Method of preparing oligomeric polyol compositions
There is provided an oligomeric polyol composition having (a) an oligomeric network containing residues of at least one polyhydroxylated aromatic compound and residues of at least one polyol having at least three hydroxyl groups; and (b) a plurality of peripheral groups having one or more pendant hydroxyl groups bound to the oligomeric network by a plurality of linking units. The residues of the polyol may optionally contain one or more oxygen ether groups, one or more amino ether groups, or both of one or more oxygen ether groups and one or more amino ether groups. Reaction of the oligomeric polyols with isocyanate monomers affords a new class of polyurethanes having superior heat and water resistance. The new polyurethanes exhibit lower peak exotherms, typically less than 250° F. during in-mold polymerization. Articles prepared from polyurethanes incorporating such oligomeric polyol compositions exhibit flexural strengths and moduli in excess of 10,000 psi and 400,000 psi respectively, and outstanding green strength.
1. A method comprising:
reacting one or more compositions containing one or more polyhydroxylated aromatic moieties with one or more monomeric polyols containing one or more oxygen ether groups having more than three secondary 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 a product oligomeric polyol composition comprising:
(i) at least one oligomeric polyol component;
(ii) the at least one monomeric polyol; and
(iii) at least one free polyhydroxylated aromatic compound;
wherein the at least one oligomeric polyol component comprises residues of either or both of the at least one monomeric polyol and the at least one polyhydroxylated aromatic compound linked by one or more carbonate groups and optionally one or more oxygen ether groups.
2. The method of claim 1 , wherein the temperature sufficient to cause formation of the product oligomeric polyol composition is 120° C. or greater and 160° C. or less during a reaction time of 45 minutes or greater and 90 minutes or less.
3. The method of claim 1 , wherein a molar ratio of the one or more polyhydroxylated aromatic moieties to the one or more monomeric polyols is 0.25 to 1 or greater and 1 to 1 or less.
4. The method of claim 1 , wherein the one or more monomeric polyols have a molecular weight of under 500 grams per mole and 130 grams per mole or greater.
5. The method of claim 1 , wherein at least a portion of the one or more monomeric polyols are tetrafunctional having four hydroxyl groups.
6. The method of claim 1 , wherein at least a portion of the one or more monomeric polyols are tetrafunctional having four secondary hydroxyl groups.
7. The method of claim 1 , wherein the at least one oligomeric polyol component comprises an oligomeric network comprising residues of the one or more polyhydroxylated aromatic moieties and residues of the one or more monomeric polyols, and a plurality of peripheral groups each comprising one or more hydroxyl groups bound to the oligomeric network by a plurality of linking units, wherein at least a portion of the linking units are oxygen atoms of carbonate linkages and optionally hydrocarbyl ether linkages.
8. The method of claim 7 , wherein at least a portion of the linking units are carbonate linkages.
9. The method of claim 1 , wherein the at least one oligomeric polyol component comprises carbonate species comprising one or more carbonate groups and two or more residues of the at least one monomeric polyol.
10. The method of claim 1 , wherein the oligomeric polyol composition is the reaction product of one or more aromatic polycarbonates containing the polyhydroxylated aromatic moieties with one or more monomeric polyols having more than three secondary hydroxyl groups;
wherein the at least one oligomeric polyol component comprises residues of one or more polyhydroxylated aromatic compounds derived from the one or more aromatic polycarbonates and residues of the one or more monomeric polyols; and
wherein at least a portion of the residues of the one or more polyhydroxylated aromatic compounds derived from the one or more aromatic polycarbonates and the residues of one or more monomeric polyols are linked by carbonate groups.
11. The method of claim 10 , wherein the one or more aromatic polycarbonates have a molecular weight of 1000 grams per mole or greater and 100,000 grams per mole or less.
12. The method of claim 10 , wherein the one or more aromatic polycarbonates comprise bisphenol A polycarbonate.
13. The method of claim 10 , wherein the reacting is carried out in the presence of a catalyst comprising an organic base, an inorganic base, a metal oxide, an organometallic compound, or a mixture of two or more of the foregoing.
14. The method of claim 10 , wherein the reacting is carried out in the presence of a catalyst comprising a metal hydroxide.
15. The method of claim 14 , wherein the metal hydroxide is potassium hydroxide.
16. The method of claim 10 , wherein the reacting is carried out in the presence of a promoter.
17. The method of claim 10 , wherein at least a portion of the reacting is carried out in the presence of at least one polyol comprising four or more primary hydroxyl groups.
18. The method of claim 10 , wherein at least a portion of the reacting is carried out in the presence of a polyhydroxylated amine comprising two or more hydroxyl groups.
19. The method of claim 10 , wherein the one or more monomeric polyols comprises a monomeric polyol having four or more secondary hydroxyl groups.
20. The method of claim 10 , wherein the temperature sufficient to cause formation of the product oligomeric polyol composition is 120° C. or greater and 160° C. or less during a reaction time of 45 minutes or greater and 90 minutes or less, and the one or more aromatic polycarbonates and the one or more monomeric polyols are reacted in a molar ratio of repeat units of the one or more aromatic polycarbonates to the one or more monomeric polyols of 0.25 to 1 or greater and 1 to 1 or less.