New ketocarboxylated polymers which comprise an ester of a ketodiacid precursor, and part of all of the hydroxy or thiol groups of a polymer having one or more pendant hydroxy or thiol groups, are useful as adhesives, coatings, membranes and the like.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention related to ketocarboxylated polymers and to their 
preparation. 
2. Background of the Invention 
It is known to react hydroxylated polymers with acids or anhydrides to 
prepare compositions for a variety of uses. In U.S. Pat. No. 3,634,472, 
monocarboxylic acids or anhydrides were reacted with hydroxy-oxetanes to 
produce compositions useful as lubricants. In Japanese patents 85/50,804 
and 56/155,203, carboxylic acid anhydrides were reacted with hydroxylated 
polymers to give products having water absorbing properties. In French 
patent 2.522,670, polycarboxylic acid anhydrides were reacted with 
hydroxylated olefin polymers to produce compositions useful for moldings. 
It is desirable to find new polymers having useful properties, such as 
better thermal stability, increased water absorption and/or decreased 
water-solubility of normally water-soluble polymers for use in adhesives, 
coatings, membrane applications and the like. 
SUMMARY OF THE INVENTION 
The present invention is directed to new ketocarboxylated polymers which 
comprise an ester of a ketodiacid precursor and part or all of the hydroxy 
or thiol groups of a polymer having one or more pendant hydroxy or thiol 
groups. Accordingly, the ketocarboxylated polymers comprise a polymer 
having one or more pendant hydroxy or thiol groups, which hydroxy or thiol 
groups have been esterified with an acid moiety derived from a ketodiacid 
presursor selected from a ketodiacid or a reactive derivative thereof or a 
spirodilactone. 
The ketocarboxylated polymers of the invention include those of formula I 
##STR1## 
wherein X is oxygen or sulfur: 
##STR2## 
is the group represented by the residue remaining after removal of the 
hydrogen atoms from the hydroxy or thiol groups of a hydroxylated or 
thiolated polymer having one or more pendant hydroxy or thiol groups; and 
A is the group represented by the residue remaining after removal of the 
hydroxy moiety from one carboxyl group of a ketodiacid precursor. Also 
included in the invention are the ketocarboxylated polymers obtained by 
crosslinking I by esterification of the second carboxyl groups of the 
ketodiacid precursor with hydroxylated or thiolated polymer. 
The invention also includes a ketocarboxylated polymer of formula I wherein 
part of the residue of the ketodiacid precursor for A is replaced with the 
group represented by the residue remaining after removal of the hydroxy 
moiety from one carboxyl group of a dicarboxylic acid precursor reactant, 
suitably the acid or the anhydride thereof, and the ketocarboxylated 
polymers obtained by crosslinking by esterification of (part or all of) 
the second carboxyl groups of said dicarboxylic acid precursor reactant 
with the hydroxy or thiol groups of the polymers containing such groups. 
Hydroxylated or Thiolated Polymer 
Any hydroxylated or thiolated polymer having one or more pendant hydroxy or 
thiol groups or a presursor polymer thereof, which can form pendant 
hydroxy or thiol groups in situ, such as prior to or during the course of 
reaction with the ketodiacid or reactive derivative thereof or 
spirodilactone, can be used to provide the moiety 
##STR3## 
in formula I. Therefore, it is not possible to define a single, simple 
structural formula which will encompass all the hydroxylated or thiolated 
polymers for use in the invention. The hydroxylated or thiolated polymer 
can have terminal and/or internally pendant hydroxy or thiol groups. 
Internally pendant hydroxy or thiol groups are hydroxy or thiol groups 
which are pendant from a portion of the polymeric backbone other than the 
ends thereof. The number of hydroxy or thiol groups can vary but there 
must be at least one and preferably more than one, present in the polymer. 
In order to obtain a desired degree of crosslinking a certain number of 
hydroxyl or thiol groups must be present in the polymer and the ketodiacid 
precursor must be the acid or a reactive derivative thereof and not a 
spirodilactaone. The ketocarboxylated polymer can be lightly to 
substantially crosslinked. Lightly can be as low as 1% and substantially 
crosslinked is when at least about 80% of all the second carboxyl groups 
of the ketodiacid precursor are used to esterify pendant hydroxy or thiol 
groups, preferably, about 90% or more of said second carboxyl groups are 
used. 
