AMIDES OF HEXAFLUOROPROPYLENE OXIDE POLYMER ACIDS AND POLYALKLENE OXIDE

Previous attempts to [...] The aziridines (ethylene-imines) and epoxides or episulfides, including monomers that form the substituted unsubstituted, have been generally inefficient in that that the reaction product was not an alternating copolymer, but was rather a mixture of homopolymers or a polyalkylene imine having pendant groups [...]. In general, a catalyst, as [...][...] ^, was considered essential in the reaction.

It was found means for copolymerizing [...] and episulfides with epoxides to produce interpolymers having alternately combined residues

aziridine and of the epoxide or the episulfide. In other words, the interpolymers and the method for preparing [...] 1. The interpolymers of the invention contain in alternate combination an aziridine of formula I

|R I

CT R*

R'

wherein R is an organic group inert and each R ' independently is hydrogen or an alkyl group, aryl or aralkyl, at least two of the R * is hydrogen, and an epoxide or episulfide of formula II

wherein X is oxygen or sulfur and each R^{1 '} or R "' independently is hydrogen or an alkyl group, alkaryl, aryl, aralkyl, alkenyl, alkoxyalkyl, [...], at least two of them are hydrogen, and a R" and a R "' which may be combined to form a five-or six-membered cycloalkyl group.

The inert organic group R may contain 1 to 25 carbon atoms and preferably it is an alkyl group, aryl, cyano-, nitro-aryl [...] ; alkenyl, aralkyl, [...], an alkyl group or six membered heterocyclic, 1 * hetero atom is a d^{1 atom oxygen}, sulfur or tertiary nitrogen, an acyl group of formula III

8 in

-C-E

where E is an alkyl group, aryl, [...], alkoxy, [...][...] group or of inert hydrocarbons above connected with another one of the groups by an ester linkage.

The [...] of the invention usually contain as terminal groups or chain extension or the residues from a auxiliary reactant having at least one active hydrogen atom. Typical examples of the reactants auxiliaries are aliphatic alcohols, aliphatic polyols, phenols, of [...], primary and secondary amines, of [...], amides and polyamides, thiols, carboxylic acids having a Ka of less than 6,5 x 1 (T^2,[...] compounds obtained by condensing an alkylene oxide with any of the above compounds, water, hydrogen sulfide and ammonia.

Preferred polymers are derived from aziridines * in which the R groups are hydrogen and epoxides in which three groups R "and R '" are hydrogen, the fourth is hydrogen or a hydrocarbon group of 1 to 20 carbon atoms.

It has been found that the copolymers are useful as stabilizers for chlorinated solvents, as vulcanization accelerators and rubber as anti-oxidants, surfactants, lubricants, binders, from acids, adjuvants for fixing dyes, adjuvants for fixing of the starch and use as flocculants.

The copolymers of the invention are exceptional in

the frame structure consists essentially of alternating mesh rings are opened and the monomer aziridine of epoxide monomer or episulfide. Therefore, copolymer backbone, excluding any terminal groups or chain extension, the periodic lattice of the copolymer contains

wherein X, R and R R*, "' and 5" have the meanings definite [...]. The mesh copolymer can be repeated up to 1,000 times or more. In some cases, the chain of the copolymer can be interrupted or terminated by the residue of an auxiliary reactant optionally included; this residue is derived from auxiliary reactant by removing an active hydrogen i.e. hydrogen replaced. A auxiliary reactant thus it can be advantageously included to provide a terminal group or group of chain extension desired in the backbone of the linear polymers of polyfunctional reactants and having 3 or more active locations can be used to provide branched polymers. Auxiliary When a reactant is present in the process, the product polymer is represented by the general structural formula IV

*^Y] n [...]_{w wherein Z is} the residue of the derived by auxiliary reactant removal-of n active hydrogen of a reactant auxiliary; A is a mesh of the aziridine ring-opened monomer B is a mesh ring opened or episulfide of epoxide monomer;

Y is hydrogen or-CR 'R' -CR 'R' - [...] j m is an integer between 1 and about 1000 ; and n is an integer which is at least 1 and which is equal to the number of active hydrogen removed by auxiliary reactant. The more generally, Y is hydrogen.

