AU606678B2 - Acid-functional poly(alkylene carbonates) - Google Patents

Description

71

I'

OPI DATE 22/09/89 AOJP DATE 19/10/89 PCr APPLN. ID 14922 88 PCT NUMBER PCT/US88/00590 8: INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (51) International Patent Classification 4 (I tern on blication Number: WO 89/ 07976 B01F 17/52, C08L 69/00 CO8G 63/62 (43 ter ationalublication Date: 8 September 1989 (08.09.89)' (21) International Application Number: PCT/US88/00590 (22) International Filing Date: 24 February 1988 (24.02.88) (71) Applicant: THE DOW CHEMICAL COMPANY [US/ US]; 2030 Dow Center Abbott Road, Midland, MI 48640 (US).

(72) Inventor: HARRIS, Robert, F. 4311 Congress, Midland, MI 48640 (US).

(74) Agent: DAMOCLES, Nemia, The Dow Chemical Company, P.O. Box 1967, Midland, MI 48641-1967

(US).

(81) Designated States: AT (European patent), AU, BE (European patent), BR, CH (European patent), DE (European patent), FR (European patent), GB (European patent), IT (European patent), JP, LU (European patent), NL (European patent), SE (European patent).

Published With imernational search report.

a-,m .7 jJ I (54)Title: POLY(ALKYLENE CARBONATE) POLYAHLS HAVING ON THE AVERAGE UP TO ONE ACID- TERMINAL MOIETY AND SALTS THEREOF (57) Abstract This invention relates to novel acid-functional poly(alkylene carbonate) polyahls and their salts having surfactarrt activities. These polyahls have, on the average, at least 0.05 and up to and including one hydrophilic terminus per molecule and can be produced by the reaction of a random non-ionic poly(alkylene carbonate) polyahl obtained by reacting a monofunctional alcohol, mercaptan, carboxylic acid, primary or secondary amine, alkyl substituted phenol or alkoxylates thereof with an alkylene carbonate and/or an alkylene oxide and/or carbon dioxide and/or a poly(alkylene carbonate) pofyahl, and admixing a compound capable of adding an acidic end group thereto. This invention also relates to novel anionic poly(alkylene carbonate) polyahis, surfactant compositions comprising the acid-functional polyahls of the invention and other non-ionic surfactants, and surfactant compositions comprising the novel acid-functional polyahls and other anr ionic surfactants.

II

ir i i i WO 89/07976 PCTUS88/00590 -1- POLY(ALKYLENE CARBONATE) POLYAHLS HAVING ON THE AVERAGE UP TO ONE ACID-TERMINAL MOIETY AND SALTS THEREOF The invention relates to polymeric, including oligomeric, compositions containing a poly(alkylene carbonate) backbone.

Poly(alkylene carbonate) polyahls are randomized polymers containing alkylene carbonate moieties and ether 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 in the backbone. A variety of surfactants have been prepared by Langdon and 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 T1 WO 89/07976 PCT/US88/00590 -2dialkyl 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 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 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.

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

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, phenolics or their ethoxylated WO 89/07976 PC/US88/00590 -3derivatives using diphenyl carbonate to give surfactants was disclosed in U.S. Patent 3.332.980.

U.S. Patent 4,267,120 to Cuscurida and Speranza describes novel polyester polycarbonates obtained by reacting a cyclic organic acid anhydride, a 1,2epoxide, carbon dioxide and a polyhydric compound in the presence of a basic catalyst. The resulting polyester polycarbonates are terminated with hydroxyl groups and are not acid-functional materials or surfactants.

These non-ionic surfactants contain a carbonate backbone which can be degraded by bases, strong acids or under biodegradative conditions. This makes these surfactants fugitive and biocompatible since they do not persist in the environment. Unfortunately, these non-ionic poly(alkylene carbonate) polyahl surfactants have limited applications due to their very poor water Ssolubility and wetting times.

In addition, these non-ionic surfactants also form poor foams evidencing poor foam stability, which is specific instances may be an advantage or a disadvantage depending on the particular application.

Also, fairly high concentrations of these non-ionic surfactants are required before any surface active properties, like lowering the surface tension of water, are evidenced.

In view of these shortcomings of poly(alkylene carbonate) polyahl surfactants, there still is a need for biodegradable surfactants having the ability to disperse in water and/or solubilized incompatible components.

1 e- WO 89/07976 PCT/US88/00590 -4- In one aspect, the present invention is a novel acid-functional poly(alkylene carbonate) polyahl polymer which has on the average at least 0.05 and up to one hydrophilic terminus per molecule. The hydrophilic terminus is preferably an acidic moiety such as -COOH, -S02H, -SO 3 H, -S04H, -P0 3

H

2 or -P04H 2 e-fr ulfeouee inate. Salts of these polyahls such as alkali metal, alkaline earth metal, ammonium and amine salts are also included in the term acidfunctional.

In another aspect of this invention, there is provided a poly(alkylene carbonate) polyahl comprising a reaction product of an adduct of at least one monofunctional alcohol, mercaptan, primary or secondary amine or carboxylic acid, C3-24 alkyl substituted phenol or ethoxylates thereof with at least one member selected from the group consisting of an alkylene carbonate, an alkylene oxide and CO2, an alkylene oxide, an alkylene carbonate and carbon dioxide, and a poly(alkylene carbonate) polyahl, and a material capable of reacting with said adduct to add on the average up to one terminal acidic group thereto. These compositions of matter have surface active properties.

This invention also provides salts of these random poly(alkylene carbonate) oligomers and polymers in the form of salts of the terminal acidic group. The salts of the polyahls also have surface active properties.

In another aspect of the invention, novel acidfunctional poly(alkylene carbonate) polyahls and salts thereof are provided, which may be used by themselves WO 89/07976 PCT/US88/00590 or in a composition of matter further comprising additional non-ionic or anionic surfactants or salts thereof.

The novel compositions of this invention combine useful surfactant properties of non-ionic surfactants with improved properties obtainable from acid-functional surfactants. In these compositions, the combination of a poly(alkylene carbonate) polyahl backbone and a terminal acid-functional moiety renders these superior surfactants. The novel compositions can be used at concentrationj much lower than the non-ionic polymers from which the present surfactants are derived, which provides a significant economic Sadvantage in terms of materials and cost savings.

These novel compositions also evidence increased water solubilities when compared with their non-ionic component. The superior characteristics of the novel polyahls permit new applications of the surfactants as well as easier handling thereof. Moreover, the increased surface active and water soluble characteristics of the present anionic polymers also result in decreased wetting times when compared with the non-ionic polymers. The present polymers also afford higher foam height and foam stabilities than those of the non-ionic poly(alkylene carbonate) polyahls.

4 30 One particularly useful characteristic of the surfactants of this invention is their ability to produce stable or readily dispersible water-based emulsions or dispersions of materials such as poly(alkylene carbonate) polyahls, polyether polyahls and polyester polyahls. These emulsions and dispersions provide a convenient low viscosity, readily -9i WO 89/07976 PCT/US88/00590 -6pumpable system that can greatly facilitate the handling of such materials.

Poly(alkylene carbonate) polyahls used in the preparation of the novel polymers of this invention are randomized polymers having a plurality of carbonate moieties and a plurality of active hydrogen moieties.

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 et al. J. Amer.

Chem. Soc. 49:3181 (1927). Illustrative of such hydrogen moieties suitable for preparing the present polymers are aliphatic, alicyclic, aryl, alkylaryl, aralkyl and polyalkyleneoxy monofunctional alcohols, mercaptans, amides, carboxylic acids, primary and secondary amines and alkyl substituted phenols and ethoxylates thereof, among others. Alkyleneoxy moiety refers herein to a repeating unit which has an alkylene group bound to oxygen.

