Amine catalysts for polyurethane foams

Abstract

The invention provides polyurethane and polyisocyanurate foams and methods for the preparation thereof. More particularly, the invention relates to open-celled, polyurethane and polyisocyanurate foams and methods for their preparation. The foams are characterized by a fine uniform cell structure and little or no foam collapse. The foams are produced with a polyol premix composition which comprises a combination of a hydrohaloolefin blowing agent, a polyol, a silicone surfactant, and a sterically hindered amine catalyst.

What is claimed is: 
     
         1 . A polyol premix composition which comprises a combination of a blowing agent, a polyol, a silicone surfactant, and a sterically hindered amine catalyst; wherein the blowing agent comprises a hydrohaloolefin, and optionally a hydrocarbon, fluorocarbon, chlorocarbon, fluorochlorocarbon, halogenated hydrocarbon, CO 2  generating material, or combinations thereof wherein the sterically hindered amine catalyst has the formula R 1 R 2 N-[A-NR 3 ] n R 4  wherein each of R 1 , R 2 , R 3 , and R 4  is independently H, a C 1  to C 8  alkyl group, a C 1  to C 8  alkenyl group, a C 1  to C 8  alcohol group, or a C 1  to C 8  ether group, or R 1  and R 2  together form a C 5  to C 7  cyclic alkyl group, a C 5  to C 7  cyclic alkenyl group, a C 5  to C 7  heterocyclic alkyl group, or a C 5  to C 7  heterocyclic alkenyl group; A is a C 1  to C 5  alkyl group, a C 1  to C 5  alkenyl group, or an ether; n is 0, 1, 2, or 3; with the proviso that the sterically hindered amine catalyst has a sum of Charton's steric parameters of about 1.65 or greater. 
     
     
         2 . The polyol premix composition of  claim 1  wherein the hydrohaloolefin comprise at least one fluoroalkene or chloroalkene containing from 3 to 4 carbon atoms and at least one carbon-carbon double bond. 
     
     
         3 . The polyol premix composition of  claim 1  wherein the hydrohaloolefin comprises a trifluoropropenes, a tetrafluoropropenes, a pentafluoropropene, a chlorodifluoropropene, a chlorotrifluoropropene, a chlorotetrafluoropropene, or combinations thereof. 
     
     
         4 . The polyol premix composition of  claim 1  wherein the hydrohaloolefin comprises 1,3,3,3-tetrafluoropropene; 2,3,3,3-tetrafluoropropene; 1,1,3,3-tetrafluoropropene; 1,2,3,3,3-pentafluoropropene; 1,1,1-trifluoropropene; 3,3,3-trifluoropropene; 1,1,1,3-tetrafluoropropene; 1,1,1,3,3-pentafluoropropene; 1,1,2,3,3-pentafluoropropene, 1,1,1,2-tetrafluoropropene; 1,1,1,2,3-pentafluoropropene, 1-chloro-3,3,3-trifluoropropene, 1,1,1,4,4,4-hexafluorobut-2-ene or structural isomers, geometric isomers or stereoisomers thereof, or combinations thereof. 
     
     
         5 . The polyol premix composition of  claim 1  wherein the hydrohaloolefin comprises 1,3,3,3-tetrafluoropropene, 1-chloro-3,3,3-trifluoropropene, or stereoisomers thereof, or combinations thereof. 
     
     
         6 . The polyol premix composition of  claim 1  wherein the blowing agent comprises water, formic acid, organic acids that produce CO 2  when they react with an isocyanate, hydrocarbons; ethers, esters, aldehydes, ketones, halogenated ethers; pentafluorobutane; pentafluoropropane; hexafluoropropane; heptafluoropropane; trans-1,2 dichloroethylene; methyl formate; 1-chloro-1,2,2,2-tetrafluoroethane; 1,1-dichloro-1-fluoroethane; 1,1,1,2-tetrafluoroethane; 1,1,1,2-tetrafluoroethane; 1-chloro 1,1-difluoroethane; 1,1,1,3,3-pentafluorobutane; 1,1,1,2,3,3,3-heptafluoropropane; trichlorofluoromethane; dichlorodifluoromethane; 1,1,1,3,3,3-hexafluoropropane; 1,1,1,2,3,3-hexafluoropropane; difluoromethane; difluoroethane; 1,1,1,3,3-pentafluoropropane; 1,1-difluoroethane; isobutane; normal pentane; isopentane; cyclopentane, or combinations thereof. 
     
