US3812218A - Diakyl alkyl and cyclic phosporamidomethyl phosphonates - Google Patents

Diakyl alkyl and cyclic phosporamidomethyl phosphonates Download PDF

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Publication number
US3812218A
US3812218A US00239799A US23979972A US3812218A US 3812218 A US3812218 A US 3812218A US 00239799 A US00239799 A US 00239799A US 23979972 A US23979972 A US 23979972A US 3812218 A US3812218 A US 3812218A
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resins
formula
flame
compounds
polymers
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US00239799A
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P Golborn
J Duffy
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Occidental Chemical Corp
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Hooker Chemical Corp
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Priority to US00239799A priority Critical patent/US3812218A/en
Priority to US239757A priority patent/US3870771A/en
Priority to GB1390773A priority patent/GB1418775A/en
Priority to FR7310953A priority patent/FR2187802B1/fr
Priority to CA167,352A priority patent/CA1004227A/en
Priority to DE2315493A priority patent/DE2315493A1/de
Priority to BE129396A priority patent/BE797476A/xx
Priority to NL7304503A priority patent/NL7304503A/xx
Priority to JP48036575A priority patent/JPS4916735A/ja
Priority to IT22420/73A priority patent/IT982664B/it
Priority to FR7333434A priority patent/FR2196341B1/fr
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Publication of US3812218A publication Critical patent/US3812218A/en
Priority to US05/537,721 priority patent/US3959551A/en
Assigned to OCCIDENTAL CHEMICAL CORPORATION reassignment OCCIDENTAL CHEMICAL CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE APRIL 1, 1982. Assignors: HOOKER CHEMICALS & PLASTICS CORP.
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • D06M13/288—Phosphonic or phosphonous acids or derivatives thereof
    • 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
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C08K5/5333—Esters of phosphonic acids
    • C08K5/5353—Esters of phosphonic acids containing also nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C08K5/5333—Esters of phosphonic acids
    • C08K5/5373—Esters of phosphonic acids containing heterocyclic rings not representing cyclic esters of phosphonic acids