The number of hydroxyl or thiol groups will vary from polymer to polymer 
depending on the desired product and the kind of properties desired for 
the intended use thereof and accordingly a precise definition thereof is 
not practical. By way of illustration, when the starting polymer is a 
polyvinyl alcohol polymer, the number of hydroxy groups is about one per 
vinyl alcohol unit. In general, the number of hydroxyl or thiol groups in 
the polymer, calculated as --(CH.sub.2 CHXH)-- groups, can be as low as 
about 1.0% by weight of the total polymer with the upper hydroxyl or thiol 
group content being determined solely by the composition of the polymer. 
The hydroxylated or thiolated polymer can be a homopolymer, copolymer, 
terpolymer or the like. 
Hydroxylated polymers which can be used in the invention include polyvinyl 
acetals, such as polyvinyl formal, polyvinyl acetal, polyvinyl butyral, 
polyvinyl valeral having hydroxyl groups; polyvinyl esters, such as 
polyvinyl acetate, polyvinyl butyrate containing hydroxyl groups; 
polyvinyl alcohol; mixtures of polyvinyl acetal and polyvinyl esters 
having hydroxyl groups; terpolymers of vinyl chloride with vinyl esters 
having hydroxyl groups; copolymers of partially hydroxylated vinyl 
chloride and polyvinyl acetate; water-soluble derivatives of cellulose, 
such as alkyl cellulose, hydroxyalkyl cellulose and hydroxyalkyl alkyl 
cellulose, such as methyl cellulose. hydroxymethyl cellulose, hydroxyethyl 
cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, 
hydroxypropyl methyl cellulose, hydroxybutyl methyl cellulose; cellulose 
esters and hydroxyalkyl cellulose esters, such as cellulose 
acetylphthalate (CAP), carboxyalkyl cellulose, carboxyalkyl alkyl 
cellulose, carboxyalkyl cellulose esters, such as carboxymethyl cellulose 
and their alkali metal salts; ethylene-vinyl acetate copolymers having 
hydroxyl groups; hydroxylated polybutadiene, hydoxylated block copolymers, 
such as SBS rubbers; hydroxylated KRATON.RTM. Thermoplastic Rubber; 
hydroxylated polyethylene and polypropylene and copolymers thereof; and 
hydroxylated copolymers of vinyl acetate and acrylate esters, such as 
polymethyl methacrylate and polyethyl methacrylate; polyphenol polymers, 
such as novolac resins, such as from formaldehyde and resorcinol; 
polyepoxide polymers, such as linear diepoxide resins, for example 
EPON.RTM. Resin 828; polyphenoxy polymers such as linear phenol-cured 
polymers of diepoxide resins; and starch, modified starch, dextrin and the 
like can also be used as the hydroxylated polymer. Of course, the 
thiolated counterparts of the hydroxylated polymers are also included. 
For example, the polymer can be of the formula II 
##STR4## 
wherein R is an alkyl group of from to 10 carbon atoms, m is at least one, 
n is from 0 to 99 and the sum of m+n is 100. 
For polymers which do not normally contain hydroxy or thiol groups, random 
hydroxyl or thiol groups can be introduced along the polymeric backbone in 
a number of ways to obtain random hydroxyl functionality. For example, 
carboxylated polymers are converted to hydroxy groups in a known manner 
such as by treating the carboxylated polymers with a base, for example, 
aqueous sodium hydroxide or the like. 
The hydroxylated or thiolated polymers used in the invention are generally 
commercially available or can be prepared by conventional methods known to 
those of skill in the polymer art. For example, polyvinyl alcohols are 
synthetic resins containing various percentages of hydroxyl and acetate 
groups and are usually prepared by the hydrolysis of polyvinyl acetate. 
Other hydroxylated polymers are disclosed in French patent 2,552,670 and 
Japanese patents 85/50,804 and 56/155,203 and in U.S. Pat. Nos. 
3,769,416, and 4,305,996, and 4,912,160, the disclosures of each of which 
are incorporated herein by reference. 
