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US2674619A - Polyoxyalkylene compounds - Google Patents

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US2674619A
US2674619A US38694553A US2674619A US 2674619 A US2674619 A US 2674619A US 38694553 A US38694553 A US 38694553A US 2674619 A US2674619 A US 2674619A
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polyoxypropylene
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molecular
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Lester G Lundsted
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Wyandotte Chemicals Corp
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D19/00Degasification of liquids
    • B01D19/02Foam dispersion or prevention
    • B01D19/04Foam dispersion or prevention by addition of chemical substances
    • B01D19/0404Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
    • B01D19/0413Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing N-atoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38Cationic compounds
    • C11D1/42Amino alcohols or amino ethers
    • C11D1/44Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S516/00Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/01Wetting, emulsifying, dispersing, or stabilizing agents
    • Y10S516/03Organic sulfoxy compound containing
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S516/00Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/01Wetting, emulsifying, dispersing, or stabilizing agents
    • Y10S516/06Protein or carboxylic compound containing
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S516/00Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/01Wetting, emulsifying, dispersing, or stabilizing agents
    • Y10S516/07Organic amine, amide, or n-base containing

Description

April 6, 1954 Filed 001.- 19. 1953 CARBON SOIL REMOVAL a1 I40F, ZOF STANDARD '6 8 (D O POLYOXYALKYLENE COMPOUNDS FiG. l

| s. LUNDSTED 2,674,619

3 Sheets-Sheet 1 ZOIO Lester G. Lundstod INVENTOR.

April 6,

Filed Oct.

CARBON SOIL REMOVAL of 90 E,% OF STANDARD L. G. LUNDSTED POLYOXYALKYLENE COMPOUNDS 3 Sheets-Sheet 2 FIG. 2

Loner G. Lands-n6 INVENTOR.

omey

A nl 6, 1954 L. e. LUNDSTED 2,674,619

POLYOXYALKYLENE COMPOUNDS Filed Oct. 19, 1955 3 Sheets-Sheet 3 FIG. 3

23l0 POLYOXYPROPYLENE POLYMER BASE I270 H'LYOXYPROPYLENE POLYMER BASE DARD cARBou son. REMOVAL m I40F, 10F STAN i OXYETHYLENE WENT Lane 6. Lundugg Patented Apr. 6, 1954 POLYOXYALKYLENE COMPOUNDS Lester G. Lundsted, Grosse Ile, Mich, assignor to Wyandotte Chemicals Corporation, Wyandotte, Mich., a corporation of Michigan Application October 19, 1953, Serial No. 386,945

18 Claims. 1

This invention relates to a group of novel polyoxyalkylene compounds which have outstandin detergent and surface active properties, and in which the hydrophobic element is a polyoxypropylene polymer having a molecular weight of at least 900. This application is a continuationin-part of my copending application, Serial No. 316,984, filed October 27, 1952, which is a continuation-in-part of my earlier filed application Serial No. 153,946, filed April 4, 1950, both applications now abandoned.

The art of producing surface active agents is old and well-developed, and it is a, well-recognized principle that all such compounds are relatively large molecules which contain both hydrophobic and hydrophilic elements. The essential hydrophobic element in the prior art surface active agents has always been a hydrocarbon radical, such as found in the long chain fatty acids and alcohols, or in the alkylaryl group of the popular alkylarylsulfonate type detergents. The hydrophllic element has frequently been a polyoxyethylene chain, such as found in nonylphenolethylene oxide condensation products.

A serious limitation of the prior art surface active agents is that the structure of any particular surface active agent is relatively fixed and it is diflicult to modify it, either as to molecular weight or the relative proportion by weight of the hydrophilic to the hydrophobic element. To prepare fatty alcohol based surface active agents having varying hydrophobic element chain lengths, it is necessary to use as many different starting materials as there are variations desired. Amon the difficulties inherent in using several starting materials are the storage and handling of many types of complex organic compounds, supply problems as to rare homologues, the different reaction conditions required in preparing the surface active agents, etc., so that it is not feasible to prepare surface active agents which differ from one another in small, uniform increments of hydrophobic element chain length. Similar difflculties are encountered in preparing petroleum based surface active agents which differ from each other only in small, finite increments of hydrophobic element chain length.

A further shortcoming of prior art nonionic surface active agents is that all the highly active compounds are liquids or pastes. While the physical form of a surface active agent does not effect its surface active properties, convenience in packaging, distribution and use makes a solid form highly desirable.

Several United States Patents, e. g. 2,213,447;

2,454,434 and 2,454,542-545, teach the use of poly oxyalkylene chains in surface active agents, but in all such patents the polyoxyalkylene chain constitutes the hydrophilic element of the surface active compound. U. S. Patent No. 2,425,845 discloses heteric or mixed polyoxyalkylene glycols, such as those which are formed when a mixture of ethylene and propylene oxides is condensed with a monoalkylene glycol, but these compounds do not possess detergent properties. It has also been previously known to react a higher aliphatic, water-insoluble monohydric alcohol sequentially with propylene oxide and ethylene oxide (U. S. Patent No. 2,174,761). The molecular weight of the polyoxypropylene chain in such a compound, even at its maximum theoretical value, is well below the minimum polyoxypropylene polymer molecular weight which has been found necessary in order to achiev the excellent detergent properties which characterize the compounds of the present invention.

It is an object of this invention to prepare novel polyoxyalkylene compounds having outstanding detergent and surface active properties and in which the hydrophobic element is a polyoxypropylene polymer.

Another object of this invention is to provide novel polyoxyalkylene compounds having excellent detergent and surface active properties and in which the molecular weight of both the hydrophobic and the hydrophilic element can b simultaneously varied within wide limits.

A further object of this invention is to provide nonionic detergents of high activity in a solid form.

