Note: Descriptions are shown in the official language in which they were submitted.
CA 02654809 2009-07-24
POLYKETAL COMPOUNDS, SYNTHESIS, AND APPLICATIONS
FIELD OF THE INVENTION
The invention relates to polyketal compounds. The compounds are synthesized by
the selective ketalization of oxocarboxylic acids, e.g. keto acids and
semialdehydes, and
esters thereof with tetrols and higher polyols that products two or more
cyclic ketal ester
moieties per molecule, wherein the cyclic ketal moieties are situated in a bis-
, tris-, or
polyketal conformation. The invention further relates to applications of these
compounds
and subsequent reactions thereof.
BACKGROUND
Many known chemical products such as surfactants, plasticizers, solvents, and
polymers are currently manufactured from non-renewable, expensive, petroleum-
derived or
natural gas-derived feedstock compounds. High raw material costs and
uncertainty of future
supplies requires the discovery and development of surfactants, plasticizers,
solvents, and
polymers that can be made from inexpensive renewable biomass-derived
feedstocks and by
simple chemical methods. Using renewable resources as feedstocks for chemical
processes
will reduce the demand on non-renewable fossil fuels currently used in the
chemical industry
and reduce the overall production of carbon dioxide, the most notable
greenhouse gas.
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CA 02654809 2009-03-05
It is desirable to provide commonly used materials, such as surfactants,
plasticizers, solvents, and polymers, from renewable feedstocks as a source of
chemical building blocks. It is desirable to provide chemical building blocks
that
are chemically and thermally stable. It is desirable to provide chemical
building
blocks having multiple functionalities for subsequent reactions. It is
desirable to
provide such materials by simple and reproducible methods that can be carried
out
with ease.
A potential source of materials that are useful as chemical building blocks
are cyclic ketals and acetals of oxocarboxylates with polyols. It is known,
for
example, that polyhydric alcohols, or polyols, having 1,2 and 1,3 hydroxy
conformations can react with a ketone or aldehyde to form a cyclic ketal or an
acetal
(Carey, F.A. and Sundberg, R.J., "Advanced Organic Chemistry Part B: Reactions
and Synthesis" 2nd ed., 1983, Plenum Press, NY, NY, p. 544). The 1,2 and 1,3
configurations of hydroxyl groups on a hydrocarbon chain are shown below as
(a)
and (b), respectively.
HOB ,OH ?H ?H
,c-C -
' %
(a) (b)
Diols such as 1,2-ethane diol (ethylene glycol) and 1,3 propanediol (propylene
glycol) are examples of such polyols. Diols having a 1,2 hydroxyl group
configuration will form dioxolanes when reacted with ketone or aldehyde
moieties,
while 1,3 diols will form dioxanes.
Various ketals arising from the reaction of oxocarboxylic acids and esters
thereof with diols and triols are known. Ono et al., J. Am. Oil Chem. Soc.
70(1), 29
(1993) disclose ketalization of ethyl pyruvate, ethyl acetoacetate, and ethyl
levulinate with various 1-0-alkyl glycerols (diols). Okohara et al., JP
04217972,
similarly disclose ketalization of ethyl levulinate with 1-0-alkyl glycerols,
followed
by saponification of the ester moiety. McCullough et al., U.S. Patent No.
5,998,092
disclose the kel alization of two keto acids with ethylene glycol. Chirila,
Revistade
Chimie 28(8), 730-3 (1977) discloses the 1:1 adduct of acetoacetate esters
with
glycerol. Gelas, Carbohydrate Research 30(1), 21-34 (1973) and Rakhmankulov et
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al., SU 722912 disclose the 1:1 adduct of pyruvate esters with glycerol and
subsequent
bicyclic lactone formation.
Ketals of glycerol and levulinic acid or an ester thereof are described in
U.S. Patent
Application No. 2008/0242721. The ketal reaction product of glycerol with a
levulinate
results in the ketal acid or ketal ester shown below,
O OH O
H+ O
OR HO-"~OH HO~O 4
OR
O
wherein R is hydrogen or an alkyl group. The use of levulinate compounds and
glycerol
based compounds is particularly useful as both of these starting materials
arise from
renewable feedstocks. Further, the ketal reaction products are useful for
synthesis of a wide
variety of surfactants, plasticizers, polymers, and the like.
Efficient synthetic routes to form various compounds based on the ketals or
acetals
of keto acids, semialdehydes, and the esters thereof are described in PCT
Patent Application
No. WO 2009/048874. The synthetic routes described in this applications is
useful as a basis
for efficient reaction of a number of oxocarboxylic acids and esters thereof
with alcohols.
It is desirable to provide new starting materials and synthetic routes to form
new
varieties of chemical building blocks for monomers, plasticizers, surfactants,
and polymers.
It is desirable to provide chemical building blocks that arise solely from
renewable
feedstocks. It is desirable to facilitate synthesis of chemical building
blocks that is simple,
inexpensive, and scalable for commercialization purposes.
SUMMARY
The invention concerns a polyketal of structure I:
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R5 R6 R6 R5
b R9
R$ b W
t-r'
O O 0 O
O O
R4 R4
R1--O a a O-R1
R2 R3 R3 R2
I
wherein
a is 1 or 2;
R1, the same or different for each occurrence, is hydrogen, a metal cation, an
organic
cation, a linear, branched, or cyclic alkyl, a linear, branched, or cyclic
alkenyl, alkynyl, aryl,
alkaryl, or an oligomeric or polymeric moiety; and optionally contains one or
more
heteroatoms;
R2, R3, R4, R5, and R6, the same or different for each occurrence, are
independently
hydrogen, a linear, branched, or cyclic alkyl, a linear, branched, or cyclic
alkenyl, alkynyl,
aryl, or alkaryl; and optionally contains one or more heteroatoms;
R7, the same or different for each occurrence, is a covalent bond or
hydroxymethylene;
R 8 and R9 are hydrogen;
a, the same or different for each occurrence, is 0 or an integer of 1 to 12;
and
b, the same or different for each occurrence, is 0 or 1,
wherein b = 0 indicates a five membered ring:
O~/O
'R4
and b = 1 indicates a 6 membered ring:
3a
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R5 R6
S-~~
O O
I R4
Preferably, in formula I above, all R2 and R3 are hydrogen, all R4 are methyl,
and all
R7 are covalent bonds.
More preferably, all a are 2, all b are 0, R8 and R9 are hydrogen, and all a
are 1 or 2.
Alternatively, in formula I, R' may be ethyl, butyl, or 2-ethylhexyl; or a
residue of
polyol. R' may also comprise isocyanate, acrylate, methacrylate, allyl, or
oxiranyl groups.
The invention is also directed to a formulation comprising one or more
polyketals of
formula I as defined above and one or more solvents or an additional polymer.
Preferably, the additional polymer is poly(3-hydroxybutyrate-co-
hydroxyvalerate),
poly(vinyl chloride), poly(lactic acid), or polystyrene.
The invention is also directed to the use of the above defined formulation as
a coating
formulation.
The invention is also directed to an article comprising the above defined
formulation.
The invention also concerns a polymeric composition comprising polymers, said
polymers comprising one or more repeat units of structure III:
R5 R6 R6 R5
R8-~A b R7 R9
O O a 0 O
O O
R4 R4
O a a O-R1
R2 R3 R3 R2
III
wherein:
R', the same or different for each occurrence, is a divalent linear, branched,
or cyclic
alkyl, a linear, branched, or cyclic alkenyl, alkynyl, aryl, alkaryl, or an
oligomeric or
polymeric moiety; and optionally contains one or more heteroatoms;
3b
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R2 to R', a and b, the same or different for each occurrence, are as defined
above for
structure I;
R8 and R9, the same or different for each occurrence, are hydrogen, a linear,
branched, or cyclic alkyl, a linear, branched, or cyclic alkenyl, alkynyl,
aryl, alkaryl, or a
polymeric moiety; and optionally contain one or more heteroatoms;
c~ the same or different for each occurrence, is an integer of at least 1; and
fl is an integer of at least 1.
Preferably, in formula III above, all R2 and R3 are hydrogen, all R4 are
methyl and
all R7 are covalent bonds. More preferably, all a are 2, all b are 0, R8 and
R9 are hydrogen,
and all a are l or 2.
The invention is further directed to a polyketal of structure I:
R6 R5
R5 6 la b
Ra b R7+
O O JJJ C IO I~ IO
O O
R R4
R2 R
R'-'O 3 R3 R2 a O-R1
(I)
wherein
a is an integer of at least 1;
R', the same or different for each occurrence, is an organic cation, a linear,
branched,
or cyclic alkyl, a linear, branched, or cyclic alkenyl, alkynyl, aryl,
alkaryl, or an oligomeric
or polymeric moiety; and optionally contains one or more heteroatoms;
R2, R3, R5, and R6 , the same or different for each occurrence, are
independently
hydrogen, a linear, branched, or cyclic alkyl, a linear, branched, or cyclic
alkenyl, alkynyl,
aryl, or alkaryl; and optionally contains one or more heteroatoms;
R4, the same or different for each occurrence, is a linear, branched, or
cyclic alkyl, a
linear, branched, or cyclic alkenyl, alkynyl, aryl, or alkaryl; and optionally
contains one or
more heteroatoms;
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R7, the same or different for each occurrence, is a covalent bond or
hydroxymethylene;
R8 and R9, the same or different, are independently hydrogen, a linear,
branched, or
cyclic alkyl, a linear, branched, or cyclic alkenyl, alkynyl, aryl, alkaryl,
or a polymeric
moiety; and optionally contains one or more heteroatoms;
a, the same or different for each occurrence, is 0 or an integer of 1 to 12;
and
b, the same or different for each occurrence, is 0 or 1, wherein b = 0
indicates a five
membered ring:
OO
and b =1 indicates a 6 membered ring:
R5 R6
O O
;2, R4
The invention is yet directed to a polyketal of structure:
R8 R7 R9
O O a O O
O O
R4 R4
R1-O a_ a O-RI
R2 R3 R3 R2
wherein.
a is an integer of at least 1;
R', the same or different for each occurrence, is hydrogen, a metal cation, an
organic
cation, a linear, branched, or cyclic alkyl, a linear, branched, or cyclic
alkenyl, alkynyl, aryl,
alkaryl, or an oligomeric or polymeric moiety; and optionally contains one or
more
heteroatoms;
3d
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R2, R3, R4, R5, and R6, the same or different for each occurrence, are
independently
hydrogen, a linear, branched, or cyclic alkyl, a linear, branched, or cyclic
alkenyl, alkynyl,
aryl, or alkaryl; and optionally contains one or more heteroatoms;
R7, the same or different for each occurence, is a covalent bond or
hydroxymethylene;
R8 and R9 , the same or different, are hydrogen, a linear, branched, or cyclic
alkyl, a
linear, branched, or cyclic alkenyl, alkynyl, aryl, alkaryl, or a polymeric
moiety; and
optionally contains one or more heteroatoms; and
a, the same or different for each occurrence, is 0 or an integer of I to 12.
The invention is also directed to a formulation comprising one or more
polymeric
compositions as described above and one or more additional polymeric
compounds, one or
more additives, or one or more solvents.
Preferably, the one or more additives is (are) a crosslinker, redox initiator,
thermal
initiator, UV initiator, UV stabilizer, thermal stabilizer, colorant,
antibacterial agent,
antifungal agent, antioxidant, plasticizer, filler, adjuvant, or a mixture
thereof.
The invention is also directed to an article comprising one or more polymeric
composition as defined above.
The invention is also directed to the use of one or more polyketals of formula
I
defined above as plasticizers, tougheners, surfactants, barrier layer
materials, interfacial
modifiers, compatibilizers, solvents, coalescing solvents, or phase transfer
materials.
The invention is further directed to the use of one or more polymeric
composition
comprising the polymer of formula III defined above as plasticizers,
tougheners, surfactants,
barrier layer compounds, interfacial modifiers, compatibilizers, or phase
transfer
compounds.
Disclosed herein are polyketal compounds having at least two contiguous or
semi-
contiguous ketal moieties per molecule. These compounds are useful in numerous
applications and materials having physical properties suitable for replacing
present fully
petrochemical-based materials such as plasticizers, surfactants, coatings
additives, and other
industrially useful applications.
3e
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The polyketal compounds of the invention are based on selective ketalization
of oxocarboxylic acids and esters thereof, with tetrols, hexols, and higher
polyols.
We have found that polyols having two or more pairs of hydroxyl groups
situated in
1,2 and 1,3 positions are able to react with multiple equivalents of keto
esters,
semialdehydes, or esters thereof to provide bisketals, trisketals, and higher
polyketals. This is true even where the hydroxyl pairs are present in a
contiguous
position relative to neighboring hydroxyl pair(s), e.g. in forming the
bisketal of
erythritol or the trisketal of sorbitol. The ability to form contiguous ketals
is
surprising because the reaction to form one ketal group on a polyol would be
expected to reduce reactivity of remaining hydroxyl groups that are situated
on
contiguous carbons.
The polyketal compounds of the invention are useful in a number of
applications. Nonlimiting examples of uses for the compounds of the invention
include uses as solvents, plasticizers, surfactants, coalescing solvents,
compatibilizing solvents, interfacial modifiers, and phase transfer materials
in one or
more formulations. Additionally, the polyketal compounds of the invention
supply
at least two carboxyl functionalities on a single molecule which in turn
supply
chemically reactive sites for forming a wide variety of dimeric, oligomeric,
or
polymeric materials with a wide scope of applications. Thus, the compounds of
the
invention can be employed as monomers having two or more reactive carboxyl
functionalities per molecule, suitable for synthesis of species such as
polyesters,
copolyesters, polymeric polyols, polyurethanes, poly(urethane urea)s,
poly(ester
urethane)s, and polycarbonates; additionally, acrylates and methacrylates,
allylic
functional polyketals, epoxy functional polyketals, and polymers formed from
these,
and the like. In some embodiments, the multiple functionalities present in the
structures of the polyketals are useful as crosslinkers for one or more
polymeric
networks.
Additional advantages and novel features of the invention will be set forth in
part in the description that follows, and in part will become apparent upon
examination of the following, or may be learned through routine
experimentation
upon practice of the invention.
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BRIEF DESCRIPTION OF THE DRAWINGS
FIG. IA -1D shows synthetic paths to reach the compounds of the
invention.
FIG. 2A - 2B shows gas chromatographs of a reaction according to the
invention.
FIG. 3A - 3B shows tensile data comparing a formulation of the invention to
a control formulation.
FIG. 4 shows thermogravimetric data for a compound of the invention.
FIG. 5 shows tensile data for a compound of the invention.
DETAILED DESCRIPTION
Various embodiments will be described in detail. Reference to various
embodiments does not limit the scope of the claims attached hereto.
Additionally,
any examples set forth in this specification are not intended to be limiting
and
merely set forth some of the many possible embodiments for the appended
claims.
The compounds of the invention have, in embodiments, one or more isomers.
Where an isomer can exist, it should be understood that the invention embodies
all
isomers thereof, including stereoisomers, conformational isomers, and cis,
trans
isomers; isolated isomers thereof; and mixtures thereof.
In some embodiments, the compounds of the invention have structure I:
R5 6 Rs 5
Re b R~ b R9
O O a 0 O
O
R4 R4
R1-O a a O-R1
R2 R3 R3 R2
I
wherein
a is an integer of at least 1;
Rl is hydrogen, a metal cation, an organic cation, a linear, branched, or
cyclic alkyl, a linear, branched, or cyclic alkenyl, alkynyl, aryl, alkaryl,
or an
oligomeric or polymeric moiety; and optionally contains one or more
heteroatoms; and R' may be the same or different for each occurrence;
5
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R2, R3, R4, R5, and R6 are independently hydrogen, a linear, branched, or
cyclic alkyl, a linear, branched, or cyclic alkenyl, alkynyl, aryl, or
alkaryl;
and optionally contains one or more heteroatoms; and R2, R3, R4, R5, and R6
may be the same or different for each occurrence;
RR is a covalent bond, methylene, ethylene, hydroxymethylene, oxygen, or -
CH2-O-CH2- and R7 is the same or different for each occurrence;
R8 and R9 are independently hydrogen, a linear, branched, or cyclic alkyl, a'
linear, branched, or cyclic alkenyl, alkynyl, aryl, alkaryl, or a polymeric
moiety; and optionally contains one or more heteroatoms;
a is 0 or an integer of l to 12; and
b is 0 or 1, wherein b = 0 indicates a five membered ring:
o O
;~ 4
and b = 1 indicates a 6 membered ring:
R5 R6
O O
R4
and b may be the same or different for each occurrence.
The compounds of the invention are adducts of at least two molar
equivalents of an oxocarboxylate with one molar equivalent of a first polyol
which is
a tetrol or higher polyol. At least two pairs of hydroxyl groups on the polyol
are
present either on contiguous carbon atoms or have one carbon atom spaced
between
hydroxyl-bearing contiguous carbon atoms. These conformations are shown as (a)
and (b) below, respectively, for a hydrocarbon based polyol.
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HO /OH OH OH
C
%
(a) (b)
As defined herein, the term "ketal" means the cyclic adduct of one equivalent
of a first polyol, as defined above, with one equivalent of an oxocarboxylate,
which
is a keto acid, semialdehyde, or ester thereof, to form the corresponding
cyclic ketal
acid, acetal acid, or ester thereof. As defined herein, the term "contiguous"
means a
chemical moiety separated from a neighboring chemical moiety solely by a
covalent
bond. As defined herein, the term "semi-contiguous" means a chemical moiety
separated from a neighboring chemical moiety by a methylene group, ethylene
group, hydroxymethylene group, an oxygen atom, or a -CH2-O-CH2- group. For the
purposes of the invention, cyclic ketal-forming polyols are polyols wherein
hydroxyl
moieties are situated in pairs as shown in a) and b) above.
As defined herein, the term "bisketal" means the ketal adduct of two molar
equivalents of an oxocarboxylate with one equivalent of a tetrol or higher
polyol to
form two contiguous or semicontiguous ketal groups. As defined herein, the
term
"trisketal" means the ketal reaction product, as defined above, of three
equivalents
of an oxocarboxylate with one equivalent of a hexol or higher polyol to form
three
contiguous or semicontiguous ketal groups. And the term "polyketal" as defined
herein means the ketal reaction product, as defined above, of at least two
equivalents
of an oxocarboxylate with one equivalent of a tetrol or higher polyol to form
at least
two contiguous or sernicontiguous ketal groups.
In embodiments, the number of ketal units is determined by the value of a.
The number a is at least 1, but in some embodiments a is up to 100; in other
embodiments the value of a is up to about 1000. In some embodiments, the
polyketals of the invention are based on the reaction of poly(vinyl alcohol)
with one
or more oxocarboxylic acids or esters to form the corresponding polyketal. In
such
embodiments, all values of b are 1 and all Rs and R6 are hydrogen. In some
such
embodiments, the value of a is as much as 100; in other such embodiments the
value
of a is as high as 250. The invention contemplates both poly(vinyl alcohol) as
the
basis for polyketals of the invention as well as copolymers thereof. For
example, in
embodiments, R8, R9, or both are polymeric moieties that are not poly(vinyl
7
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alcohol). For example, the polymeric moieties are, in certain embodiments,
polyethylene or polypropylene residues; in other embodiments the polymeric
moieties are poly(vinyl acetate) residues; other embodiments will be readily
envisioned.
In some embodiments, the invention contemplates a bisketal structure having
a Spiro group. This structure can be represented as structure II:
O Ra O O Ra
R1-0 O R
R2 R3 R3 R2
II
wherein
each Rl is independently hydrogen, a metal cation, an organic cation, a
linear, branched, or cyclic alkyl, a linear, branched, or cyclic alkenyl,
alkynyl, aryl, alkaryl, or an oligomeric or polymeric moiety; and optionally
contains one or more heteroatoms;
each R2 and R3 are independently hydrogen, a linear, branched, or cyclic
alkyl, a linear, branched, or cyclic alkenyl, alkynyl, aryl, or alkaryl; and
optionally contain one or more heteroatoms;
each R4 is independently linear, branched, or cyclic alkyl; linear, branched,
or cyclic alkenyl; alkynyl; aryl; or alkaryl; and optionally contains one or
more heteroatoms; and
each a is independently 0 or an integer of 1 to 12.
The compounds of structure II are bisketal adducts of pentaerythritol,
C(CH2OH)4i
with two molar equivalents of a keto acid or ester thereof.
Structures I and II contemplate many useful embodiments. Various
embodiments of the compounds are useful in one or more formulations; other
embodiments are useful as chemical building blocks in subsequent reactions.
Some
representative and nonlimiting examples of compounds corresponding to
structures I
and R are shown below as structures Ia to Ih and Ila, wherein each R is
independently hydrogen, a metal cation, an organic cation, a linear, branched,
or
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cyclic alkyl, a linear, branched, or cyclic alkenyl, alkynyl, aryl, alkaryl,
or an
oligomeric or polymeric moiety; and optionally contains one or more
heteroatoms:
O O .
-,/~ O R
RO~~ / 0 . 0~ - Il
O
Ia.
O 0
RO OR
O O
OH
Ib.
RO' O p OR
-~~
Ic.
HO
O
HO OR
0 0
RO~ j O
~0
Id.
HO-~Y H
O 0
Ie.
0 OH
RO)A
~ 0
O ~ II OR
HO 0 0
If .
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0 0
RO)O 0 OR
O 13,~ II
0
RO O
Ig=
H CH2 H- CHy
1+ CH2-CHZ~H
O O OH
OR
Ih.
- ~C0 O
RO 11 OXO OR
0 0
Ha.
A variety of oxocarboxylates and polyols are incorporated, in various
embodiments, into the compounds having structures I or II. Suitable examples
of
oxocarboxylates and polyols, while not limiting as to the scope of all
suitable
materials that are starting materials for the compounds having structures I
and II, are
set forth below.
"Keto acid" refers to an oxocarboxylate having at least one ketone moiety
and one carboxylic acid moiety. A compound may have more than one ketone
functionality or more than one carboxylic acid functionality. The keto acid is
not
particularly limited as to additional moieties or functionalities present in
addition to
the ketone and carboxylic acid functionalities. In some embodiments, the
compound
may also contain one or more halogen, ester, amine, thiol, ether, phosphate,
or silane
groups. Some examples of suitable keto acids include pyruvic acid, acetoacetic
acid,
levulinic acid, 5-aminolevulinic acid, oxaloacetic acid, a-ketobutyric acid, a-
ketoglutaric acid, a-ketoisovaleric acid, 5-ketohexanoic acid, cx
ketoisocaproic acid,
a-ketoadipic acid, 3-ketoadipic acid, 2-keto-4-rnethylthiobutyric acid, 4-
acetylbutyric acid, 2-keto-3-bromobutyric acid, phenylpyruvic acid, 2-keto-3-
phenylpropanoic acid, 2-ketopentanoic acid, 3-ketohexanoic acid, 4-
ketohexanoic
acid, 2-ketooctanoic acid, 3-ketooctanoic acid, 4-ketooctanoic acid, 7-
ketooctanoic
CA 02654809 2009-03-05
acid, 2-keto-4-pentenoic acid, 13-keto-9,11-octadecadienoic acid, 4-
ketostearic acid,
9-ketopalmitic acid, 4-ketoheptanedioic acid, penicillic acid, 8-keto-8-
aminopelargonic acid, 2-keto-5-aminovaleric acid, 2-succinylamino-6-
oxoheptanedioic acid, 2-oxo-3-butynoate, 3-keto-6-acetamidohexanoate, and the
like. Additionally, a keto acid may contain hydroxyl or mercapto functionality
provided it is protected, e.g. by one or more trimethylsilyl or t-butyl
groups, or one
or more other protecting groups known to those of skill in the art.
In some embodiments of the invention, the keto acid employed is levulinic
acid (4-oxopentanoic acid). Levulinic acid is an abundant feedstock that is
prepared
on an industrial scale by acidic degradation of hexoses and hexose-containing
polysaccharides such as cellulose, starch, sucrose, and the like. In other
embodiments, pyruvic acid and acetoacetic acid are other acids employed.
"Keto ester" refers to the carboxylic ester of the one or more carboxylate
functionalities of any of the above described keto acid compounds. Thus, in
embodiments where structure I is an ester, the Rl group of structure I is not
hydrogen. The R1 group is, in embodiments, a linear, branched, or cyclic alkyl
or
alkenyl group having I to 18 carbon atoms, or an aryl or alkaryl group,
wherein the
alkyl, alkenyl, aryl, or alkaryl groups can have one or more additional
functional
groups that can include, for example, halogen, ester, amine, thiol, ether, or
silane
functionalities and are not particularly limited except that the one or more
additional
functional groups do not include hydroxyl or mercapto functionality. Thus, Rl
can
be, in embodiments, methyl or ethyl; a linear or branched isomer of an alkyl
group
such as propyl, butyl, pentyl, hexyl, septyl, octyl, nonyl, decyl, undecyl,
dodecyl,
tetradecyl, cetyl, or stearyl; a cycloalkyl group such as cyclohexyl,
cyclooctyl,
norbornyl, and the like; an alkynyl group such as ethynyl, 3-methylpent-1-yn-3-
yl,
tetradec-9-yn-l-yl, and the like; an aryl and alkaryl group such as phenyl,
benzyl,
tolyl, xylyl, 5-phenylpent-l-yl, and the like; wherein the alkyl, alkenyl,
alkynyl, aryl,
or alkaryl may additionally have one or more functional groups, for example,
1, 1, 1 -
trichloro-2-methyl-2-propyl, 5-fluoro-l-pentyl, 5-amino-l-pentyl, 5-benzyloxy-
l-
pentyl, 5-methoxy-l-pentyl, 3-nitro-2-pentyl, 4-methylthio-l-butyl, 1-
carboxyhex-6-
yl, propionamid-2-yl, and the like. Rl can also be a protecting group, such as
trimethylsilyl, phosphonooxy, or a phosphatidyl group, The composition of the
Rl
group is not particularly limited; however, if there are hydroxyl or thiol
functionalities present on the Rl group they should further be protected by a
11
CA 02654809 2009-03-05
protecting group, such as trimethylsilyl, t-butyl, phosphonooxy, or another
group
generally known in the art to be a protecting group, to avoid side reactions
of the
free hydroxyl or thiol with a neighboring oxo group.
In some embodiments of the invention, esters of levulinic acid, pyruvic acid,
or acetoacetic acid are employed as the keto esters in the polyols. For
example,
ethyl levulinate or n-butyl levulinate can be employed in some embodiments of
the
invention. Levulinic esters are based on levulinic acid, an abundant feedstock
that is
prepared on an industrial scale by acidic degradation of hexoses and hexose-
containing polysaccharides such as cellulose, starch, sucrose, and the like.