Is prepared conveniently interpolymers of the invention by reacting an aziridine of formula I with an epoxide or episulfide of formula II in the liquid phase in the presence

_AOE280A2AO> with at least a trace of an auxiliary reactant having at least one active hydrogen atom. The reaction temperature is appropriately [...] between 25 and 300 °C and, preferably, , between 100 and 200 °C. However, the preferred temperature is dependent on the proportion and the reactivity of the reactants and ancillary reactivity of 1 'aziridine and 1' epoxy or episulfide. The reaction can be advantageously carried out in the presence of a non-reactive solvent liquid.

In surprisingly, may be used in the process approximately any molar ratio between 1' aziridine nitrogen substituted and 1 * expoxide or episulfide because, under suitable conditions, it is found that, in a manner unexpected, the copolymerization is stopped when one of the reactants is spent

The auxiliary reactants include: (a) alcohols as alkanols having 1 to 25 carbon atoms, for example the. methanol, ethanol, 1 'isopropanol, tert-butanol, cyclohexanol the, -the 3° [...], beta-phenethyl alcohol, 1-dodecanol, and the 1- [...] ; of alkenols having up to 20 carbon atoms, as allyl alcohol, crotyl alcohol, the carbinol methylvinyl, linoleyl alcohol; of alkynols having up to 10 carbon atoms as the propargyl alcohol, l-pentyn-5-ol, 4- [...] -2-ol; and [...] alkoxylated alcohols such as 2-methoxyethanol, 2-isobutoxyethanol, 2-phenoxyethanol, l-(2-butoxyethoxy) - 2-propanol, 1-isobutoxy-2-propanol, l-methoxy-2-propanol ; (b) aliphatic polyols as 1' ethylene glycol, propylene glycol, butylene glycol, 1,3- [...], sucrose, glucose, sorbitol, the pentaerythritol, glycerol and [...] derivatives of these polyols, polyethylene glycol, polypropylene- [...], polybutylene glycol, mono-ethers or alkyl [...] of these polyalkylene glycols, for example the phenyl ether polyethylene glycol and propylene polypropylene- [...], polyvinyl alcohol, the [...], [...] copolymers of ethylene and allylic alcohol or aorylate beta- [...] (g) phenols such as phenol, nonylphenol, resorcinol, hydroquinone, 1, 5, 5-trihydroxybenzene, the 4 - (methylthio) phenol, 1 'o- [...], thiophenol, 2- [...] & the enol, p-nitrophenol, the [...], the 4-bromophenol, 2, 4, 5-trichlorophenol, the [...] p-cresol and polyphenols such as p, p' -isopropylidenediphenol (bisphenol A) and novolak resins which are the condensation products of phenol and formaldehyde. ; (d) the alkanolamines as mono-, diet triethanolamine, mono-, diet tripropanolamine, N, N, N ', N' - [...], N, N- [...] - [...] ; (e) primary and secondary amines as aniline, butylamine, the [...], 1' allylamine, the [...], the cyclohexylamine, 1 * ethylenediamine, propylenediamine, and butylenediamine;

(f) and of [...] ^ [...] -imines as the [...], the [...], dipropylenetriamine, the [...], [...] and the condensation products and polymers of diacid halides [...] Al- [...] -diamines, for example the reaction product of the ethylenediamine and 1,3-dichloropropane and polymers up to a polyethylene imine, polypropylene-imine or [...] polytetrafluorethylene- [...] having a molecular weight of about 1 million ; (g) amides such as formamide, 1 * acetamide, benzamide, the [...], 1 'acrylamide, the [...], stearamide and as nylon and polyacrylamide ; (h) thiols as methyl mercaptan, 1' octyl-mercaptan and of sulfur-containing polymers as a polyethylene sulfide and a polypropylene sulfide (i) carboxylic acids such as benzoic acid ^ acrylic, methacrylic, adipic, acetic, heptanoic, ' [...], the tall' [...], the acids of [...], rosin, [...], linoleic, lactic., glycine, polyacrylic, polymethacrylic, p-chlorobenzoic, 2,4-dimethyl, citric, coal tar naphthenic pecially and polymers containing carboxy end groups as polybutadienes and carboxy-terminated polyesters, copolymers of ethylene and acrylic acid and (j) natural substances as carbohydrates, sugars, cellulose, starch, proteins, gums and derivatives thereof, as an active hydrogen is available, as methylcellulose.

