US3812217A - Polyfluorocycloalkyl phosphates - Google Patents

Polyfluorocycloalkyl phosphates Download PDF

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Publication number
US3812217A
US3812217A US00236978A US23697872A US3812217A US 3812217 A US3812217 A US 3812217A US 00236978 A US00236978 A US 00236978A US 23697872 A US23697872 A US 23697872A US 3812217 A US3812217 A US 3812217A
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paper
phosphate
compounds
composition
ammonium
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R Moyer
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Air Products and Chemicals Inc
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Air Products and Chemicals Inc
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Priority to GB1297085D priority Critical patent/GB1297085A/en
Priority to DE19702036179 priority patent/DE2036179A1/de
Priority to NL7010946A priority patent/NL7010946A/xx
Priority to FR7027274A priority patent/FR2055551A5/fr
Application filed by Air Products and Chemicals Inc filed Critical Air Products and Chemicals Inc
Priority to US00236978A priority patent/US3812217A/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/14—Esters of phosphoric acids containing P(=O)-halide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/117—Esters of phosphoric acids with cycloaliphatic alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/004—Surface-active compounds containing F
    • C11D1/006—Surface-active compounds containing fluorine and phosphorus
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/10—Phosphorus-containing compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/11—Halides

Definitions

  • the present invention relates to a novel class of fluoroalkyl compounds and more particularly, to polyfluorocycloalkyl phosphate compounds which can be used to render textiles, paper and other similar materials grease and oil resistant.
  • Certain polyfluoroalkyl phosphates are known in the art and are defined by the general formula where m is'an integer from 4 to 12, n is an integer from l to 16, y is a number of average value from 1.0 to 2.5 and M stands for water-solubilizing cation such as hydrogen, an alkali-metal, ammonium or substituted ammonium. Certain of these polyfluoroalkyl phosphates, whose alkyl structure contains a straight chain of at least 8 carbon atoms and not less than 9 fluorine atoms, can be used to render paper oil repellent.
  • An object of the present invention is to provide novel polyfluorocycloalkyl phosphate compounds which are useful in imparting grease and oil repellency to textile materials, paper and similar materials.
  • Another object of the present invention is to provide a method for preparing polyfluorocycloalkyl phosphates.
  • Still another object of the present invention is to provide a method of treating textile materials, paper and similar materials with polyfluorocycloalkyl phosphate compounds to render said materials grease and oil repellent.
  • n is an integer of from I to 4 and K; is fluorine or a C to C perfluoroalkyl group substituted on the 2, 3 or 4 position of cyclohexane ring.
  • novel polyfluorocyclohexanealkyl phosphate compounds of the present invention are those represented by formulas (III) and (IV):
  • K is fluorine or a C 1 to C perfluoroalkyl group substituted on the 2, 3 or 4 position of the cyclohexane ring
  • n is an integer of from I to 4
  • a is an integer of from 1 to 2
  • X in each occurance is independently selected from chlorine or any member of OM
  • M is a water-solubilizing cation of the group consisting of hydrogen, alkali metal (sodium or potassium), ammonium or substituted ammonium.
  • K, n and X for the pyrophosphates of formula IV are the same as formula III. Although a and m of IV may be integers of one or more in most instances, their values will only be one.
  • novel phosphate compounds of this invention may be prepared by two different routes having per-' ence of an organic liquid diluent such as benzene, toluene, or xylene.
  • the product produced in accordance with such method provides a complex mixture of perfluorocycloalkyl phosphate compounds, said mixture containing a major amount of compounds having structures Ill and 1V.
  • reaction certain perfluorocyclohexane alkanols are reacted with the preferred reactant, phosphorus pentoxide, in the ratio of (alkanol: phosphorus pentoxide) from about 1:1 to about 4:1 and preferably from about 1.511 to about 3:1. It has been found that the reaction may be conducted at temperatures of from about 30C to about 200C and preferably from about 45C to about 130C. Below temperatures of about 30C, it has been found that the reaction takes too long to be practical. Above about 200C, the product produced by the reaction will not provide desirable results such as oil holdout when applied to paper.