"Semialdehyde" refers to an oxocarboxylate having at least one aldehyde
functionality and one carboxylic acid functionality. A compound may have more
than one aldehyde functionality or more than one carboxylic acid
functionality. The
semialdehyde is not particularly limited as to additional moieties or
functionalities
present in addition to the aldehyde and carboxylic acid functionalities. In
some
embodiments, the semialdehyde may also contain one or more halogen, ester,
phosphate, amine, thiol, ether, or silane groups. Some examples of suitable
semialdehydes include aspartic semialdehyde, 4-oxobutanoic acid, 5-
oxopentanoic'
acid, 6-oxohexanoic acid, 7-oxoheptanoic acid, c-formylglycine, 3-oxo-2-
(phosphonooxy)-propanoic acid (tartronic semialdehyde wherein the hydroxyl
group
is protected by phosphate), 3-oxopropanoic acid (malonic semialdehyde), 2-
methyl-
3-oxopropanoic acid (methylmalonic semialdehyde), succinic semialdehyde,
adipic
Semialdehyde, 5-glutamyl semialdehyde, allysine, 2-aminomuconic semialdehyde,
4-amino-5-oxopentanoic acid, N-acetylglutamic semialdehyde, 2-amino-3-(3-
oxoprop-l-enyl)-but-2-enedioic acid, and N2-succinyl-L-glutamic-5-
semialdehyde.
Many other semialdehydes are available by carrying out ozonolysis of
unsaturated
fatty acid esters to form an aldehyde moiety at an unsaturated site, as
described by
Criegee, Angew. Chem. Int. Ed., 1975, 87, 745.
. "Semialdehyde ester" refers to the carboxylic ester of the one or more
carboxylate functionalities of any of the above described semialdehyde
compounds.
The nature of the ester group is generally the same as those described above
for the
keto ester functionalities. The composition of the ester Rl group, as shown in
Reaction I, is not particularly limited; however, if there are hydroxyl or
thiol
functionalities present on the R1 group they should further be protected by a
protecting group, such as a trimethylsilyl group or another group generally
known in
12
CA 02654809 2009-10-16
the art to be a protecting group, to avoid side reactions of the free hydroxyl
or thiol with a
neighboring oxo group.
For purposes of the invention, the term "polyol" means any alcohol having two
or
more hydroxyl groups. However, suitable polyols for use in forming the ketal
moieties of
structures I and II are tetrols and higher polyols having at least two pairs
of hydroxyl groups
wherein at least two pairs of hydroxyls are situated on contiguous or semi-
contiguous
carbons atoms, and further wherein the first of the two pairs of hydroxyls is
contiguous or
semicontiguous with respect to the second of the two pairs of hydroxyls.
Examples of
suitable polyols include erythritol, threitol, pentaerythritol, diglycerol,
xylitol, apiitol (2-
hydroxymethyl erythritol), mannitol, sorbitol, maltitol, lactitol,
dipentaerythritol,
tripentaerythritol, and higher oligomers of pentaerythritol, raffinose, and
stachyose; and
poly(vinyl alcohol) and copolymers thereof, such as MOWITALTM resin available
from the
Kuraray Company of Osaka, Japan; AQUASOLTM resin available from A. Schulman,
Inc. of
Akron, OH; or ELVANOL resin available from the DuPont Company of Wilmington,
DE.
In some embodiments, the polyol employed is erythritol. In other embodiments,
the
polyol employed is sorbitol. In other embodiments, the polyol employed is
diglycerol (a
tetrol that is a mixture of glycerol dimers). As used herein, erythritol and
threitol, which are
diastereomers, are used interchangeably in various embodiments of the
reaction. Similarly,
sorbitol and its stereoisomer mannitol are used interchangeably in various
embodiments.
Where no stereochemistry is indicated in a chemical structure, any
stereoisomer may be
employed in the embodiments of the invention.
Synthetic routes to form compounds based on the ketals or acetals of
oxocarboxylates are described in PCT patent application No. WO 2009/048874.
While
generally useful to form monoketals or acetals of oxocarboxylates with various
alcohols, the
methods disclosed in these applications do not directly address any of the
compounds
embodied in the present invention. Thus, the reactivity toward the
ketalization reaction of
more than one equivalent of an oxocarboxylate with a polyol such as a tetrol,
pentol, hexol,
or higher polyol, wherein the hydroxyls are situated on contiguous or
semicontiguous carbon
atoms, is not addressed by this methodology.
13
CA 02654809 2009-10-16
However, we have found that employing the methodology of these patent
application, with additional optimization of the ratio of reagents and amount
of acid
catalyst employed in the reactions, provides for high yield and fast reaction
times in the
formation of the compounds having structure I or II. This result is
surprising,
particularly in embodiments where contiguous pairs of hydroxyls are reacted to
form
contiguous ketals, e.g. where c = 0 in structure I, or in the case of the
Spiro- type ketals
of structure II. In such embodiments, the reactivity of the second, third, and
additional
molar equivalents of oxocarboxylate with the polyol would be expected to be
lower than
the reactivity of the first molar equivalent of oxocarboxylate toward the
polyol due to
steric bulk, restriction in degrees of freedom for remaining hydroxyl
moieties, or a
combination of these factors with other factors. However, we have found that,
in
embodiments, the reactivity of the second and subsequent molar equivalents of
oxocarboxylate toward the polyol already having one or more ketal moieties is
the same
or, in other embodiments, even higher than, the reactivity of the first molar
equivalent of
oxocarboxylate toward ketalization. Thus, in some embodiments of the formation
of the
compounds having structures I and II, adducts having only one ketal moiety per
molecule could not be isolated because the reaction proceeded to virtually
100% very
quickly once the first ketal moiety was formed.
In one nonlimiting example, the reaction of erythritol, a tetrol, and about 5
to 6
moles of oxocarboxylate per mole of erythritol (e.g., about 2.5 to 3
equivalents of
oxocarboxylate per each two equivalents of hydroxyl, or per equivalent of diol
functionality) is catalyzed with about 1 x 10-4 to 1 x 10-6 molar equivalents
of an acid
catalyst per mole of diol functionality, to provide nearly 100% conversion to
the
corresponding bisketal. The species of acid catalyst employed is not
particularly limited
in the various embodiments of the invention; any of the catalysts set forth in
this
methodology may be employed in the method of making various polyketals of the
current invention. In another example, where sorbitol, a hexol, is employed,
about 8
moles of oxocarboxylate per mole of sorbitol (e.g about 2.7 moles of
oxocarboxylate per
mole of diol functionality) with about 1 x 10-4 to 1 x 10,6 molar equivalents
of an acid
catalyst per mole of diol functionality, are reacted to provide nearly 100%
conversion to
the corresponding trisketal.
14
CA 02654809 2009-10-16
The compounds having structures I and Il are useful in many different
applications. In
various embodiments, compounds having structures I and II are
14a
CA 02654809 2009-03-05
plasticizers, tougheners, surfactants, barrier layer materials, interfacial
modifiers,
compatibilizers, solvents, coalescing solvents, or phase transfer materials in
one or
more formulations.
Plasticizers are chemical compounds added to a base composition
comprising one or more polymers with the purpose of lowering the glass
transition
temperature of the polymer composition, thereby making the composition more
flexible and amenable to processing, e.g., by melt extrusion or molding.
Plasticizers
are typically used at various effective concentrations that depend on the
desired
properties of the compounded polymer formulation. For example, in embodiments,
plasticizers are used at concentrations between 1 and 80% by weight of the
unplasticized polymer. It is understood that, depending on the polymer and the
plasticizer used, plasticizers can also confer other changes in physical and
mechanical properties of the compounded polymer, as well as changes in barrier
properties of the compounded polymer in respect to its permeability for
various
gases, water, water vapor, or organic compounds. It is also understood that
one or
more different plasticizers can be used in various blends with additional
compounds
for the preparation of an extrudable or moldable polymer composition. Such
additional compounds can include various inorganic and organic filler
compounds,
wood dust, reinforcing fibers, dyes, pigments, lubricants, anti-microbial or
anti-
fungal additives, thermal or UV stabilizers, and the like.
In some embodiments, plasticizers are mixed with a polymer at temperatures
that are above or below the melting point of the polymer. In some embodiments,
plasticizers can be introduced with a help of a solvent. Many variations of
techniques for introducing plasticizer compounds to polymer compositions are
known in the art.
In embodiments employing the compounds of structure I where a is 1, R8
and R9 are hydrogen, and Rl is ethyl, butyl, or 2-ethylhexyl, the compounds
are
plasticizers for PVC or polystyrene. In other embodiments where a is 2, R8 and
R9
are hydrogen, and Rl is ethyl, butyl, or 2-ethylhexyl, the compounds having
structure I are plasticizers for PVC. In PVC formulations, the compounds of
structure I or II are incorporated, in embodiments, at levels of up to 40% to
result in
clear blends after thermal compounding. Even at the highest loadings, the
plasticizers of structure I and II are substantially retained in PVC
formulations when
subjected to extraction in hexane, mineral oil, or soap solutions at room
temperature;
CA 02654809 2009-07-24
the amount retained is, in embodiments, the same as or better than
conventional PVC
plasticizers such as dioctyl phthalate.
In polystyrene, compounds having structure I or structure II are incorporated,
in
embodiments, at levels of up to about 60% by weight of total formulation with
excellent
compatibility, resulting in a polystyrene formulation that is transparent and
elastomeric, with
a glass transition temperature of less than -40 C, and does not phase
separate. Such a result
is surprising, because in some embodiments the compounds of the invention are
relatively
polar compared to polystyrene; in some embodiments, the compounds of the
invention are
absent of aromatic content. Such compounds would not be expected to be
miscible with
polystyrene, particularly at the very high levels of incorporation observed.
Other polymers that are, in embodiments, plasticized by one or more compounds
of
the invention include, for example, homopolymers and copolymers of
polystyrene, poly(3-
hydroxyalkanoates), poly(lactate), and various polysaccharide polymers, as
well as polyesters
described herein below and those described in PCT Patent Application No.
2008/0242721.
In other embodiments, the compounds having structures I and II are
surfactants,
interfacial modifiers, or phase transfer materials. In such embodiments,
solubility and
performance of the particular structure will depend on the media in which the
compound is
used. For example, in embodiments where R' is a metal cation or an organic
cation,
compounds having structures I and II are surfactants in certain applications.
In other
embodiments where R' is a poly(ethylene oxide) residue, compounds having
structures I and
II are surfactants when incorporated into one or more formulations. The
hydrophilic-
lipophilic balance (HLB) of the surfactant is easily tailored for any number
of applications
by changing the nature of the cation and other structural aspects of the
various R groups.
Depending on the structure of the various other R groups of structures I and
II, for example,
the compounds are, in embodiments, water soluble; in other embodiments the
compounds
are water insoluble. For example, in embodiments where one or more R2, R3, R4,
R5, R6, R8,
or R9 groups, as applicable, are hydrocarbon moieties having at least about 4
carbon atoms,
the HLB character of structures I and II is increased and in some embodiments
the
compounds are not water soluble.
16
CA 02654809 2009-03-05
For example, in some embodiments of the invention, compounds having
structures I and II are powerful solvents that are capable of removing
tenacious
surface coatings. For example, coatings such as dried and cured paint,
adhesives,
and the like are removed by compounds having structures I and II. Thus, in
embodiments, the compounds having structures I and II are useful for cleaning
applications, removal of paint such as graffiti paint, and other similar
applications.
Similarly, by varying the nature of the various R groups of structures I and
II, the compounds are, in various embodiments, phase transfer materials,
coalescing
solvents, compatibilizing solvents, or interfacial modification materials. In
some
such embodiments, R' is a cation; in other embodiments R1 is not a cation. For
example, in some embodiments, the compounds having structures I and II are
able to
make otherwise immiscible solvents miscible. In one such embodiment, a
compound of structure I wherein Rl is ethyl, R2, R3, R8, and R9 are hydrogen,
R4 is
methyl, a is 2, b and c are 0, and a is 1, the compound is capable of making a
mixture of methanol and hexane miscible. Miscibility of the two otherwise
immiscible solvents is observed from vol/vol ratios of about 5vol% to 95 vol%
methanol, or about 40 vol% to 60 vol% methanol, or about 50 vol% methanol. The
same compound, surprisingly, is also useful to make blends of water and
methanol
miscible. Miscibility of the otherwise immiscible set of solvents is observed
from
vol/vol ratios of about 5 vol% to 95 vol% methanol, or about 40 vol% to 60
vol%
methanol, or about 50% methanol, when the compound of structure I wherein R1
is
ethyl, R2, R3, R8, and R9 are hydrogen, R4 is methyl, a is 2, b and c are 0,
and a is 1
is incorporated. Similar results are seen in embodiments where a is increased
from
1 to 2. Miscibility of the solvents is gained with an addition of about 0.01
vol% to
50 vol% of the compound of structure I based on the total volume of the
combined
solvents, or about 0.1 vol% to 20 vol%, or about 1 vol% to 10 vol% of the
compound of structure I.
Various other embodiments, the compounds having structures I and II are
similarly useful in imparting miscibility to otherwise immiscible solvent
sets. What
is particularly surprising about the compounds of structures I and II is that
they are
capable of imparting miscibility to a wide range of solvents, e.g. from very
nonpolar
solvents, such as hexane, with very polar solvents, such as methanol; to
mixtures of
polar solvents such as methanol and water.
17
CA 02654809 2009-03-05
Due to the relatively high molecular weight and relatively low vapor
pressures of some compounds having structures I and II, when compared to many
commonly employed solvents such as lower alkyls having six or less carbon
atoms,
lower alcohols having six or. less carbon atoms, water, ketones such as
acetone and
methyl ethyl ketone, acetates such as ethyl acetate, and the like, one or more
compounds of the invention are advantageously employed in one or more
embodiments as coalescing solvents. Coalescing solvents are those used to form
a
single phase during the drying and curing of a coating formulation, thus they
must
have lower vapor pressure than the "main" solvent but must provide for a
miscible
blend with the coating materials in the absence of the main solvent. Latex
paints, for
example, cure by the process of coalescence, where first the water, and then
the
trace, or coalescing, solvent, evaporate and draw together and soften the
latex binder
particles and fuse them together into irreversibly bound networked structures,
so that
the paint will not redissolve in the solvent/water that originally carried it.
The
coalescing solvent must be miscible with the "main' 'solvent - in the case of
a latex,
water - in order for it to work effectively. Again, the surprising miscibility
of some
compounds having structures I and II with other solvents - and even their
ability, in
embodiments, to impart miscibility to otherwise immiscible solvent blends,
makes
them excellent coalescing solvents for a number of different formulations.
. For example, in some embodiments, the presence of about 0.5 wt% to 25
wt% of one or more compounds of the invention are mixed with various latexes
having water as the main solvent. Upon drying coatings of such latexes, in
embodiments, a continuous film forms. This is true even under conditions in
which,
for example, discontinuous films are observed to form when the one or more
compounds of the invention are not added to the latex prior to coating and
drying.
In other embodiments, about 1 wt% to 10 wt% of one or more compounds of the
invention is added to various latexes to form a continuous film upon drying of
the
latex. In still other embodiments, about 5 wt% is added to a latex to form a
continuous film upon drying of the latex. No special mixing is required, in
various
embodiments, to incorporate the one or more compounds of the invention into
latexes as coalescing solvents; no instabilities are observed when the one or
more
compounds of the invention are added and mixed into various latexes.
In some embodiments, the value of a is substantially greater than 2, for
example in some embodiments a is between about 10 and 100. In other
18
CA 02654809 2009-03-05
embodiments, a is between about 100 and 250. Such embodiments impart, in
embodiments, interfacial modification or phase transfer properties to the
compounds
of structures I and II. In other embodiments where a is substantially greater
than 2,
the compounds of structure I provide barrier layer properties to films wherein
the
compounds are incorporated. In such embodiments, the compounds of structure I
result in enhanced processability and physical properties, such as thermal
stability,
compared to conventional poly(vinyl alcohol) barrier films but retain the
desirable
aspects of barrier layers incorporating poly(vinyl alcohol), namely, oxygen
diffusion
barrier properties.
In some embodiments, the reaction of an oxocarboxylic acid or ester thereof
with a tetrol or higher polyol to result in structures I and II is limited by
compatibility of the two chemical species; that is, the oxocarboxylic acid or
ester
thereof is immiscible with the tetrol or higher polyol. In such embodiments, a
solvent may be used to provide solubility of both materials, thereby
increasing
miscibility. Solvents that may be used in such reactions include aromatic
solvents
such as toluene, benzene, and the like; ethers such as diethyl ether or
tetrahydrofuran; dimethyl formamide; dimethyl sulfoxide; hydrocarbons such as
hexane, pentane, and the like; or any other solvent found to be useful in
providing
miscibility without reacting with one or both reagents or with the acid
catalysts
typically employed in the ketal formation reaction. In other embodiments where
miscibility is a limiting factor in the reaction, incorporating some amount of
a
surfactant provides miscibility. Surfactants that can be'employed in the
reaction
include any conventional surfactant that is not reactive with the reagents and
is not
reactive in the presence of the acid catalysts typically employed in the ketal
formation reaction. For example, nonionic surfactants such as polyethylene
glycol-
propylene glycol block copolymers with alkyl endgroups, are useful in such
reactions and are not reactive with any of the reagents employed in the
ketalization
reaction.
In other embodiments where miscibility is a limiting factor in the reaction,
incorporating some amount. of the product ketal provides miscibility. For
example,
in a reaction vessel with an oxocarboxylate and a tetrol or higher polyol that
are not
miscible, adding 5% or more by weight of the corresponding ketal adduct, based
on
the weight of oxocarboxylate and polyol, to the flask results, in embodiments,
in a
homogeneous mixture. In some embodiments, 10% by weight of the corresponding
19
CA 02654809 2009-03-05
ketal adduct, based on the weight of oxocarboxylate and polyol, is required in
order
to form a homogenous mixture. In other embodiments, more than 10% by weight of
the corresponding ketal adduct, based on the weight of oxocarboxylate and
polyol, is
required in order to form a homogenous mixture.
In still other embodiments where miscibility of the reagents is a limiting
factor in the reaction, transesterification is employed after ketalization to
provide
compounds of interest that are not easily reacted in the ketalization
reaction. For
example, octadecyl pyruvate and erythritol are not, in certain embodiments,
miscible
without a solvent or surfactant. However, methyl pyruvate, ethyl pyruvate, or
the
like may be reacted with erythritol to form the product bisketal having two
methyl
ester or ethyl ester moieties, followed by transesterification with octadecyl
alcohol
to form the octadecyl ester of the bisketal.
Esterification or transesterification of various polyketal structures of the
invention is also usefully employed to impart functional groups to the
polyketals. In
certain particularly useful embodiments contemplated by structures I and II,
one or
more R1 moieties include one or more hydroxyl functionalities capable of
reacting.
with one or more electrophiles. Such structures are obtained, in embodiments,
by
reacting the carboxylic acid or ester functionalities of structure I or II
with a second
polyol, which is a diol, triol, or higher polyol that may be the same or
different from
the first polyol, the first polyol being the tetrol or higher polyol used to
form the
polyketals of structures I and H. Thus, the polyketals of structures I and II
are
converted to polyketal polyols.
The formation of such polyketal polyols are carried out, in embodiments,
using conventional techniques of esterification or transesterification to
functionalize
the compounds of structure I and H. Conventional techniques include, in some
embodiments, addition of heat and/or catalyst(s) to a mixture of a polyketal
of
structures I or II with a second polyol. Alternatively, esterification or
transesterification of an oxocarboxylate may be carried out, in some
embodiments,
prior to ketalization with a tetrol or higher polyol to yield a polyketal
polyol of
structure I or II. Such- embodiments are employed where the esterification or
transesterification is accomplished using a polyol that is incapable of
forming
substantial amounts of cyclic ketal reaction products. For example, 1,6
hexanediol
or diethylene glycol do not readily form a cyclic ketals; so they are more
readily
available for an esterification or transesterification reaction with an
oxocarboxylate.
CA 02654809 2009-03-05
In some embodiments, polyketal polyols of the invention are the products of
esterification of the carboxyl moieties present on a polyketal of structures I
and II
with a second polyol that is a diol or higher polyol. The second polyol may be
the
same as the first polyol, which is the polyol used in a ketalization reaction
to form
the polyketal of structures I and II, or it may be a different polyol. The
polyketal
polyol has at least two hydroxyl functionalities present on the Rl groups of
structures I and H.
Suitable second polyols, that is, diols and higher polyols used in the
esterification or transesterification reactions of the polyketals of structure
I or II to
result in polyketal polyols, include the tetrols and higher polyols described
above.
Additional useful polyols include diols, for example, 1,2-ethanediol (ethylene
glycol), 1,2-propanediol (propylene glycol), 1,3-propanediol, 2,2-dimethyl-1,3-
propanediol (neopentyl glycol), 2-butyl-2-ethyl-1,3-propanediol, 3-
mercaptopropane- 1,2-diol (thioglycerol), dithiothreitol, 1,2-butanediol, 1,3-
butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 3-methyl-1,5-
pentanediol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, cyclohexane-1,2-diol,
cyclohexane-1,4-diol, 1,4-dimethylolcyclohexane, 1,4-dioxane-2,3-diol, 3-
butene-
1,2-diol, 4-butenediol, 2,3-dibromobutene-1,4-diol, 1,8-octanediol, 1,10-
decanediol,
1,12-dodecanediol, benzene-1,2-diol (catechol), 3-chlorocatechol, indane-1,2-
diol,
tartaric acid, and 2,3-dihydroxyisovaleric acid, diethylene glycol (DEG),
triethylene
glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol,
tetrapropylene
glycol, xylene glycol, 1,3-benzenediol (resorcinol), 1,4-benzenediol
(hydroquinone),
o, m, or p-benzene dimethanol, o, m, or p-glycol phthalates, o, m, or p-bis-
1,2-
ethylene glycol phthalates, o, m, or p-bis-1,2-propylene glycol phthalates, o,
m, or p-
bis- 1,3 -propylene glycol phthalates, diols prepared by hydrogenation of
dimer fatty
acids, hydrogenated bisphenol A, hydrogenated bisphenol F, propoxylated
bisphenol
A, isosorbide, 2-butyne-1,4-diol, 3-hexyne-3,5-diol (SURFYNOL(D 82, available
from Air Products of Allentown, PA) and other alkyne-based polyol products
marketed under the SURFYNOL brand name by Air Products of Allentown, PA;
and also include triols, for example, 1,2,3-propanetol (glycerol), , 1,1,1-
trimethylolpropane, 1,1,1-trimethylolethane, pentaerythritol, 1,2,3-
butanetriol,
1,3,4-butanetriol, 1,2,4-butanetriol, 1,2,3-heptanetriol, 4-menthane-1,7,8-
triol, 1,2,5-
trihydroxy pentane, 1,2,6-trihydoxyhexane, 1,2,7-trihydroxyheptane, 1,2,3-
trihydroxyoctane, 1,2,3-trihydroxynonane, 1,2,4-trihydroxynonane, 1,2,3-
21
CA 02654809 2009-03-05
trihydroxyundecane, 1,2,3-trihydroxydodecane, 1,2,11-trihydroxyundecane,
1,2,12-
trihydroxydodecane, and the like.
The group of suitable second polyols also includes tetrols that do not have at
least two pairs of hydroxyls that are contiguous or semicontiguous, such as
dipentaerythritol and pentaerythritol derivatives and other polyhydric alcohol
derivatives such those sold under the trade name CHARMOR by Perstorp Polyols,
Inc. of Toledo, OH; and other polyols and polymeric polyols bearing hydroxyl
groups that are not contiguous or semi-contiguous, such as polyether polyols
based
on ethylene glycol, for example CARBOWAX polyethylene glycols (available
from Dow Company of Midland, MI), polyether diols and polyols based on
propylene glycol or combinations of ethylene glycol and propylene glycol, such
as
those sold by the Dow Company of Midland, MI, and polyether glycols such as
those produced by the 1NVISTArm Company of Wichita, KS under the trade name
TERETHANE ; dendritic polyols, for example those sold under the trade name
BOLTORN by Perstorp Polyols, Inc. of Toledo, OH; polycarbonatediols of
varying molecular weights, such as L467m, L600m, and L565m, available from
Asahi Kasei Corporation (Tokyo, Japan); polyols based on hydroxylated
vegetable
oils, such as those sold under the trade name BiOH , available from the
Cargill
Company of Wayzata, MN; hydroxyl-terminated polybutadienes, such as HTPB
R45M, sold by Aerocon Systems of San Jose, CA, polyols produced by the
Everchem Company of Media, PA, or Maskimi Polyol Sdn. Bhd. of Kajang,
Selango Darul Ehsan, Malaysia, and the polyols employed in the Union Carbide
Company (South Charleston, WV) publication by Carey et al., "Rapid Method for
Measuring the Hydroxyl Content of Polyurethane Polyols" (published on the
inter-
net at http://www.polyurethane.org/ api/doc_paper.asp?CID=1044&DID=4060).
Various polyketal polyols of the invention are, in embodiments, useful in
many of the applications described above. For example, compounds having
structure I or II wherein R1 is HO-(CH2-CH2-O-),,, are, in various
embodiments,
plasticizers, nonionic surfactants, interfacial modifiers, or phase transfer
materials.
In other embodiments, polyketal polyols having structures I or II are
employed as polyols in subsequent syntheses. For example, where structure I is
a
polyketal polyol, self condensation of structure I is carried out in
embodiments to
form dimers, oligomers, and polymers. Similar condensation reactions are
contemplated employing one or more additional diols or higher polyols and one
or
22
CA 02654809 2009-03-05
more diacids or diester compounds. Alternatively, the polyketal polyols react,
in
embodiments, with compounds such as diisocyanates, alkyl carbonates, lactones,
acrylates, methacrylates, glycidyl or other epoxy functional compounds, or
allyl
compounds. Such reactions result in various polymer precursors which usefully
participate in further reactions to form, in various embodiments, dimers,
oligomers,
polymers, and crosslinked networks.
In various embodiments, compounds having structure I or II are subjected to
subsequent reactions that result in dimeric, oligomeric, or polymeric
compounds
having structures III and N, respectively:
R5 6 R6 5
Re b R7 b R9
O O a 0 O
O O
R4 R4
O a a O-R1
R2R3 R3R2 TP
III
wherein R', R2, R3, R4, R5, R6, R7, R8, a, b, and a of structure III are the
same as
those as defined for structure I, and /3 is an integer of at least 2;
O R4 OO R4
O a O XO a O-R1
R2 3 R3 R2 p
N
wherein R', R2, R3, R4, a, and a are as defined for structure II and (3 is an
integer of
at least 2.
