United States Patent (19) (11) 4,065,435 Sakaguchi et al. 45) Dec. 27, 1977 (54) WATER-SOLUBLE POLYMERS AND (57) ABSTRACT PROCESS FOR PRODUCING THE SAME Water-soluble oxidation-reduction polymers containing 75) Inventors: Shinji Sakaguchi; Shinichi Imai; Junn therein recurring units of the formula (I): Yamaguchi; Nobuo Tsuji, all of Minami-ashigara, Japan i. (I) 73) Assignee: Fuji Photo Film Co., Ltd., -CH-C- Minami-ashigara, Japan =o -o OH (21) Appl. No.: 694,424 O N-R M (22 Filed: June 9, 1976 R

Related U.S. Application Data OH 62 Division of Ser. No. 535,657, Dec. 23, 1974, abandoned. or recurring units of formula (II): 30 Foreign Application Priority Data R2 (II) Dec. 21, 1973 Japan ...... 48-311 H 51) Int. C.’...... Co8F8/00; C08F 8/28; OH C08F 8/30 f=o -o 52 U.S.C...... 260/47 UP; 526/15; O Nan R 526/46; 526/49 M 58) Field of Search ...... 260/47 UP R 56) References Cited OH U.S. PATENT DOCUMENTS 2,710,801 6/1955 Minsk et al...... 260/47 UP wherein X represents a hydrogen atom, a halogen atom, 3,032,522 5/1962 Summers ...... 260/29.6 an alkyl group, an allyl group or an aryl group; R1 3,267,073 8/1966 Kun ...... 260/47 UP represents a hydrogen atom or an alkyl group; R2 repre 3,488,329 1/1970 Johnson ...... 260/112.5 sents a hydrogen atom, an alkyl group or an aryl group; 3,877,946 4/1975 Tsuji et al...... 96/87 R R3 represents a divalent group; and M represents a cat 3,879,205 4/1975 Fitzgerald ...... 96/14 ion. These polymers have excellent oxidation-reduction Primary Examiner-Herbert J. Lilling properties, Attorney, Agent, or Firm-Sughrue, Rothwell, Mion, Zinn and Macpeak 10 Claims, No Drawings 1. 4,065,435 U.S. Pat. No. 2,816,028 discloses polymers, which WATER-SOLUBLE POLYMERS AND PROCESS contain hydroquinone derivatives in their side chains, of FOR PRODUCING THE SAME the general formula:

CH-R-CH CH-R-CH COOH OH

-)OH wherein R represents

B B B 20 This is a Division of application Ser. No. 535,657, -ch-- -ch-- o --CH,- filed Dec. 23, 1974, and now abandoned. loot; b booh looh BACKGROUND OF THE INVENTION A &H, 1. Field of the Invention 25 The present invention relates to water-soluble poly mers. More particularly, the present invention relates to A represents a hydrogen atom, an alkyl group or a novel water-soluble oxidation-reduction polymers hav halogen atom; B represents a hydrogen atom or an alkyl ing hydroquinone structures attached to the side chains group; Z represents -O- or -NH-; x and y each of the polymers and to processes for producing the 30 represents a positive integer of 50 to 2,000; and n repre SaC. sents a positive integer of 1 to 6. 2. Description of the Prior Art The above-described polymers are, however, water Studies of polymers having oxidizing and reducing insoluble except for those polymers where R is functions have been made with the objects of utilizing such polymers as an organic oxidant, a monomer stabi 35 lizer, an electron exchanger for a battery, or an agent for preparing hydrogen peroxide, removing oxygen --CH,- contained in water, treating water or waste water in COOH industry and the like. (See U.S. Pat. Nos. 2,992,899; 2,703,792 and 2,831,045; British Pat. Nos. 891,467 and and hence possess only small oxidation-reduction ca 949,302; Ann. N.Y. Acad. Sci, 57 646 (1959) and Natl. pacities. The polymers in which R is Acad. Sci., U.S., 38934 (1952).) These oxidation-reduction polymers contain, as the B functional group having oxidizing and reducing proper ties, hydroquinone groups, thiol groups, ketone groups, 45 pyridine groups or ferrocene groups. Of these func --CH,-booH tional groups, however, hydroquinones are advanta geous for a variety of reasons, e.g., excellent oxidation are prepared using, as a starting material, poly(acrylic and reduction reversibility, appropriate oxidation or methacrylic anhydride), which are obtained by poly reduction potentials, stability and diversity of methods 50 merizing acrylic or methacrylic anhydride. However, it for their preparation, as described in large numbers of is extremely difficult to obtain soluble poly(acrylic or patents and literature references, e.g., U.S. Pat. Nos. methacrylic anhydride), because the polymerization 3,173,892 and 3,165,492; French Patent Nos. 1,362,707; reaction of acrylic or methacrylic anhydride, each of 1,362,708 and 1,336,713; K. A. Kun and H. G. Cassidy, which contains two double bonds having identical reac J. Polymer Sci., 44383 (1960); ibid., 56.83 (1962); R. E. 55 tivity, is inevitably accompanied by a cross-linking re Moser et al., ibid., A2 2401 (1964); N. Nakabayashi, action which results in the formation of insoluble gels. ibid., A-1, 6869 (1968); G. Wegner, N. Nakabayashi and Moreover, the above-described polymers are not useful H. G. Cassidy, J. Org, Chem, 32 3155 (1967); G. Weg as an additive for photographic materials. This is ner et al., J. Polymer Sci, A-1, 6 3155 (1968); H. thought to be due to the reduced oxidizing and reducing Kamogawa, ibid., B-3, 283 (1965); K. A. Kun et al., properties as a result of the electron-attracting carbonyl ibid., A3 1833 (1965); ibid., 4A-1, 847 and 859 (1966), groups attached directly to the hydroquinone nuclei of etc. the polymers. These known polymers, however, are insoluble or poorly soluble in water and have only small oxidizing SUMMARY OF THE INVENTION and reducing capacities as described, e.g., in H. G. Cas 65 An object of the present invention is to provide sidy and K. A. Kun, Oxidation-Reduction Polymers, water-soluble oxidation-reduction polymers. Interscience, New York (1965). In addition, their prepa Another object of the present invention is to provide rations are highly complicated. polymers which are useful in photography. 4,065,435 3. 4. A still further object of the present invention is to provide polymers which are useful in the production of DETAILED DESCRIPTION OF THE hydrogen peroxide, monomer stabilization, removal of INVENTION oxygen contained in water, treatment of water or waste The hydroquinones or their salts represented by the water in industry and the like. 5 formula (III) can be obtained by the methods described, Another object of the present invention is to provide e.g., in U.S. Pat. Nos. 3,062,884; 3,134,764 and a novel and convenient process for producing polymers 3,187,046; or in U.S. Patent Application Ser. No. 524,835, filed Nov. 18, 1974, (corresponding to Japanese having hydroquinone groups in their side chains. Patent Application No. 128986/1973). Still another object of the present invention is to 10 In the above general formulas, suitable examples of provide additives capable of preventing color contami alkyl groups for X are alkyl groups such as a methyl nation. group, a tert-butyl group, a 1,1,3,3-tetramethylbutyl The polymers of the present invention can be repre group, etc. Suitable examples of aryl groups for X are sented as polymers containing therein recurring units of aryl groups such as a phenyl group, a naphthyl group, a the general formula (I) or (II): 15 halogenated aryl group (e.g., a bromophenyl group, a chlorophenyl group, etc.), etc. Suitable examples of . (I) alkyl groups for R1 are alkyl groups such as a methyl -CH-C- group, an ethyl group, etc. Suitable examples of alkyl OH groups for R2 are alkyl groups having 1 to 2 carbon =o -o 20 atoms such as a methyl group and suitable examples of O N-R aryl groups for R2 are aryl groups such as a phenyl M X group. Suitable examples of divalent groups for R3 are R divalent groups such as a straight chain alkylene group having from 1 to 8 carbon atoms, a branched chain OH 25 alkylene group having from 1 to 8 carbon atoms, an R (II) arylene group or a group having the formula H OH =o -o 30 O N-R --CH g M X R