  • a phosphorus oxyhalide composition such as phosphorus oxychloride (POCI in the presence of an acid acceptor such as pyridine, and in the optional presence of an organic liquid diluent such as benzene.
  • One to two moles of the perfluorocyclohexane alkanol are employed per mole of phosphorus oxychloride and the reaction is preferably effected by heating the mixture at reflux temperature to obtain an intermediate phosphochloridate reaction product.
  • the product prepared in accordance with the phosphorus oxychloride route yields a composition containing major amounts of compounds corresponding to formula ill and no pyrophosphates of IV.
  • phos phorus oxybromide or phosphorus oxyiodide may also be used.
  • the intermediate reaction product is hydrolyzed to form the required phosphate ester, and any tertiary amine that accepts no other functional groups may be used as an acid acceptor.
  • acid acceptors are pyridine, trimethylamine, triethylamine, tripropylamine, N. N-dimethylaniline, N, N-diethylaniline and the like.
  • Suitable solvents or media for the reaction are non-proton donating solvents, such as aromatic and aliphatic hydrocarbons, halohydrocarbons, ethers and the like.
  • solvents which may be used include benzene, toluene, chlorobenzene, hexane, octane, mixed alkanes, lchlorobutane, carbon tetrachloride, dipropyl ether, dibutyl ether and dioxane.
  • the reaction may be conducted at temperatures between 0C and 110C, and preferably at a temperature between 50C and 100C for the first stage of the reaction.
  • alkali-metal sodium or potassium
  • ammonium or substituted ammonium salts may be prepared from commonly available, water soluble primary, secondary or tertiary amines which are inclusive only by way of example of organic amines, such as alkyl amines, alkanolamines, nitrogen containing hetcrocyclics, cyclic amines, polyamines, and the like.
  • Alkyl amines may be primary, secondary or tertiary and may have alkyl groups having 1 to 6 carbon atoms.
  • the alkyls may be straight chain or branch ed like methylamine, ethylamine, diethylamine, triethylamine, tripropylamine, diisobutylamine.
  • Alkyl amines also encompass mixed amines such as N-ethyl dipropylamine, N-ethyl-N-methyl propylamine, N, N- dimethyl butylamine, etc.
  • Alkanolamines which form substituted ammonium salts with the taught compounds usually have from 1 to 3 hydroxyl groups and may also be primary, secondary, or tertiary amines.
  • alkanolamines examples include monoethanolamine, diethanolamine, triethanolamine, bis (2- hydroxy-propyl) amine and pentanolamine and related compounds having 2 and 3 hydroxy groups and in the range of from 2 to 10 carbon atoms.
  • Substituted ammonium salts may be prepared from nitrogen containing heterocycles including aromatic and non-aromatic types which may or may not be substituted, like imidazole, morpholine, piperidine and alkyl substituted heterocyclics having 1 to 6 carbon atoms like 2-ethyl imidazole.
  • Cyclic amines and especially bicyclic compounds like triethylenediamine are useful salt forming agents.
  • Suitable polyamines are ethylenediamine, l, 2 propanediamine, diethylene triamine, etc.
  • salt forming compounds e.g.- .diethanolamines are used in an amount sufficient to provide the mixture with a pH in a range from about 2 or 3 to about 7, however, an amount to a pH of about 5 is regarded as most preferred.
  • the pH may be adjustedgenerally to a range of from about 2 to about 12 and more preferable from about 4 to about 10 for most applications to paper, textiles and other related substrates.
  • oil and grease resistant polyfluorocycloalkyl phosphates compositions typically may contain only by way of illustration one or more of the following: monoundecafluorocyclohexanemethyl phosphate (monoester), bis-undecafluorocyclohexanemethyl phosphate Monoester Pyroester Other polyphosphate esters may also be present, but at lower concentrations 3 percent) for products prepared with a molar ratio of 3 moles of perfluorocyclohexane alkanol to each mole of phosphorus pentoxide.
  • both his and pyrophosphate esters are ether extractable from. aqueous basic solutions, such as from solutions of standardized alkali metal hydroxides like sodium and potassium hydroxides. Monoester is not extracted by the ether and remains in the aqueous layer.
  • phosphate esters mono, bis and pyro
  • aqueous acidether extraction leaves diethanolamine in the aqueous layer free of phosphate esters.
  • EXAMPLE 111 A mixture of mono-1 ,l-dihydroperfluorocyclohexanemethyl-phosphate, bis-[ 1,1-dihydroperfluorocyclohexanemethyl] phosphate, and bis-[ l l -dihydroperfluorocyclohexanemethyl] pyrophosphate was obtained by adding 868.0'grams (2.8 moles) of 1,1-dihydroperfluorocyclohexane methanol and 131.6 grams (0.91 moles) of phosphorus pentoxide to a flame dried, nitrogen purged flask. The heterogeneous mixture was heated to F and stirred vigorously for 5 hours. After this time solution had occurred.