     
         7 . The polyol premix composition of  claim 1  wherein the silicone surfactant comprises a polysiloxane polyoxyalkylene block co-polymer. 
     
     
         8 . The polyol premix composition of  claim 1  further comprising a non-silicone, non-ionic surfactant. 
     
     
         9 . The polyol premix composition of  claim 1  wherein the polyol comprises one or more of a sucrose containing polyol; phenol; a phenol formaldehyde containing polyol; a glucose containing polyol; a sorbitol containing polyol; a methylglucoside containing polyol; an aromatic polyester polyol; glycerol; ethylene glycol; diethylene glycol; propylene glycol; graft copolymers of polyether polyols with a vinyl polymer; a copolymer of a polyether polyol with a polyurea; one or more of (a) condensed with one or more of (b):
 (a) glycerine, ethylene glycol, diethylene glycol, trimethylolpropane, ethylene diamine, pentaerythritol, soy oil, lecithin, tall oil, palm oil, castor oil; 
 (b) ethylene oxide, propylene oxide, a mixture of ethylene oxide and propylene oxide; 
 or combinations thereof. 
 
     
     
         10 . The polyol premix composition of  claim 1  wherein the sterically hindered amine catalyst comprises a sterically hindered teriary amine catalyst wherein each of R 1 , R 2  and R 3  are independently C 1  to C 8  alkyl groups. 
     
     
         11 . The polyol premix composition of  claim 1  wherein the sterically hindered amine catalyst comprises a sterically hindered secondary amine catalyst wherein R 1  and R 2  are independently C 1  to C 8  alkyl groups. 
     
     
         12 . The polyol premix composition of  claim 1  wherein the sterically hindered amine catalyst comprises at least one a sterically hindered teriary amine catalyst wherein each of R 1 , R 2  and R 3  are independently C 1  to C 8  alkyl groups, and at least one sterically hindered secondary amine catalyst wherein R 1  and R 2  are independently C 1  to C 8  alkyl groups. 
     
     
         13 . The polyol premix composition of  claim 1  wherein the sterically hindered teriary amine catalyst comprises cyclohexyldimethylamine; dicyclohexylmethylamine; ethyldiisopropylamine; dimethylcyclohexylamine; dimethylisopropylamine; methylisopropylbenzylamine; methylcyclopentylbenzylamine; isopropyl-sec-butyl-trifluoroethylamine; diethyl-(α-phenylethyl)amine, tri-n-propylamine or combinations thereof. 
     
     
         14 . The polyol premix composition of  claim 1  wherein the sterically hindered secondary amine catalyst comprises; dicyclohexylamine; t-butylisopropylamine; di-t-butylamine; cyclohexyl-t-butylamine; di-sec-butylamine, dicyclopentylamine; di-(α-trifluoromethylethyl)amine; di-(α-phenylethyl)amine; or combinations thereof. 
     
     
         15 . The polyol premix composition of  claim 1  further comprising a non-amine catalyst comprising an organometallic compound containing bismuth, lead, tin, titanium, antimony, uranium, cadmium, cobalt, thorium, aluminum, mercury, zinc, nickel, cerium, molybdenum, vanadium, copper, manganese, zirconium, potassium, sodium, or combinations thereof. 
     
     
         16 . The polyol premix composition of  claim 1  further comprising a non-amine catalyst comprising bismuth nitrate, lead 2-ethylhexoate, lead benzoate, ferric chloride, antimony trichloride, antimony glycolate, stannous salts of carboxylic acids, zinc salts of carboxylic acids, dialkyl tin salts of carboxylic acids, glycine salts, tertiary amine trimerization catalysts, quaternary ammonium carboxylates, alkali metal carboxylic acid salts, potassium acetate, potassium octoate, potassium 2-ethylhexanoate, N-(2-hydroxy-5-nonylphenol)methyl-N-methylglycinate, tin (II) 2-ethylhexanoate, dibutyltin dilaurate, or combinations thereof. 
     
     
         17 . A foamable composition comprising a mixture of an organic polyisocyanate and the polyol premix composition of  claim 1 . 
     
     
         18 . The foamable composition of  claim 14  wherein the organic polyisocyanate comprises a polymethylene polyphenyl isocyanate, methylenebis(phenyl isocyanate), toluene diisocyanate, or combinations thereof. 
     
     
         19 . A method of preparing a polyurethane or polyisocyanurate foam comprising reacting an organic polyisocyanate with the polyol premix composition of  claim 1 . 
     
     
         20 . A foam produced according to the method of  claim 19 .