OH wherein n is an integer of 1 to 4. Suitable examples of 35 straight chain alkylene groups for R3 are alkylene wherein X represents a hydrogen atom, a halogen atom groups such as -CH2-, -(CH2)2-, -(CH2)3-, etc., such as chlorine, bromine, etc., an alkyl group having and suitable examples of branched chain alkylene preferably from 1 to 8 carbon atoms, an allyl group or groups for R3 are -CH(CH3)-CH2- and an aryl group; R1 represents a hydrogen atom or an -CH(CH3)CHCH-. Suitable examples of arylene alkyl group having preferably from to 8 carbon atoms; groups for R3 are arylene groups having the formula R2 represents a hydrogen atom, an alkyl group or an aryl group; R3 represents a divalent group; M represents a cation. The polymers of the present invention can be pre 45 pared by reacting a hydroquinone compound or a salt thereof having the general formula (III): Suitable examples of substituents which can be present OH (III) on the above described groups for R3 include an alkyl 50 group (e.g., a methyl group, etc.), an alkoxy group (e.g., a methoxy group, etc.) and a halogen atom (e.g., a chlo rine atom, etc.). Suitable examples of M are a hydrogen atom, an alkali metal atom (e.g., a sodium atom, a potas sium atom, etc.) and a quaternary ammonium group X OH 55 (e.g., HN+(CH3) and HN+(CH3)). There is no critical limit on the total number of car wherein X, Rand Rs are as defined above, with a poly bon atoms in X, R3 and R1, however, the total number is mer containing therein the recurring unit of the formula preferably less than about 20, more preferably less than (IV): 15, from the standpoint of solubility. Examples of compounds represented by the general formula (III) or their derivatives are as follows: (IV) Aminoalkylhydroquinones or their derivatives, such as 2,5-dihydroxybenzylamine, 2-aminoethylhydroqui OFCC=O none, 2-(3'-aminopropyl)hydroquinone, 2-(2-amino O 65 propyl)hydroquinone, 2,5-dihydroxy-3-methylbenzyla mine, 2,5-dihydroxy-3-ethylbenzylamine, 2,5-dihy wherein R2 is as defined above followed, if necessary, droxy-3-t-butylbenzylamine, 2,5-dihydroxy-3- by neutralization. bromobenzylamine, 2,5-dihydroxy-6-bromobenzyla 4,065,435 5 6 mine, 2,5-dihydroxy-3-chlorobenzylamine, 2-(2- Examples of homo- and copolymers containing re aminobutyl)hydroquinone, 2-(3'-amino-1'-methylbutyl)- curring units of the general formula (IV) include homo hydroquinone, 2-(3'-aminopropyl)-6-methylhydroqui and copolymers obtained from maleic anhydride, citra none, 2-(3'-aminopropyl)-6-ethylhydroquinone, 2-(3'- conic anhydride or phenylmaleic anhydride. aminopropyl)-6-t-butylhydroquinone, 2-(3'-amino These homopolymers can be advantageously pre propyl)-6-bromohydroquinone, 2-(3'-aminopropyl)-6- pared with reference to the methods described, e.g., in chlorohydroquinone, 2-(3'-aminopropyl)-3-bromohy published Japanese Patent Application No. 55,980/48; droquinone, 2-(2-aminopropyl)-6-methylhydroqui J. L. Lang, J. Polymer Sci, 55 S 31 (1961); D. Bryce none, 2-(2-aminopropyl)-6-ethylhydroquinone, 2-(2'- Smith, Chem, and Ind., 2062 (1962); V. I. Stenberg, J. aminopropyl)-6-t-butylhydroquinone, 2-(2-amino 10 Org. Chem, 274111; and German Patent No. 1,662,080. propyl)-6-bromohydroquinone, 2-(2-aminopropyl)-6- The copolymers can be prepared by copolymerizing chlorohydroquinone, 2-(2-aminopropyl)-3-bromohy these monomers with other monomers. droquinone, 2-(2-aminobutyl)-6-methylhydroquinone, Any monomeric compound having at least one unsat 2-(2-aminobutyl)-6-ethylhydroquinone, 2-(2-amino urated bond capable of addition polymerization can be propyl)-6-t-butylhydroquinone, 2-(2-aminobutyl)-6- 15 generally used for copolymerization with maleic anhy bromohydroquinone, 2-(2-aminobutyl)-3-bromohy dride, citraconic anhydride or phenylmaleic anhydride. droquinone, 2-(3'-amino-1'-methylbutyl)-6-methylhy Examples of such unsaturated monomeric compounds droquinone, 2-(3'-amino-1'-methylbutyl)-6-ethylhy are as follows: droquinone, 2-(3'-amino-1'-methylbutyl)-6-t-butylhy Acrylic acids, such as acrylic acid and acrylates, e.g., 20 ethyl acrylate, propyl acrylate, butyl acrylate, amyl droquinone, 2-(3'-amino-1'-methylbutyl)-6-bronohy acrylate, ethylhexyl acrylate, octyl acrylate, t-octyl droquinone, 2-(3'-amino-1'-methylbutyl)-3-bromohy acrylate, 2-methoxyethyl acrylate, 2-butoxyethyl acry droquinone or their salts; late, 2-phenoxyethyl acrylate, chloroethyl acrylate, Aminoarylalkylhydroquinones or their derivatives cyanoethyl acrylate, dimethylaminoethyl acrylate, such as p-aminophenethylhydroquinone, 2-(4'- 25 glycidyl acrylate, benzyl acrylate, methoxybenzyl acry aminonaphthylethyl)-hydroquinone, 2-(p-aminophene late, furfuryl acrylate, tetrahydrofurfuryl acrylate, thyl)-5-methylhydroquinone, 2-(p-aminophenethyl)-5- phenyl acrylate, etc.; chlorohydroquinone, 2-(3'-methyl-4-aminophenethyl)- Methacrylic acids, such as methacrylic acid and hydroquinone, 2-(p-aminophenethyl)-5,6-dimethylhy methacrylates, e.g., methyl methacrylate, ethyl metha droquinone, 2-(p-aminophenethyl)-3,5,6-trimethylhy 30 crylate, propyl methacrylate, isopropyl methacrylate, droquinone, 2-m-aminophenethylhydroquinone, 2-y- anyl methacrylate, hexyl methacrylate, cyclohexyl (4'-aminophenyl)-f6-methylpropylhydroquinone, 2-y- methacrylate, benzyl methacrylate, cyanoacetoxyethyl (4'-aminophenyl)propylhydroquinone, 2-(4-amino-3'- methacrylate, chlorobenzyl methacrylate, octyl metha methoxyphenethyl)hydroquinone, 2-y-(3'-amino-4'- crylate, sulfopropyl methacrylate, N-ethyl-N- methylphenyl)propylhydroquinone, 2-(p-aminophene 35 phenylaminoethyl methacrylate, glycidyl methacrylate, thyl)-6-methylhydroquinone, 2-(p-aminophenethyl)-5- 2-methoxyethyl methacrylate, 2-(3-phenylpropylox bronohydroquinone, 2-(5'-aminonaphthylethyl)hy y)ethyl methacrylate, dimethylaminophenoxyethyl droquinone or their salts; methacrylate, furfuryl methacrylate, tetrahydrofurfuryl N-(2,5-dihydroxyphenylalkyl)alkylamines or their methacrylate, phenyl methacrylate, etc.; derivatives, such as N-(2,5-dihydroxyphenylmethyl)- Acrylamides, such as acrylamide and N-substituted methylamine, N-(2,5-dihydroxyphenylethyl)methyla acrylamides, e.g., methylacrylamide, ethylacrylamide, mine, N-(2,5-dihydroxyphenyl propyl)methylamine, propylacrylamide, isopropylacrylamide, butylacryla N-2-(2,5-dihydroxyphenyl)-1-methylethyl-methyla mide, t-butylacrylamide, heptylacrylamide, t-octyla mine, N-(2,5-dihydroxyphenylmethyl)ethylamine, N crylanide, cyclohexylacrylamide, benzylacrylamide, (2,5-dihydroxyphenylethyl)ethylamine, N-(2,5-dihy 45 methoxyethylacrylamide, dimethylaminoethylacryla droxyphenylpropyl)-ethylamine, N-(2,5-dihydroxy mide, phenylacrylamide, tolylacrylamide, naphthyla phenylmethyl)butylamine, N-(2,5-dihydroxy-3-methyl crylamide, dimethylacrylamide, diethylacrylamide, phenylmethyl)methylamine or their salts; dibutylacrylamide, diisobutylacrylamide, diacetona N-(2,5-dihydroxyphenylalkylaryl)alkylamines Or crylamide, methylbenzylacrylamide, benzyloxyethyla their