  • Example 11V The method of Example 111 was employed for reacting 18.1 parts l,1-dihydro-(tridecafluoro-4-methyl cyclohexane) methanol with 2.4 parts of phosphorus pentoxide (molar ratio 3:1 The heterogeneous mixture was stirred for 6 hours at a temperature not exceeding 55C.
  • Example IV A mixture of mono, bis and pyro (tridecafluoro [4-methyl] cyclohexane) methylphosphates were collected in 96 percent yield.
  • the product of Example IV was evaluated as an oleophobic paper size, in accordance with the procedure set forth in Example X.
  • EXAMPLE V (Nonadecafluoro-4-n-butylcyclohexane) methanol (25.6 parts) was reacted with phosphorus pentoxide (2.4 parts) by the procedure described in Example 111. The mixture of mono, his and pyro (nonadecafluoro-4- n-butylcyclohexane) methylphosphates thus formed, was collected in 95 percent yield.
  • EXAMPLE V1 The application of polyfluorocycloalkyl phosphate compounds to such materials as paper and textile materials is most readily done in industry from aqueous solutions.
  • aqueous solutions of the 1,1- dihydroperfluorocyclohexanemethylphosphates are easily made by first neutralizing an isopropanol solution of mono-l ,l-dihydroperfluorocyclohexanemethylphosphate, bis-( l l -dihydroperfluorocyclohexanemethyl) phosphate, bis-(l,l-dihydroperfluorocyclohexanemethyl) pyrophosphate or a mixture of Extraction of this solution with ether results in the isolation of his (B) and monoesters (C). The latter monoesters are formed by hydrolysis of the pyrophosphates which were present.
  • Example V11 Using the product mixture of Example 111, a water soluble formulation was prepared by mixing 28 parts of said product mixture, 6 parts of diethanolamine, 33 parts of isopropanol and 33 parts of water. This formulation provides a phosphate solution containing 33 percent solids.
  • Procedure 1 A measured volume of the solution of diethanolamine salts of the phosphate esters is taken up in ether and then treated with water and a measured volume of standardized 0.5 N sodium hydroxide. The ether layer contains the his and pyrophosphate esters. The monophosphate ester is extracted with the aqueous standardized alkali. The alkaline extract is acidified with an acid, such as concentrated HCl and extraction with ether results in the monoester (A) which can be titrated potentiometrically with a standardized base. From the first or second plateau of this titration in the plot of pH vs. moles of base added, the percent monoester can be determined.
  • the ether extract containing the bis and pyrophosphate esters are acidified with a dilute HCl solution.
  • EXAMPLE V111 The ammonium salt of the product mixture of Exam ple 111 was obtained by mixing 35.4 grams of said product mixture, 6.1 grams of aqueous ammonia (28 percent), 37.1 grams of isopropyl alcohol and 32.7 grams of water.
  • the formulations were applied to two types of paper: (a) a 50 lb. Natural Kraft (softwood), 0.6 percent rosin/alum sized with a basis weight of 50 pounds per 3,000 square feet, and (b) Consolith paper, a bleached coating base stock with a furnish composed of ground wood, sulfite and Kraft pulps, with a basis weight of 26 pounds per 3,000 square feet and containing 0.25 percent rosin/alum size.
  • Consolith paper a bleached coating base stock with a furnish composed of ground wood, sulfite and Kraft pulps, with a basis weight of 26 pounds per 3,000 square feet and containing 0.25 percent rosin/alum size.
  • the paper which was coated was anchored to an 8 /2 inch X l 1 inch wooden frame on all four sides with masking tape.
  • the frame was placed over a glass plate nearly the same size to insure a solid paper surface during drawdown.
  • a 20 gram aqueous sample of the desired concentration was made up by dilution of the 33 percent stock solution. (Example V11) 4.
  • a glass plate was butted against the head of the framed paper with a sheet of polyethylene spanning the gap between the glass plate and the paper frame.
  • a No. 18 wire wound rod was used to draw the sample solution down over mounted paper.
  • Example 1x Using the aforementioned procedures, the mixture of Example lll was applied to a 50 pound per ream natural Kraft Softwood paper 0.6 percent rosin/alum sized. The drying was accomplished at l 10C for about 3 minutes. Table A compares the concentration of applied fluorochemical solids with the number of hours resistance to grease penetration by three oil or grease materials, viz., nujol, corn and lard using the water soluble formulation of Example Vll. Table B makes a similar comparison using the ammonium salt of the mixture of Example ill, in which the ammonium salt was prepared in a manner similar to the procedure of Example Vlll.
