US3553129A

US3553129A - Emulsifying and textile softening phosphonium compounds, process for preparing the same and other compounds, reactive intermediates

Info

Publication number: US3553129A
Authority: US
Inventors: Terence William Rave
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1965-12-23
Filing date: 1968-08-21
Publication date: 1971-01-05
Anticipated expiration: 1988-01-05
Also published as: FR1506964A; CA796280A; US3475490A; NL6618079A; US3332874A; CH490488A; NL6618459A; GB1164664A; BE691932A; DE1617185B2; DE1617185A1; DE1593294A1; FR1516056A; BE691617A

Abstract

NOVEL PHOSPHONIUM COMPOUNDS AND PROCESSES FOR THEIR PREPARATION ARE DISCLOSED. THESE NOVEL PHOSPHONIUM COMPOUNDS ARE USEFUL AS TEXTILE SOFTENING AGENTS, EMULSIFYING AGENTS AND ANTI-BACTERIAL AGENTS.

Description

United States Patent EMULSIFYING AND TEXTILE SOFTENING PHos-' PHONIIHVI COMPOUNDS, PROCESS FOR PRE.

PARING THE SAME AND OTHER COMPOUNDS REACTIVE INTERMEDIATES Terence William Rave, Wilmington, Del., assignor to The Procter & Gamble Company, Cincinnati, Ohio, a corporation of Ohio No Drawing. Original application Dec. 30, 1965, Ser. No. 517,826, now Patent No. 3,475,490. Divided and this application Aug. 21, 1968, Ser. No. 754,478

Int. Cl. B01f 17/16; Clld 3/066; D06m U.S. Cl. 252-8.8 11 Claims ABSTRACT OF THE DISCLOSURE Novel phosphonium compounds and processes for their preparation are disclosed. These novel phosphonium compounds are useful as textile softening agents, emulsifying agents and anti-bacterial agents.

3,553,129 Patented Jan. 5, 1971 These and other objects will be apparent from the description of the invention which follows.

According to this invention, it has been found that phosphiniminophosphonium salts having the following structural formula are effective'and durable textile softening agents and effective emulsifying agents:

ea R RRPLLNLP RJRR5 wherein R is an aliphatic radical containing from 1 to about 18 carbon atoms; R R R and R are aliphatic radicals containing from 1 to about 4 carbon atoms; R is an aliphatic radical containing from about 12 to about 18 carbon atoms; and X is an anion which permits adequate solubility and hydrolytic stability of the salt.

The term "phosphiniminophosphonium is used herein to denote a compound containing a [EP;N;;PE1

linkage, which linkage is explained hereinafter. Compounds containing'this linkage have been described in the prior art. However, compounds containing this linkage which are effective textile softening agents and elfec tive emulsifying agents are not known to have been so described.

There are several textile softening agents which are presently known to be commercially available which are of much different chemical structure from the compounds j of the present invention. Some of these softening agnts while eifectively softening textiles thereby reducing or eliminating harsh feel, do not resist removal. In other words, if the softened textile is washed without reapplicar tion of softening agent, the previously applied softening agent is removed by the washing from the textile, and harsh feel is again present. A durable softening agent, that is a softening agent which resists removal even after several washings of the textile, is advantageous to the consumer in that the necessity of continual reapplication of softening agent is eliminated.

It is, therefore, an object of this invention to provide novel phosphiniminophosphonium salts which are effective ing agents.

It is a' further object of this invention to prepare phosphiniminophosphonium salts by heating aminophosphonium salts.

It is a further object of this invention to prepare phos- .60 and durable textile softening agents and effectiveemulsify phiniminophosphonium salts by reacting N-alkali-metal phosphinimines with trisubstituted phosphine dihalides or can be employed This structural formula and more particularly thelinkage in this structural formula is a resonance structure. Thus, this structural formula represents the following structural formulas which are in resonance and in which R, R R R R, R and X are defined as above:

The salts defined by this structural formula can be symmetrical or unsymmetrical. R, R R R and R can each be of different chain lengths within the same compound. The aliphatic radicals in this structural formula can be saturated or unsaturated and branched or straight chain. For example, these aliphatic radicals can be alkyl, substituted alkyl, alkenyl and substituted alkenyl radicals. The term alkyl is used herein to include only saturated carbon chains. The term alkenyl. is used hereinto include carbon chains containing one or more double bonds.

The exact nature of the anionic portion of the above phosphiniminophosphonium salts is thought to be immaterial .so far as the textile softening and emulsifying properties of these new compounds are concerned. Accordingly, virtually any organic or inorganic anion which permits adequate solubility of the phosphiniminophosphonium salts and which permits hydrolytic stability of of the salts, that is, which provides stable anionic and cationic moieties upon solution in water, may be found suitable depending upon availability and cost factors.

Thus, X in the above structural formula can suitably be, for example, a halide, such as chloride, bromide, iodide 0r fluoride; a pseudohalide, such as cyanide, azide or thiocyanate; a sulfonate such as methane sulfonate or ptoluene sulfonate; a sulfinate, such as methane sulfinate; a fiuoroborate; sulfate, sulfite, nitrate, nitrite, phosphate, borate, methosulfate, chlorate, 'bisulfate, bisulfite, acetate, hexachloroantimonate and other anions.

Preferably, the aliphatic radicals in the present phosphiniminophosphonium salts are alkyl radicals and the anion, X, is selected from the group consisting of halides and pseudohalides. Symmetrical phosphiniminophosphonium salts of the present invention are especially preferred for textile softening agents.

Emulsifying and textile softening phosphiniminophosphonium salts, none of which are known to be described in theprior art and exemplary of those within the present invention are set forth in Table I below wherein R, R R R R R5 and X are applied in the structural formula set forth above.

TABLE I R 1 R R R R X ethyl Methyl Methyl Tridecyl SOr do- Propyl. do Br Methyl do 01- do do I- Methy do do 01- EthyL. EthyL. Ethyl-.. CHaCOO- E Methyl Methyl Ethylene do 3- Methyl do ..do hyl Tetradecyl. Cl- ChloromethyL.-. do .do do.. do 3- do do d CN- Butyl Butyl HSOr Metgy Metly 8%- Oetadec l "do.-. 0.. Do. 3-hydroxypropenyl do do. Hexadecyl Cl Oleyl Methyl ..d0 d0 .d0 Oleyl Cl- *Where the valence of the anion is greater than 1, a number of cations equal to this valence are present in each salt molecule.