Additional embodiments of structures I, II, III, and N are discussed in
Sections A -
H, below.
A. Dimerization and Oligomerization Polyketals and Polyketal Polyols
The polyketal polyols having structures III and N are, in embodiments,
dimers or oligomers. A dimer is represented by either structure III or IV
where the
value of a is 2; an oligomer is represented by values of 0 of about 3 to 12.
By
23
CA 02654809 2009-03-05
adjusting and optimizing reaction conditions, it is possible, in embodiments,
to form
a high percent of dimer. In some embodiments, the polyketals having structure
I can
be dimerized or oligomerized by employing a second polyol of structure III
wherein
is between 2 and about 12. In such embodiments, the techniques employed to
make such polyols are similar to those employed to make the polyketal polyols
as
described above. In some such embodiments, a stoichiometric balance of a
compound having structure I and a second polyol is suitable to form a dimer or
oligomer of structure III instead of a monomeric polyketal polyol. Structure
IV
similarly arises from structure II.
One example of a dimerization reaction is shown in FIG. 1 A. In one
embodiment, dropwise addition of diol into a reaction flask of bisketal ester
results
in formation of a significant yield of dimer corresponding to one diol group
with two
bisketal groups. Other methods to obtain dimers where higher oligomers are not
desirable are readily envisioned.
Oligomers of polyketals and polyketal polyols, for example those having a
degree of polymerization ((3) of about 2 to 12, are readily obtained by
adjusting
reaction conditions to optimize the formation of repeat unit structures. For
example,
in the reaction of a diol with a bisketal ester, providing a 1:1 stoichiometry
and
adjusting the time and temperature of the reaction accordingly results, in
embodiments, in a mixture of oligomeric poly(bisketal)s.
In some embodiments, esterification or transesterification of polyketal acids
or esters to give polyols is carried out by employing a catalyst. The catalyst
may be
any of the known esterification or transesterification catalysts in general.
For
example, acidic catalysts such as a toluenesulfonic acid, sulfuric acid,
sulfamic acid,
or a sulfonic acid are employed in various embodiments. In other embodiments
an
organometallic catalyst is employed, for example a catalyst based on titanium
or tin,
such as titanium tetrabutoxide (Ti(OBu)4), or tin (11) octanoate. The choice
of
catalyst is not particularly limited within the scope of the invention.
In various embodiments, the dimers and oligomers of the compounds having
structures I and II are useful in the same applications as those described
above.
Thus, in various embodiments, dimers and oligomers of compounds having
structures I or II are plasticizers, surfactants, phase transfer materials,
interfacial
modifiers, and the like.
24
CA 02654809 2009-03-05
The compounds having structures III and IV are also capable of further
reaction in embodiments where one or more residual hydroxyl, ester, or acid
functionalities reside within the Rl functionality. Thus, where reactions in
sections
B to H employ "monomeric", e.g. non-dimerized or non-oligomerized, species of
structures I and II, dimers, oligomers, and polymers thereof having structures
III and
N are also suitably employed in various embodiments due to their reactivity in
the
systems as described.
B. Polyketal Polyesters
The polyketals having structures I and II are, in embodiments of the
invention, polymerized via esterification or transesterification. By forming a
polyketal polyol, or by reacting a polyketal that is not a polyol with one or
more
diols or higher polyols, transesterification can lead to dimers or oligomers,
as is
described below, and also to polymers. Bisketal esters, that is esters having
structure II or esters having structure I wherein a is 1, react with diols to
form linear
oligomers and polymers. Trisketals and higher polyketals, that is polyketals
of
structure I wherein a is 2, as well as triols and higher polyols, can also be
employed
to form the corresponding branched, hyperbranched, dendritic, or crosslinked
network polymer. Importantly, mixtures of e.g. bisketals and a minor amount of
trisketal or a higher polyketal, or mixtures of diols and a minor amount of
triols or
higher polyols, can be advantageously employed to give variable degrees of
branching and/or crosslinking.
The polyketal polyesters of the invention are represented by the compounds
having structures III and IV, wherein the values of 0 are more than about 12.
In
some embodiments the value of 13 is between about 12 and 100; in other
embodiments the value of (3 is about 100 to 500; in still other embodiments
the
value of /3 is as high as about 1000. In embodiments, the value of a in
structure III is
1. A representative example of polyester synthesis via self-condensation of a
bisketal diol is shown in FIG. 1B.
The polyketal polyesters of the invention are, in embodiments, synthesized
using conventional transesterification polymerization catalysts and
conditions. For
example, without limiting the catalyst species employed, any of the catalysts
described in section A. above are suitable catalysts for the reaction to form
various
polyketal polyesters of the invention. In embodiments, reaction conditions and
CA 02654809 2009-03-05
reagents are optimized to reach high molecular weight, maximize crystalline
content, provide transparent, colorless films, or provide other properties
idea for one
or more other applications.
The polyesters of the invention have, in embodiments, excellent thermal
stability and have superior tensile properties. In some embodiments, the
polyesters
of the invention are stable in air at temperatures of up to 250 C. In other
embodiments, the polyesters of the invention are stable in air at temperatures
up to
about 300 C. In still other embodiments, the polyesters of the invention are
stable in
air at temperatures of over 300 C.
C. Polyketal Copolyesters
Polyester copolymers are formed, in embodiments, by reacting a polyketal
acid or ester, a polyketal polyol or a dimer or oligomer thereof, with one or
more
additional diacids or diesters, diols, or a mixture thereof to give the
corresponding
copolyester. For example, a bisketal polyol can be polymerized with, for
example,
adipic acid or methyl isophthalate, to give the corresponding copolyester. A
representative example of such a copolymerization is shown in FIG. 1C. Any of
the
diols listed in previous sections are suitable for use in a copolymerization
reaction to
provide polyketal copolyesters.
The polyketal copolyesters of the invention are represented by the
compounds having structures III and IV, wherein the value of (3 is 1 or
greater; that
is, there is at least one repeat unit of structure III or N in the copolymer.
In some
embodiments the value of (3 is between about 2 and 100; in other embodiments
the
value of (3 is about 100 to 500. In embodiments, the value of a in structure
III is 1;
in other embodiments the value of a is 2. In still other embodiments,- a
mixture of
compounds of structure III, wherein a mixture of a values are used; for
example, a
mixture of compounds wherein a is 1 is employed, in embodiments, with a minor
amount of a compound of structure III wherein the value of a is 2 to impart
some
degree of branching or crosslinking. Many related variations are readily
envisioned.
Non-limiting examples of suitable diacids (or esters of diacids) suitable for
use in synthesizing the polyketal copolyesters of the invention include
aliphatic,
cycloaliphatic or aromatic dicarboxylic acids, for example, succinic acid,
glutaric
acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid,
nonanedicarboxylic acid, decanedicarboxylic acid, terephthalic acid,
isophthalic
26,
CA 02654809 2009-07-24
acid, o-phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid,
malefic acid, fumaric
acid, naphthalene dioc acid, dimerized fatty acids, or hydrogenated dimerized
fatty acids.
The methyl, ethyl, propyl, butyl or phenyl esters of the acids listed above
are suitable
substitutes for the diacid component, as well as acid anhydrides (such as o-
phthalic, maleic
or succinic acid anhydride or a mixture thereof.
In embodiments, the copolyesters of the invention are synthesized using
conventional
transesterification polymerization catalysts and conditions. For example,
without limiting the
catalyst species employed, any of the catalysts described in section A. above
are suitable
catalysts for the reaction to form various polyketal copolyesters of the
invention. In
embodiments, reaction conditions are optimized to reach high molecular weight.
Such
reaction conditions include, in embodiments, the techniques, conditions, and
catalysts
employed in polyesterification reactions described in U.S. Patent Application
No.
2008/0242721.
Crosslinked or branched analogs of various polyketal copolyesters of the
invention
are readily formed by employing a major proportion of diacids or esters
thereof, and bisketal
acids or esters thereof, with a minor proportion of, in embodiments, trisketal
or higher acid
or ester thereof, or tricarboxylic acid or higher polyacid or ester thereof.
It will be easily
understood that trisketals and higher polyketals, as well as triols and higher
polyols and
triacids and higher polyacids, can be employed to form the corresponding
crosslinked
polymer or branched polymer. Importantly, mixtures of e.g. bisketals and a
minor amount of
trisketal or a higher polyketal; or mixtures of diols and a minor amount of
triols or higher
polyols; or mixtures of diacids and a minor amount of a triacid or higher
polyacid; or a
combination of any of these can be advantageously employed to give variable
degrees of
branching and/or crosslinking. Some examples of suitable triacids include
1,3,5-trimethyl-
cyclohexane-1,3,5-tricarboxylic acid, cis or trans aconitic acid, propane-
1,2,3-tricarboxylic
acid, hemmellitic acid, isocitric acid, and the like.
In other embodiments, polyketal polyols or dimers or oligomers thereof are
employed
in the ring opening reaction of one or more lactones to form the corresponding
copolyester.
Ring opening polymerization of lactones is carried out using one or more
catalysts and using
27
CA 02654809 2009-07-24
reaction conditions suitable for ring opening polymerization. Catalysts and
reaction
conditions employed in such reactions are any of those used in the art for
ring opening
reactions of lactones. For example, some ring opening polymerization catalysts
are based on
transition metals such as zinc, tin, or titanium. Without limiting the species
of catalysts or
reaction conditions employed, any of the catalysts or reaction conditions
described in Hori et
al., U. S. Patent No. 5,516,883 or Schechtman et al., U. S. Patent No.
5,648,452 are useful.
Activated carbon as employed by Endo et al., EP 1857484 or organic catalysts
employed as
described in a web-published article from IBM Company of Armonk, NY, at
.aln~acien.it~n~.com!st/chemistr~ps-catalvsts,'RineOpeninc/ may be used to
affect the
ring opening polymerization of lactones using the polyketal polyols of the
invention as the
initiating polyol. The above examples are not limiting as to the type of
catalyst or set of
reaction conditions that can be employed in a ring opening polymerization of
lactones.
Suitable lactones for the ring opening polymerization initiated by one or more
polyketal polyols of the invention include, without limitation, propiolactone,
pivalolactone,
diketene, dimethyldiketene, 0-butyrolactone, 4-butyrolactone, 4-valerolactone,
6-caprolactone,
E-caprolactone, 5-ethenyl-5-methyloxolan-2-one, gluconolactone,
glucuronolactone, D-
galactonolactone, coumarin, hydrocoumarin, ascorbic acid lactone, a-
angelicalactone, 2-
acetylbutyrolactone, 6-propyloxan-2-one, 6-ethyloxan-2-one, ribonolactone,
arabonolactone,
X-nonalactone, bicyclononalactone, 5-nonalactone, X-decalactone, pantolactone,
2-dehydro-
pantolactone, 5-butoxolan-2-one, isocrotonolactone, 6-hexyloxan-2-one 5-
heptyloxolan-2-
one, 5-propyloxolan-2-one, 6-[(E)-pent-2-enyy]oxan-2-one, cocolactone,
isocitric lactone, 2-
hydroxy-6-methylpyran-4-one, I-oxacyclododecan-2-one, E-dodecalactone, I-
oxacyclopenta-
decan-2-one, I-oxacycloheptadecan-2-one, L-arabino-1,4-lactone, 4-hydroxy-4-
methyloxan-2 -one,
homoserine lactone, 4-methyl-7-propan-2-yloxepan-2-one, and the like.
In one embodiment of a lactone ring opening polymerization, one or more
polyketal
polyols of the invention are employed in the ring opening polymerization of
SEGETOLIDETM
(available from Segetis, Inc. of Golden Valley, MN) or its dimer to form the
corresponding
levulinate-glycerol ketal polyester. The structure of SEGETOLIDETM and its
dimer, as well
as methods for the ring opening polymerization of both compounds, are found in
U.S. Patent
Application No. 2008/0242721. The methods disclosed therein are suitable, in
embodiments,
28
CA 02654809 2009-07-24
for initiating the ring opening polymerization using the polyketal polyols of
the invention as
initiators.
The techniques used to synthesize one or more copolyesters of the invention
are, in
embodiments, the same as the techniques employed to synthesize homopolyesters
as
described in section B. Applications for copolyesters of the invention are
similar, in
embodiments, to those for homopolymers, except that a broader range of
physical properties
is available by the use of comonomers. For example, the incorporation of
terephthalate as a
diester in the copolymerization reaction leads, in embodiments, to increased
crystalline
content, which in turn increases the utility of the copolymer for applications
for which
polyesters are commonly known in the literature.
The thermal and environmental stability of one or more copolymers of the
invention,
insofar as they relate to the polyketal repeat units present in one or more
embodiments, is
excellent. As with one or more polyesters of the polyketals of the invention
formed by their
condensation with polyols, the copolyesters based on one or more polyketals of
the invention
are, in some embodiments, stable in air up to 250 C. In other embodiments, the
copolyesters
of the invention are stable in air up to 300 C. In yet other embodiments, the
copolyesters of
the invention are stable in air at temperatures in excess of 300 C. The
copolyesters of the
invention also have, in embodiments, excellent tensile properties that make
them useful for a
wide variety of commercial applications.
D. Polyketal Polyisocyanates
Polyketal polyols of structures I, II, III, and IV are employed, in
embodiments, in the
formation of polyketal polyisocyanates. The polyketal polyols that are the
precursors to
polyketal polyisocyanates are any of the polyketal polyols described above;
thus, a polyketal
polyol corresponding to structure I or II, may be employed; similarly, an
oligomer or
polymer of structure III or IV may be employed as starting materials for one
or more
polyketal polyisocyanates of the invention. In some embodiments employing
structures I or
III, the value of a is 1; in other such embodiments the value of a is 2. In
yet other such
embodiments, the value of a is as high as 100. When employing structures III
or IV, the
value of 0 is between about 2 and 12; in other such embodiments the value of
/3 is up to
about 100.
29
CA 02654809 2009-03-05
In such embodiments, at least one R1 in any of structures I, II, III, or IV
contains one or more hydroxyl moieties that are capable of reacting with a
diisocyanate or higher polyisocyanate to form a polyketal polyisocyanate by
forming
a urethane linkage. Suitable diisocyanates useful in forming one or more
polyketal
polyisocyanates of the invention include, without limitation, those
represented by
formula OCN-Z-NCO, in which Z represents a divalent aliphatic hydrocarbon
group
having 4 to 18 carbon atoms, a divalent cycloaliphatic hydrocarbon group
having 5
to 15 carbon atoms, a divalent araliphatic hydrocarbon group having 7 to 15
carbon
atoms, or a divalent aromatic hydrocarbon group having 6 to 15 carbon atoms.
Non-limiting examples of suitable organic diisocyanates include 1,4-
tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-
1,6-
hexamethylene diisocyanate, 1, 1 2-dodecamethylene diisocyanate, cyclohexane-
1,3-
diisocyanate, cyclohexane -1,4-diisocyanate, 1-isocyanato-2-isocyanatomethyl
cyclopentane, 1 -isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane
(isophorone diisocyanate or IPDI), bis-(4-isocyanatocyclohexyl) methane, 2,4'-
dicyclohexyl-methane diisocyanate, 4,4'-dicyclohexyl-methane diisocyanate, 1,3-
bis-(isocyanatomethyl)-cyclohexane, 1,4-bis-(isocyanatomethyl)-cyclohexane,
bis-
(4-isocyanato-3-methyl-cyclohexyl)methane, a, a, a',a'-tetramethyl-1,3-
xylylene
diisocyanate, a, a, a',a'-tetramethyl-1,4-xylylene diisocyanate, 1-isocyanato-
l-
methyl-4(3)-isocyanatomethyl cyclohexane, 2,4- hexahydrotolylene diisocyanate,
2,6-hexahydrotolylene diisocyanate, 1,3- phenylene diisocyanate, 1,4-phenylene
diisocyanate, 2,4- tolylene diisocyanate, 2,6-tolylene diisocyanate, 2, 2'-
diphenylmethane diisocyanate, 2,4'- diphenylmethane diisocyanate , 4,4'-
diphenylmethane diisocyanate, 1,5-diisocyanato naphthalene; and mixtures
thereof.
Also suitable for making one or more polyketal polyisocyanates of the
invention are polyisocyanates containing 3 or more isocyanate groups.
Nonlimiting
examples of suitable polyisocyanates include 4-isocyanatomethyl-1,8-
octamethylene
diisocyanate, aromatic polyisocyanates such as 4,4',4"-triphenylmethane
diisocyanate, and polyphenyl polymethylene polyisocyanates obtained by
phosgenating aniline/formaldehyde condensates.
One or more polyketal polyisocyanates of the invention are synthesized, in
some embodiments, in the form of a polyketal polyisocyanate adduct. Suitable
polyketal polyisocyanate adducts are those containing isocyanurate, uretdione,
biuret, urethane, allophanate, carbodiimide and/or oxadiazinetrione groups.
CA 02654809 2009-10-16
In some embodiments, diisocyanates employed to make one or more polyketal
polyisocyanates of the invention include the various isomers of
diphenylmethane
diisocyanate and mixtures thereof, IPDI, 4,4`-dicyclohexyl-methane
diisocyanate, and
polymeric isocyanates based on diphenylmethane diisocyanate, such as MondurTM
MRS
iavallabie from Bayer Materia1Seienee LLl V1 i ittsb it h, A).
A representative synthetic scheme for one embodiment of a polyketal
polyisocyanate
of the invention is shown in FIG. 1 D.
Methods used to make one or more polyketal polyisocyanates of the invention
include conventional techniques known in the literature for the synthesis of
polyisocyanates
from polyols and diisocyanates. A representative technique for making one or
more
polyketal polyisocyanates of the invention is that employed in U.S. patent
application No.
2008/0242721. The technique of this application employs an excess of
diisocyanate, as
determined by hydroxyl equivalents per mole of polyol, in the presence of
dibutyltin
dilaurate to give the corresponding polyisocyanate.
One or more polyisocyanates of the invention are useful, in embodiments, for
the
subsequent synthesis of polyurethanes, polyureas, and poly(urethane ureas),
and other
related structures as outlined in section E. below.
E. Polyketal Polyurethanes, Polyketal Poly(urethane urea)s, Poly(ester
urethane)s, and
Poly(ester urethane urea)s
The various polyketal polyols and polyketal polyisocyanate structures of the
invention described in any of the embodiments above are employed, in
embodiments, in the
synthesis of polyketal polyurethanes, polyketal poly(urethane urea)s, and
related structures.
Polyketal polyols as described above are reacted, in some embodiments, with
polyisocyanates that are any one of, or a blend of, the polyisocyanates listed
in section D.
above. Whereas a stoichiometric excess of polyisocyanate relative to the
polyol results in a
polyisocyanate as described in section D., a 1:1 stoichiometric ratio of
polyketal polyol and
diisocyanate results in the formation of a linear polyketal polyurethane
having more than one
repeat unit corresponding to the repeat unit of structures III or IV; that is,
for structure III, 0
is at least 1 and in embodiments is between about 2 to 100, or between about
100 and
1000. The polyisocyanate employed may be difunctional or have higher
31
CA 02654809 2009-03-05
functionality. Blends of diisocyanates with polyisocyanates having three or
more
isocyanate moieties are employed, in embodiments, to provide a tailored level
of
branching or crosslinking in the resulting polymer matrix.
In some embodiments, polyketal polyurethanes are formed by the reaction of
one or more polyketal polyols of the invention with one or more polyketal
polyisocyanates of the invention. In other embodiments, one or more polyketal
polyols are reacted with one or more polyisocyanates that are not polyketal
polyisocyanates. In still other embodiments, one or more polyketal
polyisocyanates
are reacted with one or more polyols that are not polyketal polyols, to form a
polyurethane. Useful polyols for such embodiments include both polyketal
polyols
and any of the polyols listed above as polyols, first polyols, or second
polyols.
Various other embodiments employing one or more polyketal polyols, polyketal
polyisocyanates, polyols, and polyisocyanates are easily envisioned. Blends of
polyisocyanate functional and polyhydroxylated materials are used, in
embodiments,
to form polyketal polyurethanes having a varying range of ketal content and
crosslink density and a wide range of available physical properties including
glass
transition temperature, tensile strength, ductility, and the like.
The reaction of an isocyanate group with an amine is known to form a urea
linkage. Thus, in embodiments, one or more polyketal polyisocyanates, which
already have one urethane linkage per isocyanate group, are reacted with one
or
more polyamines to form a poly(urethane urea). Suitable polyamines for forming
one or more polyketal polyurethane urea)s of the invention include, for
example,
hydrazine, ethane- 1,2-diamine, 1,6-hexanediamine, but-2-ene-1,4-diamine,
Metformin, butane-1,4- diamine, propane-1,2- diamine, benzene- 1,3-diamine, 2-
methylbenzene-1,3-diamine, 4-chlorobenzene-1,3- diamine, methanediamine, 1,3,5-
fiazine-2,4,6-triamine, N-(2-aminoethyl)ethane-1,2-diamine, N-(6-
aminohexyl)hexane- 1,6-diamine, N,N'-bis(2-aminoethyl)ethane-1,2-diamine, N-[2-
(3-aminopropylamino)ethyl]propane-1,3-diamine, 4-(3,4-diaminophenyl)benzene-
1,2-diamine, spermine (N,N-bis(3-aminopropyl)butane-1,4-diamine), a
polyethyleneimine, a polyoxyalkyleneamine having two or more amine groups,
such as those sold under the trade name JEFFAMINE , (available from the
Huntsman Corp. of Salt Lake City, UT), or any diamine or higher amine compound
such as those sold under the trade name ELASTAMINE (available from the
Huntsman Corporation).
32
CA 02654809 2009-03-05
It is known that an isocyanate can be reacted with water to form a primary
amine group and carbon dioxide; the primary amine is then available to react
with
another isocyanate group to form a urea linkage. Thus, in embodiments, one or
more polyketal polyisocyanates of the invention are reacted with water to form
one
or more polyketal polyurethane urea)s via a this known pathway. In some such
embodiments, the evolution of carbon dioxide acts as a foaming agent as the
reaction progresses, thus providing for a foamed polyketal polyurethane urea)
matrix. Water reacts with isocyanate groups to create carbon dioxide gas,
which
fills and expands cells created during the mixing process, and causes the
formation
of urea groups in a polyurethane reaction. Polyurethane and poly(urethane
urea)
foams have wide utility in the industry for applications such as automobile
cushions,
mattress material, furniture cushions, and the like.
The various polyketal polyurethanes and polyketal polyurethane urea)s of
the invention have a variable range of ketal content and a wide range of
physical
properties including glass transition temperature, clarity, rigidity and
elasticity.
In a particularly useful range of embodiments, polyketal polyurethanes or
polyketal poly(urethane urea)s are present as blocks in a copolymer with other
polyurethane or poly(urethane urea) blocks. Such block copolymers are easily
achieved by controlling stoichiometry of the reactions to reach the desired
residual
endgroups, then employing those endgroups as initiation points for an
additional
polymerization reaction with a different monomer mixture. For example, a
bisketal
diisocyanate of the invention may be reacted with ethylene glycol to form a
polyurethane oligomer; the stoichiometry of the reaction is adjusted, using
conventional techniques, to result in hydroxyl endgroups. The hydroxyl
terminated
polyurethane oligomer is then reacted with toluene diisocyanate to provide a
diblock
type polyurethane polymer.
In another useful range of embodiments, a polyketal polyester or copolyester
can be synthesized according to the methods set forth above by
homopolymerization
or copolymerization of a bisketal diol. The resulting polyester of structures
III or IV
will inherently have, or may be reacted to provide, residual hydroxyl
endgroups; the
structures III and IV further have values of fl of about 2 to 12, or about 12
to 100.
The endgroups are useful in a subsequent reaction to form a polyurethane by
reacting the hydroxyl terminated polyester or copolyester with a
polyisocyanate or a
polyketal polyisocyanate to produce a poly(ester urethane) polymer. Likewise,
other
33
CA 02654809 2009-03-05
similar embodiments may result in a poly(ester urethane urea) copolymer; the
techniques employed in forming polyketal polyurethanes and polyketal
poly(urethane urea)s may be usefully employed in making block copolymers with
hydroxyl terminated polyketal polyesters and polyketal copolyesters. It will
be
understood by one of skill that further variations are possible. For example,
when
poly(ethylene glycol) is used as the polyol to make a polyester prior to
reaction with
a polyisocyanate, the resulting block copolymer will be a polyketal poly(ester
ether
urethane) or a polyketal poly(ester ether urethane urea).
Many other embodiments will be readily envisioned; it will be appreciated
that the ketal content of the resulting polymer is variable in various
embodiments,
and a wide range of physical properties such as glass transition temperature,
tensile
strength, elasticity, and ductility are attainable in various embodiments of
the
invention.
The reactions and processes used to form various polyketal polyurethanes
and polyketal poly(urethane urea)s, as well as poly(ester urethane)s and
poly(ester
urethane urea)s of the invention employ conventional techniques of
polyurethane or
.polyurea synthesis; such techniques typically involve blending the two
reagents in a
stoichiometry that will result in oligomeric or polymeric molecular weights.
In
embodiments where polyurethane linkages are formed, the polymerization
reaction
is catalyzed. Catalysts useful in polyurethane formation include, in
embodiments,
tertiary amines. Nonlimiting examples of suitable tertiary amines include
dimethylcyclohexylamine, 1,4-diazabicyclo[2.2.2]octane (also called DABCO or
TEDA), and bis-(2-dimethylaminoethyl)ether. In other embodiments,
organometallic compounds, such as dibutyltin dilaurate, potassium octanoate,
or
bismuth octanoate may be used to catalyze polyurethane formation. In some
embodiments where polyurea linkages are formed, no additional catalyst is
required
to effect the reaction.
Processes that can be used to make these materials include, in embodiments,
reaction injection molding, prepolymerization to a coatable syrup followed by
coating and curing, and the like. The various polyketal polyurethanes,
polyketal
poly(urethane urea)s, poly(ester urethane)s, poly(ester urea)s, and poly(ester
urethane urea)s of the invention are not particularly limited as tb the
methods
employed in making and processing.
34
CA 02654809 2009-03-05
Foamed formulations employing the various polyketal polyurethanes,
polyketal poly(urethane urea)s, polyketal poly(ester urethane)s, and polyketal
poly(ester urethane urea)s of the invention are useful embodiments of the
invention.
