finished foam as well as providing good catalytic activity to yield polyurethane foam products with excellent physical properties.
  • the present invention provides a polyurethane catalyst and a polyol premix composition having the following benefits: a) provides a tertiary amine catalyst bearing amide functionality capable of providing good foam kinetics and cure including surface cure; b) improves the odor qualities as the amide does not participate in chain termination that results in detrimental foam physical properties; c) provides optimum catalytic activity and foam physical properties comparable with existing standards.
  • the catalyst composition is defined as at least one compound represented by formula (I): where R1, R 2 and R 3 are a Ci-C 3 alkyl or C 2 -C 6 alkenyl group linear or branched and R 4 is either hydrogen or Ci-C 6 alkyl or C 2 -C 6 alkenyl group linear or branched.
  • R1, R 2 , and R 3 are each independently methyl groups and R 4 is hydrogen.
  • a process includes providing a premix comprising at least one catalyst compound represented by formula (I) and contacting the pre-mix with at least one physical blowing agent including hydrofluorocarbons, hydrofluoroolefins, hydrofluorochloroolefins, hydrochlorofluorocarbons, formates, ketones such as acetone, hydrocarbons such as pentane and cyclopentane or chemical blowing agents such as water or formic acid.
  • a polyurethane composition includes a polyol component, a catalyst composition, and an isocyanate component.
  • the catalyst composition includes at least one compound represented by formula (I).
  • a polyurethane product includes at least one catalyst compound represented by formula (I) and an isocyanate component.
  • a catalyst composition includes at least one catalyst compound represented by formula (I) and/or a tertiary amine catalyst containing an isocyanate reactive group.
  • a catalyst composition includes at least one catalyst compound represented by formula (I) and/or a tertiary amine catalyst containing no isocyanate reactive group.
  • Isocyanate Index The actual amount of polyisocyanate used divided by the theoretically required stoichiometric amount of polyisocyanate required to react with all the active hydrogen in the reaction mixture, multiplied by 100. Also known as (Eq NCO/Eq of active hydrogen)x100. pphp - parts by weight per hundred weight parts polyol.
  • Polycat®-5 A commercial catalyst supplied by Evonik Corporation with a chemical name pentamethyldiethylenetriamine
  • Polycat®-8 - A commercial catalyst supplied by Evonik Corporation with a chemical name dimethylaminocyclohexane
  • the present invention is directed to a catalyst composition
  • a catalyst composition comprising at least one compound represented by formula (I): where Ri, R 2 and R 3 are a C1-C3 alkyl or C 2 -C 6 alkenyl group linear or branched and R 4 is either hydrogen or Ci-C 6 alkyl or C 2 -C 6 alkenyl group linear or branched.
  • R1, R 2 , and R 3 are each independently methyl groups and R 4 is hydrogen.
  • the present invention provides a polyurethane catalyst and a polyol premix composition having the following benefits: a) provides a tertiary amine catalyst bearing amide functionality capable of providing good foam kinetics and cure including surface cure; b) improves the odor qualities as the amide does not participate in chain termination that results in detrimental foam physical properties; c) provides optimum catalytic activity and foam physical properties comparable with existing standards.
  • the present invention provides a method for preparing a polyurethane foam which comprises contacting at least one polyisocyanate with at least one active hydrogen-containing compound in the presence of at least one blowing agent and an effective amount of a catalyst composition as defined above in formula (I) in combination with a metal catalyst and/or a tertiary amine having or not an isocyanate reactive group.
  • polyurethane foams can be produced with the novel catalyst system and novel compositions of the present invention by several methods known within the art.
  • any amount of catalyst composition as defined in formula (I) above can be used in the compositions of the present invention.
  • the present invention discloses several types of ranges. These include, but are not limited to, a range of temperatures; a range of number of atoms; a range of foam density; a range of Isocyanate Index; and a range of pphp for the blowing agent, water, surfactant, flame retardant, and catalyst composition as defined in formula (I) above.
  • the present invention discloses a range of any type, which discloses individually each possible number that such a range could reasonably encompass, as well as any sub-ranges and combinations of sub-ranges encompassed therein.
  • the present invention discloses a chemical moiety having a certain number of carbon atoms it will disclose individually every possible number that such a range could encompass.
  • R 1 and R 2 are each independently C1-3 alkyl linear or branched, C 2 -C 6 alkenyl linear or branched mean for example that an alkyl group having up to 3 carbon atoms, or in alternative language a C1-3 alkyl group, as used herein, refers to a “R 1 ” or “R 2 ” group that can be selected independently from an alkyl group having 1 , 2, or 3 carbon atoms, as well as a range between these two numbers for example, a C 2 to C 3 alkyl group.
  • the catalyst composition as defined in formula (I) is present in an amount preferably from about 0.05 to about 10 pphp, for example, the pphp in the present invention can be selected from about 0.05, about 0.06, about 0.07, about 0.08, about 0.09, about 0.1 , about 0.2, about 0.3, about 0.4, about 0.5, about 0.6, about 0.7, about 0.8, about 0.9, about 1 , about 2, about 3, about 4, about 5, about 6, about 7, about 8, about 9, or about 10.
  • all other ranges disclosed herein should be interpreted in a manner similar to these two examples.
  • the catalyst compositions can be used to make rigid foams (foam that is unable to bend or be forced out of shape) having a density of about 0.5 lb/ft 3 to about 5 lb/ft 3 , about 1 lb/ft 3 to about 4 lb/ft 3 and in some cases about 2 lb/ft 3 to about 3 lb/ft 3 .
  • the catalyst compositions can be used to make close cell rigid foam such as those typically used in spray foam insulation and appliances having desirable physical properties including dimensional stability, adhesion, friability, thermal insulation and compression strength.
  • the catalyst compositions can be used to make rigid foams having a density of about 0.5 lb/ft 3 to about 5 lb/ft 3 , about 1 lb/ft 3 to about 4 lb/ft 3 and in some cases about 2 lb/ft 3 to about 3 lb/ft 3 . Density can be measured in accordance with ASTM D3574 Test A.
  • the catalyst compositions can be used to make flexible foam including flexible slabstock foam and flexible molded foam.
  • Flexible molded foams of the invention are characterized by excellent physical properties typically have target density (ASTM 3574-A) with range of about 28 to about 80 kg/m 3 , air flow (ASTM 3574-G) with range of about 40 to about 120L/M, ILDs (indentation load deflection method ASTM 3574-B1) with range of about 150 to about 600 N, support factor (ASTM 3574-B1) with range of about 2.5 to about 3.5, preferably about 3, and resilience (ASTM 3574-H) range of about 40 to about 80%.