The reactants organic auxiliary Presently preferred are aliphatic alcohols, the [...], carboxylic acids and polyols [...] obtained by condensing alkylene oxides of 2 to 4 carbon atoms with such aliphatic alcohols and polyols,

The water is the preferred inorganic auxiliary reactant. The effect of water on the process of [...] or ' [...] is very pronounced, such as the speed of reaction increases and the molecular weight of the copolymer decreases when increases the amount of water in the reaction mixture. The water is conveniently included in the process in an amount of up to 35 mole percent, relative to the moles (has) aziridine (when using a molar excess of epoxy or episulfide), or (b) the moles of epoxide or episulfide {when using a molar excess d * aziridine), stronger [...] A-

rance, i.e. above about 35 mole percent

9 alkanolamines or mercapto-alkylene-amines are formed and n occurs a homopolymerization of monomers and epoxy/or aziridines or episulfide, Therefore, care should be taken to limit the amount of water in the processing system and reaction in the body. Mixtures of reactants auxiliary inorganic and/or organic can be used if desired.

Examples of aziridines nytrogen-substituted useful as body in response, there can be mentioned: N- [...] as the N-ethyl, -isopropyl, n-butyl-, -hexyl -3, - [...], -n-decyl, n- [...] -; N- [...] as the N-allyl, crotyl-, -and -11- [...][...] ;

n-aryl and N- [...] as the N-phenyl, N-naphthyl, and- [...] -3,5- [...] ; N- [...] as the N-benzyl, -phenethyl, -tolyl-butyl, 3,5- [...] j of the n-cyano-alkyl or N- [...] as the M-2-cyanoethyl, -10- [...], -p- [...] ; N- [...] - [...] N-2 as the (N-morpholino) ethyl,

- 8 - (N-Morpholino) But, -2 - (N-Piperidino)-Butyl, -4 - (N-Piperidino)

dodecyl-, -6 - (n-pyrrolyl) hexyl, -2 - (N-pyrrolidinyl) propyl, -1 - (tetrahydrofurfuryl), -1 - (methyl-2-thienyl) > -1 and-/ 2 (2-pyridyl) [...] ; N- [...] as N-aoétyl,

- [...], benzoyl-, -3,5- [...], -3-phenylpropionyl,

-acrylyl, crotonyl-, and- [...][...];

n- [...] N- [...] and aziridines as N-butoxyethyl, -e [...] -e [...], n- [...] 1, -2- [...], [...] -4-, -2-and-phenoxyethyl p-methylphenoxy-n- [...] ;

n- [...] esters as 2-acetate (-l " aziridinyl) ethyl, 4 - (1-aziridinyl) butyl or 2 - (2-methyl-l-aziridinyl) ethyl, butyrate 2 - (1-aziridinyl)-ethyl, 2-benzoate (1-aziridinyl) propyl or 6 - (2,2-dimethyl-l-aziridinyl) hexyl, -the 2-0-aziridinyl) octyl acetate, the 4 - (1-aziridinyl) ethyl butyrate, the 4 - (1-aziridinyl) butyrate decyl, 3 - (1-aziridinyl) propyl propionate, the acrylate or methacrylate 2 - (1-aziridinyl)-ethyl; 2 and the-methyl, 2,2-and 3- [...][...] to the corresponding substituted nitrogen.

Examples of epoxides and episulfides include epoxides and episulfides ethylene, propylene, 1,2- [...], of 2.3 butylene, 1,2-decylene, of 2.3 octylene, of [...], cyclohexene, styrene naphthylethylene, 4-phenyl-L, 2- [...] ; the glycidalethers as ethyl- [...] ether, butyl- [...] ether, decyl-glycidyl ether, phenyl-glycidyl ether, tolyl- [...] ether, allyl- [...] ether, ether crotyl- [...] and sulfur of the similarities of these compounds.

Mixtures of monomers [...] are included in the method with one or more epoxide monomers and/or episulfide. The resulting product is a [...] with openings in open cycles of monomers and epoxides or aziridines episulfides with a randomly available monomers or aziridines particular epoxide monomers or particular episulfides in the product.

If is desired ' copolymer having characteristics "block" copolymer, is this is achieved by processing one of the copolymers as reactant interested auxiliary and reacting further with another combi [...]. termination of aziridine or episulfide monomers and epoxy. Therefore, the [...] N-ethyl aziridine and ethylene oxide can be further reacted in the present operating conditions with monomers N- [...] and propylene sulfide.