Other objects and advantages of this invention will become apparent from the following detailed description thereof when read in conjunction with the accompanying drawings, in which:

Fig. 1 is a graph showing the effect of the polyoxypropylene polymer molecular weight upon detergent properties in 140 F. water,

Fig. 2 is a graph showing the efiect of the polyoxypnopylene polymer molecular weight upon detergent properties in 90 F. water, and

Fig. 3 is a. graph showing the effect of variation of polyoxyethylene content on detergent properties in 140 F. water.

NATURE OF INVENTION A new class of polyoxyalkylene compounds has been discovered which have outstanding detergent and surface active properties and in which the hydrophobic element is a polyoxypropylene polymer of at least 900 molecular weight. The

Y is the residue of an organic compound containing therein r active hydrogen atoms,

n is an integer,

a: is an integer greater than 1,

The values of n and a: are such that the molecular weight of the compound, exclusive of E, is at least 900, as determined by hydroxyl number,

E is a polyoxyalkylene chain wherein th oxygen/ carbon atom ratio is at least 0.5, and E constitutes 20-90%, by weight, of the compound.

The significance of each element of the above generic formula will be set forth in the subsequent sections of this patent.

STRUCTURE OF THE NOVEL POLYOXYAL- KYLENE COMPOUNDS The polyoxypropylene polymer, which is an intermediate in the preparation of the compounds of this invention, has the following structure;

-O(CIHQO LE! 2):

wherein n is'defined as in FormulaA.

The preferred compounds of this invention are prepared by condensing ethylene oxide, in an amount constituting 20 90% of the resultant compound, with the poiyoxypropylene polymer. Thus, these compounds have the following formula:

(C) Y[ (CaHsO) (021140) mH]:

where 'Y, n and a: are deflnedasin Formula A and rm-has a value such that'the oxyethylene groups constitute 20-90%, by weight, of the compound. When ethyleneoxide is condensed with a polyoxypropylene glycol of at least 900 molecular weight, the resulting compounds have the following structure:

where m and n are definedas previously set forth. When ethylene oxide is condensed with a D 5- oxypropylene polymer that is derived by the condensation oi" propylene oxide with adipic acid,

the resulting compounds have the following structure:

with m and n being defined as previously described.

The hydrophilic portion of the novel polyoxyalkylene compounds may be supplied by other polyoxyalkylene chains in lieu of the polyoxyethylene chain set forth in Formula C. Any polyoxyalkylene chain may be used provided that the oxygen/carbon atom ratio contained therein is at least 0.5. For example, such hydrophllic polyoxyalkylene chain may be derived from butadiene dioxide, glycidol, etc. By letting the symbol E represent generically any such polyoxyalkylene chain, Formula C may be rewritten as Formula A by simply substituting E for (CzHrOM. Formula A represents the broad generic class of compounds to which the present invention relates.

PREPARATION OF THE NOVEL POLYOXY- ALKYLENE COMPOUNDS The preparation of the surface active agents of this invention involves two steps:

1. The condensation of propylene oxide with a base compound containing a plurality of reactive hydrogen atoms to prepare a polyoxypropylene polymer of at least 900 molecular weight, and

2. The condensation of ethylene oxide, or its equivalent, with the polyoxypropylene polymer.

In the first step propylene oxide is condensed with the base compound containing the plurality of reactive hydrogen atoms to prepare the polyoxypropylene polymer, viz:

Hereinafter the base compound containing a plurality of reactive hydrogen atoms will be referred to simply as the reactive hydrogen compound. Alternatively, if desired, the polyoxypropylene polymer may be prepared by reacting a polyoxypropylene glycol with the reactive hydrogen compound, by esterification, etherification, etc. de pending upon the nature of the reactive hydrogen compound, viz:

In the second step of the preparation, the hydrophilic polyoxyalkylene chain is introduced into the molecule by condensing ethylene oxide, or its equivalent, with the polyoxypropylene polymer, viz:

As an alternative procedure the hydrophilic polyoxyalkylene chain may be introduced by etherifying the polyoxypropylene polymer with a polyoxyethylene glycol, or its equivalent.

In preparing the polyoxypropylene polymer, the condensation of propylene oxide with the reactive hydrogen compound is normally carried out at elevated temperatures and pressures in the presence of an alkaline catalyst such as sodium alkoxide, a quaternary ammonium base, or preferably sodium hydroxide. Similarly, the condensation reaction may be carried out in the presence of acid catalysts as set forth in U. 8. Patent No. 2,510,540.

Although the reaction may be carried out by simply heating a mixture of the reactants under pressure at a sufficiently high temperature, this procedure is not ordinarily used as the temperatures and pressures required are excessive and control of the reaction is diflicult. For each mol of propylene oxide reacting, an estimated 25 kilogram-calories of heat is liberated which, in the presence of a large quantity of propylene oxide, may increase the temperature and reaction rate to such an extent that the reaction assumes an explosive nature.

The preferred method of carrying out the reaction is to add the propylene oxide to a stirred, heated mixture of the de sired reactive hydrogen compound and alkaline catalyst in a sealed reaction vessel. By adding the propylene oxide to the reaction vessel at such a rate that it reacts as rapidly as added, an excess of propylene oxide is avoided and control of the reaction is simplifled.

The temperature at which the reaction is run will depend upon the particular system in qucs tion and especially upon the catalyst concentration used. Generally, at higher catalyst concer1- trations the reaction can be run at lower temperatures and correspondingly lower pressures. The temperatures and pressures required for any given reaction will vary with the reactive hydrogen compound. and the typ and concentration of catalyst used.

The condensation of ethylene oxide with the polyoxypropylene polymer is carried out in an analogous manner.