  • Nujol 2.5 0.25 lmmed. test specimen preferably much larger.
  • Com 20 lmmfli mm 5. A stopwatch or laboratory timer.
  • Lard 9 0.25 lmmed.
  • the reagents, peanut oil, l'lUjOl, liquid lard, and corn oil 1 Paper Creased lnto are separately placed in bottles 1 10 ml In each bottle)
  • Each specimen is then placed on a sheet of the book 3,; 9 'T 2$;
  • Test showed evidence of crawling (horizontal wicking of the test oil on the paper surface).
  • sample E While the product of sample E had less pyrophosphate than the product of sample A (see Example XII), sample E still provides good oleophobicity. The presence of pyrophosphates and possibly polyphosphates of an undetermined nature apparently contribute to the oleophobicity of the product.
  • EXAMPLE XIV A portion of a product corresponding to that prepared in Example VII was hydrolyzed using Procedure I and the total of the original monoester (A), bisester(B), and monoester formed by hydrolysis of pyrophosphate (C) was reformulated into an aqueous solu tion by mixing 28 parts of the mixture of (A), (B) and (C), 6 parts of diethanolamine, 33 parts of isopropanol and 33 parts of water. This reformulated solution when composition.
  • Example Vll The original product of Example Vll had pyrophosphate content of about percent.
  • Samples A to E were screened further for performance using the test for creased peanut oil holdout described in Example Vlll.
  • novel polyfluorocycloalkylphosphate compounds of this invention may be imparted to materials treated with the novel polyfluorocycloalkylphosphate compounds of this invention.
  • Said compounds also have the required water solubility to be useful as surface active agents and are well adapted to be used as dispersing agents in Where the novel compounds of this invention are used for oil repellency purposes, said compounds may be applied to a great variety of semiporous substrates, such as textile fabric, textile yarn, leather, paper, plastic sheeting, wood, ceramic clays as well as manufactured articles made therefrom, such as wearing apparel, wall paper, paper bags, cardboard boxes, porous earthenware, etc.
  • the treatment of textile fibers or other waterinsoluble solid materials with the novel polyfluorocycloalkylphosphates of this invention may be achieved by padding, spraying or brushing, using aqueous solutions of said phosphates.
  • the waterinsoluble solid materials may be treated with retention aids, water-soluble polymer possessing cationic nitrogen atoms, which cause the polyfluorocycloalkylphosphates to exhaust into the water-insoluble solid material from an aqueous solution.
  • the polyfluorocycloalkylphosphates can also be employed as internal sizing during the formation of paper.
  • a perfluorocyclohexyl phosphate selected from compounds of the formula:
  • M is a water-solubilizing cation of the group consisting of hydrogen, alkali metal, ammonium and substituted ammonium.
  • the phosphate compound of claim 1 wherein the eam emales @fleli p a h ixh- 3.
  • the phosphate compound of claim 2 wherein X is OM, M is hydrogen, a is l, n is 2 and K, is F.
  • phosphate compound of claim 2 wherein X is OM, M is diethanol ammonium, a is 2, n is l and K, is F.
  • the phosphate compound of claim 1 wherein the structural formula is 10.
  • phosphate compound of claim 9 wherein X is OM, M is diethanol ammonium, n is l and K; is F.
  • a perfluorocyclohexyl phosphate composition comprising mixtures of mono, bis and pyro compounds of the formulas:
  • K is fluorine or a C to C perfluoroalkyl group substituted on the 2, 3 or 4 position of the cyclohexane ring
  • n is an integer of from l to 4
  • a is an integer of from l to 2
  • X in each occurance is independently selected from chlorine or any member of OM
  • M is a water-solubilizing cation of the group consisting of hydrogen, alkali metal, ammonium and substituted ammonium.
  • composition of claim 13 wherein the mixture comprises compounds in which X is OM, M is hydrogen, a is l, n is 2 and K, is F.
  • composition of claim 12 wherein the mixture comprises compounds in which X is OM, M is hydrogen,aisl,nislandl(,isF.
  • composition of claim 12 wherein the mixture comprises compounds in which X is Cl, a is l, n is l and K, is F.
  • composition of claim 12 wherein the mixture comprises compounds in which X is Cl, a is 2, n is l and K, is F.
  • composition of claim 1'12 wherein the mixture comprises compounds in which X is OM, M is diethanol ammonium, a is 2, n is 4 and X, is F.
  • composition of claim 12 wherein the mixture comprises compounds in which X is OM, M is diethanol ammonium, a is l, n is l and K, is F.
  • composition of claim 12 wherein the mixture comprises compounds in which X is OM, M is diethanol ammonium, a is l and 2, n is 1 and K, is F.
  • composition ofclaim 12 including a mixture of 21.
  • n 1