derivatives, such as p-(2,5-dihydroxyphenethyl)- 50 crylamide, 3-cyanoethylacrylamide, acryloylmorpho N-methylaniline, p-(2,5-dihydroxyphenethyl)-N- line, N-methyl-N-acryloylpiperazine, N-acryloylpiper ethylaniline, N-4-(2',5'-dihydroxyphenethyl)naphthyl azine, acryloylglycine, N-g-morpholinoethylacryla methylamine, o-(2,5-dihydroxyphenethyl)-N- mide, N-acryloylhexamethyleneimine, N-2- methylaniline, o-(2,5-dihydroxy-3-methylphenethyl)-N- acetoamidethyl-N-acetylacrylamide, etc.; ethylaniline or their salts and the like. 55 Methacrylamides, such as methacrylamide and N Examples of acids which can form salts with the substituted methacrylamides, e.g., methylmethacryla compounds of the formula (III) include inorganic acids, mide, t-butylmethacrylamide, t-octylmethacrylamide, such as a hydrohalic acids, sulfuric acid, nitric acid, benzylmethacrylamide, cyclohexylmethacrylamide, carbonic acid, boric acid, etc.; and organic acids, such phenylmethacrylamide, dimethylmethacrylamide, die as formic acid, acetic acid, trifluoroacetic acid, oxalic thylmethacrylamide, dipropylmethacrylamide, N acid, malonic acid, succinic acid, maleic acid, acrylic methyl-N-phenylmethacrylamide, etc.; acid, methacrylic acid, salicyclic acid, benzoic acid, Allyl compounds such as allyl esters, e.g., allyl ace itaconic acid, etc. tate, allyl caproate, allyl caprylate, allyl laurate, allyl Of these compounds, aminoalkylhydroquinones, palmitate, allyl stearate, allyl benzoate, allyl acetoace aminoarylalkylhydroquinones, N-(2,5-dihydroxy 65 tate, etc.; and allyl ethers, e.g., allyl butyl ether, allyl phenylalkyl)alkylamines and their derivatives or salts glycidyl ether, allyl phenyl ether, etc.; are particularly advantageous from the standpoint of Vinyl ethers such as methyl vinyl ether, butyl vinyl the solubility of the redox polymers produced. ether, hexyl vinyl ether, octyl vinyl ether, decyl vinyl 4,065,435 7 8 ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, 2nd Printing, John Wiley and Sons, (1959); H. Mark, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl Encyclopedia of Polymer Science and Technology Intersci vinyl ether, 2-ethylbutyl vinyl ether, dimethylamino ence Pub. New York, (1967); E. C. Chapin, J. Polymer ethyl vinyl ether, diethylaminoethyl vinyl ether, Sci., 4 597 (1949) and the like. In the preparation of butylaminoethyl vinyl ether, benzyl vinyl ether, tetra 5 these polymers, reaction conditions such as initiator and hydrofurfuryl vinyl ether, vinyl phenyl ether, vinyl solvent used, concentration, polymerization tempera tolyl ether, vinyl chlorophenyl ether, vinyl 2,4- ture, reaction time, can be, of course, varied readily and dichlorophenyl ether, vinyl naphthyl ether, vinyl an widely in accordance with the purpose. thranil ether, etc.; There is no particular limit as to the properties of the Vinyl esters such as vinyl acetate, vinyl propionate, O polymers or copolymers containing the acid anhydride vinyl butyrate, vinyl isobutyrate, vinyl dimethylpro units which can be employed in accordance with the pionate, vinyl ethylbutyrate, vinyl valerate, vinyl cap present invention. However, these homopolymers or roate, vinyl chloroacetate, vinyl dichloroacetate, vinyl copolymers preferably have a molecular weight of methoxyacetate, vinyl butoxyacetate, vinyl phenylace about 500 to about 500,000; more preferably about 1,000 tate, vinyl lactate, vinyl g-phenylbutyrate, vinyl cy 15 to about 20,000. These ranges, however, change ac clohexylcarboxylate, vinyl benzoate, vinyl salicylate, cording to the monomer polymerized. The copolymers vinyl tetrachlorobenzoate, vinyl naphthoate, etc.; are usually obtained in the form of 1:1 molar ratio co Heterocyclic vinyl compounds such as N-vinylox polymers when prepared by conventional methods, but azolidone, vinylpyridine, vinylpicoline, N those containing from about 20% to about 60% on a vinylimidazole, N-vinylpyrrolidone, N-vinylcarbazole, 20 molar basis, particularly from about 40% to about 50% vinylthiophene, N-vinylethylacetamide, etc.; on a molar basis acid anhydride units, which can be Styrenes such as styrene, methylstyrene, dimethylsty prepared by changing the starting material charging rene, trimethylstyrene, ethylstyrene, diethylstyrene, ratio, are preferred for the convenience of operations. isopropylstyrene, butylstyrene, hexylstyrene, cyclohex The methods for reacting the compounds of the for ylstyrene, decylstyrene, benzylstyrene, chloromethyls 25 mula (III) or the salts thereof with the polymers having tyrene, trifluoromethylstyrene, ethoxymethylstyrene, the recurring units of the formula (IV) are known, and acetoxymethylstyrene, methoxystyrene, 4-methoxy-3- the conditions of the reaction can be readily determined methylstyrene, dimethoxystyrene, chlorostyrene, di to those skilled in the art, The reaction can, if desired, chlorostyrene, trichlorostyrene, tetrachlorostyrene, be carried out (1) by using the compounds of the for pentachlorostyrene, bromostyrene, dibronostyrene, 30 mula (III) or the salts thereof in an amount of about 0.2 iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4- to about 2.5 molar equivalents, preferably about 0.5 to trifluoromethylstyrene, 4-fluoro-3-trifluoromethylsty about 1.5 molar equivalents; (2) in an atmosphere of an rene, vinylbenzoic acid, methyl vinylbenzoate, etc.; inert gas, for example, methane, ethane, propane, bu Vinyl ketones such as methyl vinyl ketone, phenyl tane, argon and the like; (3) by heating the reaction vinyl ketone, methoxyethyl vinyl ketone, etc.; mixture to a temperature of about 30 C to about 150 C, Olefins such as dicyclopentadiene, ethylene, propyl preferably 60' C to 90' C; (4) by cooling the reaction ene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, mixture to from about 15° C to about -10 C; (5) with 1-heptene, 1-octene, 1-decene, 5-methyl-1-nonene, 5,5- vigorous stirring; (6) in the presence of a reducing agent dimethyl-1-octene, 4-methyl-1-hexene, 4,4-dimethyl-1- or an antioxidant; and (7) by employing a basic com pentene, 5-methyl-1-hexene, 4-methyl-1-heptene, 5 40 pound in combination with a salt of the compounds methyl-l-heptene, 4,4-dimethyl-1-hexene, 5,6,6-trimeth represented by the formula (III). yl-1-heptene, 1-dodecene, 1-octadecene, etc.; In the reaction, a solvent can be advantageously used Itaconic acids such as itaconic acid, itaconic anhy in order to make the reaction system homogeneous and dride, methyl itaconate, ethyl itaconate, etc.; avoid a localized increase in temperature. Suitable sol Crotonic acids such as crotonic acid, methyl croton 45 vents which can be employed can be chosen without ate, ethyl crotonate, butyl crotonate, hexyl crotonate, difficulty by those skilled in the art by considering solu crotonamide, etc.; bility, convenience in drying the product, reactivity, Halogenated olefins such as vinyl chloride, vinyli compatibility with water, price and the like. Examples dene chloride, chloroprene, etc.; of useful solvents