  • target density ASTM 3574-A
  • ASTM 3574-G air flow
  • ILDs indentation load deflection method ASTM 3574-B1 with range of about 150 to about 600 N
  • support factor ASTM 3574-B1
  • ASTM 3574-H support factor
  • resilience ASTM 3574-H
  • the catalyst composition as defined in formula (I) preferably comprises at least one member selected from the group consisting of 2-[2-(dimethylamino)ethoxy]-N-methyl- acetamide, 2-[2-(dimethylamino)ethoxy]-/V,/V- diethyl- acetamide, 2-[2-(dimethylamino)ethoxy]-/V,/V-dipropyl- acetamide, 2-[2- (dimethylamino)ethoxy]-/V,/V-dibutyl- acetamide, 2-[2-(dimethylamino)ethoxy]-/V,/V- dipentyl- acetamide, 2-[2-(dimethylamino)ethoxy]-/V,/V-dihexyl- acetamide, 2-[2- (dimethylamino)ethoxy]-/V-methyl-N-ethyl-acetamide
  • the catalyst composition as defined in formula (I) can be used as the sole catalyst or alternatively in combination with at least one tertiary amine catalyst.
  • the tertiary amine catalyst can have at least one isocyanate reactive group or alternatively it can be a conventional tertiary amine catalyst having no-isocyanate reactive groups.
  • isocyanate reactive groups comprise a primary hydroxyl group, a secondary hydroxyl group, a primary amine group, a secondary amine group, a urea group or an amide group.
  • tertiary amine catalysts having an isocyanate reactive group preferably include, but are not limited to N, N-bis(3- dimethylaminopropyl)-N-isopropanolamine, N, N-dimethylaminoethyl-N'-methyl ethanolamine, N, N, N'-trimethylaminopropylethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dimethyl-N', N'-2-hydroxy(propyl)-1 ,3-propylenediamine, dimethylaminopropylamine, (N, N-dimethylaminoethoxy) ethanol, methyl-hydroxy-ethyl- piperazine, bis(N, N-dimethyl-3-aminopropyl) amine, N, N-dimethylaminopropyl urea, diethylaminopropyl urea, N, N'-bis(3-di
  • the tertiary amine catalyst component is highly volatile and is not isocyanate-reactive.
  • the tertiary amine catalyst component is a volatile gelling catalyst and preferably is or includes diazobicyclooctane (triethylenediamine), 1 ,8-diazabicycloundec-7-ene, tris(dimethylaminopropyl) amine, dimethylaminocyclohexylamine, bis(dimethylaminopropyl)-N-methylamine, or combinations thereof.
  • the tertiary amine catalyst component is or includes a volatile blowing catalyst and preferably is or includes bis(dimethylaminoethyl)ether, pentamethyldiethylenetriamine, hexamethyltriethylenetetramine, heptamethyltetraethylenepentamine and related compositions and higher permethylated polyamines.
  • the tertiary amine catalyst component preferably is or includes a blowing catalyst having an isocyanate reactive group such as 2-[N- (dimethylaminoethoxyethyl)-N-methylamino]ethanol and related structures, alkoxylated polyamines, imidazole-boron compositions, amino propyl-bis(amino-ethyl) ether compositions, or combinations thereof.
  • an isocyanate reactive group such as 2-[N- (dimethylaminoethoxyethyl)-N-methylamino]ethanol and related structures, alkoxylated polyamines, imidazole-boron compositions, amino propyl-bis(amino-ethyl) ether compositions, or combinations thereof.
  • the catalyst of the present invention can also preferably be acid blocked with an acid including carboxylic acids (alkyl, substituted alkyl, alkylene, aromatic, substituted aromatic) sulfonic acids or any other organic or inorganic acid.
  • carboxylic acids alkyl, substituted alkyl, alkylene, aromatic, substituted aromatic
  • examples of preferable carboxylic acids include mono-acids, di-acids or poly-acids with or without isocyanate reactive groups.
  • Examples of preferable carboxylic acids include formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexyl carboxylic acid, neohexanoic acid, octanoic acid, neooctanoic acid, heptanoic acid, neoheptanoic acid, nonanoic acid, neononanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, neododecanoic acid, myristic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, benzoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid
  • the tertiary amine catalyst component is preferably used in conjunction with a transition metal catalyst.
  • the tertiary amine catalyst component is preferably used with an organotin compound, tin(ll) carboxylate salts, bismuth(lll) carboxylate salts, or combinations thereof.
  • transition metal catalysts such as organotin compounds or bismuth carboxylates can comprise at least one member selected from the group consisting of dibutyltin dilaurate, dimethyltin dilaurate, dimethyltin diacetate, dibutyltin diacetate, dimethyltin dilaurylmercaptide, dibutyltin dilaurylmercaptide, dimethyltin diisooctylmaleate, dibutyltin diisooctylmaleate, dimethyltin bi(2-ethylhexyl mercaptacetate), dibutyltin bi(2-ethylhexyl mercaptacetate), stannous octate, other suitable organotin catalysts, or a combination thereof.
  • Suitable bismuth carboxylate salts preferably include salts of pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexyl carboxylic acid, neohexanoic acid, octanoic acid, neooctanoic acid, heptanoic acid, neoheptanoic acid, nonanoic acid, neononanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, neododecanoic acid, and other suitable carboxylic acids.
  • transition metals of lead (Pb), iron (Fe), zinc (Zn) with pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexyl carboxylic acid, octanoic acid, neooctanoic acid, neoheptanoic acid, neodecanoic acid, neoundecanoic acid, neododecanoic acid, and other suitable carboxylic acids may also be included.
  • the catalyst composition as defined in formula (I) can be produced, for example for the case of 2-[2-(dimethylamino)ethoxy]-N-methyl- acetamide by following this procedure: a fixed bed tubular reactor, equipped with a 10 cc quartz preheat bed, was charged with 8.8 g of a CuO/ZnO/AI 2 O 3 catalyst sold under the name T-4581 material by Siid Chemie, with a typical composition of 61% CuO, 28% ZnO, and 10%. AI 2 O 3 . The reactor was pressurized with nitrogen to 20.7 bar (300 psig), and then vented to ambient. The reactor pressure was maintained by means of a backpressure controller.
  • the nitrogen purge was repeated two additional cycles, followed by three hydrogen purges.
  • the reactor was then fed hydrogen at 500 scc/m and 20.7 bar (300 psig).
  • the reactor was heated, at 1° C/minute with a resistance heater, to 250°C and held at that temperature for 4 hr to reduce the catalyst.
  • the hydrogen flow metered via a mass flow controller, was adjusted to provide a 4/1 molar ratio of hydrogen/dimethylaminoethoxyethanol (DMAEE).
  • DMAEE was fed to the reactor under pressure, via a constant flow syringe pump.
  • MMA was co-fed to the reactor under pressure, via a constant flow syringe pump at an MMA/DMAEE molar ratio of 2/1 .
  • Effluent from the reactor was analyzed by GC to give approximately 12 % of 2-[2- (dimethylamino)ethoxy]-N-methyl- acetamide which was separated and purified by distillation.
