WO1990014153A1 - Poly(alkylene carbonate) polyahls having more than one pendant acid group - Google Patents

Abstract

Poly(alkylene carbonate) polyahl polymers containing two or more acid-terminal moieties are disclosed. Acid-terminal polyahls provided herein are useful as surfactants or as intermediates for the syntheses of other polymers.

Description

POLY(ALKYLENE CARBONATE) POLYAHLS HAVING MORE THAN ONE PENDANT ACID GROUP

This invention relates to poly(alkylene carbonate) polyahls.

Poly(alkylene carbonate) polyahls are randomized polymers containing active hydrogen end groups and alkylene carbonate moieties and other moieties such as di- and higher polyalkylenoxy units. An alkylene carbonate moiety is a repeating unit comprising an alkylene group bound to a carbonate moiety. Some of the known poly(alkylene carbonate) polyahls are non-ionic surfactants.

In 1978, DE 2,712,162 to Stuehler disclosed non-ionic surfactants containing carbonate moieties in the backbone. A variety of surfactants have been described in a series of patents. U.S. Patent 4,072,704 described the coupling of polyethylene glycols and polypropylene glycols with either dialkyl carbonates or formaldehyde to give materials with surface active properties. In U.S. Patent 4,353_*834, it was described how long chain amides or sulfonamides have been coupled with hydrophilic polyglycols using dialkyl carbonates or esters of dicarboxylic acids to give materials with surface active properties. This work was extended in U.S. Patent 4,504,418 to include polyoxyalkylene polymers and monofunctional aliphatic, aromatic or aliphatic-aromatic alcohols coupled by alkyl carbonates or esters of dicarboxylic acids to give materials with surface active properties.

U.S. Patent 4,330,481 to Timberlake et al. described the preparation of surfactants by reacting

10 alcohols or alcohol ethoxylates with ethylene carbonate. These products were then further reacted with ethylene oxide to produce different surface active materials as reported in U.S. Patent 4,415,502. The preparation of -j- surfactants and functional fluids by reacting alcohols, phenols or carboxylic acids (or their alkoxylated derivatives) with alkylene carbonates or alkylene oxides and carbon dioxide was described in U.S. Patent 4,488,982 to Cuscurida.

20

U.S. Patent 4,382,014 to Sakai et al. described the preparation of surface active materials by reacting alcohols, carboxylic acids or primary or secondary amines containing four or more carbon atoms or

25 substituted phenols with alkylene carbonates in the presence of an -ate complex of a metal of Group II, III or IV of the Periodic Table having at least two alkoxyl groups.

30 Low molecular weight polyoxyethylene glycol monomethyl ethers have been coupled using phosgene or alkyl carbonates to give materials useful in formulating brake fluids and as synthetic lubricants, as disclosed in U.S. Patent 3,632,828. The coupling of monofunctional alcohols, phenols, or their ethoxylated derivatives using diphenyl carbonate to give surfactants was disclosed in U.S. Patent 3,332,980.

In 1981, U.S. Patent 4,267,120 to Cuscurida et al. described polyester polycarbonates terminated with hydroxyl groups obtained by the reaction of a cyclic organic acid anhydride, a 1,2-epoxide, carbon dioxide and a polyhydric compound in the presence of a basic catalyst. The Cuscurida et al. polymers are hydroxy-functional materials. In the Cuscurida et al. patent, the cyclic anhydride is present during polycarbonate preparation and is therefore chemically incorporated into the polymeric backbone.

The applications of non-ionic poly(alkylene carbonate) polyahl surfactants are limited due to their very poor water solubility and wetting times. In addition, these non-ionic surfactants also form poor foams evidencing poor foam stability, which in specific instances may be an advantage or a disadvantage depending on the particular application. Further, fairly high concentrations of these non-ionic surfactants are required before any surface active properties, like lowering the surface tension of water, are evidenced.

Unfortunately, conventional non-ionic poly(alkylene carbonate) polyahls are not as efficient surfactants as are desired for certain application. Therefore, there still is a need for more efficient poly(alkylene carbonate) polyahl surfactants which retain the beneficial characteristics of conventional poly(alkylene carbonate) polyahls such as biodegradability. The present invention relates to a novel, acid- -functional poly(alkylene carbonate) polyahl having more than one pendant acid moiety or salts thereof. For the purposes of this invention, the term "acid-functional polymer" encompasses polymers having on the average more than one acid moiety, salt moiety or combination thereof per polymer molecule. A group of preferred polymers have two pendant acid moieties. These difunctional polymers and salts thereof are effective anionic triblock surfactants.

In addition, this invention includes poly(alkylene carbonate) polyahls having three or more, and up to and including eight, pendant acidic moieties.

The acid-functional polymers having from two to four acid moieties are particularly useful as intermediates for preparing other monomers and polymers. As such, they can be further reacted, e.g., with polyols to produce polyesters, with polyamines to produce polyamides or with epoxy resins to produce modified epoxy resins.

The surfactant properties of the present products, i.e., the acid-functional poly(alkylene carbonate) polyahls having a terminal acidic group or salts thereof, can be varied by varying the molecular weight and the backbone structure of the polymers, the length of the substituents, -the type of the terminal acidic moieties and the molar ratio of the reactants.

The carbonate backbone of the anionic surfactants of the present invention can be degraded by bases, strong acids or by biodegradation. Accordingly, they will be degraded naturally and will not persist in the environment. This is an extremely advantageous characteristics, already required by law in many localities.

The novel compositions of this invention combine useful surfactant properties of non-ionic surfactants such as non-ionic poly(alkylene carbonate) polyahls with improved properties obtainable from anionic surfactants. The anionic properties are imparted to the present polymers by the salt forms of terminal acidic moieties appended to the polycarbonate backbone thereof. The present acid-functional surfactants and acid-functional polymer intermediates can be degraded by bases, strong acids or under biodegradative conditions. This makes them fugitive and biocompatible since they do not persist in the environment.

The combination of a non-ionic backbone and the terminal acidic moieties renders the present polymers superior surfactants, and that, at much lower concentrations than the non-ionic polymers from which the present surfactants are derived. This, in turn, provides a significant economic advantage in terms of materials and cost savings. Additionally, the present acid-functional polymers evidence increased water solubilities when compared with their non-ionic counterparts. This can translate into new applications of the surfactants as well as easier handling thereof. Moreover, the increased surface active and water soluble characteristics of the present acid-functional polymers also result in decreased wetting times when compared with the corresponding non-ionic polymers. Some of the present acid-functional polymers also afford higher foam height and foam stabilities than those of the corresponding non-ionic polymers.

The present acid-functional polymers are cost- -effective surfactants. In general, the most expensive portion of a surfactant molecule is the hydrophobic portion. In a large number of commercially important surfactants, this portion is commonly derived from fatty alcohols or fatty acids. This accounts for the high cost of manufacturing the prior art surfactants.