include alcohols such as methanol, Unsaturated nitriles such as acrylonitrile, methacry SO ethanol, isopropanol, methoxyethanol, acetoxyethanol, lonitrile, etc.; and m ethylene glycol, diethylene glycol, propylene glycol, Unsaturated compounds such as sorbic acid, cin methoxypropanol, phenoxyethanol, phenylpropanol, namic acid, methyl sorbate, glycidyl sorbate, citraconic cyclohexanol, benzyl alcohol, phenol, t-butylphenol, acid, chloroacrylic acid, mesaconic acid, maleic acid, furfuryl alcohol, tripropylene glycol and the like; hy fumaric acid, ethacrylic acid, etc. 55 drocarbons such as hexane, ligroin, cyclohexane, deca Mixtures of these compounds can also be used. Of lin, octane and the like; halogenated hydrocarbons such these monomeric compounds, acrylamides, methacryla as dichloromethane, chloroform, methylchloroform, mides, vinyl ethers, acrylic acid, vinyl acetate, N-vinyl carbon tetrachloride, dichloroethane, trichloroethane, pyrrolidone and the like are particularly preferred from chlorobenzene, dichlorobenzene and the like; ethers the standpoint of water solubility of the oxidation such as diethyl ether, dimethoxyethane, diisopropyl reduction polymers produced. ether, ethyl phenyl ether, tetrahydrofuran, dioxane, These polymers can be advantageously prepared anisole, propylene oxide, morpholine and the like; aro with reference to the methods described, e.g., in U.S. matic hydrocarbons such as benzene, toluene, xylene, Pat. Nos. 2,419,221; 2,857,365; 2,854,357; 2,917,478; ethylbenzene, cymene, cumene, styrene and the like; 2,938,016; 2,971,939; 3,046,246; 2,694,697; 3,060,155; 65 lactones and lactams such as butyrolactone, acetyl 3,010,864; 3,083,189 and 3,073,805; British Patent No. butyrolactone, pyrrollidone, N-methylpyrrolidone, vi 609,940; H. C. Hass et al., J. Polymer Sci, A 11 327 nylpyrrollidone and the like; amides such as dimethyl (1973); C. E. Schildknecht, Vinyl and Related Polymers formamide, diethylformamide, formamide, diethylace a 4,065,435 9 . 10 tamide, hexamethylenephosphoramide, tetramethylurea preferred. The amount of these compounds employed is and the like; ketones such as acetone, methyl ethyl ke preferably abeut 0.2 to 3, more preferably 0.5 to 2 molar tone, mesityl oxide, ethyl isobutyl ketone, diacetone equivalents, based on the moles of the salts of the com alcohol, cyclohexanone, methylcyclohexanone, aceto pounds represented by the formula (III). phenone and the like; acetonitrile; nitropropane; dime In the half amidation reaction, a third ingredient can thylcyanamide; carbon disulfide; dimethyl sulfoxide; be added to prevent the air oxidation of the hydro methyl ethyl sulfoxide; diethyl sulfoxide; sulfolane; quinones. Examples of such reductants or antioxidants esters such as methyl formate, dimethyl phthalate, include combinations of a metal such as tin, iron, zinc, methyl acetate, ethyl acetate, cyclohexyl acetate, amyl zinc amalgam, etc., and an acid such as hydrochloric acetate, butyl acetate, 3-methoxyethyl acetate, 3-butox 10 acid, sulfuric acid, acetic acid, etc.; combinations of a yethyl acetate, propyl propionate, dimethyl oxalate, metal such as sodium, sodium amalgam, magnesium, dimethyl maleate and the like; acids such as formic acid, magnesium amalgam, zinc, iron, etc., and water (having acetic acid, butyric acid, acrylic acid, methacrylic acid, various pH values); combinations of a metal such as and the like; amines such as pyridine; etc. Mixtures of sodium, lithium, aluminum, magnesium amalgam, zinc, these solvents can also be used, if desired. 15 etc., and an alcohol; combinations of a metal such as These solvents can be used in an amount sufficient to sodium, zinc, etc., and an alkali such as an alkali metal dissolve or disperse homogeneously the compounds hydroxide, an alcoholic alkali, liquid ammonia, etc.; represented by the formula (III) or their salts and the metallic compounds having a lower valence such as polymers or copolymers represented by the formula 'stannous chloride, ferrous sulfate, ferrous hydroxide, (IV) in a concentration of about 0.1% to about 20% by 20 titanium trichloride, etc.; non-metallic compounds weight. which act, as an oxygen-acceptor such as hydrogen Examples of basic compounds which can be em halide, a sulfur compound, e.g., sodium sulfide, sodium ployed in combination with a salt of the compounds polysulfide, ammonium sulfide, sodium sulfite, sodium represented by the formula (III) include hydroxides of dithionite, hydrogen sulfide, etc., a phosphorus com alkali metals such as lithium, sodium, potassium, etc., 25 pound, e.g., phosphorous trisulfide, phosphorous acid alkaline earth metals such as magnesium, calcium, etc., and their salts, etc., and an arsenic compound, e.g., an and ammonia or their salts of weak acids, such as car arsenite; hydrazines such as hydrazine, phenylhydra bonates, borates, acetates, etc.; and amines such as alkyl zine, hydroxylamine, etc.; aluminum hydride; sodium amines, for example, ethylamine, diethylamine, triethyl borohydride; and hydroquinone derivatives such as amine, butylamine, t-butylamine, methylpropylamine, hydroquinone monomethyl ether, hydroquinone mono methylethylbutylamine, diethylmethylamine, etc., sub ethyl ether, 2-methylhydroquinone, 2-methoxyhy stituted alkylamines, for example, ethanolamine, me droquinone, 2-t-butylhydroquinone, 2,5-di-t-butylhy thylaminoethanol, triethanolamine, etc. polyalkylene droquinone, 2,5-di-t-hexylhydroquinone, 2,5-bis polyamines, for example, ethylenediamine, diethylene (1,1,3,3'-tetramethylbutyl)hydroquinone, etc. Mix triamine, etc., alkenylamines, for example, allylamine, 35 tures of these compounds can also be used. The amount diallylamine, etc., arylamines, for example, aniline, anis of these compounds employed is preferably more than idine, naphthylamine, toluidine, N,N-dimethylaniline, about 0.001, particularly from about 0.01 to about 100% etc., arylalkylamines, for example, benzylamine, phen by weight, based on the weight of the compounds rep ethylamine, N-methylbenzylamine, etc., and nitrogen resented by the formula (III) or the salts thereof. How containing heterocyclic compounds, for example, pyri ever, the amounts can be changed depending on the dine, piperidine, piperazine, diaminobicyclooctane, N compounds used. methylpiperazine, morpholine, pyrrolidine, pyrazoline, The polymers thus obtained, which are represented indoline, 1,8-diaza-bicyclo(5,4,0)undecene-7, etc. by the formula (I) or (II), are water-soluble polymers Mixtures of these compounds can also be used. Suit having a molecular weight of about 600 to about able basic compounds to be used can be chosen without 45 600,000, preferably about 1,000 to about 20,000. difficulty by those skilled in the art on considering solu Examples of the water-soluble polymers within the bility, basicity, odor, price and the like. Of these com scope of the present invention are as follows: pounds, carbonates and organic acids are particularly

