CROSSLINKABLE POLYKETAL ESTERS, METHODS OF MANUFACTURE AND USES THEREOF

1 . A method for the manufacture of a crosslinkable polyketal ester comprising units (I)

and optionally units (VII)

wherein

H is a divalent linking group having more than 2 carbon atoms,

G is a hydrocarbon group,

R 2 is C 1 -C 6 alkyl,

R 3 is 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 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,

a=0-3, and

b=0 or 1, and optionally units (VII)

the method comprising:

(a) esterifying a hydrocarbon polyol (II)

HO-G-OH  (II)

with at least 2 equivalents of a ketocarboxy(III) and an esterification catalyst,

wherein each ketocarboxy (III) is the same or different, and wherein L is hydroxy, halide, or OR 11 wherein R 11 is a C 1 -C 4 alkyl, to form a polyketocarboxylic ester (IV)

and

(b) ketalizing polyketocarboxylic ester (IV) with a molar excess of polyol (V) or bisketal (VIII) and optionally polyol (VI)

in the presence of a ketalization catalyst to provide the crosslinkable polyketal ester comprising units (I) and optionally units (VII).

2 . The method of claim 1 , wherein the esterification is in the presence of 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 catalysts, 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 catalysts.

3 . (canceled)

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

5 . (canceled)

6 . (canceled)

7 . The method of claim 1 , wherein the polyketocarboxylic ester (IV) is isolated prior to ketalizing and the isolating is by washing or crystallizing to produce an isolated, crystallized polyketocarboxylic ester (IV).

8 . (canceled)

9 . The method of claim 1 , wherein the ketalization catalyst is camphor sulfonic acid, dodecyl benzene sulfonic acid, or a combination thereof.

10 . (canceled)

11 . The method of claim 2 , wherein the ketalization catalyst is the same as the esterification catalyst.

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

13 . (canceled)

14 . (canceled)

15 . A method for crosslinking the crosslinkable polyketal ester comprising units (I)

and optionally units (VII)

wherein

H is a divalent linking group having more than 2 carbon atoms,

G is a hydrocarbon group,

R 2 is C 1 -C 6 alkyl,

R 3 is 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 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,

a=0-3, and

b=0 or 1,

the method comprising crosslinking at least a portion of the polymer units (I) in the presence of an initiator and a crosslinking agent.

16 . The method of claim 15 , wherein the initiator is azobisisobutyronitrile, dibenzoyl peroxide, 2,3-dipentanedione peroxide, lauryl peroxide, methyl ethyl ketone peroxide, or a combination comprising at least one of the foregoing.

17 . The method of claim 15 , wherein the crosslinking agent is styrene, alpha-methyl styrene, para-methyl styrene, vinyl toluene, an acrylamide, octyl acrylamide, methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, trimethylol propane triacrylate, triallyl cyanurate, triallyl isocyanurate, diallyl maleate, diallyl tetrabromophthalate, diallyl phthalate diallyl isophthalate, α-methylene-γ-valerolactone, α-methylene-γ-butyrolactone or a combination comprising at least one of the foregoing crosslinking agents.

18 . A composition comprising crosslinkable polyketal ester comprising units (I)

and optionally units (VII)

wherein

H is a divalent linking group having more than 2 carbon atoms,

G is a hydrocarbon group,

each R 2 is independently C 1 -C 6 alkyl,

each R 3 is independently hydrogen or C 1 -C 6 alkyl,

each R 4 and R 5 are each independently hydrogen or C 1 -C 6 alkyl,

each R 6 is independently hydrogen or C 1 -C 6 alkyl, or R 3 and R 6 together with their directly attached carbons form a cycloaliphatic or aromatic ring having a total of 5-6 carbon atoms or 4-5 carbon atoms and 1-2 oxygen atoms,

each a independently is 0-3, and

each b independently is 0 or 1.

19 . The composition of claim 18 , wherein

each H is independently C2-32 alkylene, C4-8 cycloalkylene, 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,

G is a C 2 -C 32 hydrocarbon containing 1 or more straight chain, branched or cyclic groups that can be saturated, unsaturated, aromatic, or substituted with up to 12 ether oxygens,

each R 2 is independently C 1 -C 3 alkyl,

each R 3 is independently hydrogen or C 1 -C 3 alkyl,

each R 4 and R 5 is independently each hydrogen or C 1 -C 3 alkyl,

each R 6 is independently hydrogen or C 1 -C 3 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,

each a independently is 0-3, and

each b independently is 0 or 1.

20 . (canceled)

21 . (canceled)

22 . The composition of claim 18 , wherein the crosslinkable polyketal ester comprises units (Ia)

and optionally further comprises units (VII) wherein H is a C2-8 saturated alkylene or C6 arylene wherein the carboxy groups are in the 1,3 or 1,4 positions, and wherein

G is a C 2- C 6 alkylene,

R 2 is C1-2 alkyl,

R 4 is hydrogen or C 1 -C 3 alkyl,

R 5 is hydrogen or C 1 -C 3 alkyl,

a=2, and

b=0 or 1

23 . The compositions of claim 22 , wherein the crosslinkable polyketal ester comprises units (Ib)

wherein G is a C 2 -C 6 alkylene, and optionally further comprises units (VII) wherein H is a C2-8 saturated alkylene or C6 arylene wherein the carboxy groups are in the 1,3 or 1,4 positions.

24 . (canceled)

25 . A composition comprising the crosslinked product of the polyketal ester of claim 18 .

26 . The composition of claim 25 , wherein the crosslinked product is crosslinked using styrene, alpha-methyl styrene, para-methyl styrene, vinyl toluene, an acrylamide, octyl acrylamide, methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, trimethylol propane triacrylate, triallyl cyanurate, triallyl isocyanurate, diallyl maleate, diallyl tetrabromophthalate, diallyl phthalate, diallyl isophthalate, α-methylene-γ-valerolactone, α-methylene-γ-butyrolactone or a combination comprising at least one of the foregoing crosslinking agents.

27 . A composition comprising

an organic polymer; and

the crosslinkable polyketal ester comprising units (I) or the crosslinked product thereof of claim 18 .

28 . The composition of claim 27 , wherein the organic polymer is a thermoplastic or a thermosetting polymer.

29 . (canceled)

30 . (canceled)

31 . (canceled)

32 . The composition of claim 27 , further comprising an additive, where the additive is an antioxidant, an antiozonant, a thermal stabilizer, a mold release agent, a dye, a pigment, an antibacterial, a flavorant, a fragrance molecule, an aroma compound, an alkalizing agent, a pH buffer, a conditioning agent, a chelant, a solvent, a surfactant, an emulsifying agent, a foam booster, a hydrotrope, a solubilizing agent, a suspending agents, a humectant, an accelerator, a ultraviolet light absorber, or a combination comprising at least one of the foregoing additives.

33 . The composition of claim 27 , further comprising glass fibers.

34 . (canceled)

35 . An article comprising the composition of claim 18 .