The preparation of the novel polyoxyalkylene compounds of the invention is illustrated by Example 1 below:

EXAMPLE 1.PAxr A In a one-liter 3-neck round bottom flask equipped with a mechanical stirrer, reflux condenser, thermometer and propylene oxide feed inlet, there were placed 5'7 grams (0.75 mol) of propylene glycol and 7.5 grams of anhydrous sodium hydroxide. The flask was purged with nitrogen to remove air and heated to 120 C. with stirring, and until the sodium hydroxide was dissolved. Then sufficient propylene oxide was introduced into the mixture as fast as it would react until the product possessed a calculated molecular weight of 2380. The product was cooled under nitrogen, the NaOIil catalyst neutralized with sulfuric acid and the product filtered. The final product was a water-insoluble polyoxypropylene glycol having an average molecular weight of 1620 as determined by hydroxyl number or acetylation analytical test procedure.

EXAMYLE 1.-PART B five grams of ethylene oxide was added at an average temperature of 120 C., using the same technique as employed in Part A. The amount of added ethylene oxide corresponded to 17.4 of the total weight of the polyoxypropylene glycol base plus the weight ofadded ethylene oxide.

of the composition It will be noted in Part A of the above example that the molecular weight, as determined by bydroxyl number, was appreciably lower than the calculated molecular weight. Throughout this application, unless otherwise specified, it will be understood that the molecular weight of the polyoxypropylene polymer was determined by hydroxyl number using the method of Ogg et al., Industrial and Engineering Chemistry, Analytical Ed., vol. 17, p. 395, 1945.

EVALUATION TEST FOR SURFACE ACTIVITY The following test procedure was used to evaluate the surface active properties of the products of this invention:

Carbon soil removal test procedure A standard soiled cotton fabric is first prepared as follows:

Bleached, unfinished Indian Head muslin (58 x 47, 4.7 oz. per sq. yd., manufactured by Textron, Inc.) is used without pretreatment after conditioning to equilibrium at R. H. and F. A continuous 10 inch wide strip of the muslin is soiled by passing through an emulsion of colloidal carbon black and water-soluble mineral oil. After thorough impregnation of the standard muslin in the carbon black and oil emulsion, the cloth is passed through a powerrlriven household -type wringer to squeeze out any residual aqueous dispersion, the wringer pressure being so adjusted as to leave in the cloth an amount of standard soil dispersion equal to j:5% of the dry weight of the cloth. The

soiled muslin is then passed through a brush arrangement which by means of its mechanical action on the cloth controls the removability characteristics of the soil. The soiled muslin or test cloth is then dried, first in festoon under atmospheric conditions and then in an electrically heated, forced draft oven. After drying, the cloth is aged for 4 to 6 days by hanging in an atmosphere of 65% R. H. at 70 F. after which it is cut into test swatches measuring 2.5 inches-:

' inch by 3.5 1110118513 1 inch using a power driven guillotine paper cutter. Before actual use of the so-prepared standard soiled cloth, it is checked for conformance with acceptability limits by the following described carbon soil removal test in standard detergent solutions. The swatches are stored at 65% R. H. and 70 F. prior to use.

To evaluate the soil removal characteristics of synthetic detergent compositions, 0.25% by weight solutions or other desired concentrations to be tested are prepared in water and 100 ml. portions of such solution are added to each of 10 one-pint jars of a Launder- Ometer (type l2Q-EF-SPA, manufactured by Atlas Electric Devices Company) standard laundry test machine.

Fifteen A" diameter stainless steel balls are placed in each jar, after which two pieces of the previously prepared standard soiled cloth are added to each of nine jars. In the tenth jar are placed two pieces of unsoiled but pretreated cloth and this latter jar serves as a blank for deter" mining the turbidity of the detergent solution. The so-prepared jars, heated to a temperature of :2 F. in a constant temperature bath are then placed in the Launder-Ometer" and run for 10 minutes at a speed of 4212 R. P. M. The jars are then removed from the test machines and replaced in the constant temperature bath. The contents of each jar to which the standard 7 soiled cloth has been added? acoarse screen to separate the standard soiled cloth fro the soil suspension which is collected in a large beaker. The composite suspension thus attained is mixed thoroughly and a sample placed in a mm. light absorption cell. The light absorption of this composite solution. as well as the light absorption oi the solution in the tenth or blank jar containing the unsoiled cloth test pieces is then measured (by Lumetron Colorimeter). By means of a calibration curve for the "Lumetron Colorimeter, such curve being constructed by obtaining light transmission readings of known quantities of carbon black dispersion added to distilled Water, the carbon soil removal value sought (in mg. of carbon per liter of solution) is obtained by taking the diiference between the converted values of the light transmission of the composite solution or suspension from the nine jars and of the light transmisison of the suspension in the blank jar.

The carbon soil removal values are then reported as a percentage of that of a standard detergent solution used as a reference or control material; viz. by dividing the mg. of carbon removal value of the test material composition by the mg. of carbon removal value for the standard or control detergent solution which is determined concurrently in the same same standard soiled test by 100.

The standard detergent solution used throughout the tests reported herein was a 0.25% soluare poured" through the steel balls and cloth, and multiplying tion of sodium kerylbenzene-sulfonate in distilled water. was prepared The sodium kerylbenzenesulfonate by effecting a Friedel-Crafts condensation of a chlorinated petroleum hydrocarbon distillate (derived from a hydrocarbon distillate having 9-16 carbon atoms and boiling in the range of 150-300 C.) with benzene and thereafter sulfonating the kerylbenzene compound to form the kerylbenzenesulfonic acid, which was subsequently neutralized with caustic soda to form the water-soluble sodium kierylbenzenesulfonate. After the neutralization of the sulfonic acid, suificient sodium sulfate was added so that the final product contained 40% sodium kerylbenzenesulfonate and 60% sodium sulfate.