Foams are formed during the polymerization reaction, typically by the addition
of
one or more blowing agents. One example is the use of carbon dioxide evolved
in
the reaction of isocyanate with water, as described above. In other
embodiments, a
blowing agent is added to the polymer during processing to facilitate foaming
when
the polymer is heated, for example in a thermoforming process. Suitable
blowing
agents include water, certain halocarbons such as HFC-245fa (1,1,1,3,3-
pentafluoropropane) and HFC-134a (1, 1, 1,2-tetrafluoroethane), and
hydrocarbons
such as n-pentane. In some embodiments, blowing agents are incorporated into
e.g.
the polyketal polyol prior to the polymerization; in other embodiments the
blowing
agent is added as an auxiliary stream. Halocarbons and hydrocarbons are chosen
such that they have boiling points at or near room temperature; these blowing
agents
volatilize into a gas during the exothermic polymerization reaction. In
addition,
high density microcellular foams can be formed without the addition of blowing
agents by mechanically frothing or nucleating the polyol component prior to
use.
In some embodiments, surfactants are employed to modify the characteristics
of the foam during the foaming process. In embodiments, they are used to
emulsify
the liquid components, regulate cell size, and stabilize the cell structure to
prevent
collapse and surface defects. Rigid foam surfactants produce, in embodiments,
very
fine cells and very high closed cell content. In other embodiments, flexible
foam
surfactants stabilize the reaction mass while maximizing open cell content to
prevent
the foam from shrinking. The need for, and choice of, surfactant is
determined, in
embodiments, by choice of polyisocyanate, polyol, component compatibility,
system
reactivity, process conditions and equipment, tooling, part shape, and shot
weight.
Various embodiments of the polyketal polyurethanes, polyketal
poly(urethane urea)s, poly(ester urethane)s, and poly(ester urethane urea)s of
the
invention are useful in a broad range of applications. Polyurethane polymers,
in
general, are compounds of exceptional industrial utility; they find numerous
applications because the final properties of the resulting polymer can be
influenced
greatly through selection of active hydrogen monomers (typically, polyhydroxyl
compounds) and isocyanates used, and by selecting the conditions used to
prepare
the finished polymer products. Polyurethanes are lightweight, strong, durable
and
CA 02654809 2009-03-05
resistant to abrasion and corrosion. Depending on choice of monomers, a
polyurethane is stiff or flexible. Typically, incorporation of urea type
linkages
results in a more rigid material. However, with the broad range of monomer
chemistry as well as the range of linkages available from ester, urethane, and
urea
moieties in various embodiments provides extensive flexibility in choice of
structure
that leads to a broad range of properties and, in turn, applications.
Without providing any particular limitations, the various polyketal
polyurethanes, polyketal poly(urethane urea)s, polyester urethane)s, and
poly(ester
urethane urea)s of the invention are useful, in embodiments, as adhesives or
sealants,
particularly for exterior uses or building construction applications where
extremely
challenging conditions are encountered; as binders; as coating materials where
durability and/or challenging environmental conditions exist; in reactive
spray
coatings of 100% solids; as elastomers for applications such as rollers and
belts for
carrying heavy and/or abrasive materials, roller blades, and other footwear
parts
such as shoe soles; as vibration damping materials; and in the fabrication of
medical
devices, for example for surface modification, as a protective coating, or
within
moving parts (e.g. for elastomeric materials). In foamed form, these materials
also
find utility as insulation materials; low density vibration damping materials;
flexible
foam for indoor furniture such a seat cushions and mattresses, and other
similar
applications such as automobile seat cushions.
F. Polyketal ester polycarbonates
Polyketal polyols having structures I, 11, III, or IV are useful, in
embodiments, for the synthesis of polycarbonates. Where compounds of
structures I
or III are employed, the polyketal polyols useful in the synthesis of
polycarbonates
typically have a of 1 or 2. In embodiments, dimers, oligomers, or polymers
having
structures III or IV may are used to synthesize one or more polyketal
polycarbonates
of the invention, wherein the value of 3 is 2, or between about 3 and 12, or
between
about 12 and 100.
Polycarbonate synthesis is carried out, in embodiments, by employing any
known and conventional technique for making polycarbonates. One such technique
employs phosgene. For example, in one such embodiment, a bisketal diol is
treated
with sodium hydroxide, followed by an interfacial reaction between the sodium
alkoxide of the bisketal diol and phosgene. Alternatively, one or more
polyketal
36
CA 02654809 2009-03-05
polycarbonates of the invention are synthesized, in embodiments, by
transesterification of a polyketal ester with a difunctional carbonate having
the
general structure
0
R1o_O O_R11
where R10 and R" may be the same or different and are, in embodiments, a
linear,
cyclic, or branched alkyl, alkenyl, or alkynyl group; an aralkyl group, or an
aromatic
group; or R10 and R11 together with the carbonate bond forms, in some
embodiments,
a cyclic carbonate. In such embodiments, a polycarbonate is formed by a ring
opening reaction. The reaction to form polycarbonates A polyketal
polycarbonate is
also formed, in embodiments, by reacted a dibromo compound with potassium
carbonate. Thus, in one such embodiment employing the reaction conditions set
forth in the reference article, a bisketal having two or more R' groups
containing a
primary bromo moiety is reacted with potassium carbonate to form a polyketal
polycarbonate of the invention.
Polyketal ester polycarbonates employ, in embodiments, one or more
polyketal polyols of the invention; they further incorporate one or more
acyclic or
cyclic dialkyl carbonate monomers or another source of carbonate bond such as
potassium carbonate or phosgene.
The polyketal ester polycarbonates of the invention have a range of available
properties due to the broad range of polyketal polyols of the invention that
are
available as starting materials. Polycarbonates are known to be tough,
transparent,
thermally stable materials suitable for a range of engineering plastics
applications.
Suitable applications for one or more polycarbonates of the invention include,
but
are not limited to, fabrication of items requiring molding, laminating,
thermoforming
such as extruding or coextruding, or machining or other conventional means of
working. Examples of useful items include compact discs, riot shields, baby
bottles
and other water/drink bottles and food containers, electrical components,
automobile
headlamps, as a component of a safety glass laminate, eyeglass lenses, safety
helmets, and the like.
Various polyketal ester polycarbonates of the invention do not employ
Bisphenol A (4,4'- dihydroxy-2,2-diphenylpropane), the most commonly employed
37
CA 02654809 2009-03-05
polycarbonate polyol starting material. Bisphenol A has been the subject of
toxicity
concerns since the 1930s, particularly in food or drink contact applications
(e.g.,
baby bottles, water/drink bottles, food containers). One or more
polycarbonates of
the invention are, in one or more embodiments, are useful for food or drink
applications where it is desirable to eliminate Bisphenol A.
Additionally, some aliphatic polyketal ester polycarbonates of the invention
are, in some embodiments, biodegradable. Biodegradable polycarbonates are
useful
for one or more applications, for example, in food or drink contact
applications, to
enable disposable embodiments of various containers. Other applications where
biodegradability is advantageous include disposable medical supplies such as
eye
shields and the like. In various embodiments, the polyketal ester
polycarbonates of
the invention advantageously supply the desirable properties of polycarbonates
and
additionally supply biodegradability thereof.
In some embodiments, polyketal ester polycarbonates of the invention, when
terminated by hydroxyl endgroups, are suitable as diols for use in
polyurethane
synthesis. Polyketal ester polycarbonate diols are synthesized, in some
embodiments, by employing polyketal polyols in the synthesis of a
polycarbonate
and controlling stoichiometry of the polymerization in order to provide
hydroxyl
functionality at the ends of the polymer. In other embodiments, a
polycarbonate is
transesterified at each end with a diol to provide hydroxyl endgroup.
Polyketal ester
polycarbonates having hydroxyl endgroups are reacted with a diisocyanate to
form a
polyketal poly(carbonate urethane). Polyketal poly(carbonate urethane)s are
synthesized using, in some embodiments, the techniques described above to make
polyketal polyurethanes. In other embodiments, techniques used to form the
Polyketal poly(carbonate urethane)s of the invention are those outlined in
Moore et
al., Novel Co-Polymer Polycarbonate Diols for Polyurethane Elastomer
Applications, Proceedings of the Polyurethanes Expo 2003, October 1-3, 2003 (
2003, American Chemistry Council).
G. Polyketal acrylates and methacrylates, and their polymerized products
Polyketal polyols having structures I, II, 111 and IV are useful, in
embodiments, for the synthesis of acrylate or methacrylate adducts thereof.
Any of
the above embodiments of the invention wherein a polyketal has one or more
hydroxyl functionalities are, in embodiments, functionalized with one or more
38
CA 02654809 2009-03-05
acrylic functionalities. Such embodiments include structures of compounds I
and III
wherein a is 1; or wherein a is 2; or wherein a is between about 3 and 100.
Such
embodiments also include structures of compounds III and N wherein (3 is 2; or
wherein # is about 2 to 12; or wherein i3 is between about 3 and 100.
As used herein, the term "acrylic functionality" means an acrylate,
methacrylate, or other similar moiety that is capable of subsequent
polymerization or
crosslinking reactions utilizing a free radical or redox mechanism. Acrylic
functionality is imparted, in embodiments, to one or more of the polyketal
polyols of
the invention by employing conventional techniques for the reaction of
alkanols to
form acrylates and methacrylates. In one such embodiment a polyketal polyol or
a
dimer, oligomer, or polymer thereof having at least one free hydroxyl group is
employed in an esterification reaction with acrylic acid or methacrylic acid
to form a
polyketal acrylate. Another embodiment employs acrylyl chloride or methacrylyl
chloride in a reaction with a polyketal polyol of structures I, II, III, or IV
having at
least one free hydroxyl group to form the corresponding acrylic functional
polyketal
and HCI. The HCl is advantageously scavenged by a base, for example ammonia,
to
capture the acid and prevent unwanted side reactions.
In a related set of embodiments, a polyketal polyisocyanate of the invention
may be reacted with a hydroxyl-functional acrylate or methacrylate to form a
urethane moiety linking the polyketal to the acrylate or methacrylate moiety.
For
example, a polyketal polyisocyanate such as the structure shown in FIG. 1D is
reacted with a 3-methacrylyl-2-hydroxylpropyl ester to give the corresponding
polyketal urethane methacrylate. In another example, the polyketal
polyisocyanate
shown in FIG. 1D is reacted with 2-hydroxypropyl acrylate to give the
corresponding polyketal urethane acrylate. Polyurethane acrylates are known in
the
literature and are typically formed by synthesizing polyurethane from a diol
and a
diisocyanate, followed by endcapping the polyurethane isocyanate endgroup with
a
hydroxy functional acrylate or methacrylate as described herein above.
Alternatively, the polyurethane is hydroxy endcapped and is esterified with
acrylic
acid or methacrylic acid. For example, Barbeau, et al., Journal of Polymer
Science
Part B: Polymer Physics, 38(21), 2750 - 68 (2000) show a typical reaction
scheme
for a prepolymer that is a polyurethane having isocyanate endgroups, endcapped
with an acrylate group. In some embodiments, the polyketal polyisocyanates of
the
invention are acrylate functionalized using this or a similar method. The
acrylate
39
CA 02654809 2009-03-05
functionality is then polymerized to give an acrylate polymer network. In yet
another variation of this chemistry, an isocyanate endcapped material is
crosslinked
with a hydroxy-functional polymer, such as poly(2-hydroxypropyl acrylate) or
poly(vinyl alcohol); see, for example, Decker et al., Macromol. Mater. Eng.
286, 5-
16 (2001). In some embodiments, the polyketal polyisocyanates of the invention
are
functionalized with an acrylate polymer using this or a similar method.
The various polyketal acrylates and polyketal methacrylates of the invention
have, in various embodiments, one or more acrylic functionalities present as
Rl
fragments in structures I, II, III, or IV. The o~ fl-unsaturated portion of
acrylic
functionalities are capable of radical, cationic, or anionic polymerization to
result in
a polymer network. Such reactions are widely used in the industry and one or
more
acrylate functional polyketals of the invention may be reacted using any of
the
known techniques of polymerization or crosslinking of acrylate
functionalities.
Many references are available that discuss these techniques. Radical
polymerization
or crosslinking reactions initiated by thermal, redox, electromagnetic
radiation such
as ultraviolet (UV), or electron beam (ebeam) are the most common of these
known
techniques. Some useful references discussing such means of polymerization of
acrylate functional materials are Decker et al., Macromol. Mater. Eng. 286, 5-
16
(2001); Burlant, W., U.S. Patent No. 3,437,514; Endruweit, et al., Polymer
Composites 2006, 119-128; Decker, C., Pigment and Resin Technology 30(5), 278-
86 (2001); and Jbnsson et al., Progress in Organic Coatings 27, 107-22 (1996).
Other known and useful methods are those taught by U.S. Patent Nos. 3,437,514;
3,528,844; 3,542,586; 3,542,587; 3,641,210. Such polymerization reactions are
particularly advantageous where one or more polyketals of the invention are
polymerized or crosslinked, for example, in situ in a coated formulation, in a
syrup
preparation for coating, and the like. Any of the techniques employed in these
references may be advantageously employed to react the acrylate functional
polyketals of the invention, resulting in linear, branched, or crosslinked
polymer
networks.
Many useful extensions of the above embodiments of the invention are
readily envisioned wherein the acrylate functional polyketals are employed.
For
example, in one embodiment, a bisketal diol is acrylate functionalized and
employed
as a crosslinker when blended with additional acrylate functional compounds,
typically monoacrylate functional compounds, in a radical polymerization
reaction.
CA 02654809 2009-03-05
In other embodiments, any one or more of the polyketal polymers described
above
are provided with acrylic functionality by employing the reactions described
above,
to form polyketal acrylate prepolymers. In some such embodiments, the
polyketal
acrylate prepolymers are processed, for example by coating, extruding, mold
filling,
and so forth, with or without additional solvents, prior to reaction of the
acrylate
groups. The acrylate functional polyketal polymers may further be blended with
one
or more additional acrylate functional compounds and/or additional vinyl
functional
compounds. After processing, the polyketal acrylate prepolymers are reacted to
form a polymerized and/or crosslinked network. The resulting networks are
thermoset or thermoplastic, depending on whether or not the network is
crosslinked.
It is readily understood that the properties of the networks will vary greatly
depending on both the nature of the compounds used and crosslink density.
Additional acrylate functional compounds include compounds having one or
more acrylate, alkylacrylate, acrylamide, or alkylacrylamide residues. Non-
limiting
examples of useful acrylate functional compounds include acrylic acid,
methacrylic
acid, acrylamide, methacrylamide, N-hydroxymethyl acrylamide,
methacryloxyethyl
phosphate, acrylonitrile, methacrylonitrile, 2-acrylamido-2-
methylpropanesulfonic
acid and salts thereof; maleic acid, its salt, its anhydride and esters
thereof;
monohydric and polyhydric alcohol esters of acrylic and alkylacrylic acid such
as
1,6 hexane diol diacrylate, neopentyl glycol diacrylate, 1,3 butylene
dimethacrylate,
ethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol
triacrylate,
pentaerythritol tetracrylate, etc.; other oxygenated derivatives of acrylic
acid and
alkylacrylic acids, e.g., glycidyl methacrylate, hydroxyethyl methacrylate,
hydroxypropyl methacrylate, etc.; halogenated derivatives of the same, e.g.,
chloroacrylic acid and esters thereof; and diacrylates and dimethacrylates,
e.g.,
ethylene glycol diacrylate. In some embodiments, the additional acrylate
functional
compounds are present in blends with acrylate functional polyketals of up to
about
50 mole percent, such as between about 1 and about 40 mole percent, of
additional
acrylate functional compounds.
Additional vinyl functional compounds include non-acrylate functional o (3-
unsaturated compounds capable of copolymerizing with the acrylate functional
compounds and/or acrylate functional polyketals. Non-limiting examples of
additional vinyl compounds include aromatic polyvinyl compounds such as
divinyl
benzene, aromatic monovinyl compounds such as styrene, methyl substituted
41
CA 02654809 2009-03-05
styrenes such as a -methyl styrene, vinyl toluene, t-butyl styrene,
chlorostyrene, and
the like; aliphatic monovinyl compounds such as a-olefins, e.g. propylene, 1-
octene,
and the like; . Other additional vinyl functional compounds useful in blends
with the
acrylate functional polyketals are the divinyl and tetravinyl compounds
disclosed in
U.S. Patent Nos. 3,586,526; 3,586,527; 3,586,528; 3,586,529; 3,598,530;
3,586,531;
3,591,626; and 3,595,687.
H. Allyl functional polyketals
Polyketal acids and esters having structures I, II, III and IV are useful, in
embodiments, for the synthesis of allyl adducts thereof. Any of the above
embodiments of the. invention wherein a polyketal has one or more acid or
ester
groups are, in embodiments, functionalized with one or more allyl
functionalities.
Such embodiments include structures of compounds I and III wherein a is 1; or
wherein a is 2; or wherein a is between about 3 and 100. Such embodiments also
include structures of compounds Ill and IV wherein (3 is 2; or wherein (3 is
about 2 to
12; or wherein (3 is between about 3 and 100.
As used herein, the term "allyl functionality" means a -CH2-CH=CH2
moiety that is capable of subsequent polymerization or crosslinking reactions
utilizing a free radical or redox mechanism. Allylic polyketals are
polyketals,
polyketal polyols, polyketal polyamines, dimers, oligomers, and polymers
thereof
having allyl functionality.
Allyl alcohol is employed, in embodiments, to synthesize allyl derivatives of
the polyketal acids or esters thereof by esterification or transesterification
reaction
using any of the known techniques commonly employed in the literature. For
example, allyl alcohol is esterified with a free carboxylic acid in the
presence of an
organic sulfonic acid esterification catalyst and a polymerization inhibitor
in U.S.
Patent No. 2,249,768. In other embodiments, allyl alcohol is employed in a
transesterification reaction of the carboxylate moiety present on a polyketal.
Suitable methods of transesterification to form allyl esters of any of the
polyketal
esters of the invention are disclosed in Remme et al., Synlett 2007, 3, 491-3
and U.S.
Patent No. 5,710,316; other suitable methods are disclosed in Singh et al., J
Org.
Chem. 2004, 69, 209-12 and Chavan et al., Synthesis 2003, 17, 2695-8. Allyl
monohalides are also employed, in embodiments, to synthesize one or more allyl
esters of the polyketals of the invention by employing a polyketal ester and a
42
CA 02654809 2009-03-05
catalyst that is palladium halide or platinum halide, a technique employed in,
for
example, U.S. Patent No. 3,699,155. These and other methods are used, in
embodiments, to synthesize allylic esters of the polyketals of the invention.
The one or more allylic polyketals of the invention are, in embodiments,
polymerized using any of the techniques known in the literature. For example,
heating ally! monomers in the presence of thermal free-radical initiators
gives
polymeric products. Typically, allyl polymers are made by charging the allyl
monomer and a free-radical initiator to a reactor, and heating the mixture at
a
temperature effective to polymerize the monomer (see, e.g. "Kirk-Othmer
Encyclopedia of Chemical Technology," 4th ed., Volume 2, pp. 161-179).
Improved
methods of polymerizing allyl compounds are also usefully employed with one or
more allylic polyketals of the invention. For example, U.S. Patent No.
5,420,216
discloses that gradual addition of initiator is key to high conversion in
allyl
polymerization.
In some embodiments of the invention, one allyl group per molecule
provides sufficient reactivity to result in high conversion or high molecular
weight
of the radically polymerized product. In other embodiments, two or more
reactive
double bonds per molecule yields solid, high molecular weight polymers by
initiation with a suitable free-radical catalyst. Such embodiments are useful
to
provide, for example, heat-resistant cast sheets and thermoset moldings. In
some
such embodiments, the reactivity of compounds having more than one allyl group
permits polymerization in two stages: a solid prepolymer containing reactive
double
bonds is molded by heating; then completion of polymerization gives cross-
linked
articles of superior heat resistance. In embodiments, the relatively slow rate
of
polymerizations is controlled more readily th an in the polymerization of
polyfunctional vinyl compounds to give soluble prepolymers containing reactive
double bonds.
One useful embodiment of one or more allylic polyketals, of the invention
employs minor proportions of one or more polyfunctional allylic polyketals for
cross-linking or curing preformed vinyl-type polymers. Among the preformed
polymers cured by minor additions of allyl ester monomers and catalysts
followed
by heat or irradiation are polyethylene, PVC, and acrylonitrile-butadiene-
styrene
(ABS) copolymers. These reactions are examples of graft copolymerization in
which specific added peroxides or high energy radiation achieves optimum cross-
43
CA 02654809 2009-03-05
linking. In other embodiments, small proportions of mono- or polyfunctional
allylic
polyketals are added as regulators or modifiers of vinyl polymerization for
controlling molecular weight and polymer properties. In yet other embodiments,
polyfunctional allylic polyketals of high boiling point and compatibility are
employed as stabilizers against oxidative degradation and heat discoloration
of
polymers.
One useful embodiment of one or more thermoset allylic polyketals of the
invention is in moldings and coatings for electronic devices requiring high
reliability
under long-term adverse environmental conditions. These devices include
electrical
connectors and insulators in communication, computer, and aerospace systems.
Other embodiments are readily envisioned.
1. Epoxy functional polyketals
Polyketal acids, esters, polyols, and polyisocyanates having structures I, II,
111 and IV are useful, in embodiments, for the synthesis of glycidyl adducts
thereof.
Any of the above embodiments of the invention wherein a polyketal has one or
more hydroxyl functionality are, in embodiments, functionalized with one or
more
glycidyl functionalities. Such embodiments include structures of compounds I
and
III wherein a is 1; or wherein a is 2; or wherein a is between about 3 and
100. Such
embodiments also include structures of compounds III and N wherein 0 is 2; or
wherein (3is about 2 to 12; or wherein /i is between about 3 and 100.
Polyketal acids and esters having structures I, II, Ill and N are useful, in
embodiments, for the synthesis of allyl adducts thereof. Any of the above
embodiments of the invention wherein a polyketal has one or more acid or ester
groups are, in embodiments, functionalized with one or more allyl
functionalities.
As used herein, the term "glycidyl functionality" means a methyl oxirane, or
epoxy, moiety that is capable of subsequent polymerization or crosslinking
reactions utilizing a ring opening reaction. Glycidyl polyketals are
polyketals,
polyketal polyols, and dimers, oligomers, and polymers thereof having one or
more
glycidyl functionalities.
Glycidyl alcohol is employed, in some embodiments, to synthesize glycidyl
esters of the polyketal acids or esters thereof by esterification or
transesterification
reaction using any.of the known techniques commonly employed in the
literature.
For example, Chanda, M. and Roy, S., eds;, Plastics Technology Handbook, 4th
ed.,
44
CA 02654809 2009-03-05
2007 Taylor & Francis Group, LLC, pp. 4-114 to 4-116; and U.S. Patent No.
5,536,855 describe some of the methods that are useful, in embodiments, to
react
one or more polyketal acids or esters of the invention with glycidyl alcohol.
In
other embodiments, glycidyl alcohol is reacted with one or more polyketal
polyisocyanates of the invention to give the corresponding polyketal glycidyl
urethanes, using techniques commonly employed to react an alcohol with an
isocyanate group.
In other embodiments, an epihalohydrin such as epichlorohydrin is used to
functionalize one or more polyketal polyols of the invention. The reaction
between
an alcohol and epichlorohydrin to form a glycidyl ether is known in the
literature.
For example, the reaction of the alcohol Bisphenol A with epichlorohydrin is a
well
known reaction by which epoxy resins are formed. A similar process is used in
some embodiments of the invention to form one or more epoxy functional
polyketals of the invention. For example, U.S. Patent No. 5,420,312 describes
techniques of forming glycidyl ethers of alcohols. This and other conventional
techniques employed to react epichlorohydrin with an alcohol are, in
embodiments,
employed using the polyketal polyols of the invention to form glycidyl ethers.
Epichlorohydrin is also, in embodiments, reacted directly with carboxylic
acids to
form the corresponding glycidyl ester; the reaction involves ring opening of
the
glycidyl moiety, followed by dehydrochlorination to re-form the oxirane ring.
In
embodiments, glycidyl esters of one or more polyketal acids of the invention
are
formed by reacting a polyketal acid of the invention having one or more free
carboxylic acid groups with one or more equivalents of epichlorohydrin. Such a
reaction is carried out, in one or more embodiments, by employing the
techniques of
Bukowska, et al., J. Chem. Tech. and Biotech., 74: 1145-1148 (1999); Otera et
al.,
Synthesis (12), 1019-1020 (1986); U.S. Patent Nos. 3,576,827; British Patent
No.
GB 884,033; and German Patent Appl. No. DE 15945/70; or by other techniques
found in the literature. In still other embodiments, the ionic salts of the
polyketal
carboxylates of the invention are reacted with an epihalohydrin, such as
epichlorohydrin, to form the corresponding glycidyl esters. In such
embodiments,
the techniques employed by, for example, Maerker et al., J. Org. Chem. 26,
2681-
2688 (1961) are useful, among other techniques.
Another technique employed, in some embodiments, to provide glycidyl
functionality to one or more polyketal esters of the invention is to react an
CA 02654809 2009-03-05
unsaturated ester of a polyketal with a peroxide. For example, U.S. Patent No.
5,036,154 discloses a method whereby an ethylenically unsaturated ester group,
such as an allyl ester, is reacted with hydrogen peroxide in the presence of
an alkali
metal or alkaline earth metal salt of tungstic acid, phosphoric acid, and a
phase
transfer catalyst to give the epoxidized product of the unsaturated moiety.
Such a
technique is used, in embodiments, to form a glycidyl ester of a polyketal of
the
invention from the corresponding allyl ester, the allyl ester functionalized
polyketals
of the invention having been described in section H. above. Other techniques
employed in the literature are similarly useful to obtain one or more
epoxidized
products of allyl esters of the invention. For example, esterification of
various
polyketals of the invention with an unsaturated fatty acid ester is followed,
in
embodiments, by reacting the unsaturated site with hydrogen peroxide, as is
described by Du et al., J. Am. Org. Chem. Soc. 81(4) 477-480 (2004).
One or more epoxy functionalized polyketals of the invention are, in
embodiments, subsequently polymerized using standard techniques from the
literature. The polymerization of epoxy groups, for example with amines,
amides,
or anhydrides, is widely known. A useful summary of compounds and mechanisms
of curing epoxy groups is found in Chanda, M. and Roy, S., eds., Plastics
Technology Handbook, 4t' ed., m 2007 Taylor & Francis Group, LLC, pp.. 4-116
to
4-122. Any of the techniques employed or referenced therein are used, in
various
embodiments, to polymerize the epoxy groups present on one or more polyketal
glycidyl esters of the invention to form the corresponding linear or
crosslinked
polymer.