Ketodiacid Precursors 
Any spirodilactone or ketodiacid or reactive derivative thereof can be used 
to form the ketocarboxylated polymers of the invention. By reactive 
derivative of the ketodiacid is meant the corresponding diester of the 
acid or the dihalide of the acid, either of which derivative can be 
converted to the free acid group by conventional chemistry either before, 
during or subsequent to the ketocarboxylation of the polymer. 
Suitable spirodilactones useful as ketodiacid precursors in the present 
invention contain from about 7 to about 30 carbon atoms and include those 
of the formula II 
##STR5## 
wherein n is a number from 1 to 10, preferably 2. 
Suitable ketodiacids include those ketodiacids containing from about 5 to 
about 30 carbon atoms and containing one or more keto groups or their 
corresponding diester or dihalides. 
The preferred precursor is a 4-oxoheptanedioic acid compound or a 
1,6-dioxospiro[4.4]nonane-2.7-dione. The 4-oxoheptanedioic acid compound 
precursors are represented by the formula III 
##STR6## 
wherein Z independently is &gt;C(Z').sub.2 in which Z' is hydrogen, lower 
alkyl, lower halo or aryl of up to 10 carbon atoms (e.g., phenyl), or Z is 
such that two adjacent Z groups together form a ring system Z" of 1 to 2 
rings, each ring of from 5 to 7 ring atoms, up to two of which ring atoms 
are selected from nitrogen, oxygen or sulfur atoms, or mixtures thereof, 
with the remainder being carbon atoms, there being up to 14 carbon atoms 
in each Z", two of which ring carbon atoms form a bridge between the keto 
and carbonyl carbon atoms connected by adjacent Z groups, and Y is 
hydroxy, lower alkoxy or halo, preferably middle halo. 
When the Z moieties are linked together to form a ring system the ring 
system is aromatic, cycloaliphatic or heterocyclic and is hydrocarbyl 
containing only atoms of carbon and hydrogen besides any heteroatoms or 
substituted hydrocarbon containing additional atoms such as halogen, 
preferably middle halogen, in the form of inert carbon atom substituents. 
In one embodiment employing the ketodiacid compound precursor, each Z 
moiety is &gt;C(Z').sub.2 and the ketodiacid compound is an 4-oxoheptanedioic 
acid compound. In one such embodiment, largely because of a particularly 
convenient method of producing the precursor, a preferred 
4-oxoheptanedioic acid compound has at least one hydrogen on the carbon 
atom adjacent to each carboxy function, that is, at least one Z' on each 
carbon atom adjacent to a carboxy function is hydrogen. Such 
4-oxoheptanedioic acid compounds are represented by the formula IIIa 
##STR7## 
wherein Z' and Y have the previously stated meanings. Such 
4-oxoheptanedioic acid compounds include 4-oxoheptanedioic acid, dimethyl 
4-oxoheptanedioate, 2,6-dimethylheptanedioic acid, 
2,3,5,6-tetramethyl-4-oxoheptanedioyl chloride, di-n-propyl 
2,6-di-n-butyl-4-heptaneodioate, 
7-carbomethoxy-3,3,5,5-tetramethyl-4-oxoheptanedioic acid and the like. 
The preferred ketodiacids of the above formula IIIa are those wherein each 
Z' is hydrogen or methyl, especially hydrogen, and each Y is hydroxy or 
methoxy, especially hydroxy. 
These ketodiacid compounds are known compounds or are produced by known 
methods, but the esters of formula IIIa, i.e., the compounds wherein Y is 
alkoxy, are produced by reaction of formaldehyde with an 
.alpha.,.beta.-ethylenically unsaturated carboxylic acid ester such as 
methyl acrylate, ethyl methacrylate, methyl crotonate, methyl ethacrylate, 
propyl 2,3-dimethylbutanoate and the like. This reaction is conducted in 
the presence of a catalyst system which comprises a thiazolium salt and a 
tertiary amine and produces the dialkyl 4-oxoheptanedioate derivative in 
good yield. This process is described in greater detail in copending U.S. 
Pat. No. 4,800,231, incorporated herein by reference. Conversion of the 
esters thereby obtained to free acids or acid halides is by conventional 
methods as is the general interconversion of the acids, esters or acid 
halides of formula IIIa. 