Compound 1 --CH,-gHegH-gH---gH-gH), OH p =O =o f=O =o CH, OH NHCH OH OH

x : y : z = 50: 49: 1

4,065,435 17 18 -continued x : y : z = 48; 46: 6 Compound 19 re-CH-CH-)-e-H-H), p =O =o OH f=o ONa NH O CHCH CH

OH x : y = 50:50 Compound 20 --CH-cHe-cH-pH-9-e-cH-gH) oH OH O CEO CEO l CO CE go on NHCH, pe OH NHCH CH 69 l NH-CH OH OH

OH x : y : z = 50: 48: 2 Compound 21 eCH-H), H-H), OH CONH CEO CEO l OH NHCH O

OH x : y = 56 : 44 Compound 22 -e-CH-cH-e-cH-gH-e-gH-gH-i- oH p =o -o f=o -o CH OH NH-H-CH, OH OH CH

OH x : y : z = 50: 48: 2 Compound 23 re-CH-gHegH-cH-9-e-gH-gH-i- OH -o -o =o -o O OH NHCHCHCH OH OH CH

OH x : y : z = 50:47: 3 Compounds 1, 2, 4, 5, 8, 10, 13, 19, 20 and 21 are particularly preferred compounds of this invention. The water-soluble polymers of the present invention water in industry, or as a monomer stabilizer or an can be employed as an oxidation-reduction polymeric 65 organic antioxidant. The polymers can also be used in a material. They can be utilized, for example, in the prep- photographic light-sensitive material to improve the aration of hydrogen peroxide, the removing of oxygen physical characteristics, for example, to prevent color contained in water and the treatment of water or waste staining to a great extent. 4,065,435 19 20 The present invention is further illustrated by the following examples. Unless otherwise indicated, all Elemental Analysis parts, percents, ratios and the like are by weight. C H N EXAMPLE 1. Found (%) 5.43 6.07 3.46 Preparation of Compound 1 To a 2 1 three-necked flask equipped with a stirring The product had a limiting viscosity, as determined in a rod, athermometer, a gas-delivery tube and a dropping 1% aqueous sodium chloride solution at 30 C, of 0.32, funnel, and placed on a steam bath, were added 10 g of 10 EXAMPLE 3 2,5-dihydroxybenzylamine and 200 ml of N,N-dime thylformamide, and the materials dissolved. Nitrogen Preparation of Compound 3 gas was passed through the reactor to displace the air, To a 2 1 three-necked flask equipped with a stirrer, a and the temperature was increased to 70° C. A solution thermometer and a gas-delivery tube, and placed on a of 56.1 g of copoly(methyl vinyl ether-maleic anhy 15 steam bath, were added 65.5g of copoly(vinyl acetate dride) (molar ratio = 1:1) in 300 ml of N,N-dimethyl maleic anhydride) (molar ratio 1:1), 88.3 g of 2-(2- formamide was added over a period of about 20 min aminopropyl)hydroquinone and 875 ml of N,N-dime utes. Immediately after the beginning of the addition, 40 thylformamide, and the materials dissolved. After the g of powdered 2,5-dihydroxybenzylamine were added 20 temperature was increased to 70 C, 29.9 g of sodium portionwise over a period of 15 minutes. After the addi hydrogen carbonate was added over a period of about tion was completed, the reaction solution was stirred 20 minutes with the addition of 50 ml of distilled water. for an additional 3.5 hours, and cooled to 35 C, and 600 The reaction mixture was stirred an additional 3.5 hours ml of dichloromethane was poured into the reaction at 70 C, and poured into 3.5 l of dichloromethane while mixture. The resulting mixture was then poured into 21 25 stirring with an agitator. The precipitate formed was of dichloromethane to reprecipitate while stirring with dissolved in 1,000 ml of distilled water, and the resulting an agitator, and the agitation was continued an addi solution was charged in a cellulose tube, and dialyzed tional 30 minutes. The resulting mixture was allowed to against running water. The resulting solution was dried stand to precipitate, the solvent was removed by decan in a freeze drier to obtain 9.26 g of light brown powder. tation, and 1.51 of dichloromethane was rapidly poured 30 therein. After the agitation was continued an additional 1.5 hours, the precipitate was filtered by suction, washed with three 150 ml portions of dichloromethane, Elemental Analysis and immediately freeze-dried to give 98 g of a brown 35 C H powder. Found (%) S3.62 4.10 2.84

Elemental Analysis The product had a limiting viscosity, as determined in a C H N 1% aqueous sodium chloride solution at 30 C, of 0.47. Calculated (%) 56.95 5.76 4.75 EXAMPLE 4 Found (%) 57.18 5.62 4.67 Preparation of Compound 5 The product had a limiting viscosity, as determined in a To a 31 three-necked flask equipped with a stirrer, a 1% aqueous sodium chloride solution at 30 C, of 0.25. 45 thermometer, a gas-delivery tube and a dropping-fun nel, and placed on a steam bath, were added 76 g of EXAMPLE 2. 2,5-dihydroxybenzylamine and N,N-dimethylforma Preparation of Compound 2 mide, and the materials dissolved. Nitrogen gas was To a 500 ml three-necked flask equipped with a stir 50 passed through the reactor to displace the air, and the rer, a thermometer and a gas-delivery tube, and placed temperature was increased to 75 C. A solution of 100 g on a steam bath, were added 10 g of 2-(3-aminopropyl)- of copoly(ethylene-maleic anhydride) (molar ratio = hydroquinone hydrobromide, 3.75 g of copoly(methyl 1:1) in 100 ml of N,N-dimethylformamide was added vinyl ether-maleic anhydride) (molar ratio = 1:1) and dropwise to the mixture over a period of about 20 min 360 ml of N,N-dimethylformamide, and the materials 55 utes. Immediately after the beginning of the addition, 40 dissolved. After the temperature was increased to 70 C, g of powdered 2,5-dihydroxybenzene was added por 4.13 g of sodium hydrogen carbonate was added por tionwise over a period of about 15 minutes. The result. tionwise over a period of about 5 minutes with the ing mixture was stirred an additional 3 hours at 75 C, addition of 10 ml of distilled water. The reaction mix and poured into 12 l of dichloromethane while stirring ture was stirred for an additional 3 hours, and then with an agitator. After stirring about 30 minutes, the poured into 1.5 l of dichloromethane to form a precipi reaction mixture was allowed to stand to precipitate, tate while stirring with an agitator. The precipitate was and the solvent was then removed by decantation. 