Alkylene carbonate and alkyleneoxy moieties may be respectively represented by the following formulae C(R2)2-C(R2)2-OC02O and

C(R

2 2

-C(R

2 2 -07 wherein R 2 is as hereinafter defined.

The acid-functional polymers of this invention can be prepared from non-ionic poly(alkylene carbonate) polyahls produced by the prcaesa of U.S. AppliUtion WO 89/07976 iDi addition convenien with an a -COOH, cy haloacids i PCT[US88/00590 -7- 885,118 filed on July 1i,1986 by the preSent_.

-or by othr known processes, followed by the thereto of an acid-terminal group. This is tly done by reacting the non-ionic polymer cid group donor, such as, in the case of clic anhydrides, acid anhydrides and I 15 Preferred acid-functional polymers of this invention may be prepared by reacting adducts of monofunctional alcohols, carboxylic acids, mercaptans, primary or second amines, C3_24 alkyl substituted phenols or

C

2

-C

5 0 alkoxylates thereof, and either alkylene carbonates, alkylene oxides and C0 2 a mixture of alkylene carbonates, alkylene oxides and C02 or poly(alkylene carbonate) polyahls with materials capable of reacting with the adducts to add an acidic end group thereto.

Many of the adducts formed prior to the addition of the acid-functional moiety are known compositions and can be represented by the formula

R

1 wherein

R

1 is a residue from a C4- 30 monofunctional alcohol, mercaptan, carboxylic acid, primary or secondary amine, or C3_24 alkyl substituted phenols or C 2

-C

5 0 alkoxylates of a monofunctional alcohol, mercaptan, carboxylic acid, primary or secondary amine or alkyl WO 89/07976 PCT/US88/00590 -8phenol, X is separately in each occurrence

-ZCOOC(R

2 2

-C(R

2 2 -O-C(R2) 2

-C(R

2 2 when alkylene carbonates or alkylene oxides and CO 2 are used, wherein Z is 0, S, NH, or NR 3 and R 3 is C1-24 alkyl, Y is separately in each occurrence -0-C(R2)2- C(R2) 2 when alkylene carbonates or alkylene oxides and CO 2 are used,

R

2 is separately in each occurrence hydrogen,

C

1 2 0 alkyl, C 7 2 0 aralkyl, C6- 2 0 aryl, C 7 2 0 alkylaryl, C1-20 alkenyl or intertly substituted C1- 20 hydrocarbon, I is a residue of an initiator if a separate initiator is used to form the poly(alkylene process described in co-pending U.S.

Applicati n Serial No. 885,118, or a residue of a modifier f the poly(alkylene carbonate) polyahl is p duced as in U.S. Applications Serial Nos. 79 211 filed on November 18, 1985 and 809,675 file on December 16, 1985.

I is preferably he residue of a polyfunctional C4_ 30 alcohol, amine or mercaptan, n is separately in ea occurrence between 1 and Im is separately in each o currence between 0 k is separately in each occurrence between 0 and 200, and k is separately in each occu ence between 0 to 8; with the provisio that X, and I are spacd in the.p.o-ymer backbne

V

i -8acarbonate) polyahl, or a residue of a modifier if the poly(alkylene carbonate) polyahl is produced as in US Patents Nos 4,686,273 and 4,686,274.

I is preferably the residue of a polyfunctional C4-30 alcohol, amine or mercaptan, n is separately in each occurrence between 2 and m is separately in each occurrence between 0 and 200, and k is separately in each occurrence between 0 to 8; with the proviso that X, Y and I are randomly spaced in the ipolymer backbone.

o oo@ go 0o 0 Zo.Y

DMW

WO 89/07976 PCT/US88/00590 -9- As indicated hereinabove, the starting materials for the preparation of the acid-functional polymers of this invention are poly(alkylene carbonate) polyahls formed from a monofunctional alcohol, mercaptan, carboxylic acid, primary or secondary amine,

C

3 -24 alkyl phenols or alkoxylates thereof, and alkylene carbonate and/or ethylene oxide and CO 2 and/or alkylene carbonate, alkylene oxide and CO 2 and/or a poly(alkylene carbonate) polyahl, and a donor capable of reacting with the adduct to add a terminal acidic moiety to th.e polymer.

Useful monofunctional alcohols particularly suited for the practice of this invention are C4-C30 alkyl alcohols and their C 2

-C

5 0 alkoxylate derivatives, although others may also be used. Alkoxylates can be formed by reacting alcohols with alkylene oxides.

Preferred monofunctional alcohols are C4-C24 alkyl alcohols, still more preferred monofunctional alcohols are C 6

-C

2 0 alkyl alcohols and the most preferred monofunctional alcohols are C 8

-C

18 alkyl alcohols, such as octanol, dodecanol, tetradecanol, hexadecanol and octadecanol.

Suitable monofunctional mercaptans for the synthesis of the present non-ionic polymers are C4-30 alkyl mercaptans and their C 2

-C

50 alkoxylate derivates, although others may be used. Alkoxylates can be formed by reacting mercaptans with alkylene oxides. Preferred monofunctional mercaptans are C4-24 alkyl mercaptans, more preferred are C.6 20 alkyl mercaptans, and the most preferred are C8- 18 alkyl mercaptans such as octylmercaptan, dodecylmercaptan and octadecylmercaptan. However, other mercaptans can also be used.

-Nne-ionico polymeF oomposition2 basedon monofunfctional i 1 WO 89/07976 PCT/US88/00590 -e1eptn re d in .App rliation Seri..

885118fied n Jly1~,196-by t p~s-n- tmnweto_.

As monofunctional carboxylic acids for the synthesis of the non-ionic poly(alkylene carbonate) polyahls, C 4

-C

30 alkyl carboxylic acids and their

C

2

-C

50 alkoxylate derivatives, among others, may be used. Alkoxylates can be formed by reacting carboxylic acids with alkylene oxides. Preferred are C4-C 24 alkyl carboxylic acids, more preferred are C 6

-C

20 alkyl carboxylic acids, and the most preferred are Cg-C18 alkyl carboxylic acids such as lauric acid, stearic acid and oleic acid. However, other carboxylic acids may also be employed.

Suitable monofunctional primary amines for the synthesis of the present non-ionic polymers are C 4

-C

30 alkylamines and their C 2

-C

50 alkoxylate derivatives, among others. Preferred are C4-C 24 alkylamines, still more preferred are Cg-C 20 alkylamines, and the most preferred are Cg-C 18 alkylamines such as octylamine, dodecylamine, tetradecylamine, hexadecylamine and octadecylamine. However, other primary amines may also be used. Alkoxylates can be formed by reacting amines with alkylene oxides.

As monofunctional secondary amines C4-C 30 dialkylamines and their alkoxylate derivatives are suitable. Preferred secondary amines are C4-C24 dialkylamines, still more preferred are C 6

-C

20 dialkylamines, and the most preferred are Cg-C 18 dialkylamines such as N,N-dioctylamine, N,Ndidodecylamine, N-octyl, N-decylamine, N-methyl, N- WO 89/07976 PCT/US88/00590 -11dodecylamine, N-methyl, N-octadecylamine and N-methyl, N-oleylamine, but others may also be used.