  • the catalyst system or compositions of the present invention can preferably further comprise other catalytic materials such as carboxylate salts in any amount.
  • the other catalytic materials are selected from alkali metal salts, alkaline earth metal salts, and quaternary ammonium carboxylate salts including, but are not limited to, potassium formate, potassium acetate, potassium propionate, potassium butanoate, potassium pentanoate, potassium hexanoate, potassium heptanoate, potassium octoate, potassium 2-ethylhexanoate, potassium decanoate, potassium butyrate, potassium isobutyrate, potassium nonante, potassium stearate, sodium octoate, lithium stearate, sodium caprioate, lithium octoate, 2- hydroxypropyltrimethylammonium octoate solution, and the like, or any combination thereof.
  • the amount of the other catalytic materials and salts can range from about 0 pphp to about 20 pphp, about 0.1 pphp to about 15 pphp and in some cases about 0.5 pphp to about 10 pphp.
  • catalyst composition of this invention can include mixtures or combinations of more than one catalyst compound as defined in formula (I). Additionally, in another embodiment the catalyst composition of the present invention can preferably also further comprise at least one urethane catalyst having no isocyanate reactive groups.
  • catalyst compositions can be prepared by combining or contacting the catalyst composition as defined in formula (I) with at least one tertiary amine having or not at least one isocyanate reactive group and optionally with an alkali metal carboxylate salt. This typically occurs in solution form.
  • compositions and methods are described in terms of “comprising” various components or steps, the compositions and methods can also “consist essentially of’ or “consist of’ the various components or steps.
  • Polyisocyanates that are useful in the PIR/PUR foam formation process preferably include, but are not limited to, hexamethylene diisocyanate, isophorone diisocyanate, phenylene diisocyanate, toluene diisocyanate (TDI), diphenyl methane diisocyanate isomers (MDI), hydrated MDI and 1 ,5-naphthalene diisocyanate.
  • TDI toluene diisocyanate
  • MDI diphenyl methane diisocyanate isomers
  • hydrated MDI and 1 ,5-naphthalene diisocyanate hydrated MDI and 1 ,5-naphthalene diisocyanate.
  • 2,4-TDI, 2,6-TDI, and mixtures thereof can be readily employed in the present invention.
  • suitable mixtures of diisocyanates include, but are not limited to, those known in the art as crude MDI, or PAPI, which contain 4,4’-diphenylmethane diisocyanate along with other isomeric and analogous higher polyisocyanates.
  • prepolymers of polyisocyanates comprising a partially pre-reacted mixture of polyisocyanates and polyether or polyester polyol are suitable.
  • the polyisocyanate comprises MDI, or consists essentially of MDI or mixtures of MDI’s.
  • the catalyst system, compositions, and methods of producing PIR/PUR foam of the present invention can be used to manufacture many types of foam.
  • This catalyst system is useful, for example, in the formation of foam products for rigid and flame retardant applications, which usually require a high Isocyanate Index.
  • Isocyanate Index is the actual amount of polyisocyanate used divided by the theoretically required stoichiometric amount of polyisocyanate required to react with all the active hydrogen in the reaction mixture, multiplied by 100.
  • Isocyanate Index (Eq NCO/Eq of active hydrogen)x100, wherein Eq NCO is the number of NCO functional groups in the polyisocyanate, and Eq of active hydrogen is the number of equivalent active hydrogen atoms.
  • Foam products which are produced with an Isocyanate Index from about 10 to about 800 are within the scope of this invention.
  • the Isocyanate Index ranges from about 20 to about 700, from about 30 to about 650, from about 50 to about 600, or from about 70 to about 500.
  • Active hydrogen-containing compounds for use with the foregoing polyisocyanates in forming the polyisocyanurate/polyurethane foams of this invention can be any of those organic compounds having at least two hydroxyl groups such as, for example, polyols.
  • Polyols that are typically used in PIR/PUR foam formation processes include polyalkylene ether and polyester polyols.
  • the polyalkylene ether polyol includes the poly(alkyleneoxide) polymers such as poly(ethyleneoxide) and poly(propyleneoxide) polymers and copolymers with terminal hydroxyl groups derived from polyhydric compounds, including diols and triols, These preferably include, but are not limited to, ethylene glycol, propylene glycol, 1 ,3-butane diol, 1 ,4-butane diol, 1 ,6-hexane diol, neopentyl glycol, diethylene glycol, dipropylene glycol, pentaerythritol, glycerol, diglycerol, trimethylol propane, cyclohexane diol, and sugars such as sucrose and like low molecular weight polyols.
  • poly(alkyleneoxide) polymers such as poly(ethyleneoxide) and poly(propyleneoxide) polymers and copolymers with terminal hydroxyl groups derived from poly
  • Amine polyether polyols can be used in the present invention. These can be prepared when an amine such as, for example, ethylenediamine, diethylenetriamine, tolylenediamine, diphenylmethanediamine, or triethanolamine is reacted with ethylene oxide or propylene oxide.
  • an amine such as, for example, ethylenediamine, diethylenetriamine, tolylenediamine, diphenylmethanediamine, or triethanolamine is reacted with ethylene oxide or propylene oxide.
  • a single high molecular weight polyether polyol, or a mixture of high molecular weight polyether polyols, such as mixtures of different multifunctional materials and/or different molecular weight or different chemical composition materials can be used.
  • polyester polyols can be used, including those produced when a dicarboxylic acid is reacted with an excess of a diol.
  • Non-limiting examples include adipic acid or phathalic acid or phthalic anhydride reacting with ethylene glycol or butanediol.
  • Polyols useful in the present invention can be produced by reacting a lactone with an excess of a diol, for example, caprolactone reacted with propylene glycol.
  • active hydrogen-containing compounds such as polyester polyols and polyether polyols, and combinations thereof, are useful in the present invention.
  • the polyol can have an OH number of about 5 to about 600, about 100 to about 600 and in some cases about 50 to about 100 and a functionality of about 2 to about 8, about 3 to about 6 and in some cases about 4 to about 6.
  • the amount of polyol can range from about 0 pphp to about 100 pphp about 10 pphp to about 90 pphp and in some cases about 20 pphp to about 80 PPhp.
  • suitable blowing agents that can be used alone or in combination preferably include, but are not limited to, water, methylene chloride, acetone, hydrofluorocarbons (HFCs), hydrochlorocarbons (HCCs), hydrofluoroolefins (HFOs), chlorofluoroolefins (CFOs), hydrochloroolefins (HCOs), hydrofluorochloroolefins (HFCOs), hydrochlorofluorocarbons (HCFCs), chloroolefins, formates and hydrocarbons.
  • HFCs hydrofluorocarbons
  • HCCs hydrochlorocarbons
  • HFOs hydrofluoroolefins
  • CFOs chlorofluoroolefins
  • HCOs hydrochloroolefins
  • HFCOs hydrofluorochloroolefins
  • HCFCs hydrochlorofluorocarbons
  • HFCs include, but are not limited to, HFC-245fa, HFC-134a, and HFC-365; illustrative examples of HCFCs include, but are not limited to, HCFC-141 b, HCFC-22, and HCFC-123.