10 Somewhat less expensive surfactants are those derived from poly(propylene oxides) as the source of the hydrophobic portion. The surfactants of this invention derive their hydrophobic nature from the content of « - carbon dioxide in their backbone. Since CO2 is among the least expensive sources which can be used as the hydrophobic portion of a surfactant, the acid-functional surfactants of this invention are extremely cost-effective.

20

In addition to their lower cost, a significantly lower amount thereof is required than of the corresponding non-ionic surfactants from which they are derived, which make the present acid-functional

25 surfactants still more economically attractive. Since these surfactants contain CO2 in their backbone, they are fugitive and do not persist in the environment.

They can be readily degraded by bases, strong acids or by biological degradation to water-soluble, non-surface

30 active materials. These novel acid-functional polymers can be produced by the reactions of poly(alkylene carbonate) polyahls with acid donor materials.

Poly(alkylene carbonate) polyahls are randomized polymers having a plurality of carbonate moieties and a plurality of active hydrogen moieties and optionally other moieties such as di- and higher polyalkyleneoxy units. An alkylene carbonate moiety is a repeating unit which has an alkylene group bound to a carbonate moiety. An active hydrogen moiety is a moiety containing a hydrogen atom which, because of its position in the moiety, displays significant activity according to the Zerewitnoff test described by Kohler,

J. Amer. Chem. Soc, 49:3181 (1927). Illustrative of such active hydrogen moieties are -C00H, -OH, -NH₂,

-NH-, -C0NH₂, -SH and -C0NH-. Alkyleneoxy moiety refers herein to a repeating unit which has an alkylene group bound to oxygen. Alkylene carbonate and alkyleneoxy moieties are respectively represented by the following formula C(R²)₂-C(R²)₂-0C0

II

0 and

wherein R² is as hereinafter defined.

Preferred poly(alkylene carbonate) polyahls are random polymers represented by the formula:

0 R¹[X C(R²)₂C(R²)₂0-)yKC(R²)₂C(R²)₂0CQ*χ-(-R¹ (XA)_n.-, )_Z-H]_n

wherein

R¹ is separately in each occurrence an n-valent hydrocarbon radical or hydrocarbon radical which can contain one or more heteroatoms of 0, N or S; R² is separately in each occurrence hydrogen, halogen, a nitro group, a cyano group, a C-_]__2Q hydrocarbyl group or a C-_]_₂₀ hydrocarbyl group substituted with one or more of the following: a halo, cyano, nitro, thioalkyl, tert-amino, alkoxy, aryloxy, aralkoxy, carbonyldioxyalkyl, carbonyldioxyaryl, carbonyldioxyaralkyl, alkoxycarbonyl, aryloxycarbonyl, aralkoxycarbonyl, alkylcarbonyl, arylcarbonyl, aralkylcarbonyl, alkylsulfinyl, arylsulfinyl, aralkylsulfinyl, alkylsulfonyl, arylsulfonyl, or aralkylsulfonyl group;

x is separately in each occurrence S , 0 , NH , 0 0 0

II II II

-CO- , -0C0- , or -0CNH- ;

A is separately in each occurrence 0

II C(R²)₂C(R²)₂-0CQ-)-_χ, -fC(R²)₂C(R²)₂0 _y or

combinations thereof or a covalent bond;

Q is separately in each occurrence 0, S or NH provided that all carbonate moieties are internal because terminal carbonate moieties are unstable and form OH moieties by the elimination of C0₂;

n is separately in each occurrence an integer of from 1 to 25; x is separately in each occurrence an integer of from 1 to 40;

y is separately in each occurrence an integer of from 1 to 120; and

z is separately in each occurrence an integer of from 0 to 5.

A more preferred class of poly(alkylene carbonate) polyahls are poly(alkylene carbonate) polyols generally corresponding to the aforementioned formula wherein R , R², and n are as previously defined; X is oxygen; x is separately in each occurrence an integer of from 2 to 10; y is separately in each occurrence an integer of from 5 to 15 and z is an integer of from 0 to 2; provided that the ratio of y to x is from 1:1 to 3:1.

In the hereinbefore-defined formulas, R¹ is preferably an aliphatic or cycloaliphatic hydrocarbon containing one or more oxygen, nitrogen or sulfur moieties; R^ is more preferably an n-valent alkane or cycloalkene, or an n-valent alkane or cycloalkane containing one or more oxygen, nitrogen or sulfur moieties; R' is even more preferably an n-valent C-_j_ _Q alkane or an n-valent C-_|_I alkane substituted with one or more oxygen moieties. R² is preferably hydrogen, C-_|_ ø alkyl, C-_]__2Q haloalkyl, C-_|__2Q alkenyl or phenyl; R2 is more preferably hydrogen, C-_|_3 alkyl, C₂_ alkenyl or phenyl; R² is even more preferably hydrogen, methyl or ethyl; R² is even more preferably hydrogen or methyl, and, most preferably, hydrogen. X is preferably S, 0 or NH and X is most preferably 0. Preferably, n is an integer of 1 to 10, inclusive, more preferably, 1 to 5, inclusive, most preferably, 1 or 2. As used herein, the term "polyahl" includes polyfunctional compounds having on average more than 1 active hydrogen moiety as defined hereinbefore. Specifically included within the definition of polyahl are polyols, polyamines, polyamides, polymercaptans and polyacids. Examples of polyahls suitable for use in the instant invention may be found in U.S. Patent 4,465,713 at column 2, line 42, through column 5, line 17.

Poly(alkylene carbonate) polyahl starting materials useful in this invention are prepared by any method known in the art, such as the condensation of an alkylene carbonate, carbon dioxide and an alkylene oxide, or mixtures of an alkylene carbonate, an alkylene oxide and/or C0₂, with an organic compound containing one or more active hydrogens atoms (initiator) in the presence of an alkaline catalyst or metal salt of an alkaline compound. Examples of these poly(alkylene carbonate) polyols and methods for preparing these polyols are contained in U.S. Patent 3,896,090 to

Maximovich, U.S. Patent 3,689,462 to Maximovich, U.S. Patent 3,313,782 to Springmann, U.S. Patent Nos. 3,248,414, 3,248,415 and 3,248,416 to Stevens. Alternatively, the poly(alkylene carbonate) polyahls can be prepared by reacting a dialkyl or diaryl carbonate with an initiator with two or more hydroxyl moieties. See, for example, U.S. Patent 4,476,293 and U.S. Patent 4,191,705.

The poly(alkylene carbonate) polyahls used as starting materials may also contain the residue of an initiator as well as unreacted starting materials and other relatively volatile reaction products. The poly(alkylene carbonate) polyahl starting materials can be modified with other active hydrogen compounds prior to reaction with acid donor materials by the processes of U.S. Applications Serial Nos. 799,211 filed on November 18, 1985; 750,362 filed on July 1, 1985; 809,675 filed on December 16, 1985; 831,761 filed on February 21, 1986 and 885,118 filed on July 14, 1986 by the present inventor.