The chain length of the [...] is variable and it is found that it varies inversely with respect to the amount of auxiliary reactant in the process. Therefore, copolymers are obtained having the longer chain segments copolymer when there is little or no auxiliary reactant present. Auxiliary When the reactant is present in a large amount, i.e. more than 0.2 equivalent of active hydrogen per mol of the monomer i epoxide or aziridine episulfide, according to which of the monomers which is present in smaller amount, oligomers of the copolymer are obtained which contain an average of 1 to 10 mesh copolymer. using an excess significant auxiliary reactant, can be obtained to compounds which contain as few as one single mesh [...] or less with active hydrogen, because it is not necessary that each active hydrogen is replaced by a chain segment [...], in particular in the polyfunctional auxiliary reactants as polyvinyl alcohol, of polyalkylene glycols, and polyalkylene-polyamines of carbohydrates.

Can be easily increase the chain length of the [...] using a [...] auxiliary [...] in response. Therefore, when there is 1' water, methanol or ethylene glycol present, the copolymer is substantially linear.

When using auxiliary of the reactants such as glycerol, the obtained copolymer which is branched, each of the three chains being attached to the residue of glycerol and is completed at the other end by hydroxy groups or amino groups, according to the monomer that provides the terminal groups.

Typically, the terminal group is a hydroxyl group.

The relative reactivities of the monomers and the auxiliary relative reactivities of the reactants are generally well known. For example, it is known that 1' d^{1 ethylene} oxide is more reactive that 1^{1 propylene oxide or} butylene oxide j it is known that N-ethyl aziridine is more reactive than N- [...] ; carbon substituted aziridines are generally less reactive than the corresponding non-homologous [...] ; and it is known that the carboxylic acids are more reactive than alcohols ; therefore, addition, the compounds used in the method are reagents and the greater the proportion of auxiliary reactant is strong, lower can be the reaction temperature to provide a given speed of polymerization. According to the above, a preferred temperature for the reactions fast enough, for reasons of convenience and economy, is between 50 and 120 °C about, and for the reactions slower the preferred temperature is above 100 °C and below 250 °C.

The body in response must be held in contact with each other until the desired copolymer. A suitable reaction time may vary from a few hours to a few days after the reaction temperature and the reactivity of the aziridine body reaction and epoxy. Typically, a reaction time of 6 hours to 48. is sufficient and is therefore preferred.

The reaction pressure is such that it maintains the reaction mixture that is essentially liquid and normally atmospheric pressure or a higher pressure. It is preferred atmospheric pressure or the autogenous pressure.

The reaction may be carried out without a solvent or in an inert solvent, such as benzene, toluene and xylene.

The reaction may be carried out as a batch operation in which all ingredients are mixed simultaneously or in the form of a continuous operation in which the reactants are introduced continuously or in small amounts in the system. In either operation, the polymer product can be treated as a reactant auxiliary in subsequent reactions or [...] examination because it contains at least one active hydrogen which can be removed to provide a location where a fire-place chain segment copolymer can be attached.

[...] The physical state of the varies from a low viscosity liquid state to a solid state, and other physical properties, since the solubility, vary also depending on the molecular weight, the functionality and substituents at the initial reactants. Therefore, the products can be prepared as required so that they are suitable for a multitude of needs simply by varying the nature and proportions of the reactant-and/or reactant. auxiliary. All copolymers have the common property of contain atoms of basic amino groups of atoms and divalent oxygen or sulfur in the chain of the polymer.

Some of the [...] may have a tendency

an alteration in the color aging. [...] can prevent virtually completely damage 1s. color in liquid products by adding a stabilizing amount d^{! an antioxidant}, such as sodium borohydride, of the [...] or hydrazine hydrate copolymer,

The following non-limiting examples will exhibit well how the invention can be implemented:

Is introduced the aziridine nitrogen substituted and the expoxide or episulfide equipped to agitation in an autoclave. The.

closes the autoclave in a sealed manner, is heated to the desired temperature of reaction and holds the body in response under such conditions of temperature and pressure by mixing until the desired product of the reaction is formed " are removed volatile components under reduced pressure and the product is collected.

When using a reactant auxiliary, using the procedure above, except that the reactant is generally introduced with the reactant and epoxide or aziridine episulfide. The order of adding the auxiliary reactant is not important.