  • Exemplary hydrocarbons include, but are not limited to, n-pentane, iso-pentane, cyclopentane, and the like, or any combination thereof.
  • the blowing agent or mixture of blowing agents comprises at least one hydrocarbon.
  • the blowing agent comprises n-pentane.
  • the blowing agent consists essentially of n-pentane or mixtures of n-pentane with one or more blowing agents.
  • hydrohaloolefin blowing agents are HFO- 1234ze (trans-1 ,3,3,3-Tetrafluoroprop-1-ene), HFO-1234yf (2,3,3, 3-Tetrafluoropropene) and HFCO-1233zd (1-Propene,1-chloro-3,3,3-trifluoro), among other HFOs.
  • the blowing agent component comprises a hydrohaloolefin, preferably comprising at least one of trans-HFO-1234ze and HFCO-1233zd, and optionally a hydrocarbon, fluorocarbon, chlorocarbon, fluorochlorocarbon, halogenated hydrocarbon, ether, fluorinated ether, ester, aldehyde, ketone, carbon dioxide generating material, or combinations thereof.
  • the hydrohaloolefin preferably comprises at least one halooalkene such as a fluoroalkene or chloroalkene containing from 3 to 4 carbon atoms and at least one carbon-carbon double bond.
  • Preferred hydrohaloolefins non-exclusively include trifluoropropenes, tetrafluoropropenes such as (HFO-1234), pentafluoropropenes such as (HFO-1225), chlorotrifluoropropenes such as (HFO-1233), chlorodifluoro propenes, chlorotrifluoropropenes, chlorotetrafluoropropenes, and combinations of these.
  • Other preferred blowing agents comprise the tetrafluoropropene, pentafluoropropene, and chlorotrifluoropropene compounds in which the unsaturated terminal carbon has not more than one fluorine or chlorine substituent. Included are
  • HFO-1234ze 1 ,1 ,3,3-tetrafluoropropene; 1 , 2, 3,3,3- pentafluoropropene (HFO-1225ye); 1 ,1 ,1- trifluoropropene; 1 ,1 ,1 ,3,3-pentafluoropropene (HFO 1225zc); 1 ,1 ,1 ,3,3,3-hexafluorobut-2-ene, 1 ,1 , 2, 3, 3- pentafluoropropene (HFO- 1225yc); 1 ,1 , 1 ,2, 3- pentafluoropropene (HFO-1225yez); 1-chloro-3,3,3-trifluoropropene (HFCO-1233zd); 1 ,1 ,1 ,4,4,4- hexafluorobut-2-ene or combinations thereof, and any and all structural isomers, geometric is
  • Preferred optional blowing agents non-exclusively include water, formic acid, organic acids that produce carbon dioxide when they react with an isocyanate, hydrocarbons; ethers, halogenated ethers; pentafluorobutane; pentafluoropropane; hexafluoropropane; heptafluoropropane; trans- 1 ,2 dichloro-ethylene; methyl formate; 1 -chloro- 1 ,2, 2,2- tetrafluoroethane; 1 ,1-dichloro-1-fluoroethane; 1 ,1 ,1 ,2-tetrafluoroethane; 1 , 1 ,2,2- tetrafluoroethane; 1-chloro-1 ,1 -difluoroethane; 1 ,1 ,1 ,3,3-pentafluorobutane;
  • the blowing agent component is usually present in the polyol premix composition in an amount of from about 1 wt.% to about 30 wt.%, preferably from about 3 wt.% to about 25 wt.%, and more preferably from about 5 wt.% to about 25 wt.%, by weight of the polyol premix composition.
  • the hydrohaloolefin component is usually present in the blowing agent component in an amount of from about 5 wt.% to about 90 wt.%, preferably from about 7 wt.% to about 80 wt.%, and more preferably from about 10 wt.% to about 70 wt.%, by weight of the blowing agent component; and the optional blowing agent is usually present in the blowing agent component in an amount of from about 95 wt.
  • CFCs chlorofluorocarbons
  • a chlorofluorocarbon (CFC) is an alkane in which all hydrogen atoms are substituted with chlorine and fluorine atoms. Examples of CFCs include trichlorofluoromethane and dichlorodifluoromethane.
  • 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 is present in amounts from about 5 to about 80 parts by weight per hundred weight parts of the at least one active hydrogen-containing compound.
  • the blowing agent is present in amounts from about 10 to about 60, from about 15 to about 50, or from about 20 to about 40, parts by weight per hundred weight parts of the at least one active hydrogen-containing compound.
  • the blowing agent is present in amounts from about 5 to about 80 parts by weight per hundred weight parts polyol (pphp), from about 10 to about 60 pphp, from about 15 to about 50 pphp, or from about 20 to about 40 PPhp.
  • water is present in the formulation, for use as a blowing agent or otherwise, water is present in amounts up to about 60 parts by weight per hundred weight parts of the at least one active hydrogen-containing compound.
  • the at least one active hydrogen-containing compound is an at least one polyol, water can range from 0 to about 15 pphp. In another embodiment, water can range from 0 to about 10 pphp, from 0 to about 8 pphp, from 0 to about 6 pphp, or from 0 to about 4 pphp.
  • conventional urethane catalysts having no isocyanate reactive group can preferably be employed to accelerate the reaction to form polyurethanes, and can be used as a further component of the catalyst systems and compositions of the present invention to produce polyisocyanurate/polyurethane foam.
  • Urethane catalysts suitable for use herein preferably include, but are not limited to, metal salt catalysts, such as organotins, and amine compounds, such as triethylenediamine (TEDA), N-methylimidazole, 1 ,2-dimethyl-imidazole, N-methylmorpholine (commercially available as the DABCO® NMM catalyst), N-ethylmorpholine (commercially available as the DABCO® NEM catalyst), triethylamine (commercially available as the DABCO® TETN catalyst), N,N’-dimethylpiperazine, 1 ,3,5-tris(dimethylaminopropyl)hexahydrotriazine (commercially available as the Polycat® 41 catalyst), 2,4,6- tris(dimethylaminomethyl)phenol (commercially available as the DABCO TMR® 30 catalyst), N-methyldicyclohexylamine (commercially available as the Polycat® 12 catalyst), pentamethyldipropylene triamine (commercial
  • the present invention can be used with tertiary amine catalysts having isocyanate reactive groups.
  • the isocyanate reactive groups present in the tertiary amine gelling co-catalyst consist essentially of primary amine, secondary amine, secondary-hydroxyl group, amide and urea.
