Polyol compositions
Disclosed are polyol compositions with a low viscosity that exhibit superior heat resistance, enhanced stability in the presence of water, improved strength, hardness, and molding characteristics relative to known polyurethane materials. Disclosed is a polyol composition comprising: (a) at least one monomeric polyol comprising three or more hydroxyl groups; (b) at least one higher polyol comprising three or more hydroxyl groups; and (c) at least one polyhydroxylated aromatic compound; wherein the at least one higher polyol comprises residues of either or both of the at least one monomeric polyol and the polyhydroxylated aromatic compound linked by one or more carbonate groups, oxygen ether groups, or a combination thereof. Disclosed are methods of preparing the disclosed compositions. Disclosed are articles prepared from the disclosed compositions that exhibit flexural strengths in excess of 10,000 psi and flexural moduli in excess of 400,000 psi, and exhibit outstanding green strength.
1. A polyol composition comprising:
(a) at least one monomeric polyol comprising three or more hydroxyl groups;
(b) at least one higher polyol comprising three or more hydroxyl groups; and
(c) at least one polyhydroxylated aromatic compound;
wherein the at least one higher polyol comprises residues of either the at least one monomeric polyol or both of the at least one monomeric polyol and the polyhydroxylated aromatic compound, wherein the residues are linked by one or more carbonate groups, oxygen ether groups, or a combination thereof, and
wherein the polyol composition has a viscosity of less than 5000 cps at 150 degrees Fahrenheit and wherein the at least one polyhydroxylated aromatic compound is present in an amount greater than 16 percent by weight and less than 35 percent by weight based on total weight of the polyol composition.
2. The composition of claim 1 , wherein the at least one monomeric polyol comprises three or more secondary hydroxyl groups.
3. The composition of claim 1 , wherein the at least one monomeric polyol comprises one or more oxygen ether groups.
4. The composition of claim 1 , wherein the at least one monomeric polyol comprises four or more hydroxyl groups.
5. The composition of claim 1 , wherein the at least one monomeric polyol comprises four or more secondary hydroxyl groups.
6. The composition of claim 1 , wherein the at least one monomeric polyol comprises a mixture of polyols having an average molecular weight of less than 500 grams per mole.
7. The composition of claim 1 , wherein the at least one monomeric polyol comprises a C 2 to C 4 alkoxylated polyether polyol.
8. The composition of claim 1 , wherein the at least one higher polyol comprises one or more carbonate groups and two or more residues of the at least one monomeric polyol.
9. The composition of claim 1 , wherein the at least one monomeric polyol is present in an amount greater than 10 percent and less than 90 percent by weight based on the total weight of the polyol composition; and the at least one higher polyol is present in an amount greater than 5 percent by weight and less than 70 percent based on the total weight of the polyol composition.
10. A method of making the polyol composition of claim 1 , comprising contacting one or more compositions containing one or more polyhydroxylated aromatic moieties with one or more monomeric polyols having three or more hydroxyl groups in the presence of at least one activating agent and an effective amount of at least one of a catalyst, a promoter or a mixture thereof, at a temperature sufficient to cause formation of the at least one higher polyol to provide the polyol composition.
11. A method of making the polyol composition of claim 1 , comprising contacting at least one aromatic carbonate with one or more monomeric polyols having three or more hydroxyl groups in the presence of an effective amount of at least one of a catalyst, a promoter or a mixture thereof, at a temperature sufficient to cause formation of the at least one higher polyol to provide the polyol composition;
wherein the at least one aromatic carbonate comprises one or more residues of the polyhydroxylated aromatic compound; and
wherein the at least one polyhydroxylated aromatic compound is derived from the one or more residues of the polyhydroxylated aromatic compound of the at least one aromatic carbonate.
12. The method of claim 11 , wherein the at least one aromatic carbonate is an oligomeric polycarbonate, a polymeric polycarbonate, or a mixture thereof.
13. The composition of claim 1 , prepared by a method comprising contacting one or more aromatic carbonates with one or more monomeric polyols having three or more hydroxyl groups in the presence of an effective amount of at least one of a catalyst, a promoter or a mixture thereof, under conditions sufficient to cause formation of the at least one higher polyol to provide the polyol composition;
wherein at least a portion of the at least one polyhydroxylated aromatic compound is derived from the one or more aromatic carbonates.
14. A polyurethane composition prepared by reacting the polyol composition of claim 1 with one or more polyisocyanates, latent polyisocyanates or mixtures thereof, optionally in the presence of a catalyst, under conditions sufficient to cause at least a portion of hydroxyl groups of the at least one monomeric polyol, at least a portion of the hydroxyl groups of the at least one higher polyol, and at least a portion of hydroxyl groups of the at least one polyhydroxylated aromatic compound to react with isocyanate groups or latent isocyanate groups of the one or more polyisocyanates or the latent polyisocyanates to form urethane linkages of the polyurethane composition.
15. A polyurethane composition comprising residue of the polyol composition of claim 1 and residue of one or more polyisocyanates or latent polyisocyanates; wherein urethane linkages of the polyurethane composition are formed by reaction of at least a portion of the hydroxyl groups of the at least one monomeric polyol, at least a portion of hydroxyl groups of the at least one higher polyol, and at least a portion of hydroxyl groups of the at least one polyhydroxylated aromatic compound with isocyanate groups of polyisocyanates or latent isocyanate groups of latent polyisocyanates.
16. An article comprising the composition of claim 9 , which exhibits a heat distortion temperature greater than 110 degrees centigrade, a flexural strength greater than 10,000 psi and a flexural modulus greater than 500,000 psi.
17. A method comprising: contacting the polyol composition of claim 1 with one or more polyisocyanates, latent polyisocyanates or mixtures thereof, optionally in the presence of a catalyst under conditions sufficient to cause at least a portion of hydroxyl groups of the at least one monomeric polyol, at least a portion of hydroxyl groups of the at least one higher polyol, and at least a portion of hydroxyl groups of the at least one polyhydroxylated aromatic compound to react with one or more isocyanate groups or latent isocyanate groups of the polyisocyanates or the latent polyisocyanates to form a polyurethane product.
18. A method comprising:
(a) mixing a first reactant comprising either or both of one or more polyisocyanates and one or more latent polyisocyanates with a second reactant comprising one or more polyol compositions of claim 1 to form a reactive mixture;
(b) transferring the reactive mixture into a mold; and
(c) curing the reactive mixture within the mold to afford a molded part;
wherein during step (c) at least a portion of hydroxyl groups of the at least one monomeric polyol, at least a portion of hydroxyl groups of the at least one higher polyol, and at least a portion of hydroxyl groups of the at least one polyhydroxylated aromatic compound react with isocyanate groups or latent isocyanate groups of the one or more polyisocyanates or the one or more latent polyisocyanates to form a polyurethane product.
19. A composition comprising:
(a) a first part comprising either or both of a polyisocyanate and a latent polyisocyanate;
and
(b) a second part comprising a polyol composition of claim 1 ;
wherein when the first part and the second part are contacted the composition cures by reaction of at least a portion of hydroxyl groups of the at least one monomeric polyol, at least a portion of hydroxyl groups of the at least one higher polyol, and at least a portion of hydroxyl groups of the at least one polyhydroxylated aromatic compound with isocyanate groups or latent isocyanate groups of the polyisocyanates or the latent polyisocyanates.
20. The composition of claim 1 , wherein a molar ratio of hydroxyl groups to carbonate groups is greater than 5 and less than 14.