As previously stated, the above-described phosphiniminophosphonium salts are especially useful as emulsifying agents. These salts ordinarily can be used to produce oil-in-water emulsions that are stable for more than one hour, the weight ratio of emulsifier to oil phase generally ranging from about 1:1000 to about 3:1. For example, these salts provide stable water emulsions of dry cleaning solvents, such as tetrachloroethylene, and of other organic solvents, such as carbn tetrachloride. Moreover, these salts provide stable water emulsions of glyceride oils, such as cottonseed oil or soybean oil. In the preparation of such emulsions the phosphiniminophosphonium salt is preferably first dispersed in the oil phase to be emulsified, and the oil-emulsifier combination is then mixed with the water phase. This is because these phosphiniminophosphonium salts tend to cause the formation of viscous solutions or gels when added by themselves to the water phase thereby making it difiicult to emulsify oil phase which is added to the water phase thereafter.

Morcver, these phosphiniminophosphonium salts are especially useful as textile softening agents. First of all, they effectively soften textiles, for example, towels, thereby reducing or eliminating harsh feel. Moreover, they are durable softening agents and after application to textiles resist removal and provide softening effect even after five to ten washings of such textiles. Thus, these salts are suitably used as active ingredients in textile softener compositions, as softening agents in industrial textile treatment where durable softening effect is desirable or necessary, and as additives to detergent compositions.

The textile softener compositions referred to above can be in the form of liquids, granular products, tablets, and in other forms.

For example, a liquid textile softener composition can comprise from about 1% to about 15 by weight phosphiniminophosphonium salt and from about 85% to about 99% water. Such compositions also contain preferably from about 1% to about 50%, and more preferably from about 1% to about 10%, by weight of an alcohol containing from 1 to about 4 carbon atoms, such as, for example, ethanol or isopropanol, in place of an equal weight of water. This alcoholic component reduces the viscosity of the softener composition thereby causing it to be more readily pourable and also reduces the tendency of the composition to become a gel. This alcoholic ingredient also desirably acts as a freeze point depressant thereby reducing the possibility of the composition freezing during shipping whereby the compositions container is possibly ruptured. Thus, a preferred liquid textile softener composition herein consists essentially by weight of from about 1% to about %phosphiniminophosphonium salt, from about 1% to about 50% alcohol, and from about 35% to about 98% water while an especially preferred liquid textile softener composition herein consists essentially by weight of from about 1% to about 15% phosphiniminophosphonium salt, from about 1% to about 10% alcohol and from about 75% to about 98% water. Optional ingredients for the present liquid textile softener compositions include, for example, perfume, coloring agent, and up to about 1% or more of a nonionic detergent such as, for example, nonyl phenoxy polyoxyethylene ethanol, containing 5 to 25 moles of ethylene oxide per mole of phenol, to help stabilize the composition.

A granular textile softener composition can be prepared simply by mixing urea with the present phosphiniminophosphonium salts. These compositions can comprise, for example, from about 5% to about 50% phosphiniminophosphonium salt and from about 5 0% to about urea.

These granular compositions can be compressed into tablets.

These softener compositions are applied, for example, by the housewife to textiles during laundering. The housewife can cause the application of such a softener composition simply by adding it, for example, by pouring, into the rinse water which is present during the rinse cycle of washing machine operation. For effective and durable softening the textile softener composition is added to the rinse water in amount sufficient to provide a concentration of phosphiniminophosphonium salt in the rinse water ranging from about 10 p.p.m. to about 500 p.p.m. and preferably from about 25 p.p.m. to about 100 p.p.m.

Turning now to industrial applications, the present phosphiniminophosphonium salts are advantageously employed in many industrial textile treating operations where durable softening effect is desired. For example, the above 7 described textile softener composition can be applied to yard goods by passing such yard goods through a pad containing this composition. Or yard goods can be treated with the present phosphiniminophosphonium salts at the same time they are treated with wash wear resins, for example, cyclic ethylene urea, to provide softer feel since treatment with wash wear resins alone usually produces textiles having harsh feel.

As explained above, these phosphiniminophosphonium salts can be employed as durable softening agent-additives to various detergent compositions, and ordinarily comprise from about 1% to about 15% by weight of such detergent compositions. The detergent active in these detergent compositions is any detergent which is compatible with the phosphiniminophosphonium salt additive. This detergent active is preferably a nonionic synthetic detergent or a zwitterionic synthetic detergent since the phosphiniminophosphonium salt being cationic is compatible with these detergents while such salt may not be compatible with soap and with anionic synthetic detergents. The phosphiniminophosphonium salt additive can also be used in combination with cationic detergents or with ampholytic or amphoteric detergents with the pH of the system adjusted so that such detergents are ca tionic detergents. The detergent active ordinarily comprises from about 5% to about 95% by weight of these detergent compositions.

with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.

For example, a well-known class of nonionic synthetic detergents is made available on the market under the trade name Pluronic. These compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxidewith propylene glycol. The hydrophobic portion of the molecule, which, of course, exhibits water insolubility, has a molecular weight of about 1500 to 1800. The addition of polyoxyethylene radicals'to this hydrophobic portion tends to increase the water solubility of the molecule as a whole and the liquid character of the products is retained up to the point where polyoxyethylene content is about 50% of the total weight of the condensation product. Other suitable nonionic synthetic detergents include:

(1) The polyethylene oxide condensates "of alkyl phenols, e.g., the condensation products of alkyl phenols The above mentioned nonionic synthetic detergents may be broadly defined as compounds produced by the condensation of alkylene oxide groups(hydrophilic in nature) having an alkyl radical containing from about: 6 to 12..

carbon atoms in either straight chain or branched chain configuration, with ethylene-oxide, the said ethylene oxide being present in" amounts'e'qu'al to 5 to 25 moles of ethylene oxide .per mole of alkyl phenol. The' alkyl substituent in such compounds may be' derived froin polymerized propylene, 'diisobutylene, octane, or nonane, for

example. p 7 v v (2) Those derivedfrom the condensation ofethylene oxide with the product resulting from the reaction' of propylene oxide and ethylene diamin-produtits whichmay be varied in composition dependingupon balance between the hydrophobic and hydrophilic elements which is desired. For example, compounds containing from about.- to'about 80% polyoxyethylene by weight-and having I a molecular structure of about 5 000 to about l1,000 resulting from the-reaction of ethylene oxide groups with a. hydrophobic base, constituted ofvthe reactionproduct of a coconut alcohol ethylene oxide';condensate having from A l(+) R NR"Z wherein R contains from about 10 to about 18 carbon atoms and from about 0 to about 5 ether linkages, wherein R and R are each selected from the group consisting of alkyl groups containing from 1 to about 3 carbon atoms, wherein R is selected from the group consisting of alkylene and hydroxy substituted alkylene groups containing from 1 to about 4 carbon atoms, and wherein Z 'is selected from the group consisting of groups. Specific examples of such compounds are 1- (hexadecyldimethyla-mmonio)propane 3 sulfonate, 1- I (dodecyldimethylammonio)butane 3 sulfonate, and 1- (dodecyldimethylammonio) acetate. Some other common examples 01f these detergents are described in US. Pats. 2,082,275; 2,129,264, 2,217,846; 2,255,082, 2,702,279.

