Indian Patents
Title of Invention

GLYCEROL LEVULINATE KETALS AND THEIR USE
Abstract The present disclosure relates to the preparation of ketal compounds from glycerol and levulinic acid and esters, and uses thereof.
Full Text CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of United States Provisional Patent
Application No. 60/738,988 entitled "Glycerol levulinate ketals and their use", filed.
on November 22, 2005, which is incorporated by reference in its entirety herein..
TECHNICAL FIELD
The present disclosure relates to the preparation of ketal compounds from
glyeerol. and levulinic acid and esters.
BACKGROUND
Many known chemical products such as surfactants, plastieizcrs, 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. Glyeerol
is an inexpensive renewable compound that is readily available as a by-product of
biodiesel production or via fermentation of carbohydrates. Levulinic (4-
oxopentanoic) acid is another 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. Chemical products produced from these
two materials could fill a need for inexpensive, renewable consumer and industrial
products.
SUMMARY •
Provided herein are ketal compounds prepared from glyeerol and levulinic
acid or derivatives thereof. In certain embodiments, such ketal compounds can have
the formula:


wherein R1 is hydrogen or a carbon atom of a levulinate fragment; R2 is hydroxyl,
an oxygen atom of glycerol,. or an oxygen atom of an esterified glycerol fragment;
and p is an integer. Compounds of this formulation can be prepared through the
reaction of glycerol. or a glycerol derivative having the formula:

wherein. R and R are independently selected from the group consisting of
hydrogen; linear, branched., or cyclic alkyl; linear, branched, or cyclic alkenyl; aryl,
and arlyalkyl; and a levulinic acid, levulinic ester, angelicalactone, or a dialkyl. ketal
of levnlinic ester. The reaction can be effected in the presence of an acid catalyst,
and under conditions sufficient to provide for removal of water from the reaction
mixture.
In another embodiment, a .ketal compound can have the formula;

wherein R9 is hydrogen or a carboxyl moiety; R10 is OR11, or N(RI2)2; R11 and R12
sure independently hydrogen or a linear, branched, or cyclic alleyl; and p is an
integer. This compound can be combined with a monohydric alcohol or carboxylic
ester, and a reaction can be effected in the presence of a base catalyst.
An example of a product resulting from such a reaction can include:


wherein R3 is hydrogen; methyl; linear, branched, or cyclic alkyl; linear, branched,
or cyclic alkenyl; aryl, aralkyl, and alkyloxyalkyl; and X is selected from hydrogen
or

wherein R6 is selected from hydrogen; linear, branched, or cyclic alkyl; linear,
branched or cyclic alkenyl; aryl; aralkyl; and alkyloxyalkyl. In some embodiments,
it is preferred that R3 is selected from a C3-C30 LInear, branched, or cyclic alkyl;
linear, branched, or cyclic alkenyl; aralkyl; and alkyloxyalkyl. In another
embodiment, when R3is hydrogen,, the reaction product can be present as a salt.
Suitable sate can include alkali, alkali-earth, ammonia, and amine salts.
In another embodiment, the compound having formula:

wherein R9 is hydrogen or a carboxyl moiety; R10 is OR11, or N(R12)2; R11 and R12
are independently hydrogen or a linear, branched, or cyclic alkyl; and p is an
integer, can undergo a reaction in the presence of a trans-eslerification catalyst
Examples of compounds resulting from such a reaction can include:

In a further embodiment, compounds can be prepared which have the
formula;


wherein R3 is hydrogen; methyl; linear, branched, or cyclic alkyl; linear, branched,
or cyclic aikenyl; aryl, aralkyl, and alkyloxyalkyl; and Y is selected 'from the group
consisting of:

wherein one of R7 or R8 is hydrogen and the other is a C1-C30 linear alkyl; one of A
or B is hydrogen and the other is an ester; and m and n are independently integers
from 0 to 20, wherein the sum of tn+n is in the range from 8 to 21. In some
embodiments, it is preferred that R3 is selected from C1-C30 linear, branched, or
cyclic alkyl; linear, branched, or cyclic alkenyl; aralkyl; and alkyloxyalkyl. In
another embodiment, R7 or R8 is a C6-C30 linear alkyl, or preferably a C6-C14 linear
alkyl. .In certain embodiments, when. R3 is hydrogen, the compounds can be present
as a salt. Suitable salts cart include alkali, alkali-earth, ammonia, and amine salts,
Any of the compounds above can optionally be isolated or prepared in either
the cis or trans confirmation, In some cases, the compounds can be predominantly

in the cis configuration, i.e., the substituted oxymethylane moiety attached to the
dioxolane ring is predominantly in the cis configuration relative to the configuration
of the side chain bearing the carboxyl group. Preferably, the compounds are
isolated or prepared exclusively in the cis configuration. Alternatively, the
compounds can be isolated or prepared in predominantly the trans configuration,
i.e., fee substituted oxymethylene. moiety attached to the dioxolane ring is
predominantly in the trans configuration relative to the configuration of fee side
chain bearing the earboxyl group. As above, the compounds are preferably isolated
or prepared exclusively in the trans configuration.
Also provided herein is a polymeric compound comprising a unit having the
formula:

wherein q is an integer.
This polymer, and any of the compounds described above, can be combined
with a base polymer to form a plasticized polymer composition. Examples of base
polymers can include vinyl chloride polymer, poly(3-hydmxyalkanoate) polymer,
poly(lactate) polymer, and polysaccharide polymer.
The details of one or more embodiments of the invention are set forth in the
description below. Other features, objects, and advantages of the invention will be
apparent from the description and from the claims. .
DETAILED DESCRIPTION
The present disclosure provides a series of glycerol-deriyed compounds that
are based on the formation of a ketal with the ketone group of levulinic acid.
Glycerol-levulinate ketal compounds can be produced by reacting approximately
one molar equivalent of glycerol with approximately one molar equivalent of

levulinic acid in the presence of an acid catalyst, and under conditions allowing for
removal of water, typically by distillation. The reaction is preferably carried out
using between 0.7 to 1.3 molar equivalents of Ievulinic acid, although the reaction
can be carried out with, lower or higher amounts of levulinic acid. However, when
the amount of levulinic acid is too low, much of the glycerol remains unreacted.
Alternatively,; if the amount of levulinic acid is too high, then di and tri-levulinate
esters of glycerol are formed in large quantities, thereby reducing the yield, of the
desired ketal adducts of giycerol and levuiinate.
During the course of the reaction between one equivalent of giycerol and one
equivalent of levutinale, two equivalents of water are formed. Water can
conveniently be removed by distillation, or by an azeotropic distillation in the
presence of a suitable inert solvent such as hexane, heptane, toluene, benzene, and
the like. When about two equivalents of water have been removed from the reaction
mixture, the reaction mixture contains predominantly a polymeric levulinate-
glyceroJ kef al adduct comprising a repeat unit having formula (1):

wherein the R1 is hydrogen or a earboxyl atom of a levuiinate fragment, and
wherein R is hydroxyl, an oxygen atom of a giycerol, or an oxygen atom of an
esterified glycerol fragment, and wherein p is an integer.
The product is a polymer that is, in the absence of other compounds and
impurities typically terminated at its ends by a levulinoyl group and by a giycerol
ester fragment.
The value of p depends on may factors and may significantly vary,
depending on how much water has been removed, the reactant ratio, acid catalyst
aad severity of the heating conditions used to remove water. The purity of the
giycerol and levulimate are also factors. Relatively impure industrial grades of
giycerol and levuiinate give adducte wherein p is in a range typically between 1 aad
10. However, even with pure glycerol and icvulinate it is difficult to Obtain

polymers with p values significantly in excess of 30. It has been found feat the
direct polyeondensation reaction between glycerb) and levulinate becomes staggered
due to formation of the polymers of formula (1'), wherein R1 is represented by a
gamma-valerolactone derivative, as shown herein:

If heated for sufficiently long time, the compound (1') will slowly rearrange
to a levulinoyl-terminated polymer, thereby allowing for further polymer growth.
However, In Industrial practice, it is not practical or necessary to rely on such long
reaction times, and it is preferred (hat the polycondensation reaction be stopped
when about 70 to 95% of the theoretical amount of water has been collected. The
resulting polymers comprise glycerol fragments that are esterified at more than one
hydroxyl group, and such fragments are recognized herein as points of polymer
branching or points of repeat unit inversion, wherein the repeat unit is of formula
Depending on the severity of the conditions of the reaction, some ether bond
formation, resulting in diglyeeryl fragments, or some elimination of hydroxyl
groups from glycerol, to form acrolein, is possible. It is also possible that some
angeiicalactone formation from levulinate also occurs and this product may be
isolated and re-used. Typically, the polymeric adduct of glycerol and levulinate
prepared from industrial grade glycerol and levulinate is a very viscous, semi-
transparent or transparent liquid with a pale yellowish-brownish to near colorless
botsey-like appearance due to traces of unidentified byproducts. However, even in
the presence of these by-products, the final polymeric adduct comprising the repeat
unit of formula (1) is found herein to be useful in the preparation of compounds and
various intermediates.
Similarly to the free ievutinic acid, levulinic esters of monohydric alkanols,
beta- and gamma-angelicalactones, and 4,4-dialkoxypenanoate esters (which are
esters of ketals of levulinic acid with monohydric alkanols) are also suitable to

practice the synthesis of the glyeerol levulinate ketal compounds comprising the
repeat unit of formula (1). Any of these levulinic derivatives can be used in the
synthesis of the glycerol levnlinate ketal compounds in a substantially pure form, or
in a mixture. The mixtures can comprise any of the above compounds with a
quantity of free levulinic acid. When mixtures of the levulinic derivatives are used
to make the glycerol levulinate ketal compounds, it is preferred that about one molar
equivalent of these compounds is used per molar equivalent of glycerol.
Similarly, in the synthesis of the glycerol levulinate ketal compounds, some
or all of the glycerol can. be replaced with a glycerol ketaS or acetal of formula (2);

wherein R4 and R5 arc each Independently selected from hydrogen; linear, branched,
or cyclic aikyl; linear, branched, or cyclic alkenyl; ary!; or aralkyl. Preferably, R4
and R5 are not both hydrogen.
Mono, di and tri esters of glycerol with simple C1-C8 linear or branched
alkanoic acids can also be used instead of glycerol, or in. a mixture with glycerol.
Monolevulinate ester of glycerol is also a suitable starting material.
Synthesis of the condensation polymeric glycerol levulinate ketai adduct
comprising the repeat unit of formula (.1) of glycerol is carried out with glycerol and
levuiinic acid, which are fully miscibie compounds. For industrial practice, glycero!
and levuiinic aeid do not need to be anhydrous and'thus may contain varying
amounts of water. However, it is preferred that these starting materials do not
contain, excessive amounts of water, as this results in a less efficient use of
equipment. Typically, glycerol and levuiinic acid with water contents of about 10%
or less are preferred.
Synthesis of the polymeric levulinate-glycerol ketal adduct comprising the
repeat unit of formula (1) typically requires the presence of a suitable acid catalyst.
Non-limiting examples of such catalysts include strong mineral acids, such as
sulfuric, hydrochloric, hydrofluoroboric, hydrobrornic acids, p-toluenesulfonic acid,
camphorosulfonic acid, rnethanesulfonic acid, and like, Various resins that contain
protonated sulfonic acid, groups are also useful as they can be easily recovered after

completion of the reaction. Examples of acids also include Lewis acids. For
example, boron trifluoride and various complexes of BF3, exemplified by BF3
diethyl etherate. Silica, acidic-alumina, titaraia., zirconia, various acidic clays, and
mixed aluminum or magnesium oxides can be used, Activated carbon derivatives
comprising mineral acid, sulfonic acid, or Lewis acid derivatives can also be used.
One of ordinary skill in the art can practice many variations on the part of the
catalyst composition and the amounts used in the preparation described herein,
Amount and type of catalyst depends on the specific chemical composition of the
epoxide and glycerol or glycerol derivative of formula (3), used in the reaction and
can be readily established by one skilled in the art. It is preferred, however, that
low-cosl catalysts that impart minimal or negligible corrosion effects on the
equipment used in the synthesis, and have low volatility, toxicity, and
environmental impacts, or can be easily neutralized to innocuous compounds,, are
used, Sulferic acid is one such preferred catalyst. The reaction of condensation of
glycerol and levulinic acid can be carried out without a catalyst, but, for industrial
purposes, these reaction conditions are generally too slow to be practical, ia order "
to yield industrial quantities of compounds comprising the repeat unit of formula
(1), it is preferred that the condensation be accelerated by use of a catalyst and
elevated temperature sufficient to remove water from the reaction mixture without
undue time expenditure. The condensation reaction may optionally also be carried
out under reduced pressure to facilitate removal, of water, and to minimize formation
of discolored by-products.
An adduct of glycerol and levulinate comprising ketal fragments of formula
(I) can be further subjected to chemical reactions to yield derivatives of glycerol
and levulinate.
Trans-eterification with alcohols
Products can be obtained when polymeric compounds comprising the repeat
units of formula (I) are treated under trans-esterification conditions with a
rnonohydric alcohol. Typically, such reactions are carried out with an alcohol in the
presence of abase, such as alkali or alkali-earth hydroxides or alkoxides. The

catalyst can be used in a soluble or insoluble form. Many trans-esterification base
catalysts are known in the art, and the present disclosure is Hot limited to the use of
a particular catalyst.
Such trans-esterification reactions can result in the formation of a mixture of
cis and trans- stereoisomers of a hydroxyestar compound having formula (3);