_The[...] of the products are analyzed by one or more/following methods of analysis: gas-liquid partition chromatography (CPG-L), infrared (IR), nuclear magnetic resonance (NMR) and by passage through a chromatography (GPC) salt EXAMPLE 1

By using the general procedure above, are reacted together N-ethyl aziridine ( [...] ) and propylene oxide (PO) to various temperatures and reaction time to give copolymers. Traces water is present in the monomers (100 to J00 parts per million), the autoclave is stainless steel or glass and the pressure is the autogenous pressure. The results are given in Table I:

TABLE I

3T

1

2

3

4

5

6

7

8

9

10

The copolymers above are liquid colors ranging from light yellow to amber. They are soluble in benzene, ethanol, 1 * acetone, n-hexane, ^ CCl and insoluble in water. Regardless the molar ratio of aziridine and epoxy monomers in response " the product copolymer contains still approximately equal molar amounts of each reactant. Table I-A The indicates the molar ratio of the reactant Used and the molar ratio of nitrogen/ [...] found in the resulting copolymers.

' Example 2

By using substantially the same equipment and the same general procedure, is reacted monomers and other aziridines epoxides.

In Table II according to, and below, the following abbreviations are used: = [...] N-ethyl aziridine ; = [...] N- [...]; = [...] N- [...]; = [...] N- [...] = j [...] N-(2-cyano) [...] ; = [...] N-(2-morpholino) ethyl aziridine ; = [...] N- [...] ;

[...] = 2-acetate (l- [...] & oyl)-ethyl; EO = ethylene oxide; propylene oxide PO = ; = Mix-I a substance commercially available which is a mixture of hydrocarbon to^{ant ^}^12^has groups is 1,2 -epoxy; g = 20.5 Mix-II PO and 2.32 g of EO} = allyl glycidyl ether AGE j CPO = cyclopentene oxide;

[...] and = styrene oxide.

TABLE

The copolymers of Table II have [...] -N/0 substantially equal to those provided by theory and the following:

water, ethanol, acetone, ethylene-glycol, hexane, CCl ^ (water insoluble)

ethanol, acetone and benzene (insoluble in water) water, ethanol, acetone

acetone, (water insoluble, ethanol or benzene)

ethanol, benzene (insoluble in water or acetone) undetermined'

acetone, benzene (insoluble in water or ethanol) ethanol, acetone, benzene (water insoluble) ethanol, acetone, benzene

_AOE280A2AO> ethanol, acetone, benzene (water insoluble) acetone, benzene (water insoluble)

* acetone, n-hexane (water insoluble)

3

By using the general procedure and equipment in 1*1 'example, I, is determined the effect of 1' water in the and the results are given in Table III " The reaction^{c 130 C}, spontaneous pressure and 20 hours kept constant. A U- [...] mole of each experiment.

TABLE III

100% of the monomer_{9 epoxide or aziridine whichever is present} by the molar amount the smallest_e

[...] 4

By using substantially the same equipment and the same procedure as described in Mode [...] General, , 021 passed several experiments N-ethyl aziridine oxide^{^1} 8 d^{8 ethylene or propylene} and various alcohols as body reacted "_{e sants auxiliary The results are} given in Table 17.

In the experiments 11 and 16 above, and replace [...][...] MEA as aziridine in response " In the experiments above, EO = ethylene oxide; PO = propylene oxide;

N- [...] = [...] ; AEM = 2-ethyl (l-aziridinyl).: ¥Eg ethylene-glycol; [...] = diethylene glycol;

Gly = glycerol ; = triethanolamine TEA ; = [...] methyl ether propylene glycol; [...] = phenyl ether 1' ethylene-glycol ;

E-300 its polyethylene glycol having an average molecular weight of about 300 ; P-400 = polypropylene glycol having an average molecular weight of 400 ; CP-3000 = un polyoxypropylene glycol initiated once the glycerol having an average molecular weight of about 3000 ; CP =- [...] a ' polyoxyalkylene glycol initiated once the glycerine in which the portion is a polyoxyalkylene [...] of oxyethylene oxypropylene groups and in a molar ratio of about 80:20 to 90:10, respectively, and has an average molecular weight of about 4100 ; BFF = polyvinyl alcohol;

Oct 1-octanol = ; = 1- [...][...] ; [...] = 1-octadecanol;

1 = eicosanol a commercially available product which is a mixture of higher alcohols consisting essentially of 1-eicosanol; isoprop = isopropanol: t-butyl = t-butanol; WP = 4 - (methylthio) phenol; Novo = a novolak resin having a functionality of 6.0 to 6,5_AOE280A2AO>

Example 5

By using substantially the same equipment and

the same procedure as described in Mode [...] General, is-passed several experiments in which is reacted N-ethyl aziridine and propylene oxide with various representative auxiliary reactants. The results are presented in Table below.