Organic compounds suitable as modifiers for modifying poly(alkylene carbonate) polyahls according to this invention are polyfunctional materials which are reactive with the carbonate and/or active hydrogen moieties of poly(alkylene carbonate) polyahls.

Most polyahls are reactive with the carbonate moieties of poly(alkylene carbonate) polyahls. Typical polyahls include polyols, polyamines, polyamides, polymercaptans and polyacids.

The polyols are preferred among the foregoing polyahls. Examples of such polyols are polyol polyethers, polyol polyesters, hydroxy functional acrylic polymers, hydroxyl-containing epoxy resins, polyhydroxy terminated polyurethane polymers, polyhydroxyl-containing phosphorus compounds and alkylene oxide adducts of polyhydric thioethers including polythioethers, acetals including polyacetals, aliphatic and aromatic polyols and thiols including polythiols, amines including aromatic, aliphatic and heterocyclic amines, polyamines and mixtures thereof. Alkylene oxide adducts of compounds which contain two or more different groups within the above-defined classes may also be used such as amino alcohols which contain an amino group and a hydroxyl group. Alkylene adducts of compounds which contain one -3H group and one -OH group as well as those which contain an amino group and a -SH group may also be used.

A variety of amines can function as the modifier. Any polyfunctional amino compound can be used that is less volatile than the dialkylene glycol, trialkylene glycol or initiator molecule that is being removed during molecular weight advancement. A preferred class of polyamines are those prepared by the reductive amination of polyols. Examples of such polyamines can be found in U.S. Patent Nos. 3,128,311; 3,152,998; 3,347,926; 3,654,370; 4,014,933 and 4,153,581.

It is preferred to remove the catalysts used to prepare the starting poly(alkylene carbonate) polyahls prior to the performance of the present process. However, in some cases the catalyst is advantageously retained in the pol (alkylene carbonate) polyahl and is used to catalyze reaction with acid donor materials.

The acid donor materials capable of reacting with the poly(alkylene carbonate) polyahls to add terminal acidic groups thereto may be selected from a large number of compounds known in the art. Suitable acid-terminal moieties are -C00H, -S0₂H, -SO3H, -SO4H, -P0i_|H₂, -PU3H₂ or sulfosuccinates. The following are provided by means of example of acid donor materials.

Cyclic anhydrides selected from the group consisting of alkylcyclic anhydrides, cycloalkylcylic anhydrides, arylcyclic anhydrides, alklaryl cyclic anhydrides and aralkylcyclic anhydrides. Among these, more preferred are Cj_j__22| alkylcyclic anhydrides, Cg_ i cycloalkylcyclic anhydrides, Cg_₂i_j aralkylcyclic anhydrides,

alkylarylcyclic anhydrides. The anhydrides may be further substituted with halogens, alkyl, alkyl carbonyl and aryl, among other substituents. Examples include succinic anhydride, maleic anhydride, phthalic anhydride, bromomaleic anhydride, dichloromaleic anhydride, dimethylmaleic anhydride, dimethylsuccinic anhydride, 2-dodecen-1-yl succinic anhydride, glutaric anhydride, heptanoic anhydride, hexanoic anhydride, homophthalic anhydride, 3-methylglutaric anhydride, methylsuccinic anhydride and 2-phenylglutaric anhydride. The most preferred anhydrides are succinic anhydride, maleic anhydride and phthalic anhydride. However, any anhydride can be used which is capable of reacting with a monofunctional alcohol, mercaptan, carboxylic acid or primary or secondary amine to provide a terminal carboxylic acid moiety.

The formation of sulfosuccinates is a special case of cyclic anhydride reactions. A poly(alkylene carbonate) polyahl is allowed to react with maleic anhydride and sodium bisulfite. A sulfosuccinate has the following structure:

-CH₂CH-C0₂H

Other types of compounds capable of adding a terminal acidic group to the non-ionic polymers are compounds containing sulfonic acid, sulfinic acid or sulfuric acid terminal moieties and salts thereof. By means of example, halosulfonic acids and salts thereof, such as chlorosulfonic acid, sodium chlorosulfonate and chloroethylsulfonic acid can be used. Preferred among these are chlorosulfonic acid, chlorosulfinic acid and chloroethylsulfinic acid.

Still another group of compounds capable of adding an acidic group to a polymer to form the present acid-functional polymers are, e.g., halocarboxylic acids and salts thereof such as chloroacetic acid, sodium chloroacetate, bromoacetic acid, and chloropropionic acid. Most preferred is monochloroacetic acid. Still another group of compounds capable of adding a terminal acidic group are, e.g., inorganic acid anhydrides such

In general, any compound capable of adding a terminal acidic group to non-ionic poly(alkylene carbonate) polyahls without degrading such adduct is suitable for use within the present contest.

The addition of the acidic terminal group to the poly(alkylene carbonate) polyahl is dependent on the nature of the acid donor and the poly(alkylene carbonate) polyahl.

By means of example, the reaction of the substrate polyahls with a carboxylic acid moiety-adding compound will be described in general terms. However, the general requirements are extendable to the reactions adding to the polyahls other terminal acid-functional groups, as well.

Cyclic carboxylic acid anhydrides are the most preferred class of materials used to add a terminal acidic group. Reaction is carried out by contacting a poly(alkylene carbonate)polyahl as defined above with a cyclic carboxylic acid anhydride at temperatures from 80°C to 180°C for a period of minutes to hours. Optionally, a basic catalyst such as an alkali metal or alkaline earth metal carbonate, alkoxide, stannate or borate, or a tertiary amine can be used to increase the reaction rate, if desired. Preferably, a catalyst is not used, thereby eliminating the need for catalyst removal after reaction.

The molar ratio of active hydrogen groups on the poly(alkylene carbonate) polyahl to the cyclic carboxylic acid anhydride can be about 1:1 or greater, provided that more than one acid moiety is incorporated per molecule.

This reaction which chemically incorporates a carboxylic acid-functional moiety on the end of the poly(alkylene carbonate) polyahl is preferably carried out in the absence of a solvent and the product can be used for many applications without further purification. The reaction may, however, be conducted in the presence of inert solvents, if desired. Conversion of the cyclic carboxylic acid anhydride is near 100 percent in most cases. Progress of the reaction can be conveniently followed by monitoring the disappearance of the cyclic anhydride by size exclusion chromatography, or infrared or nuclear magnetic resonance techniques.

When haloacids are used as the source of the acid moiety, they can be added to the poly(alkylene carbonate) polyahl in a solvent, such as methylene chloride, in the presence of a compound capable of acting as an acid acceptor, such as pyridine or triethylamine. The thus obtained product can be recovered after neutralization, removal of by-product salt and solvent stripping. A variety of known neutralizing substances can be used to obtain the salts of the novel acid-functional polymers, such as alkali metal salts, alkaline earth metal salts, amine salts such as alkyl ammonium, cycloalkyl ammonium, alkylaryl ammonium, aryl ammonium and aralkyl ammonium salts, and ammonium salts.