wherein R3 is a linear, branched, or cyclic alkyl or alkenyl, aryl, aralkyl, or
alkyloxyalkyl.
A typical procedure for making the hydroxyester of formula (3) involves use
of an excess of alcohol which, after neutralization of the base catalyst, is removed
by distillation, The Irans-esterification reaction with an alcohol typically also
results in the formation of minor quantities of free glycerol that readily separates as
an alcohol-immiscible liquid from the alcoholic solutions of hydroxyester (3), ester
of levulinic acid, and the R3OH alcohol used in the trans-esterification. The latter
compound can be readily separated from the hydroxyester of formula (3) by
distillation, typically under reduced pressure, and, if desired, re-used in the synthesis
of the glycerol-levulinate ketal polymeric adduct comprising the repeat unit of
formula (1).
It has been found that the cis- and trans- isomers of the compound of
formula (3) can be readily separated from each other by distillation using ordinary
distillation equipment known in the art, such as distillation columns with sufficient
number of plates, falling film, distillation columns, and the like. Preferably,
distillation to separate cis- and trans-isomers of the compound of formula (3) is
earned out under reduced pressure and in the relative absence of a trans-
esterification catalyst. The latter condition is beneficial as it minhnizes
polymerization of the compound of formula (3), as well as formation of a free
alcohol, R3OH, which can make maintenance of sufficient vacuum difficult.
However, the distillation maybe carried out without complete removal of trans-
esterification catalyst, and any -and istilled oligomers can be recovered and re-used

for preparation of the compound of formula (3) by the base-catalyzed reaction
disclosed above.
It has also been found that alkaline trans-esterification reaction of ketal-ester
co-polymers of glycerol and levalinate comprising the repeat units of formula (i)
yield mixtures of reaction products that largely comprise the cis and trans-isommrs
of the compounds of formula {1), which are 1,2-ketals of glycerol and a levulinate
ester with alcohol R3OH, Only negligible traces of 1,3-glycerol ketals of esterified
levulinate are found in such product mixtures,
Trang-esterification with carboxylic esters
In a related embodiment, the trans-esterification in the presence of base is
carried out under conditions similar to that described above for an alcoholic trans-
esterification, except that instead of an alcohol, an ester of a carboxylic acid and an
alkanol Is used. In this case, stereoisomers of carboxylic esters of glycerol
levulinate ketal of formula (4) are formed:

wherein R3 is a linear, branched, or cyclic alkyl or alkenyl, aryl, arallkyl, or
alkyloxyalkyl, and R6 is hydrogen., or is a linear, branched, or cyclic alkyl or
aikenyl, aryl, arakyl, alkyloxyalkyl, or oxoalkyl.
The synthesis of compound (4) using trans-esterification with the carboxylic
ester is also typically accompanied by the formation of minor quantities-of
levulinate ester, glycerol, glycerol mono, di and tri esters of the carboxylic acid-
R6COOH, and of varying quantities of the compound of formula. (3). The quantity
of the compound of formula (3) depends largely on the value of p specified in the
structure of the repeat unit of formula (1) described above; polymeric ketal adducts
having lower values of p tend to produce higher relative quantities of the compound
of formula (3) in relation to the compound of formula (4). The reaction products
from base-catalyzed trans-esterification with carboxylic esters are typically
separated and purified by distillation.

De-polymerzing trans -esterification of polymeric glycerol levulinate ketal adducts
In. another embodiment, a polymer comprising a glyceroi levutinate ketal
adduct comprising a unit of formula (la):



wherein R9 is hydrogen or a carboxyl moiety; R10 is OR11, or N(Rl2)2; R11 and R12
are independently hydrogen or a linear, branched, or cyclic alkyl; and p is an
integer. In some embodiments, OR11 can. be a fragment of a monohydric or a
polyhydric alcohol. The compound comprising the unit of formula (1a) is subjected
to a trans-esterification reaction, resulting in a depolymcrization that provides for
the formation of a bicyclic lactone-ketal adduct of glyceroi and levutinate, named
herein "segetolide" ("lactone of a crop field"), having formula (5):

7-methyl-3,8,10-trioxabicyclo(5.2.1]decan-4-one.
A further embodiment includes the provision of a cyclic dimex of segetolide
(5). Such a cyclic dimer (named herein "bis-segetolide") is a cyclic bis-lactone
(diolide) bis-ketal having formula 5{a):

Typical lys such a depolymerizing trans-esterificatton reaction, is carried, out
under substantially anhydrous reaction conditions, and in the presence of an acid or
abase catalyst. Alternatively, one or more of many other catalysts known in the art
to catalyze esterification or trans-esterification reactions, such as those known in the

art of synthesis of various polyesters, may be used- Numerous examples of catalysts
for synthesizing of compounds of formulae (5) and/or (5a) by depolymerization of
polymers comprising repeat units of formula (la) caa be: found in the art of
polyester synthesis. Description of such catalysts and methods of their use can be
found,, for example, in United States Patents Nos. 4,133,800,4,205,157, 4,208,527,
5,028,667, 5,095,098, S,2l0,l08, 5,208,297, 5,202,413, 5,292,859 5,342,969,
5,565,545, and 6,-828,272.

wherein R9 is hydrogen or a carboxyl moiety; R10 is OR11, or N(R11)2; R11 and R12
are independently hydrogen, or a linear, branched, or cyclic alkyl; and p Is an
Under such conditions, the cyclic ketal lactones of formulae (5) and/or 5{a)
are in equilibrium with one another, the polymeric compound, and various
-oligomers comprising the unit of formula (1a). Under sufficient temperature,
typically in the range of 160-300°C, and, preferably, wider reduced pressure, a
vapor phase comprising ketal lactones of formulae (5) and (5a) is formed. The
compounds of formulae (5) and (5a) are typically separated from the reaction
mixture by distillation under reduce pressure, and separated from each other, if
desired, by distillation. Further purification of the compounds of formulae (5) and
(5a) can be achieved by repeated distillations, or by using a high efficiency
distillation column. By adjusting the temperature and pressure of the distillation, it
is possible to obtain the compound of formula (5) substantially free of the
compound of formula (5a) without difficulty, as these two compounds.have a large
difference in 'boiling temperatures. It is understood that if an. effective trans-
esterification catalyst is present in the preparation of substantially pure compounds
of formula (5) and/or 5(a), such compounds may equilibrate to form a. mixture of
these to compounds, as well as varying quantities of polymers comprising the cis-
isomers of the units of formula (1b):

integer. In some embodiments, OR11 can be a fragment of a monohydric or a
polyhydric alcohol
When depolymerization is conducted in the presence of a catalyst, using a
polymer comprising a mixture with approximately equal quantity of cis- and trans-
units of formula (I), approximately half of the quantity of the polymeric adduct
comprising the cis- and trans- isomeric units of formula (1) can be converted to the
compound of formula (5), The remainder of the undistifled polymeric adduct
consists predominantly, or exclusively, of the units of formula (1) having the trans-
stereoohemistry (1 c):

wherein R9 is hydrogen or a carboxyl moiety; R10 is OR11, or N(R13)2; R11. and R12
are independently hydrogen or a linear, branched, or cyclic alky); and p is an
integer. In some embodiments, OR11 can be a fragment of a monohydric or a
polyhydric alcohol.
During depotymerization of polymers comprising the unit of formula (la)
conducted in the absence of an effective amount of an acid catalyst that allows the
irans-ketal to re-equilibrate to a mixture of cis- and trans- ketals, the compounds of
formulae (5) and (5 a) are formed only from the cis-isomers of units of formula (lb).
In general, the quantity of the products of compound of formulae (5) and
(5a) that can be produced is limited by the abundance of the cis-fragments of the
formula (1 b) in the polymer used for depolyrnerlzation.
When depolymerization of the polymer comprising units of formula (i) is
conducted in the presence of an acid catalyst, both cis- and trans- isomers of the
units are in quiltbrium, and thus both cis- and trans- units can be converted to the
compound of formula (5) and/or 5(a), It is preferred, however, that when an acid
catalyst is used to conduct the depolymerization reaction, the temperatures of the
reaction not be allowed to exceed 120-130 °C to avoid excessive decomposition of
glycerol to acrolein, and formation of glyceryl ethers.

After the compounds of formula (5) and/or (5a) have been substantially
removed by distillation, the resulting depolymerization product is a useful polymer
typically comprising predominantly, or exclusively, the tram-fragments of formula
(1c). Such can be further converted, for example, by using trans-esterification with
an excess alcohol or an ester in the presence of base. Under such, conditions,
compounds of formula (3) and (4) comprising predominantly, or exclusively, the
trans-isomers of the compounds of formula (3a) and (4a), respectively, are thus
prepared:



Similarly, the bi cyclic lac-tone keta! compounds of formula (5) and/or 5(a)
are readily converted by a base-catalyzed trans-esterification with an alcohol or an
ester to the corresponding cis-isomers of the hydroxyester (3b) and diester (4b):

The glyeerol ketal derivatives of levulinic esters of formula (3), (4), (5), and
5(a), as well as the separated individual cis- and trans- stereoisomers (3a), (3b),
(4a), and (4b), are excellent solvents for a variety of both hydrophobic compounds
(e.g., fats, oils,, greases, waxes, varnishes) and many hydrophilic compounds.
Compounds of formula (3), wherein R3 is a C1-C5 lower alkyl, are miscible with
water in a broad range of concentrations. Therefore, these compounds are useful as
part of various formulations in applications such as degreasing, paint thiners, paint
removal or as part of formulated adhesives. Because of their relatively slow
evaporation under ordinary environmental conditions (which can be controlled by
selecting appropriate length of R6 and R3 groups), and because of a low agreeable or
negligible odor, these compounds are also useful as eoalescent solvents in various

latex paints and coatings where they can be supplied to the frmulation in addition
to, or instead of, typical petroleum-derived solvents suck as 2,2,4-trimethyl-1,3-
pentanediol monoisobutyrate or disobutyrste, ketones, and aromatic hydrocarbons.
The compounds (3) and (4), as well as any individual or mixed
stereoisoxners thereof, have also been found to be useful as plasticizers.with various
polymers, such as poly(vinyl chlaride), poly(3-hydroxyalkanoates), poly(3-
hydroxybutyrate), poly(lactate), and polysaccharides.
Poly(vinyl chloride) polymers, PVC, are fromopolymers or co-polymers of
vinyl chloride. Many PVC compounds of various degree of polymerization, cross-
linking and co-polymer composition are known in the art and are produced
industrially.
Poly(3-hydroxyalkanoates), PHA, are polyester homopolymers or co-
polymers of 3-hydroxyalkanoic acids. Preferably, PHA is composed of linear 3-
hydroxyaikanoic fragments having from 3 to 18 carbon atom atoms, Poly(3-
hydroxybutyrate), PHB, is a homopolymer that is produced biologically, for
example by various microorganisms. A pure PHB polymer is a brittle polymer
having a narrow range of processing temperatures, and it decomposes readily at
temperatures that are only 20-30 "C above its melting temperature.
Poly(lactate), or poiy(lactide), PL A, is a known polyester homopolymer
comprising repeat units of lactic acid of various stereochemistry.
Polysaccharides are homopolymers and co-polymers, linear or branched,
comprising hexose or pentose fragments connected via glycosyl linkages. The
polysaccharides may optionally contain various additional groups such as acylamido
groups, sulfate ester groups, carboxylic ester groups, alkyl and hydroxyalkyl ether
groups and the like. Such additional groups may be present in polysaccharides
derived from natural sources or can be artificially introduced (i.e., by aeyktion. of
cellulose). Examples of polysaccharides include acylated derivatives of cellulose
and starch, as well as native or acylated chitin and pectin,
Plasticizers are chemical compounds added to a base composition
comprising one or more of the above 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, and
depending on the polymer used and desired properties of the compounded polymer
formulations, plasticizers can be used at concentrations between 1 and 80% by
weight of the unplasticized polymer. It is understood that, depending on the
polymer and the plasticjzec 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 extradable or moidable polymer composition.
Such additional compounds can include various inorganic and organic filler
compounds, wood dust, reinforcing fibers, dyes, pigments, stabilizers, lubricants,
anti-microbial additives, and the like,
Plasticizers 'are typically mixed with a polymer by mixing at temperatures
that are above or below the melting point of the polymer. Plasticizers can also be
introduced with a help of an optional volatile solvent. Many variations of
techniques for introducing plasticizer compounds to polymer compositions are
known in the art,
For use as plasticizers, compounds of formula (3) and {4) are preferably
selected from compounds wherein R3 and R6 are C1-C23 linear or branched alkyls,
and preferably C1-C12. Specific choices for R3 and R6 depend on the polymer
selected for plasticization and on the intended properties and application.
The glyccrol ketal levulinic adducts of formula (3), (4)s and (5a) are useful
as plasticizer compounds for PVC, poly(3-hydroxyalkanoates), poly(lactate), and
various polysacchamte polymers. Compounds of formula (3), (4) and (Sa) are
compatible with, these polymers across abroad range of concentrations.
Compounds of formula (4) and (5a) are preferred for plasticization of PVC, as
plasticizers with a substantial content of free hydroxyl group are generally not
desired in compounded PVC resins due to stability problems of the PVC resin. By
selecting various R3 and R6 moieties in the reactants used in the synthesis of these

adducts, it is also possible to fine-tune the properties of the plasticizer not only In,
respect to best plasticixation properties and best compatibility, but also in respect to
the barrier properties of the resulting polymer, e.g., its permeability to moisture,
gases, solvents, water leaching, and odor and state retention. Depending on the
desired properties, compounds of formula (3), (4), and (5 a) can be used at various
concentrations, typically, between. 5 and 80% by weight of the plasticized polymer
composition. However, in practice it is sufficient to provide 5 to 25% by weight
plasticizer to achieve significant lowering of the glass transition point and thus
obtain useful polymeric compositions. The plasticizer compounds (3), (4), and (5a)
can be used as individual compounds or as mixtures, including mixtures comprising
other plasticizers known in the art such as aromatic and aliphatic diearboxylic
esters, epoxidized triglycerides, and the like;
Synthesis of polymeric glycerol levulinate ketal compounds from the monomers of
The compound of formula (5) and the compounds of formulae (3) and (4),
inclusive of compounds with defined cis- or trans- stereochemistry, such as (3a),
(3b), (4a), (4b), can be further polymerized to provide for a variety of co-polymer
compositions of glycerol and levulmate having at least one unit of formula (6):