Definitions

  • ABSTRACT New compounds are disclosed of the formula:
  • This invention relates to novel compounds of the formula wherein R is phenyl, lower alkenyl and halogen substituted and unsubstituted lower alkyl of l-6 carbon atoms, m is an integer from l-2 wherein m is 2, R is alkoxy of l-8 carbon atoms and when m is l, R is alkylene dioxy of 2-8 carbon atoms.
  • the invention includes methods of applying the above novel compounds to normally flammable textiles and thermoplastic, thermosetting and elastomeric resin compositions so as to render them flame retardant.
  • a further process for imparting flame resistance to cellulosic materials is by the esterification of the cellulose with diammonium hydrogen ortho-phosphate. Textile products so treated however are subjected to metathesis reaction with cations during washing, and must be regenerated by reacting the wash product with an ammonium chloride solution.
  • thermoplastic resin compositions which are flame retardant is of considerable commercial importance.
  • articles as castings, moldings, foamed or laminated structures and the like are required, or are at least desired, to be resistant to fire and flame and to possess the ability to endure heat without deterioration.
  • the use of various materials incorporated into thermoplastic resins so as to improve the flame retardancy thereof has been known.
  • Many compounds have been commercially available for such use, among them being chlorostyrene copolymers,
  • chlorinated paraffin wax in admixture with triphenyl styrene, chlorinated paraffins and aliphatic antimonical compounds, as well as antimony oxide-chlorinated hydrocarbon mixtures.
  • a problem associated with these compounds has been however, the fact that generally a large amount, i.e., upwards of 35 percent of additive, must be incorporated into the resin in order to make it sufficiently flame retardant. Such large amounts of additive may deliteriously affect the physical characteristics of the thermoplastic resin, as well as substantially complicating and increasing the cost of preparation thereof.
  • a further problem is that these prior art additives tend to crystallize or oil out of the resin after a relatively short time of incorporation.
  • the present invention relates to a group of compounds which may be added to thermoplastic resins in relatively small amounts and still produce satisfactory flame retardant compositions which will not crystallize nor oil out of the resin after incorporation therein.
  • R is phenyl, lower alkenyl and halogen substituted and unsubstituted lower alkyl of l-6 carbon atoms
  • m is an integer from l-2 wherein when m is 2, R is alkoxyof 1-8 carbon atoms and when m is 1, R is alkylene dioxy of 28 carbon atoms.
  • a further object is to provide a process for treating normally flammable thermoplastic resin compositions to render them flame retardant.
  • a particular object is to devise a composition comprising normally flammable cellulosic, proteinaceous or analogous manmade materials and an effective flame retardant amount of the compound represented by the formula (mmi wncmr orv wherein R, R and in are as above described.
  • a further particular object is to devise a composition comprising normallyflammable thermoplastic polymer and aneffective flame retarding amount of the before described novel compound.
  • novel compounds for imparting flame retardancy to textiles and thermoplastic, thermosetting and elastomeric resin materials of the formula:
  • R is phenyl, lower alkyl and halogen substituted and unsubstituted lower alkyl of l-6 carbon atoms
  • m is an integer from l-2 wherein when m is 2, R is alkoxy of 1-8 carbon atoms and when m is l, R is alkylene dioxy of 2-8 carbon atoms. More specifically, the preferred compounds of the present invention include these compounds wherein R is lower alkyl of l6 carbon atoms and m is 2.
  • Illustrative examples of compounds of the present invention include, for instance, compounds of the general formula such as O O -NH-CHr-QTOCHQ:
  • vention is accomplished by reacting a N- hydroxymethyl phosphoramidate of the formula with a trialkyl phosphite of the formula wherein R, R and m are as previously described neat, or in the presence ofa suitable solvent, or in an excess of the phosphite.
  • the reaction is carried out for about 1 to about 6 hours at a temperature of about C to about C.
  • the solvent, excess phosphite, or other volatile material is thereafter stripped, under reduced pressure, or otherwise removed from the product.
  • Suitable solvents include benzene, toluene, xylene, aliphatic, or aromatic hydrocarbons, glymes, diglymes, dimethyl formamide and the like.
  • Typical N- hydroxymethyl phosphoramidate operable as reactants herein include One or more of the novel compounds of this invention may be applied to textile materials by conventional finishing techniques such as by thermal pad curing so as to incorporate into the textile a flame retardant amount thereof.
  • the compounds of this invention have advantages over the flame retardant agents of the prior art in that they may be used on a variety of textile materials of different chemical composition, and they may be applied by a variety of methods. They may be applied to materials in either the fiber or fabric form to give flame retarding materials with minimum detectable physical changes in the quality or hand of the textile material.