EFFECT OF POLYOXYPROPYLENE POLY- MER MOLECULAR WEIGHT ON SURFACE ACTIVE PROPERTIES A fundamental feature of this invention resides in the discovery that a polyoxypropylene polymer is sufllciently hydrophobic at a critical minimum molecular weight to serve as the hydrophobic element of surface active agents. The effect and criticalness of the polyoxypropylene polymer molecular weight upon surface active properties is illustrated by Example 2.

EXAMPLE 2 Eight polyoxypropylene polymers were prepared by condensing propylene oxide with propylene glycol following the procedure of Example 1, Part A. The molecular weights of the polyoxypropylene polymers were varied over a wide range and an approximately standard or uniform quantity (viz: 44-48% of the total weight of the product), of ethylene'oxide was added thereto. The procedure of adding the ethylene oxide was the same as that employed in Example 1, Part B. Each of the compounds was then evaluated for carbon soil removal value at 140 F. by the protest run and on the The results are'set TABLE I Molecular Polyoxy- Detergeucy Weight ethylene Carbon Run It Polyoxy- Content, emoval pro ylene Percent of 0.25% at 140 Po ymer Compound F.

The data of the above table are plotted in the attached Fig. 1. It is seen that at polyoxypropylene polymer molecular weights of below 900 the detergency oi the compounds is low, but that at approximately 900 molecular weight there is an inflection in the curve and the carbon soil removal value reaches 100% of standard. Above 900 molecular weight the curve climbs very rapidly to the approximately 225% of standard value at approximately 1100 molecular weight and then levels off, but stays at these high values.

As noted in the above example, all polyoxyalkylene compounds in which the polyoxypropylone polymer has a molecular weight of at least 900 have good detergency at 140 R, which is a conventional temperature used in laundry operations. The products of this invention in which the polyoxypropylene polymer portion has a. molecular weight in excess of 2000 are a preferred embodiment of the invention in that they have exceptionally high detergency in cold water, viz. F. The effect of polyoxy'propylene polymer molecular weight on cold water detergency is illustrated in the following example.

EXAMPLE 3 Five polyoxypropylene polymers of varying molecular weights were prepared by condensing propylene oxide with propylene glycol following the procedure of Example 1, Part A. Ethylene oxide was added to each of the polyxypropylene polymers to prepare compounds having an approximately equivalent quantity of oxyethylene groups (viz: 44-51% of the total weight of the product). Each of the compounds was then evaluated for carbonsoil removal value at the low temperature of 90 F. The results are set forth in Table II below:

TABLE II Molecular Polyoxy- Detergency' Weight ethylene Carbon Soil Run i Polyoxy- Content, Removal propylene Percent of 0.25% at 90 Po ymer Oompoundi F.

l, 48 101 l, 270 44 112 1, 620 51 121 2, s20 44 210 2, 600 47 197 The attached Fig. 2 is based upon the data of the above table. It isseen that at below molecular weights of approximately 2000 the cold water detergency lies within the range of approximately IOU-% of standard. but thatat approximately 2000 molecular weight there is an inflection in the curve and that at all values in excess there of the very high cold water detergency of 200% of standard or more isobtained. These results are particularlly significant inthatthey exceed the values that are obtained with the highest quality soap in much hotter water. of course, the advantages of obtaining high detergency in cold water are obvious.

EFFECT OF POLYOXYETHYLENE CONTENT ON SURFACE ACTIVE PROPERTIES The polyoxyethylene groups must constitute approximately 20-90% of the novel polyoxyalkylene compounds if good detergent values are to be obtained. The criticalness of this range is established by the following example:

EXAMPLE 4 Varying quantities of ethylene oxide were added to 2 polyoxypropylene glycols of 1270 and 2310 molecular weight following the procedure of Example 1, Part B, to prepare compounds having widely varying oxyethylene contents. The resulting compounds were subjected to the carbon soil removal test previously set forth and the results are shown in the following table:

TABLE III Molecular Polyoxy- Detergeney, Weight ethylene Carbon Soil Run Polyoxy- Content, Removal propylene Percent of 0.25% at 140 Polymer Compound F.

l, 270 T 68 1,270 2B 91 1,27) 33 146 1,270 44 202 1, 270 52 225 1, 270 68 20B 1, 270 1 80 141 2,320 as 115 2, 320 37 216 2, 320 44 232 2, 320 52 214 2,320 67 208 2, 320 80 175 When the above data are plotted shaped" curves are obtained which define area of good detergency. It will be seen that the limits of 20-90% encompass the area of good detergency, and wherein the curves rather abruptly change slope from the bordering low detergency values at below 20%, oxyethylene content. The limits of approximately 40-70% oxyethylene content pin point the area or maximum detergency. Essentially the same limits apply when other hydrophilic polyoxyalkylene chains, such as those derived from butadiene dioxide, glycidol, etc. and other alkylene oxides wherein the oxygen/carbon atom ratio is at least 0.5, are contained in the novel polyoxyalkylene compounds.

EFFECT OF Y ON SURFACE ACTIVE. PROPER'ITES As noted heretobefore, the polyoxypropylene is prepared by condensing propylene oxide with a base compound containing a plurality of reactive hydrogen atoms. The function of the base compound is to furnish reactive hydrogen atoms which initiate the polymerization of the propylene oxide and, since the base compound constitutes only a small proportion of the high molecular weight polyoxyalkylene compounds, it ordinarily does not have an influence on the properties thereof. In other words, the particular base compound employed in preparing the novel polyoxyalkylene compounds is not critical so long as it furnishes at least 2 reactive hydrogen atoms, and operable polyoxyalkylene compounds are obtained regardless of the particular base compound employed in the preparation of the polyoxypropylene polymer. Ordinarily it is in Fig. 3, bell the and above 90%,

i. It is sufficiently labile to open the epoxide ring of 1,2 propylene oxide, and