Applications of epoxy polymers are numerous and broad in scope. Due to
their high strength, variable crosslink density, and variable chemical
starting
materials, epoxies have found broad applicability for numerous applications.
Many
of the most common applications are set forth in Chanda, M. and Roy, S., eds.,
Plastics Technology Handbook, 4`h ed., 2007 Taylor & Francis Group, LLC, pp.
2-80 to 2-81, 7-26, and 4-124-to 4-125. The epoxy resins formed by curing the
30- epoxy functional polyketal esters of the invention are, in various
embodiments,
useful in one or more of these applications.
The polyketal compounds and dimers, oligomers, and polymers having
structures I, II, III, and N, further as embodied in sections A. to I., are
useful in a
wide variety of industrially useful and significant applications. The various
46
CA 02654809 2009-07-24
polyketal polymers of the invention are, in embodiments, used in blends,
optionally obtained
by reactive extrusion. Blends include blends of various species of the
polyketal polymers of
the invention as well as blends with such polymers as aliphatic/aromatic
copolyesters, as for
example polybutylene terephthalate adipate (PBTA), polybutylene terephthalate
succinate
(PBTS), and polybutylene terephthalate glutarate (PBTG); biodegradable
polyesters such as
polylactic acid, poly-E-caprolactone, polyhydroxybutyrates such as poly-3-
hydroxybutyrates,
poly-4-hydroxybutyrates and polyhydroxybutyrate-valerate, polyhydroxybutyrate-
propanoate,
polyhydroxybutyrate-hexanoate, polyhydroxybutyrate-decanoate,
polyhydroxybutyrate-
dodecanoate, polyhydroxy-butyrate-hexadecanoate, polyhydroxybutyrate-
octadecanoate, and
polyalkylene succinates and their copolymers with adipic acid, lactic acid or
lactide and
caprolactone and their combinations, and the like; polystyrene and copolymers
thereof,
polyurethanes; polycarbonates; polyamides such as Nylon* 6 and Nylon* 6,6;
polyolefins
such as polyethylene, polypropylene, and copolymers thereof; or any other
industrially
useful polymeric compounds. Blends also include, in some embodiments,
composites with
gelatinized, destructed and/or complexed starch, natural starch, flours, and
other materials of
natural, vegetable or inorganic origin. One or more polyketal polymers of the
invention are,
in some embodiments, blended with polymers of natural origin, such as starch,
cellulose,
chitosan, alginates, natural rubbers or natural fibers (such as for example
jute, kenaf, hemp).
The starches and celluloses can be modified, such as starch or cellulose
esters with a degree
of substitution of between 0.2 and 2.5, hydroxypropylated starches, or
modified starches
with fatty chains, among others.
The various polyketal compounds and polymers made therefrom according to the
invention, and blends of thereof, possess properties and values of viscosity
that render them
suitable for use, by appropriately adjusting the molecular weight, in numerous
practical
applications, such as films, injection-molded products, extrusion coated
products, fibers,
foams, thermoformed products, extruded profiles and sheets, extrusion blow
molding,
injection blow molding, rotomolding, stretch blow molding and the like.
In the case of films, production technologies like film blowing, casting, and
coextrusion can be used. Moreover such films can be subject to monoaxial or
biaxial
orientation in line or after film production. It is also possible that the
stretching is
* trademarks
47
CA 02654809 2009-03-05
obtained in presence of an highly filled material with inorganic fillers. In
such a
case, the stretching can generate micropores and the so obtained film can be
suitable
for hygiene applications.
The various polyketal compounds and polymers made therefrom according
to the invention are suitable for the production of films. A "film" is
defined, for the
purposes of various embodiments of the invention, as a sheet type material
that is
flexible to e.g. bending and is between about 1 m to 5mm thick. Films may be
made using one or more polyketal polymers of the invention; or they can be
made
using another polymer blended with a polyketal compound. Films employing
various polyketal compounds and polymers made therefrom of the invention are,
in
embodiments, one-directional or two-directional, single layer or multilayer,
and
employ one or more polyketal polymers of the invention as a single component
or in
a blend with other materials, as described above. The films are useful for
various
applications including agricultural mulching films; printable films for
graphics or
text; cling films (extensible films) for foodstuffs, films for bales in the
agricultural
sector and for wrapping of refuse; shrink films such as for example for
pallets,
mineral water, six pack rings, and so on; bags and liners such as for
collection of
refuse, holding foodstuffs, gathering mowed grass and yard waste, and the
like;
thermoformed single-layer and multilayer packaging for foodstuffs, such as for
example containers for milk, yogurt, meat, beverages, etc.; and in multilayer
laminates with layers of paper, plastic materials, aluminum, and metalized
films for
a wide variety of applications.
The various polyketal compounds and polymers made therefrom of the
invention are also useful for coatings that form a layer on top of a film, an
article,
and the like. A coating may be up to several millimeters thick, or it may be a
single
molecular layer. Coatings of the invention are applied, in embodiments, by
extrusion coating, die coating, slot coating, brush coating, spray coating, or
any
other generally known technique employed in the coating industry. Coatings
employing various polyketal compounds and polymers made therefrom of the
invention are useful as protective coatings, paint components, adhesives or
glues,
barrier layers, and the like. One or more coatings of the invention are
applied, in
embodiments, with or without additional solvent(s), such as coalescing
solvents, and
with our without additives such as UV blocking agents, antibacterial agents,
48
CA 02654809 2009-03-05
colorants, fillers, and the like. One or more coatings of the invention are,
in some
embodiments, crosslinked after application.
Various polyketal compounds and polymers made therefrom of the invention
are also useful in forming articles. An "article", as defined for the purposes
of the
invention, includes objects that are be rigid or flexible; that exist as
standalone
objects or as part of an assembly or laminate; and that include one or more
polyketal
compounds and polymers made therefrom of the invention or a blend thereof,
optionally with one or more additional materials. Some examples of useful
articles
that include various polyketal compounds and polymers made therefrom of the
invention are punnets for foodstuffs, I-beams for construction,. casings for
e.g. pens,
computer screens, and the like; parts for automobile construction, table tops,
and the
like; decorative items such as lamp parts, jewelry, vases, architectural
features, and
the like; children's toys; drink bottles; and many other articles. The
invention is not
particularly limited in terms of what articles may be formed employing the
various
polyketal compounds and polymers made therefrom of the invention.
Articles that can be formed include foamed articles. Foaming of
polyurethanes are discussed above; those techniques and others generally known
in
the industry are used, in embodiments, to form foamed articles from the
various
polyketal compounds and polymers made therefrom of the invention. Foamed
articles include both rigid and flexible foams. Some examples of useful foamed
materials include cushions for automobile seats, interior or exterior
furniture, and the
like; foamed or foamable beads for the production of pieces formed by
sintering;
foamed blocks made up of pre-foamed particles; foamed sheets, thermoformed
foamed sheets, and containers obtained therefrom for the packaging of
foodstuffs.
Articles also include fibrous articles. Examples of fibrous articles include
standard scale fibers, microfibers, nanofibers, and composite fibers.
Composite
fibers have, in embodiments, a core constituted by a rigid polymer such as
PLA,
PET, PTT, etc. and an external shell made with one or more polyketal compounds
and polymers made therefrom of the invention; other composite fibers have
various
section configurations (from round to multilobed). Fibers also include flaked
fibers,
woven and non-woven fabrics or spun-bonded or thermobonded fabrics for the
sanitary sector, the hygiene sector, the agricultural sector, georemediation,
landscaping and the clothing sector.
49
CA 02654809 2009-03-05
The present invention contemplates, in one embodiment, a polyketal having
structure I:
RS s R6 R5
Rg b R7 R9
0 O a b 0 O
O O
R4 R4
R1_0 a a O-R'
R2 R3 R3 R2
I
wherein
a is an integer of at least 1;
Rl is hydrogen, a metal cation, an organic cation, a linear, branched, or
cyclic alkyl, a linear, branched, or cyclic alkenyl, alkynyl, aryl, alkaryl,
or an
oligomeric or polymeric moiety; and optionally contains one or more
heteroatoms; and Rl may be the same or different for each occurrence;
R2, R3, R4, R5, and R6 are independently hydrogen, a linear, branched, or
cyclic alkyl, a linear, branched, or cyclic alkenyl, alkynyl, aryl, or
alkaryl;
and optionally contains one or more heteroatoms; and R2, R3, R4, R5, and R6
may be the same or different for each occurrence;
R7 is a covalent bond, methylene, ethylene, hydroxymethylene, oxygen, or -
CH2-O-CHZ- and R7 is the same or different for each occurrence;
R8 and R9 are independently hydrogen, a linear, branched, or cyclic alkyl, a
linear, branched, or cyclic alkenyl, alkynyl, aryl, alkaryl, or a polymeric
moiety; and optionally contains one or more heteroatoms;
a is 0 or an integer of 1 to 12; and
b is 0 or 1 wherein b = 0 indicates a five membered ring,
Ox0
'~' R4
b = 1 indicates a 6 membered ring,
50
CA 02654809 2009-03-05
R5 R6
O 0
R4
and b may be the same or different for each occurrence.
The R' group of the polyketal I is, in embodiments, ethyl, butyl, or 2-
ethylhexyl. The R1 group of the polyketal I is, in embodiments, the residue of
a
polyol. The polyol is, in embodiments, ethylene glycol, diethylene glycol,
pentaerythritol, 1,6-hexanediol, glycerol, or diglycerol. The Rl group of the
polyketal I contains, in embodiments, one or more isocyanate, acrylate,
methacrylate, allyl, or oxirane groups. In embodiments of the polyketal I, all
R2 and
R3 are hydrogen, all R4 are methyl, and all values of a equal 2. In
embodiments of
the polyketal I, all values of b equal 0. In embodiments of the polyketal I,
all values
of b equal 1 and all R5 and R6 are hydrogen. In embodiments of the polyketal
I, a
equals 1 or 2 and R8 and R9 are hydrogen. In embodiments of the polyketal I, a
equals 1 and b equals 0. In embodiments of the polyketal I, a is between about
2
and 1000, all values of b equal 1, and all R5 and R6 are hydrogen. In some
such
embodiments, a is between about 10 and 100. In some such embodiments, one or
more of R8 and R9 are residues of a polymer. In some such embodiments, the
polymer residue is a poly(vinyl alcohol) residue, poly(vinyl acetate) residue,
polyethylene residue, polypropylene residue, or a random or block copolymer
residue thereof.
The present invention contemplates a formulation comprising the polyketal
having structure I. The formulation comprises, in embodiments, one or more
additional polymers. The one or more additional polymers comprise, in
embodiments, poly(3-hydroxybutyrate-co-3-hydroxyvalerate), poly(vinyl
chloride),
poly(lactic acid), or polystyrene. In the formulation, the polyketal having
structure I
is, in embodiments, a plasticizer, a toughener, a surfactant, a coalescing
solvent, a
compatibilizer, a barrier layer compound, an interfacial modifier, or a phase
transfer
compound. The formulation can further comprise one or more solvents. The one
or
more solvents comprise, in embodiments, two immiscible solvents, wherein the
formulation comprises a homogeneous mixture. In some embodiments of the
formulation comprising two immiscible solvents, wherein the formulation
comprises
51
CA 02654809 2009-03-05
a homogeneous mixture, the polyketal of structure I is about 0.01 vol% to 50
vol%
percent based on total volume of the one or more solvents, and the homogeneous
mixture comprises between about 5 vol% to 95 vol% methanol based on the total
volume of the one or more solvents. In other embodiments of the formulation
comprising two immiscible solvents, wherein the formulation comprises a
homogeneous mixture, the polyketal of structure I is present at about 0.1 vol%
to 20
vol% based on the total volume of the one or more solvents. In other
embodiments
of the formulation comprising two immiscible solvents, wherein the formulation
comprises a homogeneous mixture, the polyketal of structure I is present at
about 1
vol% to 10 vol% based on the total volume of the one or more solvents. In some
embodiments of the formulation comprising two immiscible solvents, wherein the
formulation comprises a homogeneous mixture, the two immiscible solvents
comprise a hexane methanol blend or a methanol water blend. In some
embodiments of the formulation comprising a hexane methanol blend or a
methanol
water blend, the methanol is present at about 50 vol% based on the total
volume of
the one or more solvents. In some embodiments of the formulation comprising a
hexane methanol blend or a methanol water blend, the polyketal R, is butyl,
R2, R3,
R8, and R9 are hydrogen, a is 2, b and c are 0, and a is 1. In embodiments,
the
formulation comprising the polyketal of structure I is a coating formulation.
In
embodiments, the formulation comprising the polyketal of structure I is an
adhesive
formulation.
The present invention contemplates an article comprising the polyketal
having structure I. In embodiments, the article comprising the polyketal
having
structure I is coated, cast, extruded, coextruded, profile extruded, blow
molded,
injection molded, co-injection molded, thermoformed, or reaction injection
molded.
In embodiments, the article comprising the polyketal having structure I
comprises
two or more layers and the polyketal of structure I is present in at least one
layer. In
embodiments, the article comprising the polyketal having structure I comprises
a
film, a sheet, a fiber, a foamed article, a woven fabric, a nonwoven fabric,
or a
pressure sensitive adhesive tape, or a paint coating.
The present invention contemplates a bisketal having structure II:
52
CA 02654809 2009-03-05
O Ra OXO Ra O
R'-OO O a O-R1
R2 R3 R3 R2
II
wherein:
R1 is hydrogen, a metal cation, an organic cation, a linear, branched, or
cyclic alkyl, a linear, branched, or cyclic alkenyl, alkynyl, aryl, alkaryl,
or an
oligomeric or polymeric moiety; and optionally contains one or more
heteroatoms;
and R' is the same or different for each occurrence;
R2 and R3 are independently hydrogen, a linear, branched, or cyclic alkyl, a
linear, branched, or cyclic alkenyl, allcynyl, aryl, or alkaryl; and
optionally contains
one or more heteroatoms; and R2 and R3 are the same or different for each
occurrence;
R4 is a linear, branched, or cyclic alkyl, a linear, branched, or cyclic
alkenyl,
alkynyl, aryl, or alkaryl; and optionally contains one or more heteroatoms;
and R4 is
the same or different for each occurrence; and
a is O or an integer of 1 to 12.
In some embodiments of the bisketal of structure II, one or more R' is ethyl,
butyl,
or 2-ethylhexyl. In some embodiments of the bisketal of structure II, one or
more R'
is the residue of a polyol. In some embodiments of the bisketal of structure
II
wherein one or more R1 is the residue of a polyol, the one or more polyol is
ethylene
glycol, diethylene glycol, pentaerythritol, 1,6-hexanediol, glycerol, or
diglycerol. In
some embodiments of the bisketal of structure II, one or more R1 comprises one
or
more isocyanate, acrylate, methacrylate, allyl, or oxirane groups. In some
embodiments of the bisketal of structure II, all R2 and R3 are hydrogen, all
R4 are
methyl, and all values of a equal 2.
The present invention contemplates a formulation comprising one or more
bisketals of structure H. In some embodiments of the formulation comprising
one or
more bisketals of structure II, the formulation further comprises one or more
polymers. The one or more polymers comprise, in embodiments, poly(3-
hydroxybutyrate-co-3-hydroxyvalerate), poly(vinyl chloride), poly(lactic
acid), or
polystyrene. In some embodiments of the formulation comprising one or more
bisketals of structure II, one or more bisketals is a plasticizer, a
toughener, a
53-
CA 02654809 2009-03-05
surfactant, a barrier layer compound, a coalescing solvent, a compatibilizing
agent,
an interfacial modifier, or a phase transfer compound. In some embodiments of
the
formulation comprising one or more bisketals of structure II, the formulation
is a
coating formulation. In some embodiments of the formulation comprising one or
more bisketals of structure II, the fonnulation is an adhesive fonnulation. In
some
embodiments of the formulation comprising one or more bisketals of structure
II, the
formulation further comprises one or more solvents. In some embodiments of the
formulation comprising one or more bisketals of structure II and further
comprising
one or more solvents, the one or more solvents comprise two immiscible
solvents
and the formulation comprises a homogeneous mixture. In some embodiments of
the
formulation comprising one or more bisketals of structure II, the formulation
further
comprises one or more additives. In some embodiments of the formulation
comprising one or more bisketals of structure II wherein the formulation
further
comprises one or more additives, the one or more additives comprise one or
more
crosslinkers, redox initiators, thermal initiators, UV initiators, UV
stabilizers,
colorants, thermal stabilizers, antibacterial agents, antifungal agents,
antioxidants,
plasticizers, fillers, adjuvants, or a mixture thereof.
The present invention contemplates an article comprising the polyketal
having structure H. In embodiments, the article comprising the polyketal
having
structure II is coated, cast, extruded, coextruded, profile extruded, blow
molded,
injection molded, co-injection molded, thermoformed, or reaction injection
molded.
In embodiments, the article comprising the polyketal having structure II
comprises
two or more layers and the polyketal of structure II is present in at least
one layer.
In embodiments, the article comprising the polyketal having structure II
comprises a
film, a sheet, a fiber, a foamed article, a woven fabric, a nonwoven fabric,
or a
pressure sensitive adhesive tape, or a paint coating.
The present invention contemplates a polymeric composition comprising one
or more repeat units comprising structure III:
54
CA 02654809 2009-03-05
R5 s R6 R5
R8 R7 b R9
O O a 0 O
O O
R4 R4
O a a -R1
R2 R3 R3 R2
III
wherein
R' is a linear, branched, or cyclic alkyl, a linear, branched, or cyclic
alkenyl,
alkynyl, aryl, alkaryl, or an oligomeric or polymeric moiety; and optionally
contains
one or more heteroatoms; and R' is the same or different for each occurrence;
R2, R3, R4, R5, and R6 are independently hydrogen, a linear, branched, or
cyclic alkyl, a linear, branched, or cyclic alkenyl, alkynyl, aryl, or
alkaryl; and
optionally contains one or more heteroatoms; and R2, R3, R4, R5, and R6 is the
same
or different for each occurrence;
R7 is a covalent bond, methylene, ethylene, hydroxymethylene, oxygen, or -
CH2-O-CH2- and R7 is the same or different for each occurrence;
R8 and R9 are independently hydrogen, a linear, branched, or cyclic alkyl, a
linear, branched, or cyclic alkenyl, alkynyl, aryl, alkaryl, or a polymeric
moiety; and
optionally contains one or more heteroatoms;
a is 0 or an integer of l to 12; and
b is 0 or 1 wherein b = 0 indicates a five membered ring,
0 0
~N4
b = 1 indicates a 6 membered ring,
R5 R6
0 0
R4
and b may be the same or different for each occurrence;
CA 02654809 2009-03-05
a is an integer of at least 1; and
(3 is an integer of at least 1.
In some embodiments of the polymeric composition having structure III, a equal
2,
all R2 and R3 are hydrogen, and all R4 are methyl. In some embodiments of the
polymeric composition having structure III, all b equal 0. In embodiments of
the
polymeric composition having structure III, all values of b equal 1 and all R5
and R6
are hydrogen. In embodiments of the polymeric composition having structure
III, a
equals 1 or 2 and R8 and R9 are hydrogen. In embodiments of the polymeric
composition having structure III, a equals 1 and b equals 0. In embodiments of
the
polyketal I, a is between about 2 and 1000, all values of b equal 1, and all
R5 and R6
are hydrogen. In some embodiments of the polymeric composition having
structure
III, 1 is about 1. In some embodiments of the polymeric composition having
structure III, (3 is between about 2 and 12. In some embodiments of the
polymeric
composition having structure III, 0 is between about 12 and 100. In some
embodiments of the polymeric composition having structure 111 0 is between
about
100 and 1000. In some embodiments of the polymeric composition having
structure
III, one or more additional repeat units comprise one or more ester groups,
ether
groups, or a combination thereof. In some such embodiments the additional
repeat
units comprising one or more ester groups comprise isophthalate,
terephthalate, or
adipate residues. In some embodiments of the polymeric composition having
structure III, one or more additional repeat units comprise urethane,
(urethane urea),
(ester urethane), (ester urethane urea), (ester ether urethane), or (ester
ether urethane
urea) groups. In some embodiments of the polymeric composition having
structure
III, one or more additional repeat units comprise carbonate groups. In some
embodiments of the polymeric composition having structure III, one or more
additional repeat units comprise the residue of one or more polymerized
acrylate,
methacrylate, oxirane, or allyl groups.
The present invention contemplates a formulation comprising the polymeric
composition having structure III. In embodiments, the formulation comprising
the
polymeric composition having structure III further comprises one or more
additional
polymeric compounds. In embodiments, the one or more additional polymeric
compounds comprise poly(3 -hydroxybutyrate-co-3-hydroxyvalerate), poly(vinyl
56
CA 02654809 2009-03-05
chloride), poly(lactic acid), or polystyrene. In embodiments of the
formulation
comprising the polymeric composition having structure III, the polymeric
composition having structure III is a plasticizer, a toughener, a surfactant,
a barrier
layer compound, an interfacial modifier, a compatibilizer, or a phase transfer
compound. In embodiments, the formulation comprising the polymeric composition
having structure III further comprises one or more additives. In embodiments
of the
formulation comprising the polymeric composition having structure III and one
or
more additives, the one or more additives comprise one or more crosslinkers,
redox
initiators, thermal initiators, UV initiators, UV stabilizers, colorants,
thermal
stabilizers, antibacterial agents, antifungal agents, antioxidants,
plasticizers, fillers,
adjuvants, or a mixture thereof. In embodiments, the formulation comprising
the
polymeric composition having structure III formulation is a coating
formulation. In
embodiments, the formulation comprising the polymeric composition having
structure III is an adhesive formulation. In embodiments, the formulation
comprising
the polymeric composition having structure III, the formulation further
comprises
one or more solvents.
The present invention contemplates an article comprising the polymeric
composition having structure III. In embodiments, the article comprising the
polymeric composition having structure III is coated, cast, extruded,
coextruded,
profile extruded, blow molded, thermoformed, injection molded, coinjection
molded, or reaction injection molded. In embodiments, the article comprising
the
polymeric composition having structure III comprises two or more layers and
the
polymeric composition of structure III is present in at least one layer. In
embodiments, the article comprising the polymeric composition having structure
III
comprises a film, a sheet, a fiber, a foamed article, a woven fabric, a
nonwoven
fabric, or a pressure sensitive adhesive tape, or a paint coating.
The present invention contemplates a polymeric composition having one or
more repeat units comprising structure IV:
O Ra =K0 Ra O
O a 0 O a I R1--
R 2 R3 R3 R2
IV
57
CA 02654809 2009-03-05
wherein
R' is a linear, branched, or cyclic alkyl, a linear, branched, or cyclic
alkenyl,
alkynyl, aryl, alkaryl, or an oligomeric or polymeric moiety; and optionally
contains
one or more heteroatoms; and R' is the same or different for each occurrence;
R2 and R3 are independently hydrogen, a linear, branched, or cyclic alkyl, a
linear, branched, or cyclic alkenyl, aikynyl, aryl, or alkaryl; and optionally
contains
one or more heteroatoms; and R2 and R3 are the same or different for each
occurrence;
R4 is a linear, branched, or cyclic alkyl, a linear, branched, or cyclic
alkenyl,
alkynyl, aryl, or alkaryl; and optionally contains one or more heteroatoms;
and R4 is
the same or different for each occurrence;
a is 0 or an integer of 1 to 12; and
(3 is an integer of at least 1.
In some embodiments of the polymeric composition having structure IV, all a
equal
2, all R2 and R3 are hydrogen, and all R4 are methyl. In some embodiments of
the
polymeric composition having structure IV, 3 is about 1. In some embodiments
of
the polymeric composition having structure IV, (3 is between about 2 and 12.
In
some embodiments of the polymeric composition having structure IV, (3 is
between
about 12 and 100. In some embodiments of the polymeric composition having
structure IV, 0 is between about 100 and 1000. In some embodiments of the
polymeric composition having structure IV, one or more additional repeat units
comprise one or more ester groups, ether groups, or a combination thereof. In
some
such embodiments the additional repeat units comprise one or more ester groups
comprise isophthalate, terephthalate, or adipate residues. In some embodiments
of
the polymeric composition having structure IV, one or more repeat units
comprise
urethane, (urethane urea), (ester urethane), (ester urethane urea), (ester
ether
urethane), or (ester ether urethane urea) groups. In some embodiments of the
polymeric composition having structure IV, one or more additional repeat units
comprise one or more carbonate groups. In some embodiments of the polymeric
composition having structure IV, one or more repeat units comprise the residue
of
one or more polymerized acrylate, methacrylate, oxirane, or allyl groups.
58
CA 02654809 2009-03-05
The present invention contemplates a formulation comprising the polymeric
composition having structure N. In embodiments, the formulation comprising the
polymeric composition having structure IV further comprises one or more
additional
polymeric compounds. In embodiments, the one or more additional polymeric
compounds comprise poly(3-hydroxybutyrate-co-3-hydroxyvalerate), poly(vinyl
chloride), poly(lactic acid), or polystyrene. In embodiments of the
formulation
comprising the polymeric composition having structure IV, the polymeric
composition having structure N is a plasticizer, a toughener, a surfactant, a
barrier
layer compound, an interfacial modifier, a compatibilizer, or a phase transfer
compound. In embodiments, the formulation comprising the polymeric composition
having structure N further comprises one or more additives. In embodiments of
the
formulation comprising the polymeric composition having structure N and one or
more additives, the one or more additives comprise one or more crosslinkers,
redox
initiators, thermal initiators, UV initiators, UV stabilizers, colorants,
thermal
stabilizers, antibacterial agents, antifungal agents, antioxidants,
plasticizers, fillers,
adjuvants, or a mixture thereof. In embodiments, the formulation comprising
the
polymeric composition having structure N formulation is a coating formulation.
In
embodiments, the formulation comprising the polymeric composition having
structure N is an adhesive formulation. In embodiments, the formulation
comprising the polymeric composition having structure IV, the formulation
further
comprises one or more solvents.
The present invention contemplates an article comprising the polymeric
composition having structure N. In embodiments, the article comprising the
polymeric composition having structure N is coated, cast, extruded,
coextruded,
profile extruded, blow molded, thermoformed, injection molded, coinjection
molded, or reaction injection molded. In embodiments, the article comprising
the
polymeric composition having structure N comprises two or more layers and the
polymeric composition of structure III is present in at least one layer. In
embodiments, the article comprising the polymeric composition having structure
III
comprises a film, a sheet, a fiber, a foamed article, a woven fabric, a
nonwoven
fabric, or a pressure sensitive adhesive tape, or a paint coating.