  • the products of this invention may be applied to cellulosic materials in several ways to give a durable flame retardant treatment.
  • the products of this invention may be reacted with formaldehyde to give N- hydroxymethyl derivatives which can react with cellulosic materials in a known manner.
  • aqueous mixtures of the products with formaldehyde, urea, trimethylol melamine or other known cellulose crosslinking agents may be applied to a cellulose substrate with the aid of an acidic catalyst by a pad dry process.
  • N-hydroxymethyl derivative of the products of this invention prepared by the condensation of the products with formaldehyde, are mixed in an aqueous medium with trimethylol melamine and a Lewis acid catalyst such as NH CI or Zn(NO '6H O.
  • the cellulosic material is immersed in an aqueous solution of the methylol derivative, trimethylol melamine, and Zn(l lO -6H O and squeezed on a two roll padder to 70-90 percent wet weight pick-up.
  • the material is dried at 220-270F for 1-3 minutes and cured at 300-370F for 1-6 minutes in a circulating air oven.
  • the samples are then washed in hot water and dried.
  • the finished samples have a flame retardant add-on of about 40 percent and preferably about to about 25 percent by weight.
  • the flame retardant agents of this invention may be applied to various textiles such as cellulosic or, proteinaceous materials.
  • cellulosic materials applicant intends to embrace cotton, rayon, paper, regenerated cellulose and cellulose derivatives which retain a cellulose backbone of at least one hydroxy substituent per repeatin'gglucose unit.
  • proteinaceous material applicant intends to embrace those textile materials comprising the functional groups of proteins such as the various animal wools, hairs and furs.
  • the flame retardant compounds or additives of the invention may be incorporated into thermoplastic resin compositions by any known method. That is to say, the flame retardant additive may be added to the resin by milling the resin and the additive on, for example, a two-roll mill, or in a Banbury mixer etc., or it may be added by molding or extruding the additive and resin simultaneously, or by merely blending it with the resin in powder form and thereafter forming the desired article. Additionally, the flame-retardant may be added during the resin manufacture, i.e., during the polymerization procedure by which the resin is made, provided the catalysts etc. and other ingredients of the polymerization system are inert thereto.
  • the compounds of this invention may be incorporated into the thermoplastic resin in flame-retarding amounts, i.e. generally amounts ranging from about 5 percent by weight, to about 50 percent by weight, preferably from about percent by weight, to about 40 percent by weight, based on the weight of the polymer, have been found sufficient.
  • thermoplastic resin embraced within the scope of this invention include the homopolymers and copolymers of unsaturated aliphatic, alicyclic, and aromatic hydrocarbons. Suitable monomers are ethylene, propylene, butene, pentene, hexene, heptene, octene, 2-methylpropenel, 3-methylbutene-l, 4-methylpentenel, 4-methylhexene- 1,5-methylhexene-l, bicyclo- (2.2.l)-2-heptene, butadiene, pentadiene, hexadiene, isoprene, 2,3-dimethylbutadienel ,3, Z-methylpentadiene-l,3, 4-vinylcyclohexene, vinylcyclohexene, cyclopentadiene, styrene and methylstyrene, and the like.
  • Suitable monomers are ethylene, propylene, butene, pentene,
  • polymers in addition to the above-described olefin polymers that are useful in the invention include polyindene, indenecoumarone resins; polymers of acrylate esters and polymers of methacrylate esters, acrylate and methacrylate resins such as ethyl acrylate, nbutyl methacrylate, isobutyl methacrylate, ethyl methacrylate and methyl methacrylate; alkyd resins and paint vehicles, such as bodied linseed oil; cellulose derivatives such as cellulose acetate, cellulose acetate butyrate, cellulose nitrate, ethyl cellulose, hydroxyethyl cellulose, methyl cellulose and sodium carboxymethyl cellulose; epoxy resins; furan resins (furfuryl alcohol or furfuralketone); hydrocarbon resins from petroleum; isobutylene resins (polyisobutylene); isocyanate resins (polyurethanes); melamine resin
  • the polymers of the invention can be in various physical forms, suchas shaped articles, for example, moldings, sheets, rods, and the like; fibers, coatings, films and fabrics, and the like.
  • the compounds of this invention have been found to have particular utility in ABS resins and in elastomeric materials such as acrylic rubber; acrylonitrilebutadiene styrene terpolymers; butadieneacrylonitrile copolymers; butyl rubber; chlorinated rubbers, e.g., polyvinyl chloride resins, chloroprene rubber, chlorosulfonated polyethylene; ethylene polymers, e.g., ethylene-propylene copolymers, ethylene-propylene terpolymers; fluorinated rubbers, butadiene rubbers, e.g., styrenebutadiene rubber, isobutyl-ene polymers, polybutadiene polymers, polyisobutylene rubbers, polyisoprene rubbers; polysultide rubbers; silicon rubbers; urethane rubbers; high styrene resins latices, high styrene resins, vinyl resin