2. It reacts with methyl magnesium iodide to liberate methane in the classical Zerewitinofl reaction (see Niederl and Niederl, Micromethods of Quantitative Organic Analysis, p. 263, John Wiley and Sons, New York city, 1946).

lhe reactive hydrogen atoms which will fulfill the above two conditions are normally activated by being a member of a functional group containin an oxygen atom, e. g. a hydroxyl group, a phenol group, a carboxylic acid group; a. basic nitrogen atom, e. g. an amine group, a hydrazine group, an imine group, an amide group, a guanidine group, a sulionamide group, a urea group, a thiourea group; or a sulfur atom, e. g, a, mercaptan, a, thiophenol, a thiocarboxylic acid, hydrogen sulfide. Alternatively, certain hydrogen atoms may be activated by proximity to carbonyl groups such as those found in cyanoaoetic esters, acetoacetic esters, malonic esters, as is well known in the art. Specific examples or base compounds which may be used in preparing the polyoxypropyleno polymers include ethylene glycol, 1,3 butylene glycol, oxalic acid, glycolic acid, mono-, di-, and triethanolamine. butylamine, aniline, resorcinol, diethylmalonate, etc.

The equivalency of all such base compounds in initiating the condensation of propylene oxide to form the polyoxypropylene polymer is illustrated by the following example.

EXAMPLE 5 Propylene oxide was condensed with, respectively, acetamide, 1,5 pentanediol, glycerine, ethylene diamine, benzene sulfonamide and sucrose to form polyoxypropylene polymers having molecular weights in excess of 900. The general procedure employed was that of Example 1, Part A except for certain minor changes in technique which will be obvious to those skilled in the art. Ethylene oxide was then condensed with the resulting polyoxypropylene polymers to prepare detergent compounds which were evaluated by the method previously set forth. The structure of the resulting compounds and the detergent values thereof are set forth in the following table:

TABLE IV Molecular Polyoxy- Detergency, Weight ethylene Carbon Soil Base Compound (Y) Polyoxy- Content, Removal propylene Percent of 0.25% at P0 ymer Compound F.

While any reactive hydrogen compound containing 2 or more reactive hydrogen atoms may be used in preparing the polyoxypropylene com-- pounds herein disclosed and claimed, the polyoxyalkylene compounds derived from certain specific base compounds have unusual and unsteam and at least one reactive hydrogen atom attached to a nitrogen atom, e. g. ethylene diamine, have exceptionally good cold water detergency and lime soap dispersing powers. Such compounds are more specifically disclosed and claimed in my copending application, Serial No. 349,283, filed April 16, 1953.

CHARACTERISTICS AND APPLICATIONS OF THE NOVEL POLYOXYALKYLENE COM- POUNDS -The compounds of this invention, in addition to the previously described outstanding ability to remove soil from a textile fabric (i. e. detergency is measured by carbon soil removal values) also possess remarkable ability to retain the soil suspended in solution once it is removed. This latter ability is measured by the whiteness retention test, described as follows:

Whiteness retention test procedure Bleached, unfinished, clean Indian Head muslin, county 58 x 7, weight 4.7 oz./sq. yd. (Nashua Manufacturing Company), is cut into swatches measuring 2 x 3 The light reflectance of each side of everyswatch is measured by means of a Hunter Multipurpose Refiectometer equipped with a green flltenusing a standard white backing with a reflectance of 68.8% behind the cloth swatch. The average of such values of each side of each test piece is calculated and recorded. A standard soil suspension is prepared bydiluting 28.55 grams of an aqueous carbon dispersion containing 35% carbon (Aqua Blak B, Binney and Smith 00.) to 1 liter in a volumetric flask of distilled water.

A 0.25% distilled water solution of the detergent compound to be tested is then made up by adding 2.5 grams of the compound to a small amount of distilled water in a 1 liter volumetric flask. The previously prepared'soil suspension is shaken vigorously and 50 ml. then pipetted into the flask containing the detergent. Sui'ltit cient distilled water is then added to this flask to make up to the one-liter mark.

The resultant mixture of detergent and carbon soil suspension is pipetted in 100 ml. portions into each of5 Launder-Ometer jars, each jar containing fifteen 54," stainless steel balls. The jars and contents are brought to a temperature of 140:2 F. in a constant water bath, then placed in the Launder-Ometer and rotated for 5 minutes at 42:2 R. P. M. The Launder-Ometer" is thereafter stopped and without removing the jars from the machine, the lids are opened and two standard cloth swatches, prepared as previously described, are placed in each jar after soaking for exactly 1 minute in distilled water without subsequent draining. The lids are replaced on the jars and the latter are rotated for an additional 30 minutes in the "Launder- Ometer. V'I'he swatches are then removed and .immediatelyrinsedby flowingB liters of distilled.

water continuously through a rinsing flask while shaking, and for a periodtoifi minutes. rimmediately after rinsin the swatches a ieiremov'ed from the rinsing flask and placed on flat clean paper towels. The swatches are pressed on 5 a laundry press set at a temperature of 3283 338 F. After pressing, the reflectance of both sides of each swatch is again measured. by the Hunter Reflectometer andthe average reflectance of all swatches calculated and recorded. The whiteness retention value is then calculatd as follows:

Per cent whiteness retention (W. R.)=

a e. reflectance after soilinglilj!) ave. reflectance before soiling The whiteness retention values are reported herein as a percentage of that determined in the standard detergent solution described under the "Carbon soil removal test procedureyyiz. by dividing the. percent whiteness retention determined in the test material by the percent whiteness retention determined in the standard control detergent solution which is determined concurrently in the same test run and on the same standard test cloth, and multiplying by 100.

The numerical values obtained with several representative compounds of this invention are set forth in the table below:

TABLE V Molecular Weight Polyoxypropylene Polymer I Run Compound Condensation product of propylene oxide and propylene glycol.

