Polyhydroxy ketal ester adducts, methods of manufacture and uses thereof

1. A method for the manufacture of a polyhydroxy ketal adduct I

wherein

G is a C2-32 alkylene, C2-32 alkenylene, C4-8 cycloalkylene, C5-8 cycloalkenylene, C6-12 arylene, or C2-32 —(R 12 O) q R 12 _wherein each R 12 is methylene, ethylene, 1,3-propylene, or 1,2-propylene and q=1-31, wherein G has a valence of t, wherein t=2-12,

each R 2 is independently C1-6 alkyl,

each R 3 , R 4 , and R 6 is each independently hydrogen, C1-6 alkyl, —OR 8 wherein R 8 is C1-4 alkyl, or —C(O)R 9 wherein R 9 is C1-4 alkyl,

each R 7 is independently C1-6 alkylene, or C1-6 alkylene substituted with one —OR 8 group wherein R 8 is C1-3 alkyl, or —C(O)R 9 wherein R 9 is C1-2 alkyl,

each a is independently=0-3,

each b is independently=0-1,

each m is independently=1-50,

p=0-11,

q-n=0-10, and

n=1-12, provided that p+n≧2, q≧n, and p+(q-n)+n=t, wherein t=2-12, and is the valence of G,

the method comprising

(a) esterifying a polyol II,

G-[OH] t   II

with a compound III

wherein G in formula II is the same as G in formula I, t in formula II has the same value as the valence of G in formula I, R 2 and a in formula III are the same as the R 2 and a in formula I, L is hydroxy, halide, —OC(═O)R 11 , or —OR 11 wherein R 11 is a C1-3 alkyl, wherein the molar ratio of the compound III to the polyol II is greater than or equal to about 1.5:1;

in the presence of an esterification catalyst, wherein the esterification catalyst is about 2 to 20,000 parts per million relative to the sum of the weights of the polyol II and the compound III, to form a ketocarboxylic ester IV

wherein R 2 , a, p, and q in formula (IV) are the same as R 2 , a, p, and q in formula I; and

(b) ketalizing ketocarboxylic ester IV with a polyol V

in the presence of a ketalization catalyst, to provide the polyhydroxy ketal adduct I,

wherein R 3 , R 4 , R 6 , R 7 , and b in formula V are the same as R 3 , R 4 , R 6 , R 7 , and b in formula I, and wherein the ketocarboxylic ester IV and the polyol V are provided in amounts such that the molar ratio of the polyol V to the ketocarboxylic ester IV is greater than or equal to about 2.

2. The method of claim 1 , wherein the esterification catalyst is a sulfuric acid, arylsulfonic acid, hydrate of an aryl sulfonic acid, p-toluenesulfonic acid monohydrate, methane sulfonic acid, camphor sulfonic acid, dodecyl benzene sulfonic acid, perchloric acid, hydrobromic acid, or hydrochloric acid esterification catalyst, or a combination comprising at least one of the foregoing protic acids, or a titanium tetraalkoxide, aluminum trialkoxide, tin(II) alkoxide, tin carboxylate, organo-tin alkoxide, organo-tin carboxylate, or a combination comprising at least one of the foregoing aprotic catalysts.

3. The method of claim 1 , wherein the esterification catalyst is heterogenous.

4. The method of claim 1 , wherein the esterifying of the polyol II with the compound III is conducted at a temperature of about 100 to about 260° C. and at atmospheric pressure or in a vacuum of about 10 to less than 760 torr.

5. The method of claim 1 , wherein the ketocarboxylic ester IV is not isolated prior to the ketalizing.

6. The method of claim 1 , wherein the ketocarboxylic ester IV is isolated prior to ketalizing.

7. The method of claim 6 , wherein the isolating is by washing or crystallizing to produce an isolated, crystallized ketocarboxylic ester IV.

8. The method of claim 7 , wherein the isolated, crystallized ketocarboxylic ester IV is recrystallized prior to ketalizing.

9. The method of claim 1 , wherein the ketalization catalyst is camphor sulfonic acid or a heterogeneous cation exchange resin.

10. The method of claim 1 , wherein the ketalization catalyst is the same as the esterification catalyst.

11. The method of claim 1 , wherein the ketalizing of the ketocarboxylic ester IV with the polyol V is conducted at a temperature of about 60 to about 200° C. under a vacuum or under an inert gas purge.

12. The method of claim 1 , wherein excess ketocarboxylic ester IV is isolated from the ketalization mixture comprising polyhydroxy ketal adduct I by crystallization of ketocarboxylic ester IV.

13. The method of claim 1 , further comprising decanting excess polyol V from the ketalization mixture comprising polyhydroxy ketal adduct I.

14. The method of claim 1 , wherein polyhydroxy ketal adduct I is

wherein

G is a C2-6 alkylene or —(CH 2 CH 2 OCH 2 CH 2 )—,

each m is independently=1 to 10, and

n=1 and p =1, or n=2 and p=0.

15. The method of claim 1 , wherein G is a C2-6 alkylene.

16. The method of claim 1 , wherein G is a C2-4 alkylene.