The ampholytic and amphoteric detergents mentioned above are represented' by detergents such as dodecylbetaalanine, N-alkyltaurines such as the one prepared by reacting dodecylamine with sodium isethionate according to the teaching of US. 2,658,072, N-higher' alkylaspartic' acids such as those producedaccording to the teaching of US. 2,438,091, and the products sold under the trade I name Miranol and described in US. Pat. 2,528,378.

The detergent compositions herein contain from about 0% w 90%, preferably from 10% to 90%, by weight product of aliphatic alcohols 10 to 30 moles of ethylene oxide per mole of coconut,- alcohol, the coconut alcohol fraction-having from 10 to 14 carbon atoms. i I v (4) Trialkyl amine oxides and trialkyl phosphine oxides wherein one alkyl'radical contains from about 10 to about 18 carbon atoms, from 0 to about'5 ether linkages, and from 0 to about 2 hydroxy groups'and. wherein the other two alkyl radicals each contain from lfto about 3 carbon atoms, from 0 to about Zether linkages, and from 0 to about 2 hydroxy groups. Specific examples are dodecyl diethanol amine oxide and tetradecyl dimethyl phosphine oxide.

(5) Dialkyl sulfoxide detergents having the formula wherein R is a hydrocarbon group containing from about 10 to about 20 carbon atoms, from 0' to igbout 5 ofwater-soluble alkaline detergency builder salts, either of the organic'or inorganic types, and should provide a about 0.7:1 to about 9:1. Examples of suitable watersoluble inorganic alkaline detergency builder salts m alkali" metal carbonates, borates, phosphates, polyphos- -phat'es,-bicarbonates and silicates. Specific examples of such. salts are sodium and potassium tetraborates, bicar bonates, carbonates, tripolyphosphates, pyrophosphates, orthophosphates, and hexametaphosphates. Examples of suitable organic alkaline detergency builder salts 'are:'

" (1) water-soluble aminopolycarboxylates (e.g., sodium a carbon chain containing no ether-linkagesand containing about 10 to 18 carbon" atoms, and"wherein'-R' -is'a short alkyl chain containing from about-"Ito about-3 carbon atoms having 0-2 "hydroxyl groups attached "to and potassium ethylenediaminetetraacetates, nitrilotriace-" tates, and N-(2-hydroxyethyl)nitrilo diacetates); (2)

waterasoluble salts of phytic acid (e.g., sodium and phytates- -see US. Pat. 2,739,942); (3) water-soluble salts of ethane 1 hydroxyd,l-diphosphonate (e.g., the

trisodium. and tripotassium salts-see US. Pat. 3,159,-

581); 1(4) water-soluble salts of methylene diphosphonic acid (e.g., trisodium and tripotassium methylene diphosphonate and the other salts described in the phonic acids (e.g., tr'isodium and tripotassium ethylidene,

isopropylidene, 'benzylmethylidene, and halomethylidene diphosphonates and the other substituted methylene diphosphonates disclosed in the copending application of Clarence H. Roy, Ser. No. 266,055, filed Mar. 18, 1963 and now US. Pat. 3,422,021); (6) water-soluble salts of polycarboxylate polymers and copolymers as described in the copending application of Francis L. Deihl, Ser. No. 269,359, filed Apr. 1, 1963 and now US. Pat. 3,308,067. (Specifically, a polyelectrolyte builder material comprising a water-soluble salt of a polymeric aliphatic polycarboxylic acid having the following structural relationships as to the position of the carboxylate groups and possessing the following prescribed physical characteristics:) (a) a minimum molecular weight of about 350 calculated as to the acid form; (b) an equivalent weight of about 50 to about 80 calculated as to the acid form; (c) at least 45 mole percent of the monomeric species having at least two carboxyl radicals separated from each other by not more than two carbon atoms; (d) the site of attachment to the polymer chain or any carboxylcontaining radical being separated by not more than 3 carbon atoms along the polymer chain from the site of attachment of the next carboxyl-containing radical. Specific examples are polymers of itaconic acid, aconitic acid, maleic acid, mesaconic acid, fumaric acid, methylene malonic acid, and citraconic aid and copolymers with themselves and other compatible monomers such as ethylene), and (7) mixtures thereof.

Mixtures of organic and/or inorganic builders can be used and are generally desirable. Especially preferred are the mixtures of builders disclosed in the copending application of Burton H. Gedge, Ser. No. 398,705, filed Sept. 23, 1964 and now US. Pat. 3,392,121, e.g., ternary mixtures of sodium tripolyphosphate, sodium nitrilotriacetate, and trisodium ethane 1 hydroxy 1,1 diphosphonate.

These detergent compositions can optionally contain from about 1% to about 50%, preferably about 1% to about 10%, by weight of an alcohol containing 1 to about 4 carbon atoms such as, for example, isopropanol or ethanol, to reduce the viscosity of the composition thereby causing it to be more readily pourable and also to reduce the tendency of the composition to become a gel.

These detergent compositions can also contain any of the usual adjuvants, diluents and additives, for example, perfumes, anti-tarnishing agents (e.g., sodium and potas sium silicates and benzotriazole), anti-redeposition agents =(e.g., alkali metal and ammonium salts of carboxymethyl cellulose), 'bacteriostatic agents, dyes or pigments (including optical brighteners), suds builders, suds depressors, and the like, without detracting from the advantageous properties of the composition.

Normally the organic detergent components, the build ers, the phosphiniminophosphonium salt component, and the minor ingredients are incorporated into the composition prior to conversion into final product form, e.g., detergent granules, flakes, etc., but they can also be added individually in the form of particles or as liquids.

Turning now to processes for preparing the abovedescribed phosphiniminophosphonium salts, these salts can be prepared by any of a number of processes but preferably are prepared according to one of two novel processes described hereinafter. These novel processes can be used to prepare not only the above phosphiniminophosphonium salts which are effective and durable softening agents and effective emulsifying agents, but also other phosphiniminophosphonium salts known in the prior art which do not possess these advantageous softening and emulsifying properties but which are effective antibacterial agents. Accordingly, these processes are described hereinafter with sufiicient breadth to cover not only the preparation of the above novel phosphiniminophosphonium salts but also the preparation of these other phosphiniminophosphonium salts which are known in the prior at and which are effective antibacterial agents.

