Catalyst compositions and methods for making foam
View Patent ↗A composition and process to make polyisocyanurate or polyurethane foam using a catalyst composition comprising at least one bismuth carboxylate catalyst and one or more co-catalysts selected from the group of alkali metal carboxylates and quaternary ammonium carboxylate salts, such that the resultant foam has improved insulation properties. The polyisocyanurate or polyurethane foams produced by this catalyst composition and method are useful for laminated boardstock, construction panels, appliance insulation, and spray-applied insulation.
1. A catalyst composition for making a polyisocyanurate/polyurethane foam comprising at least one bismuth carboxylate salt selected from the group consisting of bismuth neodecanoate, bismuth octoate, bismuth versalate, bismuth naphthenate, bismuth pivalate, bismuth acetate, bismuth subcarbonate, and bismuth citrate and at least one member selected from the group consisting of potassium carboxylate salts and quaternary ammonium carboxylate salts,
wherein a molar ratio of the potassium carboxylate or quaternary ammonium carboxylate to the Bismuth carboxylate is between 44 to 1 and 50 to 1; wherein the use level of potassium carboxylate or quaternary ammonium carboxylate is 2.5-3.5% by weight of the total resin; and wherein the use level of bismuth carboxylate is 0.2-0.3% by weight of the total resin.
2. The composition of claim 1 wherein the quaternary ammonium carboxylate salt and the potassium carboxylate salt comprise at least one member selected from the group consisting of potassium pivalate, tetramethylammonium pivalate, potassium octoate, potassium acetate, potassium acrylate, 2-hydroxylpropyltrimethylammonium pivalate, 2-hydroxylpropyltriethylammonium pivalate, tetraethylammonium pivalate, tetrapropylammonium pivalate, tetrabutylammonium pivalate, potassium triethylacetate, tetramethylammonium triethylacetate, 2-hydroxylpropyltrimethylammonium triethylacetate, 2-hydroxylpropyltriethylammonium triethylacetate, tetraethylammonium triethylacetate, tetrapropylammonium triethylacetate, tetrabutylammonium triethylacetate, potassium neoheptanoate, tetramethylammonium neoheptanoate, 2-hydroxylpropyltrimethylammonium neoheptanoate, 2-hydroxylpropyltriethylammonium neoheptanoate, tetraethylammonium neoheptanoate, tetrapropylammonium neoheptanoate, tetrabutylammonium neoheptanoate, potassium neooctanoate, tetramethylammonium neooctanoate, 2-hydroxylpropyltrimethylammonium neooctanoate, 2-hydroxylpropyltriethylammonium neooctanoate, tetraethylammonium neooctanoate, tetrapropylammonium neooctanoate, tetrabutylammonium neooctanoate, and mixtures thereof.
3. The composition of claim 1 wherein the composition is substantially free of tin compounds.
4. A method for making foam comprising contacting at least one polyol, at least one isocyanate and at least one blowing agent in the presence of the composition of claim 1 .
5. The method of claim 4 wherein the polyol comprises at least one polyester polyol.
6. The method of claim 4 wherein the isocyanate comprises at least one member selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate, phenylene diisocyanate, toluene diisocyanate (“TDI”), and 4,4′-diphenyl methane diisocyanate (“MDI”).
7. The method of claim 4 wherein the method comprises at least one step selected from the group of spraying, molding and laminating.
8. The method of claim 4 wherein the blowing agent comprises at least one member selected from the group consisting of water, hydrofluorocarbon, carbon dioxide, hydrohaloolefin and hydrocarbon.
9. The method of claim 4 further comprising at least one tertiary amine catalyst.
10. A foam obtained by the method of claim 4 .
11. The foam of claim 10 wherein the foam has an R-value of about 6.5 to about 7.5.
12. The foam of claim 10 wherein the foam has an average cell diameter of about 50 to about 500 microns.
13. The foam of claim 12 , wherein a minimum cell diameter is less than 59 microns.
14. The foam of claim 12 wherein the foam has an average cell diameter of about 50 to about 154 microns.
15. A method for producing a polyisocyanurate foam by contacting at least one isocyanate with at least one polyol in the presence of at least one amine catalyst, at least one blowing agent, and at least one carboxylate catalyst comprising at least one bismuthcarboxylate selected from the group consisting of bismuth neodecanoate, bismuth octoate, bismuth versalate, bismuth naphthenate, bismuth pivalate, bismuth acetate, bismuth subcarbonate, and bismuth citrate and at least one of ammoniumcarboxylate and potassiumcarboxylate salts,
wherein a molar ratio of the potassiumcarboxylate or ammoniumcarboxylate to the bismuthcarboxylate is between 44 to 1 and 50 to 1; wherein the use level of potassium carboxylate is 2.5-3.5% by weight of the total resin; and wherein the use level of bismuth carboxylate is 0.2-0.3% by weight of the total resin.
16. A method for preparing a polyisocyanurate/polyurethane foam which comprises contacting at least one polyisocyanate with a premix comprising at least one polyol, at least one blowing agent, and a catalytic amount of a catalyst composition comprising a solution of at least one member selected from the group of bismuth neodecanoate, bismuth octoate, bismuth versalate, bismuth naphthenate, and bismuth pivalate; and at least one member selected from the group consisting of potassium pivalate, tetramethylammonium pivalate, potassium octoate, potassium acetate, potassium acrylate 2-hydroxylpropyltrimethylammonium pivalate, 2-hydroxylpropyltriethylammonium pivalate, tetraethylammonium pivalate, tetrapropylammonium pivalate, tetrabutylammonium pivalate, potassium triethylacetate, tetramethylammonium triethylacetate, 2-hydroxylpropyltrimethylammonium triethylacetate, 2-hydroxylpropyltriethylammonium triethylacetate, tetraethylammonium triethylacetate, tetrapropylammonium triethylacetate, tetrabutylammonium triethylacetate, potassium neoheptanoate, tetramethylammonium neoheptanoate, 2-hydroxylpropyltrimethylammonium neoheptanoate, 2-hydroxylpropyltriethylammonium neoheptanoate, tetraethylammonium neoheptanoate, tetrapropylammonium neoheptanoate, tetrabutylammonium neoheptanoate, potassium neooctanoate, tetramethylammonium neooctanoate, 2-hydroxylpropyltrimethylammonium neooctanoate, 2-hydroxylpropyltriethylammonium neooctanoate, tetraethylammonium neooctanoate, tetrapropylammonium neooctanoate, and tetrabutylammonium neooctanoate, and wherein a molar ratio of the potassium carboxylate or quaternary ammonium carboxylate to the Bismuth carboxylate is between 44 to 1 and 50 to 1; wherein the use level of potassium carboxylate is 2.5-3.5% by weight of the total resin; and wherein the use level of bismuth carboxylate is 0.2-0.3% by weight of the total resin.