The present invention contemplates a polyketal having structure V:
59
CA 02654809 2009-03-05
Rz R3 2
R4 b b R5
O O a 0 O
CH3 H3C
R1-O a a O-R1
V
wherein
R1 is hydrogen, a metal cation, an organic cation, a linear, branched, or
cyclic alkyl, a linear, branched, or cyclic alkenyl, alkynyl, aryl, alkaryl,
or an
oligomeric or polymeric moiety; and optionally contains one or more
heteroatoms;
and R' is the same or different for each occurrence;
R2 and R3 are independently hydrogen, a linear, branched, or cyclic alkyl, a
linear, branched, or cyclic alkenyl, alkynyl, aryl, or alkaryl; and optionally
contains
one or more heteroatoms; and R2, R3, R4, R5, and R6 is the same or different
for each
occurrence;
R4 and R5 are independently hydrogen, a linear, branched, or cyclic alkyl, a
linear, branched, or cyclic alkenyl, alkynyl, aryl, alkaryl, or a polymeric
moiety; and
optionally contain one or more heteroatoms;
a is 0 or an integer of 1 to 12 and a is the same or different for each
occurrence;
b is 0 or 1 wherein b = 0 indicates a five membered ring,
o~o
' CH3
b =1 indicates a 6 membered ring,
R2 R3
OO
- CH3
and b may be the same or different for each occurrence; and
a is an integer of at least 1.
CA 02654809 2009-03-05
In some embodiments of the polymeric composition having structure V, one or
more
R' is ethyl, butyl, or 2-ethylhexyl. In some embodiments of the polymeric
composition having structure V, one or more R' is the residue of a polyol. In
some
embodiments of the polymeric composition having structure V wherein R' is the
residue of a polyol, the polyol is ethylene glycol, diethylene glycol,
pentaerythritol,
1,6-hexanediol, glycerol, or diglycerol. In some embodiments of the bisketal
of
structure V, one or more R' comprises one or more isocyanate, acrylate,
methacrylate, allyl, or oxirane groups. In some embodiments of the polymeric
composition having structure V, all values of a equal 2. In some embodiments
of the
polymeric composition having structure V, all values of b equal 0. In some
embodiments of the polymeric composition having structure V, all values of b
equal
1 and all R3 and R4 are hydrogen. In some embodiments of the polymeric
composition having structure V, a equals 1 or 2 and R4 and R5 are hydrogen. In
some embodiments of the polymeric composition having structure V, a is between
about 2 and 1000, all values of b equal 1, and all R3 and R4 are hydrogen. In
some
such embodiments, the value of a is between about 10 and 100. In some
embodiments of the polymeric composition having structure V, one or more of R4
and R5 are residues of a polymer. In some embodiments of the polymeric
composition having structure V wherein one or more of R4 and R5 are residues
of a
polymer, the polymer is poly(vinyl alcohol), poly(vinyl acetate),
polyethylene,
polypropylene, or a random or block copolymer thereof.
The present invention contemplates a formulation comprising the polyketal
having structure V. The formulation comprising the polyketal having structure
V
comprises, in embodiments, one or more polymers. The one or more polymers
comprise, in embodiments, poly(3-hydroxybutyrate-co-3-hydroxyvalerate),
poly(vinyl chloride), poly(lactic acid), or polystyrene. In the formulation,
the
polyketal having structure V is, in embodiments, a plasticizer, a toughener, a
surfactant, a coalescing solvent, a compatibilizer, a barrier layer compound,
an
interfacial modifier, or a phase transfer compound. The formulation comprising
the
polyketal having structure V can further comprise one or more solvents. The
one or
more solvents comprise, in embodiments, two immiscible solvents, wherein the
formulation comprises a homogeneous mixture. In some embodiments of the
formulation comprising the polyketal having structure V and further comprising
two
immiscible solvents wherein the formulation comprises a homogeneous mixture,
the
61
CA 02654809 2009-03-05
polyketal of structure V is about 0.01 vol% to 50 vol% percent based on total
volume of the one or more solvents, and the homogeneous mixture comprises
between about 5 vol% to 95 vol% methanol based on the total volume of the one
or
more solvents. In other embodiments of the formulation comprising the
polyketal
having structure V and further comprising two immiscible solvents wherein the
formulation comprises a homogeneous mixture, the polyketal of structure V is
present at about 0.1 vol% to 20 vol% based on the total volume of the one or
more
solvents. In other embodiments of the formulation comprising the polyketal
having
structure V, further comprising two immiscible solvents wherein the
formulation
comprises a homogeneous mixture, the polyketal of structure V is present at
about 1
vol% to 10 vol% based on the total volume of the one or more solvents. In some
embodiments of the formulation comprising the polyketal having structure V and
further comprising two immiscible solvents wherein the formulation comprises a
homogeneous mixture, the two immiscible solvents comprise a hexane methanol
blend or a methanol water blend. In some embodiments of the formulation
comprising the polyketal having structure V and further comprising a hexane
methanol blend or a methanol water blend, the methanol is present at about 50
vol%
based on the total volume of the one or more solvents. In some embodiments of
the
formulation comprising the polyketal having structure V and further comprising
a
hexane methanol blend or a methanol water blend, Rl is butyl, R4 and R5 are
hydrogen, a is 2, b is 0, and a is 1. In embodiments, the formulation
comprising the
polyketal of structure V is a coating formulation. In embodiments, the
formulation
comprising the polyketal of structure V is an adhesive formulation.
The present invention contemplates an article comprising the polyketal
having structure V. In embodiments, the article comprising the polyketal
having
structure V is coated, cast, extruded, coextruded, profile extruded, blow
molded,
injection molded, co-injection molded, thermoformed, or reaction injection
molded.
In embodiments, the article comprising the polyketal having structure V
comprises
two or more layers and the polyketal of structure V is present in at least one
layer.
In embodiments, the article comprising the polyketal having structure V
comprises a
film, a sheet, a fiber, a foamed article, a woven fabric, a nonwoven fabric,
or a
pressure sensitive adhesive tape, or a paint coating.
The present invention contemplates a polyketal having the structure VI:
62
CA 02654809 2009-03-05
H
0 o a 0
iO 0"
-C~/
R1 0 0
VI
wherein
R' is hydrogen, a metal cation, an organic cation, a linear, branched, or
cyclic alkyl, a linear, branched, or cyclic alkenyl, alkenyl, aryl, alkaryl,
or an
oligomeric or polymeric moiety; and optionally contains one or more
heteroatoms;
and R1 is the same or different for each occurrence; and
ais 1 or2.
In embodiments of the polyketal having structure VI, one or more R1 is ethyl,
butyl,
or 2-ethylhexyl. In embodiments of the polyketal having structure VI, one or
more
R1 is the residue of a polyol. In embodiments of the polyketal having
structure VI
wherein one or more R' is the residue of a polyol, the polyol is ethylene
glycol,
diethylene glycol, pentaerythritol, 1,6-hexanediol, glycerol, or diglycerol.
In some
embodiments of the bisketal of structure VI, one or more R' comprises one or
more
isocyanate, acrylate, methacrylate, allyl, or oxirane groups.
The present invention contemplates a formulation comprising the polyketal
having structure VI. The formulation comprising the polyketal having structure
VI
comprises, in embodiments, one or more polymers. The one or more polymers
comprise, in embodiments, poly(3-hydroxybutyrate-co-3-hydroxyvalerate),
poly(vinyl chloride), poly(lactic acid), or polystyrene. In the formulation,
the
polyketal having structure VI is, in embodiments, a plasticizer, a toughener,
a
surfactant, a coalescing solvent, a compatibilizer, a barrier layer compound,
an
interfacial modifier, or a phase transfer compound. The formulation comprising
the
polyketal having structure VI can further comprise one or more solvents. The
one or
more solvents comprise, in embodiments, two immiscible solvents, wherein the
formulation comprises a homogeneous mixture. In some embodiments of the
formulation comprising the polyketal having structure VI and further
comprising
two immiscible solvents wherein the formulation comprises a homogeneous
63
CA 02654809 2009-03-05
mixture, the polyketal of structure VI is about 0.01 vol% to 50 vol% percent
based
on total volume of the one or more solvents, and the homogeneous mixture
comprises between about 5 vol% to 95 vol% methanol based on the total volume
of
the one or more solvents. In other embodiments of the formulation comprising
the
polyketal having structure VI and further comprising two immiscible solvents
wherein the formulation comprises a homogeneous mixture, the polyketal of
structure VI is present at about 0.1 vol% to 20 vol% based on the total volume
of the
one or more solvents. In other embodiments of the formulation comprising the
polyketal having structure VI, further comprising two immiscible solvents
wherein
the formulation comprises a homogeneous mixture, the polyketal of structure VI
is
present at about 1 vol% to 10 vol% based on the total volume of the one or
more
solvents. In some embodiments of the formulation comprising the polyketal
having
structure VI and further comprising two immiscible solvents wherein the
formulation comprises a homogeneous mixture, the two immiscible solvents
comprise a hexane methanol blend or a methanol water blend. In some
embodiments of the formulation comprising the polyketal having structure VI
and
further comprising a hexane methanol blend or a methanol water blend, the
methanol is present at about 50 vol% based on the total volume of the one or
more
solvents. In some embodiments of the formulation comprising the polyketal
having
structure VI and further comprising a hexane methanol blend or a methanol
water
blend, R, is butyl and a is 1. In embodiments, the formulation comprising the
polyketal of structure VI is a coating formulation. In embodiments, the
formulation
comprising the polyketal of structure VI is an adhesive formulation.
The present invention contemplates an article comprising the polyketal
having structure VI. In embodiments, the article comprising the polyketal
having
structure VI is coated, cast, extruded, coextruded, profile extruded, blow
molded,
injection molded, co-injection molded, thermoformed, or reaction injection
molded.
In embodiments, the article comprising the polyketal having structure VI
comprises
two or more layers and the polyketal of structure VI is present in at least
one layer.
In embodiments, the article comprising the polyketal having structure VI
comprises
a film, a sheet, a fiber, a foamed article, a woven fabric, a nonwoven fabric,
or a
pressure sensitive adhesive tape, or a paint coating.
The present invention contemplates a polymeric composition comprising one
or more repeat units comprising structure VII:
64
CA 02654809 2009-03-05
R2 R3 R3 ~R2
R4 4JAbT4, ' 1--R5
O O O O
ilL- / SH3 H3C>C l.~
O a a O-Ri
R
VII
wherein
R' is a linear, branched, or cyclic alkyl, a linear, branched, or cyclic
alkenyl,
alkynyl, aryl, alkaryl, or an oligomeric or polymeric moiety; and optionally
contains
one or more heteroatoms; and R1 is the same or different for each occurrence;
R2 and R3 are independently hydrogen, a linear, branched, or cyclic alkyl, a
linear, branched, or cyclic alkenyl, alkynyl, aryl, or alkaryl; and optionally
contains
one or more heteroatoms; and R2, R3, R4, R5, and R6 is the same or different
for each
occurrence;
R4 and R5 are independently hydrogen, a linear, branched, or cyclic alkyl, a
linear, branched, or cyclic alkenyl, alkynyl, aryl, alkaryl, or a polymeric
moiety; and
optionally contain one or more heteroatoms;
a is 0 or an integer of 1 to 12 and a is the same or different for each
occurrence;
b is 0 or 1 wherein b = 0 indicates a five membered ring,
O~O
' CH3
b = 1 indicates a 6 membered ring,
R2 R3
OO
CH3
and b may be the same or different for each occurrence; and
a is an integer of at least 1; and
CA 02654809 2009-03-05
(3 is an integer of at least 1.
In embodiments of the polymeric composition comprising one or more repeat
units
comprising structure VII, all a equal 2. In embodiments of the polymeric
composition comprising one or more repeat units comprising structure VII, all
b
equal 0.
In some embodiments of the polymeric composition having structure VII, all
values of b equal 1 and all R3 and R4 are hydrogen. In some embodiments of the
polymeric composition having structure VII, a equals 1 or 2 and R4 and R5 are
hydrogen. In some embodiments of the polymeric composition having structure
VII,
a is between about 2 and 1000, all values of b equal 1, and all R3 and R4 are
hydrogen. In some such embodiments, the value of a is between about 10 and
100.
In some embodiments of the polymeric composition having structure VII, one or
more of R4 and R5 are residues of a polymer. In some embodiments of the
polymeric composition having structure VII wherein one or more of R4 and R5
are
residues of a polymer, the polymer is poly(vinyl alcohol), poly(vinyl
acetate),
polyethylene, polypropylene, or a random or block copolymer thereof. In
embodiments of the polymeric composition comprising one or more repeat units
comprising structure VII, one or more additional repeat units comprise one or
more
ester groups, ether groups, or a combination thereof. In some such embodiments
the
additional repeat units comprise one or more ester groups comprise
isophthalate,
terephthalate, or adipate residues. In embodiments of the polymeric
composition
comprising one or more repeat units comprising structure VII, one or more
additional repeat units comprise urethane, (urethane urea), (ester urethane),
(ester
urethane urea), (ester ether urethane), or (ester ether urethane urea) groups.
In
embodiments of the polymeric composition comprising one or more repeat units
comprising structure VII, one or more additional repeat units comprise a
carbonate
group. In embodiments of the polymeric composition comprising one or more
repeat units comprising structure VII, one or more repeat units comprise a
polymerized residue of an acrylate, methacrylate, oxirane, or allyl group.
The present invention contemplates a formulation comprising the polyketal
having structure VII. In embodiments, the formulation comprising the polyketal
having structure VII further comprises one or more additional polymeric
compounds. In embodiments, the formulation comprising the polyketal having
66
CA 02654809 2009-03-05
structure VII and one or more additional polymeric compounds, the one or more
additional polymeric compounds comprise poly(3-hydroxybutyrate-co-3-
hydroxyvalerate), poly(vinyl chloride), poly(lactic acid), or polystyrene. In
embodiments of the formulation comprising the polyketal having structure VII,
the
polyketal having structure VII is a plasticizer, a toughener, a surfactant, a
barrier
layer compound, an interfacial modifier, a compatibilizer, or a phase transfer
compound. In embodiments, the formulation comprising the polyketal having
structure VII further comprises one or more additives. In embodiments, the
formulation comprising the polyketal having structure VII and one or more
additives, the one or more additives comprise one or more crosslinkers, redox
initiators, thermal initiators, UV initiators, UV stabilizers, colorants,
thermal
stabilizers, antibacterial agents, antifungal agents, antioxidants,
plasticizers, fillers,
adjuvants, or a mixture thereof. In embodiments, the formulation comprising
the
polyketal having structure VII is a coating formulation. In embodiments, the
formulation comprising the polyketal having structure VII is an adhesive
formulation. In embodiments, the formulation comprising the polyketal having
structure VII further comprises one or more solvents.
The present invention contemplates an article comprising the polyketal
having structure VII. In embodiments, the article comprising the polyketal
having
structure VII is coated, cast, extruded, coextruded, profile extruded, blow
molded,
injection molded, co-injection molded, thermoformed, or reaction injection
molded.
In embodiments, the article comprising the polyketal having structure VII
comprises
two or more layers and the polyketal of structure VII is present in at least
one layer.
In embodiments, the article comprising the polyketal having structure VII
comprises
a film, a sheet, a fiber, a foamed article, a woven fabric, a nonwoven fabric,
or a
pressure sensitive adhesive tape, or a paint coating.
The present invention contemplates a polymeric composition comprising one
or more repeat units comprising structure VIII:
67
CA 02654809 2009-03-05
H
0 o a o
-C:/ O O-R~
O
O
VIII
wherein
R' is hydrogen, a metal cation, an organic cation, a linear, branched, or
-cyclic alkyl, a linear, branched, or cyclic alkenyl, alkynyl, aryl, alkaryl,
or an
oligomeric or polymeric moiety; and optionally contains one or more
heteroatoms;
and R' is the same or different for each occurrence;
a is 1 or 2; and
0 is an integer of at least 1.
In embodiments of the polymeric composition having structure VIII, a is 1. In
embodiments of the polymeric composition having structure VIII, j3 is about 1.
In
embodiments of the polymeric composition having structure.Vif, ft is between
about 2 and 12. In embodiments of the polymeric composition having structure
VIII, /3 is between about 12 and 100. In embodiments of the polymeric
composition
having structure VIII, Q is between about 100 and 1000. In embodiments; the
polymeric composition having structure VIII comprises one or more additional
repeat units comprising one or more ester groups, ether groups, or a
combination
thereof. In some such embodiments the additional repeat units comprise one or
more ester groups comprise isophthalate, terephthalate, or adipate residues.
In
embodiments, the polymeric composition having structure VIII comprises one or
more repeat units comprising urethane, (urethane urea), (ester urethane),
(ester
urethane urea), (ester ether urethane), or (ester ether urethane urea) groups.
In
embodiments, the polymeric composition having structure VIII comprises one or
more repeat units comprising carbonate groups. In embodiments, the polymeric
composition having structure VIII comprises a polymerized residue of an
acrylate,
methacrylate, oxirane, or allyl group.
68
CA 02654809 2009-03-05
The present invention contemplates a formulation comprising one or more
polymeric compositions having structure VIII. In embodiments of the
formulation
comprising one or more compositions having structure VIII the formulation
further
comprises one or more additional polymeric compounds. In embodiments of the
formulation comprising one or more compositions having structure VIII and
further
comprising one or more additional polymeric compounds, the one or more
additional polymeric compounds comprise poly(3-hydroxybutyrate-co-3-
hydroxyvalerate), poly(vinyl chloride), poly(lactic acid), or polystyrene. In
embodiments of the formulation comprising one or more compositions having
structure VIII, the one or more polymeric compositions is a plasticizer, a
toughener,
a surfactant, a barrier layer compound, an interfacial modifier, a
compatibilizer, or a
phase transfer compound. In embodiments of the formulation comprising one or
more compositions having structure VIII, the formulation further comprises one
or
more additives. In embodiments of the formulation comprising one or more
compositions having structure VIII and further comprising one or more
additives,
the one or more additives comprise one or more crosslinkers, redox initiators,
thermal initiators, UV initiators, UV stabilizers, colorants, thermal
stabilizers,
antibacterial agents, antifungal agents, antioxidants, plasticizers, fillers,
adjuvants, or
a mixture thereof. In embodiments of the formulation comprising one or more
compositions having structure VIII, the formulation is a coating formulation.
In
embodiments of the formulation comprising one or more compositions having
structure VIII, the formulation is an adhesive formulation. In embodiments of
the
formulation comprising one or more compositions having structure VIII, the
formulation further comprises one or more solvents.
The present invention contemplates an article comprising the polyketal
having structure VIII. In embodiments, the article comprising the polyketal
having
structure VIII is coated, cast, extruded, coextruded, profile extruded, blow
molded,
injection molded, co-injection molded, thermoformed, or reaction injection
molded.
In embodiments, the article comprising the polyketal having structure VIII
comprises two or more layers and the polyketal of structure VIII is present in
at least
one layer. In embodiments, the article comprising the polyketal having
structure
VIII comprises a film, a sheet, a fiber, a foamed article, a woven fabric, a
nonwoven
fabric, or a pressure sensitive adhesive tape, or a paint coating.
The present invention contemplates a bisketal having structure IX:
69
CA 02654809 2009-03-05
O O
0OxO%~` OAR'
H3C 0 O CH3
IX
wherein R' is hydrogen, a metal cation, an organic cation, a linear, branched,
or
cyclic alkyl, a linear, branched, or cyclic alkenyl, alkynyl, aryl, alkaryl,.
or an
oligomeric or polymeric moiety; and optionally contains one or more
heteroatoms;
and Rl is the same or different for each occurrence. In some embodiments of
the
bisketal of structure IX, one or more R1 is ethyl, butyl, or 2-ethylhexyl. In
some
embodiments of the bisketal of structure IX, one or more R1 is the residue of
a
polyol. In some embodiments of the bisketal of structure IX wherein one or
more R1
is the residue of a polyol, the one or more polyol is ethylene glycol,
diethylene
glycol, pentaerythritol, 1,6-hexanediol, glycerol, or diglycerol. In some
embodiments of the bisketal of structure IX, one or more R1 comprises one or
more
isocyanate, acrylate, methacrylate, allyl, or oxirane groups.
The present invention contemplates a formulation comprising one or more
bisketals of structure IX. In some embodiments of the formulation comprising
one
or more bisketals of structure IX, the formulation further comprises one or
more
polymers. The one or more polymers comprise, in embodiments, poly(3-
hydroxybutyrate-co-3-hydroxyvalerate), poly(vinyl chloride), poly(lactic
acid), or
polystyrene. In some embodiments of the formulation comprising one or more
bisketals. of structure IX, one or more bisketals is a plasticizer, a
toughener, a
surfactant, a barrier layer compound, a coalescing solvent, a compatibilizing
agent,
an interfacial modifier, or a phase transfer compound. In some embodiments of
the
formulation comprising one or more bisketals of structure IX, the formulation
is a
coating formulation. In some embodiments of the formulation comprising one or
more bisketals of structure IX, the formulation is an adhesive formulation. In
some
embodiments of the formulation comprising one or more bisketals of structure
IX,
the formulation further comprises one or more solvents. In some embodiments of
the formulation comprising one or more bisketals of structure IX and further
comprising one or more solvents, the one or more solvents comprise two
immiscible
solvents and the formulation comprises a homogeneous mixture. In some
embodiments of the formulation comprising one or more bisketals of structure
IX,
the formulation further comprises one or more additives. In some embodiments
of
CA 02654809 2009-03-05
the formulation comprising one or more bisketals of structure IX wherein the
formulation further comprises one or. more additives, the one or more
additives
comprise one or more crosslinkers, redox initiators, thermal initiators, UV
initiators,
UV stabilizers, colorants, thermal stabilizers, antibacterial agents,
antifungal agents,
antioxidants, plasticizers, -fillers, adjuvants, or a mixture thereof.
The present invention contemplates an article comprising the polyketal
having structure IX. In embodiments, the article comprising the polyketal
having
structure IX is coated, cast, extruded, coextruded, profile extruded, blow
molded,
injection molded, co-injection molded, thermoformed, or reaction injection
molded.
In embodiments, the article comprising the polyketal having structure IX
comprises
two or more layers and the polyketal of structure IX is present in at least
one layer.
In embodiments, the article comprising the polyketal having structure IX
comprises
a film, a sheet, a fiber, a foamed article, a woven fabric, a nonwoven fabric,
or a
pressure sensitive adhesive tape, or a paint coating.
The present invention contemplates a polymeric composition having one or
more repeat units comprising structure X:
O O O
Hs
X
wherein R' is a linear, branched, or cyclic alkyl, a linear, branched, or
cyclic
alkenyl, alkynyl, aryl, alkaryl, or an oligomeric or polymeric moiety; and
optionally
contains one or more heteroatoms; and R' is the same or different for each
occurrence, and (3 is an integer of at least 1. In embodiments of the
polymeric
composition having structure X, (3 is about 1. In embodiments of the polymeric
composition having structure X, (3 is between about 2 and 12. In embodiments
of
the polymeric composition having structure X, 3 is between about 12 and 100.
In
embodiments of the polymeric composition having structure X, (3 is between
about
100 and 1000. In embodiments, the polymeric composition having structure X
comprises one or more additional repeat units comprising one or more
ester.groups,
ether groups, or a combination thereof, In some such embodiments the
additional
repeat units comprise one or more ester groups comprise isophthalate,
terephthalate,
or adipate residues. In some embodiments of the polymeric composition having
71
CA 02654809 2009-03-05
structure X, one or more repeat units comprise urethane, (urethane urea),
(ester
urethane), (ester urethane urea), (ester ether urethane), or (ester ether
urethane urea)
groups. In some embodiments of the polymeric composition having structure X,
one
or more additional repeat units comprise one or more carbonate groups. In some
embodiments of the polymeric' composition having structure X, one or more
repeat
units comprise the residue of one or more polymerized acrylate, methacrylate,
oxirane, or allyl groups.
The present invention contemplates a formulation comprising the polymeric
composition having structure X. In embodiments, the formulation comprising the
polymeric composition having structure X further comprises one or more
additional
polymeric compounds. In embodiments, the one or more additional polymeric
compounds comprise poly(3-hydroxybutyrate-co-3-hydroxyvalerate), poly(vinyl
chloride), poly(lactic acid), or polystyrene. In embodiments of the
formulation
comprising the polymeric composition having structure X, the polymeric
composition having structure X is a plasticizer, a toughener, a surfactant, a
barrier
layer compound, an interfacial modifier, a compatibilizer, or a phase transfer
compound. In embodiments, the formulation comprising the polymeric composition
having structure X further comprises one or more additives. In embodiments of
the
formulation comprising the polymeric composition having structure X and one or
more additives, the one or more additives comprise one or more crosslinkers,
redox
initiators, thermal initiators, UV initiators, UV stabilizers, colorants,
thermal
stabilizers, antibacterial agents, antifungal agents, antioxidants,
plasticizers, fillers,
adjuvants, or a mixture thereof. In embodiments, the formulation comprising
the
polymeric composition having structure X formulation is a coating formulation.
In
embodiments, the formulation comprising the polymeric composition having
structure X is an adhesive formulation. In embodiments, the formulation
comprising
the polymeric composition having structure X, the formulation further
comprises
one or more solvents.
The present invention contemplates an article comprising the polymeric
composition having structure X. In embodiments, the article comprising the
polymeric composition having structure X is coated, cast, extruded,
coextruded,
profile extruded, blow molded, thermoformed, injection molded, coinjection
molded, or reaction injection molded. In embodiments, the article comprising
the
polymeric composition having structure X comprises two or more layers and the
72
CA 02654809 2009-07-24
polymeric composition having structure X comprises two or more layers and the
polymeric
composition of structure III is present in at least one layer. In embodiments,
the article
comprising the polymeric composition having structure III comprises a film, a
sheet, a fiber,
a foamed article, a woven fabric, a nonwoven fabric, or a pressure sensitive
adhesive tape, or
a paint coating.
EXPERIMENTAL SECTION
General Laboratory Procedures
Gas Chromatography (GC) and GC-Mass Spectrometry (CC-MS) Analyses
GC and GC-MS analyses are carried out according to standard laboratory
techniques.