In one of these novel processes symmetrical phosphiniminophosphonium salts are prepared by heating an aminophosphonium salt having the formula 9 RlzRlsRllP Nfl wherein R is a radical selected from the group consisting of aliphatic radicals containing from 1 to 18 carbon atoms, phenyl and substituted phenyl; R and R are radicals selected from the group consisting of aliphatic radicals containing 1 to about 4 carbon atoms, phenyl and substituted phenyl; and Y is an anion selected from the group consisting of halides (such as chloride, bromide and iodide), cyanide, and azide. R R and R can each be of different chain lengths within the same compound. The aliphatic radicals in this formula can be saturated or unsaturated and branched or straight chain. For example, these aliphatic radicals can be alkyl, alkenyl, substituted alkyl, and substituted alkenyl radicals, the terms alkyl and alkenyl being defined as previously.

Suitable aminophosphonium salts are set forth in Table II below wherein R R R and Y are applied in the structural formula set forth above.

Dodecyl(tetrapropy1ene Dodecyl(stlsraight chain) p-Methylphenyl Benzyl The above aminophosphonium salts are heated in an inert atmosphere, for example under vacuum, at a temperature ranging from about C. to about 300 C. for a period ranging from about 0.5 hour to about 30 hours to provide essentially complete reaction. Reaction temperatures ranging from about C. to 260 C. and reaction times ranging from about 1 hour to about 20 hours are preferred.

It is preferred that no reaction solvent be employed 1n this process since the use of a reaction solvent lowers the concentration of aminophosphonium salt and can therefore necessitate longer reaction times. If no reaction solvent is employed a reaction temperature at least 20 C. above the melting point of the aminophosphonium salt reactant is essential. If a reaction solvent is employed, such reaction solvent must be inert with respect to the aminophosphonium salt and any reaction product and is preferably a high boiling point aromatic or aliphatic hydrocarbon, such as, for example, dodecane.

The following equation represents a typical example of the reaction of this process:

The phosphiniminophosphonium product is separated from by-product by any conventional separation technique, for example, by selectively dissolving the product in a solvent, separating the dissolved product from undissolved by-product by filtration, and evaporating the filtrate to yield substantially pure product.

The aminophosphonium salt reactant of this process while not readily available commercially, can be easily prepared. For example, aminophosphonium chlorides are conveniently prepared by reacting the appropriate trisubstituted phosphine in an inert atmosphere'and at room temperature with chloramine gas. The preparation of trisubstituted phosphines is described in Hays, Ser. No. 461,669, filed June 7, 1965 and now U.S. Pat. 3,389,183.

Turning now to the second of the two novel processes described herein for preparing phosphiniminophosphonium salts, this process can be employed to prepare either symmetrical or unsymmetrical phosphiniminophosphonium salts. In this process an N-alkali-metal phosphinimine is reacted with a trisubstituted phosphine dihalide or dipseudohalide.

The N-alkali-metal phosphinimine for use herein is believed to be a novel compound. It has the structural formula wherein R is a radical selected from the group consisting of aliphatic radicals containing from 1 to about 18 carbon atoms, phenyl, and substituted phenyl; R and R are radicals selected from the group consisting of aliphatic radicals containing 1 to about 4 carbon atoms, phenyl, and substituted phenyl; and M is an alkali metal selected from the group consisting of sodium, potassium, and lithium. R R and R can each be of different chain lengths within the same compound and can be saturated or unsaturated and branched or straight chain. For example, these aliphatic radicals can be alkyl, alkenyl, substituted alkyl, and substituted alkenyl radicals, the terms alkyl and alkenyl being defined as hereinbefore.

Suitable N-alkali-metal phosphinimines are set forth in Table III below wherein R R R and M are applied in the structural formula set forth above.

TABLE III X15 R50 R17 M Methyl Methyl Methyl Sodium. Ethyl Ethylene Sameas abve.. Potassium Butyl Butyl l Octyl P Dodecyl (tetrapro- Methyl Methyl Sodium.

py ne i Dodecyl(straight Same as above" Same as above Lithium.

chain Hexadecyl Ethyl do Potassium. Oleyl Methyl -do Lithium. Ihenyl Phenyl PhenyL. Same. Styryl Styryl Styry Do. oEthylphenyl o-EthylphenyL. o-EthylphenyL- Potassium. 3phenylpropyl 3-phenylpropyL. 3-phenylpropyl Sodium.

The trisubstituted phosphine dihalide or dipseudohalide for use herein has the structural formula R18R19R20PY21 wherein R is a radical selected from the group consisting of aliphatic radicals containing from 1 to about 18 carbon atoms, phenyl, and substituted phenyl; R and R are radicals selected from the group consisting of aliphatic radicals containing from 1 to about 4 carbon atoms, phenyl, and substituted phenyl; and Y is selected from the group consisting of (1) halogens, such as chlorine, bromine, and iodine, and (2) pseudohalogens selected from the group consisting of cyanide and azide, R R and R can each be of different chain lengths within the same compound and can be saturated or unsaturated and branched or straight chain. The term aliphatic is defined as hereinbefore. Each Y can be different in the same compound.

The above N-alkali-metal phosphinimines are reacted with the above trisubstituted phosphine dihalides or dipseudohalides in an inert atmosphere, for example under argon, at a temperature ranging from about 0 C. to about 50 C. for a period ranging from about 0.5 hour to about 30 hours to provide essentially complete re action. Room temperature is a preferred reaction temperature. Reaction times ranging from about 1 hour to about 20 hours are preferred.

A reaction solvent is employed in this process which is compatible with the above reactants and with the reaction product. This reaction solvent is preferably an aliphatic or aromatic hydrocarbon such as benzene, hexane, dodecane, and the like.

16 hours (0 119) 3P=NLi O12H25(CH3) zPClg room temperature The phosphiniminophosphonium salt product is easily separated from by-product since ordinarily the product is dissolved in the reaction solvent while the by-product is not. For example, the product can be isolated by decanting the solvent phase and evaporating this phase to yield substantially pure product.

