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,
R2 is C1-C6 alkyl,
R3 is hydrogen or C1-C6 alkyl,
R4 and R5 are each independently hydrogen or C1-C6 alkyl,
R6 is hydrogen or C1-C6 alkyl, or R3 and R6 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\u2003\u2003(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 OR11 wherein R11 is a C1-C4 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\xb0 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\xb0 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,
R2 is C1-C6 alkyl,
R3 is hydrogen or C1-C6 alkyl,
R4 and R5 are each independently hydrogen or C1-C6 alkyl,
R6 is hydrogen or C1-C6 alkyl, or R3 and R6 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, \u03b1-methylene-\u03b3-valerolactone, \u03b1-methylene-\u03b3-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 R2 is independently C1-C6 alkyl,
each R3 is independently hydrogen or C1-C6 alkyl,
each R4 and R5 are each independently hydrogen or C1-C6 alkyl,
each R6 is independently hydrogen or C1-C6 alkyl, or R3 and R6 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-(R12O)qR12\u2014 wherein each R12 is methylene, ethylene, 1,3-propylene, or 1,2-propylene and q=1-31,
G is a C2-C32 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 R2 is independently C1-C3 alkyl,
each R3 is independently hydrogen or C1-C3 alkyl,
each R4 and R5 is independently each hydrogen or C1-C3 alkyl,
each R6 is independently hydrogen or C1-C3 alkyl, or R3 and R6 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 C2-C6 alkylene,
R2 is C1-2 alkyl,
R4 is hydrogen or C1-C3 alkyl,
R5 is hydrogen or C1-C3 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 C2-C6 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, \u03b1-methylene-\u03b3-valerolactone, \u03b1-methylene-\u03b3-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.
The claims below are in addition to those above.
All refrences to claim(s) which appear below refer to the numbering after this setence.
1. An articulated structure which includes a plurality of discrete, movably connected structure elements which are moveable between
an extended configuration wherein the elements define two spaced, substantially parallel wall surfaces having operatively upper and lower ends and a roof surface transversely oriented relative to the wall surfaces, the structure elements each having a roof defining portion and two wall defining portions, the roof defining portion being connected to operatively upper ends of the wall defining portions; and
a retracted configuration wherein the elements are nested in a compacted configuration.
2. A structure as claimed in claim 1 which includes a first end and a second end, at least the first end having a closure member.
3. A structure as claimed in claim 2 wherein the closure member is in the form of an articulated roll door.
4. A structure as claimed in claim 1 wherein the structure elements defining the wall surfaces include end structure elements and mid structure elements, the end structure elements at at least the first or second ends of the structure being provided with pivot connections near the operatively lower ends, allowing the end structure elements to collapse downwardly into a closed configuration.
5. A structure element as claimed in claim 4 wherein the pivot connections are provided for the end structure element at both the first and second ends of the structure.
6. A structure as claimed in claim 4 wherein locking mechanisms are provided to lock the end structure element in their collapsed configuration.
7. A structure as claimed in claims 1 wherein the structure includes tracks on which the wall defining portions of the structure elements bear, in use.
8. A structure as claimed in claim 7 wherein the tracks include rollers over which at least some of the wall defining portions of the structure elements move, in use.
9. A structure as claimed in claims 1 which includes a motor for extending and retracting the structure elements.
10. A structure as claimed in claim 9 wherein the motor is remotely operable.
11. A structure element for an articulated structure as claimed in claims 1, which includes a substantially rectangular sheet of material having connection formations for movably connecting the structure element to a complementary structure element.
12. A structure element as claimed in claim 11 wherein the sheet material is in the form of sheet metal.
13. (Canceled)
14. (Canceled)
15. A structure as claimed in claim 5 wherein locking mechanisms are provided to lock the end structure element in their collapsed configuration.