  • gelling catalysts preferably include N,N-bis(3-dimethylamino-propyl)-N-(2-hydroxypropyl) amine; N,N-dimethyl-N’,N’-bis(2-hydroxypropyl)-1 ,3-propylenediamine; dimethylaminopropylamine (DMAPA); N-methyl-N-2-hydroxypropyl-piperazine, bis(dimethylaminopropyl)amine (POLYCAT® 15), dimethylaminopropylurea and N,N’- bis(3-dimethylaminopropyl) urea (DABCO® NE1060, DABCO® NE1070, DABCO® NE1080 and DABCO® NE1082), 1 ,3-bis(dimethylamino)-2-propanol, 6-dimethylamino- 1-hexanol, N-(3-aminopropyl)imidazole, N-(2-hydroxypropyl
  • blowing co-catalysts containing isocyanate reactive groups that can be used with the above mentioned gelling catalysts preferably include 2- [N-(dimethylaminoethoxyethyl)-N-methylamino]ethanol (DABCO® NE200), N,N,N’- trimethyl-N’-3-aminopropyl-bis(aminoethyl) ether (DABCO® NE300).
  • Suitable urethane catalysts that can be used in combination with the catalyst in the present invention preferably also include acid blocked tertiary amines with acids including carboxylic acids (alkyl, substituted alkyl, alkylene, aromatic, substituted aromatic) sulfonic acids or any other organic or inorganic acid.
  • carboxylic acids alkyl, substituted alkyl, alkylene, aromatic, substituted aromatic
  • Examples of carboxylic acids preferably include mono-acids, di-acids or poly-acids with or without isocyanate reactive groups.
  • Examples of preferable carboxylic acids include formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, neopentanoic acid, hexanoic acid, 2- ethylhexyl carboxylic acid, neohexanoic acid, octanoic acid, neooctanoic acid, heptanoic acid, neoheptanoic acid, nonanoic acid, neononanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, neododecanoic acid, myristic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, benzoic acid, oxalic acid, malonic acid, succinic acid, glutaric
  • the tertiary amine catalyst component can preferably also be used in conjunction with a metal catalyst.
  • the tertiary amine catalyst component is preferably used with an organotin compound, tin(ll) carboxylate salts, bismuth(lll) carboxylate salts, or combinations thereof.
  • metal catalysts such as organotin compounds or bismuth carboxylates can comprise at least one member selected from the group consisting of dibutyltin dilaurate, dimethyltin dilaurate, dimethyltin diacetate, dibutyltin diacetate, dimethyltin dilaurylmercaptide, dibutyltin dilaurylmercaptide, dimethyltin diisooctylmaleate, dibutyltin diisooctylmaleate, dimethyltin bi(2-ethylhexyl mercaptacetate), dibutyltin bi(2-ethylhexyl mercaptacetate), stannous octoate, other suitable organotin catalysts, or a combination thereof.
  • Suitable bismuth carboxylate salts preferably include salts of pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexyl carboxylic acid, neohexanoic acid, octanoic acid, neooctanoic acid, heptanoic acid, neoheptanoic acid, nonanoic acid, neononanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, neododecanoic acid, and other suitable carboxylic acids.
  • salts of metals of lead (Pb), iron (Fe), zinc (Zn) with pentanoic acid, neopentanoic acid, hexanoic acid, 2- ethylhexyl carboxylic acid, octanoic acid, neooctanoic acid, neoheptanoic acid, neodecanoic acid, neoundecanoic acid, neododecanoic acid, and other suitable carboxylic acids may also be included.
  • the present invention can preferably further comprise other catalytic materials such as carboxylate salts in any amount.
  • alkali metal, alkaline earth metal, and quaternary ammonium carboxylate salts include, but are not limited to, potassium formate, potassium acetate, potassium propionate, potassium butanoate, potassium pentanoate, potassium hexanoate, potassium heptanoate, potassium octoate, potassium 2-ethylhexanoate, potassium decanoate, potassium butyrate, potassium isobutyrate, potassium nonante, potassium stearate, sodium octoate, lithium stearate, sodium caprioate, lithium octoate, 2- hydroxypropyltrimethylammonium octoate solution, tetramethylammonium carboxylates, tetralkylammonium carboxylates such as tetramethylammonium pivalate (supplied by Evonik Corporation as DABCO®
  • the urethane catalyst can be present in the formulation from 0 to about 10 pphp, from 0 to about 8 pphp, from 0 to about 6 pphp, from 0 to about 4 pphp, from 0 to about 2 pphp, or from 0 to about 1 pphp. In another embodiment, the urethane catalyst is present from 0 to about 0.8 pphp, from 0 to about 0.6 pphp, from 0 to about 0.4 pphp, or from 0 to about 0.2 pphp.
  • additives can preferably be employed in the PIR/PUR foam formulation to tailor specific properties.
  • These addititives preferably include, but are not limited to, cell stabilizers, flame retardants, chain extenders, epoxy resins, acrylic resins, fillers, pigments, or any combination thereof. It is understood that other mixtures or materials that are known in the art can be included in the foam formulations and are within the scope of the present invention.
  • Cell stabilizers include surfactants such as organopolysiloxanes. Silicon surfactants can be present in the foam formulation in amounts from about 0.5 to about 10 pphp, about 0.6 to about 9 pphp, about 0.7 to about 8 pphp, about 0.8 to about 7 pphp, about 0.9 to about 6 pphp, about 1 to about 5 pphp, or about 1 .1 to about 4 pphp.
  • Useful flame retardants include halogenated organophosphorous compounds and non- halogenated compounds.
  • a non-limiting example of a halogenated flame retardant is trichloropropylphosphate (TCPP).
  • triethylphosphate ester (TEP) and DMMP are non-halogenated flame retardants.
  • flame retardants can be present in the foam formulation in amounts from 0 to about 50 pphp, from 0 to about 40 pphp, from 0 to about 30 pphp, or from 0 to about 20 pphp.
  • the flame retardant is present from 0 to about 15 pphp, 0 to about 10 pphp, 0 to about 7 pphp, or 0 to about 5 pphp.
  • Chain extenders such as ethylene glycol and butane diol can also be employed in the present invention.
  • Ethylene glycol for instance, can also be present in the formulation as a diluent or solvent for the carboxylate salt catalysts of the present invention.
  • One preferred embodiment of the present invention provides for a polyurethane composition comprising the contact product of at least one active hydrogen-containing compound, at least one blowing agent, and at least one catalyst composition as defined above in formula (I).
  • Another preferred embodiment provides a composition comprising the contact product of at least one polyisocyanate, at least one blowing agent, and at least one catalyst composition as defined above in formula (I) used in combination with at least one tertiary amine having at least one isocyanate reactive group.
  • Another preferred embodiment provides a composition comprising the contact product of at least one polyisocyanate, at least one blowing agent, and at least one catalyst composition as defined above in formula (I) used in combination with at least one tertiary amine having no isocyanate reactive group.
  • the composition can further comprise the catalyst composition as defined above in formula (I) with at least one urethane catalyst having no isocyanate reactive group and at least one urethane catalyst having an isocyanate reactive group.