  • Padding was done on a standard two roll laboratory padder at a gauge pressure of 60 pounds per square inch in all cases. Drying and curing during processing were done with a standard laboratory textile circulating air oven. Washing and drying was done in standard home top loading automatic washer and dryer. Flammability testing was done in accordance with the American Association of Textile Chemists and Colorist Test Method 34-1969, the standard vertical char method.
  • ASTM Test D2863-70 used in accordance with the following examples, generally provides for the comparison of relative flammability of self-supporting plastics by measuring the minimum concentration of oxygen in a slowly rising mixture of oxygen and nitrogen that will support combustion.
  • the procedure encompasses supporting cylindrical test specimens 70-150 mm X 8 mm vertically in a glass tube fitted with controlled upward oxygen/nitrogen gas flow. The top of the specimen is ignited and oxygen flow is adjusted until it reaches that minimum rate at which the specimen is extinguished before burning 3 minutes or 50 mm whichever happens first.
  • the oxygen index(n) is then calculated as follows:
  • O is the volumetric flow ofoxygen, at the mindant additive.
  • Each sample is marked at points 1 inch and 4 inches from its end and held, marked end in the flame, at a 45 angle in a controlled burner flame (1 inch flame length) for two 30 second attempts. The movement of the flame up the length of the sample through the two points is measured for rate of burning, non-burning or self-extinguishing characteristics.
  • SE self-extinguishing
  • NB nonburning
  • EXAMPLE 11 Preparation of EXAMPLE lll rai t saef- A 250 ml. flask was charged with 18.3 g. (0.1 mole) of N-hydroxymethyl diethylphosphoramidate and 27g. (0.1 mole) of tris-2-chloroethyl phosphite. The reaction mixture was heated at C for 2 hours, then stripped at 120C under a reduced pressure of 2 mm mercury to yield 39g. of a clear liquid. This product was shown, by infrared and nuclear magnetic resonance spectroscopy, to be essentially pure.
  • N-hydroxymethyl-( l-isopropyl-2,2-dimethyl)-1, 3 propylidenyl phosphoramidate, 59.3 g. (0.25 mole) was mixed with 37g. (0.3 mole) of trimethyl phosphite and 80 ml. diglyme in a 250 ml. flask.
  • the reaction mixture was slowly heated to 1 15C and held at this tem- EXAMPLE VI
  • To 70 parts of polypropylene was added 30 parts of N-(diethylphosphonomethyl) diethylphosphoramidate and dry blended for about minutes. The resulting mixture was then brought to a melt and thoroughly mixed for about minutes.
  • Trimethylol melamine 20 g. was added with 5.0g of ammonium chloride.
  • a sample of 5.0 oz. per square yard cotton sheeting was immersed in the above solution and padded through a two roll laboratory padder, at about lb' per sq. in. gauge pressure, to give a wetpick-up of about 92 percent.
  • the sample was dried in a circulating air oven for about 2.0 minutes at about 250F and then cured for about 4.0 minutes at about 350F.
  • the sample was then washed in an automatic washer using Tide as the detergent, and tumble dried. Flame retardancy was then determined by the standard vertical char test AATCC D34-l969 and oxygen index test ASTM D2863-70. The weight add-on was 22.3 percent.
  • Durability towashing was determined bywashing the sample through one cycle of an automatic washerusing Tide as the detergent. l
  • EXAMPLE XXlll N-( Diallylphosphonomethyl )diethylphosphoroamidate 40g was mixed with 60 g offormalin (40 percent) solution and stirredovernight at room temperature at a pH of 8.5-9.5. The pH was adjusted to 7.0 with hy- Flammability tests Oxygen Percent Example Additive Polymer index D-635 additive- VI i H H Polypropylene 23.2 NB 30 omommm-NrPoHr-P oomomn VII H Polystyrene 5 2 3.0 NB 30 (CHaGH2O)zP-NHCH:P(OCHzCHzCl):-
  • a sample of rayon staple fiber was immersed in the solution and excess solution removed by passing through a two roll padder at about 60 lb. gauge pressure to give a wet pick-up of about l%.
  • the sample was then dried about 2.5 minutes at about 250F and cured for about 5.0 minutes at about 350F in a circulating air oven.
  • the sample was washed by hand in a water detergent mixture for 3 minutes and then dried. Flammability was determined by holding an end of the fiber in a bunson flame for approximately 2 sec. and withdrawmg.
  • a compound of the formula 1. A compound of the formula 3. A compound of claim I of the formula 4. A compound of claim I of the formula 5. A compound of claim I of the formula Flammability testing Percent Example Compound Textile magi $35 3; Initial 1 InitgiIl XXII 0 Cotton 92 22. 3 3.7 in. 4.1 in. 24. 3
  • ABS resins should read --ABS resins; ABS polyvinyl.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Molecular Biology (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Fireproofing Substances (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
US00239799A 1972-03-30 1972-03-30 Diakyl alkyl and cyclic phosporamidomethyl phosphonates Expired - Lifetime US3812218A (en)

