Process for adding methine UV light absorbers to PET prepared by direct esterification
View Patent ↗A method for incorporating a UV light absorbing compound into a polyester prepared using direct esterification of reactants selected from a dicarboxylic acid and a diol. The method comprises reacting the reactants in an esterifying reactor under conditions sufficient to form an esterified product including at least one of an ester, an oligomer, or mixture having an ester and a mixture of low molecular weight polyester; polymerizing the esterified product in a polycondensation reactor to form a polyester; and adding the UV absorbing compound to the esterified products when at least 50% of the carboxy groups initially present in the reactants have been esterified to obtain a yield of UV absorbing compound incorporated into the polyester of greater than 25%. Articles utilizing the UV protected polyester prepared by the method of the invention are additionally disclosed.
1. A method for incorporating a UV light absorbing compound into a polyester prepared using direct esterification of reactants comprising a dicarboxylic acid and a diol, said method comprising:
a. combining said reactants in an esterifying reactor under conditions sufficient to form an esterified product comprising at least one of: an ester, an oligomer, a low molecular weight polyester and mixtures thereof;
b. polymerizing the esterified product in a polycondensation reactor to form a polyester; and
c. adding at least one UV absorbing compound to at least one of said esterification reactor or polycondensation reactor when at least 50% of the carboxy groups initially present in the reactants have been esterified, wherein said UV absorbing compound includes at least one 4-oxybenzylidene radical of Formula I:
wherein X is hydrogen or up to two moieties selected from the group consisting of hydroxy, C 1 -C 6 alkyl, C 1 -C 6 alkoxy and halogen, and wherein the UV absorbing compound includes a polyester reactive group.
2. The method of claim 1 wherein said dicarboxylic acid is selected from the group consisting of aliphatic, alicyclic, or aromatic dicarboxylic acids.
3. The method of claim 2 wherein said dicarboxylic acid is selected from the group consisting of terephthalic acid; naphthalene dicarboxylic acid; isophthalic acid; 1,4-cyclohexanedicarboxylic acid; 1,3-cyclohexanedicarboxylic acid; succinic acid; glutaric acid; adipic acid; sebacic acid; and 1,12-dodecanedioic acid.
4. The method of claim 1 wherein said diol is selected from the group consisting of ethylene glycol; 1,4-cyclohexanedimethanol; 1,2-propanediol; 1,3-propanediol; 1,4-butanediol; 2,2-dimethyl-1,3-propanediol; 1,6-hexanediol; 1,2-cyclohexanediol; 1,4-cyclohexanediol; 1,2-cyclohexanedimethanol; 1,3-cyclohexanedimethanol; 2,2,4,4-tetramethyl-1,3-cyclobutane diol; X,8bis(hydroxymethyl)tricyclo-[5.2.1.0]-decane wherein X represents 3, 4, or 5; diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol; diols containing from about 2 to about 18 carbon atoms in each aliphatic moiety and mixtures thereof.
5. The method of claim 1 wherein said polyester comprises greater than 50 mole % terephthalic acid residues and greater than 50 mole % ethylene glycol residues, wherein the acid component has 100 mole % and the diol component has 100 mole %.
6. The method of claim 1 wherein said polyester comprises greater than 75 mole % terephthalic acid residues and greater than 75 mole % ethylene glycol residues, wherein the acid component has 100 mole % and the diol component has 100 mole %.
7. The method of claim 1 wherein said UV absorbing compound is added to at least one of said reactors when at least about 70% of the carboxy groups initially present in the reactants have been esterified.
8. The method of claim 1 wherein said UV absorbing compound is added to at least one of said reactors when at least about 80% of the carboxy groups initially present in the reactants have been esterified.
9. The method of claim 1 wherein said UV absorbing compound is added to at least one of said reactors when at least about 85% of the carboxy groups initially present in the reactants have been esterified.
10. The method of claim 1 wherein said UV absorbing compound is added to at least one of said reactors when greater than about 90% of the carboxy groups initially present in the reactants have been esterified.
11. The method of anyone of claims 1 , and 7 - 10 wherein from 0-100% of said UV absorbing compound is added to the esterification reactor.
12. The method of claim 11 wherein from 0 to about 80% of said UV absorbing compound is added to the esterification reactor.
13. The method of claim 11 wherein from 0 to about 50% of said UV absorbing compound is added to the esterification reactor.
14. The method of claim 1 wherein from 0-100% of said UV absorbing compound is added to the polycondensation reactor.
15. The method of claim 1 wherein greater than 50% of said UV absorbing compound is added to the polycondensation reactor.
16. The method of claim 1 wherein greater than 80% of said UV absorbing compound is added to the polycondensation reactor.
17. The method of claim 1 wherein greater than 95% of said UV absorbing compound is added to the polycondensation reactor.