In a second embodiment of the ketodiacid compound precursor, the 
4-ketodiacid incorporates cyclic moieties between the keto group and the 
carboxy functions. i.e., two adjacent Z moieties form a fused cyclic ring 
structure Z" of 1 to 2 rings, each ring of from 5 to 7 ring atoms, up to 2 
of which ring atoms are selected from nitrogen, oxygen, or sulfur atoms or 
mixtures thereof, with the remainder being carbon atoms, there being up to 
14 carbon atoms in each Z", two of which ring carbon atoms form a bridge 
between the (keto and carbonyl) atoms connected by adjacent Z groups. Such 
diacid compounds are presented by the formula IIIb 
##STR8## 
wherein Y and Z" have the previously stated meanings. Illustrative of 
these cyclic ketodiacid compounds are di(2-carboxycyclohexyl) ketone, 
di(2-carboxyphenyl) ketone, di(2-carbopropoxycyclo-4-pentenyl) ketone, 
di(2-chlorocarbonylphenyl) ketone, di(2-carboxypyridyl) ketone, 
2-carboxyphenyl N-methyl-3-carboxy-2-pyrryl ketone, 
di(3-carbethoxy-2-morpholyl) ketone, di(3-carbomethoxy-2-napthyl) ketone 
and the like. The preferred cyclic ketodiacid compounds of formula IIIb 
are those wherein each Z" is a ring system of from 5 to 6 carbon atoms, 
inclusive, and up to one nitrogen atom, such as pyrido and particularly 
benzo. 
Such ketodiacids are known compounds or are produced by known methods, such 
as the method of U.S. Pat. No. 1,999,181 or the method of Cava et al, J. 
Am. Chem. Soc., 20, 6022 (1955). 
In yet another embodiment of the ketodiacid compound precursor, the 
ketodiacid incorporates one fused cyclic moiety with the remainder of the 
Z moieties being &gt;C(Z').sub.2, i.e., the compounds are of the formula IIIc 
##STR9## 
wherein Y, Z' and Z" have the previously stated meanings. Such ketodiacids 
of one cyclic moiety are illustrated by 3-(2-carboxybenzoyl)propionic 
acid, 3-(2-carbomethoxy-2-pyridyloyl)-2-ethyl-propionic acid, ethyl 
3-(2-carbethoxybenzoyl)propionate, 3-(2-carboxy-4-methylbenzoylbutyrl) 
chloride and the like. The ketodiacids of the above formula IIIc are known 
compounds or are produced by known methods. For example, 
2-carboxymethylbenzaldehyde reacts with methyl acrylate according to the 
general teachings of U.S. Pat. No. 4,800,231, to produce methyl 
3-(2-carbomethoxybenzoyl)propionate. 
In another embodiment of the invention, the ketodiacid precursor is a 
1,6-dioxaspiro[4.4]nonane-2,7-dione compound wherein the spiro ring system 
is substituted with hydrogen, alkyl or halogen, or which incorporates 
fused cyclic substituents which include the 3-and 4- spiro ring positions 
and/or the 8- and 9-spiro ring positions of the spiro ring system. 
The precursor, in terms of the terms of the polymers of formula I, is 
represented by the formula IV 
##STR10## 
wherein Z has the previously stated meaning. In the embodiment of these 
precursors of the above formula IV wherein each Z is &gt;C(Z').sub.2, the 
spirodilactone is represented by the formula IVa 
##STR11## 
wherein Z' has the previously stated meaning. Illustrative of such 
spiro-dilactones are 1,6-dioxaspiro[4.4]nonane-2,7-dione, 
3.8-dimethyl-1,6-dioxaspiro[4.4]nonane-2,7-dione, 
3,4,8,9-tetramethyl-1,6-dioxaspiro[4.4]-nonane-2,7-dione, 
4,9-diphenyl-1,6-diazaspiro[4.4]nonane-2,7-dione, 
3,3,8,8-tetramethyl-1,6-dioxaspiro[4.4]nonane-2,7-dione, 
3,3,4,4,8,8,9,9,-octamethyl-1,6-dioxaspiro[4.4]nonane-2,7-dione, 
3,4,8,9-tetrafluoro-1,6-dioxaspiro[4.4]nonane-2,7-dione and the like. The 
preferred spirodilactones of the above formula IVa are those wherein at 
least one Z' of each Z'-substituted carbon atom is hydrogen. 
