Polyketal adducts, methods of manufacture and uses thereof
Disclosed herein is a polyketal adduct obtained by forming an ester between a hydrocarbon polyol and a ketocarboxylic acid to produce an intermediate polyketocarboxylic ester. The intermediate polyketocarboxylic ester can be purified via crystallization to achieve purities of greater than 99.0% and then ketalized to produce the polyketal adduct, which can be used in polymer compositions. The polyketal adduct I is obtained at high purity and at high yield.
1. A method for the manufacture of a composition comprising a polyketal adduct I
wherein
G is ethylene, 1,4-butylene, or 1,6-hexylene having a valence of g, wherein g=2,
R 2 is methyl,
R 3 is each independently hydrogen or C 1 -C 6 alkyl,
R 4 and R 5 are each independently hydrogen or C 1 -C 6 alkyl,
R 6 is each independently
hydrogen or C 1 -C 6 alkyl, or
R 3 and R 6 together with their directly attached carbons form a fused cycloaliphatic or aromatic ring having a total of 5-6 carbon atoms or 4-5 carbon atoms and 1-2 oxygen atoms,
R 7 is each independently hydrogen, C 1 -C 6 alkyl, or C 5 -C 6 cycloalkyl that is optionally substituted with an oxygen in the ring and further optionally substituted with 1-2—OR 10 wherein R 10 is C 1 -C 3 alkyl,
a is 2,
b is each independently 0 or 1,
the method comprising forming an ester between a hydrocarbon polyol II
G-[OH] g II
and a ketocarboxy compound III in the presence of an ester-forming catalyst,
wherein
each ketocarboxy compound III is the same or different,
L is hydroxy, and
the forming an ester is conducted with at least 0.75 equivalents of the ketocarboxy compound III per one equivalent of hydroxy group in the hydrocarbon polyol II, to form a polyketocarboxylic ester IV
and
ketalizing polyketocarboxylic ester IV with a molar excess of polyol V relative to the Moles of polyketocarboxylic ester IV
in the presence of a ketalization catalyst to provide the polyketal adduct I having less than 7 wt % of oligomers, wherein the oligomers are reaction byproducts that have a molecular weight higher than the molecular weight of the polyketal adduct I.
2. The method of claim 1 , wherein the forming an ester is in the presence of 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 ester-forming catalyst, or a titanium tetraalkoxide, aluminum trialkoxide, tin II alkoxide, tin II carboxylate, organo-tin alkoxide, organo-tin carboxylate, levulinic acid, a tertiary amine, a quaternary ammonium hydroxide, a metal oxide, a metal hydroxide, or a combination thereof.
3. The method of claim 1 , wherein the ester-forming catalyst is heterogeneous.
4. The method of claim 1 , wherein the forming the ester between the hydrocarbon polyol II and the ketocarboxy compound III is conducted at a temperature of about 100 to about 260° C. and at a pressure of about 10 to 760 torr inclusive.
5. The method of claim 1 , wherein the polyketocarboxylic ester IV is not isolated prior to the ketalizing.
6. The method of claim 1 , wherein the polyketocarboxylic 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 polyketocarboxylic ester IV.
8. The method of claim 7 , wherein the isolated polyketocarboxylic ester IV is recrystallized prior to ketalizing.
9. The method of claim 1 , wherein the ketalization catalyst is camphor sulfonic acid, dodecyl benzene sulfonic acid, sulfuric acid, hydrochloric acid, or a combination thereof.
10. The method of claim 1 , wherein the ketalization catalyst is a heterogeneous acid catalyst.
11. The method of claim 2 , wherein the ketalization catalyst is the same as the ester-forming catalyst.
12. The method of claim 1 , wherein the ketalizing of the polyketocarboxylic 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.
13. The method of claim 1 , further comprising distilling excess polyol V from the polyketal adduct I.
14. The method of claim 1 , further comprising removing the ketalization catalyst from the polyketal adduct I comprising using a base, buffer, or anion exchange resin.
15. The method of claim 1 , wherein the polyketal adduct I after ketalizing has a purity of greater than 50 wt % without further purification.
16. The method of claim 1 , wherein polyketal adduct I comprises less than 1 wt % of an oligomer with a molecular weight greater than 500 Daltons.
17. The method of claim 1 , wherein the polyketal adduct I has a yellowness index of less than 200 as measured by ASTM E313.