Suitable monofunctional alkyl phenols are

C

3

-C

3 0 alkyl substituted phenols and C 2

-C

5 0 alkoxylates thereof. More preferred are C 3

-C

2 4 alkyl substituted phenols, still more preferred are C 3

-C

18 alkyl substituted phenols, and most preferred are C4-C12 alkyl substituted phenols. However, other monofunctional phenols or alkoxylates thereof may also be used within the confines of this invention. Alkoxylates can be formed by reacting alkenols with alkylene oxides.

The hereinabove monofunctional compounds may also contain other substituents such as halo, cyano, nitriles, nitro alkoxy groups, alkenes, thioalkyl, tertiary amino which are inert to reaction conditions.

Thus, in the hereinabove chemical structure, R 1 is preferably a monovalent hydrocarbon radical which may be substituted with hydrogen, lower alkyl, alkyleneoxy and non-reactive substituents including 0, N or S. R 1 is more preferably an aliphatic, 2 alkyleneoxy, cycloaliphatic, aryl, alkylaryl or arylalkyl hydrocarbyl residue containing one or more oxygen, nitrogen or sulfur moieties. R1 is still more preferably a monovalent alkane, alkyleneoxy or cycloalkane which is substituted with hydrogen or one or more oxygen, nitrogen or sulfur moieties. R 1 is even more preferably a monovalent C 6

-C

18 aliphatic or

C

6

-C

30 cycloaliphatic hydrocarbon.

R

2 is preferably hydrogen, C1- 2 0 alkyl, C1- 20 haloalkyl, C1- 2 0 alkenyl or C6- 20 phenyl, more WO 89/07976 PCJ'1US88/00590 -12preferably hydrogen, C 1 3 alkyl, C 2 3 alkenyl, or phenyl, even more preferably hydrogen, methyl or ethyl, still more preferably hydrogen or methyl, and most preferably, hydrogen.

Each R 2 may also separately be in each occur-rence hydrogen, halogen, nitro, cyano, Cl- 20 hydroxycarbyl substituted with hydrogen or one or more of halo, cyano, nitro, thioalkyl, tert-amino, C 1 18 alkoxy, C 6 18 aryloxy, C 7 20 aralkoxy, carbonylj dioxy(C..

18 alkyl, carbonyl dioxy (C 6 20 aryl, carbonyl dioxy(C 7 24 aralkyl, Cl-.

18 alkoxy carbonyl,

C

6 18 aryloxycarbonyl, C 7 20 aralkoxycarbonyl, Cl-.

18 ycrbnl C 6 20 aralcarbonyl,

C

7 20

C

1 18 aJlkylsulfinyl, C6- 20 arylsulfinyl, C7-.20 aralkylsulfinyl, Cl 1 8.

alkylsulfanyl, C 6 20 arylsulfonyl or C7-.20 aralkylsuilfonyl.

1 is a residue of the initiator used to make the poly(alkylene carbonate) polyahl. I is, typically, the residue from a polyahl such as a polyfunctional alcohol, mercaptan or amine. Polyfunctional alcohols include polyols such a glycerine, ethylene glycol, 1,4butanediol, polyether polyols, polyester polyols and hydroxy-'functional acrylic polymers. Polyfunctional mercaptans include 1 ,6-hexanedithiol, 1, 12-dodecanedithiol and 1,18-octadecanedithiol. Polyfunctional amines include 1,6-diaminohexane and 1,12-diaminododecane. However, other initiators may also be used within the confines of this invention.

The non-ionic poly(alkylene carbonate& pol.yahls obtained from monofunctional alcohols, carboxylic acids or primary or secondary amines, or alkyl phenols or L: -r I I 31-- WO 89/07976 PCT/US88/00590 -13alkoxylates thereof with alkylene carbonate or alkylene oxides and CO 2 can be formed by any method known in the art without any compositional limitations. Alcoholinitiated reactions of alkylene oxides and CO 2 are operational within the context of this invention.

The non-ionic polymers may also be prepared by the methods described in U.S. Applications Serial Nos.

750,362 filed July 1, 1985; 885,118 filed July 14, 1986; 799,211 filed November 18, 1985 and 809,675 filed December 16, 1985, by the same inventor.

The proportion of X to Y in the poly(alkylene carbonate) polyahl is determined by the process used and the molar proportion of the reactants, as well as the reaction conditions such as temperature, time, catalyst and catalyst concentration. The thus-formed non-ionic poly(alkylene carbonate) polyahls are random polymers, wherein the proportion of X, Y and I and the length of the polymer is determined by the values of n, m and k. The values of n, m and k may thus be used to vary the average molecular weight of the adducts.

Preferred values of n are 1 to 40, still more 2 preferred are between 1 and 20, and most preferred are between 1 and 10. Preferred values of m are 0 to 200, more preferred are between 0 and 100, and still more preferred are between 0 and 50. Preferred k values are between 0 and 8, more preferably between 0 and 3, and still more preferably between 0 and 1.

A preferred average molecular weight of the polymers is between 300 and 10,000, more preferably between 300 and 5000, and still more preferably between 500 and 3000.

-7

M,

-13 a- Suitable acid-terminal molieties are -COOH, -SO 2

H,

-so 3 H, -SO 4 H, -PO 4 H 2 rP 3 H2* 0 *00*00 000* 0@ 00 0 0S@000 9 0 0 *0 0 0@ 00 0 DD4W WO 89/07976 PCT/US88/00590 R X-14wherein R, X, Y, I, n, m and k as previously S--sulfosuocinate.dThe novel acid-functional poly(alkylene Icarbonate) polyahls of this invention are represented by the following structural formula.

RI-(X)n-(Y)m-I)k-O-A wherein R

I

X, Y, I, n, m and k are as previously defined and A is an acid functional moiety.

In an embodiment of this invention A is represented by the formula -(R4)g-B wherein R 4 is an alkylene, carbonylalkylene, alkenylene, carbonylalkenylene, (C 5 arylyene, or cycloalkenylene, and B is the acid-terminal moiety.

The acid donors capable of reacting with the poly(alkylenecarbonate) polyahls to add a terminal acidic group thereto may be selected from a large number of compounds known in the art. By means of example, the following are provided.

Cyclic anhydrides selected from the group consisting of alkylcyclic anhydrides, cycloalkylcyclic anhydrides, arylcyclic anhydrides, alkylarylcyclic anhydrides and aralkylcyclic anhydrides. Among these, the more preferred are C 4 2 4 alkylcyclic anhydrides,

C

8 2 4 cycloalkylcyclic anhydrides, C8-24 aralkylcyclic anhydrides and C 8 2 4 alkylarylcyclic anhydrides. The anhydrides may be further substituted with halogens, alkyl, alkyl carbonyl and aryl, among other WO 89/07976 PCT/US88/00590 substituents. Examples include succinic anhydride, maleic anhydride, phthalic anhydride, bromoaleic anhydride, dichloromaleic anhydride, dimethylmaleic anhydride, dimethylsuccinic anhydride, 2-dodecen-1-lyl 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 Swhich is capable of reacting with a monofunctional alcohol, mercaptan, carboxylic acid or primary or secondary amine to provide a terminal carboxylic acid moiety.

case of cyclic anhy ride reactions. A poly(alkylene carbonate)polyahl is allowed to react with maleic anhydride and sodium b'sulfite. The sulfosuccinate moiety has the followin structure:

-CH

2 CH-CO2 S0 3

H

Other types of compound 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 heir salts. By means of example, halosulfonic acids nd salts thereof, such as chlorosulfonic acid, sodium chl\orosulfonate and chloroethyl1l fonic acid can be used. C Pefrred among r 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 their salts. By means of example, halosulfonic acids and salts thereof, such as chlorosulfonic acid, sodium chlorosulfonate and chloroethylsulfonic acid can be used. Preferred among

I

a a* .a aa

DMW

a~u WO 89/07976 PCT/US88/00590 -16these 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 halocarboxylic acids and salts thereof such as chloroacetic acid, sodium chloroacetate, bromoacetic acid, and chloropropionic acid. Most preferred is monochlcroacetic acid. Still another group of compounds capable of adding a terminal acidic group are inorganic acid anhydrides such as P205 and S0 3 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 context.