The compounds of formula IVa are known compounds or are produced by known 
methods such as the process of Pariza et al, Synthetic Communications. 
Vol. 13(3), pp. 243-254 (1983), herein incorporated by reference. 
In the embodiment of the precursors of the above formula IV which 
incorporates a fused cyclic moiety as a part of the two rings of the spiro 
ring system, the spirodilactones are represented by the formula IVb 
##STR12## 
wherein Z" has the previously stated meaning. Typical compounds of this 
formula IVb are 3,4,8,9-dibenzo-1,6-dioxaspiro[4.4]nonane-2-7-dione, 
3,4,8,9-di(cyclopentano)-1,6-dioxaspiro[4.4]nonane-2,7-dione, 
3,4,8,9-di(4-methylbenzo)-1,6-dioxaspiro[4.4]nonane-2,7-dione, 
3,4,8-9-di-(pyrido)-1,6-dio xaspiro[4.4]noname-2,7-dione and the like. 
These compounds are known compounds or are produced by known methods, for 
example, the process of the above Cava et al article or by the process of 
U.S. Pat. No. 1,999,181. 
In a third embodiment of the spirodilactone spirodilactam precursor, a 
cyclic moiety is fused to one spiro ring and the other spiro ring is free 
from fused ring substituents. Such spirodilactones are represented by the 
formula IVc 
##STR13## 
wherein Z' and Z" have the previously stated meanings. Such 
spirodilactones are illustrated by 
3-methyl-8.9-benzo-1.6-dioxaspiro[4.4]-nonane-2,7-dione, 
3,4-benzo-1,6-dioxaspiro[4.4]nonane-2,7-dione, and 
3,3,4,4-tetramethyl-8,9-morphoyl-1,6-diazaspiro[4.4]nonane-2,7-dione and 
the like. The spirodilactones of the above formula IVc are produced by 
known methods, for example, the dehydration of the corresponding 
ketodiacid. By way of illustration, 
3,4-benzo-1,6-dioxaspiro-[4.4]nonane-2,7-dione, is produced by dehydration 
of 3-(2-carboxy-benzoyl)propionic acid through application of heat. 
In general, the preferred precursors are hydrocarbon except for the oxygen 
atoms of the lactone moieties, and particularly preferred are those 
spirodilactones which are free from fused ring substituents (formula IVa) 
or those which have a fused ring substituent on each of the spiro rings 
(formula IVb). An especially preferred spirodilactone spirodilactam 
precursor of the first class is 1,6-dioxaspiro[4.4]nonane-2,7-dione 
The acyclic 4-oxoheptanedioic acid compounds are known or are produced by 
the methods described above, but certain of the esters are also produced 
by the reaction of formaldehyde and unsaturated carboxylic acid esters by 
the process disclosed and claimed in U.S. Pat. No. 4,800,231. 
Interconversion of the acids, esters or acid halides of formula III is by 
conventional methods. The production of 4-oxoheptanedioic acid compounds 
of formula IV which contain cyclic moieties is by the process of Cava et 
al, J. Am. Chem. Soc., 77. 6022 (1955). The spirodilactones of formula IV 
are produced by the process of Pariza et al, Synthetic Communications, 
Vol. 13(3), pp. 243-254 (1983), or by the process of U.S. Pat No. 
1,999,181. 
Dicarboxylic Acid Precursor 
Any dicarboxylic acid or reactive derivative thereof which can form esters 
with the pendant hydroxy or thiol groups of the polymer can be used as the 
optional dicarboxylic acid precursor reactant to replace part of the 
ketodiacid precursor. This includes the free diacid, the diesters of the 
acid, the dihalides or preferably the anhydride. 