wherein q is an integer.
The cyclic ketal-lactone compounds of formula (5) and (Sa) are particularly
suitable for use in polymerization under ring opening living polymerization
conditions. Such conditions are well known in the art and are known to yield high .
molecular weight melt-processable polymers suitable for a variety of uses in the
manufacturing of various plastics and. fibers.. For example, U.S. Patents Nos.
5,028,667, 5,292,859, 5,095,098, and 5,210,108 contain descriptions of catalysts
and methods of use suitable for carrying out living polymerization of various

lactones and mixtures thereof. Similarly, J, Macromolecules (2001, 34, 864,1 -8648)
contains a description of conditions and catalysts for polymerizing dioxanones.
These conditions and catalysts have beeri found to be useful in the polymerization or
co-polymerization of compounds of formula 5 and/or 5(a) to form perfectly
alternating ketal-ester copolymers of glycerol and levulioate comprising the cis-unit
of formula (lb). Such polymers are clear thermoplastic transparent polymers that
can be obtained in a practically colorless form and can be melt-processed, extruded,
'cast, and rolled to a variety of shapes.
Synthesis of polymers comprising the unit of formula (6) are not limited to
living polymerization. The hydroxyesters (3) and diesters (4) can also be converted
to useful polymers comprising at least one unit of formula (6) by a
polycondensation reaction in the presence of a suitable catalyst. The art of synthesis
of various polyesters by polycondensation is old and many examples of suitable
catalysts are known.. It has been found that many known catalysts for the synthesis
of polyesters can be used to make polymers comprising at least one unit of formula
(6). Non-limiting examples of suitable catalysts include alkali and transitional metal
aikoxides, germanium oxide, alkali metal alkoxides, sodium, and acids. Further
examples include various alkoxldes of titanium and tin (H) octanoate. Other
descriptions of catalysis and methods of their use can be found, for example, in
United States Patents Nos. 4,133,800, 4,205,157, 4,208,527.5,028,667,5,095,098,
5,210,108, 5,208,2.97, 5,202,413, 5,292,859 5,342,969, 5,565,545, 6,828,272, and
references cited therein.
The compounds of formulae (3) and (4), inclusive of compounds with
defined cis- or tram- stereochemistry, such as (3a), (3b), (4a), and (4b), are typically
polymerized in the presence of an effective quantity of a polycondensation catalyst,
and under conditions allowing for the removal of an alcohol (R3OH) or an ester
(R6COOR3) by distillation. For polymerization of these compounds, it is preferred
(but not necessary) that the R3OH alcohol is a primary or secondary alcohol, and it
is also preferred that the ester of formula R6COOR3 and/or the alcohol R3OH that
form during polycondensation have boiling points sufficiently below-the boiling

point of the monomers of formula (3), (4), and/or(5) so that they can be removed.
with ease from the body of the forming polymer.
The polymerization.; reactions can be carried out in the presence of an inert
solvent, or in a neat form,. Preferred non-limiting examples of solvents are
hydrocarbons, haJogenated hydrocarbons, and ethers..
The properties of the resulting polymers differ, depending OH the degree of
polymerization and the stereochemistry of the monomers used in their synthesis. .
The ester-ketal polymers of glycerol and levulinate comprising the unit of
formula (6) are useful as polymeric plasticizers with various polymers. For
'example, these polymers are used for plasticizing PVC, polyesters such as PHA,
PHB, and PLA, and polysaccharides such as acylated cellulose. For plasticization
of these polymers,, the ester-ketal polymers of glycerol arc blended with
unplasticized polymers typically at elevated temperatures, sufficient to melt or-soften
the ingredient with the highest melting point, and preferably, under Inert, atmosphere
(to minimize any decomposition of the polymer plasticized). Plasticization with
these compounds can also be accomplished with the aid of a solvent that is typically
removed after a homogeneous blend is obtained. Plasticized compositions may
contain other additives such as stabilizers, inorganic and organic fillers, reinforcing
fibers, pigments, dyes, and the like, Plasticized compositions comprising the
polymers having ester-ketal repeat units of formula (6) can be cast or molded or
extruded into films, fibers, tubing, pipes, and other objects of various shapes that are
typically used to produce various consumer and industrial products from, other
known plastieized compositions of PVC, PHA, PHB, PLA, and polysaccharides.
Reaction of glycerol levulinate ketal compounds with epoxides of normal alpha-
olefins
In another embodiment, the compounds of formula (3) are reacted with
epoxid.es. Preferably, the compounds of formula (3) are esters and not free acids or
salts. The epoxides are epoxides of normal alpha-olefins (NAO) or epoxidized
unsaturated fatty acid esters.

The first set of reaction products can be formed fey the reaction of
compounds of formula (3) and NAO epoxides. The resulting products have a
formula (7):

wherein R3 is a linear, branched, or cyclic alkyl or alkenyl, aryl, aralkyl, or
alkyloxyalkyl, and one of R7 or R8 is hydrogen and the other Is a C6-C30 linear alkyl,
Preferably, a C6-C14 linear alkyl.
Compounds of formula (7) are prepared from the 1,2-epoxides of MAO
having formula (8):.

wherein R9 is a C6-C30 linear alkyl, and preferably, a C6-C30 linear alkyl
The compounds of formula (8) are reacted with' the compounds of formula
(3) in the presence of an acid catalyst, and optionally, an inert co-solvent
Typically, catalysts for reacting epoxides with the compound of formula (3)
include various acids that are known in the art. Such conditions are generally
applicable to the reactions of the compound of formula (3) with Epoxidized
unsaturated fatty acid esters.. Non-limiting examples of such catalysts include
strong mineral acids, such as sulfuric, hydrochloric, hydrofluoroboric, hydrobromic
acids, P-tolueiiesulfonic acid, camphorosulfonic acid,, metfaanesulfonic acid, and
like, Various resins that contain psotonated sulfonic acid groups are also useful as
.they can be easily recovered after completion of the reaction. Examples of acids
also include Lewis acids.. For example, boron trifluoride and various complexes of
BF3, exemplified by-BF3 diethyl etherate, are also useful. - Examples of other Lewis
acids include anhydrous SnCl2, SnCl4, TiCl4, AlCl3, silica, acidic alumina, titania,
zirconia, various acidic clays, mixed aluminum, or magnesium oxides, and the like.
Activated carbon derivatives comprising mineral acid, sulfonic acid, or Lewis acid
derivatives can also be used.

The present disclosure is not limited to a specific catalyst or an amount of
catalyst. One of ordinary skill in the art can practice many variations on the part of
the catalyst composition and the amounts used in the preparation described herein.
Elevated temperatures may be -used to accelerate the reaction with less reactive
catalysts, however, the tempera toe of the reaction mixture is not critical for
succeeding in making a quantity of the glyceryi ether product, as even with less
active catalysts the reaction still proceeds to yield the desired compounds. Amount
and type of catalyst depends on the specific chemical composition of the epoxide
and of the compound of formula (3) used in the reaction, and can be readily
established by one skilled in the art.'
The reaction with epoxides can be carried out in the presence of an optional
co-solvent that is inert under reaction conditions and is typically removed at the end
of the reaction by distillation. Typically, it is desired to use a sufficient quantity of a
co-solvent or a reactant, such as the compound of formula (3), to minimize cross-
linking of the epoxides via ether bond formation. Non-limiting examples of suitable
co-solvents include saturated hydrocarbons,-ethers, and polyethers. Typically, any
excess solvent and un-reacted starting material are removed after completion of the
reaction by distillation at normal or reduced pressure. It is also preferred to
neutralize or otherwise remove the acid catalyst prior to distillation.
Because the compounds of formula (3) are very good solvents for NAO
epoxides, the reaction between epoxide and the glycerol derivative of formula (3}
can also be conveniently conducted in the excess of the latter compound, typically at
2 to 20 times molar excess. When insufficient excess of the compound (3) is used,
oligomeric polyether adducts of epoxide and the compound of formula (3) are
formed.
The compounds of formula (7) are further converted by saponification to the
alkali or alkali-earth metal salts of the carboxylic acid having formula (7a).


Saponlfication is typically carried out in water or water-alcohol mixtures in
the presence of a sufficient amount of alkali or alkali-earth metal hydroxide or
carbonate, and after removal of any excess of the compound of formula (3) and/or
co-solvent, e.g. by distillation under reduced pressure. The salts of the compound
of formula (7a) can, be stored and used in an aqueous solution, or, after evaporation
of water and any volatile co-solvents, in a substantially anhydrous neat form.
Reaction of glycerol levulinate ketal compounds with epoxides of unsaturated fatty
acid esters
Another set of compounds is provided herein by using reaction of the
compound of formula (3)-with epoxides of unsaturated fatty acid esters. Preferably,
the compounds of formula (3) are esters and not free acids or salts. These epoxides
are prepared in the manner substantially similar to the above-described methods for
making compounds of formula (7) from the NAO epoxides of formula (8).
Unsaturated fatty acids mean linear monocarboxylic acids having from 10 to
24 carbon atoms and at least one double bond. The double bonds can be in any
position, conjugated with each other or non-conjugated, but not in allenic
arrangements, and any of the double bonds can be independently cis or trans.
Preferably, unsaturated fatty acids have one to three double bonds. Fatty acids can
also be composed of a mixture of various unsaturated and saturated fatty acids, for
example, as in the triglycerides of various vegetable oils, fish oils, and palm oils.
Esters of unsaturated fatty acids mean esters of the above-described fatty
acids with monohydric or with polyhydric alcohols.
Monohydric alcohols are linear or branched primary or secondary alkanols
or alkoxyalkanols having from 1 to 12 carbon atoms. Preferred examples of
alkanols are methanol, ethanol, propanol, isopropanol, butanol, secondary butanol,
isobutanot, isoarayl alcohol, 2-ethylhexanol. Preferred alkoxyalkanols are primary
or secondary alcohols having from 3 to 12 carbon atoms, wherein a linear, branched,
or cyclic aikoxy group having from 1 to 8 carbon atoms is located at a vicinal
position to the hydroxyl group. Such alkoxyalkanols are typically derived by
opening an atkyl oxirane with an. alkanol Another suitable example of an

atkoxyalkanol is tetrahydrofurfuryl alcohol readily accessible via hydrogenatton of
furfural. The most preferred are morsobydric alcohols due to their availability, cost
and'Satisfactory stability of their esters.
Polyhydric alcohols are linear or branched polyhydroxylated alkanes having
from i to 6 hydroxyl groups. Typical examples are ethylene glycol, propylene 1,2-
and 1,3-diots, butylerse glycol isomers, glycerol, 1,2,4-trihydroxybutane,
pentaerythritol, xylitol, ribitol, sorbitol, mannitol, and gaiactitol Polyhydric
alcohols can optionally contain, one or more ether bonds, and suitable examples of
such polyhydrie alcohols are isosorbide, sorbitane isomers, and diglycerol.
It is preferred that substantially all hydroxy! groups of the polyhydrie
alcohol are esterified with an tmsaturated fatty acid group. It is understood that in
the industrial practice it may not be practical to achieve a Ml esterification. It is
also understood that in -the industrial practice, where mixed fatty acid compositions
are used, not all of the fatty acid groups can be unsaturated arid some fully saturated
fatty acid groups can be present. In fact, it is cost-advantageous to use mixtures of
unsaturated and saturated fatty acid esters such as present in triglycerid.es of typical
vegetable oils (e.g. soybean oil, linseed oil, canola oil, safflower oil, sunflower oil,
corn oil, castor oil, their blends and the like); It is preferred, however, that the
mixed fatty acid esters contain predominantly unsaturated fatty acid esters. It is also
preferred that a fatty acid .tester with a high content of mono-unsaturated fatty acid
ester is used, such as compositions found in high oleic canola oil. Esters of 10-
undecylenic acid are also preferred. Another preferred starting material is a mixture
of methyl esters of fatty acids derived by trans-esterification of vegetable oils (e.g.,
of soybean oil, canola oil and other unsaturated triglycerides commonly used in the
industrial production of various biodiesel fuels).
Various unsaturated fatty acid esters can be optionally blended, mixed,
partially hydrogenarated, or otherwise isomerized to change position or
stereochemistry of the double bonds.
Epoxidized unsaturated fatty acid ester means that at least one of the double
bonds of the unsaturated fatty acid ester is oxidized to an epoxy group. Such
oxidations are well known in the art and can be readily accomplished in an

industrial scale, e.g., by using hydrogen peroxide and a carboxylic acid (e.g.,
formate or acetate), or by the balohydrin method. It is preferred however, that
epoxidation. of a majority or all of the double bonds present in the unsaturated fatty
acid ester is accomplished. It is understood that in practice, epoxidized fatty acid
esters may contain various quantities of by-products arising from, hydrolysis or
rearrangement of epoxides and from cross-linking of the fatty acid chains. Use of
epoxidized fatty acid esters containing small quantities of epoxidation by-products
and epoxide decomposition by-products is fully within the scope of the present
disclosure,
Ethers derived from epoxid.es of mono-unsaturated fatty acid esters and
compound of formula (3) have formula (9);

wherein R3 is a linear, branched, or- cyclic alkyl or alkenyl, aryl, aralkyl, or
alkyloxyalkyl, one of A or B is H and the other is an esterified carboxyl, and n and
m are integers each having values from 0 to 20, and the value of the sum of m+n is
in the range.from 3 to 21.
When bis-epoxides or tris-epoxides of unsamrated fatty acid esters having
epoxy groups positioned in a close proximity to each other are used, an intramolecular
epoxidc opening reaction takes place, resulting in the formation of one or
more ether bonds each connecting two carbon atoms of the continuous fatty acid
carbon chain. Typically, such ether bonds result in the formation of a
tetrahydrofuran (major) and tetrahydropyran (minor) rings. Thereby forming
complex, mixtures of the stereoisomers of oxygenated derivatives of unsauurated
fatty acid esters comprising pendant ether groups derived from the compound of
formula (3).