TABLE VI 50 Molecular Weight Polycrypropylene olylner Polyoxyethylene Content, Percent of Compound Drave's Sink Time Runii l Condensation product of propylene oxide and propylene glycol.

Illustrative of the surface tension lowering by the compounds of this invention are the following results:

TABLE VII Molecular Polyoxy- Surface Weight ethylene Tension Run I Polyoxy- Content, 0.1% at propylene Percent of 25 0..

olymer 1 Compound Dynes/cm.

l l, 270 44 35 2 l, 620 81 37 2, 320 37 34 600 47 35 I Condensation product of propylene oxide and propylene glycol.

A desirable characteristic of the polyoxyalkylene compounds of this invention is that both the hydrophobic and the hydrophilic elements thereof can be varied over an extremely wide range of molecular weights. By merely changing the quantity of propylene oxide added to the reactive hydrogen compound it is possible to prepare a wide range of hydrophobic elements that differ from one another in small, finite increments of polyoxypropylene polymer molecular weight. Similarly, varying quantities of ethylene oxide can be added to any of the above-described hydrophobic elements to prepare surface active agents, which differ from each other only in small, finite increments of polyoxyethylene content. By proper selection of reaction conditions, it is possible to vary over a wide range: (1) the hydrophobic polyoxypropylene polymer molecular weight, (2) the hydrophiiic poiyoxyethylene content and (3) the hydrophobic polyoxypropylene polymer molecular weight/hydrophilic polyo-xyethylene content ratio. The facility with which the structure of the surface active agents can be varied is highly advantageous in that surface active agents can be "tailor made to perform specific functions.

In addition to their surface active properties, the polyoxyalkylene compounds of this invention have many other diverse applications in the industrial arts. For example, these compounds have an excellent plasticizing action on a wide range of thermoplastic and thermosetting resins. In this regard, attention is directed to the copending applications of Lester G. Lundsted and J. P. McMahon, Serial No. 231,650, filed June 14, 1951, and Serial No. 259,476, filed December 1. 1951.

In the appended claims, the term cogeneric mixture is used. This is a term that has been coined to designate a series of closely related, touching homologues that are obtained by condensing a plurality of alkylene oxide units with a reactive hydrogen compound (see United States Patent 2,549,438, particularly the section beginning at column 12, line 40).

Also in certain of the claims, organic compounds containing a plurality of reactive hydrogen atoms are defined as having a detergency factor of less than 100. The detergency factor is the measure of the phobic character of any organic compound containing one or more reactive hydrogens and is determined as follows:

Varying quantities of ethylene oxide are added to the reactive hydrogen compound to prepare oxyethylene adducts containing 20:57,], 30:5%. 40:5%, 50:5% and 60-15% oxyethylene content. Distilled water solutions of 0.25% concentration are prepared with each of the adducts. The carbon soil removal value of each adduct is determined at 140 F. following the procedure described by Vaughn and Suter, The Journal of the American Oil Chemists Society, vol. XXVII, No. '7, pp. 249-257. As a control, the carbon soil removal value of an 0.25% distilled water solution of a standard sodium allcvlarylsulfonate detergent is determined concurrently at 140 F. and on the same batch of soiled cloth. The standard detergent is sodium kerylbenzenesulfonate which is prepared by effecting a Friedel-Crafts condensation of a chlorinated petroleum hydrocarbon distillate (derived from a hydrocarbon distillate having 9-16 carbon atoms and boiling in the range of l50-300 C.) with benzene and thereafter sulfonating the kerylbenzene comdetergent-forming, hydro- 14 pound to form the kerylbenzene sulfonic acid, which is subsequently neutralized with caustic soda to fo-rm the water-soluble sodium kerylbenzenesulfonate. After the neutralization of the suli'onic acid, sufficient sodium sulfate is added so that the final product contains 40% sodium kerylbenzenesulfonate and 60% sodium sulfate.

The carbon soil removal values of the oxyethylene adducts are reported on a comparative basis with the standard sodium alkylarylsulfonate detergent being assigned an arbitrary value of 100. The highest carbon soil removal value obtained with the five oxyethylene adducts is then taken as the detergency factor of the reactive hydrogen compound.

What is claimed is:

1. A cogeneric mixture of conjugated polyoxypropylene-polyoxyethylene compounds containing in their structure oxypropylene groups, oxyethylene groups and an organic radical derived from an organic compound containing a plurality of reactive hydrogen atoms; the compounds being characterized in that all of the oxypropylene groups are present in polyoxypropylene chains that are attached to the organic radical at the site of a reactive hydrogen atom thereby constituting a polyoxypropylene polymer; the oxyethylene groups being attached to the polyoxypropylene polymer in polyoxyethylene chains; the average molecular weight of the polyoxyp-ropylene polymers in the mixture being at least 900, as determined by hydroxyl number, and the oxyethylene groups present constituting 20-90%, by weight, of the mixture.

2. A cogeneric mixture of conjugated polyoxypropylene-polyoxyethylene compounds containing in their structure oxypropylene groups, oxyethylene groups and an organic radical derived from an organic compound containing a plurality of reactive hydrogen atoms; the compounds being characterized in that all of the oxypropylene groups are present in polyoxypropylene chains that are attached to the organic radical at the site of a reactive hydrogen atom thereby constituting a polyoxypropylene polymer; the oxyethylene groups being attached to the polyoxypropylene polymer in polyoxyethylene chains; the average molecular weight of the poiyoxypropylene polymers in the mixture being at least 900, as determined by hydroxyl number, and the oxyethylene groups present constituting 40-70 by weight, of the mixture.