18. The method of claim 1 wherein said UV absorbing compound comprises at least one compound selected from the group consisting of compounds represented by Formulae II-VII:
wherein:
R is selected from the group consisting of hydrogen, C 1 -C 12 -alkyl, substituted C 1 -C 12 -alkyl, aryl, C 3 -C 8 -cycloalkyl, C 3 -C 8 -alkenyl and —(CHR′CHR″O—) p CH 2 —CH 2 —R 5 , wherein p is an integer from 1 to 100;
R′ and R″ are independently selected from the group consisting of hydrogen and C 1 -C 12 alkyl;
n is a whole number ranging from 2 to 4;
R 1 is selected from the group consisting of —CO 2 R 6 and cyano;
R 2 is selected from the group consisting of cyano, —CO 2 R 6 , C 1 -C 6 -alkylsulfonyl, arylsulfonyl, carbamoyl, C 1 -C 6 -alkanoyl, aroyl, aryl, and heteroaryl;
R 3 is selected form the group consisting of —COR 7 , —CON(R 7 )R 8 and —SO 2 R 7 ;
R 4 is selected from the group consisting of:
R 5 is selected from the group consisting of hydrogen, hydroxy, C 1 -C 6 -alkoxy, C 1 -C 6 -alkanoyloxy and aryloxy;
R 6 is selected from the group consisting of hydrogen, C 1 -C 12 -alkyl, substituted C 1 -C 12 -alkyl, —(CHR′CHR″O—) p CH 2 CH 2 R 5 , C 3 -C 8 -alkenyl, C 3 -C 8 -cycloalkyl, aryl, and cyano, wherein p is an integer from 1 to 100;
R 7 is selected from the group consisting of C 1 -C 8 -alkyl, C 3 -C 7 -cycloalkyl and aryl;
R 8 is selected from the group consisting of hydrogen, C 1 -C 8 -alkyl, C 3 -C 8 -cycloalkyl and aryl;
R 9 is selected from the group consisting of C 1 -C 12 -alkylene, arylene and C 3 -C 8 -cycloalkylene, and —(CHR′CHR″O′—) p CHR′CHR″—, wherein p is an integer from 1 to 100;
L is a divalent organic linking groups bonded by non-oxo carbon atoms;
L 1 is a di, tri, or tetravalent linking group, wherein the divalent radical is selected from the group consisting of C 2 -C 12 - alkylene, —(CHR′CHR″O—) p CHR′CHR″—, C 1 -C 2 -alkylene-1,4-phenylnene-C 1 -C 2 -alkylene, —CH 2 CH 2 O-1,4-phenylene-OCH 2 CH 2 , and —CH 2 -1,4-cyclohexylene-CH 2 —, wherein p is an integer from 1 to 100 and wherein the trivalent and tetravalent radicals are selected from the group consisting of C 3 -C 8 aliphatic hydrocarbon having three or four covalent bonds;
A and A 1 are independently selected from the group consisting of 1,4-phenylene and 1,4-phenylene substituted with one or two groups selected from the group consisting of hydroxy, halogen, C 1 -C 6 -alkyl and C 1 -C 6 -alkoxy.
19. The method of claim 18 wherein said alkoxylated moiety represented by the formula —(CHR′CHR″O—)p is selected from the group consisting of ethylene oxide residues, propylene oxide residues, or residues of both, and p is less than about 50.
20. The method of claim 19 wherein p is from 1-3.
21. The method of claim 18 wherein said UV absorbing compound is selected from the group consisting of compounds represented by Formulae VIII-X:
wherein:
R′ 9 is selected from the group consisting of hydrogen, C 1 -C 6 -alkyl and —(CHR′CHR″O—) p CH 2 CH 2 OR 12 , wherein p is an integer from 1 to 100;
R 10 is selected from the group consisting of hydrogen and C 1 -C 6 -alkoxy;
R 11 is selected from the group consisting of C 1 -C 6 -alkyl; cyclohexyl, phenyl, and —(CHR′CHR″O—) p R 12 , and wherein p is an integer from 1 to 100;
R 12 is selected from the group consisting of hydrogen and C 1 -C 6 alkyl;
L 2 is selected from the group consisting of C 2 -C 6 -alkylene, —(CH 2 CH 2 O) p —CH 2 CH 2 , and —CH 2 -cyclohexane-1,4-diyl-CH 2 —, wherein p is an integer from 1 to 100; and
L 3 is selected from the group consisting of C 2 -C 6 -alkylene, —(CH 2 CH 2 O) p —CH 2 CH 2 and C 3 -C 8 -alkenylene, wherein p is an integer from 1 to 100.
22. The method of claim 18 wherein said UV absorbing compound is selected from the compounds represented by Formulae XI and XII:
23. The method of claim 1 wherein the amount of UV absorbing compound incorporated into said polyester has a yield greater than 25%.
24. The method of claim 23 wherein the yield is greater than 40%.
25. The method of claim 23 wherein the yield is greater than 50%.
26. The method of claim 23 wherein the yield is greater than 75%.