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

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 acidfunctional 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 r- WO 89/07976 PCTJUS88/00590 -17a cyclic carboxylic acid anhydride at temperatures of from 80 0 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 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 1:1 or greater, provided that no more than one acid moiety is incorporated per molecule.

The 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 Sused 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.

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.

1 WO 89/07976 PCT/US88/00590 -18- A variety of known neutralizing substances can be used to obtain the salts of the novel acidfunctional 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 in large part on which particular salt is required for a specific application, since different 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 alkylamines (up to C 2 0 alkylamines) are one preferred I class of materials. However, others outside of this range may also be used. Among the alkali metal salts, i 20 lithium, sodium and potassium are most preferred.

Among the alkaline earth metal salts, calcium and magnesium 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, 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 backbone hydrolysis. Typically, the neutralizing agent is added slowly to the acidfunctional poly(alkylene carbonate) polyahl while monitoring the pH of the product. In this wax any -7 J ~1 i l I-:l~_lyT.i_-Uill--lII_ I a"l WO 89/07976 PCT/US88/00590 ,I -19desired percentage of the acid moieties can be neutralized up to 100 percent.

The characteristics of the novel acidfunctional 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 depending on the particular application the polymer is utilized for. Thus, when a polymer product having a high anionic characteristic is desired, the ratio of non-ionic polymer to acid group donor may be 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 such cases, a partial conversion of the non-ionic polymer to the acid-functional form may be desirable, whereby some non-ionic and some acidfunctional moieties are present in the product. The proportion of non-ionic polymer to acid group donor may be as high as desired, particularly in cases where only a slight anionic characteristic is desired. A proportion of 20:1 of non-ionic polymer to acid group is within the confines of the invention. A particularly useful range of proportions of the nonionic polymer to the acid group donor is between 4:1 and 1:1, more preferably between 1.5 and 1:1.

The characteristics of the novel acidfunctional polymers and their salts can be varied by adjusting, for example, the proportion of monofunctional compound in the polymer backbone to alkylene i WO 89/07976 PCT/US88/00590 carbonate and/or alkylene glycol moieties in the polymer backbone, the polymer molecular weight, the composition of acid-functional group present, the amount of acid-functional group present as a salt and the composition of the cationic portion of the salt.

In some cases, a mixture of the present acidfunctional 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 staring materials herein or other known poiy(alkylene carbonate) polyahls. Also suitable are other non-ionic polymers such as the modified poly(alkylene carbonate) polyahls described in U.S. Applications Serial Nos.

809,675 filed on December 16, 1985, or 799,211 filed on November 18, 1985, by the same inventor. Other nonionic materials can be used in combination with the present ionic surfactants such as polyether polyahls, polyester polyahls, alcohol ethoxylates and phenolic ethoxylates.

The surfactants of this invention can also be used in combination with other anionic surfactants.

Examples of such anionic surfactants include carboxylic acids, oxyacetates, sulfonates, ether sulfates, phosphates, sulfosuccinates and their salts.

fl The present anionic surfactants are used in significantly smaller quantites than the corresponding non-ionic surfactants for a variety of applications.

When the anionic surfactants are utilized to lower the surface tension of water, only a 10 weight percent WO 89/07976 PCT/US88/00590 -34- On nnnlin IT-n nmk;- -4 WO 89/07976 PCT/US88/00590 -21fraction of the required non-ionic surfactant is needed in many cases.

When used by themselves, they can be effective in amounts between 0.0002 weight percent and 10 weight percent. Preferably they are added in amounts between 0.0005 weight percent and 2 weight percent of the total volume, and still more preferably between 0.001 weight percent and 1 weight percent.

When used in a composition with other surfactants,, the novel polyahls are incorporated in amounts between 0.0002 weight percent and 5 weight percent of the final volume, more preferably between 0.0005 weight percent and 2 weight percent, and still more preferably between 0.001 weight percent and 1 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 compositions can also be varied in accordance with the specific application for which they are intended. Such amounts of other surfactants are generally about the same as the amounts listed in the preceding paragraph for the surfactants of this invention.

Having now described the invention in general terms, the following examples are included for illustrative purposes only, and are not meant to limit the scope of the invention or the claims. Unless s ~l WO 89/07976 PCT/US88/00590 -22otherwise stated, all parts and percentages are by weight.

P

4 4

I

Examole 1: Reaction Products of Ethylene Carbonate (EC) with Alcohols These were prepared by known procedures, e.g., Timberlake, U.S. 4,330,481. The desired molar ratio of EC and alcohol (see Table 1 hereinbelow) were heated with stirring under a nitrogen atmosphere in the presence of sodium stannate trihydrate (1.0 weight percent) as catalyst to a high EC conversion. After the reaction was complete, the catalyst was removed by stirring theproduct (20 weight percent in acetone) 15 with Fluorosil (1 g 10 1 g product) for 3 hours, followed by filtration and solvent removal. The characteristics of the products are described in Table 1.

20 TABLE 1: Reaction products of Ethylene Carbonate with Alcohols Sample Number Initiator

A

B

C

D

E

F

G

n-butanol n-hexanol n-octanol n-decanol n-dodecanol n-dodecanol n-dodecanol

EC:

Initiator Ratio 10 10 10 10 5 10 20 Reaction Time hrs 25 252 22 22 21h 214 21h Reaction Temp.

160 150 160 160.

160 160 160

EC

Conversion 99.6 98.0 100.0 99.4 100.0 100.0 96.5 Examole 2: Reaction Product of EC:n-Octanol (10:1) Adduct with Succinic Anhydride Ethylene carbonate (331.95 g, 3.768 mol) and octanol (49.07 g, 0.3768 mol) were added to a 500 ml, 3-necked flask equipped with a stirrer, condenser, S WO 89/07976 PCT/US88/00590 -23thermometer and temperature controller and maintained under a nitrogen atmosphere. The reactor was heated to 175°C and sodium stannate trihydrate (3.81 g, 1.0 weight percent) was added as catalyst. The reaction was terminated after 7 hours at 175 0 C. The EC conversion was 97.5 percent.

A portion of the above EC:-octanol product (226.1 g, 0.30 mol hydroxyl) and succinic anhydride (30.0 g, 0.30 mol) were combined in the same reaction apparatus used above and were heated for one hour at 120 0 C. Proton NMR and capillary gas chromatographic analysis both indicated 100 percent conversion of succinic anhydride. The catalyst was removed by treating a solution of the product in acetone weight percent) with Fluorosil (1 g 10 g product), stirring for 3 hours, filtering and removing the solvent on a rotary evaporator. The adduct was a straw-colored viscous liquid.

The results of NMR analysis were as follows: 0.7-1.8 8 (multiplet, CH 3

(CH

2 6 1.00) 2.9-3.1 8 (singlet, -02CCH 2

CH

2

CO

2 0.94) 3.4-4.0 8 (multiplet, -CH2OCH 2 6.39) 4.1-4.5 8 (multiplet, -CH 2 0CO 2

CH

2 4.23).

The IR data were consistent with the assigned structure.

Mn 552, Mw 1,101, PDI 1.99.

Titration: 1.105 meq C02H/g.