  • the compositions can preferably further comprise at least one additive selected from at least one cell stabilizer, at least one flame retardant, at least one chain extender, at least one epoxy resin, at least one acrylic resin, at least one filler, at least one pigment, or any combination thereof.
  • the present invention provides a method for preparing a polyurethane foam as well as a polyisocyanurate/polyurethane (PIR/PUR) foam which comprises contacting at least one polyisocyanate with at least one active hydrogen-containing compound, in the presence of at least one blowing agent and an effective amount of catalyst composition as defined above in formula (I).
  • PIR/PUR polyisocyanurate/polyurethane
  • PUR as well as PIR/PUR foams can be produced having a density from about 8 Kg/m 3 to about 250 Kg/m 3 (about 0.5 lb/ft 3 to about 15.5 lb/ft 3 ), or from about 24 Kg/m 3 to about 60 Kg/m 3 (about 1.5 lb/ft 3 to about 3.75 lb/ft 3 ).
  • Another preferred embodiment provides a method for preparing a polyurethane foam which comprises contacting at least one polyisocyanate with at least one active hydrogen-containing compound in the presence of at least one blowing agent and an effective amount of catalyst composition as defined above in formula (I), wherein the catalyst composition is present in a tertiary amine having or not an isocyanate reactive group.
  • Another preferred embodiment provides a method for preparing a polyurethane foam which comprises contacting at least one polyisocyanate with at least one active hydrogen-containing compound in the presence of at least one blowing agent and an effective amount of catalyst composition as defined above in formula (I), wherein the catalyst composition is present in combination with a metal catalyst, a tertiary amine having or not an isocyanate reactive group, or a combination thereof.
  • the present invention can be used in a wide range of methods for making rigid closed-cell foams, rigid open cell foams, flexible foam including flexible slabstock foam and flexible molded foam as well as semi-flexible foam and microcellular foam.
  • inventive methods comprise pouring, molding, spraying, among other rigid foam production methods.
  • inventive method relates to a method for making a laminated foam.
  • the inventive foam can be laminated to a wide range of substrates including wood, steel, paper and plastic.
  • the method for preparing PUR as well as PIR/PUR foams also can provide lower ammoniacal odor polyol premix when compared to other commercially available catalyst systems.
  • the catalyst composition as defined above in formula (I) is preferably present in the foam formulation in a catalytically effective amount.
  • the catalyst composition is present in amounts from about 0.05 to about 20 parts by weight per hundred weight parts of the at least one active hydrogen-containing compound, excluding the weight contribution of the catalyst system diluent.
  • the catalyst composition is present in amounts from about 0.4 to about 10 parts by weight per hundred weight parts of the at least one active hydrogen-containing compound, or from about 0.8 to about 8 parts by weight per hundred weight parts of the at least one active hydrogen-containing compound.
  • the catalyst composition is present in amounts from about 0.05 to about 10 parts by weight per hundred weight parts polyol (pphp). In another embodiment, the catalyst composition is present in amounts from about 0.2 to about 9.5 pphp, about 0.4 to about 9 pphp, about 0.6 to about 8.5 pphp, or about 0.8 to about 8 pphp.
  • the components of the foam formulation are contacted substantially contemporaneously.
  • the foam formulation of the present invention can further comprise at least one urethane catalyst.
  • the method of producing PIR/PUR foams can preferably further comprise the presence of at least one additive selected from at least one cell stabilizer, at least one flame retardant, at least one chain extender, at least one epoxy resin, at least one acrylic resin, at least one filler, at least one pigment, or any combination thereof.
  • at least one additive selected from at least one cell stabilizer, at least one flame retardant, at least one chain extender, at least one epoxy resin, at least one acrylic resin, at least one filler, at least one pigment, or any combination thereof.
  • all of the components, including optional components are contacted substantially contemporaneously.
  • a premix of ingredients other than the at least one polyisocyanate are contacted first, followed by the addition of the at least one polyisocyanate.
  • the at least one active hydrogen-containing compound, the at least one blowing agent, the at least one cell stabilizer, and the catalyst composition of the present invention are contacted initially to form a premix.
  • the premix is then contacted with the at least one polyisocyanate to produce PUR or PIR/PUR foams in accordance with the method of the present invention.
  • the premix preferably further comprises at least one urethane catalyst.
  • the premix can preferably further comprise at least one additive selected from at least one cell stabilizer, at least one flame retardant, at least one chain extender, at least one epoxy resin, at least one acrylic resin, at least one filler, at least one pigment, or any combination thereof.
  • One embodiment of the present invention provides a method for preparing a polyurethane, polyisocyanurate, polyisocyanurate/polyurethane foam comprising:
  • a premix comprising: i) at least one polyol; ii) about 1 to about 80 parts by weight per hundred weight parts of the polyol (pphp) blowing agent; iii) about 0.5 to about 10 pphp silicon surfactant; iv) zero to about 60 pphp water; v) zero to about 50 pphp flame retardant; vi) zero to about 10 pphp urethane catalyst; and vii) about 0.05 to about 20 pphp of a catalyst composition as defined above in formula (I); and
  • a catalyst composition comprising at least one compound represented by formula (I): wherein:
  • Ri, R 2 , and R 3 are each independently C1-C3 alkyl, or C 2 -C 6 alkenyl linear or branched;
  • R 4 is hydrogen, Ci-C 3 alkyl, or C 2 -C 6 alkenyl linear or branched.
  • Item 2 The catalyst composition of item 1 , wherein Ri, R 2 , and R 3 are each independently methyl groups and R 4 is hydrogen.
  • Item 3 The catalyst composition of item 1 , wherein the at least one compound represented by formula (I) is selected from the group consisting of 2-[2- (dimethylamino)ethoxy]-N-methyl- acetamide, 2-[2-(dimethylamino)ethoxy]-A/,A/-diethyl- acetamide, 2-[2-(dimethylamino)ethoxy]-A/,A/-dipropyl- acetamide, 2-[2- (dimethylamino)ethoxy]-/V,/V-dibutyl- acetamide, 2-[2-(dimethylamino)ethoxy]-A/,A/- dipentyl- acetamide, 2-[2-(dimethylamino)ethoxy]-A/,A/-dihexyl- acetamide, 2-[2- (dimethylamino)ethoxy]-/V-methyl-N-ethyl-acetamide, 2-
  • Item 4 The catalyst composition of any of items 1-3 further comprising a tertiary amine catalyst having or not an isocyanate reactive group.
  • Item 5 The catalyst composition of item 4, wherein the tertiary amine catalyst has at least one isocyanate reactive group comprising a primary hydroxyl group, a secondary hydroxyl group, a primary amine group, a secondary amine group, a urea group or an amide group.