The choice of the particular neutralizing agent used depends to a great extent on which particular salt is required for a specific application since different

10 salts may have widely different compatibilities with other materials in end use applications. Amines such as ammonia, methylamine, dimethylamine, trimethylamine, ethylamines, propylamines, butylamines and longer chain

-j- alkylamines (up to C_2Q alkylamines) are one preferred class of materials. However, others outside of this range may also be used. Among the alkali metal salts, lithium, sodium and potassium are most preferred. Among the alkaline earth metal salts, calcium and magnesium

20 are most preferred.

The method of neutralizing the acid-functional poly(alkylene carbonate) polyahl is important. When strong bases such as alkali metal hydroxides are used, 25 it is important that local excesses of the hydroxides are never present during the neutralization since such conditions lead to hydrolysis of the poly(alkylene carbonate) polyahl backbone. Amines such as ammonia are particularly useful since local excesses do not lead to

30 backbone hydrolysis. Typically, the neutralizing agent is added slowly to the acid-functional poly(alkylene carbonate) polyahl while monitoring the pH of the product. In this way any desired percentage of the acid moieties can be neutralized up to 100 percent. The characteristics cf the novel acid-functional poly(alkylene carbonate) polyahl polymers including their salts can be modified by adjusting the proportion of non-ionic poly(alkylene carbonate) polyahl to the acid group donor compound. A different proportion of ionic to non-ionic characteristics may be desirable for particular applications of the polymer. Thus, when a polymer product having a high anionic characteristic is desired, the ratio of non-ionic polymer to acid group donor may be about 1:1. This will provide a complete conversion of the non-ionic polymer to the anionic polymer.

However, other applications may require a different balance of non-ionic and anionic surfactant capabilities. In some cases a material may be required that has some acid functionality and some hydroxyl or amino functionality as in the case of a chemical intermediate. In such cases, a partial conversion of the non-ionic polymer to the anionic form may be desirable, whereby some non-ionic and some anionic moieties are present in the product. The proportion of non-ionic polymer to acid group donor may be as high as desired. As long as there are, on the average, greater than one acid-functional group per molecule of poly(alkylene carbonate) polyahl. A particularly useful range of proportions of the non-ionic polymer to the acid group donor is between about 1:1.1 and 1:8, more preferably between about 1:2 and 1:4.

The characteristics of the novel acid-functional polymers and their salts can be varied by adjusting, for example, the proportion of the amount of the acid-functional moieties that are converted to salts and the amount present as free acids, βtily partial neutralization may be preferred in some cases,

One preferred class of compositions of the present invention are those compositions which can function as triblock surfactants. These compositions have a poly(alkylene carbonate) backbone and two acid-functional end groups. Such compositions are preferably used in their salt forms and function as anionic surfactants. 0

Another preferred class of compositions are those produced from modified poly(alkylene carbonate) polyahls. These compositions have a random arrangement of both poly(alkylene carbonate) moieties and modifier

15 moieties in their backbone. In this way, the structure of the backbone can be adjusted to give the required hydrophobic properties for a given application. The acid-functional end groups are the source of the _Q hydrophilic properties, particularly those present as salts.

The modified poly(alkylene carbonate) backbone materials are also useful when a particular _pj- compatibility of the surfactant backbone with a particular phase or substrate is required. The backbone can be modified in such a way as to enhance or to minimize such compatibilities.

30 As polymer intermediates, the degree and type of modifier or modifiers used in the backbone of a modified poly(alkylene carbonate) polyahl can have a substantial effect on final polymer properties.

In some cases, a mixture of the present acid-functional polymers with a different non-ionic polymer may be the more suitable solution. For such purposes, an additional non-ionic surfactant may be physically blended in after the present anionic surfactant is prepared. Useful for this application are non-ionic poly(alkylene carbonate) polyahls utilized as starting materials herein or other known poly(alkylene carbonate) polyahls. Also suitable are other non-ionic polymers such as the modified poly(alkylene carbonate) polyahls described in co-pending U.S. Applications Serial Nos. 809,675 or 799,211 by the same inventor, which are herein incorporated in their entireties by reference. Other non-ionic materials can be used in combination with the present acid-functional surfactants such as polyether polyahls, polyester polyahls, alcohol ethoxylates and phenolic ethoxylates.

The surfactants of this invention can also be used in combination with conventional anionic surfactants. Examples of such conventional anionic surfactants include carboxylic acids, oxyacetates, sulfonates, ether sulfates, phosphates, sulfosuccinates and salts thereof.

The present acid-functional surfactants are used in significantly smaller quantities than the corresponding non-ionic surfactants for a variety of applications. When the acid-functional surfactants are utilized to lower the surface tension of water, only a 10 weight percent fraction of the required non-ionic surfactant is needed in many cases.

When used by themselves, the acid-functional surfactants can be effective in amounts between about 0.0002 weight percent and about 10 weight percent. Preferably, they are added in amounts between 0.0005 weight percent and 2.0 weight percent of the total volume, and still more preferably between 0.001 weight percent and 1.0 weight percent.

When used in a composition with other surfactants, the novel acid-functional polyahls are incorporated in amounts between 0.0002 weight percent and 5.0 weight percent of the total volume, more preferably between 0.0005 weight percent and 2.0 weight percent and still more preferably between 0.001 weight

10 percent and 1.0 weight percent. However, the amount of the present surfactants incorporated into such compositions may also be varied outside of the hereinabove stated range as appropriate or required for « - different applications.

The amounts of other surfactants incorporated in the compositicns can also be varied in accordance with the specific application they are intended for.

20 Another preferred class of compositions of the present invention are compositions which can function as intermediates for preparing polymers. These compositions have, on the average, at least about two ₂t- acid-functional end groups per molecule. Higher functionality can be required in certain applications. In such cases, three or more, and up to eight inclusively, acid-functional end groups per molecule can be employed.

30

A wide variety of polymeric materials can be made from the acid-functional compositions of this invention. For example, any polymers can be made that are typically made from polycarboxylic acids, such as, polyesters, polyamides and epoxy resins. The molecular weight and functionality of the resultant polymer can be controlled by the stoichiometry of the reaction. In some cases, it may be desirable to have a high molecular weight polymer whereas in other cases it may be desirable to have a lower molecular weight material with a particular kind of functionality.

Variations in reaction stoichiometry can be illustrated by considering the reactions of the acid-functional poly(alkylene carbonate) polyahls of this invention with epoxy resins. When an equivalent ratio of carboxylic acid to epoxy near 1:1 is used, a relatively high molecular weight resin can be produced. As the equivalent ratio of carboxylic acid to epoxy is lowered, epoxy-functional resins are produced. These epoxy resins are modified with poly(alkylene carbonate) moieties in their backbone. If the equivalent ratio of carboxylic acid to epoxy is increased to above 1:1, carboxylic acid functional polymers and oligomers are produced in which the polymer backbone has been modified with epoxy resin moieties.