Standard GC analysis is carried out by flame ionization detector. The
integration peak areas
of all peaks in the chromatogram are automatically calculated by an Agilent
Technologies
ChemStationTM (Agilent Technologies of Santa Clara, CA). The calculated peak
areas are
reported as a weighted percent (expressed as abundance) relative to the area
of all of the
detected peaks in the chromatogram (total area). These calculations are used
elsewhere
herein to report all percent yield, percent yield "based on theoretical",
percent yield "as
determined by GC", percent yield "as determined by GC-MS", and any other
percent
reaction statements resulting from GC or GC-MS analyses.
Gel Permeation Chromatography (GPC)
Molecular weight determination is carried out by GPC using a WatersTM
Isocratic
HPLC System (from Waters Corp. of Milford, Massachusetts) that includes a
WatersTM 2414
Differential Refractometer, Waters"' 1515 Isocratic Pump, Waters rM 717
Autosampler, and
WatersTM Column Heater and EmpowerTM GPC Software for molecular weight
analysis. For
samples with an expected molecular weight of 20,000-400,000 Daltons a PLge1TM
Mixed D
5 m column, 300X7.5 mm, is used; for samples with an expected molecular weight
of less
than 20,000 a PLge1TM Mixed E 5 m column, 300X7.5 mm, is used; and for samples
with an
expected molecular weight between 20,000 and 2,000,000 a PLge1TM Mixed C 5 m
column,
300X7.5 mm is used. All columns were obtained from Polymer Labs, a division of
Varian
Inc. of Palo Alto, CA. THE mobile phase is employed at 1 ml/min and weight
average
molecular weight (Mw,) is calculated against polystyrene narrow molecular
weight standards.
73
CA 02654809 2009-07-24
Differential Scanning Calorimetry (DSC)
1. Determination of glass transition temperature (Tg)
Glass transition temperature is determined by following ASTM D-3418, employing
a
TA Q200TM instrument with refrigerated cooling and TA Thermal AdvantageTM
software
(from TA Instruments of New Castle, DE). Homogeneous samples of between about
5 and
15mg are prepared, weighed, placed in a TzeroTM pan and crimped with a TzeroTM
lid, (pan
and lid both available from TA Instruments). The mass of the sample is entered
into the
Thermal AdvantageTM software. The thermal analysis is carried out according to
one of the
three sets of parameters below:
PARAMETER SET 1
Cycle 0: Equilibrate at -80 C
Isotherm for 2.00 minutes
End of Cycle 0
Cycle 1: Ramp 10 C/min to 150 C
Isotherm for 2.00 minutes
End of Cycle 1
Cycle 2:Ramp 10 C/min to -80 C
Isotherm for 2.00 minutes
End of Cycle 2
Cycle 3: Ramp 10 C/min to 150 C
Isotherm for 2.00 minutes
End of Cycle 3
Repeat at Cycle 0
PARAMETER SET 2
Cycle 0: Equilibrate at -150 C
Isotherm for 5.00 minutes
End of Cycle 0
Cycle 1: Ramp 10 C/min to 150 C
Isotherm for 5.00 minutes
End of Cycle 1
Cycle 2: Ramp 10 C/min to -150 C
Isotherm for 5.00 minutes
End of Cycle 2
Cycle 3: Ramp 10 C/min to 150 C
Isotherm for 5.00 minutes
End of Cycle 3
Repeat at Cycle 0
74
CA 02654809 2009-07-24
PARAMETER SET 3
Cycle 0: Equilibrate at -40 C
Isotherm for 2.00 minutes
End of Cycle 0
Cycle 1: Ramp 10 C/min to 240 C
Isotherm for 2.00 minutes
End of Cycle 1
Cycle 2:Ramp 10 C/min to -40 C
Isotherm for 2.00 minutes
End of Cycle 2
Cycle 3: Ramp 10 C/min to 240 C
Isotherm for 2.00 minutes
End of Cycle 3
Repeat at Cycle 0
2. Determination of degradation temperature
Degradation temperatures are determined using DSC according to ASTM E698-05.
Rheological Characterization
The viscosity of a material is determined by BrookfieldTM viscometry, using a
BrookfieldTM DV2+Pro viscometer (available from the BrookfieldTM Engineering
Laboratories of Middleborough, MA). The appropriate spindle is chosen
dependent on
sample viscosity. Samples are analyzed at 25 C unless a different temperature
is stated.
Hydroxyl Number
Hydroxyl numbers are determined according to ASTM E1899-02.
Thermogravimetric Analysis (TGA)
TGA is conducted utilizing a TA Q5OTM with TA Thermal AdvantageTM software
(from TA Instruments of New Castle, DE). A homogeneous sample weighing
approximately
30 milligrams is placed into the TGA platinum sample pan. Samples are analyzed
under a
nitrogen atmosphere. The TGA temperature profile is listed below:
Equilibrate at 30 C
Ramp 10 C/min to 800 C
CA 02654809 2009-07-24
Dynamic Mechanical Analysis (DMA)
DMA is conducted utilizing a TATM Q800 with liquid nitrogen cooling with TA
Thermal AdvantageTM software (from TA Instruments of New Castle, DE). A
uniform
sample is prepared to fit the appropriate sample mounting clamp (extension,
dual cantilever,
compression, etc.). The appropriate sample dimensions are measured and entered
into the
Thermal Advantage software. Typical experimental run conditions are listed
below:
Strain 0.1%
Frequency 1 Hz
Force Track 125%
Cycle:
Equilibrate at -100 C
Isotherm for 5 min.
Ramp 3 C/min to 200 C
Specific Gravity
Specific gravity is determined by the "weight per gallon" technique (ASTM
D1475-
98). A Gardner' ASTM weight per gallon cup (83.2 mL) is first weighed. The cup
is then
filled with the sample and reweighed. The weight of the sample is determined
by
subtracting the cup weight from the [sample + cup] weight. The sample weight
is then
multiplied by 0.01202 to obtain the specific gravity.
Refractive Index
Refractive index is measured by placing several drops of the material to be
tested on
the refracting prism surface of a WAY"' Refractometer (obtained from Sun
Instruments of
Torrence, CA) and then closed by locking the light entrance prism. The
refractive index was
read once cross-hair was centered by adjusting the refractometer knob. The
temperature of
the refractometer was maintained at 25 C during measurement by a circulating
chiller.
Compounding
Compounding of commercially available polymeric materials is carried out using
a
variety of mixing equipment. Mixtures are formed using one of the following
procedures.
76
CA 02654809 2009-03-05
1. HAAKE MiniLab II (from Thermo Scientific of Waltham, MA)
The experimental compound and selected polymer are pre-mixed by hand
after weighing components into a vessel. The screws of the compounder are set
to
co-rotate at 150 rpm. The system is set under a continual nitrogen purge.
Temperature settings are varied depending on the polymer that is being
extruded, as
indicated below. The material is fed into the compounder using either a manual
feed
(column and hand-held piston) or a pneumatic automatic feed. Blending time for
the
samples is between 10-15 minutes, with 10 minute runs being the most common.
Poly(vinyl chloride), Mõ = 55,000, MH, = 97,000 from the Sigma Aldrich
Company of St. Louis, MO: 165-170 C
Poly(hydroxybutyrate-co-hydroxyvalerate) from Tianan Biologic of Zhejiang
Province, China: 165 C
Polystyrene from Entec Polymers of Orlando, FL: 180 C
Polylactic acid from NatureWorks of Minnetonka, MN: 200 C
2. HAAKE PolyLab (from Thermo Scientific of Waltham, MA)
The experimental compound and selected polymer are pre-mixed by hand
(approximately 50g batches) after weighing components into a vessel.
Temperature settings in the compounder are varied depending on the polymer
being
compounded; for example, PVC is compounded at temperatures ranging between
about 150 C and 170 C depending on blend composition. Lower mass loadings are
sometimes run at a higher temperature. The screws are set to co-rotate at 100
rpm.
The pre-mixed material is fed into the compounder via a gravity feed system.
After
adding all the material to the compounder, the system is set under a continual
nitrogen purge. Blending time in the compounder is generally about 10 minutes
at
which time the screws are stopped and the material is removed from the mixer.
3. Daca Microcompounder (from Daca Instruments of Santa Barbara, CA)
The experimental compound and selected polymer are pre-mixed by hand
(approximately 5g batches) after weighing components into a vessel. The
compounder is preheated to the set temperature and screws are set to co-rotate
at 100
rpm. Temperature settings are varied depending on the polymer being extruded.
For example, PVC is compounded at temperatures ranging between about 150 C to
170 C depending on blend composition. Lower mass loadings are sometimes run at
a higher temperature. The pre-mixed material is fed manually into the
compounder
through the sample chamber via a hand-held piston. After adding all material
to the
77
CA 02654809 2009-03-05
compounder the system is set under a continual nitrogen purge. Blending time
for
the samples is generally about 10 minutes, followed by an additional 10
minutes to
form an extruded rod from the blended sample.
Example 1
A 500 ml 3-neck round bottom flask was charged with 36.64g (0.3 mol)
erythritol (obtained from the Cargill Company of Wayzata, MN) and 346.01g (2.4
mol) ethyl levulinate (obtained from the Sigma Aldrich Company of St. Louis,
MO).
The flask was equipped with a Dean Stark trap, mechanical stirrer, and
thermocouple. The contents of the flask were heated to 80 C, at which point
15.99 l of concentrated sulfuric acid (obtained from the Sigma Aldrich
Company)
was added to the reaction flask via a metered microliter pipette. A vacuum was
applied to the reaction flask, slowly bringing the pressure down to 40 ton.
This
pressure was maintained with stirring while liquid was observed to collect in
the
Dean Stark trap. About 1 hour, 45 minutes after addition of sulfuric acid, the
vacuum was released and a small sample was removed from the reaction flask.
The
vacuum was then reestablished. After an additional 1 hour, 15 minutes reaction
time, liquid had stopped collecting in the Dean Stark trap. The vacuum was
released, and the contents of the flask were allowed to cool to ambient
temperature.
A second sample was removed from the reaction flask.
Both samples removed were analyzed by GC-MS. The GC portions of the
analyses are shown in FIGS. 2A and 2B. FIG. 2A shows the GC of the sample
removed after the initial 1 hour, 45 minutes of reaction time. FIG 2B shows
the GC
of the sample removed after a total of 3 hours reaction time, or an additional
1 hour,
15 minutes after the first sample was taken. The percentages of products were
calculated by disregarding the presence of ethyl levulinate, because of the
excess
molar equivalents of ethyl levulinate used in the reaction. Thus, the
percentages of
erythritol, the monoketal of erythritol with one molar equivalent of ethyl
levulinate;
and the bisketal of erythritol with two molar equivalents of ethyl levulinate
were
calculated by determination of their relative GC peak areas. The sample
removed at
1 hour, 45 minutes was found to contain 93.03% of the bisketal, 6.97% of the
monoketal, and 0% erythritol by GC peak area. The sample removed after the
additional 1 hour, 15 minutes reaction time was found to contain 100% of the
bisketal.
78
CA 02654809 2009-03-05
Examples 2-11
Using the procedure of Example 1, various polyketal compounds were
synthesized. Table 1 shows reagents, temperature, and time of reaction as well
as
the percent yield of products obtained at the end of the reaction, as
determined by
GC-MS (GC peak area) employing the calculation described in Example 1. Unless
noted, the pressure of the reaction vessel was 30 ton during the reaction.
Butyl levulinate was obtained from the Sigma Aldrich Company of St.
Louis, MO. Ethyl acetoacetate was obtained from Acros Organics of Geel,
Belgium. Sorbitol was obtained from Acros Organics. Mannitol was obtained from
the Sigma Aldrich Company. Pentaerythritol was obtained from the Sigma Aldrich
Company. Diglycerol was obtained from Tokyo Kasei Kogyo of Tokyo, Japan.
Sulfamic acid was obtained from the Sigma Aldrich Company. Amberlyst -15 was
obtained from the Rohm and Haas Company of Philadelphia, PA.
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CA 02654809 2009-03-05
Table 1. Synthetic conditions for polyketals and analysis of same.
Expt. Oxocarboxylate, Polyol, Catalyst, Temp., Time, Product, % by
No. g (mol) g (mol) unit (mol) C min. CC peak area
cone. H2SO4 erythritol: 0
ethyl levulinate erythritol 0.352m1 monoketal: 2.46
951.52 (6.6) 146.54 (1.2) (6.6x104) 90 240 bisketal: 97.54
cone. H2S04 sorbitol:0
3 ethyl levulinate sorbitol 0.016m1 105 480 monoketal:0
346.01 (2.4) 54.65 (0.3) (3x10'4) bisketal: 0
trisketal: 100
cone. H2SO4 mannitol: 0
4 ethyl levulinate niannitol 0.016m1 105 480 monoketal:0
346.01 (2.4) 54.65 (0.3) (3x10) bisketal: 0
triskctal: 100
cone. H2SO4 erythritol: 0
butyl levulinate erythritol 0.0293ml monoketal: 1.00
947.21 (5.5) 122.12 (1.0) (5.5x10 ) 120 240 bisketal: 99.00
sorbitol: 0
6 butyl levulinate sorbitol conc. H2SO4 120 240 monoketal: 0
1205.58 (7) 182.17(1) 0.053m1(0.001) bisketal: 0
triskctal: 100
7 ethyl levulinate pcntaerythritol conc. H2S04 120 240 erythritol: 0
158.59 (1-.1) 27.23 (0.2) . 0.0293ml monoketal: 0
(5.5x 10) bisketal: 100
8 ethyl levulinate diglycerol cone. H2SO4 90 480 diglycerol: 0
237.88 (1.65) 49.85 (0.3) 0.0088m1 monoketal: 0
(1.65x10) biskctal: 100
sulfamic acid erythritol: 0
9 ethyl levulinate erythritol 0.16g 90 480 monoketal: 0
237.88 (1.65) 36.64 (0.3) (1.65x10) bisketal; 100
Amberlyst 15 erythritol: 0
ethyl levulinate erythritol (dry), 0.234g 90 480 monoketal: 1.00
237.88 (1.65) 36.64 (0.3) (5.5xI0)t'~ bisketal: 99.00
11 (2) ethyl acetoacetate erythritol cone. H2S04 80 480 erythritol: 0
214.73g(1.65) 36.64 (0.3) 0.0088m1 monoketal: 0
(1.65x10) bisketal: 100
5 (1) Molar equivalents of H+
(2) Pressure of the reaction vessel was 100 torr.
CA 02654809 2009-03-05
Examples12-15
An 896g sample of the polyketal made according to Example 3 was added to
the addition flask of a short path wiped film evaporator equipped with carbon
blades. A vacuum was applied to the apparatus until the pressure in the
apparatus
reached 100 millitorr. While under vacuum the entire apparatus was heated to
150 C. The wiped film column blades were rotated at 70% at the maximum rate
available on the apparatus. The cold finger of the wiped film apparatus was
adjusted
to 0 C using a refrigerated chiller. Upon reaching the target temperature the
contents of the reaction flask were dripped into the wiped film column at a
rate of
160 drops/minute. After 3 hours, 15 minutes the contents of the addition flask
had
been emptied into the column. The non-distilled residue that was captured was
analyzed by GPC, GC-MS, and 1H NMR.
Using the same procedure, the compounds according to Examples 1, 5, and 6
were purified and analyzed. The results of subsequent analyses are shown in
Table
2.
Table 2. Compounds purified and analysis of purified products by GPC, GC-MS,
Example Polyketal, % Polyketal, % Polyketal, % Polyketal,
No. Example No. GPC GC-MS 1H NMR
12 1 100 99.70 98.7
13 3 100 99.90 99.39
14 5 100 99.90 99.4
15 6 100 99.80 98.8
and 1H NMR.
Example 16
A 250 ml, 3-neck round bottom flask connected with a Dean Stark trap was
charged with 20.Og (0.053mol) of the compound made according to Example 2 and
42.42g (0.32 mol) of 2-ethyl-l-hexanol (obtained from Acros Organics of Morris
Plains, NJ) A homogeneous solution formed upon mixing. To the mixture was
81
CA 02654809 2009-03-05
added 0.42g (0.0062 mol) of sodium ethoxide (obtained from the Acros
Organics).
The flask was then heated using a heating mantle. When the temperature of the
contents of the flask reached 138 C the contents were observed to start
bubbling.
After bubbling commenced, the temperature of the flask contents was slowly
observed to reach 160 C, at which point the bubbling rate decreased. When
bubbling stopped altogether, the temperature of the flask contents was
increased to
175 C. Additional bubbling in the contents of the reaction flask was observed
while
the temperature was being raised. When the contents of the reaction flask
reached
175 C the bubbling stopped. About 5.7m1 of liquid was observed in the Dean
Stark
trap at the point where no further bubbling was observed. The contents of the
flask
were allowed to cool to room temperature. The total reaction time from the
point of
the initial heating was 2 hours 10 minutes. After the contents of the flask
reached
room temperature they were filtered through using a KIMAX Buchner fritted
glass
funnel with medium porosity (10 - 15 microns) (available from Gerresheimer
Glass
Inc. of Vineland, NJ), and 1.0g of monobasic potassium phosphate (obtained
from
Sigma Aldrich of St. Louis, MO) was added to the filtered contents of the
reaction
flask in an Erlenmeyer flask. This mixture was stirred overnight at room
temperature. The contents of the flask were filtered again using a KIMAX
Buchner funnel with medium porosity (10 - 15 m), and the filtrate was
analyzed by
GC-MS. The GC-MS showed that the transesterification was 96% complete.
The contents of the reaction flask were placed in a 250m1 single neck round
bottom flask and mounted onto a rotary evaporator. The rotary evaporator was
operated at 3.8 torr, at a bath temperature of 160 C, for about 30 minutes.
The
resulting material was again analyzed by GC-MS, which showed that
substantially
all of the excess 2-ethyl-l-hexanol was stripped from the contents of the
flask.
Example 17
Using the technique employed in Example 16, 28.01g (0.05mol) of the
compound synthesized according to Example 3, 58.49g (0.45mo1) of 2-ethyl-1-
hexanol and 0.58g (0.0085mol) of sodium ethoxide were reacted. Initial
bubbling of
the contents was observed to occur at about 136 C and the reaction temperature
at
the end of the reaction was 174 C. GC-MS of the reacted contents of the flask
showed that the reaction was 100% ethylhexyl ester of tris levulinate-sorbitol
ketal.
82
CA 02654809 2009-07-24
Example 18
The refractive index, density, and viscosity at room temperature of polyketal
materials were measured. The results of these measurements are shown in Table
3. The
values obtained were compared to that of dioctyl phthalate (DOP) obtained from
the Sigma
Aldrich Company of St. Louis, MO.
Table 3. Physical properties of polyketals.
Polyketal of Example No.
Properties DOP 2 5 16 6 3
Refractive index (25 C) 1.4866 1.456 1.456 1.4593 1.4646 1.4644
Density (g/ml) 0.981 1.123 1.079 1.035 1.211 1.034
Viscosity (cp) 54.1 83 76 136 1363 710
Examples 19-41
Various polyketals and DOP (dioctyl phthalate) were compounded with polyvinyl
chloride (PVC) of number average molecular weight (Mõ) 55,000, weight average
molecular
weight (Mõ) 97,000 (obtained from the Sigma Aldrich Company of St. Louis, MO).
First. a
stabilized PVC mixture was formed by admixing 66.5g of the polyvinyl chloride,
2.5g of
Vikoflex 7170T"' epoxidized soybean oil (from Arkema, Inc. of Philadelphia,
PA) and 1.Og
Thenno-Chek SP175T"' thermal stabilizer (from Ferro Corp. of Cleveland, OH).
Then 3.5g
of stabilized PVC mixture was then admixed with DOP or a polyketal compound to
form a
PVC/plasticizer admixture in the desired ratio. For example, to form a
PVC/plasticizer
mixture with 30 wt% plasticizer, 1.5g of DOP or polyketal compound was admixed
with the
3.5g of stabilized PVC mixture.
The PVC/plasticizer mixtures were compounded using one of the standard
Compounding procedures outlined in the General Laboratory Procedures section
above. The
glass transition temperature (Tg) for each extruded product was measured. The
compounding
of PVC with DOP and various polyketals of the invention, and the Tg of the
resulting
blends, is shown in Table 4.
83
CA 02654809 2009-07-24
Table 4. PVC compounding and resulting T. of the compounded PVC blends.
Weight `%
polyketal
Compounding Polyketal, in
Example Procedure Compounding Example stabilized
No. No. Temp., No. PVC Tg,
19 3 180 None N/A 67.22
20 3 160 N/A - DOP 30 -7
21 3 170 12 20 23.66
22 3 160 12 30 -5.14
23 2 160 12 33.3 -2.91
24 3 150 12 40 -21.71
25 3 170 14 20 20.04
26 3 160 14 30 -6.06
27 2 160 14 33.3 -9.74
28 3 150 14 40 -27.13
29 3 170 16 20 18.01
30 3 160 16 30 -9.09
31 3 150 16 40 -34.98
32 3 170 13 1 20 36.53
33 3 160 13 30 16.46
34 2 160 13 33.3 13.97
35 3 150 13 40 -5.85
36 3 170 15 20 29.47
37 3 160 15 30 8.93
38 2 160 15 33.3 3.19
39 3 150 15 40 -8.61
40 3 160 17 30 2.195
41 3 150 17 40 -15.655
Examples 42 - 48
Various samples of compounded PVC blends were tested for durability by weight
loss due to
extraction and volatility according to ASTM D1239. The extractions were
carried out in
hexane. mineral oil, and a saturated solution of Ivory SoapTM (bar form,
available from the
Procter and Gamble Co. of Cincinnati, OH) obtained by flaking the soap and
weighing the
84
CA 02654809 2009-07-24
soap flakes and water into a flask sufficient to form a I wt% mixture of soap,
and stirring
until no further soap dissolved at ambient temperature. The weight loss from
PVC, measured
according to ASTM D1239, is expressed as weight percent in Table 5. The data
show that
one or more compounds of the invention provide extraction properties that are
as good as or
better than those of dioctyl phthalate.
Example 49
PVC powder type 2095 (obtained from Georgia Gulf Corporation of Atlanta, GA)
was premixed with l% by weight THERM-CHECK?- SP175 (obtained from Ferro
Corporation of Cleveland, OH) and 2.5% by weight epoxidized soybean oil
(obtained from
Arkema. Inc. of Philadelphia, PA) was hand mixed with PVC powder for
approximately 2
minutes to form a stabilized PVC mixture. To the stabilized PVC mixture was
added 33.33%
by weight (50 phr) of dioctyl phthalate (obtained from the Sigma Aldrich
Company of St.
Louis. MO); this was mixed with a paddle mixer at approximately 50 rpm for 5
minutes,
forming a crumbly powder.
The powder was transferred into the feed hopper of a 27m m BRABENDER twin-
screw extruder (obtained from C.W. BRABENDER 1z~ Instruments, Inc. of South
Hackensack, NJ). The material was extruded at 155 C, 70 rpm, through a 2mm
rod die. The
material was then cooled by a water bath and fed into a BRABENDER 1z
pelletizer (obtained
from C.W. BRABENDER Instruments). Pelletized material was fed into a Nisseimi
injection molder (obtained from Nissei America, Inc. of Anaheim, CA) with
temperature set
to 165 C in all three heating zones as well as the nozzle. The mold was a
geometry type I
tensile bar (see General Laboratory Procedure), with temperature set at 25 C.
The screw
speed was set at 30%, with a shot size of 5n-in and a 5% back pressure was
used to fill the
mold. Injection and transfer pressure was maintained at 46.5 MPa with a mold
fill time of
1.01 sec. and recovery time of 11.5 sec. Automatic ejection was disabled and
the parts were
removed from the mold manually.
The tensile properties of samples (3 samples per test) were measured according
to the
General Laboratory Procedure, with strain rate of 100mm/min. The resulting
plot of stress
vs. strain is shown in FIG. 3A, and peak stress, percent strain at break. and
Youn~T's modulus
at 2'!,o strain are reported in Table 6.
CA 02654809 2009-03-05
Table 5. Percent weight loss of samples by extraction and volatilization.
C17
Duo .v Q t~h : a C~w~ N.. o `d
V
p
:O\ t C -1 s:.
0 0;
k m x
3
07
tom) tJ th OC.. -=-
UJ tom) t $ O~ P oo' ~+ . e9 M
W A 4y .l Q.', \ yr
Ir,
r= [v N tJ .O p~ =
=W. '.'.O ;.a Z O O' A
o c o 0 0 o n ~. Cr
N z C O O' '.Cfl
v; ,tea a chi, o'`~
4 cz Jam` .n- 0..
O .V. Z -W to C ~=
;oopooa= ~ ..r. ~
~o~=Zot5 o c \,
O O b O Q ~~,,' .~ ~.
i.A v 'v Z C CD Q O,: 0Q
Oo 0 0' o Q .Q ;'.
.
86
CA 02654809 2009-03-05
Example 50
The procedure according to Example 49 was repeated, except that instead of
dioctyl phthalate, 33.33% by weight (50 phr) of the polyketal compound
prepared
according to Example 14 was added to the stabilized PVC mixture. The resulting
plot of stress vs. strain is shown in FIG. 3B, and peak stress, percent strain
at break,
and Young's modulus at 2% strain are reported in Table 6.
The data of Examples 49 and 50 taken together show that replacing dioctyl
phthalate with the compound prepared according to Example 14 results in a
compounded polymer having physical properties that are at least commensurate
with
those of the dioctyl phthalate compounded polymer.
Table 6. Tensile properties of plasticized PVC.
Modulus at 2%
Example. No. Peak Stress, Mpa Strain at Break, % Strain, MPa
49 13.3+/-0.3 288.6 +/- 18.7 8.8+/-0.5
50 14.9+/-0.2 307.0+/- 7.3 8.0+/-0.4
Examples 51-65
Using compounding method 1 as described in the General Laboratory Procedures
section above, polyketals of the invention were compounded into various
polymers,
followed by DSC analysis of Tg for the blended materials. The polymers
compounded were
PHBV: Poly(hydroxybutyrate-co-hydroxyvalerate) from Tianan Biologic of
Zhejiang Province, China
PLA: Polylactic acid from NatureWorks of Minnetonka, MN
PS: Polystyrene from Entec Polymers of Orlando, FL
The blends and resulting Tg measurements are shown in Table 7.
87
CA 02654809 2009-03-05
Table 7. Polyketal blends and resulting Tg as measured by DSC.