61 of dissolved in 150 ml of distilled water. The resulting dichloromethane was poured quickly on the precepi solution was charged in a cellulose tube (semipermeable 65 tate, and the agitator was operated one hour. The pre membrane) and dialyzed about 25 hours against running cipitate was filtered, washed with three 400 ml portions water. The mixture was freeze-dried to obtain 13.2 g of of dichloromethane, and immediately freeze-dried. The a light brown powder. yield of the product was 193g. 4,065,435 21 22 The product had a limiting viscosity, as determined in a Elemental Analysis 1% aqueous sodium chloride solution at 30 C, or 0.16. C . H. N EXAMPLE 7 Found (%) 58.62 5.97 5.30 Preparation of Compound 15 To a 1 1 three-necked flask equipped with a stirrer, a The product had a limiting viscosity, as determined in a thermometer, a gas-delivery tube and a dropping-fun 1% aqueous sodium chloride solution at 30 C, of 0.21. nel, and placed on a steam bath, were added 20 g of EXAMPLE 5 10 2,5-dihydroxybenzylamine and 350 ml of N,N-dime Preparation of Compound 9 thylformamide, and the materials dissolved. Nitrogen gas was passed through the reactor to replace the air, To a 1 1 three-necked flask equipped with a stirrer, a and the temperature was increased to 80 C. A solution thermometer and a gas-delivery tube, and placed on a of 21.15 g of copoly(isobutylene-maleic anhydride) steam bath, were added 20 g of 2,5-dihydroxy-6- 15 (molar ratio 32 1:1) in 210 ml of N,N-dimethylforma bromobenzylamine hydrobromide, 113 g of copoly(a- mide was added dropwise over a period of about 10 crylamide-maleic anhydride) (molar ratio = 1:1) and minutes. The reaction solution was stirred an additional 500 ml of N,N-dimethylformamide, and the materials 2.5 hours, and then poured into 21 of ethyl acetate while dispersed. After the temperature was increased to 80 stirring with an agitator. After stirring about 30 min C, 3.55g of sodium carbonate was added thereto over a period of about 10 minutes with the addition of 100 ml 20 utes, the mixture was allowed to stand to precipitate the of distilled water. The reaction mixture was stirred an solid contents, and the solvent was removed by decan additional 3 hours at 80 C, and poured into 25 l of tation. The resulting precipitate was dissolved in 500 ml dichloromethane while stirring with an agitator. The of a 0.5 N aqueous sodium carbonate solution, and the precipitate obtained was dissolved in 200 ml of distilled solution was charged in a tube of a dialysis membrane, water, and the resulting solution was changed in a cellu 25 and dialyzed for about 30 minutes against running wa lose tube, and dialyzed against running water. The re ter. The resulting mixture was dried in a freeze drier to sulting solution was dried in a freeze drier to obtain 22.5 obtain 37.9 g of the product. g of a brown powder. Elemental Analysis 30 C H Elemental Analysis C H N Found (%) 55.51 5.62 3.87 Found (%) 4.08 3.40 6.80 The product had a limiting viscosity, as determined in a The product had a limiting viscosity, as determined in a 35 1% aqueous sodium chloride solution at 30 C, of 0.18. 1% aqueous sodium chloride solution at 30 C, or 0.10. EXAMPLE 8 EXAMPLE 6 Preparation of Compound 17 Preparation of Compound 11 To a 300 ml three-necked flask equipped with a stir To a 2 1 three-necked flask equipped with a stirrer, a rer, a thermometer, a gas-delivery tube and a dropping thermometer, a gas-delivery tube and a dropping-fun funnel, and placed on a steam bath, were added 6.76 g of nel, and placed on a steam bath, were added 10 g of 2,5-dihydroxybenzylamine and 50 ml of N,N-dimethyl 2,5-dihydroxy-3-t-butylbenzene and 300 ml of N,N- formamide, and the materials dissolved. Nitrogen gas dimethylformamide, and the materials dissolved. Nitro 45 was passed through the reactor to replace the air and gen gas was passed through the reactor to replace the the temperature was increased to 70° C. A solution of 10 air, and the temperature was increased to 75° C. A g of copoly(styrene-citraconic anhydride) (molar ratio solution of 20.2 g of copoly(N,N-dimethyla = 1:1) in 50 ml of tetrahydrofuran was added dropwise crylanidemaleic anhydride) (molar ratio = 1:1) in 200 over a period of about 10 minutes. The reaction mixture ml of N,N-dimethylformamide was added dropwise 50 was stirred an additional 2 hours at 70 C, and poured over a period of about 15 minutes. Immediately after the into 600 ml of dichloromethane while stirring with an beginning of the addition, 10 g of powdered 2,5-dihy agitator. The resulting precipitate was dissolved in 150 droxy-3-t-butylbenzene was added portionwise over a ml of a 0.4 N aqueous sodium hydroxide solution, and period of about 10 minutes. The reaction mixture was the solution was charged in a tube of a dialysis mem stirred an additional 3 hours at 75 C, and then poured 55 brane, dialyzed for about 25 hours against running wa into 3 l of dichloromethane while stirring with an agita ter, and then freeze-dried. The yield of the product was tor. The resulting precipitate was dissolved in 300 ml of 16.5 g. a 0.5 N aqueous potassium carbonate solution, and the solution obtained was charged in a tube of a dialysis Elemental Analysis membrane, and dialyzed for about 40 minutes against 60 C H running water. The resulting solution was dried in a 63.5 5.27 freeze drier to obtain 30.6 g of product. Found (%) 3.53 The product had a limiting viscosity, as determined in a Elemental Analysis 65 1% aqueous sodium chloride solution at 30 C, of 0.13. C H Use of copoly(styrene-phenyl maleic anhydride) also Found (%) 53.0 5.88 6.27 provides similar excellent results to copoly(styrene citraconic anhydride) used above.