For example, representative isomers of the such surfactant products from a
bis epoxide derived from adi-unsaturated fatty acid having two double bonds
separated by a methylene group have formulae (10a) and (10b):

Compounds of formula (10a) and (10b) axe typically formed as mixtures that
also comprise other adducts such as di(glycery1 levulinate keta!) ether adducts
resulting from opening of each of the epoxy groups with a different molecule of the
compound of formula (3), resulting in oxygenated fatty acid derivatives comprising
two hydroxyl groups and two pendant ether (glyceryl levulinate ketal) groups.
Preferably, the ether adducts of epoxidized fatty acid esters arc formed by
the reaction of the compound of formula (3), in the presence of a catalyst, followed
by the removal of any excess compound of formula (3) and any co-solvent by
distillation, under reduced pressure:
Alternatively, the adducts of epoxidized unsaturated fatty acid esters and
compound of formula (3) can be prepared by treating epoxidized triglycerides with
the compound of formula (3) in the presence of a catalyst. In such alternative
embodiment, triglyceride polyol compounds are formed, These compounds have
free secondary' hydroxyl groups and (glyceryl levulinate ketal ester) ether pendant
groups attached to the fatty acid chains. Optionally, ether bonds may also be
present in such adducts and the ether bonds can connect two carbon atoms of one
fatty add chain (thereby forming a tetrahydrofuran or tetrahydropyran ring) or two
different fatty acid chains.
Such adducts of glycerol, or of a ketal/acetal protected glycerol, with the
epoxidized triglycerides are typically prepared from known, in the art epoxidized
soybean, oil, linseed oil, and the like. These'adducts are found herein to be useful to

produce compounds of formulae (9), (10a)» and (10b) The conversion of the
triglyceride adducts to the compounds of formulae (9), (10a), and (10b) can be
accomplished by a trans-esterification reaction with a moeohydric alkanol in the
presence of a catalytic amount of base. The non-limiting examples of syllable bases
are hydroxides of alkali or alkali-earth metals or alkoxides of alkali metals and
alkanols.
The carboxyl group in the ether adducts of compound (3) and the
hydroxylated fatty acid esters can be further subjected to saponification to furnish a
salt (typically, alkali, alkali-earth, ammonium, or arninc salt of the dicarboxylic
compounds having formulae (11), 12(a), and 12(b):

wherein one of E or D is hydrogen and the other is carboxyl. Alternatively, the salt
compounds of formulae (11), 12(a), and 12(b) are obtained by direct saponification
of the adduct of the compound of formula (3) with epoxidized trig!ycerides.
The carboxyl group of the compounds of formula (7 a), (13), 12(a), and 12(b)
or of the compounds of formulae (7), (9), (10a), and (10b) can also be amidated with
a primary or a secondary alkylamine or an aminoaicohol.
The alkali metal salts, alkali-earth metal salts, amine or ammonium salts, and
amides of the carboxylic acids of formulae (7a), (11), 12(a), and 12(b) are useful
ionic mild surfactants that can be used in various formulations.
The surfactants derived from the carboxyiic acids of formulae (7a), (11),
12(a), 12(b) are stable in cold and hot aqueous solutions in a broad range of pH
(e.g., pH 4 to pH 13). 'Their surfactant, emulsifying, and micelle-forming properties

are not negatively affected by the presence of alkali-earth metal ions in the solution.
This makes them useful in formulations intended for use in hard water.
These compounds of can be used alone or in various combinations with
other surfactants, solvents., glycols, polyols, fragrances, colors,,biologically-active
and inert additives, enzymes, and wetting agents that constitute the base
compositions of preparations used in cleaning, dishwashing, laundry, cosmetic and
personal care products, degreasing preparations, and the like. Effective
concentrations for use of the surfactant compounds of coropoends derived from the
carboxylic acids of the formulae (7a), (11), 12(a), and 12(b) depend on the intended
use of the formulation and can be easily established empirically by one of ordinary
skills in the art. The effective concentrations for these compotinds typically range
from 0.001 % to 100% of the formulated product
It has also been found that compounds of formulae (7), (9a), (10a), (10b),
and the adduct of the compound of formula (3) with epoxidized triglycerid.es are
also useful as plasticizers for .PVC, polyesters such as PHA, P.HB,. PLA, and
polysaccharides.
Co-polymers of glycerol levulinate ketals with other monomers
In another embodiment, glycerol ketal monomers selected, from compounds
having formulae (3), (4), (5) and (5a), and any stereoisomers thereof, can be used in
the synthesis of co-polymers with a variety of other monomers known in the art. It
has been foond that copolymers comprising the ketal repeat units of formula (1a)
have a broad range of physical properties, and can be prepared through a
condensation or trans-esterification reaction of the monomers of formulae (3), (4),
(5), and (5a) with one or more compounds selected from various polyhydric
alcohols, di and tri-carboxylic acids, hydroxyacids, and cyclic esters.
Non-limiting examples of useful polyhydric alcohels include dihydric
alcohols of linear or branched alkanes having from 2 to 20 carbon atoms, glycerol,
diglycerol, isosorbide, sorbitol, xylitol, erythritol, pentaerythritol, trimethylolethane,
trimethylol propane, diethylene glycol, neopentyl glycol, polyethers such as
hydroxyl-terminated poly(ethyleneoxide), poly(propyleneoxide), and the like.

Examples of suitable dicarboxylic acids include either free acids, lower alkyl
esters, or anhydrides of succinicic acid, maleie acid, adipic acid, isomers of phthalic
acids, trimellitic acid, citric acid,- itaconic acid, and isomers of naphthalene
dicarboxylic acid.
Examples of hydroxyacids and esters thereof can also be used as co-
polymers, and can include lactic acid,, glyeolic acid, 3-hydroxypropionic acid, and
3-hydroxyalkanoic acids.
Hydroxyacids can be further exemplified by hydroxylated derivatives of
fatty acids and esters thereof, including triglycerides. Such hydroxylated fatty acid
esters including polyhydric hydroxyl derivatives known in the art have been.
obtained, for example, by reacting epoxidized fatty acid esters with one or more
compounds haying a hydroxyl group, wherein one or more of the ox inane groups is
subjected to an epoxide opening reaction.
Suitable hydroxyacids can be further exemplified by hydroxylated aromatic
carboxylic acids such as hydroxylated'benzole acids, toluic acids, naphthoic acids,
cinnamic acids, ferralic acid, and the like.
Lactide, glycolide, 1,4-dioxan-2~ones, alkylated 1,4-dioxan-2-ones, epsilon-
caprolactone, and 1,4-d doxepan-2-ones are suitable non-limiting examples of cyclic
esters.
Among other suitable co-monomers for making co-polymers of glycerol
lesvulinatc ketals comprising the repeating units of formula (1a) include compounds
of formulae (7),(9), (10a), (10b), and also, compounds of formula (7b):

wherein R3 is a linear, branched, or cyclic aikyi or alkeny], aryl, aralkyl, or
alkyloxyalkyl, and one of R7 or R8 is H and the other Is hydrogen, or a C1-C30 linear
alkyi.
Compounds of formula (7b), compounds with linear alkyls of shorter than 6
carbon atoms can be prepared by reacting compounds of formula (3) with
corresponding linear alkyl epoxides in a way substantially similar to that described

above for the preparation of the compound (7). Conditions 'for the reaction of a
compound of formula (3) with volatile epoxides such as propylene oxide and
ethylene oxide, include conducting the reaction under pressure.
Co-polymer preparation from the monomers of formulae (3), (4), (5), and
(5a) and one or more compounds selected from polyhydric alcohols, di and tri-
carboxylic acids, hydroxyacids, and cyclic esters can be accomplished by using one
or more of the catalysts and conditions described above for the preparation of
homopolymers comprising fee repeating unit of formula (la). The resulting co-
polymers cart be terminated with either hydroxyls or esterified earboxyls. Polymers
can be linear, branched, star-shaped, or cross-linked, and can be random co-
polymers, block copolymers, graft copolymera, or any combination thereof.
Of particular interest and utility are the hydroxyl terminated polymers and
co-polymers comprising the repeating units of formula (la). Such compounds have
been found to be useful for making polyurethane polymers with widely varying .
properties,
Many polyurethane polymers and methods of their preparation are known in
the art. Polyurethane polymers 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.
Many of the polymers comprising the repeating unit of formula (6) are
useful for making polyurethane polymers,. For use in polyurethane synthesis, a
polymer comprising the repeating unit of formula (6) can be prepared in a hydroxyl-
terminated form, wherein two or more hydroxyl groups are present on average per
representative polymer structure. This is typically accomplished by carrying out
the polymerization reaction with at least one monomer selected front the
stereoisorners of compounds of formula (3), (4), (5), and (5a) in the presence a
sufficient amount of a co-polymer polyhydric alcohol having two or more hydroxyl
groups, so that polymerization product has preferably an average molecular weight
in excess of 500 Da, more preferably, in excess of 1000 Da, and has two or more

hydroxyl groups. The resulting polymerization product comprising the unit of
formula (6) can be a linear, branched, cross-linked, or star-shaped polymer. One or
more of such polymerization product comprising the unit of formula (6) can then be
used as polyol compounds in a reaction with one or more isocyanate compounds
having two or more isocyanate groups. Many suitable isocyanate compounds are
known in the art of polyurethane synthesis. Non-limiting examples of isocyanate
compounds include diisocyanate compounds such as tolylene diisocyamte isomers,
hexarrsethytene diisocyanate, pentameihylene diisocyanate, isophorone diisocyanate,
4,4'-methyleebis(phenyl isocyanate), and the like. Further non-limiting examples
of isocyanate compounds include poJyisocyanate compounds, and can be obtained
by reacting one of the above diisocyanate compounds with a polyhydric alcohol or a
polyhydric amine. Non-limiting examples of suitable polyisocyanatc compounds
also include adducts of one or more diisocyanate compounds obtained by reacting
one or more of the polyhydric products comprising the repeating unit of formula (6)
under conditions sufficient to cause reaction between the hydroxyl group and an .
isocyanate group.. It has been found that such polyisocyanate compounds can be
obtained by mixing appropriate quantities of various aliphatic and/or aromatic
diisocyanate-compounds with a polyhydric alcohol comprising the repeating units of
formula (6), and causing reaction to occur by means of heating and/or with catalysts
sufficient to accelerate the reaction. Non-limiting examples of typical catalysts
suitable for making the polyisocyanate compounds include dibutyl tin dilaurate, 1,4-
diazabicyclo[2.2.2]octane (DABCO™, TED), and the like, The .reaction of making
a polyisocyanate compound from a polyhydric alcohol comprising the units of .
formula (6) can be carried out in the presence of an inert solvent, which may
optionally be removed at the end of the reaction by distillation.
One or more of the polyhydric alcohols comprising a repeating unit of
formula (6) can then be reacted with one or more isocyanate compounds having two
or more isocyanate groaps per representative molecule, thereby providing for a
polyurethane polymer comprising one ore more units of formula (6) per
representative polymer molecule.

Such reactions occur readily under conditions typically known to those in
the art of palyurethane synthesis, and include use of one ore more catalysts known
in the art and/or elevated temperatures. Non-limiting representative examples of
typical catalysts include dibutyi tin diiaurate and DABCO. Elevated temperatures
expedite formation of the desired polyurethane polymer, and typically, temperatures
between 30 and 160°C are sufficient to commence and accelerate the reaction. The
reaction can be conducted at temperatures outside of the specified range, however,
at lower temperatures, the reactions may be quite slow, while at higher
temperatures, side reactions and partial polymer decomposition may occur, in
general, preparation of polyurethane polymers comprising repeat units of formula
(6) is an exothermic reaction and is successful without additional heating. Synthesis
of polyurethane polymer comprising units of formula (6) is preferably carried out
under substantially anhydrous conditions. If small quantities of water are present,
the product is typically a foam polymer comprising both urethane and urea linkages.
If a foam polymer is desired, the reaction is carried out using one more inert
propellant compounds known in the art.
Various polyurethane polymers comprising units of formula (6) can thus be
prepared and used to manufacture a plethora of polyurethane goods that in a way
substantially similar to polyurethane polymers known in the art. Pol yurethane
polymers comprising the units of formula (6) can be solid or viscous liquids, rigid or
flexible, and they can be prepared as thermoset or thermoplastic polymers.
Depending on the specific polymer composition, they can be cast, extruded, or
otherwise shaped in a variety of forms needed to manufacture finished polymer
goods. The polyurethane polymers comprising units of formula (6) can contain
various additives known in the art, such organic or inorganic fillers, pigments,
stabilizers, anti-oxidants, and lubricants
The polyurethane polymers disclosed herein are made with use of low-cost
renewable monomers to provide the predominant part of the weight of the resulting
polymers, thereby offering a cost advantage when compared to the known in the ait
polyurethanes made predominantly or exclusively with use of non-renewable
petroleum- or coal-derived monomers.

