Carboxy-terminated oligomeric polyester compositions and method for making
View Patent ↗The present invention provides carboxy-terminated oligomeric polyester compositions useful in the preparation of “weatherable” polymeric materials, for example weatherable copolyestercarbonates. In one aspect the present invention provides an oligomeric polyester composition comprising structural units derived from at least one diacid, at least one diaryl carbonate and at least one diol. The structural units derived from the diacid are present in a molar excess of from about 10% to about 40% based on a ratio of moles of diacid-derived structural units to moles of diol-derived structural units present in the oligomeric polyester composition. The oligomeric polyester composition is further characterized by the presence of at least some phenoxy end groups.
1. A method for preparing a composition comprising a carboxy-terminated oligomeric polyester, said method comprising heating a reaction mixture to a temperature in a range from about 140 to 300° C., said reaction comprising
a transition metal alkoxide Lewis acid catalyst;
a diacid selected from the group consisting of diacids of formula IV and formula V
wherein, R 3 and R 4 are independently at each occurrence a halogen atom, a nitro group, a cyano group, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 12 aromatic radical; “b” is an integer from 0 to 4; and “c” is an integer from 0 to 4;
a diol having formula VIII
HO—R 2 —OH Formula VIII
wherein R 2 is an aromatic radical of formula IX
wherein R 7 is independently at each occurrence a halogen atom, a nitro group, a cyano group, a C 1 -C 14 aliphatic radical, a C 4 -C 14 cycloaliphatic radical, or a C 6 -C 14 aromatic radical; and “f” is an integer from 0 to 4; and
a diaryl carbonate has formula VI
wherein R 5 and R 6 are independently at each occurrence a halogen atom, a nitro group, a cyano group, C 1 -C 20 aliphatic radical, C 3 -C 20 cycloaliphatic radical, or a C 6 -C 20 aromatic radical; “d” is an integer from 0 to 5; and “e” is an integer from 0 to 5; and
wherein said diacid and said diol are present in an amount corresponding to a molar ratio of diacid to diol of between about 10% to about 40% excess diacid based on the amount of diol.
2. The method according to claim 1 , wherein “b”,“c”,“d”,“e”, and “f” are zero.
3. The method according to claim 1 wherein said catalyst is titanium butoxide (Ti(OBu) 4 ), dicarboxylic acid is isophthalic and/or terephthalic acid, said diol is resorcinol, and said diaryl carbonate is diphenyl carbonate.
4. The method according to claim 3 , wherein said reaction mixture further comprises sodium hydroxy phosphate co-catalyst.
5. The method according to claim 1 wherein said catalyst comprises a Group JYB metal alkoxides, a Group IVA metal oxide, a Group IVA metal carboxylate or antimony trioxide.
6. The method according to claim 1 wherein said catalyst is selected from the group consisting of titanium butoxide (Ti(OBu) 4 ), titanium isopropoxide (Ti(OiPr) 4 ), titanium phenoxide (Ti(OPh) 4 ), antimony trioxide, zirconium butoxide (Zr(OBu) 4 ), dialkyltin dialkoxides, dibutyltin oxide, dibutyltin diesters, and tin phenoxide.
7. The method according to claim 1 wherein said catalyst is titanium butoxide (Ti(OBu) 4 ).
8. The method according to claim 1 wherein said catalyst is present in an amount corresponding to from about 20 parts per million to about 1% based on the weight of diol employed.
9. The method according to claim 1 wherein said reaction mixture further comprises a co-catalyst, said co-catalyst comprising a metal hydroxy phosphate.
10. The method according to claim 9 , wherein said co-catalyst comprises sodium hydroxy phosphate.
11. The method according to claim 9 , wherein said co-catalyst is present in a molar ratio ranging from about 2:1 to about 10:1 based on the moles of catalyst employed.
12. The method according to claim 1 wherein said at least one diaryl carbonate and at least one diol are present in an amount corresponding to a molar ratio of diaryl carbonate to diol, said molar ratio of diaryl carbonate to diol being in a range between about 1.5 to 1 to about 2.5 to 1.