3. A cogeneric mixture of conjugated polyoxypropylene-polyoxyethylene compounds containing in their structure oxypropylene groups, oxyethylene groups and an organic radical derived from an organic compound containing a plurality of reactive hydrogen atoms; the compounds being characterized in that all of the oxypropylene groups are present in polyoxypropylene chains that are attached to the organic radical at the site of a reactive hydrogen atom thereby constituting a polyoxypropylene polymer; the oxyethylene groups being attached to the polyoxypropylene polymer in polyoxyethylene chains; the average molecular weight of the polyoxypropylene polymers in the mixture being at least 2000, as determined by hydroxy number, and the oxyethylene groups present constituting 20-90%, by weight, of the mixture.

4. A cogeneric mixture of conjugated polyoxypropylene-polyoxyethylene compounds containing in their structure oxypropylene groups, oxyethylene groups and an organic radical derived from an organic compound containing a plurality constituting a oxypropylene the average propylene polymers in the mixture being at least 2000,'as determined by hydroxyl number, and the oxyethylene by weight, of the mixture.

of at least 0.5 and an the oxypropylpresent in 'polyoxypropylene at the site of a reactive hydrogen atom thereby polyoxypropylene polymer; the oxyethylene groups being attached to the polypolymer in polyoxyethylene chains; molecular weight of the polyoxygroups present constituting 40-70%,

5. A cogeneric mixture of conjugated polyoxyalkylene compounds containing in their structure oxypropylene groups. hydrophilic oxyalkylene groups having an oxygen/carbon atom ratio organic radical derived from an organic compound containing a plurality of reactive hydrogen atoms; the compounds being characterized in that all of the oxypropylene groups are present in polyoxypropylene chains that are attached to the organic radical at the site of a reactive hydrogen atom thereby constituting a polyoxypropylene polymer; the hydrophilic oxyalkylene groups being attached to the polyoxypropylene polymer in polyoxyalkylene chains; the average molecular weight of the polyoxypropylene polymers in the mixture being at least 900, as determined by hydroxyl number, and the hydrophillc oxyalkylene groups present constituting 20-90%, by weight, of the mixture.

6. A cogeneric mixture of conjugated polyoxyalkylene compoundscontaining in their structure oxypropylene groups. hydrophilic oxyalkylene groups having an oxygen/carbon atom ratio of at least 0.5 and an organic radical derived from an organic compound containing a plurality of reactive hydrogen atoms; the compounds being mixture.

7. A cogenerio mixture of conjugated polyoxyalkylene compounds containing in their structure oxypropylene groups, hydrophilic-oxyalkylene groups havingan oxygen/ carbon atom ratio of at least 0.5 and an organicradical derived from an organic compound containing a plurality of reactive hydrogen atoms; the compounds being characterized in that all of the oxypropylene groups are present in polyoxypropylene chains that are attached to the organic radical at the site of a reactive hydrogen atom thereby constituting a polyoxypropylene polymer; the hydrophilic oxyalkylene groups being attached to the polyoxypropylene polymer in polyoxyailwlene chains; the average molecular weight of the polyoxypropylene polymers in the'mixture being at least 2000, as determined by hydroxyl number, and the hydrophilic oxyalkylene groups present constituting 20-90%, by weight, of the mixture.

8. A cogeneric mixture of conjugated polyoxyalkylene compounds containing in their structure oxypropylene groups, hydrophilic oxyalkylene groups having an oxygen/carbon atom ratio of at ieast 0.5 I and an organic radieaiiderived irom reactive hydrogen atoms;

. philicoxyalkylene groups being attached to the t at least 2000, as determined polyoxypropylene polymer in vpolyoxyaikylene chains: the average molecular. weightaofithe polyoxypropylene polymersin thezmixture being by. hydroxyl number, and the hydrophilic oxyalkylenegroups present constituting 40-70%, by weight, ofithe mixture.

9. A cogeneric' mixture of conjugatedcpolyoxypropylene-polyoxyethylene compounds containing in their structure oxypropylene groups, oxyethylene groupsand an organic radicai derived from. an organic compound containing aplurality oi reactive hydrogen atoms and having a detergency factor of less than 100; the compounds being characterized in that all of the oxypropylene groups are present in poiyoxypropylene chains that are attachedtothe organic radical at the site of a reactive hydrogen atom chains; the average molecular weight of the polyoxypropylene polymers in the mixture beingat least 900, as determined by hydroxyl number. and the oxyethylene groups present constituting 20-90%, by weight, of the mixture; said compounds having a carbon soil removal value or at least 100.

10. A cogeneric mixture. of conjugated polyoxyprop-ylene-polyoxyethylene compounds containing in their structure oxypropylene groups,

an organic radicalderived from an organic compound containing a plurality of reactive hydrogen atoms and having a detergency factor of less than 100; the compounds being characterized in that all 01 the oxypropylene groups are present in polyoxypropyl-ene chains that areattached to the organic radical at the site of a reactive hydrogen atom thereby constituting a poiyoxypropylene polymer; theoxyethylene groups being attached'to V the polyoxypro-pylene polymer in polyoxyethyli and the oxyethylene groups present constituting 40-70%, by-weight, of the mixture; said compounds having a carbon soil removal value of at least 100.

11. A cogeneric mixture of oxypropylene-polyoxyethylene compounds containing in their structure oxypropylene groups, oxyethylene groups and an organic radical derived from an organic compound containing a. plurality of reactive hydrogen atoms and having a'detergency factor. of less than 100; the compounds being characterized in that all of the oxypropylen'e groups are present in polyoxypropylene chains that are attached to the organic radical at the'site of a reactive hydrogen atom thereby constituting a polyoxypropylene polymer; the oxyethylene groups being attached to the polyoxypropylene polymer in *poiyoxyethylene chains; the'average molecular weight of the polyoxypropylene polymers in the mixture being at least 2000, as determined by hydroxylnumber, and-the conjugated polyoxyethylene groups present constituting 20-90%, by weight, of the mixture; said compounds havng a carbon soil removal value of at least 100.