Suitable dicarboxylic acid precursors include dicarboxylic acids having at 
least about 3 to about 24 carbon atoms and include' for example, lower 
aliphatic dicarboxylic acids, such as malonic acid, succinic acid, maleic 
acid, glutaric acid, adipic acid, suberic acid. sebacic acid as well as 
higher aliphatic dicarboxylic acids containing between about 11 and about 
22 carbon atoms, such as undecanedioic and dodecanedioic acids as well as 
tri- , tetra- , penta- , hexa- , hepta- , octa-decanedioic acids and 
similar higher aliphatic dicarboxylic acids. Also useful are aromatic 
dicarboxylic acids, such as phthalic acid, isophthalic acid, terphthalic 
acid, tetrahydrophthalic acid and similar aromatic dicarboxylic acids. 
Preferably, the dicarboxylic acid precursor is an aromatic acid anhydride, 
especially phthalic anhydride. 
The ketocarboxylated polymers of the invention comprise from about 1% to 
about 50% equivalent of said dicarboxylic acid based on the total hydroxy 
groups in the polymer reactant, preferably from about 5% to about 30%. 
Preparation 
A process for preparing a ketocarboxylated polymer of the invention 
comprises treating a hydroxylated or thiolated polymer having one or more 
pendant hydroxy or thiol groups or a presursor polymer thereof in the 
liquid phase under acidic conditions with a ketodiacid precursor. The 
desired ketocarboxylated polymer can be isolated from the reaction mixture 
by conventional methods, such as filtering the mixture, washing with 
water, and removing any solvent or excess reactants by distillation, 
preferably under reduced pressure. 
The reaction is conducted under acidic conditions, which is most readily 
accomplished by the use of an acid as a reaction diluent, which can also 
aid in maintaining the liquid phase reaction conditions. For example, the 
acidic compound can be acetic acid or the like. 
While the reaction can proceed without the aid of a catalyst, it is 
optionally conducted in the presence of one or more catalytic compounds. 
When the ketodiacid precursor is a spirodilactone, the catalyst is a basic 
compound, which will not interfere with the reaction. Suitable basic 
compounds are selected from alkali and alkaline earth metal salts, 
alkoxides, onium compounds, for example, ammonium or phosphonium salts, 
and the like. For example, the catalyst can be sodium acetate or the like. 
Such materials are present in a catalytically effective amount which is an 
equivalent amount or less than the amount of spirodilactone. 
When the ketodiacid precursor is a ketodiacid or reactive derivative 
thereof, the catalyst is any material that is suitable as an 
esterification or transesterification catalyst, including strong acids, 
such as sulfuric, benzenesulfonic, hydrochloric acid or the like, tin 
salts, organo-titanium compounds, silica gel, cation-exchange resins and 
the like. 
When the ketodiacid precursor is the acid halide, the reaction mixture 
should contain a halide acceptor, which is usually an amine of the type 
conventionally known in the art for the purpose of accepting halide ions 
formed during a reaction, for example, pyridne or the like. Part of up to 
essentially all of the hydroxy or thiol groups can be esterified with part 
or all of one or both carboxyl groups of the ketodiacid precursor 
(optionally replaced in part by dicarboxylic acid precursor). It is 
preferred that the reaction be conducted until the desired, usually 
substantially complete, mono- or diesterification (crosslinking) of the 
hydroxylated or thiolated polymer has been obtained. The degree of mono- 
or diesterification can be as low as about 1% of the hydroxy or thiol 
groups with the upper limit being as high as about 80% or preferably about 
90% to about 100% of the hydroxy or thiol groups in the polymer. 
The amount of ketodiacid precursor used depends on the degree of 
esterification desired. If monoesterification is desired in which the 
product is a half ester containing an ester group and a carboxylic acid 
group, then at least an equivalent amount of ketodiacid or spirodilactone 
to hydroxy or thiol groups is used, and preferably an excess of up to 20% 
by weight over the stoichiometric proportions required in order to ensure 
substantially complete monoesterification. If diesterification 
(crosslinking) is desired by at least some degree of esterification with 
both carboxyl groups, the reactant must be a ketodiacid or reactive 
derivative thereof and not a spirodilactone, and the proportions of the 
acid or reactive derivative can be adjusted as can be determined by those 
of skill in the art to give the desired amount of crosslinking. 
The reaction is usually conducted at normal pressures, although lower and 
higher pressures can be used. The reaction temperature can vary but good 
reactions are obtained when the reaction is conducted at elevated 
temperatures of from about 50 to about 150 degrees C., preferably from 
about 60 to about 100 degrees C. 