A portion of the adduct was converted to its 2hydroxyethylamine salt as follows. The adduct (2.50 g) ja" WO 89/07976 PCT/US88/00590 and 100 ml deionized water were added to a 4-oz (113 g) bottle and shaken. An insoluble sticky white solid was obtained. 2-Hydroxyethylamine was then added dropwise with stirring while monitoring the pH. When the pH reached 6.20 the content of the bottle was washed into a 250 ml volumetric flask with deionized water. The salt was very water soluble (2.50 g non-ionic surfactant/250 1.00 weight percent anionic surfactant).

The surface tension was studied as a function of concentration. The results obtained are summarized in Table 2 hereinbelow.

Table 2: Surface Tension (dynes/cm) Concentration (wt in deionized water) Anionic Surfactant (2-hydroxyethylamine salt) Ii isR^ 2 0.4 0.1 0.04 0.01 0.004 0.002 31.2 32.2 35.3 35.4 39.9 39.2 39.0 Non-ionic Surfactant Precursor Not soluble Not soluble 32.2 37.3 44.3 60.0 61.7 These results show that the anionic surfactant of this invention had a greater than 10 fold water solubility when compared to the non-succinic anhydride capped analog and had good surface activity at less than 1/10 the concentration of the non-capped analog.

i-i WO 89/07976 PCTJUS88/00590 Examole 3: Reaction Product of EC:n-Dodecanol (10:1) Adduct with Succinic Anhydride Ethylene carbonate (310.50 g, 3.524 mol), ndodecanol (65.67 g, 0.352 mol) and sodium stannate trihydrate (3.76 g, 1.0 weight percent) were combined in the same reaction system used in Example 2 above.

The reaction vessel was then heated for 6 hours at 175 0 C. The EC conversion was 95.7 percent.

A portion of the above EC:n-dodecanol product (243.0 g, 0.30 mol hydroxyl) and succinic anhydride 930.0 g, 0.30 mol) were combined in the same reaction apparatus used in Example 2 above and heated for 1 hour at 120°C. Proton NMR and capillary gas chromatographic analysis both indicated 100 percent conversion of succinic anhydride. The catalyst was removed as in Example 2 above. The adduct was a straw-colored viscous liquid.

The NMR analysis was as follows: 0.7-1.9 8 (multiplet, CH 3

(CH

2 10 1.00) 2.6-2.8 8 (singlet, -O 2

CCH

2 CHCO2-, 0.99) 3.5-4.0 8 (multiplet, -CH2OCH 2 5.81) 4.1-4.5 8 (multiplet, -CH20CO 2

CH

2 4.18) The IR spectrographic data were consistent with the assigned structure.

Mn 611, Mw 1044, PDI 1.71.

Titration: 1.103 meq C02H/g.

i i .i j i

U

i: WO 89/07976 PCT/US88/00590 -26- ExamDle 4: Reaction Product of EC:n-Butanol (10:1) Adduct with Succinic Anhydride Ethylene carbonate (180.87 g, 2.053 mol), nbutanol (15.22 g, 0.2053 mol) and sodium stannate trihydrate (1.96 g, 1.0 weight percent) were combined in the same reaction apparatus setup used in Example 2 above except that a 250 ml flask was used. The reaction vessel was heated for 20.5 hours at 150 0 C. The EC conversion obtained was 95.0 percent.

A portion of the above EC:n-butanol product (144.0 g, 0.20 mol hydroxyl) and succinic anhydride (20.0 g, 0.20 mol) were combined in the a same reaction setup used above and heated for one hour at 1200C.

Proton NMR and capillarly gas chromatographic analysis both indicated 100 percent conversion of the succinic anhydride. The catalyst was removed as in Example 1 above the adduct obtained was a straw-colored viscous liquid.

The NMR analysis was as follows: 0.7-1.9 8 (multiplet, CH 3

(CH

2 6 1.00) 2.6-2.8 8 (singlet, -02CCH 2

CH

2 C02-, 1.06) 3.5-4.0 8 (multiplet, -CH 2 0CH 2 6.27) 4.1-4.5 8 (multiplet, -CH20CO 2

CH

2 5.64).

The IR spectrum was consistent with the assigned structure.

Mn 589, Mw 1,030, PDI 1.75.

Titration: 1.159 meq C02H/g.

Examole 5: Reaction Product of EC:n-Octanol (10:1) Adduct with Maleic Anhydride WO 89/07976 PCT/US88/00590 -27- Ethylene carbonate (175.54 g, 1.993 mol), noctanol (25.95 g, 0.1993 mol) and sodium stannate trihydrate (2.02 g, 1.0 weight percent) were combined in the reaction system used in Example 4 above. The reaction vessel was heated for 16 hours at 150 0 C. The EC conversion was 87.0 percent.

A portion of the above EC:n-octanol product (155.2 g, 0.19 mol hydroxyl) and maleic anhydride (18.63 g, 0.19 mol) were combined in the same reaction apparatus used above and heated for one hour at 120 0

C.

Proton NMR and capillary gas chromatographic analyses both indicated 100 percent conversion of the maleic anhydride. The catalyst was removed as in Example 2 above. The adduct obtained was a staw-colored viscous liquid.

The NMR analysis was as follows: 0.7-1.8 8 (multiplet, CH 3

(CH

2 6 1.00) 3.5-3.9 6 (multiplet, -CH20CH 2 5.23) 4.1-4.5 6 (multiplet, -CH20C0 2

CH

2 4.77) 6.2-6.3 6 (singlet, -0 2 CCH=CHC02-, 0.91).

The IR specatrographic data was consistent with the assigned structure.

Titration: 1.028 meq C02H/g.

ExamDle 6: Reaction Product of EC:Oleyl Alcohol (10:1) Adduct with Succinic Anhydride Ethylene carbonate (153.76 g, 1.745 mel), oleyl alcohol (46.77 g, 0.1745 mol) and sodium stannate trihydrate (2.00 g, 1.0 weight percent) were combined in the reaction apparatus used in Example 4 above. The WO 89/07976 PCT/US88/00590 -28reaction vessel was heated for 23 hours at 150 0

C,

resulting in 95.1 percent conversion of EC.

A portion of the above EC:oleyl alcohol product (158.0 g, 0.17 mol hydroxyl) and succinic anhydride (17.0 g, 0.170 mol) were combined in the apparatus used above and heated for one hour at 120 0 C. Proton NMR and capillary gas chromatographic analyses both indicated 100 percent conversion of the succinic anhydride. The catalyst was removed as in Example 2 above. The adduct obtained was a straw-colored viscous liquid.

The results of NMR analysis were as follows: 0.7-1.9 8 (multiplet, oleyl, 1.00) 2.6-2.7 6 (singlet, -02CCH2CH 2 CO2- 0.68) 3.5-3.9 8 (multiplet, -CH20CH 2 3.18) 4.1-4.5 8 (multiplet, -CH20CO 2

CH

2 2.94).

Mn 618, Mw 906, PDI 1.47.

Titration: 0.762 meq C02H/g.

Examole 7: Reaction Product.of EC:n-Dodecanol.(5:1) Adduct With Succinic Anhydride A portion of sample E (35.00 g, 0.1027 mol hydroxyl) from Example 1 above, succinic anhydride (10.27 g, 0.1027 mol) and sodium stannate trihydrate (0.45 g, 1.0 weight percent) were heated at 120 0 C for one hour. Proton NMR analysis indicated complete anhydride conversion. The catalyst was removed as in Example 2 above. The adduct was a straw-colored low viscosity liquid.

of NMR analysis were as follows: The results of NMR analysis were as follows: 27 I WO 89/07976 PCTIUS88/00590 -29- 0.7-1.9 2.6-2.7 3.6-3.9 4.1-14.5 (muJltiplet, (singlet, (multiplet, (multiplet,

CH

3

(CH

2 10-

-O

2

CCH

2

CH

2 C02-,

-CH

2

OCH

2

-CH

2 000 2

CH

2 1.02) 2.6) 2.2).