  • Item 6 The catalyst composition of item 4 or 5, wherein the tertiary amine catalyst is selected from the group consisting of N, N-bis(3-dimethylaminopropyl)-N- isopropanolamine; N, N-dimethylaminoethyl-N'-methyl ethanolamine; N, N, N'- trimethylaminopropylethanolamine; N, N-dimethylethanolamine; N, N- diethylethanolamine; N, N-dimethyl-N', N'-2-hydroxy(propyl)-1 ,3-propylenediamine; dimethylaminopropylamine; (N, N-dimethylaminoethoxy) ethanol; methyl-hydroxy-ethyl- piperazine; bis(N, N-dimethyl-3-aminopropyl) amine; N, N-dimethylaminopropyl urea; diethylaminopropyl urea; N, N'-bis(
  • Item 7 The catalyst composition of any of items 1-6, wherein the catalyst composition is acid blocked with a carboxylic or sulfonic acid.
  • Item 8 The catalyst composition of item 7, wherein the composition is acid blocked with an acid selected from the group consisting of formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexyl carboxylic acid, neohexanoic acid, octanoic acid, neooctanoic acid, heptanoic acid, neoheptanoic acid, nonanoic acid, neononanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, neododecanoic acid, myristic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, benzoic acid, ox
  • Item 9 The catalyst composition of any of items 1-8 further comprising a transition metal catalyst.
  • Item 10 The catalyst composition of claim 9 wherein the transition metal catalyst is an organotin compound, tin(ll) carboxylate salt, bismuth(lll) carboxylate salt, or combination thereof.
  • Item 11 The catalyst composition of any of items 1-10 further comprising catalytic materials selected from the group consisting of potassium formate, potassium acetate, potassium propionate, potassium butanoate, potassium pentanoate, potassium hexanoate, potassium heptanoate, potassium octoate, potassium 2-ethylhexanoate, potassium decanoate, potassium butyrate, potassium isobutyrate, potassium nonante, potassium stearate, sodium octoate, lithium stearate, sodium caprioate, lithium octoate, 2-hydroxypropyltrimethylammonium octoate solution, or any combination thereof.
  • a polyurethane composition comprising the contact product of at least one active hydrogen-containing compound, at least one blowing agent, and the catalyst composition of any of items 1-3.
  • Item 13 The polyurethane composition of item 12, further comprising a tertiary amine having or not an isocyanate reactive group.
  • Item 14 The polyurethane composition of item 12 or 13, further comprising at least one additive selected from at least one cell stabilizer, at least one flame retardant, at least one chain extender, at least one epoxy resin, at least one acrylic resin, at least one filler, at least one pigment, or any combination thereof.
  • Item 15 A method for preparing a polyurethane foam comprising contacting at least one polyisocyanate with at least one active hydrogen-containing compound in the presence of at least one blowing agent and the catalyst composition defined in any of items 1-3.
  • Item 16 The method of item 15, wherein the catalyst composition is present in combination with a metal catalyst, a tertiary amine having or not an isocyanate reactive group, or a combination thereof.
  • the reactor was heated, at 1°C/minute with a resistance heater, to 250°C and held at that temperature for 4 hr to reduce the catalyst.
  • the hydrogen flow metered via a mass flow controller, was adjusted to provide a 4/1 molar ratio of hydrogen/dimethylaminoethoxyethanol (DMAEE).
  • DMAEE was fed to the reactor under pressure, via a constant flow syringe pump.
  • MMA was co-fed to the reactor under pressure, via a constant flow syringe pump at an MMA/DMAEE molar ratio of 2/1 .
  • Effluent from the reactor was analyzed by GC to give approximately 12 % of 2-[2-(dimethylamino)ethoxy]-/V-methyl- acetamide (DMAEMAc) which was separated and purified by distillation.
  • DMAEMAc 2-[2-(dimethylamino)ethoxy]-/V-methyl- acetamide
  • DMAEMAc A crude sample of DMAEMAc was made using the same procedure as described in Example 1. The sample was produced by distillation after removing N,N,N’-trimethyl- aminoethylether (TMAEE) as well as excess starting material (DMAEE) and small amounts of BDMAEE (bis-dimethylaminoethylether) to yield 25 % of crude DMAEMAc.
  • TMAEE N,N,N’-trimethyl- aminoethylether
  • DMAEE excess starting material
  • BDMAEE bis-dimethylaminoethylether
  • Crude DMAEMAc composition is mainly 50-60 % DMAEMAc, 10-20 % N-methyl-N,N- bis(dimethylaminoethoxyethyl)amine, 4-8 % N,N-bis(dimethylaminoethoxyethyl)amine and about 4-6 % 2-[2-(dimethylamino)ethoxy]-/V-methyl-N-(dimethylamino ethoxyethyl)- acetamide.
  • Example 2 A crude sample of DMAEMAc described in Example 2 was distilled off under nitrogen to give a clear liquid composed of DMAEMAc.
  • the sample was produced by distillation after removing N-methyl-N,N-bis(dimethylaminoethoxyethyl)amine, N,N- bis(dimethylaminoethoxyethyl)amine, 2-[2-(dimethylamino)ethoxy]-A/-methyl-N- (dimethylamino ethoxyethyl)-acetamide as well as other heavy impurities.
  • Foaming performance can be evaluated by comparing the foam height versus time for standards and new amine catalyst.
  • Foam height profile can be measured by automated rate of rise equipment, utilizing free-rise cup foam samples with a FOMAT sonar rate-of- rise device (hereafter referred to as a "ROR").
  • the FOMAT device comprises a sonar sensor that measures and records the height in millimeters (mm) of the rising foam sample versus time in seconds (s), directly after mixing all components of the formulation.
  • the FOMAT standard software generates both height versus time plots and velocity versus time plots. These plots are useful for comparing the relative reactivity of different catalyst formulations.
  • Flexible foam can be prepared by combining a total weight of about 300 g of the ingredients in Table 1 other than the isocyanate in a 32-oz (951 ml) paper cup. This premix formulation is then mixed for about 10 seconds at about 6,000 rpm using an overhead stirrer fitted with a 2-inch (5.1 cm) diameter stirring paddle. Sufficient toluene diisocyanate is then added to achieve the desired Isocyanate Index of about 100, and the formulation is mixed well for about another 6 seconds at about 6,000 rpm using the same stirrer. The cup is then placed under the FOMAT sensor. The start time for ROR measurement is automated for the FOMAT and begins directly after the end of the final mixing. Once the cup is placed under the ROR, the chemical mixture begins to polymerize. Since the walls of the cup restrict the expansion in all but the vertical direction, this expansion manifests itself in this experiment as an increase in height with passing time.
  • This increase in height can also be displayed as a rate of changing height (velocity) versus time.