The polyurethane polymers comprising units of formula (6) are also
recyclable at the monomer level. If so desired, at the end of their useful life, the
polyurethane polymers comprising the units of formula (6) can be treated by a trans-
esterification reaction, to allow for the decomposition of the polymers and the
formation of one or more monomers of formulae (3), (4), (5), and (5a), which can be
recovered, purified and re-used.
EXAMPLES
Example 1
36 g of levulinic acid of 98% purity, 28 g of glycerol of 99% purity, 0.08 ml
of concentrated sulfuric acid, and 60 ml of n-beptane were stirred in a round bottom
flask equipped with a Dean-Starks adapter. The whole was brought to reflux by
means of heating in an oil bath, and was refluxed for approximately 36 hours or
until about 11ml of water was collected in the trap of the adapter, The reaction
mixture was neutralized by the addition of 0.2 g of calcium carbonate. The heptane
was removed, and reaction mixture cooled, yielding approximately 53.2 g of a very
viscous, pale-brownish, honey-like polymeric adduct that comprised compounds
having structural repeating units of formula (1).
Example 2
20,3 g of the polymeric adduct prepared in Example 1 was dissolved in SO
nil of methanol containing 0.4 g of sodium methoxide. The resulting solution, was
stirred at room temperature, allowing, for small quantities of. free glycerol to separate
on the bottom and on the walls of the reaction flask. The solution was filtered
through a fiberglass wool plug, neutralized by vigorous stirring for 30 min with 2 g
of anhydrous potassium dihydrogen phosphate, diluted with 100 ml of methyl tert-
butyl.ether (MTBE), and dried over anhydrous sodium sulfate. The solution was
then filtered. MTBE and excess methanol were removed under reduce pressure,
yielding 23.1 g of clear, slightly yellowish, practically odorless liquid that was
analyzed by gas chromatography-mass spectrometry (GC-MS). The liquid was
found to contain about 15% methyl levulinate and about 82% of the stereoisomers
of the compound having formula (14):


The stereoisomers o f the compound of formula (14) were detected as two
partially' separable peaks "on the GC chromatogram having approximately similar
integration areas. The peaks had the following representative mass-spectra:
A mass-spectrum of the compound eluting with retention time of
approximately 15.06 min;



Example 3
5 g of the reaction product obtained in Example 1 were mixed with 20 ml of
ethyl acetate and 0.2 g of potassium t-butoxide. The whole was stirred for about 45
min, and complete dissolution of the polymeric starting material was observed. The
reaction mixture was neutralized by stirring with 2 g of anhydrous potassium
dihydrogea phosphate for about 1 hr, dried over anhydrous sodium sulfate, filtered,
and the excess ethyl acetate was evaporated under reduced pressure. The resulting
oily, transparent, pale-yellowish liquid (6.2 g) was analyzed by GC-MS and was
found to contain approximately 14% of ethyl levulinate, approximately 25% of
hydroxyeshsr isomers of formula (16):


Example 4
5 g of polymeric adduct prepared according to Example 1, and 0.2 g of
potassium t-butoxide were stirred at 120-125 °C under vacuum (1mm, 2hr), artel
about 1 ml of clear distillate was collected. The distillate was analyzed by GC-MS
and was found to contain predominantly the Jaetone ketal of formula (5). The
compound of formula (5) had a representative electron ionization mass-spectrum
shown below:


10 ml of the hydroxyester of formula (14) obtained in Example 2 was heated
with stirring under vacuum (6 mm, 80 aC, 4 hours) until ethyl levulinatc was
substantially removed, as tested by GC-MS. The resulting liquid was mixed with 2
g of decene-1,2-oxide of 94%purity (Vicolox® 10 brand, Arkema Group), and a
complete dissolution, of epoxide 'was observed at room temperature, 0,025 ml of
boron trifluoride diethyl etherate was introduced into the stirred reaction mixture
and an exothermic reaction, was observed with the temperature rising briefly to
about 50 oC, The reaction mixture was stirred for 20 min and an aliquot was taken
for GC-MS analysis. The analysis showed complete conversion of the epoxide to
several stereo jsomers of the hydroxyester ketal compounds of formula (19a) and
(9b).


compounds (19a), (19b) (Example 7) or compounds (20a), (20b) (Example 8), 10
till of water was added to the resulting product mixtures, and the esters were ■ ■
saponified with slight excess of 0.1 N aqueous NaOH to give the corresponding
sodium salts in aqueous solution. These solutions had emulsifying and surfactant
properties that were not affected by the presence of 1 g/L calcium chloride or
magnesium chloride.
Example 9
Levulinic acid (98% purity, 697.3 g), glycerol (99% purity, 554,2 g),
concentrated sulfuric acid (0.2Sg), and a stirring bar were placed in. a weighted 2-
liter round-bottom evaporating flask, and the whole was set to rotate at 100 rpm on a
rotary evaporator equipped with an efficient vertical condenser cooled/to 4 oC, and a
vacuum was applied using a vacuum pump capable of providing an eventual
vacuum of 6 mm. The flask was rotated and heated using an oil bath with an initial
temperature setting of 80 °C. A rapid distillation of water was observed. After
approximately 130 ml of water was collected in a receiving flask, the bath
temperature was increased to 115 °C, and distillation of water was continued until
the rate of distillation had decreased to approximately less than 1 mL per 15 min.
The bath temperature than.was then, increased to 150 °C, and the reaction mixture
was heated under a 0.2 mm vacuum for 1 hour. The reaction was then stopped, and
the temperature of the reaction product was allowed to equilibrate to room
temperature. The resulting polymerization product (1054.3 g) at room temperature
was a. viscous, slightly brownish, sticky, syrup-like liquid, and was practically
insoluble in cold water.
The catalyst was then neutralized by adding 2 grams of dry sodium
bicarbonate, and by stirring the content of the flask on a rotary evaporator at 100 °C
for 2 hours, white a 6 mm vacuum was applied. The neutralized reaction product
was allowed to coo! to room temperature, and any insoluble inorganic matter was
allowed to settle. The resulting viscous liquid co-polymer was stored at room
temperature, and was used in subsequent examples in a decanted or filtered form, .

The resulting product was predominantly a polymer comprising the
repeating unit of formula (1).
Example 10
Levultnic acid (98% purity, 696.1 g), glycerol (99.5% purity, 607.5 g),
concentrated sulfuric acid (1.0 g)7 and a stirring bar were placed in a weighted 2-
liter round-bottom evaporating flask, and the whole was set to rotate at 100 rpm on a
rotary evaporator equipped with an efficient vertical condenser cooled at 4 °C, and a
vacuum was applied using a vacuum pump capable of providing an eventual
vacuum of 6 ram. The flask was rotated and heated using an oil bath with an initial
" temperature setting of 80 °C. A rapid distillation of water was observed. After
approximately 110 ml of water was collected in a receiving flask, the bath
temperature was increased to 110 °C, and distillation of wafer was continued until
the rate of distillation had decreased to approximately less than 1 mL per 60 min
(this took approximately 5 hours). The reaction was- then stopped, and the
temperature of the reaction product was allowed to equilibrate to room temperature.
The resulting-polymerization product (3 087 g) at room temperature was a viscous,
practically colorless, sticky syrup-like liquid sparingly soluble in cold water.
The resulting product was predominantly a polymer comprising the
repeating unit of formula (1),
Example 11
Levulinic acid (98% purity, 700.1 g), glycerol (99.0 % purity, 607,4 g),
concentrated sulfuric acid (0,4 g), and a stirring bar were placed in a weighted 2-
liter round-bottom evaporating flask, and the whole was set to rotate at 100 rpm on a
rotary evaporator equipped with an efficient vertical condenser cooled at 4 °C, and a
vacuum was applied using a vacuum pump capable of providing an eventual
vacuum, of 6 mm. The flask was rotated and heated using an oil bath with an initial
temperature setting of 80 °C. A rapid distillation of water was observed. After
approximately 130 ml of water was collected in a receiving flask, the bath
temperature was increased to 105 °C, and distillation of water was continued until it

and practically subsided (approximately 6 hoars). The reaction was then stopped,
and the temperature of the reaction product was allowed to equilibrate to room
temperature.' The resulting polymerization product (1097 g) at room temperature
was a viscous, practically colorless, sticky, syrup-like liquid sparingly soluble in
cold water.
The resulting product was predominantly a polymer comprising the
repeating unit of formula (1).
Example 12
A mixture 1.05 mol of triacetyl glycerol, 2.1 .mol of glycerol,. 1.96 mol of
solketal, 2.65 mol of ethyl levulinate, 1.7 mol of levulinic acid, 0.4 mol of alpha-
angelica Jactone and 0.2 .ml of concentrated sulfuric acid was mapietically stirred ■
and heated under nitrogen to 100-105 °C in a round bottom flask equipped with a
water-cooled condenser. Distillation of a mixture of acetone, ethano), water,, acetic
acid and ethyl acetate was observed. Heating with stirring was continued until the
distillation alid practically subsided (about 16 hours). The resulting viscous,
transparent, slightly yellowish liquid was poured into a 2 h evaporation flask, and
the whole was heated on a rotary evaporator to 110-115 °C at a reduced pressure
using a vacuum pump capable of providing an eventual vacuum of 6 mm. After
distillation of the water and vplatiles has subsided (approximately 6 hours), the
resulting viscous polymerization product (939 g) was cooled down to room
temperature.
The resulting product was predominantly a polymer comprising the
repeating unit of formula (1).'
Example 13
A mixture of 1.02 mol of glyceml, 2,95 mol of levulinic acid and 0,2 g of
sulftiric acid was heated on a rotary evaporator to 80-90 °C at a reduced pressure a
vacuum pump capable of providing an eventual vacuum of 6 ram, until distillation
of water had practically subsided. The resulting product (385 g) was a mixture of

ester products comprising predominantly trilevttliiioyl gjyccrol and 1,2-dilevulinoyl
glycerol.
Example 14
The synthesis was carried out according to Example 11, except that the
starting reaction .mixture additionally contained 40.2 grams of a mixture of glyceryl
esters prepared according to example .13. The resulting product (1139 g) was a
glycerol-branched polymer comprising the repeating unit of formula (I),
Example /5
The synthesis was carried, out according, to Example 14, except the added
amount of ester prepared according to the Example 14 was 82.2 g. The resulting
polymer (1226 g) was a glycerol-branched polymer comprising tfie repeating unit of
formula (1). ■ '
Example 16
1021 g of the polymeric product comprising the repeating unit of formula (1)
prepared according to Example 11 was slowly poured (over period of 1 hour) into a
stirred reactor containing 1.2 liters of a methanolic solution containing 6 grams of
sodium methoxide. After stirring at room temperature for S hours, the content of the
reactor were collected., and the methanol was evaporated at reduced pressure using a
rotary evaporator. The resulting yellowish-orange liquid was transferred to a
separatory forme! and thoroughly mixed, with 0.8 L of tert-butyl methy! ether. The
contents were allowed to stand for 4 hours and separate into two layers. The lower
level containing primarily glycerol, sodium salt of compound (3), wherein R3 its H,
and small quantities of sodium levulinate, was discarded,.and the upper layer was
stripped of the tert-butyl methyl ether using a rotary evaporator. The resulting
slightly yellowish liquid (992 g) was analyzed by GC-MS and was found to contain
approximately 12% of methyl levulinate, approximately 80% of the compound of
formula (3), wherein R3 is methyl, as a mixture of approximately equal amounts of


cis- arid trans-isomers, and small quantities of the compound of formula (5) and
stereoisomers of compounds having formulae (21) and (22) (ca, 1 % each):
The resulting mixture of stereoisomers of compound of formula (3) was
further purified by removal of methyl levulinate at a reduced pressure, and then
further purified by distillation using a falling film column under 0.5-1 millibar
vacuum and a temperature set at 130 °C. The residual undistiiled compounds 21
and 22 were collected and treated with methanol containing 0.2% sodium
methoxide, to yield a 20:80 mixture of methyl levullnate and the compound of
formula (3).
Example 17
The reaction was carried! out. according to Example 16, except that ethanol
was used in the reaction instead of methane!, and the starting polymeric product
(732 g) was prepared according to Example 12, The resulting product was analyzed
by GC-MS and was found to contain approximately 9% of ethyl levulinate and 88%
of the compound of formula (3), wherein R3 is methyl, as a mix tare of
approximately equal amounts of cis- and trans- isomers. The compound of formula
(3) was then further purified hy distilling out ethyl levulinate at a reduced pressure.
Example 18
301,2 g of the polymer prepared according to Example 9 were stirred with
500 ml of n-butanol containing 6 grams of sodium hydroxide at room temperature
for 24 hours. The resulting transparent yellowish solution was stripped of excess n-
butanol on a rotary evaporator "under reduced pressure, and the whole was mixed

with 600 ml of n-heptane in a separatory funnel The lower layer, containing .
primarily glycerol and sodium levulinate and the sodium salt of the compound of
formula (3), wherein R3 is B, was-discarded, and the upper layer was filtered
through a paper towel. The resulting practically colorless filtrate was stripped of
heptane on a rotary evaporator, to yield a clear colorless liquid (385 g) that was
analyzed by GC-MS. The liquid was found to contain approximately 24% butyl'
levulfinate and approximately 73% of a 1:1 mixture of cis- and trans-isomers of the
compound, of formula (3), wherein R3 is n-butyt
The compound (3) was then further purified by distilling out butyi Jevulinate
at a reduced pressure.
Example 19-23
5 grams of a, 1.2:1 cis-trans Isomer mixture of the compound of formula (3),
prepared according lo Example 16 , wherein R3 is methyl, (96% pure, purified by
distillation) were dissolved in 20 ml of each of the following:
(19) absolute ethanol with approximately 0.2% w/w sodium ethoxide,
(20) anhydrous n-butano) with approximately 0.2% w/w sodium n-botoxide,
(21) anhydrous isobutanol with approximately 0.4% sodium isobutoxide,
(22)anhydrous isoansyl alcohol with 0.3% sodium 3-methyl butoxidc,
(23) 2-ethylhexyl alcohol with 0.3% sodium 2-ethylhexoxid.e.
The solutions were stirred for 12 hrs by means of magnetic stirring at room
temperature (26 °C), Progression of the trans-esterification reaction was monitored
by analyzing small aliquots of the reaction mixtwes by GC-MS. Formation of
esters of formula (3) was observed, wherein R3 is ethyl (Example 19) n-butyl
(Example 20), isobutyl (Example 21), isoamyl (Example 22), and 2-ethylhexyl
(Example 23). The reaction did not result in any significant change of the cis/trans
isomer ratio. After trans-esterification was complete the reaction mixtures were
neutralized by stirring for 8 hours with finely powdered potassium dihydrogen
phosphate, and filtered. Excess alcohol was distilled from each sample under
reduced pressure, thereby yielding the compounds of formula (3) in heat form as