Mn =405, Mw 500, PDI =1.23.

Titration: 2.5140 meq CO 2 H/g.

Exarnole 8: Reaction Product EC:n-Dodecanol (20:1) Adduct With Succinic Anhydride A portion of sample G (26.19 g, 0.0353 mol hydroxyl); from Example 1, succinic anhydride (3.53 g, 0.0353 mol) and sodium stannate trihydrate (0.29 g, weight percent) were heated at 120 0 C for one hour.

Proton NMR spectral analysis indicated complete anhydride conversion. The catalyst was removed as in Example 2 above. The adduct obtained was a strawcolored viscous liquid.

The results of NMR analysis were as follows: 0.7-1.9 2.6-2.7 3.6-3.9 4.1-14.5 8 (multiplet, 8 (singlet, 8 (multiplet, 8 (multiplet,

CH

3

(CH

2 10-' -0 2

CCH

2

CH

2 C02-

-CH

2

OCH

2

-CH

2 OC0 2

CH

2 1.21) 10.6) 8.7).

Mn =868, mw =1,730, PDI =1.99.

Titration: 1.221 meq CO 2 H/g.

WO 89/07976 PCT/US88/00590 Examole 9: Reaction Product of EC:n-3utanol (25:1) Adduct with Succinic Anhydride Ethylene carbonate (213.63 g, 2.425 mol), nbutanol (7.19 g, 0.0970 mol) and sodium stannate trihydrate (2.20 g, 1.0 weight percent) were combined in the reaction system used in Example 4 above. The reaction vessel was heated for 49 hours at 150 0

C,

resulting in 90.0 percent EC conversion, 24.0 weight percent CO 2 Succinic anhydride (9.70 g, 0.097 mol) was added and the reaction mixture heated at 120°C for one hour. Proton NMR analysis indicated complete conversion of succinic anhydride. The catalyst was then removed as in Example 2 above. The adduct was a Sstraw-colored liquid.

The results of NMR analysis were as follows: 0.7-1.9 8 (multiplet, CH 3

(CH

2 2 2.6-2.7 8 (singlet, -0 2

CCH

2

CH

2 CO2- 3.6-3.9 8 (multiplet, -CH2OCH 2 19.0) 4.1-4.5 8 (multiplet, -CH2OCO 2

CH

2 15.2).

Mn 755 My 2,274, PDI 3.0.1.

Titration: 0.493 meq C02H/g.

Example 10: Reaction Product of EC:n-Octanol (10:1) Adduct with Phthalic Anhydride Ethylene carboante (174.78 g, 1.984 mol), noctanol (25.84 g, 0.1984 mol) and sodium stannate trihydrate (2.00 g, 1.0 weight percent) were combined in the same apparatus used in Example 4 above. The reaction vessel was heated for 16 hours at 150°C, resulting in an EC conversion of 94.5%. Phthalic anhydride (29.33 g, 0.198 mol) was added and the 1 i -i I i-1- ._14-~11rl 2 WO 89/07976 PCT/US8/005 -31reactants were heated for five hours at 1200C. The catalyst was then removed as in Example 2 above. The adduct was a straw-colored viscous liquid.

The results of NMR analysis were as follows: 0.7-1.9 8 (multiplet, 3.5-4.0 8 (multiplet, 4.1-4.5 8 (multiplet, 7.5-8.0 8 (multiplet,

CH

3

(CH

2

-CH

2 0CH 2

-CH

2 0CO 2

CH

2 aromatic, 5.73) 4.55) 0.99).

Mn 879 Mw 1,025, PDI 1.92.

Titration: 1.021 meq CO 2 H/g.

Selected property data and surfactant profiles corresponding to the above examples have been summarized in Table 3 hereinbelow.

i- TABLE 3: SURFACTANT PROPERTIES PROFILE Sample Ex. 4 Ex. 9 Ex. 2 Ex. 5 Ex. 10 Ex. 7 Ex. 3 Ex. 8 Ex. 6 Initator n-butanol n-butanol n-octanol n-octanol n-octanol n-dodecanol n-dodecanol n-dodecanol oleyl alcohol EC.:Init.

Ratio 10:1 25:1 10:1 10:1 10:1 5:1 10:1 20:1 10:1 Wt

CO

2 Before Anhydride Reaction 26.9 24.0 23.4 23.8 22.2 15.7 21.2 25.7 20.3 Anhydride Succinic Succinic Succinic Maleic Phthalic Succinic Succinic Succinic Succinic Heq C02-Hq 1.159 0.493 1.105 1.028 1.021 2.540 1.103 1.221 0.762 Surface Tension a) (dynes/cm) 43.4 46.5 33.6 34.3 33.1 36.0 36.9 44.0 37.2 Wetting Timet(bI (Hin) >60 108 11 13 15 6.5 20 22 7 Initial Foam Height(c) (mm) 10 22 33 40 30 130 90 130 32 Foam Stability After Min) 0 18 78 77 Ammonium salt, 0.1% in water Modified Draves-Clarkson Test Ross-Miles Test WO 89/07976 PCT/US88/00590 -33- Examole 11: Reaction Product of a Poly(ethylene carbonate) Polyol with n-Octadecylmercaptan and Succinic Anhydride A poly(ethylene carbonate) polyol (Mn of 2076, 27.4 weight percent CO2) was prepared from ethylene oxide and carbon dioxide using diethylene glycol as initiator.

A sample of the poly(ethylene carbonate) polyol (100.1 n-octadecylmercaptan (17.19 g) and sodium stannate trihydrate (0.59 g) were combined in the same equipment used in Example 4. The flask was heated for hours at 1750°C. On cooling to ambient temperature, the product (113.5 g) was a white wax (Mn 1457).

A portion of the white wax was (81.3 g, 0.0792 mol) and succinic anhydride (7.92 g, 0.0792 mol) were combined and heated for one hour at 120°C in the same equipment as used above. Size exclusion chromatography showed 100 percent cuccinic anhydride conversion.

Proton NMR was consistent with the expected structure.

Surface tension was 46.5 dynes/cm (0.1 percent aqueous solution of the ammonium salt; 23°C).

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

Example 12: Reaction Product of a Poly(ethylene carbonate) Polyol with n-Dodecylamine and Succinic Anhydride A sample of the same poly(ethylene carbonate) polyol used in Example 11 (100.2 g) and n-dodecylamine (27.80 g) were combined in the same equipment used in Example 4. The flask was heated for 6 hours at 125 0

C.

WO 89/07976 PCT/US88/00590 -34- On cooling to ambient temperature, the product (122.9 g) was a white wax (Mn 1019).

A portion of the white wax (89.3 g, 0.185 mol end groups) and succinic anhydride (18.4 g, 0.185 mol) were combined and heated for one hour at 120 0 C in the same equipment as used above. Size exclusion chromatography showed 100 percent succinic anhydride conversion.

NMR Spectrographic data were as follows: I0.7-1.6 6 (multiplet, CH 3

(CH

2 10 2.6-2.8 (singlet, -0 2

CCH

2

CH

2 C02-, 1.2) 3.4-3.9 8 (multiplet, -CH2 0

CH

2 9.6) 4.0-4.5 8 (multiplet, -CH2OCO 2

CH

2 3.8).