Example Polyketal Wgt %
No. Polymer of Example ple Polyketal Tg, C
51 PHBV None N/A 4.53
52 PHBV 14 33.3 <-80
53 PHBV 15 33.3 -59
54 PLA None N/A 60.8
55 PLA 14 5 51.81
56 PLA 14 33.3 33.01
57 PLA 15 33.3 34.7
58 PS None N/A 96.55
59 PS 14 9.1 65.28
60 PS 14 23.1 41.83
61 PS 14 33.3 29.35
62 PS 14 50 -44.83
63 PS 14 56.1 -53.2
64 PS 13 33.3 24.08
65 PS 13 50 -43.59
Example 66
A 250 ml 3-neck round bottom flask was charged with 20.05 grams (0.03
mol) of the compound prepared according to Example 13 and 1.61 grams (0.018
mol) of butane diol. The flask was equipped with a Dean Stark trap and
condenser,
a magnetic stirrer, and a thermocouple. The flask was heated to 140 C at which
point 0.96 g of titanium N isopropoxide was added to the reaction flask via a
3ml
syringe. Nitrogen purge of the reaction flask was started while stirring the
contents
of the flask at 170 rpm. The temperature in the flask was raised over 1 hour
to
180 C, then held at that temperature for 30 minutes, followed by raising the
temperature to 190 C and holding at that temperature for 30 additional
minutes.
Vacuum was then applied to the reaction flask, slowly bringing the pressure
down to
200 ton. This pressure was maintained, and liquid was observed to collect in
the
Dean Stark trap. After 30 minutes, the temperature was increased to 200 C and
the
vacuum was increased to 100 torr for an additional 30 minutes. Additional
liquid
was collected in the Dean Stark trap.
The contents of the Dean Stark trap were weighed and determined to
represent 94 weight percent yield based on expected loss of ethanol.
88
CA 02654809 2009-03-05
Example 67
A 100 ml 3-neck round bottom flask was charged with 50.1 grams (0.12
mol) of the compound synthesized according to Example 14 and 5.25 grams (0.06
mol) of anhydrous butane diol (obtained from the Sigma-Aldrich Company of St.
Louis, MO). The flask was equipped with Dean Stark trap and condenser,
magnetic
stirrer, nitrogen purge and a thermocouple. The flask was heated to 130 C at
which
point 2 L of titanium IV isopropoxide was added to the reaction flask by
injecting
it under the liquid level of the contents of the reaction flask via a metered
microliter
pipette. The reaction was heated to 210 C over 40 minutes. Liquid was observed
to collect in the Dean Stark trap. The reaction was allowed to react at 210 C
for 90
minutes, followed by 6.5 hours at 220 C. The contents of the flask were
allowed to
cool to ambient temperature under the nitrogen purge.
The reaction contents were analyzed by GPC. The peak percent area is
shown in Table 8. The peak at retention time 9.353 corresponds to the compound
of
Example 14.
Table 8. Retention times and corresponding height and areas for the GPC peaks.
Retention Area % Area Height
Time (nin)
8.169 219189 32.72 6645
8.423 126093 18.82 9096
8.779 171603 25.61 12564
9.353 153088 22.85 13412
Example 68
A 250m1, 4-neck flask was charged with 100.Og (0.267mol) of the compound
synthesized according to Example 12 and 51.05g (0.419mol) of 1,6-hexane diol
(obtained from Acros Organics of Geel, Belgium). The flask was equipped with a
magnetic stir bar, Dean Stark trap and condenser, thermocouple, and nitrogen
inlet.
The reaction flask was stirred and a vacuum was applied to a pressure of about
15
torr. While under vacuum, the flask was heated to 100 C using a heating mantle
and
held at that temperature for 30 minutes. The vacuum was released and nitrogen
was
89
CA 02654809 2009-03-05
streamed in through the inlet. The flask was briefly opened and 30 l of
titanium
isopropoxide (obtained from Acros Organics) was added neat, using a metered
microliter pipette. The nitrogen stream was maintained with stirring, and the
temperature of the reaction flask was increased to 200 C. Liquid was observed
to
S collect in the Dean Stark trap. After 3 hours, liquid was observed to stop
collecting
in the Dean Stark trap. At this point, the trap was observed to hold 30.Oml of
liquid.
The theoretical yield of ethanol in the reaction is 31.2m1.
The contents of the reaction flask were cooled to ambient temperature. The
contents of the reaction flask were analyzed by 1H NMR, and 13C NMR, GPC, and
hydroxyl number. The NMRs showed no traces of ethyl ester or ethanol. The GPC
data gave Mn of 1107 and Mw of 2909, for a polydispersity index of 1.8.
Hydroxyl
number was measured as 125 (theoretical 112), indicating molecular weight of
898.
Example 69
A I liter, 4 neck roundbottom flask was charged with 198.5g (1.68 mol) 1,6-
hexanediol (obtained from Acros Organics of Geel, Belgium) and 400 g (1.07
mol)
of the compound synthesized according to Example 12. The flask was equipped
with a thermocouple and Dean-Stark trap and condenser having a vacuum adapter.
The horizontal glass tubing leading to the Dean-Stark trap was wrapped with
heat
tape. The apparatus was attached to a vacuum pump. The flask was heated to
100 C using a heating mantle, and a vacuum of about 7-8 torr was applied to
the
flask for 30 to 60 minutes to dry and melt the 1,6-hexanediol.
The vacuum was released and the vacuum adapter was replaced with a
connection to a bubbler. The round-bottom flask was further fitted with a
mechanical stirrer and a nitrogen inlet. A moderate flow of nitrogen gas was
swept
through the headspace of the flask, and the controller for the heat tape was
set to 2.5
out of a possible 10. Stirring was begun, and 120 L (200ppm based on total
reactor
charge) titanium tetrabutoxide (obtained from Acros Organics) was added via
metered micropipette. The temperature set point of the controller was
increased to
200 C. When the temperature inside the flask was observed to reach 170 C, a
liquid
was observed to begin collecting in the Dean-Stark trap. The reaction was
continued
until 125mL of liquid had collected. The flask was cooled to ambient
temperature.
and the contents of the flask were poured into a sealed bottle for storage.
CA 02654809 2009-03-05
13C and 1H NMR analysis of the cooled flask contents showed no remaining
ethanol or ethyl ester groups. GPC showed a small amount of residual 1,6-
hexanediol but none of the compound of Example 12. Brookfield viscosity of the
polyol was 9313 cP at 25 C and 282 cP at 80 C. The hydroxyl value was 131
(theoretical value: 56). The glass transition temperature as determined by DSC
was
-49 C. No melting endotherm was observed.
Example 70
A 3-necked, 100 mL round bottom flask was charged with 50.1 g (0.13 mot)
of the compound prepared according to Example 12 and 18.1 g (0.17 mol) of
diethylene glycol (DEG, obtained from Fisher Scientific of Waltham, MA). The
flask was equipped with an overhead mechanical stirrer, an inlet for nitrogen,
and a
Dean-Stark trap with overhead condenser and nitrogen inlet. The flask was
purged
with nitrogen and degassed with three vacuum/nitrogen cycles at room
temperature,
and then a nitrogen sweep was applied through the flask. The contents of the
flask
were then warmed to 173 C under nitrogen purge. After the contents reached
173C,
8.0 gL of titanium IV isopropoxide (obtained from the Sigma-Aldrich Company of
St. Louis, MO) was injected into the reaction mixture under nitrogen purge.
The
nitrogen sweep was then discontinued. A J-KEM Temperature Controller
(obtained from J-KEM Scientific, Inc. of St. Louis, MO) was used to monitor
the
temperature of an oil bath that was heated by a hot plate. The temperature was
controlled by successive changes in the temperature setting of the hot plate.
The
temperature reached about 215 C after about 130 minutes total reaction time,
then
was ramped to 230 C over about the next 60 minutes and was held at between
about
230 C and 235 C for the remainder of the reaction. Nitrogen was sweep was
restarted after about 112 minutes of reaction time, when it was noticed that
liquid
had stopped collecting in the Dean Stark trap. After about 183 minutes after
nitrogen sweep was restarted, the rate of liquid collection in the Dean Stark
trap
slowed down once again, and vacuum was applied to the system. The vacuum was
observed to ramp from about 30 ton to about 5 ton over about 50 minutes. When
no further liquid was observed to collect in the Dean Stark trap, the reaction
was
shut down by cooling the reaction to ambient temperature and releasing the
vacuum.
The total heating reaction time was about 353 minutes.
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CA 02654809 2009-03-05
The material in the reaction flask was light orange in color, viscous,
transparent, and soluble in THE The material was analyzed by GPC, DSC, and
TGA. The weight average molecular weight was 163,798 g/mol; number average
molecular weight was 10,920 gfmol, for a polydispersity of 15. DSC gave a
glass
transition temperature of -7 C. The TGA showed that the polymer was thermally
stable up to a temperature of about 300 C. The TGA plot is shown in FIG. 4.
Examples 71-74
Using the synthetic technique employed in Example 70, additional
copolymers were made using the polyketal compound of Example 12. Table 9
shows materials used, time of reaction, and GPC and DSC data measured for
polymers made with 1,2-ethanediol (obtained from Fisher Scientific of Waltham,
MA), 1,4-butanediol (obtained from Riedel-de-Haen Fine Chemicals of Seelze,
Germany), 1,6-hexanediol (obtained from Acros Organics of Geel, Belgium) and
1,10-decanediol (obtained from Acros Organics). All polymers were transparent,
and were colorless to orange in color.
Table 9. Synthetic data and measurements for polymers made from the polyketal
of
Ex.12.
t~ -d b
04
9 n
= w .S ~
71 1,2-ethane diol 0.21 0.14 2.8 x 10"5 345 7638 5875 1.3 -7
72 1,4-butane diol 0.18 0.14 2.7 x 10"5 390 34174 6572 5.2 -13
73 1,6-hexane diol 0.17 0.14 2.7 x 10-5 420 123658 9368 13.2 -17
74 1,10-- o ane 0.96 0.96 2.7 x 10-5 415 54304 7758 7 -33
Example 75
A I liter, 3-neck flask was charged with 351.8g (0.940 mol) of the compound
synthesized and purified according to Example 12 and 138.7g (1.17 mol) of 1,6-
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CA 02654809 2009-03-05
hexane diol (obtained from Acros Organics of Geel, Belgium). The flask was
equipped with a magnetic stir bar, Dean Stark trap and condenser,
thermocouple,
and nitrogen inlet. The reaction flask was stirred and a vacuum was applied to
a
pressure of 15 torr. While under vacuum, the flask was heated to 100 C using a
heating mantle and held at that temperature for 30 minutes. The vacuum was
then
released and nitrogen was streamed in through the inlet. The flask was briefly
opened and 98 l (200 ppm) of titanium isopropoxide (obtained from Acros
Organics) was added neat, using a metered pipette. The nitrogen stream shut
off and
the flask was stirred and the temperature of the reaction flask was increased
to
200 C. Liquid was observed to collect in the Dean Stark trap. After 2 hours,
48m1
of a liquid had collected in the Dean Stark trap and the rate of collection
had slowed
significantly. At this point, a nitrogen sweep through the flask was started
and an
additional 19.5 ml of liquid was observed to collect in the Dean Stark trap
over the
next 3 hours. At this point, a total of 67.5 ml of liquid had been collected.
The
theoretical yield of ethanol in the reaction is 68.3 ml. The contents of the
reaction
flask were cooled to ambient temperature.
The polyol contents of the reaction flask were analyzed by GPC, Brookfield
viscosity, DSC and hydroxyl number. The GPC data gave Mn of 1975 and Mw of
4720, for a polydispersity index of 2.4. Hydroxyl number was 69 (theoretical
56),
indicating molecular weight of 1626. Brookfield viscosity at 80 C was 1837 cP.
DSC gave a glass transition temperature of -31 C.
A 250m1, 3-neck round bottom flask was charged with 200.Og of the polyol
synthesized in the above reaction. The flask was equipped with a magnetic stir
bar,
a nitrogen inlet, a nitrogen outlet, and a thermocouple. The flask was placed
in a
heating mantle and heated to 80 C. Nitrogen was blown in through the inlet and
out
of the outlet while the temperature was maintained with stirring for
approximately
16 hours to result in the dried reaction product. A 500m1 resin kettle was
charged
with 60.49 g (0.242mol) of methylene diphenyl-4,4'- diisocyanate (MDI,
obtained
from the Sigma-Aldrich Company of St. Louis, MO). The resin kettle was then
clamped to its lid, which was equipped with a mechanical stirrer, nitrogen
inlet,
nitrogen outlet, and a thermocouple. Nitrogen was flowed through the inlet and
out
of the outlet, with stirring, while the flask was heated to 80 C using a
heating
mantle. To the flask was added 164.5 g (0.10 mol) of the dried polyol. The
heat and
stirring were maintained for 3 hours, after which isocyanate value was
measured by
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CA 02654809 2009-03-05
removing a sample from the resin kettle. The isocyanate number was measured to
be 3.0 weight percent. The theoretical value was 5.3 weight percent.
A 250m1, 3-neck roundbottom flask was charged with an undetermined
amount of 1,3-propanediol (obtained from Sigma-Aldrich Company). The flask was
equipped with nitrogen inlet, nitrogen outlet, thermocouple, and a magnetic
stir bar,
and heating with stirring and nitrogen flow for approximately 16 hours at 80
C, to
provide dried 1,3-propanediol. A 20.Og aliquot of the dried 1,3-propanediol
were
removed from the drying flask and placed in a beaker along with 5 l of
dibutyltin
dilaurate (obtained from Air Products and Chemicals, Inc. of Allentown, PA).
The diol and tin catalyst were mixed briefly by hand, and then 5.7g of the
mixture was added to the resin flask containing the reaction product of above,
which
had been preheated to 80 C under nitrogen flow. The mixture of was stirred for
approximately 2 minutes.
The contents of the resin flask were partially emptied into a custom made
Teflon mold measuring 25.4 cm x 25.4cm x 0.5mm. The mold was preheated in an
oven to 110 C. After filling the mold with the mixture from the resin flask,
the
mold was covered with Teflon coated aluminum foil (BYTAC , obtained from
Fisher Scientific of Waltham, MA). A second sheet of Teflon coated aluminum
foil
was placed under the mold. A 0.1524cm thick steel plate was placed on top and
a
second plate placed beneath the Teflon covered aluminum foil, to form a
compression molding "sandwich". The sandwich was placed in a Carver Model
4122 pneumatic heated platen press (obtained from Carver, Inc. of Wabash, IN)
of
that was preheated to 105 C. The press was closed and pressure of 5,000 lbs
applied
to the sandwich. The heat and pressure were maintained for 1 hour. The mold
was
then removed from the press and placed in an oven at 110 C for 24 hours. The
sample was removed from the oven and a solid, flexible molded sheet comprising
the material from the resin flask was removed from the mold.
A second compression molding sandwich was formed by layering the
molded sheet on its two major sides Teflon coated aluminum foil sheets and
steel
plates. The second sandwich was placed in the press that was preheated to 192
C.
The platens of the press were closed so as to contact the sandwich but without
adding measurable pressure. This position was maintained for approximately 3
minutes in order to preheat the sandwich. The pressure was then increased to
5,000
lbs. and this was maintained for 5 minutes. The sandwich was removed from the
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CA 02654809 2009-03-05
press and allowed to cool for approximately 1 minute before removing a pressed
film from the sandwich.
The pressed film was measured to be about 0.5mm thick, was substantially
uniform and without bubbles, was transparent, and had a very slight yellow
color.
The pressed film was characterized by DMA, DSC, and tensile testing. The DMA
showed that the peak of the tan S was at 33.1 C. DSC showed that the T. was
13.0 C with a broad melting peak at about 208 C. Tensile testing was carried
out
according to ASTM D1708, using 100 mm/min; the strain at break was 409%, peak
stress was 25.1 MPa; modulus was 6.40 MPa at 2% strain, 6.87 MPa at 100%
strain,
and 4.30 MPa at 300% strain.
Example 76
A 250m14-neck round bottom flask was charged with 44.48g (0.229mol) of
dimethyl terephalate (DMT, obtained from the Sigma-Aldrich Company of St.
Louis, MO), 50.60g (0.135mo1) of the compound made according to Example 12,
and 49.86g (0.553mo1) of 1,4-butane diol (obtained from the Sigma Aldrich
Chemical Company). The flask was equipped with a Dean Stark trap and
condenser,
a nitrogen/vacuum inlet, and a mechanical stirrer. The flask was degassed with
5
vacuum/nitrogen cycles wherein the vacuum applied to the flask was
approximately
9 torr. After the 5 degassing cycles, 29.3 .d (200ppm) of titanium
tetrabutoxide
(obtained from Acros Organics of Geel, Belgium) was injected into the contents
of
the reaction flask with a metered micro pipette, and the contents of the
reaction flask
were degassed an additional 5 times. The flask was placed in an oil bath with
the
temperature set to 180 C and was stirred, under nitrogen, for 2.5 hours after
which
time the oil bath temperature was increased to 190 C and this temperature was
maintained for 105 minutes; the temperature was then raised again to 200 C and
this
temperature maintained for an additional 2 hours. Vacuum was then applied to
the
flask with a Teflon pump and over the ensuing 50 minutes, the pressure in the
reaction flask decreased from about 75 torr to 25 ton. A second Teflon pump
was
then added in tandem with the first Teflon pump and the vacuum in the reaction
flask was brought down to 5.5 torn; this pressure was maintained for about 2
hours
and 45 minutes. The temperature in the flask was then slowly raised to 210 C
over
the next 2.5 hours. The temperature of 210 C, and the pressure of 5.5 ton were
maintained for the next 10.5 hours. Then the pressure in the flask was reduced
again
CA 02654809 2009-07-24
by replacing the TeflonT l pUnlpS with an oil primp: the pressure in the
reaction flask went
from I ton- to about 300 11m11itoI7 and this pressure was maintained for about
1.5 hours. The
reaction flask was then backfilled with nitrogen and allowed to cool to
ambient temperature.
The contents of the reaction flask were analyzed by GPC, DSC, and tensile
testing.
The GPC gave a weight average molecular weight of 232,000 g/mol and a
polydispersity
index of 17. The DSC gave a glass transition temperature of 4 C, a melting
temperature of
133 C, and a heat of fusion All... of 23.4 J/g. The tensile testing, which was
carried out with
six samples employing the technique of ASTM D638, showed that the force at
break was
13.0 MPa and a strain at break was 620 /,. The stress-strain profile for the
six samples is
shown in FIG. 5.
The data in FIG. 5 show that the polyesters of the invention have tensile
properties
that make them suitable for use as structural materials. Packaging films,
fibers, and other
articles suitable for commercial applications can be made using the polyketal
polyesters of
the invention.
Examples 77-79
The glycerol ketal of butyl levulinate was synthesized and purified according
to the
procedures set forth in U.S. Patent Appl. No. 2008/0242721. A copolymer of the
glycerol ketal
of butyl levulinate with butylene terephthalate (obtained from the Sigmla-
Aldrich Company of
St. Louis, MO), or p(LGK-co-BT), was synthesized according to the techniques
set forth in
U.S. Patent Appl. No. 2008/0242721. The molar ratio of monomers was 1:1. The
molecular
weight of the p(LGK-co-BT) copolymer was analyzed by GPC, which determined
that the
weight average molecular weight was about 215,000 with a polydispersity index
of 10.
The materials were mixed with the polyketal synthesized and purified according
to
Example 14 using the procedure outlined in the General Laboratory Procedures
for
compounding using the Haake PolyLab, with the following modifications. The
polymer and
polyketal were fed into the compounder via a gravity feed system without hand
mixing, and
the temperature in the compounder was set to 140 C.
After compounding, the mixtures were analyzed by DSC to determine glass
transition temperature and melt temperature. The mixtures and the DSC results
are shown in
Table 10.
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CA 02654809 2009-03-05
Table 10. Effect on Tg, Tm of p(LGK-co-BT) when blended with the polyketal of
Example 14.
Polyketal of Tg Tm
Example Example 14, ( C) ( C)
wt%
77 0 16 115
78 10 -4 112
79 20 -16 111
Examples 80-85
The ability of the compounds of the invention to compatibilize mixtures of
solvents that are otherwise immiscible was tested in the following six
experiments.
Example 80. Equal volumes of hexane and methanol were place in a
scintillation vial. The two solvents formed two clear and distinct layers.
About 10
vol% of the polyketal synthesized according to the procedure of Example 14 was
added based on the volume of the combined solvents. Upon brief shaking by
hand,
the two immiscible liquids formed a single layer.
Example 81. Equal volumes of water and methanol were placed in a
scintillation vial. The two solvents formed two clear and distinctly visible
layers.
About 10 vol% of the polyketal synthesized according to the procedure of
Example
14 was added based on the volume of the combined solvents. Upon brief shaking
by
hand, the two immiscible liquids formed a single layer.
Example 82. A centrifuge vial was charged with 3 ml methanol and 3 ml
hexane. 80 gL of the compound synthesized and purified according to the
procedure
of Example 12 was added to the vial. Upon brief shaking by hand, most of the
solvent mixture was homogeneous in appearance, with a very small layer of
separated solvent remaining on the top of the volume of liquid. An additional
20 L
of the compound synthesized and purified according to the procedure of Example
12
97
CA 02654809 2009-07-24
was added to the vial. Upon brief shaking by hand, the mixture became
completely
homogeneous in appearance. The sample was then placed in a centrifuge and spun
at 3000
rpm for about 10 minutes and was still a homogeneous mixture upon removal from
the
centrifuge.
Example 83. A centrifuge vial was charged with 3 ml methanol and 3 nil hexane.
80
pL of the compound synthesized and purified according to the procedure of
Example 14 was
added to the vial. Upon brief shaking by hand, most of the solvent mixture was
homogeneous in appearance, with a very small layer of separated solvent
remaining on the
top of the volume of liquid. An additional 20 pL of the compound synthesized
and purified
according to the procedure of Example 14 was added to the vial. Upon brief
shaking by
hand, the mixture became completely homogeneous in appearance. The sample was
then
placed in a centrifuge and spun at 3000 rpm for about 10 minutes and was still
a
homogeneous mixture upon removal from the centrifuge.
Example 84. A centrifuge vial was charged with 3 ml water and 3 ml
dichloromethane. Aliquots of the compound synthesized and purified according
to the
procedure of Example 12 was added to the vial, with brief hand shaking between
aliquots.
After a total of about 3 ml of the compound synthesized and purified according
to the
procedure of Example 12 was added, the sample did not become homogeneous.
Example 85. The procedure of Example 81 was repeated using the compound
synthesized and purified according to the procedure of Example 14, with the
same result.
Examples 86-89
Various polyketal compounds according to the invention were mixed with
RhoplexT"' SGI OM Latex (obtained from the Rohm and Haas Company of
Philadelphia, PA).
In each case, 0.25g of the polyketal compound was added to 5.0- of latex in a
scintillation vial,
and the vial was mixed by placing on a vortex shaker for 1 minute. The
mixtures were then cast
onto cleaned glass panels using a 6 mil (0.254 mm) notched draw down bar
(obtained from
the Pioneer-Dietecs Corporation of Weymouth, MA). These panels were then
placed into a
refrigerator at 4 C for 2 hours. The resulting films were 3mil thick. The
films were examined
visually for continuity of the film and for surface defects. The result of
visual examination
of the films is reported in Table 11.
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CA 02654809 2009-07-24
Table 11. Visual assessment of films formed from blends of commercial latex
with
polyketal compounds.
Example Polyketal
No. , Ex. No.
Appearance of Film
86 none discontinuous film
87 12 continuous film, some fish eyes o
air bubbles
88 14 discontinuous film, some fish eyes
or air bubt les
89 15 discontinuous film, some fish eyes
air bubbles
Examples 90-101
Smooth finish steel panels (obtained from the Q-Lab Corporation of Westlake,
OH)
were cleaned by washing four times with acetone, followed by wiping with a
KIMWIPE
(obtained from the Kimberly-Clark Corporation of Irving, TX). The panels were
then coated
with paint samples by spraying or brushing a commercial paint formulation onto
a panel and
allowing the paint to dry for about 24 hours under ambient laboratory
conditions. The
commercial paint formulations used were:
1. Appliance Epoxy - Gloss White Rustoleum 788IT111, obtained from the Rust-
Oleum
Corporation, of Vernon Hills, IL
2. ZinsserTM Bulls Eye 1-2-3 Deep Tint (white), obtained from William Zinsser
&
Company, Inc. of Somerset, New Jersey
3. PromarTM 200 Interior Latex Low Sheen ES Enamel, Extra White. B20www 1251,
obtained from the Sherwin-Williams Company of Cleveland, Ohio
4. RhoplexTM SGIOM latex, obtained from the Rohm and Haas Company of
Philadelphia. PA.
The panels were laid flat on a laboratory bench, and two drops of a polyketal
were
applied by a plastic eyedropper to each panel. The panel was undisturbed for
about 10
minutes. Then the panels were wiped off using a KIMWIPE . The wiped
99
CA 02654809 2009-03-05
surfaces of the panels were visually inspected. The results of visual
inspection are
shown in Table 12.
Table 12. Observations after applying polyketal compounds to paint coated
steel
panels, followed by wiping the areas of application.
Example Paint Polyketal,
No. Formulation, Example Observations
No. No.
90 1 12 No effect on film
91 1 14 No effect on film
92 1 15 No effect on film
Penetrated and removed surface layer of
93 2 12 film. Definite circle where solvent was
applied.
Penetrated and removed surface layer of
.94 2 14 film. Definite circle where solvent was
applied.
95 2 15 No effect on film
Penetrated and removed surface layer of
96 3 12 film. Removed down to bare metal in
places. Definite circle where solvent was
applied.
Penetrated and removed surface layer of
97 3 14 film. Removed down to bare metal in
places. Definite circle where solvent was
applied.
Penetrated and removed surface layer of
98 3 15 film. Definite circle where solvent was
applied.
Penetrated and removed surface layer of
99 4 12 film. Removed down to bare metal.
Definite circle where solvent was applied.
Penetrated and removed surface layer of
100 4 14 film. Removed down to bare metal.
Definite circle where solvent was applied.
100
CA 02654809 2009-03-05
Penetrated and removed surface layer of
101 4 15 film. Removed down to bare metal.
Definite circle where solvent was applied.
The present invention may suitably comprise, consist of, or consist
essentially of, any of the disclosed or recited elements. The invention
illustratively
disclosed herein can be suitably practiced in the absence of any element which
is not
specifically disclosed herein. The various embodiments described above are
provided by way of illustration only and should not be construed to limit the
claims
attached hereto. It will be recognized that various modifications and changes
may
be made without following the example embodiments and applications illustrated
and described herein, and without departing from the true spirit and scope of
the
following claims.
101