. . 4,065,435 23 24 of copoly(vinyl acetate-maleic anhydride) (molar ratio EXAMPLE 9 = 1:1) in 600 ml of tetrahydrofuran and 80 ml of N,N- Preparation of Compound 18 dimethylformamide was added dropwise over a period To a 1 1 three-necked flask equipped with a stirrer, a of 20 minutes. Immediately after the beginning of the thermometer and a gas-delivery tube, and placed on a addition, 70 g of 2,5-dihydroxybenzylamine was added steam bath, were added 9.8g of poly(maleic anhydride), dropwise over a period of 15 minutes. The reaction 11 g of 2,5-dihydroxybenzylamine hydrobromide, 12.85 solution was stirred on additional 3.5 hours, and poured g of 2-(p-methylaminophenethyl)-6-methylhydroqui into 41 of dichloromethane to reprecipitate the product none and 400 ml of N,N-dimethylformamide, and the while stirring with an agitator. After stirring 30 min materials dissolved. After the temperature was in 10 utes, the resulting mixture was allowed to stand, and the creased to 80 C, 0.1 g of sodium hydrosulfite and 2.65 solvent was removed by decantation. 3 l of dichloro g of sodium carbonate was added over a period of about methane was poured quickly onto the precipitate, and 5 minutes with the addition of 10 ml of distilled water. the resulting mixture was stirred for 1 hour. The precip The reaction mixture was stirred an additional 3 hours itate was filtered by suction, washed with three 300 ml at 80 C, and poured into 2 l of dichloromethane while 15 portions of dichloromethane, and immediately freeze stirring with an agitator. The resulting precipitate was dried to obtain 218 g of light brown powder. dissolved in 400 ml of a 1N aqueous sodium carbonate solution, and the solution obtained was dialyzed for 40 hours against running water, and freeze-dried to obtain Elemental Analysis 25g of a brown powder. 20 C N Calculated (%) 55.83 5.29 4.46 Found (%) 55.7 5.33 4.39 Elemental Analysis C H The product had a limiting viscosity, as determined in a Found (%) 55.3 4.33 3.9 25 1% aqueous sodium chloride solution at 30 C, of 0.27. The product had a limiting viscosity, as determined in a EXAMPLE 12 1% aqueous sodium chloride solution at 30 C, of 0.08. Preparation of Compound 21 EXAMPLE 10 In a 1 1 three necked flask were placed 100 g of pow 30 dered copoly(acrylamide-maleic anhydride) (molar Preparation of Compound 19 ratio = 1:1) and 73.34 g of 2,5-dihydroxybenzylamine. To a 1 1 three-necked flask equipped with a stirrer, a The reactor was then equipped with a stirrer, a ther thermometer, a gas-delivery tube and a dropping-fun mometer and a gas-delivery tube and placed on a steam nel, and placed on a steam bath, were placed 35 g of bath. To this reactor were added 500 ml of N,N-dime p-aminophenethylhydroquinone and 300 ml of N,N- 35 thylformamide, and the materials dispersed. Nitrogen dimethylformamide, and the materials dissolved. Nitro gas was passed through the reactor to displace the air, gen gas was passed through the reactor to displace the and 150 ml of distilled water was added to dissolve the air, and the temperature was increased to 75 C. A mixture. After stirring for 3 hours, the reaction solution solution of 28.1 g of copoly(vinyl chloride-maleic anhy was cooled to 35 C, and 70 ml of acetone was poured dride) (molar ratio = 1:1) in 300 ml of N,N-dimethyl therein with stirring. The resulting solution was poured formamide was added dropwise over a period of about into 2.5 l of acetone with vigorous stirring, and the 20 minutes. The reaction solution was stirred an addi precipitate was separated by decantation. 21 of acetone tional 2 hours at 75 C, and poured into 251 of dichloro was poured onto the precipitate, and the resulting mix methane with stirring. The resulting precipitate was ture was stirred vigorously for 1 hour. The precipitate dissolved in 500 ml of a 0.5 Naqueous sodium carbonate 45 solution, and stirred for 1 hour at 50 C. The solution was filtered by suction, and vacuum dried to obtain was charged in a cellophane tube, dialyzed for about 30 152.4 g of brown powder. hours against running water, and dried in a freeze-drier to obtain 61 g of brown powder. Elemental Analysis SO C H Elemental Analysis Found (%) 55.60 5.56 9.82 C H N Calculated (%) 60.69 5.06 3.22 The product had a limiting viscosity, as determined in a Found (%) 60.57 5.31 3.20 55 1% aqueous sodium chloride solution at 30 C, of 0.14. The product had a limiting viscosity, as determined in a EXAMPLE 1.3 1% aqueous sodium chloride solution at 30 C, of 0.64. Preparation of Compound 22 EXAMPLE 11 To a 1 1 three-necked flask equipped with a stirrer, a thermometer and a gas-delivery tube, and placed on a Preparation of Compound 20 steam bath, were added 8.5 g of copoly(maleic anhy To a 2 1 three-necked flask equipped with a stirrer, a dride-methyl vinyl ether) (molar ratio = 1:1), 13.5g of thermometer, gas-delivery tube and a dropping-funnel, 2-(2-aminopropyl)hydroquinone hydrobromide and 400 and placed on a steam bath, were added 30 g of 2,5- ml of N,N-dimethylformamide, and the materials dis dihydroxybenzylamine and 600 ml of N,N-dimethylfor 65 solved. After the solution was heated to 65 C, 5.8 g of mamide, and the materials dissolved. Nitrogen gas was sodium hydrogen carbonate was added portionwise passed through the reactor to displace the air, and the over a period of about 10 minutes, and 10 ml of distilled temperature was increased to 70° C. A solution of 126g water was added thereinto at the same time. After stir 4,065,435 25 26 ring an additional 4 hours at 60' C, the reaction solution was poured into 1.5l of dichloromethane while stirring with an agitator. The resulting precipitate was dissolved . - (II) in 150 ml of distilled water, and the solution was charged in a cellulose tube (semi-permeable membrane), -o-p OH dialyzed for about 30 hours against running water, and O N-R freeze-dried to obtain 15.8g of a reddish brown pow M X der. - R