Acid-functional poly(alkylene carbonate) polyahls with greater than two acidic moieties per molecule are useful for adding controlled amounts of cross-linking to the resultant polymer.

The above discussion generally describes the present invention. A more complete understanding can be obtained by reference to the following specific examples, which are provided herein for purposes of illustration only, and are not intended to be limiting unless otherwise specified. In the examples, all parts and percentages are by weight unless otherwise indicated. The molecular weights and distributions are determined by size exclusion chromatography (SEC) on Waters Ultrastyragel^® 1,000 A and 10,000 A (1 and 10 micrometers) columns arranged in series, using tetrahydrofuran (THF) as the mobil phase and calibrated with narrow molecular weight poly(ethylene glycol) standards. For purposes of this invention Mn refers to 0 number average molecular weight, Mw refers to weight average molecular weight, Peak refers to molecular weight at the peak of the molecular weight curve, PDI refers to poly dispersity index and is equal to Mn/ Mw. Brookfield LV viscometer equipped with a No. 4 spindle.

15

EXAMPLES

Example 1: Surfactant Prepared from an Ethylene

Carbonate: Diethylene Glycol (50:1) Adduct With Succinic Anhydride 0 A poly(ethylene carbonate) polyol (Sample 1), was prepared from ethylene carbonate (812.8 g, 9.226 mol), diethylene glycol (19.58 g, 0.1845 mol) and sodium stannate trihydrate (8.32 g, 1.0 weight percent). _pc- After 49 hours at 150°C, the EC conversion was

95.0 weight percent and 28.7 weight percent C0₂. The catalyst was removed by dissolving the product in acetone (20 percent in acetone), stirring with anhydrous magnesium silicate (1 g/20 g product) for 2 hours,

30 filtering and stripping the solvent on a rotary evaporator. A portion of the product (26.60 g, 0.0163 mol OH) was combined with succinic anhydride (1.63 g, 0.0163 mol) and sodium stannate trihydrate (0.28 g, 1.0 weight percent) and heated at 120°C for one hour (Sample 23) •

The NMR spectroscopic analysis yielded:

2.6-2.7 δ(singlet, -0₂CCH₂CH₂C0₂-, 1.0) 3-6-3.9 δ(multiplet, -CH₂0CH₂-, 11.7) 4.0-4.4 δ(multiplet, -CH₂0C0₂CH₂-, 8.9)

Titration: 0.609 meq C0₂H/g. Example 2: Surfactant Prepared From an Advanced

Ethylene Carbonate: Diethylene Glycol (50:1) Adduct with Succinic Anhydride

A. A poly(ethylene carbonate) polyol (Sample 2 in Tables Nos. 1 and 2) was prepared from ethylene carbonate and monoethylene glycol (50:1) by a procedure similar to the one in Example 1 above. The product contained 1.75 percent OH and 27.6 weight percent C0₂. A portion of this product (25.00 g, 0.257 mol OH) was combined with succinic anhydride (2.58 g, 0.0257 mol) and sodium stannate trihydrate (0.27 g, 1.0 weight percent) in a 50 ml, 3-necked flask equipped with overhead stirrer, condenser, thermometer, temperature controller and maintained under a nitrogen atmosphere. The flask was heated to 120°C for one hour. Proton NMR (nuclear magnetic resonance) spectroscopic data shows complete conversion of the succinic anhydride. The product (27.0 g) is a very viscous straw-colored liquid (Sample 22). Molecular Weight (By SEC):

Mn=1071

Hw=3662, and

PDI=3.33

Proton NMR spectroscopic data analysis resulted in:

2.6-2.7 δ(singlet, -0₂CCH₂CH₂C0₂-, 1.0)

3.6-3.9 δ(multiplet, ^' -CH₂0CH₂-, 7.8)

₁₀ 4.1-4.5 δ(multiplet, -CH₂0C0₂CH₂-, 6.1)

Titration: 1.168 meq C0₂H/g.

B. A portion of Sample 2 was advanced to a higher molecular weight by heating under a 1.3 mm Hg

15 vacuum to a pot temperature of 210°C while removing volatiles overhead (Sample 3; 1.02 percent OH, 29.3 weight percent C0₂). A portion of Sample 3 (25.00 g, 0.0150 mol OH) was combined with succinic _P0 anhydride (1.50 g, 0.0150 mol) and sodium stannate trihydrate (0.26 g, 1.0 weight percent) in the same apparatus used in (A) above, and the flask was heated to 120°C for one hour.

₂c Proton NMR spectroscopic analysis indicates complete conversion of the succinic anhydride.

The product (25.5 g) was a very viscous straw-colored liquid (Sample 4).

30 Determination of Molecular Weight (by SEC)

Mn=2749 Mw=5515, and PDI=2.01 Proton NMR spectroscopic analysis yielded the following results:

2.6-2.7 δ(singlet, -0₂CCH₂CH₂C0₂-, 1.0)

3.6-3.9 δ(multiplet, -CH₂0CH₂-, 19.8)

4.1-4.5 δ(multiplet, -CH₂0C0₂CH₂-, 17-3)

Tritration indicated: 0.921 meq C0 H/g,

Example 3: Surfactant Prepared From an Ethylene

Carbonate: Diethylene Glycol (200:1) Adduct with Succinic Anhydride

A polyethylene carbonate) polyol (Sample 5 in Tables Nos. 1 and 2) was prepared from ethylene carbonate (875.2 g, 9.9342 mol), diethylene glycol (5.27 g, 00497 mol) and sodium stannate trihydrate

(8.80 g, 1.0 weight percent). After 108 hours at 150°C, the ethylene carbonate conversion was 94.3 percent; 28.2 weight percent C0₂. The catalyst was removed by the same procedure used in Example 1. The product contained 1.15 percent OH and 28.2 weight percent C0₂« A portion of this product (32.72 g, 0.0221 mol OH) was combined with succinic anhydride (2.21 g, 0.0221 mol) and sodium stannate trihydrate (0.35 g, 1.0 weight percent) and heated at 120°C for one hour (Sample 6).

Proton NMR spectroscopic analysis yielded:

2.6-2.7 δ(singlet, -0₂CCH₂CH₂C0₂-, 1.0)

3.6-3.9 δ(multiplet, -CH₂0CH₂-, 13-8) 4.1-4.5 δ(multiplet, -CH₂0C0₂CH₂-, 10.5)

Titration: 0.599 meq C0₂H/g. Example 4: Surfactant Prepared From an Advanced

Ethylene Carbonate: Monoethylene Glycol (100:1) Adduct With Succinic Anhydride

A poly(ethylene carbonate) polyol (Sample 7) was prepared from ethylene carbonate and monoethylene glycol (100:1) by a procedure similar to Example 1. A portion of the product (catalyst removed) was advanced to higher molecular weight by heating under a 0.5 mm Hg vacuum to a pot temperature of 220°C while removing volatiles overhead (Sample 8). This product contained 0.46 percent OH and 30.0 weight percent C0₂.