Priority Applications (12)

Application Number Priority Date Filing Date Title
US00239799A US3812218A (en) 1972-03-30 1972-03-30 Diakyl alkyl and cyclic phosporamidomethyl phosphonates
US239757A US3870771A (en) 1972-03-30 1972-03-30 Dialkyl alkyl and aromatic sulfonamidomethyl phosphonates
GB1390773A GB1418775A (en) 1972-03-30 1973-03-22 Phosphonate ester derivatives having flame-retardant properties
FR7310953A FR2187802B1 (enrdf_load_html_response) 1972-03-30 1973-03-27
DE2315493A DE2315493A1 (de) 1972-03-30 1973-03-28 Phosphonsaeureverbindungen, verfahren zu deren herstellung und deren verwendung als flammschutzmittel fuer textilien und thermoplastische, hitzehaertbare oder elastomere kunstharze
BE129396A BE797476A (fr) 1972-03-30 1973-03-28 Nouveaux adjuvants retardant l'inflammation contenant du phospore
CA167,352A CA1004227A (en) 1972-03-30 1973-03-28 Phosphorus containing fire retardant additives
NL7304503A NL7304503A (enrdf_load_html_response) 1972-03-30 1973-03-30
JP48036575A JPS4916735A (enrdf_load_html_response) 1972-03-30 1973-03-30
IT22420/73A IT982664B (it) 1972-03-30 1973-03-30 Additivi anti incendio contenenti fosforo
FR7333434A FR2196341B1 (enrdf_load_html_response) 1972-03-30 1973-09-18
US05/537,721 US3959551A (en) 1972-03-30 1974-12-31 Dialkyl alkyl and aromatic sulfonamidomethyl phosphonates

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US00239799A US3812218A (en) 1972-03-30 1972-03-30 Diakyl alkyl and cyclic phosporamidomethyl phosphonates
US239757A US3870771A (en) 1972-03-30 1972-03-30 Dialkyl alkyl and aromatic sulfonamidomethyl phosphonates

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US43848174A Continuation-In-Part 1974-01-31 1974-01-31

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US00239799A Expired - Lifetime US3812218A (en) 1972-03-30 1972-03-30 Diakyl alkyl and cyclic phosporamidomethyl phosphonates
US239757A Expired - Lifetime US3870771A (en) 1972-03-30 1972-03-30 Dialkyl alkyl and aromatic sulfonamidomethyl phosphonates

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US239757A Expired - Lifetime US3870771A (en) 1972-03-30 1972-03-30 Dialkyl alkyl and aromatic sulfonamidomethyl phosphonates