Surface tension was 34.4 dynes/cm (0.1 percent aqueous solution of the ammonium salt; 23°C).

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

Example 13: Reaction Product 'of a Poly(ethylene carbonate) Polyol with n-Hexadecylamine and Succinic Anhydride A sample of the same poly(ethylene carbonate polyol used in Example 11 (100.3 g) and n-hexadecylamine (27.80 g) were combined in the same equipment used in Example 4. The flask was heated for 6 hours at S125 0 C. On cooling to ambient temperature, the product (114.4 g) was a white wax (Mn 1657).

A portion of the white wax (82.0 g, 0.1335 mol end groups) and succinic anhydride (13.35 g, 0.1335 mol) were combined and heated for one hour at 120 0 C in 7 WO 89/07976 PCT/US88/00590 the same equipment used above. Size exclusion chromatography showed 100 percent succinic anhydride conversion. Proton NMR spectrographic data were consistent with the expected structure. Surface tension was 40.5 dynes/cm (0.1 percent aqueous solution of the ammonium salt; 23°C).

Examole 14: Reaction Product of an Ethylene C:"'bonate: n-Hexanol (10:1) Adduct with 2-Dodecen-1lyl Succinic Anhydride Ethylene carbonate (357.3 g, 4.056 mol), nhexanol (41.44 g, 0.4056 mol) and sodium stannate trihydrate (3.99 g, 1.0 weight percent) were combined in the reaction system used in Example 2. The fla=sk was heated for 25.5 hours at 160°C; 98.0 percent ethylene carbonate conversion.

A portion of the product formed above (70.0 g, 0.0957 mol OH) and 2-dodecen-l-yl succinic anhydride (28.42 g, 0.0957 mol) were combined and heated for two hours at 120°C in the same equipment used in Example 11.

Proton NMR spectrographic data was consistent with the expected structure. Surface tension was 35.7 dynes/cm (0.1 percent aqueous solution of the ammonium salt; 23°C).

This example shows that substituted succinic anhydrides can be used to make the novel composition of this invention.

Example 15: The Use of Surfactants of this Invention to Make Water-Based Polyols A. A modified poly(ethylene carbonate) polyol (70.9 percent P-725 modified, Mn of 1937, 5.0 g) and WO 89/07976 PCT/US88/00590 -36water (5.0 g) were combined with thorough agitation.

The mixture rapidly settled into two immersible liquid phases. A solution containing the surfactant of Example 3 (0.50 g) as the ammonium salt dissolved in water (1.0 g) was added with thorough agitation. A white emulsion was formed which slowly separated after standing overnight at ambient conditions and was readily redisperible.

The same experiment as above was repeated except that the surfactant of Example 6 (as the ammonium salt) was used instead of the surfactant of Example 3. A white emulsion was formed. Only a small Sportion separated after standing overnight at ambient conditions and it was readily redispersible.

B. A modified poly(ethylene carbonate) polyol v (51.2 percent, P-725 modified, Mn of 2141, 3.0 g) and water (3.0 g) were combined with thorough agitation.

The mixture rapidly settled into immiscible liquid Sphases when the agitation was removed. A solution containing the surfactant of Example 3 (0.30 g) as the ammonium salt dissolved in water (0.7 g) was added with thorough agitation. A white emulsion was formed which slowly separated after standing overnight at ambient conditions and was readily redispersible.

C. A modified poly(ethylene carbonate) polyol (27.7 percent, P-425 modified, Mn of 2132, 11.2 g) and water (9.5 g) were combined with thorough agitation.

The mixture rapidly separated into two immiscible liquid phases. A solution containing the surfactant of Example 3 (0.56 g) as the ammonium salt dissolved in water (1.5 g) was added with thorough agitation A white emulsion was formed which had a Brookfiled I W89/ F 5 07976

-I

07976 PCr/US88/00590 -37viscosity of 300 cps (0.3 Pa-s) (the Brookfield viscosity of the modified poly(ethylene carbonate polyol before being converted to a water-based fluid was 14,900 cps (14.9 Pa-s). The emulsion separated after standing over night at ambient conditions but was readily redispersible.

A

I

U

U,

D. A poly(propylene glycol) of 2000 molecular weight (10.0 g) and water (10.0 g) were combined with thorough agitation. The mixture rapidly separated into two immiscible liquid phases. A solution containing the surfactant of Example 3 (1.0 g) as the ammonium salt dissolved in water (2.0 g) was added with thorough agitation. A white emulsion was formed which was Sstable after standing over night at ambient conditions.

E. A diethylene glycol adipate diol of 2000 molecular weight (Formrez 11-56, a product of Witco Chemical Company, 3.3 g) and water (3.3 g) were combined with thorough agitation. The mixture separated into two immiscible liquid phases. A solution containing the surfactant of Example 3 (0.30 g) as the ammonium salt dissolved in water (0.7 25 g) was added with thorough agitation. A white emulsion was formed which separated after standing overnight at ambient conditions and was readily redispersible.

This example shows that the novel surfactants of this invention are useful for preparing water-based systems of polyether polyols, polyester polyols and modified poly(alkylene carbonate) polyahls.

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 -38the scope and spirit of this invention. Accordingly, it is not intended that the scope of the claims appended hereto be limited to the description as set forth herein, but rather that the claims be construed as encompassing all the features of patentable novelty which reside in the present invention, including all features which would be treated as equivalents thereof by those skilled in the art to which this invention pertains.

I

Claims (10)

1. An acid-functional polymer having a poly(alkylene carbonate) backbone and on the average at least 0.C5 and up to and including one terminal acid group per molecule or a salt thereof.

2. -Te acid-functional polymer ,-Claim 1 comprising a random poly(alkylene carbonate) polyahl obtained by reacting a monofunctional C4- 3 0 alcohol, alcohol alkoxylate, mercaptan, mercaptan alkoxylate, carboxylic acid, carboxylic acid alkoxylate, primary or secondary amine, primary or secondary amine alkoxylate, C3-24 alkylphenol or alkylphenol alkoxylate with an alkylene carbonate, an alkylene oxide and carbon dioxide, an alkylene carbonate, alkylene oxide and carbon dioxide or a poly(alkylene carbonate) polyahl, and (II) a residue of a donor capable of reacting with said reaction product to add a terminal acidic group thereto. O as c\c&'net'A

3. Th polymer -ef-Claim 2 wherein the donor capable of reacting with said reaction product to add a terminal acidic group thereto is selected from the group consisting of cyclic organic acid anhydrides, :i 7 halo and haloalkyl sulfonic acids, halo and haloalkyl carboxylic acids and inorganic acid anhydrides.

4. A polymer as claimed in claim 3 wherein the donor capable of reacting with said reaction product to add a terminal acidic group is a cyclic organic acid anhydride selected from the group consisting of succinic anhydride, phthalic anhydride and maleic anhydride. An acid-functional polymer as claimed in any one of claims 1 to 4 in the form of a metal salt, amine salt or ammonium salt.

