Polyurethane foams containing silicone surfactants
View Patent ↗The present invention relates to polyurethane foam prepared from a polyurethane foam-forming reaction mixture possessing a silicone copolymer surfactant, methods for making the surfactant, and a process for preparing low density polyurethane foams.
1. A polyurethane foam obtained from a foam forming composition comprising a silicone copolymer surfactant having the formula:
MD x D′ y M,
wherein,
M represents (CH 3 ) 3 SiO 1/2 , or (CH 3 ) 2 RSiO 1/2
D represents (CH 3 ) 2 SiO 2/2 ,
D′ represents (CH 3 )RSiO 2/2 ,
x+y is 50 to 150; y is at least 3; the ratio of x to y is 3 to 15; and R is a polyether independently selected from the group consisting of:
i) at least one polyoxyalkylene moiety having the formula:
—C n H 2n O(C 2 H 4 O) a (C 3 H 6 O) b R′ and possessing a number average molecular weight from 2,300 to 5,500, wherein n is 2 to 4, a is a number such that the oxyethylene residue constitute 20 to 60 percent by the weight of the alkylene oxide residues of the polyoxyalkylene polyether, b is a number such that the propylene oxide residue constitute 80 to 40 percent by the weight of the alkylene oxide residues of the polyoxyalkylene polyether, and R′ represents an alkyl group having 1 to 4 carbon atoms or —C(O)CH 3 ;
ii) at least one polyoxyalkylene moiety having the formula:
—C n′ H 2n′ O(C 2 H 4 O) a′ (C 3 H 6 O) b′ R″ and possessing a number average molecular weight from 800 to 2,200, wherein n′ is 2 to 4, a′ is a number such that the oxyethylene residues constitute 20 to 60 percent by weight of the alkylene oxide residues of the polyoxyalkylene polyether, b′ is a number such that the propylene oxide residue constitute 80 to 40 percent by the weight of the alkylene oxide residues of the polyoxyalkylene polyether, and R″ represents an alkyl group having 1 to 4 carbon atoms or —C(O)CH 3 ; and,
iii) at least one polyoxyalkylene moiety having the formula:
—C n″ H 2n″ O(C 2 H 4 O) a″ (C 3 H 6 O) b″ H and possessing a number average molecular weight of 1,400 to 2,300, n″ is 2 to 4, a″ is a number such that the oxyethylene residues constitute 20 to 60 percent by weight of the alkylene oxide residues of the polyoxyalkylene polyether, and b″ is a number such that the propylene oxide residue constitute 80 to 40 percent by the weight of the alkylene oxide residues of the polyoxyalkylene polyether, with the proviso that MD x D′ y M has at least one each of components (i), (ii), and (iii), where the blend number average molecular weight of the overall polyoxyalkylene polyethyer containing substitutents R in the composition is from 2,050 to 2,350 and component (iii) constitutes 10 to 60 mole percent of the total amount of polyether.
2. The polyurethane foam of claim 1 wherein a is a number that ranges form 10.5 to 75, and b is a number that ranges from 16 to 76.
3. The polyurethane foam of claim 1 wherein a′ is a number that ranges from 4 to 30, and b′ is an a number that ranges from 11 to 30.
4. The polyurethane foam of claim 1 wherein a″ is a number that ranges from 6 to 32, and b″ is a number that ranges from 10 to 32.
5. The polyurethane foam of claim 1 wherein component (i) is from 35 to 60 mole percent of the total amount of polyether and has a number average molecular weight of 2,300 to 4,000, and a weight ratio of oxyethylene/propylene oxide of 2 to 3; component (ii) is less than 30 mole percent of the total amount of polyether and has a number average molecular weight of 1,300 to 1,600 and a weight ratio of oxyethylene/propylene oxide of 2 to 3; and component (iii) is 10 to 60 mole percent of the total amount of polyether and has a number average molecular weight of 1,500 to 1,600 and a weight ratio of oxyethylene/propylene oxide of 2 to 3, with the proviso that x+y is 77 and the ratio x/y is 14.
6. The polyurethane foam of claim 5 wherein component (iii) is 20 to 40 mole percent of the total amount of polyether.
7. The polyurethane foam of claim 1 wherein the total amount of polyether has an average molecular weight from 2,000 to 2,400.
8. The polyurethane foam of claim 1 further comprising a diluent.
9. The polyurethane foam of claim 8 wherein the diluent is dipropylene glycol.
10. The polyurethane foam of claim 1 wherein the average oxyethylene/propylene weight ratio of the polyether is 2 to 3.
11. The polyurethane foam of claim 1 wherein the foam forming reaction mixture further comprises at least one polyol, at least one isocyanate source, at least one polyurethane catalyst, and, optionally, at least one additional component selected from the group consisting of filler, blowing agent, other polymer and/or copolymer, chain extender, crosslinker, reinforcement, pigment, tint, dye, colorant, flame retardant, antioxidant, antiozonant, UV stabilizer, anti-static agent, biocide and biostat.
12. The polyurethane foam of claim 11 wherein the polyol is at least one selected from the group consisting of polyether polyol, polyester polyol, polycaprolactone polyol, polycarbonate polyol, polybutadiene polyol, hydroxyl-terminated polyolefin polyols, graphed polyol, and polyol derived from a natural source.
13. The polyurethane foam of claim 12 wherein the grafted polyol is at least one selected from the group consisting of styrene/acrylonitrile (SAN) graphed polyether polyol, acrylonitrile (AN)-graphed polyether polyol, and graphed polyester polyol.
14. The polyurethane foam of claim 11 wherein the polyol is at least one selected from the group consisting of polyether-terminated polybutadiene or polyether-terminated polyols derived from a natural source.
15. The polyurethane foam of claim 11 wherein the isocyanate source is at least one selected from the group consisting of methanediphenyl diisocyanate (MDI), polymeric MDI, modified MDI, prepolymers of MDI, toluenediisocyanate (TDI), prepolymers of TDI, and modified TDI.
16. The polyurethane foam of claim 15 wherein isocyanate source is at least one selected from the group consisting of 4,4′ methanediphenyl diisocyanate, 2,4′ methanediphenyl diisocyanate, 2,2′ methanediphenyl diisocyanate, 2,4-toluenediisocyanate and 2,6-toluene diisocyanate.
17. The polyurethane foam of claim 11 wherein the catalyst comprises at least one selected from the group consisting of organometallic catalysts, alkali metal carboxylates catalysts, heavy metal-based catalysts, triethylene diamine, tin-based, and tertiary amine urethane catalysts.
18. The polyurethane foam of claim 11 wherein the catalyst is at least one selected from the group consisting of nickelacetoacetonate, ironacetoacetonate, bismuth-based catalysts, zinc-based catalysts, potassium octoate, potassium acetate, sodium acetate, sodium octoate, and quaternary ammonium carboxylate.
19. The polyurethane foam of claim 1 wherein the foam has a density of 20 kg/m 3 or less.
20. The polyurethane foam of claim 1 wherein the foam has a density of 12 kg/m 3 or less.