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JP (1) JPS4916735A (enrdf_load_html_response)
BE (1) BE797476A (enrdf_load_html_response)
CA (1) CA1004227A (enrdf_load_html_response)
DE (1) DE2315493A1 (enrdf_load_html_response)
FR (2) FR2187802B1 (enrdf_load_html_response)
GB (1) GB1418775A (enrdf_load_html_response)
IT (1) IT982664B (enrdf_load_html_response)
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4061604A (en) * 1974-12-18 1977-12-06 Ciba-Geigy Corporation Flameproofing of plastics
US6388046B1 (en) 1998-08-31 2002-05-14 General Electric Company Flame retardant resin compositions containing phosphoramides, and method for making
US6433046B1 (en) 1999-01-22 2002-08-13 General Electric Company Flame retardant resin compositions containing phosphoramides, and method of making
US6569929B2 (en) 1999-01-22 2003-05-27 General Electric Company Method to prepare phosphoramides, and resin compositions containing them
US20050054553A1 (en) * 2003-06-27 2005-03-10 The Procter & Gamble Company Liquid fabric softening compositions comprising flame retardant

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3959551A (en) * 1972-03-30 1976-05-25 Hooker Chemicals & Plastics Corporation Dialkyl alkyl and aromatic sulfonamidomethyl phosphonates
US4031170A (en) * 1973-08-06 1977-06-21 Monsanto Company Phosphorus compounds
US4032601A (en) * 1973-08-06 1977-06-28 Monsanto Company Process for the production of sulfonamide phosphonates
DE2424243A1 (de) * 1974-05-18 1975-11-27 Bayer Ag Perfluoralkansulfonamidoalkanphosphonsaeure- bzw. -phosphinsaeurederivate
US4202706A (en) * 1979-03-12 1980-05-13 Minnesota Mining And Manufacturing Company Corrosion resistance treatment of aluminum with N-alkyl-fluoroaliphaticsulfonamidophosphonic acids and salts thereof
JPS5610500A (en) * 1979-07-09 1981-02-02 Hiroyasu Hanawa Automatic punchinggmachine
ES2250150T3 (es) 1999-07-06 2006-04-16 Methylgene, Inc. Inhibidores de sulfonamidometilfosfonato de la beta-lactamasa.
US6921756B2 (en) * 1999-07-06 2005-07-26 Methylgene, Inc. Inhibitors of β-lactamase
US6884791B2 (en) * 1999-07-06 2005-04-26 Methylgene, Inc. Inhibitors of β-lactamase

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2635112A (en) * 1949-07-28 1953-04-14 Research Corp Process for producing aminomethylphosphonic acid compounds

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4061604A (en) * 1974-12-18 1977-12-06 Ciba-Geigy Corporation Flameproofing of plastics
US6388046B1 (en) 1998-08-31 2002-05-14 General Electric Company Flame retardant resin compositions containing phosphoramides, and method for making
US6433046B1 (en) 1999-01-22 2002-08-13 General Electric Company Flame retardant resin compositions containing phosphoramides, and method of making
US6569929B2 (en) 1999-01-22 2003-05-27 General Electric Company Method to prepare phosphoramides, and resin compositions containing them
US20050054553A1 (en) * 2003-06-27 2005-03-10 The Procter & Gamble Company Liquid fabric softening compositions comprising flame retardant

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BE797476A (fr) 1973-09-28
NL7304503A (enrdf_load_html_response) 1973-10-02
FR2187802A1 (enrdf_load_html_response) 1974-01-18
GB1418775A (en) 1975-12-24
IT982664B (it) 1974-10-21
FR2196341A1 (enrdf_load_html_response) 1974-03-15
US3870771A (en) 1975-03-11
JPS4916735A (enrdf_load_html_response) 1974-02-14
DE2315493A1 (de) 1973-10-04
CA1004227A (en) 1977-01-25
FR2187802B1 (enrdf_load_html_response) 1976-06-11
FR2196341B1 (enrdf_load_html_response) 1977-03-11

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