6. An acid-functional polymer as claimed in any one of claims 1 to 5 having the formula R A wherein R 1 is independently in each occurrence a C_ 24 aliphatic, C 6 24 cycloaliphatic, a C1-24 aliphatic or C6-24 cycloaliphatic alkoxylata containing 1-30 alkyleneoxy moieties, a C 3 24 alkyl substituted phenol or a C_ 24 hydrocarbon substituted with one or more substituents having oxygen, nitrogen or sulfur, X is separately in each occurrence -ZCOOC(R 2 2 -(-C(R2-O-C(R 2 2-C(R 2 )2- wherein. Z is separately in each occurrence selected from the 3 3 group consisting of -NH, or -NR wherein R is C- 2 4 alkyl, with the proviso that at least two of all Z's are oxygen. Y is separately in each occurrence -O-C(R wherein R is independently in each occurrence hydrogen, C 1 2 0 alkyl, C1-20 haloalkyl, C1-20 alkenyl or phenyl, I is separately in each occurrence the residue of a polyfunctional C2 2 4 aliphatic, C 6 3 0 cyclo- DW DMW _i i W'O 89/07976 PCT/US88/00590 -41- aliphatic or C6-30 aromatic alcohol, mercaptan, amine or phenol which optionally also contains one or more oxygen, nitrogen or sulfur, m is independently in each occurrence 0 to 200, n is independently in each occurrence to and k is independently in each occurrence 0 to 8, A is an acid functional moiety; with the proviso that X, Y and I are randomly spaced in the polymer backbone. n. cs cltckMe&/\

7. eel acid-functional polymer o- Claim 6 wherein R is independently in each occurrence a Smonovalent C1- 20 alkane, or C6- 20 cycloalkane or C6-20 alkyl which contains 1-15 alkyleneoxy moieties, substituted with hydrogen or one or more oxygen, nitrogen or sulfur moieties, R 2 is independently in each occurrence hydrogen, halogen, nitro, cyano, C1- 2 0 hydroxycarbyl substituted with hydrogen or one or more of halo, cyano, nitro, thioalkyl, tert-amino, C_. 18 alkoxy, C 6 g 18 aryloxy, C 7 2 0 aralkoxy, carbonyl dioxy(C 1 18 )alkyl, carbonyl dioxy(C6- 20 )aryl, carbonyl dioxy(C7- 20 )aralkyl, C 1 -18 alkoxy carbonyl, C6- 2 0 aryloxycarbonyl, C 7 20 aralkoxycarbonyl, C-_ 18 alkylcarbonyl, (C6- 2 0 aralcarbonyl, C7-20 aralkylcarbonyl, CI. 18 alkylsulfinyl, C6- 20 arylsulfinyl, (C 7 2 0 aralkylsulfinyl, C 1 18 alkylsulfonyl, C6-20 arylsulfonyl or C 7 2 0 aralkylsulfonyl, and A is represented by the formula -B, Swherein R4 is a carbonyl alkylene, carbonyl alkenylene, C 5 -8 arylene, alkylene, alkenylene or cycloalkylene, WO 89/07976 PCT/US88/00590 S-42- and B is a residue of -COOH, -S0 2 H, -S0 3 H, -S04H, S-P0 4 H 2 PO 3 H 2 oCr zulfosuocinat

8. An acid-functional poly(alkylene carbonate) polyahl prepared by a process comprising reacting a random non-ionic poly(alkylene carbonate) polyahl obtained by reacting a monofunctional (C4-C 30 alcohol, carboxylic acid, primary or secondary amine, mercaptan, (C 3 -C 2 4)alkyl phenol or alkoxylates thereof with an alkylene carbonate, an alklene oxide and CO 2 an alkylene oxide, an alkylene carbonate and C0 2 or a poly(alkylene carbonate) polyahl, to obtain a random non-ionic poly(alkylene carbonate) polyahl, l admixing a compound capable of reacting with the reaction product to add a terminal acidic group ithereto; the proportion of said random non-ionic poly(alkylene carbonate) polyahl to said compound between 20:1 and 1:1. between 5 weight percent and 95 weight percent of an acid-functional polymer as claimed in any one of Claims 1 to 7, and between 95 weight percent and 5 weight percent of a non-ionic polymer, wherein said non-ionic polymer is selected from the group consisting of non-ionic poly(alkylene carbonate) polyahls, polyether polyahls, polyester polyahls, alcohol alkoxylates alkylphenol alkoxylates, carboxylic acid alkoxylates and amine Salkoxylates. _i -43- A stable water-based emulsion or dispersion comprising: the surfactant composition as claimed in claim 9, and one or more materials selected from the group consisting of polyether polyahls, polyester polyahls and poly(alkylene carbonate) polyahls.

11. An acid-functional polymer as claimed in claim 1 substantially as hereinbefore described with reference to any one of the examples.

12. An acid-functional poly(alkylene carbonate) as claimed in claim 8 substantially as hereinbefore described with reference to any one of the examples. S 13. A surfactant composition as claimed in claim 9 substantially as hereinbefore described with reference to any one of the examples.

14. An emulsion or dispersion as claimed in claim S substantially as hereinbefore described with reference to any one of the examples. 9 DATED: 8 November 1990 *0 PHILLIPS ORMONDE FITZPATRICK C Patent Attorneys for: THE DOW CHEMICAL COMPANY 1870U DMW\ DMW INTERNATIONAL SEARCH REPORT International Application No. PCT/1S88/00590 I. CLASSIFICATION OF SUBJECT MATTER (if several classification symbols apply, indicate all) 6 According to Inlernational Patent Classification (IPC) or to both National Classification and IPC INT. CL B01F 17/52; C08L 69/00; C08G 63/62 U.S. CL: 252/351; 524/537; 525/439; 528/370; 558/262 II. FIELDS SEARCHED Minimum Documentation Searched 7 Classification System Classification Symbols U.S. 252/351, 353, 354, 356,357, DIG 1: 524/537, 525/439, 461, 462 466; 528/370; 558/262, 265, 266, 268 Documentation Searched other than Minimum Documentation to the Extent that such Documents are Included in the Fields Searched s III. DOCUMENTS CONSIDERED TO BE RELEVANT a Category Cilation of Document, II with indication, where appropriate, of the relevant passages 12 Relevant to Claim No. 13 X US, A, 4,686,274, 11 AUGUST 1987, SEE COLUMN 5, LINES 1-10 'T 68: COLUMN 8, LINES 6 TO 21. CO)UJJM 10, LINES 3 TO 11,(HARRIS E'T ZL.) A US, A, 4,330,481, 18 MAY 1982, SEE THE ENTIRE DOCUENT 1-10 (TIMBERLAKE ET AL.) A US, A, 4,382,014, 03 MAY 1983 SEE COLUMN 3, LINES 1-10 6 Tn 57, SAKAI ET AL) A US, A, 4,488,982, 18 TFXEMBER 1984, SEE CIIUMN 2, 1-10 LINES 48 TO 68: CDIiMN 3, LINFS 1 TO 67,(CUSCURIDA ET BL) SSpecial categories of cited documents: to later document published after the international filing date document defining the general state of the art which is not or priority date and not in conflict with the application but considered to be of particular relevance cited to understand the principle or theory underlying the invention earlier document but published on or after the international X document of particular relevance the cmed nvention filing date document of particular relevance; the claimed invention fif ing date cannot be considered novel or cannot be considered to document which may throw doubts on priority claim(s) or involve an inventive step which is cited to establish the publication date of another citation or other special reason (as specified) Y" document of particular relevance; the claimed invention cannot be considered to involve an inventive step when the document referring to an oral disclosure, use, exhibition or document is combined with one or more other such docu. other means ments, such combination being obvious to a person skilled document published prior to the international filing date but in the art. later than the priority date claimed document member of the same patent family IV. CERTIFICATION Date of the Actual Completion of the International Search Date of Mailing of this International Search Report 12 MAY 1988 1 4 JUN 1988 International Searching Authority Signature of Authorized Oficer ISA/US Tfr___EODOP) PET_ ILLJ orm PCTISMl210 (uo s (Rw.11487)