A portion of the product (25.5 g, 0.00691 mol) was combined with succinic anhydride (0.69 g, 0.00691 mole) and sodium stannate trihydrate (0.26 g, 1.0 weight percent) and heated at 120°C for one hour (Sample 9). Proton NMR spectroscopic analysis yielded:

2.6-2.7 δ(singlet, -0₂CCH₂CH₂C0₂-, 1.0) 3.6-3-9 δ(multiplet, -CH 0CH₂-, 45.5) 4.1-4.5 δ(multiplet, -CH₂0C0₂CH₂-, 37.0)

Example 5: Surfactants Prepared from P-400 Modified Pol (Ethylene Carbonate) Polyols and Succinic Anhydride

A poly(ethylene carbonate) polyol (Sample 10) was prepared from ethylene carbonate (379.07 g, 4.3027 mol), diethylene glycol (9.13 g, 0.0861 mol) and sodium stannate trihydrate (3.88 g, 1.0 weight percent). After 46 hours at 150°C, the ethylene carbonate conversion was 96.2 percent; 29.6 weight percent C0₂ (by NMR). A portion of Sample 10 (262.3 g, 75 weight percent) as described in Tables 1 and 2 containing the sodium stannate catalyst and a poly(propylene glycol) of Mn 400 (87.4 g, 25 weight percent) was heated at 150°C for 4.75 hours to effect transesterification. The catalyst was then removed by the same procedure used in Example 1. The product was Sample 11 (328 g, 3.36 percent OH, 21.1 weight percent C0₂).

A. A portion of Sample 11 (27.08 g, 0.0472 mol OH) as described in Tables 1 and 2 was combined with succinic anhydride (4.72 g, 0.0472 mol) and sodium stannate trihydrate (0.32 g, 1.0 weight percent) and heated at 120°C for one hour (Sample 12).

Proton NMR spectroscope analysis yielded:

0.9-1.3 δ(multiplet, CH₃-, 1.8)

2.6-2.7 δ(singlet, —0₂CCH CH₂C0₂—, 1.0) 3.2-3.9 δ(multiplet, ether, 5.4)

4.0-4.4 δ(multiplet, -CH₂0C0₂CH₂-, 2.6)

Titration: 1.851 meq C0₂H/g.

B. A portion of Sample 11 was advanced to higher molecular weight by heating under a 0.1 mm Hg vacuum to a pot temperature of 184°C while removing volatiles (mainly diethylene glycol) overhead (Sample 13; 3.37 percent OH, 19.8 percent C0₂).

A portion of Sample 13 (20.29 g, 0.0178 mol OH) was combined with succinic anhydride •( 1.78 g, 0.0178 mol) and sodium stannate trihydrate (0.22 g, 1.0 weight percent) and heated at 120°C for one hour (Sample 14).

Proton NMR spectroscopic analysis yielded:

0.9-1.3 δ(multiplet, CHC3-, 4.7)

2.6-2.7 δ(singlet, -0₂CCH₂CH₂C0₂- 1.0) 3.2-3.9 δ(multiplet, - ether, 13-2)

4.0-4.4 δ(multiplet, -CH₂0C0₂CH₂-, 7.2)

Titration: 0.909 meq C0₂H/g.

-- C. A portion of Sample 11 was advanced to higher molecular weight by heating under a 0.1 mm Hg vacuum to a pot temperature of 220°C while removing volatiles (mainly diethylene glycol) overhead (Sample 15; 0.56 percent OH, 20.9 percent C0₂) . A

10 portion of Sample 15 (22.5 g, 0.0074 moi OH) was combined with succinic anhydride (0.74 g, 0.00740 mol) and sodium stannate trihydrate (0.23 g, 1.0 weight percent) and heated at 120°C for one hour (Sample 16).

15 Proton NMR spectroscopic analysis yielded:

0.9-1.4 δ(multiplet, CH -, 12.4)

2.6-2.7 δ(singlet, -0₂CCH₂CH₂C0₂-, 1.0)

3.2-3.9 δ(multiplet, ether 34.6)

20 4.0-4.4 δ(multiplet, -CH₂0C0₂CH -, 17.2)

Example 6: Surfactants Prepared From P-1200 Modified Poly(Ethylene Carbonate) Polyols and Succinic Anhydride

₂₅ A poly(ethylene carbonate) polyol (Sample 16) was prepared from ethylene carbonate (402.0 g, 4.5630 mol), diethylene glycol (9.68 g, 0.0913 mol) and sodium stannate trihydrate (4.12 g, 1.0 weight percent). After 45 hours at 150°C the ethylene carbonate

30 conversion was 95.8 percent; 30.5 weight percent C0 (by NMR). A portion of Sample 16 (285.8 g, 75 weight percent) containing the sodium stannate catalyst and a poly(propylene glycol) of Mn 1200 (95.3 g, 25 weight percent) were heated at 150°C for 6-1/2 hours to effect transesterification. The catalyst was removed as in Example 1 above (Sample 17, 22.9 weight percent C0₂).

A. A portion of Sample 17 (37.58 g, 0.0328 mol OH) was combined with succinic anhydride (3.28 g, 0.0328 mol) and sodium stannate trihydrate 0.41 g, 1.0 weight percent) and heated at 120°C for one hour (Sample 18).

Proton NMR spectroscopic analysis yielded:

0.9-1.3 δ(multiplet, CH3-, 4.7)

2.6-2.7 δ(singlet, —O2CCH2CH2CO2—, 1.0)

3.2-3.9 δ(multiplet, ether, 14.2)

4.0-4.4 δ(multiplet, -CH₂0C0 CH₂-, 7.0)

Titration: 0.908 meq C0₂H/g.

B. A portion of Sample 17 was advanced to higher molecular weight by heating under a 3-4 mm Hg vacuum to a pot temperature of 216°C while removing volatiles (mainly diethylene glycol) overhead (Sample 18; 1.19 percent OH and 21.7 weight percent C0 ). A portion of Sample 18 (24.32 g, 0.01702 mol OH) was combined with succinic anhydride (1.70 g, 0.01702 mol) and sodium stannate trihydrate (0.26 g, 1.0 weight percent) and heated at 120°C for one hour (Sample 19).

Proton NMR spectroscopic analysis yielded:

0.9-1.3 δ(multiplet, CH₃-, 5.4)

2.6-2.7 δ(singlet, 0₂CCH₂CH₂C0₂—, 1.0)

3.2-3.9 δ(multiplet, ether, 16.7)

4.0-4.4 δ(multiplet, -CH₂0C0₂CH₂-, 8.6) Titration: 0.790 meq C0₂H/g.