a beaker and was allowed to cool. The polymeric product formed was a viscoelastic
thermoplastic teal-ester polymer comprising repeating units of formula (6) with a
melting point to .65-70 oC; it had a considerable brown discoloration.
Example 26
The polymer synthesis was carried out according to- Example 25, except 0.08
g of titanium (IV) isopropoxide was used instead of sodium metboxide, and the
reaction was carried out at 220-240 °C for 3 hours. The content of the flask became
viscous. A small polymer specimen, was drawn front the flask, cooled and triturated
with t-butyl methyl ether to determine the presence of starting monomer and any
oligomers by GC-MS analysis. The polymer was practically insoluble in this
solvent. The solvent extract was found to contain small quantities of compounds
(5), (5a), (21), and a trace of the stereoisomers of acyclic oligomers of formula (23):

wherein t is an integer having value from 2 to. 4, and R1 is methyl.
. Next,, a 6 ram vacuum was applied, and the temperature was raised to 260-
280 °C for about 1 hoar. The,-reaction mixture was allowed, to cool to about 140 °C
under vacuum, and then about 24 grams of the molten.-polymer was poured out of
the flask into a beaker. The resulting product was a transparent, practically
colorless, viscoelastic thermoplastic polymer comprising repeating units of formula
(6), The polymer had a melting point in the range of 70-75 °C- The polymer
remaining in the flask (15 g) was used in the subsequent examples.-
. Example 27 ... .
Example 27A
The polymer synthesis was carried out according to Example 25, except that
46 g of the compound of formula (3) having a cis/trans isomer ratio of 12:88 was

used. The resulting product (36 g) was a transparent, practically colorless,
viscoelastic, thermoplastic polymer comprising repeating units of formula (6). It
had a melting point in the range of 85-90 °C,
Example 27B ' '
The polymer synthesis was-carried out according to Example 25, except that ;
41 g of the compound of formula (3) having a cis/trans isomer ratio of 92:8. The
resulting product (29 g) was a transparent, practically colorless, viscodastic,
thermoplastic polymer comprising repeating units of formula (6). It. "had a melting
point in the range of 90-95 °C.
Example 28
The polymer synthesis was carried out according to Example 25, except that
44 g of the compound of formula (3) having a cis/trans isomer ratio of 52:48,
wherein R3 is n-btttyl was used. The resulting, product (26 g) was a transparent
practically colorless viscoelastlc thermoplastic polymer comprising repeating units
of formula (6), It had. a melting: point in the range of 72-77 oC.
Example 29
15 g of the polymer prepared in Example 24 were heated in a round bottom,
flask equipped with a magnetic stirrer, a short-path distillation head, and a receiving
Mask in an oil bath maintained at 280-300 °C under vacuum using a pump capable
of providing art eventual vacuum, of 0,08 mm. A distillation of clear transparent
liquid was observed, and approximately 6.2 g of distillate was collected la the
receiving flask cooled by means of an ice hath. The liquid was analyzed by GC-MS
and was found to contain approximately 62% of the compound of formula (5) and
approximately 34% of the compound of formula (5a).
The compound of formula (5a) had a representative electron ionization
mass-spectrum shown below:


The polymer remaining in the flask was trans-esterified with 20 ml of
methanol containing 0.2% of sodium methoxide. The methanolic solution was
analyzed by GC-MS were found to contain a 98% pure sample of the compound of
formula (3), R3-CH3, with the ratio of cis-trans- isomers of approximately 22:78,
Example 30
130.6 g of polymer repeating units of formula (6) prepared according to
conditions described in Example 25 were placed in a round-bottom flask and 0,3 g
of tin (II) 2-ethylhexanoate catalyst, were added. The flasks was equipped, with-a
magnetic stirrer, parged with nitrogen, and was heated to approximately 160 oC to
melt the content and dissolve the catalyst. Vacuum was applied using a pump
capable of providing an eventual vacuum of 0.1 mm, and the temperature of the
flask -was Increased to approximately 280-300 °C, Distillation of a clear, slightly
yellowish liquid was observed, and the distillate (58 g) was collected in a receiving
flask cooled by means of ice bath.
Tbe distillate was cooled and analyzed by GC-MS and was found to contain
approximately 57% of the compound of formula (5a) and 40% of the compound of
formula (5a). 46 grams of the resulting mixture of compounds were separated by
distillation under reduced pressure using a Kugelrohr-type apparatus providing a

fraction containing 22 grams of 96% pure compound of formula, (5), and a fraction
containing 14 grams of 94% pure compound of formula (5a), Both compounds
were obtained as colorless practically odorless liquids that-solidified to waxy solids
on prolonged standing,
The polymer remaining in the flask was trans-esterified with mcthanol
containing 0.2% of sodium methoxide. The methartolic solution was analyzed by
GC-MS and were found to contain, a 96% pure the compound of formula (3),
R3-CH3, with the ratio of cis-trans isomers of approximately 1.9:81.
Examples 31-32
2 grams of one of the compound of formula (S) or the compound of formula
(5a) were each dissolved in 10 ΜL of methanol containing 0. S% sodium methoxide,
and. the solution was stirred for 20 min at room temperature. The resulting solutions
were each analyzed by GC-MS and were found to contain a practically pure (over
99%) cis- isomer of the compound of formula (3b), R3=CH3.
Example 33
8.6 grams of the compound of formula (5) prepared according to Example
30 and 0.03 g of tin (II) Z-ethylfeexanoate were heated to 180-220 °C, with stirring
under nitrogen. The content of the .reaction mixture had become viscous, and after
45 min the .reaction was stopped, and the content of the flask was cooled to room
temperature. The resulting product was a polymer (8,3 g) comprising repeating
units of formula (6) predominantly having a cis configuration. The polymer was a
transparent, practically colorless, viscoelastic, thermoplastic polymer, with a
melting temperature in the range of 95-100 °C.

Examples 34-49 . '
Linear and branched co-polymers comprising repeating units of formula (6)
and having two or more ends of the polymer chains terminated with hydroxy]
groups were prepared by co-polymerizing 0.1 mol of 99.4% pure compound of
formula (3) (R3=CH3, 51:49 mixture of cis/trans isomers) and one of the following:
(34) 0.011 mol of 1,1,1-tris(hydroxymethyl)ethane,
(35) 0.006 moJ of 1,1,1 -tris(hydroxymethyl)ethane,
(36) 0.010 mol of 1,1 1-tris(hydroxymethyl)propane,
(37) 0.008 mo) of pentaerythritol,.
(39) 0.006 mol of glycerol,
(40) 0,002 mol of sorbitol,
(41) 0.003 mol of xylito],
(42) 0.006 mol of erythritol,
(43) 0.09 molof 1,4-butane diol
(44) 0.012 mol of diethylene glycol,
(45) 0.013 mol of 1,3-propanediol,
(46) 0.015 mol of neopentyl glycol
(47) 0.02 mol of polyethylene glycol of average mol. weight of 1,200 Da,
(4$) same as Example. 34, plus 0.001 mol of dimethyl adipate,
(49) same as Example 37, plus 0.002 mol of dimethyl terephthalate.
The polymerisation reactions were carried out in round bottom flasks
equipped with a vertical condenser and a distillation head with side arm attached to
a receiving flask. All reactions were carried out in the presence of titanium
isopropylsle (50 mg) as a catalyst, under nitrogen, by stirring, and Wealing the
reaction mixtures in an oil bath maintained at 220-230 oC for about 3 hours (until
distillation of methanol practically subsided). After that, the bath temperature was
reduced to about 160 °C, and the reaction mixtures were stirred for 1 hr under
vacuum using a pump capable of providing an eventual vacuum of 6 mm. The
resulting viscous, transparent, practically colorless liquids were cooled to room
temperature and stored for subsequent use. The amounts of polymers obtained were
commensurate with the calculated (theoretical) loss of methanol and no more than

an additional 4% weight loss. The prepared, polymers were very viscous liquids at
room temperatures..
The resulting polymers were linear co-polymers (Examples 43-47) or
branched co-polymers (Examples 34-42,48, and 49). The co-polymers comprising
repeating units of formula (6) had two or more ends of the polymer chains
terminated with hydroxyl groups.
Example 50
10-1 grams of polymer comprising repeating units of formula (I), prepared
according to Example 9,3.0 grams of isophorone disocyanate, artel 0.032 grams of
dibutyi tin dilaurate were thoroughly mixed together in a dry box, using a glass
stirring rod, at room temperature. The viscosity of the resulting solution gradually
increased. The reaction mixture was then heated to 130 °C for 30 min, with
occasional stirring using a glass stirring rod, and formation of a viscous
thermoplastic, practically colorless, transparent polymer was observed. The
resulting polymer mass was then cooled to room temperature and solidified. The
resulting polyurethane polymer comprising repeating units of formula (1) was a
rigid practically transparent polymer with weak cold flow properties. At
temperatures below 15 °C, it was brittle. The polymer had a melting point in 90-95
°C range and was amenable to melt processing and extrusion. No significant
deterioration in polymer properties were observed after 4 melt/cool cycles. The
polymer was insoluble in water and practically insoluble in the ordinary organic
solvents such as hydrocarbons, ethers, or alcohols.
Example 51
The synthesis was carried out according to Example 50, except that the
quantity of isophorone diisocyanate was increased to 1.78 g. -. The resulting polymer
at room temperature was a viscous transparent, adhesive-like thermoplastic product
with good adhesion properties to paper, aluminum foil and low-energy surfaces such
as polyethylene and polypropylene. The polymer was practically insoluble in water.

Example 52
The synthesis of polyurethane polymer was carried out according to
Example 50, except that 1,42 g of hexamethyleae 1,6-dtisocyanate was used instead
of isopborone diisocyanate- The resulting hot polymer was allowed to cool to room
temperature, and to stay in open air for 24 hours. The product obtained by such.a
method was a flexible foam, it was a fully cured polyurethane polymer comprising
repeating units of formula (I), and its properties did not change considerably over
time. The polyurethane polymer was a practically colorless (off-white) thermoset
polymer, and it could not be successfully re-processed by melt extrusion. The
product was practically insoluble in water and in ordinary organic solvents such as
hydrocarbons, ethers, or alcohols.
Example 53
The synthesis of polyurethane polymer was carried out according to
Example 52, except that 1.46 g of tolyiene diisocyanate (S0;20 isomer mixture ) was
used instead of isophorone diisoeyanate. The product was a rigid foam. It was a
folly cured polyurethane polymer comprising repeating units of formula (1), and its
properties did not change considerably over time. The polyurethane polymer was a
yellowish thermoset polymer, which could not be successfully re-propessed by melt
extrusion. The product was practically insoluble in water and in ordinary organic
solvents such as hydrocarbons, ethers, or alcohols.
Example 53
The synthesis of polyurethane polymer was carried out according to the
Example 52, except that 2.28. g of 4,4'-methylenebis(phenyl isocyanate) was used
instead of tolylene diisocyanate. The product was a rigid foam similar in its
properties and appearance to the product obtained in Example 52.
Example 54
7.02 grams of the branched hydroxyl terminated polymer prepared according
to Example 34,2.03 grams of hexamethylene 1,6-diisocyanate, and 0.03 g of

DABCO were thoroughly mixed in a glass via! placed in a dry box. A rapid
exothermic reaction was observed with the temperature of the reaction mixture
briefly rising to 95-100 °C, The content of the reaction mixture rapidly solidified
(in Jess than 4 minutes) to a transparent, slightly brownish product laving
practically no inclusions of gas bubbles. The resulting polyurethane polymer
comprising fragments of formula (6) was cooled down and retrieved from the vial
by breaking the vial. The resulting polyurethane polymer was a highly cross-linked,
viscoelastic polymer with .memory properties.. The resulting polymer was
practically insoluble in water and in ordinary organic solvents such as hydrocarbons,
ethers, or alcohols. The product was a chermoset polymer and it could not be re--
processed by melt extrusion without deterioration in polymer properties.
Example 55
The synthesis was carried out. according to Example 54, except that the 7,08
g of a branched, hydroxyl-terminated polymer was used as a starting material, and
was prepared according to the. Example 48. The resulting polyurethane was very
similar to the polymer obtained in Example 54, except it was a considerably more
rigid .rubbery polymer.
Example 56,
5.8 g of 94% pure decene-1,2--oxide.were dissolved in 20,8 g of compound
of formula (3) (R3 = methyl, 99.5% purity, 51:49 cis/trans isomer mixture). The
whole was stirred at room temperature, and 0,08 g of boron trifluoride diethyl
etherate was introduced,. An exothermic reaction was observed. The whole was
stirred for 1 hour, and the reaction mixture was allowed to cool to room
temperature. The liquid was analyzed by GC-MS and was found to contain a
mixture of isomers of compounds of the compounds of formula (7), wherein one R7
is n-optyl and R8 is hydrogen, and R7 is hydrogen and R8 is n-octyl.