The product of 9 is washed with water, the product is washed methanol 12 and 13,15 and 16 are washed benzene for elimination of any residual reactants.

By using substantially the same equipment and the same procedure as in the above example 1, except that 50 [...]^{5 benzene} are included as reaction medium, 37 is reacted. " 5 S [...] with 24.6 g PO during 22 hours at 174 °C under the autogenous pressure. The liquid product weighs 46.1 g. The product obtained is the same as the copolymers in the example 1 .

propylene

By using substantially the same equipment and the same procedure as described in the ' example 1, is reacted. 67.5 g N-ethyl aziridine with 4-2.1 g of propylene sulfide during 20 hours to 174 °C under the autogenous pressure. The liquid copolymer (41.5 g) following elementary analysis, based on the mesh (- [...] -N ()- CH_{2 CH} (CH ^)-S -).

Table vi

Various Representative have been tested as stabilizers for the trichloroethylene in a ess ai accelerated oxidation of 48 hours as described in the Federal standard of the United States of America and 0-Τ-β34Α MIL-7003 _AOE280A2AO> The results are the following:

TABLE [...]

The stabilizer "A" is the product of the example I, No. 2;

"b" is described in Table IX, no. 9 J "C" and^{n D} "are described in Table IV, no. 13 and 23, respectively j" E^{, s described in} Table V, no. 7 I and "f" is described in Table II, no. 11.

The present copolymers, particularly those in which R is an alkyl group, alkenyl, or [...][...], are useful in the rubber industry as antioxidants and die vulcanization accelerators in rubber compositions which are vulcanised by sulphur® For example, the [...] of (A) N- [...] and propylene oxide (traces of water present in the body in response), (B) N-ethyl aziridine and propylene oxide (traces of water present in the body in response) and (G) N- [...] and propylene oxide ( [...] with a polyethylene glycol having an average molecular weight of 300 about and traces of water present in the body in response) are all effective as vulcanization accelerators, providing good cure rate and a exceptionally good protection of the sample against the reversion of the vulcanization and as antioxidants in an amount of 4.5 parts by weight in the following normal composition of masterbatch styrene-butadiene rubber (SBR):

Table viii

Test results are the following ':

[...] -samples non-aged

c [...] and correspond directly to the description above

(C) D is a test sample blank having the composition de-VIII.

Samples vulcanized during 20 minutes are then aged in air for 72 hours at 100 °C and their physical properties are measured again as above. The results are summarized in the following table: ( [...] ASTM D 575-53 (1965)).

X table

Properties physical-samples aged in air

Good results are achieved like using an amount accelerator, e.g. 0*05 to 20 parts by weight, to 100 parts by weight of rubber, other copolymers in a vulcanizable rubber composition.

The present copolymers are fixators protic acids. Therefore, they are useful as d * arid acceptors in chemical processes as aosorbeurs and acid gas. Sulphur dioxide, carbon dioxide and other acid components may be removed from gas streams by contacting these currents with the copolymers alone or with aqueous or organic solutions of these copolymers.

Susceptibility tinctorial many synthetic and natural fibers, for example cotton, the products known under the trademark "nylon", rayons, etc..., is improved by subjecting the fibers to the present process and examination, are dyed fibers are then examined. For example, tissue product known under the trademark "nylon" and reacts with [...] PO into a fabric which is easily dyed [...] when it is immersed in alcohol solutions of Eric Green and Eosin Blue. The dyed fabric is stable to washing alcoholic, the tissue product known under the trademark "nylon" untreated does not support any appreciable amount of the dye.

Attachment of the starch is greatly enhanced [...] a starch is used, i.e. if a starch is used which has been modified by the present reaction of [...]. For example, aqueous slurries of (1) described in the starch [...] Table V, No. IJ and (2) corn starch (the control) each are agitated during 15 minutes with cellulose fibers from a filter paper ground. The cellulose is separated by filtration of each mixture and the amount of starch [...] or corn starch remaining in the filtrate is determined by a normal iodometric titration. Cellulose retains 95.2 % the weight of the starch[...] and f only 21.5 ° the weight of corn starch.

Copolymers N-ethyl aziridine, of ethylene oxide and one auxiliary reactant are tested as surfactants techniques according to the test described in ASTM standards and D-1173,D-1331 D-228I _AOE280A2AO> The copolymers are described in Table IV, * no. 18 and 19 respectively.