C. A portion of Sample 17 was advanced to higher molecular weight by heating under a 0.2-1 mm Hg vacuum to a pot temperature of 237°C while removing volatiles (mainly diethylene glycol) overhead

(Sample 20; 0.41 percent OH and 19.3 weight percent C0₂). A portion of Sample 20 (17.7 g, 0.00427 mol OH) is combined with succinic anhydride (0.43 g, 0.00427 mol) and sodium stannate trihydrate (0.18 g, 1.0 weight percent) and heated at 120°C for one hour (Sample 21).

Proton NMR spectroscopic analysis yielded:

0.9-1.4 δ(multiplet, CH₃-, 18.0)

2.6-2.7 δ(singlet, —O2CCH2CH2CO —, 1.0)

3.2-3.9 δ(multiplet, ether, 56.7)

4.0-4.4 δ(multiplet, -CH₂0C0₂CH₂-, 30.0)

Example 7: Surfactant Prepared From 1,12-Diamino- dodecane Modified Poly(Ethylene Carbonate) Polyahl and Succinic Anhydride

A poly(ethylene carbonate) polyol (Mn of 2076, 27.4 weight percent C0₂) was prepared from ethylene oxide and carbon dioxide using diethylene glycol as initiator.

A sample of the poly(ethylene carbonate) polyol (100.5 g) and 1,12-diaminododecane (20.04 g) were combined in a 250 ml flask equipped with condenser, thermometer, and overhead stirrer and maintained under a nitrogen cover. The flask was heated for 4 hours at 125°C. On cooling to ambient temperature, the product (116.6 g) was a white wax (Mn of 1184). A portion of the white wax (84.6 g, 0.221 mol end groups) and succinic anhydride (22.0 g, 0.221 mol) were combined and heated for one hour at 120°C in the same equipment as used above. Size exclusion chromatography showed 100 percent succinic anhydride

5 conversion.

Proton NMR spectroscopic analysis yielded:

1.2-1.6 δ(singlet, (-CH₂)₁₀- 1.0)

10 2.6-2.8 δ(singlet, -0₂CCH₂CH₂C0₂-, 2.5)

3.4-3.9 δ(multiplet, -CH₂0CH₂-, 15.3)

4.0-4.5 δ(multiplet, -CH₂0C0₂CH₂-, 5.6)

Surface tension was 52.8 dynes/cm (52.8 x 10""3 15 N/m) (0.1 percent aqueous solution of the ammonium salt; 23°C).

This example shows that polyamines can be used to make the novel compositions of this invention.

20

Example 8: Surfactant Prepared From 1 , 10-Decanediol

Modified Poly(Ethylene Carbonate) Polyol and

Succinic Anhydride

A sample of the same polyethylene carbonate) _pt- polyol used in Example 7 (100.8 g) , 1 , 10-decanediol

(17.40 g) and sodium stannate trihydrate (0.59 g) were combined in the same equipment used in Example 7. The flask was heated for 3 hours at 150°C. On cooling to ambient temperature, the product (116.5 g) was a light 30 straw-colored viscous liquid (Mn 1,179).

A portion of the viscous liquid (83.3 g, 0.221 mol OH) and succinic anhydride (22.0 g, 0.221 mol) were combined and heated for one hour at 120°C in the same equipment as used above. Size exclusion chromatography showed 100 percent succinic anhydride conversion.

The product was a light yellow viscous liquid having a Brookfield viscosity of 27,100 cps (27.1 Pa-s) at 25°C; Mn is 1301.

Proton NMR spectroscopic analysis yielded:

1.2-2.0 δ( ultiplet, (-CH₂)₁₀- 1.0) 2.6-2.8 δCsinglet, -0₂CCH₂CH₂C0₂-, 2.9)

3.4-3.9 δ(multiplet, -CH₂0CH₂-, 17.5)

4.0-4.5 δ(multiplet, -CH₂0C0₂CH₂-, 7.8)

Surface tension was 48.0 dynes/cm (48 x 10~3 N/m) (0.1 percent aqueous solution of the ammonium salt; 23°C).

This example shows that an oleophilic diol can be used to make the novel compositions of this _Q invention.

The data corresponding to the above examples are given in the Tables hereinbelow. Table 1 contains information on the starting materials whereas Table 2 t- has information on the properties of the polymers obtained.

0

I Too insoluble in THF for accurate SEC determination N. D. not determined

^aAmmonium Salts, 0.1 weight percent in water ^bASTM D-1331 test procedure

°The Syndrome Tape Modification of the Draves-Clarkson wetting test using a nine-inch strip of unmercerized natural cotton cloth tape attached to a one gram hook which in turn is attached to a forty gram weight by thread was used to determine wetting c time. The solution concentration was 0.1% by weight surfactant in deionized water. The arrangement was dropped into a 500 ml. of the surfactant solution. When the tape was wetted, it dropped to the bottom of the graduated cylinder indicating the wetting time.

Foam height was determined using the Hamilton Blender (Model No. 636-3) Foam Test 250 ml of a 0.1? by weight surfactant/water 1 solution was whipped at low speed for one minute. The solution and foam were poured into a standard 500 ml. graduated cylinder having a 4.7 centimeter diameter. The foam height was measured immediately and after five minutes.

N.D. - not determined

15

Example 9: Acid-Functional Poly(Ethylene Carbonate) Polyahl Prepared From An Advanced Poly(Ethylene Carbonate) Polyol

A poly(ethylene carbonate) polyol (Mn of 750,

20 20.0 percent C0₂) was prepared from ethylene oxide and carbon dioxide using diethylene glycol as initiator. A sample of the poly(ethylene carbonate) polyol (1080.7 g) was placed in a 1-liter flask and was heated to 235°C at ₂c 10 mm vacuum to produce a higher molecular weight poly(ethylene carbonate) polyol (Mn of 2279; 873.4 g).

A portion of this higher molecular weight poly(ethylene carbonate) polyol (505.0 g, 0.443 moles 3Q hydroxyl) and succinic anhydride (44.30 g, 0.443 moles) were combined and heated with stirring for 2 hours at 120°C. Proton NMR spectroscopic analysis indicated essentially complete anhydride conversion. Titration of the carboxylic acid end groups with 0.1 N NaOH indicated a molecular weight of 2498. Carbon-13 NMR analysis was consistent with the expected structure. Example 10: Acid-Functional .Poly(Ethylene Carbonate) Polyahl Prepared From an Advanced Poly(Ethylene Carbonate) Polyol

The pol (ethylene carbonate) polyol (Mn of 750) starting material used in Example 9 (853-7 g) was heated to 171°C at 10 mm vacuum to produce a higher molecular weight poly(ethylene carbonate) polyol (Mn of 980 by SEC; 819.0 g).