The reaction is usually conducted by forming a mixture of the hydroxylated 
or thiolated polymer, the ketodiacid precursor and optionally one or more 
dicarboxylic acid reactants, preferably the dicarboxylic acid anhydride, 
and optionally one or more catalytic materials and/or diluents or the like 
and heating the resulting mixture while agitating, e.g., stirring, until 
the desired esterification takes place and recovering the ketocarboxylated 
polymer product. 
The ketocarboxylated polymers of the invention have a molecular weight in 
the range of from about 1,000 to about 500,000, preferably from about 
10,000 to about 100,000. 
Use 
The ketocarboxylated polymers of the invention have a variety of uses 
depending on the kind of polymer backbone, the molecular weight and the 
degree of hydroxylation or mercaptation in the polymer reactant, the 
degree of subsequent ketocarboxylation in the final product and the 
degree, if any, of the crosslinking in the final product. Depending on the 
polymer, the products can be very hydrophillic and can be used wherever 
such properties are desired in polymeric materials, such as household or 
personal care products. 
The ketocarboxylated polymers can be used in adhesives, as coating, as 
membranes, as molding materials and the like. For example, when the 
polymer backbone is polyvinyl alcohol, the ketocarboxylated polymer of the 
invention can absorb many times its own weight of water and such property 
can be used in oil recovery fluids, in inks, in the medical field, e.g., 
as a material for contact lens membranes, in the food industry, in 
agriculture or the like. Other uses include: as a sizing for paper, in 
fabric treating and the like.

ILLUSTRATIVE EMBODIMENTS 
The following embodiments are provided to illustrate the invention and 
should not be regarded as limiting it in any way. Nuclear Magnetic 
Resonance Spectra analyses were used to confirm the structure of the 
products. 
EMBODIMENT 1 
Polyvinyl Alcohol 4-Ketopimelate 
A mixture of 44 g of polyvinyl alcohol and 10 g of 
1,6-dioxa-spiro[4.4]nonane-2,7-dione, 200 ml of acetic acid and 20 g of 
sodium acetate was stirred for 3 hours at 85 degrees C. After cooling the 
resulting mixture, water was added to wash the product and a quantitative 
yield of the desired product was obtained having the formula 
##STR14## 
EMBODIMENT 2 
Polyvinyl Alcohol 4-Ketopimelate Phthalate 
A mixture of 44 g of polyvinyl alcohol and 10 g of 
1,6-dioxa-spiro[4.4]nonane-2,7-dione, 10 g of phthalic anhydride' 300 ml 
of acetic acid and 20 g of sodium acetate was stirred for 3 hours at 85 
degrees C. After cooling the resulting mixture, water was added to wash 
the product and a quantitative yield g of the desired product was obtained 
having the formula 
##STR15## 
EMBODIMENT 3 
Hydroxypropyl Cellulose 4-Ketopimelate 
A mixture of 40 g of hydroxypropyl cellulose and 40 g of 
1,6-dioxaspiro[4.4]nonane-2,7-dione, 300 ml of acetic acid and 20 g of 
sodium acetate was stirred for 3 hours at 85 degrees C. After cooling the 
resulting mixture, water was added to wash the product and a quantitative 
yield of the desired product was obtained. 
EMBODIMENT 4 
Hydroxypropyl Cellulose 4-Ketopimelate Phthlate 
A mixture of 20 g of hydroxypropyl cellulose and 10 g of 
1,6-dioxaspiro[4.4]nonane-2,7-dione. 10 g of phthalic anhydride' 150 ml of 
acetic acid and 10 g of sodium acetate was stirred for 3 hours at 85 
degrees C. After cooling the resulting mixture, water was added to wash 
the product and a quantitative yield of the desired product was obtained. 
EMBODIMENT 5 
Cellulose Acetate 4-Ketopimelate 
A mixture of 10 g of cellulose acetate and 10 g of 
1,6-dioxaspiro[4.4]nonane-2,7-dione, 75 ml of acetic acid and 5 g of 
sodium acetate was stirred for 3 hours at 85 degrees C. After cooling the 
resulting mixture, water was added to wash the product and quantitative 
yield of the desired product was obtained.