Amine catalysts for polyurethane foams

Patent metadata

Field	Value
Publication number	US-9550854-B2
Application number	US-24160608-A
Country	US
Kind code	B2
Filing date	Sep 30, 2008
Priority date	Oct 12, 2007
Publication date	Jan 24, 2017
Grant date	Jan 24, 2017

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.

First claim

What is claimed is:

1. A polyol premix composition which comprises a combination of from about 1 wt. % to about 30 wt. % of a blowing agent, from about 60 wt % to about 95 wt % of a polyol, from about 0.5 wt % to about 5 wt % of a silicone surfactant, and a sterically hindered amine catalyst; wherein the blowing agent comprises trans-1,3,3,3-tetrafluoropropene, 1-chloro-3,3,3-trifluoropropene or combinations of these and the sterically hindered amine catalyst comprises a catalyst selected from the group consisting of; dimethylcyclohexylamine, dicyclohexylmethylamine, dicyclohexylamine; t-butylisopropylamine; di-sec-butylamine, diisopropylamine; diisopropylethylamine; dimethylisopropylamine, and combinations thereof, wherein the amounts of each component are by weight of the polyol premix composition and wherein the premix comprises less than 5 wt. % of fluoride ion after exposure to 120° F. for three days.

2. The polyol premix composition of claim 1 wherein the blowing agent further comprises a co-blowing agent selected from the group consisting of 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, and combinations thereof.

3. The polyol premix composition of claim 1 wherein the silicone surfactant comprises a polysiloxane polyoxyalkylene block co-polymer.

4. The polyol premix composition of claim 1 further comprising a non-silicone, non-ionic surfactant.

5. The polyol premix composition of claim 1 wherein the polyol is selected from the group consisting of 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; and combinations thereof.

6. The polyol premix composition of claim 1 wherein the sterically hindered amine catalyst is selected from the group consisting of dimethylcyclohexylamine; dicyclohexylmethylamine and combinations thereof.

7. The polyol premix composition of claim 1 further comprising a non-amine catalyst comprising an organometallic compound containing a metal selected from the group consisting of bismuth, lead, tin, titanium, antimony, uranium, cadmium, cobalt, thorium, aluminum, mercury, zinc, nickel, cerium, molybdenum, vanadium, copper, manganese, zirconium, potassium, sodium, and combinations thereof.

8. The polyol premix composition of claim 1 further comprising a non-amine catalyst selected from the group consisting of 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, alkali metal carboxylic acid salts, potassium acetate, potassium octoate, potassium 2-ethylhexanoate, tin (II) 2-ethylhexanoate, dibutyltin dilaurate, and combinations thereof.

9. A foamable composition comprising a mixture of an organic polyisocyanate and the polyol premix composition of claim 1 .

10. The foamable composition of claim 9 wherein the organic polyisocyanate comprises a polymethylene polyphenyl isocyanate, methylenebis(phenyl isocyanate), toluene diisocyanate, or combinations thereof.

11. A method of preparing a polyurethane or polyisocyanurate foam comprising reacting an organic polyisocyanate with the polyol premix composition of claim 1 .

12. A foam produced according to the method of claim 11 .

13. The polyol premix composition of claim 1 wherein the blowing agent further comprises a co-blowing agent selected from the group consisting of a hydrocarbon, a fluorocarbon, a chlorocarbon, a fluorochlorocarbon, a halogenated hydrocarbon, a CO 2 generating material, and combinations thereof.

14. A polyol premix composition which comprises a combination of from about 1 wt. % to about 30 wt. % of a blowing agent, from about 60 wt % to about 95 wt % of a polyol, from about 0.5 wt % to about 5 wt % of a silicone surfactant, and a sterically hindered amine catalyst; wherein the blowing agent comprises trans 1,3,3,3-tetrafluoropropene; wherein the sterically hindered amine catalyst comprises a catalyst selected from the group consisting of dicyclohexylmethylamine; dimethylcyclohexylamine; dimethylisopropylamine; dicyclohexylamine; t-butylisopropylamine; di-sec-butylamine, diisopropylamine dimethylisopropylamine; combinations thereof, wherein the amounts of each component are by weight of the polyol premix composition and wherein the premix comprises less than 5 wt. % of fluoride ion after exposure to 120° F. for three days.

15. The polyol premix composition of claim 14 wherein the sterically hindered amine catalyst is selected from the group consisting of dimethylcyclohexylamine; dicyclohexylmethylamine; and combinations thereof.

16. A polyol premix composition which comprises a combination of from about 1 wt. % to about 30 wt. % of a blowing agent, from about 60 wt % to about 95 wt % of a polyol, from about 0.5 wt % to about 5 wt % of a silicone surfactant, a non-amine catalyst and a sterically hindered amine catalyst; wherein the blowing agent comprises trans-1,3,3,3-tetrafluoropropene, and the sterically hindered amine catalyst comprises a catalyst selected from the group consisting of dicyclohexylmethylamine; dimethylcyclohexylamine, dicyclohexylamine; t-butylisopropylamine; di-sec-butylamine, diisopropylamine; diisopropylethylamine; dimethylisopropylamine, and combinations thereof, wherein the amounts of each component are by weight of the polyol premix composition and wherein the premix comprises less than 5 wt. % of fluoride ion after exposure to 120° F. for 62 hours.

17. The polyol premix composition of claim 16 wherein the non-amine catalyst comprises an organometallic compound containing a metal selected from the group consisting of bismuth, lead, tin, titanium, antimony, uranium, cadmium, cobalt, thorium, aluminum, mercury, zinc, nickel, cerium, molybdenum, vanadium, copper, manganese, zirconium, potassium, sodium, and combinations thereof.

18. The polyol premix composition of claim 16 wherein the non-amine catalyst is selected from the group consisting of 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, alkali metal carboxylic acid salts, potassium acetate, potassium octoate, potassium 2-ethylhexanoate,

Assignees

• Van Der Puy Michael
• Williams David J
• Nair Haridasan K
• Nalewajek David
• Honeywell Int Inc

Inventors

• Van Der Puy Michael
• Williams David J
• Nair Haridasan K
• Nalewajek David

Classifications

• C08J9/144

  containing carbon, halogen and hydrogen only · CPC title

• C08J2203/18

  Binary blends of expanding agents · CPC title

• C08G18/1816 Primary

  having carbocyclic groups · CPC title

• C08J9/149

  Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143 · CPC title

• C08J2205/046

  Unimodal pore distribution · CPC title