A portion of this higher molecular weight poly(ethylene carbonate) polyol (818.9 g, 1.67 moles hydroxyl) and succinic anhydride (167-13 g, 1.67 moles) were combined and heated with stirring for 2 hours at 120°C. Proton NMR spectroscopic analysis indicated essentially complete anhydride conversion. Titration of the carboxylic acid end groups indicated a molecular weight of 1050. Carbon-13 NMR analysis was consistent with the expected structure.

Examples 9 and 10 illustrate a preferred procedure for making the products of this invention wherein no catalyst is used.

Example 11: Reaction Products of Acid-Modified

Poly(Ethylene Carbonate) Polyahls with Epoxy Resins

A portion of the acid-functional poly(ethylene carbonate) polyol product of Example 10 (105.0 g, 0.200 moles -CO2H), a liquid epoxy resin based on bisphenol A and epichlorohydrin (73.6 g, 0.402 moles epoxy) and a phosphonium acetate catalyst, 0.94 g, 0.5 weight percent) were combined in a 250 ml flask equipped with overhead stirring, thermometer and heater, and maintained under a nitrogen atmosphere. The contents of the flask were heated at 110°C for 75 minutes and then cooled to ambient temperature. The product was a viscous amber liquid with the following properties: epoxy equivalent weight was 940; Brookfield viscosity was 890,000 cps (890 Pa-s) at 25°C. Carbon-13 NMR and SEC analysis yielded results which are consistent with the expected structure of an epoxy resin containing a poly(ethylene carbonate) backbone.

A portion of this resin (62.5 g) was advanced to a higher molecular weight resin by heating with bisphenol A (6.67 g) for 1 hour at 125°C. Size exclusion chromatography indicated complete bisphenol A conversion. The product was a viscous brown liquid with an epoxy equivalent weight of 4185.

This experiment shows that the acid-functional poly(alkylene carbonate) polyahls of this invention can function as polymer intermediates by reacting with epoxy resins to produce higher molecular weight epoxy resins containing poly(alkylene carbonate) moieties in their backbone.

It is understood that various other modifications will be apparent to, and can readily be made by, those skilled in the art without departing from the scope and spirit of this invention. Accordingly, it is not intended that the scope of the claims appended hereto be limited to the description of said forth herein, but rather that the claims be construded as encompassing all the patentable novelty features that reside in the present invention, including all features that would be treated as equivalents thereof by those skilled in the art to which this invention pertains.

Claims

1. An acid-functional polymer having a poly(alkylene carbonate) backbone and on the average greater than one pendant acid moiety or salts thereof.

2. A polymer as claimed in Claim 1 wherein the pendant acid moiety is -C00H, -S0₂H, -SO3H, -SO4H,

-Pθ3H₂, -P0i_|H₂ or sulfosuccinate.

3- A polymer as claimed in Claim 1 which is the reaction product of:

(a) a poly(alkylene carbonate) polyahl which is a randomized polymer represented by the formula

0

II

R¹[X-eC(R²)₂C(R²)₂0^_y- (C(R²)₂C(R )₂0CQ^ fR¹(XA)_n_₁)_z-H]_n

wherein

R' is separately in each occurrence an n-valent hydrocarbon radical or hydrocarbon radical which can contain one or more heteroatoms of 0, N or S;

R² is separately in each occurrence hydrogen, halogen, nitro, cyano, C-_|_₂g hydrocarbyl or C-_|__2Q hydrocarbyl substituted with one or more halo, cyano, nitro, thioalkyl, tert-amino, alkoxy, aryloxy, aralkoxy, carbonyldioxyalkyl, carbonyldioxyaryl, carbonyldioxyaralkyl, alkoxycarbonyl, aryloxycarbonyl, aralkoxycarbonyl, alkylcarbonyl, arylcarbonyl, aralkylcarbonyl, alkylsulfinyl, aralkylsufinyl, alkylsulfonyl, arylsulfonyl or aralkylsulfonyl;

5

X is separately in each occurrence S, 0, NH,

0 0 0

II II II

-CO , -0C0- or -0CNH-;

10 A is separately in each occurrence

0

II

-(-C(R²)₂C(R²)₂-0CQ-)-_χ , -C(R²)₂C(R²)₂0-)-_y ,

,₅ combination thereof or a covalent bond;

Q is separately in each occurrence 0, S or NH provided that all carbonate moieties are internal because terminal carbonate moieties are unstable and _P0 form OH moieties by the elimination of C0₂;

n is separately in each occurrence an integer of from 1 to 25;

x is separately in each occurrence an integer

25 of from 1 to 40;

y is separately in each occurrence an integer of from 1 to 120; and

30 z is separately in each occurrence an integer of from 0 to 5, and (b) an acid donor material capable of reacting with the poly(alkylene carbonate) polyahl to add terminal acid-functional groups thereto.

4. A polymer as claimed in Claim 3 wherein the donor capable of reacting to add terminal acid- functional groups thereto is a

cyclic organic acid anhydride, halo or haloalkyl sulfonic acid, halo or haloalkyl carboxylic acid, or inorganic acid anhydrides.

5. A polymer as claimed in Claim 1 wherein the acid moiety is a salt which is an alkyl, cycloalkyl, alkylaryl, aralkyl, hydroxyalkyl, hydroxycycloalkyl, hydroxalkylaryl, or hydroxyaralkyl amine salts.

6. A polymer as claimed in Claim 3 wherein

X is 0, S or NH, 0 x is separately in each occurrence an integer from 2 to 10,

y is separately in each occurrence an π integer from 5 to 15, and

z is an integer from 0 to 2, provided that the ratio of y to x is from about 1:1 to 3:1.

0

7. A polymer as claimed in Claim 6 wherein

(1) R' is aliphatic or cycloaliphatic hydrocarbon containing one or more oxygen, nitrogen, or sulfur moieties;

R² is hydrogen, C₁_₂₀ alkyl, C-_|_₂₀ haloalkyl, C-_|_₂g alkenyl or phenyl;

x is S, 0, or NH; and

₀ n is an integer from 1 to 10;

(2) R' is an n-valent alkane or cycloalkane or an n-valent alkane or cycloalkane containing one or more oxygen, nitrogen, or sulfur moieties; 5

R* is hydrogen, methyl or ethyl;

X is 0; and

n is an integer from 1 to 5; or 0

(3) R is an n-valent C-_j_-_|Q alkane or an n-valent C-_]_-_|0 alkane substituted with one or more oxygen moieties;

c R² is hydrogen or methyl; and

n is 1 or 2.

8. A polymer as claimed in Claim 1 having a poly(alkylene carbonate) backbone and at least one modifier in the backbone.

9. A polymer as claimed in Claim 8 wherein said modifier is a

polyamine, polyester , cyclic anhydride, or a polyahl containing two or more functional groups.

10. A composition comprising

between 5 weight percent and 95 weight percent of the polyahl of Claim 1, and

between 95 weight percent and 5 weight percent of a non-ionic polymer or a. different anionic polymer.