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Molecular Biology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Paper (AREA)
US00236978A 1969-07-23 1972-03-22 Polyfluorocycloalkyl phosphates Expired - Lifetime US3812217A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
GB1297085D GB1297085A (ja) 1969-07-23 1970-07-17
DE19702036179 DE2036179A1 (de) 1969-07-23 1970-07-21 Polyfluorcycloalkylphosphate
NL7010946A NL7010946A (ja) 1969-07-23 1970-07-23
FR7027274A FR2055551A5 (ja) 1969-07-23 1970-07-23
US00236978A US3812217A (en) 1969-07-23 1972-03-22 Polyfluorocycloalkyl phosphates

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Application Number Priority Date Filing Date Title
US84419769A 1969-07-23 1969-07-23
US3917570A 1970-05-20 1970-05-20
US00236978A US3812217A (en) 1969-07-23 1972-03-22 Polyfluorocycloalkyl phosphates

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DE (1) DE2036179A1 (ja)
FR (1) FR2055551A5 (ja)
GB (1) GB1297085A (ja)
NL (1) NL7010946A (ja)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4192831A (en) * 1975-02-17 1980-03-11 Basf Aktiengesellschaft Manufacture of salts of O,S-dithiophosphoric acids
WO1999021947A1 (en) * 1997-10-28 1999-05-06 E.I. Du Pont De Nemours And Company Compositions and processes for drying substrates
US20070173426A1 (en) * 2006-01-26 2007-07-26 Longoria John M Masonry stain resistance agents
US20110303620A1 (en) * 2010-06-10 2011-12-15 Di Gao Superoleophobic and Superhydrophilic Fabric Filters for Rapid Water-Oil Separation

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4192831A (en) * 1975-02-17 1980-03-11 Basf Aktiengesellschaft Manufacture of salts of O,S-dithiophosphoric acids
WO1999021947A1 (en) * 1997-10-28 1999-05-06 E.I. Du Pont De Nemours And Company Compositions and processes for drying substrates
US20070173426A1 (en) * 2006-01-26 2007-07-26 Longoria John M Masonry stain resistance agents
US20110303620A1 (en) * 2010-06-10 2011-12-15 Di Gao Superoleophobic and Superhydrophilic Fabric Filters for Rapid Water-Oil Separation
US8695810B2 (en) * 2010-06-10 2014-04-15 University of Pittsburgh—of the Commonwealth System of Higher Education Superoleophobic and superhydrophilic fabric filters for rapid water-oil separation

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DE2036179A1 (de) 1971-02-18
NL7010946A (ja) 1971-01-26
FR2055551A5 (ja) 1971-05-07
GB1297085A (ja) 1972-11-22

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