Examples S7~64
The reactions of Examples 56 were repeated using different epoxides., as
follows:
(5?) octadecene-1,2-oxide 8.1' g,
(58) hexadecene-1,2~oxide 8.2 g,
(59) tetradecene-1,2-oxide 5,2 g,
(60) dodecene-1,2-oxide 5,6 g,
(61) hex ane-1,2-exide 4.6 g,
(62) butane-1,2-oxide 4.8 g,
(63) propylene-1,2-oxicle 3.6 g,
.{64) ethylene oxide 2.2 g.
The reactions of Examples 63 mid 64 were carried out in pressurized glass
vessels, while the other reactions were carried out at. atmospheric pressure. The
reaction mixtures were analyzed by GC-MS and were found to contain compounds
of formula (7) with combinations of R7 and R8 corresponding to the chain lengths of
the starting epoxides, a«d the unreacted compound of formula (3).
Examples 65-73
10 g of each of the reaction mixtures obtained in Examples 56-64 were
placed in round bottom flasks equipped with a magnetic stirrer, a condenser, and a
distillation head with an adapter connected to a receiving flask. 0.08 g of titanium
(IV) isopropoxide and 0,5 g of trimethylol propane was added to each of the flasks,
and the solutions were heated under nitrogen using an oil bath set at 200-220 oC.
After distillation of methanol had practically subsided (about 3 hours), the bath
temperature was decreased to 140-160 °C, and the stiring was continued for 1 hour
under vactrum using a pump capable of providing an eventual vacuum of 6 mm. A
weight loss was observed that was commensurate with the theoretical loss of
methanol due to a complete hydroxyester polymerization, as measured by the
weight of the resulting polymer products. An additional weight loss was also
observed, commensurate with presence of inert volatile impurities in the starting
epoxides used in Examples 56-64. The resulting polymeric products were cooled to

room temperature, purged with nitrogen and stored at room temperature. The
polymeric products were highly viscous colorless or slightly yellowish transparent
or semi-transparent liquids at room temperature. The polymeric products were
branched hydroxyl-teraainated random co-polymers comprising repeating units of
formula (6) and repeating units of formula (24);

The co-polymeric hydroxyl-tentiinated compounds prepared in this example
were found to be suitable for making rigid and flexible polyurethanes trader
conditions substantially similar to those described in Examples 50-55.
Example 74
The reaction was carried out according to Example 56, except that the
epoxide used was 10.2 g of a fully epoxidized soybean oil (Vicoflex® 7170,
Arkema).
Example 75
506.2 grams of a fully epoxidised soybean oil (Vicoflex 7170 brand,
Arkema) were mixed with 1 L of anhydrous methanolic solution containing 2,1 g of
sodium methoxide, and the resulting mixture was magnetically stirred at room
temperature (18 °C) for 6 hours. The progression of trans-esterification over time
was followed by gas chrowatography. After the trans-esterification reaction was
found to he substantially complete, the reaction mixture was neutralized by the
addition of 12.S grams of finely powdered anhydrous potassium dihydrogen ,
phosphate, followed by an additional stirring overnight (12 hours). The resulting
mixture was filtered and the methanol was evaporated under reduced pressure using
a rotary evaporator with a water bath set to 40 °C. The resulting oil was dissolved
in 1 L of hexanes, filtered, and the hexanes were removed under reduced pressure

using a rotary evaporator. A clear transparent product with weak oily odor (485 g)
was thereby obtained and was analyzed by .GC-MS. When -using a TIC integration
method, the oil.was {bund to contain approximately 9% methyl hexadecanoate, 5%
methyl octadecanoate, 42% methyl 9,10-epoxy-9~octadecenaate, 40% isomers of
methyl 9,10,-12,13-bisepoxy-9,12-octadecenoate, and small quantities of the esters
of other saturated and epoxtdized unsaturated fatty acids.
Example 76
The synthesis was carried out according to Example 56, except that the
epoxide used was S.2 g of the mixture of epoxidized unsaturated fatty acid esters
prepared according to Example 75. The reaction mixture was analyzed by GC-MS
and was found to comprise reaction products having Formulae (9), (10a), (10b),
unreacted the compound of formula {3}» and the rnethyl.esters of hexadecanoic and
octadecanoic acid in quantities commensurate to their amounts in the starting
material.
Example 77
0.4 g of the reaction product mixture obtained in Example 74 was trans-
esterified by dissolving it in 4 ml of methanof containing 0,5% sodium methoxide,
and the whole was stirred for 4 hr at room temperature. The reaction mixture was
neutralized by stirring with powdered 0.32 g of anhydrous potassium dihydrogen
phosphate for 1 hour, filtered and analyzed by GC-MS. The product mixture was
found to/be practically identical to the that obtained in Example 76.
Examples 78-79
10 g of one of the reaction product mixtures obtained in Examples 74 or 76
were treated according to the conditions of Examples 65-73. The resulting product
was a cross-liked co-polymer containing repeating units of formula (I.) and
fragments derived from the modified fatty acid ester derivatives of formulae (9),
(10a),, and (10b). The resulting polymers were rubbery transparent thermoset
elastomers with moderate yellow-orange discoloration. The polymers were

practically insoluble in water, acetone, methylethylketone, hydrocarbons, ethers,
and esters.
Approximately 0,2 g of each of the polymers obtained in this- Example were
de-polymerized by treatment according to the conditions -described in Example 77.
The GC-MS analysis of the resulting mixture of de-polymerized products showed
that the mixture had a substantially similar composition to that observed in
Examples 76 and 77, with the exception of the content of the methyl esters of
hexadecanoie and octadecanote acid, which' was less than 2%.
Example 80
(a) The reaction was carried out according to Example 74 on a 5,4 fold scale,
Powdered sodium fluoride (1 g) was added to neutralize the catalyst, and the whole
was stirred for 18 hours at room temperature and filtered. The excess of compound
(3) distilled out at reduced pressure to give approximately 81 g of a modified
triglyceride adduct having approximately 4.6 hydroxyl groups per molecule of
triglyceride (a free-flowing transparent viscous liquid with moderate yellow-orange
discoloration).
(b) 20.1 grains of this product were thoroughly mixed with 3.2 grams of
hexamethylcne-1,6-diisocyanate and 50 mg of dibutyl tin dilaurate, and the mixture
was cured for 1 hour at 105 °C. The resulting polyurethane polymer was a closed-
cell, flexible, soft, fully cured yellow foam (thermoset polymer).
Example 81
(a) The modified triglyceride synthesis was carried out according to
Example 80, except that addition of sodium fluoride was omitted. The resulting
product was a partially cross-linked adduct with molecular weight of approximately
4500 Da.
(b) 19.3 grams of this product was thoroughly mixed with 13 grams of
hexamethylene-1,6-diisoeyanate and 50 mg of dibutyl tin dilaurate, and the mixture
was cured for 1 hour at 105 °C. The resulting polyurethane polymer was a closed-

cell, flexible, soft, yellow, fully-cured foam (a thermoset polymer) with properties
very similar to those obtained in Example 80.
Examples 82-83
The polyurethane foams obtained in Examples 80 and 81 were
depolymerized according to Example 77. The resulting product mixture was found
to be substantially similar to those observed in Examples 76 and 77, with the
exception of the presence of the compound of formula (3) which was present in the
products of the present Examples only in small quantities (2-3)%.
Example 84
5.1 g of branched hydroxy-terminated co-polymer prepared according to
Example 36 were dissolved in 8 g of tolylene diisocyanate (80:20 isomer mixture),
and 0,02 g of dibutyl tin dilaurate was added. The whole was heated with vigorous
stirring to 85-90 °C under nitrogen, and the excess tolylene diisocyanate was
evaporated under reduced pressure. The resulting polymeric product (7.3 g) is an
isocyanate-terminated branched polymer (a polyisocyanate) comprising repeating
units of formula (6). The product was a viscous yellowish transparent liquid.
Examples 85-86
The .synthesis of polyurethane foams was carried out according to Examples -
80 and 81, except that the synthesis was carried out with, 2.6 g of the polyisocyanate
polymer obtained in Example 84, instead of hexamethylene diisocyanate. The
resulting polyurethane foams were similar in their properties to the foams obtained
in Examples 80 and 81, except they were more rigid.
Examples 87-88
One of the following;
(Example 87) 15,6 grams of the modified triglyceride prepared according to
Example 80(a), or

(Example 88} 15.1 p-ams of the fatty estsr adduct prepared according to
Example 76, followed by distillation of excess compound of formula (3), was
reftuxed in 100 ml of methanol containing 0,05% of p-tohiene sulfonic acid, to
effect a trans-esterification reaction. The solution was monitored, by GC-MS for
appearance of methyl levulinate and methyl 4,4-methoxypentanoate. After the
reaction was deemed complete (about 6 hours), both solutions were neutralized with
100 mg of sodium bicarbonate, filtered, and stripped of methanol under reduced
pressure, to give a mixture of 1 -glyceryl ether modified fatty acid esters (as oily
liquids).
The glyceryl ether adducts were then mixed with 0.2 g of titanium
isopropylate and heated to 95-100 °C tinder 6 mm vacuum, with stirring, until the
content had become viscous (about 3 tare), to give highly branched or crosslinked
polyester-polyetber compounds having molecular weights of approximately 3,500
Da.
5 gram portions of each of the resulting cross-linked polymers were mixed
with. 0.5 ml of methylethyiketone and 0.3 grams of tolylene diisocyamate, and 0.01 g
of dibutyl tin dilaurate was added. The mixtures were each stirred thoroughly and
placed in a vacuum oven set at 100 eC, incubated at atmospheric pressure for about
15 mm, and then a vacuum was applied using a pump capable of providing an
eventual 6 mm vacuum. The reaction mixtures were then left at 6 mm vacuum at
100 °C for 2 tars, and then cooled down and brought to atmospheric pressure. The
resulting polyurethanes were propellant-expandsd, semi-rigid foams with density of
about 0.22 g per cm3.
Example 89
30 grams of a cellulose acetate polymer with 39.8% acetyl content and Mn
ca. 30,000 (Sigma-Aldrich Cat No. 18,095-5) were mixed with 50 grams of the
compound of formula (3) (R3=methyl, 99.5% purity, 51/49 cm/trans mixture of
isomers), and 0.2 grams of titanium isopropylate was added. The whole was stirred
and heated to 160-180 °C for 6 hours under nitrogen at atmospheric pressure, and
thai under 1 ram vacuum, to remove any unreacted compound of formula (3). The

resulting polymer (42g) was a water-insoluble polyhydroxylated graft polymer with
a cellulose polymer backbone and pendant groups comprising repeating units of
formula (6), the polymer was a transparent agar-like gel practically insoluble in
water.
Example 90
Reaction product mixtures comprising epoxide adducts prepared in
Examples 56-67 and 76 were each stripped of the excess of hydroxyester compound
of formula (3) by distillation under reduced pressure. 3.2-3.3 grams of each of the
resulting products were saponified with 10 ml of 1M sodium hydroxide by vigorous
stirring for 2 hrs at 85-90 °C. Excess base was neutralized by titration with aqueous
hydrochloric acid to pH 8-9, and the solutions were diluted with water to a final
volume of 15 ml. The solutions of sodium salts of the saponified adducts of the
compound of formula (3) with the various epoxides were then examined for their
surfactant properties using a 1:1 hexane-water emulsion forming test, and by
evaluating the stability of such emulsions in-the presence and in the absence of
calcium or magnesium ions (final concentrations of 1% CaCl2 or 1% MgCl2 were
used in the emulsion tests). In addition the saponified compounds were also tested
in hexane-water emulsion tests at pH 3, and non-saponified compounds were also
tested for their surfactant properties at pH 7. All emulsion tests were performed at
room temperature.
Salts of the compounds obtained by saponification of the epoxide adducts of
Example 76 and of Examples 56-60 were found to be good surfactants capable of
forming and supporting stable hexane-water emulsions, and their surfactant
properties were not adversely affected by the presence of calcium or magnesium
ions. At acidic pH, the properties of the compounds Example 76 and Examples 56-
60 were also found satisfactory. Non-saponified compounds.of Examples 56-60
were found to be "water-in-oil" type emulsifiers.

Example 91
Plasticized polymer compositions and various blends of the polymeric
compounds comprising fragment of formula (6) were prepared by a melt mixing and
extrusion method, using one of the following polymers:
(a) PVC, poly(vinylchloride) powder (average Mn ca. 55,000,
average Mw 97,000, inherent viscosity 0.92, relative viscosity
2.23, supplier Sigma-Aldrich Company, Cat. No. 34,677-2),
(b) PHB, poly(3-hydroxybutyrate), (natural origin, Tm 72 oC,
supplied by Sigma-Aldrich Cat. No, 36,3S0-2),.
(c) AC, a cellulose acetate polymer with 39,8% acetyl content and
Mn ca, 30,000 (Sigma-Aldrich Cat. No, 18,095-5),
(d) PLA (L-polylactide, inherent viscosity 0,90-1.20, Average Mw
10,000-150,000, Tg 48.5 °C, Supplied by Sigma-Aldrich
Company, Cat. No. 53, 117-0).
Plasticized and blended compositions were prepared at a 5 g scale by prc-
mixing cold ingredients. Each of the resulting mixtures were individually fed into a
pre-cleaned, miniature twin-screw mixer-extruder chamber of a Daca
Microcompounder (Daca Instruments) under nitrogen, with the mixing chamber
heated to 5-10 °C above the melting temperature of the component with the highest
melting point, and the motor speed was set to 100 rpm. The samples were mixed for
about 5 minutes, and the resulting melt was then extruded out of the mixing
chamber as a flexible rod (diameter 3 mm), which was immediately cooled to room
temperature in ambient air.
The plastlcizers and the polymer blends were tested at several concentrations
including at least one compound of the present disclosure at 5,10,25, and 50% by
weight of the resulting composition.
Glass transition temperature data (by differential scanning calorimetry), and
plasticizer exudation data were collected using plasticized specimens cut from the
extruded rods that have shown a satisfactory compatibility and acceptably low
levels of exudation of the polymer composition components.