The reactants in this process are not readily available commercially but can be prepared by a number of methods. For example, N-alkali-metal phosphinimines can be prepared by reacting an aminophosphonium halide or pseudohalide, e.g., chloride, the preparation of which is described hereinbefore, with aliphatic hydrocarbon alkali-metal salt. Two equivalents of aliphatic hydrocarbon alkali-metal, R M, are employed for each equivalent of aminophosphonium halide or pseudohalide,

In these structural formulae R R R and M are defined as previously; R is an aliphatic radical containing from 1 to about 12 carbon atoms, the term aliphatic being defined as previously; and Y is selected from the group consisting of chloride, bromide, iodide, azide, and cyanide. The reaction is conveniently carried out without external heating at a temperature ranging from about 10 C. to about C. in an inert atmosphere, such as argon, with a reaction time ranging from about 0.5 hour to about 10 hours or more. The following equation represents a typical example of the preparation of an N-alkalimetal phosphinimine:

3 hours 9)3 2041110 LiCl The trisubstituted dihalide or dipseudohalide can be conveniently prepared, for example, by reacting trisubstituted phosphines with a halogen or pseudo'halogen. This reaction is carried out with no external heating, for example in a solvent such as benzene and in an inert atmosphere such as argon. Reaction is substantially complete within about 10 minutes. As previously mentioned, the preparation of trisubstituted phosphines is described in Hays, Ser. No. 461,669, filed June 7, 1965 and now U.S. Pat. 3,389,183.

It is noted that the reactants in the above two novel processes for the production of phophiniminophosphonium salts contain as anion-producing constituents only halogens and the pseudohalogens, azide and cyanide. This limitation in the structure of the reactants is essential for the production of high yields of phosphiniminophosphonium salt since reactants containing oxygencontaining anion-producing constituents for example produce high yields of by-products. Thus, these two novel processes are advantageously used directly only to produce phosphiniminophosphonium halides, azides and cyanides. However, the anions in the phosphiniminophosphonium salt products produced by these novel processes can be converted to other anions by means of conventional techniques, for example, by means of an ion exchange column. 1

All percentages and parts herein are by weight unless otherwise specified. All aliphatic radicals herein are straight chain unless otherwise specified. In all reactions herein where such reaction is carried out under an inert atmosphere, any inert atmosphere can be employed; for

I 1 example, these reactions can be carried out in a vacuum or under inert gases such as argon, nitrogen or helium. The following examples are illustrative of the present invention and are not to be construed in any way as limiting the scope of the invention.

EXAMPLE I Preparation of dimethyldodecylphosphiniminodimethyldodecylphosphonium chloride 6a C12H25( C a)2 N I C s)2 12 Dimethyldodecylaminophosphonium chloride,

C12I'{25(CI I3)2PGa NI'I2C1e was prepared as follows: A 500-ml. three-necked roundbottomed flask was fitted with a gas inlet tube, a paddle stirrer driven by an electric motor, and a gas outlet tube connected to a mineral oil bubbler. Twelve grams of dimethyldodecylphosphine prepared according to the method of Hays, Ser. No. 461,669, filed June 7, 1965, and now US. Pat. 3,389,183, was added to the flask which previously had been evacuated and filled with argon. Then 300 ml. of dry benzene was added. The gas 25 inlet tube was arranged so as to extend below the surface of the benzene and then was connected to a chloramine gas generator. Two equivalents of chloramine gas were then passed into the phosphine solution causing heat evolution and a white precipitate to form. The mixture was stirred under argon for one hour without external heating to ensure complete reaction. The white solid in the resulting solid-solution mixture was separated from the solution by filtering. The white solid was then extracted twice with 300 ml. portion of acetonitrile at 82 C., and the remaining white solid, primarily consisting of ammonium chloride, was discarded. The acetonitrile was evaporated from the combined extracts to yield a white solid. Recrystallization of this white solid from 300 ml. of acetonitrile yielded 12 grams of substantially pure dimethyldodecylaminophosphonium chloride.

In a heavy-walled glass pyrolysis tube was placed 2.622 grams (9.3 mmoles) of the above prepared dimethyldodecylaminophosphonium chloride. The tube with its contents was then evacuated to 0.1 mm. Hg, sealed at this pressure, and placed in an oil bath that had been preheated to 195 C. Heating was maintained at this temperature for 16 hours. After cooling to room temperature, the tube was opened to the air and the crystalline mass partially dissolved in ml. of benzene at 80 C. The insoluble solid was removed by filtration and shown to be ammonium chloride by infrared analysis. The benzene filtrate was evaporated in vacuo to yield a white solid which was recrystallized from 40 ml. of /50 volume benzene-hexane mixture to yield 1.352 grams of dimethyldodecylphosphiniminodimethyldodecylphosphonium chloride EXAMPLE II Preparation of dimethyltetradecylphosphiniminodimethyltetradecylphosphonium chloride to be ammonium chloride by infrared analysis. The filtrate was evaporated to give a white solid which was recrystallized from acetonitrile to yield 1.46 grams of substantially pure dimethyltetradecylphosphiniminodimethyltetradecylphosphonium chloride.

EXAMPLE III Preparation of dimethylhexadecylphosphiniminodimethylhexadecylphosphonium chloride In a heavy-walled glass pyrolysis tube was placed 5.150 grams (15.25 mmoles) of dimethylhexadecylaminophosphonium chloride, C H (CH P NH Cl synthesized in a manner similar to the dimethyldodecylaminophosphonium chloride of Example I. The tube with its contents was then evacuated to 0.1 mm. Hg, sealed at this pressure, and placed in an oil bath that had been preheated to 200 C. Heating was continued at this temperature for 16 hours. After cooling to room temperature the crystalline mass was partially dissolved in ml. of acetonitrile at 82 C. The insoluble solid was removed by filtration and was shown to be ammonium chloride by infrared analysis. The filtrate was cooled to deposit white crystals which were recrystallized from acetonitrile to yield 2.96 grams of substantially pure dimethylhexadecylphosphiniminodimethylhexadecylphosphonium chloride.

EXAMPLE IV Preparation of triphenylphosphiniminotriphenylphosphonium chloride GB @PmNaP (in In a heavy-walled glass pyrolysis tube was placed 10.29 grams (32.8 mmoles) of triphenylaminophosphonium chloride, PNH Cl synthesized in a manner similar to the dimethyldodecylaminophosphonium chloride of EX- ample I. The tube with its contents was then evacuated to 0.1 mm. Hg, sealed at this pressure, and placed in an oil bath that had been preheated to 255 C. Heating was maintained at this temperature for 20 hours during which time the contents of the tube turned black. After cooling to room temperature, the entire crystalline mass which resulted was dissolved in 150 ml. of water at 0, treated with charcoal to remove color and filtered to separate the resulting colorless solution and the charcoal. The colorless filtrate was cooled to deposit white crystals. The crystals were separated from the remaining solution by decanting. The crystals were allowed to dry to provide 7.80 grams of substantially pure triphenylphosphiniminotriphenylphosphonium chloride.