  • TOC Top of the Cup
  • Foam pads were prepared by adding a tertiary amine catalyst to about 302 g of a premix (prepared as in Table 1) in a 32 oz (951 ml) paper cup. The formulation was mixed for about 10 seconds at about 6,000 RPM using an overhead stirrer fitted with a 2-inch (5.1 cm) diameter stirring paddle. The toluene diisocyanate was then added, and the formulation was mixed well for about another 6 seconds at about 6,000 RPM using the same stirrer, after which it was poured into a pre-heated mold at 70°C and demolded after 4 minutes. The foam pads were removed from the mold, hand crushed, weighed and machine crushed at 75% pad thickness. Foam pads were stored under constant temperature and humidity condition for 48 hours before being cut and tested.
  • Table 4 Physical Properties of TDI Polyurethane Flexible Molded Foam with 40 Kg/m 3 Density and Index 100
  • Table 4 shows the ambient and humid aged physical properties of flexible molded polyurethane pads made with the standard reactive gelling/blowing amine catalysts Dabco®33LV/DABCO®BL11 and compared with the new gelling catalysts DMAEMAc (Example 3) and “Crude DMAEMAc” (Example 2) in both cases with blowing catalyst DABCO®NE300.
  • Table 4 shows that the ambient physical properties were very similar providing foam pads with excellent physical properties.
  • Table 4 also shows the physical properties after humid ageing using Volkswagen ageing procedure. The evaluation showed new gelling catalysts Pure-DMAEMAc and Crude-DMAEMAc performed similarly to a standard reactive catalyst DABCO®33LV, Foams made using the inventive catalyst have an overall better performance under humid ageing.
  • Foam pads were prepared by adding a tertiary amine catalyst to about 302 g of a premix (prepared as in Table 1) in a 32 oz (951 ml) paper cup. The formulation was mixed for about 10 seconds at about 6,000 RPM using an overhead stirrer fitted with a 2-inch (5.1 cm) diameter stirring paddle. The toluene diisocyanate was then added, and the formulation was mixed well for about another 6 seconds at about 6,000 RPM using the same stirrer, after which it was poured into a pre-heated mold at 70°C and demolded after 4 minutes. The foam pads were removed from the mold, hand crushed, weighed and machine crushed at 75% pad thickness. Foam pads were stored under constant temperature and humidity condition for 48 hours before being cut and tested.
  • Table 5 Polyurethane TDI Flexible Molded Data l Mold data performed in all cases with 0.17 pphp of blowing amine catalyst N,N,N'-trimethyl-N'-3-aminopropyl- bis(aminoethyl) ether; 2 Dabco®NE1070 a mixture of mono and bis-dimethylaminopropyl urea dissolved in polyethylene glycol-200
  • Mold data performed in all cases with 0.17 pphp of blowing amine catalyst N,N,N'-trimethyl-N'- (3-aminopropyl)-bis(aminoethyl) ether 2 ; Volkswagen ageing procedure: Place samples to be tested in a dry oven at 90’0 for 24 hours for drying. Once dried, age samples for 200 hours 90° C and 100% relative humidity. Samples are then dried after.
  • Table 6 shows the ambient and humid aged physical properties of flexible molded polyurethane pads made with the standard reactive gelling/blowing amine catalysts Dabco®NE1070/DABCO®NE300 and compared with the new gelling catalysts pure-DMAEMAc and crude-DMAEMAc in both cases with blowing catalyst DABCO®NE300.
  • Table 6 shows that the ambient physical properties were very similar providing foam pads with excellent physical properties.
  • Table 6 also shows the physical properties after humid ageing using Volkswagen ageing procedure. The evaluation showed new gelling catalysts pure-DMAEMAc and crude-DMAEMAc performed similarly to a standard reactive catalyst DABCO®NE1070, Foams made using the inventive catalyst have an overall better performance under humid ageing.
  • EXAMPLE 7 (Inventive) This example describes the performance of DMAEM Ac in a typical closed cell rigid foam formulation
  • Stepanpol®PS2352 is a polyester polyol with a OH number of about 240 available from Stephan and Pluracol®SG-360 is a polyol sucrose/glycerine initiated polyol with a functionality af 4 and a hydroxyl number of 350-375 available from BASF.
  • the table below shows the amount of catalyst needed for matching the string gel time in a standard rigid formulation when distilled (pure) DMAEMAc and non-distilled (crude) DMAEMAc are used as sole catalysts.
  • DMAEMAc and non-distilled (crude) DMAEMAc can be used in a rigid formulation in combination with a blowing catalyst such as Polycat®5 also commercially available from Evonik Corporation.
  • pure DMAEMAc and crude DMAEMAc are useful catalysts in the preparation of various types of polyurethane foams including rigid and flexible.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne une composition de catalyseur comprenant au moins un composé représenté par la formule (I) dans laquelle : R1, R2, et R3 sont chacun indépendamment alkyle en C1-C3, ou alcényle linéaire ou ramifié en C2-C6 ; et R4 est hydrogène, alkyle en C1-C3, ou alcényle linéaire ou ramifié en C2-C6.
PCT/EP2023/069424 2022-07-28 2023-07-13 Composition d'amino-amide tertiaire utile dans la fabrication de polymères de polyuréthane WO2024022832A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3816339A (en) 1972-02-22 1974-06-11 Abbott Lab Urethane catalyst
EP1038894A2 (fr) * 1999-03-26 2000-09-27 Air Products And Chemicals, Inc. Compositions de catalyseurs pour la préparation de polyuréthanes
US6156814A (en) * 1999-03-26 2000-12-05 Air Products And Chemicals, Inc. Amido functional amine catalysts for the production of polyurethanes
US6737446B1 (en) 2003-01-03 2004-05-18 Air Products And Chemicals, Inc. Tertiary amino alkyl amide catalysts for improving the physical properties of polyurethane foams
US7169823B2 (en) 2003-03-10 2007-01-30 Air Products And Chemicals, Inc. Tertiary alkanolamine polyurethane catalysts derived from long chain alkyl and fatty carboxylic acids
WO2016196643A1 (fr) * 2015-06-01 2016-12-08 Air Products And Chemicals, Inc. Catalyseurs aminés réactifs pour applications de polyuréthane

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3816339A (en) 1972-02-22 1974-06-11 Abbott Lab Urethane catalyst
EP1038894A2 (fr) * 1999-03-26 2000-09-27 Air Products And Chemicals, Inc. Compositions de catalyseurs pour la préparation de polyuréthanes
US6156814A (en) * 1999-03-26 2000-12-05 Air Products And Chemicals, Inc. Amido functional amine catalysts for the production of polyurethanes
US6737446B1 (en) 2003-01-03 2004-05-18 Air Products And Chemicals, Inc. Tertiary amino alkyl amide catalysts for improving the physical properties of polyurethane foams
US7169823B2 (en) 2003-03-10 2007-01-30 Air Products And Chemicals, Inc. Tertiary alkanolamine polyurethane catalysts derived from long chain alkyl and fatty carboxylic acids
WO2016196643A1 (fr) * 2015-06-01 2016-12-08 Air Products And Chemicals, Inc. Catalyseurs aminés réactifs pour applications de polyuréthane

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