Polymer Wends comprising one of PHB, PLA, .and AC. were .found
compatible in a broad concentration range with the polymeric compounds prepared
in Examples 26-28,33, 50,? 51 / 65.-73, 89. "Such blends were significantly
plasticized, as displayed by significantly lowered glass transition points in
comparison with non-plasticized PHB, PLA, and AC The same compounds were
also found to have limited compatibility with FVC (up to 10%), reducing the glass
transition point of the plasticized PVC by about 15-30 °C.
PHB, PLA, AC polymers were also successfully plasticized with compounds
prepared in Examples 34-49, as well as with the compound of formula (5); (5a), and
with the compound of formula (3) and (4), except cases wherein R3 was H.
Among the compounds tested, the PVC polymer was most successfully
plasticized with compounds prepared according to Examples 80{a), 81 (a), 57-61, 76
(after removal of excess of compound 3 by distillation), compounds of formula 5a,
and compounds of formula (3) and (4), wherein both R3 and R6 were C4-C8 linear or
branched alkyls.
Example 92
2.1 grams of the polyurethane polymer comprising repeating unite of
formula (6) obtained in Example 52 were stirred at room temperature in 15 ml of
absolute ethanol containing 0.5*8% of sodium ethoxide until complete dissolution was
observed (about 5 hours).. The resulting solution was neutralized by stirring for 1
hour with powdered potassium dihydrogen phosphate, and the ethanol was distilled
out under reduced pressure. The residue was dissolved in tert-butyl methyl, ether
and filtered. The filtrate was analyzed by GC-MS and was found to contain 95%
pure compound of formula (3) (R3=Et, cis/irans isomer mixture). The tert-butyl
methyl ether was evaporated under reduced pressure, yielding about 1.52 g of the
neat compound of formula (3)
Example 93
The reaction was carried out according to Example 92, except the
polyurethane polymer was 23 grams of the polymer prepared in Example 54, and n-

butanol with 0.3% of sodium n-butoxide was used. The resulting neat monomer
(1.78 g) was a 97% pure compound of formula (3) (R3=n-Bw, cis/trans isomer
mixture),
A number of embodiments of the disclosure have been described.
Nevertheless, it will be understood that various modifications maybe made without
departing from, the spirit and scope of the disclosure. Accordingly, other
embodiments are within the scope of the following claims.

WE CLAIM :
1. A compound having the formula:



wherein R3 is hydrogen; methyl; linear, branched, or cyclic alkyl; linear, branched, or
cyclic alkenyl; aryl; aralkyl; and alkyloxyalkyl; and
X is selected from hydrogen, or

wherein R is selected from hydrogen; linear, branched, or cyclic alkyl;
linear, branched or cyclic alkenyl; aryl; aralkyl; oxoalkyl; and alkyloxy alkyl; or a salt
thereof.

wherein R is hydrogen; methyl; linear, branched or cyclic alkyl; or cyclic alkyl; linear,
branched or cyclic alkenyl; aryl; aralkyl, or alkyloxyalkyl; and



wherein one of R7 or R8 is hydrogen and the other is a C1-C30 linear alkyl, one of A or B is
hydrogen and the other is an ester, and m and n are independently integers from 0 to 20,
such that the sum of m+n = 8 to 21; or a salt thereof.
3. The compound of either of claims 1 or 2, wherein R3 is selected from a C3-
C30 linear, branched, or cyclic alkyl; linear, branched, or cyclic alkenyl; aralkyl; and
alkyloxyalkyl.
4. The compound of claim 2, wherein one of R7 or R8 is a C6-C30 linear alkyl.
5. The compound of claim 3, wherein one of R7 or R8 is a C6-C14 linear
alkyl.
6. The compound of either of claims 1 or 2, wherein the substituted
oxymethylene moiety attached to the dioxolane ring is predominantly in the cis
configuration relative to the configuration of the side chain bearing the carboxyl group.
7. The compound of either of claims 1 or 2, wherein the substituted
oxymethylene moiety attached to the dioxolane ring is predominantly in the trans
configuration relative to the configuration of the side chain bearing the carboxyl group.
8. The compound of either of claims 1 or 2 wherein the substituted
oxymethylene moiety attached to the dioxolane ring is exclusively in the cis configuration
relative to the configuration of the side chain bearing the carboxyl group.
9. The compound of claim 1 or 2 wherein the substituted oxymethylene
moiety attached to the dioxolane ring is exclusively in the trans configuration relative to
the configuration of the side chain bearing the carboxyl group.
10. The compound of either of claims 1 or 2, wherein R3 is hydrogen.
11. The compound of claim 10, wherein the compound is the salt of an alkali
metal, an alkaline-earth metal, ammonia, or an amine.


wherein
R1 is hydrogen or a carbon atom of a levulinate fragment or a y-
valerolactone derivative;
R2 is hydroxyl, an oxygen atom of glycerol, an oxygen atom of an esterified
glycerol fragment, an oxygen atom of a diglyceryl fragment, or an acrolein
fragment; and
p is an integer from 1 to 100;
the method comprising reacting glycerol or a compound having the formula:



R4 and R5 are independently selected from the group comprising hydrogen;
methyl; linear, branched or cyclic alkyl; linear, branched or cyclic alkenyl; aryl,
and arylalkyl; or
a mono-, di-, or tri- ester of glycerol with a linear or branched alkanoic acid
having one to six carbon atoms; or
a mixture of glycerol and a mono-, di-, or tri- ester of glycerol with a linear
or branched alkanoic acid having one to six carbon atoms; or
a monolevulinate ester of glycerol;
with a levulinic derivative in the presence of an acid catalyst and under conditions
sufficient for removal of water from the reaction mixture.
15. A method for preparing a compound of claim 1, the method comprising
reacting a compound having the formula:

wherein:
R9 is hydrogen or a carboxyl moiety;
R10 is OR11,orN(R12)2;
R11 and R12 are independently hydrogen, methyl or a linear, branched, or
cyclic
alkyl; and
p is an integer;
with a monohydric alcohol or a carboxylic ester in the presence of a base catalyst.
16. A method for preparing a compound of claim 12, the method comprising
reacting a compound having the formula:



The polymer of claim 19 wherein the polymer comprises a polyurethane.
21. The polymer of claim 19 wherein the polymer further comprises units
derived from a compound of claim 2.
22. A plasticized polymer composition comprising:

a) a base polymer; and
b) a compound of any of claims 1, 2, or 19.

23. The plasticized polymer composition of claim 22, wherein the base
polymer comprises vinyl chloride polymer, poly(3-hydroxyalkanoate) polymer,
poly(lactate) polymer, or polysaccharide polymer.
24. The method of claim 14 wherein the levulinic derivative comprises a
levulinic acid, levulinic ester, angelicalactone, or a dialkyl ketal of levulinic ester, or a
mixture of two or more thereof.
25. A compound having the structure:

wherein
R1 is hydrogen or a carbon atom of a levulinate fragment or a γ-valerolactone
derivative; R2 is hydroxyl, an oxygen atom of glycerol, or an oxygen atom of an esterified
glycerol fragment, an oxygen atom of a diglyceryl fragment, or an acrolein fragment; and
p is an integer from 1 to 100.
26. A compound having the formula:


wherein R9 is hydrogen, methyl, or a carboxyl moiety; R10 is OR11 or N(RI2)2; R11
is hydrogen, methyl, or a linear, branched, or cyclic alkyl; and R12 is hydrogen, methyl, or
a linear, branched, or cyclic alkyl; and p is an integer.

wherein
R3 is hydrogen; methyl; linear, branched or cyclic alkyl; linear, branched or cyclic
alkenyl; aryl; aralkyl; or alkyloxyalkyl; and
R6 is hydrogen; methyl; linear, branched or cyclic alkyl; linear, branched or cyclic
alkenyl; aryl; aralkyl; oxoalkyl; or alkyloxyalkyl, or a salt thereof.
28. A plasticized polymer composition comprising
a) a base polymer, and
b) a plasticizer comprising one or more of the compounds:


wherein
R3 is hydrogen; methyl; linear, branched or cyclic alkyl; linear, branched or cyclic
alkenyl; aryl; aralkyl; or alkyloxyalkyl;
R6 is hydrogen, methyl, linear, branched or cyclic alkyl; linear, branched or cyclic
alkenyl; aryl; aralkyl; oxoalkyl; or alkyloxyalkyl; and
q is an integer.
29. A method of making a polymer comprising one or more repeat units having
the structure:


wherein
R3 is hydrogen, methyl, linear, branched or cyclic alkyl, linear, branched or cyclic
alkenyl, aryl, aralkyl, or alkyloxyalkyl;
in the presence of a polycondensation catalyst to form a polymer.
30. A method of making a polymer comprising one or more repeat units
comprising:

wherein
R is hydrogen, methyl, linear, branched or cyclic alkyl; linear, branched or cyclic
alkenyl; aryl, aralkyl, or alkyloxyalkyl;
R is hydrogen, linear, branched or cyclic alkyl; linear, branched or cyclic alkenyl;
aryl, aralkyl, oxoalkyl, or alkyloxyalkyl;
in the presence of a polycondensation catalyst to form the polymer.
31. A method of making a polymer comprising one or more repeat units
comprising:


wherein
R3 is hydrogen; methyl; linear, branched or cyclic alkyl; linear, branched or cyclic
alkenyl; aryl; aralkyl; or alkyloxyalkyl;
with a compound comprising an epoxide of either a normal a-olefin or an unsaturated fatty
acid ester in the presence of an acid catalyst to form the compound.
33. A surfactant comprising an alkali metal salt, an alkali-earth metal salt,
amine salt, or ammonium salt of one or more of the compounds:


wherein one of R or R is hydrogen and the other is a C1-C30 linear alkyl; one of E or D is
hydrogen and the other is carboxyl; and m and n are independently integers from 0 to 20,
such that the sum of m+n = 8 to 21.
34. A composition comprising the surfactant of claim 33.
35. A surfactant comprising an amide of one or more of the compounds:




wherein
R3 is hydrogen; methyl; linear, branched or cyclic alkyl; linear, branched or cyclic
alkenyl; aryl; aralkyl or alkyloxyalkyl;
one of R7 or R8 is hydrogen and the other is a C1-C30 linear alkyl;
one of A or B is hydrogen and the other is an ester, and m and n are independently
integers from 0 to 20, such that the sum of m+n = 8 to 21; and
one of E or D is hydrogen and the other is carboxyl.

The present disclosure relates to the preparation of ketal compounds from glycerol and
levulinic acid and esters, and uses thereof.

Documents:

02471-kolnp-2008-abstract.pdf

02471-kolnp-2008-claims.pdf

02471-kolnp-2008-correspondence others.pdf

02471-kolnp-2008-description complete.pdf

02471-kolnp-2008-form 1.pdf

02471-kolnp-2008-form 2.pdf

02471-kolnp-2008-form 3.pdf

02471-kolnp-2008-form 5.pdf

02471-kolnp-2008-international publication.pdf

02471-kolnp-2008-international search report.pdf

02471-kolnp-2008-pct request form.pdf

02471-kolnp-2008-priority document.pdf

2471-KOLNP-2008-(04-04-2014)-CLAIMS.pdf

2471-KOLNP-2008-(04-04-2014)-CORRESPONDENCE.pdf

2471-KOLNP-2008-(04-04-2014)-FORM-1.pdf

2471-KOLNP-2008-(04-04-2014)-FORM-13.pdf

2471-KOLNP-2008-(04-04-2014)-FORM-2.pdf

2471-KOLNP-2008-(04-04-2014)-FORM-3.pdf

2471-KOLNP-2008-(04-04-2014)-FORM-5.pdf

2471-KOLNP-2008-(04-04-2014)-OTHERS-1.pdf

2471-KOLNP-2008-(04-04-2014)-OTHERS.pdf

2471-KOLNP-2008-(07-04-2014)-CORRESPONDENCE.pdf

2471-KOLNP-2008-(07-04-2014)-OTHERS.pdf

2471-KOLNP-2008-(22-04-2014)-CORRESPONDENCE.pdf

2471-KOLNP-2008-(22-04-2014)-OTHERS.pdf

2471-KOLNP-2008-CORRESPONDENCE 1.1.pdf

2471-KOLNP-2008-CORRESPONDENCE 1.2.pdf

2471-KOLNP-2008-CORRESPONDENCE 1.3.pdf

2471-KOLNP-2008-FORM 18.pdf

2471-KOLNP-2008-PA-1.1.pdf

2471-KOLNP-2008-PA.pdf

FORM13.pdf

PETITION UNDER RULE 137.pdf


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Patent Number 263389
Indian Patent Application Number 2471/KOLNP/2008
PG Journal Number 44/2014
Publication Date 31-Oct-2014
Grant Date 27-Oct-2014
Date of Filing 19-Jun-2008
Name of Patentee SEGETIS INC.
Applicant Address 680 MENDELSSOHN AVE, N.GOLDEN VALLEY, MINNESOTA 554127,
Inventors:
# Inventor's Name Inventor's Address
1 SELIFONOV, SERGEY 4625 MERRIMAC LANE NORTH, PLYMOUTH, MINNESOTA 55446
PCT International Classification Number A01N 57/00
PCT International Application Number PCT/US2006/045200
PCT International Filing date 2006-11-22
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 60/738,988 2005-11-22 U.S.A.