Other symmetrical phosphiniminophosphonium salts are prepared if molar equivalents of other aminophosphonium salts are substituted for the aminophosphonium salts in the above examples. For example, trimethylphosphiniminotrimethylphosphonium bromide is prepared if trimethylaminophosphonium bromide is substituted for the dimethyldodecylaminophosphonium chloride of Example I; dibutylundecylphosphiniminodibutylundecylphosphonium iodide is prepared if dibutylundecylaminophosphonium iodide is substituted for the dimethyltetradecylaminophosphonium chloride of Example II; dimethyloleylphosphiniminodimethyloleylphosphonium azide is prepared if dimethyloleylaminophosphonium azide is substituted for the dimethylhexadecylaminophosphonium chloride in Example III; and dimethyl p methylphenylphosphiniminodimethyl-p-methylphenylphosphonium cyanide is prepared if dimethyl p methylphenylaminophosphonium cyanide is substituted for the triphenylaminophosphonium chloride of Example IV.

The triphenylphosphiniminotriphenylphosphonium chloride prepared in Example IV and the trimethylphosphin- 13 iminotrimethylphosphonium bromide and dimethyl p methylphenylphosphiniminoimethyl p methylphenylphosphonium cyanide prepared above are efiective antibacterial agents.

EXAMPLE V Preparation of dimethyldodecylphosphiniminotri'butylphosphonium chloride N-lithiotributylphosphinimine, (n-C H P=NLi, was prepared as follows: In a 100 ml. one-necked roundbottom flask was placed 11.57 grams (45.7 mmoles) of tri-n-butylaminophosphonium chloride, (n-C H P+ N I-I Cl9, and 30 ml. of benzee under an atmosphere of argon. A solution of tri-n-butylaminophosphonium chloride in benzene was then formed by means of vigorous stirring with a magnetic stirrer. To this solution at room temperature was added 57.4 ml. of 1.59 normal solution of n-butyl lithium-hexane solution (91.2 mmoles of n-butyl lithium or about 2 equivalents), and vigorous heat and gas evolution occurred. The resulting yellow solution was stirred for three hours under argon without addition of external heat. The resulting solution containing N-lithiotributylphosphinimine was used hereinafter without isolation or purification of the formed intermediate. The above tri-n-butylamiuophosphonium chloride was synthesized in a manner similar to the dimethyldodecylaminophosphonium chloride of Example I.

Dimethyldodecylphosphine dichloride was then prepared as follows: In a one-necked 100 ml. round-bottomed flask equipped with a rubber cap and filled with argon was placed 7.05 grams (30.7 mmoles) of dimethyldodecylphosphine, and 50 ml. of dry benzene. The formed solution was vigorously stirred while 772 ml. of chlorine gas was injected into the cappedflask. The reaction mixture was then stirred for one hour at room temperature. The resulting solution containing dimethyldodecylphosphine dichloride was used hereinafter without isolation or purification of the formed intermediate. The above dimethyldodecylphosphine was prepared by the method of Hays, previously referred to.

At this point the above-formed N-lithiotributylphosimine solution was added to the above-formed dimethyldodecylph'osphine dichloride solution. This addition was stirred for 16 hours with no external heating to provide an insoluble white SOlLld and a clear supernatant. The clear supernatant was decanted to separate it from the solid. Evaporation of solvent from the supernatant liquid gave a yellow oil. This oil was dissolved in 50 ml. of carbon tetrachloride at 76 C. After cooling to C., a white solid was deposited. Recrystallization of this solid from carbon tetrachloride yielded 14.58 grams of dimethyldodecylphosphiniminotributylphosphonium chloride.

Other phosphiniminophosphonium salts are prepared by the method of this example if molar equivalents of other N-alkali-metal phosphinimines are substituted for the N-lithiophosphinimine above and/ or molar equivalents monoiodidemonocyanide to form a mixture of dimethylp ethylphenylphosphiniminiobutylphosphonium iodide and cyanide. 1

vThehalide and pseudohalide anions of the phosphiniminophosphonium salts formed in Examples I-V above can be converted to other anions by conventional ion exchange techniques. For example, the dimethyldodecylphosphiniminotributylphosphonium chloride formed above can be converted to dimethyldodecylphosphiniminotributylphosphonium nitrate in this manner.

EXAMPLE VI Emulsions of carbon tetrachloride One-fourth gram of dimethyldodecylphosphiniminotributylphosphonium chloride prepared in Example V was mixed with 4 ml. of carbon tetrachloride. This mixture was mixed with 4 ml. of water to provide a carbon tetrachloride/Water emulsion which is stable for more than twelve hours.

Substantially equal emulsification results were obtained when the phosphiniminophosphonium salts prepared in Examples I, II and III were substituted for the dimethyldodecylphosphiniminotributylphosphonium chloride above. Astable emulsion was not formed when the triphen ylphosphiniminotriphenylphosphonium chloride prepared in Example IV was substituted for the dimethyldode'cylphosphiniminotributylphosphonium chloride above.

The above carbon tetrachloride/water emulsions are useful in'the dry cleaning of textiles and as broad spectrum solvents suitable for cleaning articles soiled with both oil-soluble and water-soluble soils.

EXAMPLE VII Tetrachloroethylene emulsions A composition containing the new phosphiniminophosphonium salts suitable for use in the dry cleaning of textiles contains:

Percent Dimethyldodecylphosphiniminotributylphosphonium chloride 2.0 Water 0.5 Tetrachloroethylene 97.5

For application to textiles this composition can be diluted to contain as much as 50% water. After being mixed, this diluted composition is an emulsion which is stable for at least 1 hour, and as such is suitable for application to textiles for dry cleaning purposes.

Other new phosphiniminophosphonium salts, for exarnple, thecompounds prepared in Examples I, II, and III can replace the dimethyldodecylphosphiniminotributylphosphonium chloride in the above example to provide stable emulsions upon dilution of the composition.

Ordinarily, useful dry cleaning compositions consist essentially of from about 0.5% to about 5% phosphiniminophosphonium salt, from about 0.5% to about 50% water and from about 45% to about 99% tetrachloroethylene.

The following two examples illustrate textile softener compositions containing the new phosphiniminophosphonium salts. These compositions are applied to textiles as water solutions containing 50 ppm. phosphiniminophosphonium salt. When so applied'these compositions provide effective and durable softening. The scftening effect remains even after five washings of the treated textile.