12. A cogeneric mixture of conjugated polyoxypropylene-polyoxyethylene compounds containing in their structure oxypropylene groups, oxyethylene groups and an organic radical derived from an organic compound containing a plurality of reactive hydrogen atoms and having a detergency factor of less than 100; the compounds being characterized in that all of the oxypropylene groups are present in polyoxypropylene chains that are attached to the organic radical at the site of a reactive hydrogen atom thereby constituting a polyoxypropylene polymer; the oxyethylene groups being attached to the polyoxypropylene polymer in polyoxyethylene chains; the average molecular weight of the polyoxypropylene polymers in the mixture being at least 2000, as determined by hydroxyl number, and the oxyethylene groups present constituting 40-70%, by weight, of the mixture; said compounds having a carbon soil removal value of at least 100.

13. A cogeneric mixture of conjugated polyoxypropylene-polyoxyethylene compounds containing in their structure oxypropylene groups. oxyethylene groups and an organic radical derived from an organic compound containing a plurality of reactive hydrogen atoms, said compound having a molecular weight of less than 200, the reactive hydrogen atoms of said organic compound being members of functional groups containing an element selected from the group consisting of oxygen, sulfur and nitrogen; the compounds being characterized in that all of the oxypropylene groups are present in polyoxypropylene chains that are attached to the organic radical at the site of a reactive hydrogen atom thereby constituting a polyoxypropylene polymer; the oxyethylene groups being attached to the polyoxypropylene polymer in polyoxyethylene chains; the average molecular weight of the polyoxypropylene polymers in the mixture being at least 900, as determined by hydroxyl number, and. the oxyethylene groups present constituting 20-90%, by weight, of the mixture: said. compounds having a carbon soil removal value of at least 100.

14. A cogeneric mixture of conjugated polyoxypropylene-polyoxyethylene compounds containing in their structure oxypropylene groups. oxyethylene groups and an organic radical derived from a polyhydric alcohol having a molecular weight of less than 200; the com pounds being characterized in that all of the oxypropylene groups are present in polyoxypropylene chains that are attached to the organic radical at the site of a reactive hydrogen atom thereby constituting a polyoxypropylene polymer; the oxyethylene groups being attached to the polyoxypropylene polymer in polyoxyethylene chains; the average molecular weight of the polyoxypropylene polymers in the mixture being at least 900, as determined by hydroxyl number. and the oxyethylene groups present constituting 20-90%, by weight, of the mixture.

15. A cogeneric mixture of conjugated poly- 18 oxypropylene-polyoxyethylene compounds containing in their structure oxvpropylene groups, oxyethylene groups and an organic radical derived from a carboxylic acid amide having a molecular weight of less than 200; the compounds being characterized ln that all of the oxyp-ropylene groups are present in polyoxypropylene chains that are attached to the organic radical at the site of a reactive hydrogen atom. thereby constituting a polyoxypropylene polymer; the oxyethylene groups being attached to the polyoxypropylene polymer in polyoxyethylene chains; the average molecular weight of the polyoxypropylene polymers in the mixture being at least 900, as determined by hydroxyl number, and the oxyethylene groups present constituting 29-90%, by weight, of the mixture.

16. A cogeneric mixture of conjugated polyoxypropylene-polyoxyethylene compounds containing in their structure oxypropylene groups, oxyethylene groups and an organic radical derived from an arylsulfonamide having a plurality of reactive hydrogen atoms and a molecular weight of less than 200; the compounds being characterized in that all of the oxypropylene groups are present in polyoxypropylene chains that are attached to the organic radical at the site of a reactive hydrogen atom thereby constituting a polyoxypropylene polymer; the oxyethylene groups being attached to the polyoxypropylene polymer in polyoxyethylene chains; the average molecular weight of the polyoxypropylene polymers in the mixture being at least 900, as determined by hydroxyl number, and the oxyethylene groups present constituting 20-90%, by weight, of the mixture.

17. A cogeneric mixture of conjugated polyoxypropylene-polyoxyethylene compounds containing in their structure oxypropylene groups, oxyethylene groups and an organic radical derived from a polybasic carboxylic acid having a molecular weight of less than 200; the compounds being characterized in that all of the oxypropylene groups are present in polyoxypropylene chains that are attached to the organic radical at the site of a reactive hydrogen atom thereby constituting a polyoxypropylene polymer; the oxyethylene groups being attached to the polyoxypropylene polymer in polyoxyethylene chains; the average molecular weight of the polyoxypropylene polymers in the mixture being at least 900, as determined by hydroxyl number, and the oxyethylene groups present constituting 20-90%, by weight, of the mixture.

18. Compounds having improved detergent properties, according to the formula:

where 3 equals at least 15; and (C2H4O)a:+.1:' equals 20-90%, of the total weight of the compound.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,549,439 De Groote et a1 Apr. 17, 1951 2,552,529 De Groote May 15, 1951

Claims (1)

17. A COGENERIC MIXTURE OF CONJUGATED POLUOXYPROPYLENE-POLYOXYETHYLENE COMPOUND CONTAINING IN THEIR STRUCTURE OXYPROPYLENE GROUPS, OXYETHYLENE GROUPS AND AN ORGANIC RADICAL DERIVED FROM A POLYBASIC CARBOXYLIC ACID HAVING A MOLECULAR WEIGHT OF LESS THAN 200; THE COMPOUNDS BEING CHARACTERIZED IN THAT ALL OF THE OXYPROPULENE GROUPS ARE PRESENT IN POLYOXYPROPYLENE CHAINS THAT ARE ATTACHED TO THE ORGANIC RADICAL AT THE SITE OF A REACTIVE HYDROGEN ATOM THEREBY CONSTITUTING A POLYOXYPROPYLENE POLYMER; THE
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