10 OH Elemental Analysis . . . ; : C H N wherein X represents a hydrogen atom, a halogen atom, Found (%) 46.76 5.75 3.97 an alkyl group, an allyl group or an aryl group; R1 represents a hydrogen atom or an alkyl group; R2 repre 15 sents a hydrogen atom, an alkyl group or an aryl group; The product had a limiting viscosity, as determined in a R3 represents a divalent group selected from the group 1% aqueous sodium chloride solution at 30 C, of 0.49. consisting of a straight chain alkylene group having 1 to EXAMPLE 14 8 carbon atoms; a branched chain alkylene group hav ing 1 to 8 carbon atoms; an arylene group and a group Preparation of Compound 23 20 having the formula: To a 2 1 three-necked flask equipped with a stirrer, a thermometer and a gas-delivery tube, and placed on a steam bath, were added 70.65 g of 2-(3-aminopropyl)hy droquinone hydrobromide, 52.42 g of copoly(vinyl acetate-maleic anhydride) (molar ratio = 1:1) and 700 25 -(CH), ml of N,N-dimethylformamide, and the materials dis solved. After the solution was heated to 75 C, 23.9 g of sodium hydrogen carbonate was added portionwise wherein n is an integer of 1 to 4; and M is selected from over a period of about 15 minutes, and 50 ml of distilled 30 the group consisting of a hydrogen atom, an alkalimetal water was poured thereinto at the same time. After atom and a quaternary ammonium group. stirring an additional 3 hours at 75 C, the reaction 2. The polymer as claimed in claim 1, wherein X and solution was poured into 31 of dichloromethane while Reach represents a hydrogen atom or an alkyl group stirring with an agitator. The resulting precipitate was having from 1 to 8 carbon atoms. dissolved in 1000 ml of distilled water, charged in a 35 3. The polymer as claimed in claim 1, wherein X and cellulose tube, dialyzed for 40 hours against running Reach represents an alkyl group having from 1 to 4 water, and freeze-dried to obtain 90.3 g of a brown carbon atoms. powder. 4. The polymer as claimed in claim 1, wherein X represents a chlorine atom or a bromine atom. 5. The polymer as claimed in claim 1, wherein X Elemental Analysis represents a hydrogen atom. C . H N 6. The polymer as claimed in claim 1, wherein R3 Found (%) 54.7 3.84 3.59 represents an alkylene group having from 1 to 8 carbon atoms. The product had a limiting viscosity, as determined in a 45 7. The polymer as claimed in claim 6, wherein R3 1% aqueous sodium chloride solution at 30 C, of 0.36. represents an alkylene group having from 1 to 3 carbon While the invention has been described in detail and atoms. with reference to specific embodiments thereof, it will 8. The polymer of claim 1, prepared from maleic be apparent to one skilled in the art that various changes anhydride, citraconic anhydride or phenyl maleic anhy and modifications can be made therein without depart 50 dride. ing from the spirit and scope thereof. 9. A process for producing the water-soluble poly What is claimed is: mers as claimed in claim 1, comprising reacting a hydro 1. A water soluble homopolymer or copolymer con quinone compound of the formula (III) taining in its main chain recurring units of the formula 55 (I): OH R-NH

X OH wherein X represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group; R represents a hydro .65 gen atom or an alkyl group; and R3 represents a divalent group selected from the group consisting of a straight chain alkylene group having 1 to 8 carbon atoms; a or the formula (II): branched chain alkylene group having 1 to 8 carbon 4,065,435 27 28 wherein n is an integer of 1 to 4 or a salt thereof; with atoms; an arylene group and a group having the for- homopolymer, or copy containing in its main chain the recurring units of the formula (IV): mula:

10 10. The process of claim 9, wherein said polymer having recurring units of the formula (IV) is prepared -(CH), from maleic anhydride, citraconic anhydride or phenyl maleic anhydride. 15

25

30

35

45

50

55 . UNITED STATES PATENT OFFICE Page 1 of 2 CERTIFICATE OF CORRECTION Patent No. 4,065, 435 Dated December 27, 1977

O Inventor (s ) SHINJI SAKAGUCH It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below: O Claim l, delete formula (I) and formula (II) and insert therefor: 2 O -CH f f EO CeO O

O M (I) l O

O

O

O

O

o UNITED STATES PATENT OFFICE Page 2 of 2 CERTIFICATE OF CORRECTION

Patent No. 4,065. 435 Dated December-27 l977

O Inventor(s) SHINJI SAKAGUCH It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below: O

R 2 H O - - --0 i-o OH (II) O N-R M 3 X R OH signed and Sealed this O Twelfth Day of December 197a SEAL Attest

O R C. MASON DONALD W. BANNER Attesting Officer Corrissioner of Patents and Trademarks

O

O