EXAMPLE VHI A suitable liquid textile softener composition contains:

Percent Dimethylhexadecylphosphiniminodimethylhexadecylphosphonium chloride 5 Isopropanol 2 3,4,4-trichlorocarbanilide 1 The condensation product of 9 moles of ethylene oxide with 1 mole of nonylphenol 1 Color 0.003 Perfume 0.25

Water balance 1 5 EXAMPLE 1x A suitable granular textile softener composition contains:

Percent Urea 75 Dimethylhexadecylphosphiniminodimethylhexadecylphosphonium chloride 25 EXAMPLE X In the manufacture of sheeting, 80 x 80 cotton sheeting is passed through a pad containing a water solution of dimethyloctadecylphosphiniminodimethyloctadecylphosphonium chloride. The water solution contains 75 p.p.m. of the phosphiniminophosphonium salt. The sheeting is effectively softened and retains this softened effect even after the consumer has washed it five times with no application of textile softener.

Other new phosphinimidophosphonium salts, e.g., the compounds prepared in Examples I, II, III and V, can be used in this example in place of the dimethyloctadecyl salt with similar results.

The following Examples XI-XVII illustrate heavy-duty laundry detergent compositions which contain as a softening agent the new phosphiniminophosphonium salts of this invention. These detergent compositions can be used to clean and soften textiles such as sheets and towels.

EXAMPLE XI Percent Dimethyldodecylphosphiniminotributylphosphonium chloride 3 Tallow alcohol ethoxylated with moles of ethylene oxide per mole of alcohol Sodium tripolyphosphate 50 Sodium sulfate 32 EXAMPLE XII Percent Dimethyloctadecylphosphiniminotrimethylphosphonium sulfate 7 Coconut alcohol (2%C 66%C 23 %C 9%- C ethoxylated with 6 moles of ethylene oxide 16 EXAMPLE XV Percent Dimethylhexadecylphosphiniminotrimethylphosphonium borate 15 Dimethyldodecylamine oxide 15 Tetrapotassium pyrophosphate 30 Sodium toluene sulfonate 8 Ethanol 10 Water 29 EXAMPLE XVI Percent Dimethyltetradecylphosphiniminodimethyltetradecylphosphonium acetate 5 Dimethyldodecylphosphine oxide 15 Sodium tripolyphosphate 60 Sodium sulfate 20 EXAMPLE XVII Percent Diethylpentadecylphosphiniminotrimethylphosphoniurn iodide 5 Dimethylcoconut (2%C 66%-C 23 %C 9%C alkylammonio hydroxypropane sulfonate- 20 Trisodium ethylidene diphosphonate 30 Sodium sulfate 45 The following Examples XVIII and XIX illustrate light-duty liquid detergent compositions containing as a softening agent the new phosphiniminophosphonium salts of this invention. These detergent compositions are suitable for cleaning and softening delicate clothing such as sweaters or underwear.

EXAMPLE XVIII Percent Dimethylhexadecylphosphiniminodimethylhexadecylphosphonium chloride 10 Component A, described below 35 Ethanol 10 Water 45 EXAMPLE XIX Percent Dimethyldodecylphosphiniminodimethyldodecylphosphonium chloride 10 Component A, described below 32 Ethanol 10 Water 48 In the above examples component A is a tertiary amine oxide having a long alkyl chain derived from middle cut coconut alcohol (containing 2%Cm, 66%C 23 %C and 9%C and two methyl groups.

Other phosphiniminophosphonium salts can be substituted for the phosphiniminophosphonium salts of Examples XI-XIX to provide laundry detergents. For example,

dimethyltetradecylphosphiniminodimethyltetradecylphosphonium chloride can be substituted for the dimethyldodecylphosphiniminodimethyl- I dodecylphosphonium chloride of Example XIX to provide a light-duty liquid detergent having softening properties. Moreover, various other detergent actives can be substituted for the detergent actives in Examples XI-XIX above. For example, various ampholytic detergents, e.g., dodecyl-beta-alanine, the sodium salt of N-dodecyl taurine, or disodium N- dodecyl aspartate, can replace component A in Examples XVIII and XIX above to provide light-duty liquid detergents, having softening properties.

The previously described novel phosphiniminophosphonium salts also have utility as antibacterial agents, wetting agents, detergents, solubilizing agents, waterproofing agents, and gelling or thickening agents. These salts also are very soluble and thus are very advantageously used in various compositions such as softener compositions and detergent compositions; this is because they remain in solution even though the composition containing them freezes and later thaws. On the other hand, conventional softening additives which are suspended in such compositions tend to separate from the rest of the composition under these same freezing-thawing circumstances.

IEXAMPLE xx' N-lithiodimethyldodecylphosphinimine was prepared by reacting dimethyldodecylaminophosphonium chloride with n-butyl lithium according to the method for preparing N-lithiotributylphosphinimine in Example V. This prepared compound is a reactive intermediate and can be used It the preparation of the novel phosphiniminophosphonium salts of this invention according to the second of the two novel processes described herein. For example, this N-lithiodimethyldodecylphosphinimine can be reacted with tributylphosphine dichloride to produce dimethyldodecylphosphiniminotributylphosphonium chloride.

I claim:

1. A liquid textile softener composition consisting essentially by weight of from about 1% to about 15% of a phosphiniminophosphonium salt having the structural formula wherein R is alkyl of from 1 to about 18 carbon atoms; R R R and R are each alkyl of from 1 to about 4 carbon atoms; R is alkyl of from about 12 to about 18 carbon atoms; and X is an anion which permits solubility and hydrolytic stability of the salt; and from about 85% an mp n r 11 11 11 wherein R is alkyl of from 1 to about 18 carbon atoms; R R R and R are each alkyl of from 1 to about 4 carbon atoms; R is alkyl of from about 12 to about 18 carbon atoms; and X is an anion which permits solubility and hydrolytic stability of the salt; and from about 50% to about 95% urea.

5. The method of softening textiles by the application of a water solution of a phosphiniminophosphonium salt having the structural formula wherein R is alkyl of from 1 to about 18 carbon atoms; R R, R and R are each alkyl of from 1 to about 4 carbon atoms; R is alkyl of from about 12 to about 18 carbon atoms; and X is an anion which permits solubility and hydrolytic stability of the salt; said solution containing from about p.p.m. to about 500 p.p.m. of said salt.

6. The method of claim 5 wherein the concentration 1 8 of phosphiniminophosphonium salt in said solution ranges from about 25 p.p.m. to about 100 p.p.m.

7. A softener and detergent composition consisting essentially of by weight:

(I) from about 1% to about 15 of a phosphiniminophosphonium salt having the structural formula PR R R wherein R is alkyl of from 1 to about 18 carbon atoms; R R R and R are each alkyl of from 1 to about 4 carbon atoms; R is alkyl of from about 12 to about 18 carbon atoms; and X is an anion which permits solubility and hydrolytic stability of the salt;

(II) from about 5% to about 95% of a compatible detergent selected from the group consisting of nonionic, Zwitterionic, and ampholytic synthetic detergents; and

(III) from about 0% to about water-soluble alkaline detergency builder salt.

8. The softener and deteryent composition of claim 7 wherein the amount of water-soluble alkaline detergency builder salt present is from about 10% to about 90% by weight of the composition.

9. The softener and detergent composition of claim 8 wherein an alcohol containing from 1 to about 4 carbon atoms is present in an amount of from about 1% to about 5 0% by weight of the composition.

10. The softener and detergent composition of claim 9 wherein the alcohol is present in an amount of from about 1% to about 10%.

11. The softener and detergent composition of claim 9 consisting essentially of:

(I) from about 1% to about 15% of the phosphiniminophosphonium salt of claim 9; (II) from about 5% to about of a compatible detergent selected from the group consisting of (1) nonionic synthetic detergents selected from the group consisting of:

(a) alkyl phenol polyethylene oxide condensates wherein the alkyl radical contains from about 6 to about 12 carbon atoms and containing from about 5 to about 25 moles of ethylene oxide per mole of phenol,

(b) compounds containing from about 40% to about 80% polyoxyethylene by weight and having a molecular weight of from about 5000 to about 11,000, resulting from the reaction of ethylene oxide with a hydrophobic base constituted of the reaction product of ethylene diamine and excess propylene oxide, said base having a molecular weight of from about*2500 to about 3000,

(c) the condensation product of aliphatic alcohols having 8 to about 18 carbon atoms with from about 10 to about 30 moles of ethylene oxide per mole of alcohol,

((1) trialkyl amine oxides wherein one alkyl radical contains from about 10 to about 18 carbon atoms, from 0 to about 5 ether linkages, and from 0 to about 2 hydroxy groups, and wherein the other two alkyl radicals each contains from 1 to about 3 carbon atoms, from 0 to about 2 ether linkages, and from 0 to about 2 hydroxy groups,

(e) trialkyl phosphine oxides wherein one alkyl radical contains from 10 to 18 carbon atoms, from 0 to about 5 ether linkages, and from 0 to about 2 hydroxy groups, and wherein the other two alkyl radicals each contain from 1 to about 3 carbon atoms, from 0 to about 2 ether linkages, and from 0 to about 2 hydroxy groups,

(f) dialkyl sulfoxides having the formula wherein R is an alkyl radical containing from about 10 to about 20 carbon atoms, from about to about ether linkages, and from about 0 to about 3 hydroxyl groups, there being at least one moiety of R which constitutes a carbon chain containing no ether linkages and containing from to 18 carbon atoms, and wherein R is a short alkyl chain containing from about 1 to about 3 carbon atoms having 02 hydroxyl groups attached to said short alkyl chain; (2) zwitterionic detergents having the formula wherein R is an alkyl radical containing from about 10 to about 18 carbon atoms and from about 9 to about 5 ether linkages, wherein R and R are each selected from the group consisting of alkyl groups containing from 1 to about 3 carbon atoms and hydroxy alkyl groups containing from 1 to about 3 carbon atoms, wherein R is selected from the group consisting of alkylene and hydroxy substituted alkylene groups containing from 1 to about 4 carbon atoms, and wherein Z is selected from the group consisting of 0 II II C0 and -ISIO groups (3) amphoteric detergents selected from the group consisting of:

(a) alkyl-beta-alanines, (b) N-alkyl taurines, (c) N-alkyl aspartates, and (d) mixtures thereof wherein the alkyl groups contain from about 8 to about 18 carbon atoms, and (4) mixtures thereof;

20 (III) from about 10% to about 90% of builder salts selected from the group consisting of:

(1) inorganic salts selected from the group consisting of sodium and potassium (a) tetraborates, (b) bicarbonates, (c) carbonates, (d) tripolyphosphates, (e) pyrophosphates, (f) orthophosphates, (g) hexametaphosphates, and (h) mixtures thereof;

(2) organic salts selected from the group consisting of sodium and potassium (a) ethylenediaminetetraacetates, (b) nitrilo triacetates, (c) N (2 hydroxyethyl)-nitrilo diacetates, (d) phytates, (e) ethane-1-hydroxy-1,1-diphosphonates, (f) isopropylidine diphosphonates, (g) benzyl methylidene diphosphonates, (h) halomethylidene diphosphonates, (i) mixtures thereof;

(3) polycarboxylate builder materials comprising water-solub1e salts of polymeric aliphatic polycarboxylic acids having the following structural relationships as to the position of the carboxylate groups and possessing the following prescribed physical characteristics: (a) a minimum molecular weight of 350 calculated as to acid form; (b) an equivalent weight of about 50 to about 80 calculated as to acid form; (0) at least 45 mole percent of the monomeric species having at least two carboxyl radicals separated from each other by not more than two carbon atoms; and (d) the site of attachment to the polymer chain of carboxyl-containing radical being separated by not more than three carbon atoms along the polymer chain from the site of attachment of the next carboxyl-containing radical being separated by not more than three carbon atoms along the polymer chain from the site of attachment of the next carboxyl-containing radical.

References Cited UNITED STATES PATENTS LEON D. ROSDOL, Primary Examiner P. E. WILLIS, Assistant Examiner U.S. Cl. X.R.

233 3 UNITE STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,553,129 Dated January 5', 1971 Inventor(s) Terrence William Rave It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

[- Column 6, lines 64 and 65, (e.g. sodium and phytates see U.S Pat. 2,739,942) should read (e.g. sodium and potassium phytates See U.S. Pat. 2,739,942)

Column 9, line 49, formuls R R R PY should read R R R 'PY Column 13, lines 46 and 47 "This addition was stirred f1 16 hours with no external heating should read This addit was effected with all compounds under argon. The mixture wa stirred for 16 hours with no external heating Column 13, line 69, "tributyllphosphinemonoiodidemonocyanide" should read tributylphosphinemonoiodidemonocyanide Column 15, line 53, "Dimethyloctadecylphosphiniminotrimethylphosphonium sulfate" should read Dibutyloctadecy phosphiniminodimethyloleylphosphonium nitrate Column 16, line 3, under the heading "Percent" the figu: "15" should read 8 Column 17, line 16, "used n" should read used in Column 18, line 23, "deteryent" should read detergen1 Signed and sealed this 8th day of June 1971 (SEAL) Attest: L EDWARD M.FLE1GHER,JR. WILLIAM E. SCHUYLER, JE

Attasting Officer 1 Commissioner of Patent: