US3823206A - N-phosphonomethyl amides - Google Patents

N-phosphonomethyl amides Download PDF

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US3823206A
US3823206A US23979372A US3823206A US 3823206 A US3823206 A US 3823206A US 23979372 A US23979372 A US 23979372A US 3823206 A US3823206 A US 3823206A
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flame
mole
resins
compounds
carbon atoms
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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 US05239784 priority Critical patent/US3803269A/en
Priority to US05239793 priority patent/US3823206A/en
Priority to JP3443173A priority patent/JPS499090A/ja
Priority to CA167,354A priority patent/CA1006171A/en
Priority to GB1518573A priority patent/GB1432013A/en
Priority to BE129535A priority patent/BE797632A/fr
Priority to NL7304500A priority patent/NL7304500A/xx
Priority to DE2316043A priority patent/DE2316043A1/de
Priority to FR7311582A priority patent/FR2178236B1/fr
Priority to IT2242273A priority patent/IT982666B/it
Priority to US37482673 priority patent/US3901650A/en
Priority to US05393868 priority patent/US3895161A/en
Application granted granted Critical
Publication of US3823206A publication Critical patent/US3823206A/en
Priority to US05/531,646 priority patent/US3935162A/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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/92—Fire or heat protection feature
    • Y10S428/921—Fire or flameproofing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S521/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S521/906—Polyurethane cellular product containing unreacted flame-retardant material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S521/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S521/907—Nonurethane flameproofed cellular product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/2938—Coating on discrete and individual rods, strands or filaments
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2631—Coating or impregnation provides heat or fire protection
    • Y10T442/2672—Phosphorus containing
    • Y10T442/268—Phosphorus and nitrogen containing compound

Definitions

  • R' is selected from the group consisting of phenyl, lower alkenyl and halogen substituted and unsubstituted lower alkyl of 1-6 carbon atoms
  • y is an integer from 1-2 provided that when y is 1, R is selected from the group consisting of hydrogen, lower alkyl of 28 carbon atoms, benzyl, dialkylphosphonoalkyl and phenoxymethylene and when y is 2, R is lower alkylene of 1-4 carbon atoms.
  • the compounds of the invention are useful as flame retardant agents for textile materials and in the production of polymers and copolymers which possess flame retardant properties.
  • Flame retardant textiles have been produced by depositing metal oxides, within or on the textile fibers, by the successive precipitation of ferric oxides and a mixture of tungstic acid and stannic oxide or by successive deposition of antimony trioxide and titaniumdioxide.
  • Such processes require plural treatment bathsin which strongly acidic solutions are employedt'hus posing the problem of possible textile degradation.
  • metal oxide coatings on textile materials create difliculties in subsequent dyeing processes which deleteriously afiect the hand of the finished product.
  • Another process involves the use of a single processing bath wherein a dispersion of a chlorinated hydrocarbon andfinely divided antimony oxide is padded on the textile material.
  • antimony oxide will react with hydrogen chloride, generated by degradation of the chlorinated hydrocarbon, to form antimony oxychloride which acts to suppress flame.
  • This combination of a chlorinated bydrocarbon and finely divided antimony oxide are not acceptable finishes for closely woven textiles as they deleteriously afl ect the hand of the finished product.
  • a further process for imparting flame resistance to cellulosic materials is by the esterification of the cellulose with diammonium hydrogen orthophosphate. 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, thermosetting and elastomeric 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, thermosetting and elastomeric resins so as to improve the flame retardancy thereof has been known.
  • R is selected from the group consisting of phenyl, lower alkenyl and halogen substituted-and unsubstituted lower alkyl of 16 carbon atoms
  • y is an integer from 1-2 provided that when y is l, R is selected from the group consisting of hydrogen, lower alkyl of 28 carbon atoms, benzyl, dialkylphosphonoalkyl and phenoxymethylene and when y is 2, R is lower alkylene of 1-4 carbon atoms.
  • Another object is to provide flame retarding thermoplastic, thermosetting or elastomeric resin composif" tions comprising normally flammable resin materials.
  • composition comprising normally flammable cellulosic, proteinaceous or analo gous man-made materials and an effective flame retardant amount of the compound represented by the formula wherein R, R and y are as above described.
  • a further particular object is to devise a composition comprising normally flammable thermoplastic, thermosetting or elastomeric polymer and an effective flame retarding amount of the before described novel compound.
  • novel compounds for imparting flame retardancy to textiles and resin materials, of the formula wherein R' is selected from the group consisting of phenyl, lower allyl and halogen substituted and unsubstituted lower alkyl of 1-6 carbon atoms, y is an integer from 1-2 provided that when y is 1, R is selected from the group consisting of hydrogen, lower alkyl of 2-8 carbon atoms, benzyl, dialkylphosphonoalkyl and phenoxymethylene and when y is 2, R is lower alkylene of 1-4 carbon atoms. More specifically, the preferred compounds of the present invention include these compounds wherein R' is lower alkyl of 1-6 carbon atoms.
  • compounds of the present invention include, for instance, compounds of the general formula such as H H HCNHCHzP CH5):
  • compositions of the present invention is accomplished by reacting an N-hydroxymethyl amide of the formula R NHCHzOH with a trialkyl phosphite of the formula (R'O) P wherein R and R are as previously described in a suitable solvent an excess of phosphite or neat.
  • the reaction occurs at elevated temperatures and is continued for about 1 to about 12 hours. Temperatures are generally about 50 C. to about 160 C. Preferably reaction is continued from about 3 to about 6 hours at a temperature of about C. to about C.
  • the solvent or other volatile matter, is thereafter stripped, or otherwise removed from the product.
  • Suitable solvents include benzene, toluene, xylene, glymes, dimethyl formamide, aliphatic or aromatic hydrocarbons.
  • Typical N-hydroxymethyl amides operable as reactants herein include CHaCHgCHaCHzHlNHCHaOH O CH:CHz N-CH:OH
  • novel compounds of this invention may be applied to textile materials by conventional finishing techniques such as by thermal induced 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.
  • Products of this invention may be applied to cellulosic material 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 cellulose substrate with the aid of an, acidic catalyst by a padding 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 cata lyst such as NH Cl or Zn(NO -6H O.
  • the cellulosic material is immersed in an aqueous solution of the methylol derivative, trimethylol melamine, and
  • the material is dried at 220-270 F. for 1-3 minutes and cured at 300370 F. 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 to about 40% and preferably about to about 25% by weight.
  • the flame retardant agents of this invention may be applied to various textiles such as cellulosic materials, proteinaceous materials and blends of cellulosic or proteinaceous materials with analagous manmade fibers.
  • 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 repeating glucose 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 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% by weight, to about 50% by weight, preferably from about 20% by weight, to about 40% by weight, based on the weight of the polymer, have been found sufficient.
  • Resins 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-methylpropene-1, 3-methylbutene- 1, 4-methylpentene-1, 4-methylhexene-1, 5-methylhexene- 1, bicycle-(2.2.1)-2-heptene, butadiene, pentadiene, hexa- 6 diene, isoprene, 2,3-dimethylbutadiene-l,3, 2-methylpentadiene-1,3, 4-vinylcyclohexene, vinylcyclohexene, cyclopentadiene, styrene and methylstyrene, and the like.
  • 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, n-butyl 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 celluose and sodium carboxymethy cellulose; epoxy resins; furan resins (furfuryl alcohol or furfural-ketone); hydrocarbon resins from petroleum; isobutylene resins (polyisobutylene); isocyanate resins (polyurethan
  • the polymers of the invention can be in various physical forms, such as 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; acrylonitrile-butadiene styrene terpolymers; butadiene-acryloniuile 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., styrene-butadiene rubber, isobutylene polymers, polybutadiene polymers, polyisobutaylene rubbers, polyisoprene rubbers; polysulfide rubbers; silicon rubbers; urethane rubbers; high styrene resins latices, high styrene resins
  • 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 support ing cylindrical test specimens 70-150 x 8.0mm. 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:
  • n, percent (100x0 (Oz-I-Nz) wherein O is the volumetric flow of oxygen, at the minimal rate and N is the corresponding volumetric flow rate of nitrogen.
  • a modification of ASTM Test D635-68 used in accordance with the following examples, generally provides for the comparison of burning rates, self-extinguishment and non-burning characteristics of plastics in the form of sheets, bars, plates or panels.
  • the procedure encompasses preparing cylindrical plastic samples of 150-200 mm. x 8 mm. diameter with and without the subject flame retardant 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 degree 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.
  • a sample is rated SE (self-extinguishing) if the flame burns through the first point but extinguishes before reaching the second point.
  • SE self-extinguishing
  • NB non-burning
  • AATCC test method 34-1969 The Vertical Char Test, used in accordance with the following examples, generally provides for the comparison of relative flammability of 2% inch x 10 inch fabric test specimens when exposed to a controlled burner flame, under controlled conditions, for periods of 12.0 and 3.0 seconds. Charred specimens are thereafter subjected to controlled tearing tests, using tabulated weights, to determine the average tear length as representing the char length of the fabric. In addition, samples which are wholly consumed by the flame are rated (B) and sample which do not burn are rated (NB). For comparison purposes, it should be noted that untreated samples of the fabrics used in the examples of this case would be consumed for this test.
  • EXAMPLE IV A 1 liter flask was fitted with reflux condenser, stirring and thermometer. The flask was charged with 430 g. 1.86 mole) of N-hydroxymethyl diethylphosponoacetamide and 248 g. (2.0 mole) of trimethyl phosphite. The reaction mixture was heated for about 13 hours at about C. Excess trimethyl phosphite was removed by vacuum distillation to give 528.5 g. of a thick yellow liquid.
  • the product structure was confirmed by elemental analysis and infrared and nuclear magnetic resonance spectroscopy to diethylphosphonoacetamide.
  • Trimethyl phosphite (2.0 mole) was mixed with N- hydroxymethyl 3 dimethylphosphonopropionamide (1.0 mole) in a one liter flask, fitted with thermometer, mechanical stirrer, distillate take off, and reflux condenser, and heated to reflux for about 2 hours. A mixture of methanol and trimethyl phosphite was removed as distillate and an equivalent volume of trimethyl phosphite added during the second hour of reflux.
  • EXAMPLE VI Preparation of A 500 ml. round bottomed flask was charged with 124 g. (1.0 mole) of trimethyl phosphite and heated to 100 C. To this was added 132 g. (0.8 mole) of N-hydroxymethylphenylacetamide over a ten minute period of time. The mixture was held at about 96 for about six hours, cooled, filtered, and stripped, at 100 C. and 0.25 mm. Hg, to give a 64% yield of the desired product in the form of a pale yellow oil. Elemental analysis as well as infrared and nuclear magnetic resonance spectroscopy confirmed the structure.
  • EXAMPLE X Preparation of N-diphenyl phosphonomethyl propionamide, was prepared in 82.2% yield by heating N-hydroxymethylpropionamide (0.2 mole) and triphenyl phosphite (0.2 mole) at about 130 for about 5 hours. After the heating period was completc'phenol Was removed under reduced pressure (2 mm. Hg) at 120. The product structure was 10 confirmed by infrared and nuclear magnetic resonance spectroscopy.
  • EXAMPLE XIII Thirty parts of N-dimethylphosphonomethyl butylamide and seventy parts of polystyrene were dry blended for about 5 minutes. This mixture was then brought to a melt and mixed thoroughly for about 15 minutes, cooled, and chopped into small pieces. These pieces were then molded into a solid cylinder 200 mm. x 8 mm. and tested by ASTM tests D2863-70 and D635-68 as described above. Results of these tests are contained in Table I.
  • EXAMPLE XXV II 5.0 02. cotton sheeting was padded through a solution containing 30 parts of N-dimethylphosphonomethyl-3-dimethylphosphonopropionamide, 10 parts of trimethylolmelamine, 30 parts of 40% formalin solution, 25 parts of water and 5 parts of Zn(NO .6H O.
  • the sheeting was squeezed to a 80% wet pick-up by means of a two roll laboratory padder, and thereafter dried at about 250 F. for about two minutes and cured at about 340 for about 4 minutes in a circulating air oven. The sheeting was then washed for one wash cycle, in a standard home type automatic Washer with Tide detergent and tumble dried. A resin add-on of 24.7% was obtained. The sheeting was then subjected to AATCC test method 34-1969 and had a calculated char length of 4.5 inches. The sheeting was then subjected to one hooker boil and when tested by AATTC test method 34-4969 had a calculated char length of 5.5 inches.
  • EXAMPLE XXVIII 8.0 oz. per sq. yd.
  • wool Bedford cord was padded through the solution of Example XXVII and squeezed to 60% wet pick-up. After drying curing and washing as in Example XXVII a Resin add-on of 17.7% was obtained.
  • Initial testing under AATCC test method 34-1969 indicates a 1.5 inch calculated char length.
  • the wool Bedford cord was then subjected to 24 additional washes in a standard home type automatic washer using Tide de- 1 1 tergent and tumble dried. Testing by method 34-1969 indicated a calculated char length of 3.0 inches.
  • Example XXIX A rayon staple fiber sample was immersed in the solution of Example XXVII and squeezed to 100% Weight gain. The sample was dried for minutes at 240 F. and cured minutes at 340 F., washed in hot tap water, and dried to give a 32% add-on.
  • a treated sample is self-extinguishing if ignited in a Bunsen flame and then removed while an untreated sample is completely consumed.
  • the treated sample remains self-extinguishing after 10 home washes in an automatic washer.
  • EXAMPLE XXX A solution of N-dimethylphosphonomethylphenyl acetamide (0.2 mole) and 38% formalin solution (0.2 mole) in 50 g. of water was refluxed about one hour at a pH of 9 and then stirred an additional 3 hours at room temperature. The pH was adjusted to 7.0 and 20 g. of trimethylolmelamine and 5 g. of magnesium chloride hexahydrate added. 5.0 oz. cotton sheeting was padded through the solution and squeezed to a wet pick-up of 120% on a two roll laboratory padder. The sheeting was then dried at about 240 F. for about 2 minutes and cured at about 350 F. for about 3 minutes in a circulating air oven. The sheeting was then Washed by hand for about 5 minutes using Tide detergent. Testing under AATCC method 24-1969 gave a 2.0 inch calculated char length. After subjected to a second hand washing as above described, testing gave a 1.9 inch calculated char length.
  • treated wool was then dried at about 250 F. for about 2 minutes and cured at about 350 F. for about 4 minutes in a circulating air oven. The treated wool was then Washed by hand for about five minutes using Tide detergent and tumble dried. A resin add-on of 41% and oxygen index of 28 was calculated. The thus treated wool was then subjected to AATCC method 34-1969- and found to have a calculated char length of 3.0 inches. The treated wool was then subjected to 4 additional hand Washes, on above described, and after testing by method 34-196-9 had a char length of 4.0 inches.
  • Example XXXI 6 oz. per sq. yd. wool was treated by the process of Example XXXI using the above described padding solution. Resin add-on was calculated to be 30% and oxygen index 28. Testing under method 34-1969 after one wash gave a calculated char length of 3.6 inches and after 4 additional washings, a calculated char length of 4.0 inches.
  • EXAMPLE XXXIH N-dimethylphosphonomethylformamide (40 g.) was mixed with 40% formalin solution g.) and stirred overnight at pH 9-10. The pH was adjusted to 7.0 with hydrochloric acid and then 23 g. of a 50% solution of a methylolated melamine and 5 g. of ammonium chloride were added.
  • a rayon staple fiber was immersed in the above solution and squeezed to about wet pick-up on a two roll laboratory padder. The fiber was then dried in a circulating air oven for about five minutes at about 250 and cured about ten minutes at about 350, washed in hot water by hand, and air dried giving about 32% resin add-on.
  • the oxygen index of the fiber was calculated as 29.5 as compared to 19.5 for untreated fiber.
  • the treated samples self-extinguished when a Bunsen flame was applied for 2 seconds and removed while untreated samples burned completely.
  • the self-extinguishing character is maintained after 5 hot water, hand washings.
  • a compound of Claim 1 of the formula 1 A compound of the formula wherein R is selected from the group consisting of phenyl,
  • a compound of Claim 1 of the formula 10 A compound of Claim 1 of the formula atoms.
  • a compound of Claim 1 of the formula (i: H CH:CHZ%NHOHZIIL(O)2 H N 2P(OCHa)2 12.
  • a compound of Claim 1 of the formula 3.
  • a compound of Claim 1 of the formula 0 H J H -NH0Hz-%(0CHCH0D (cH 0)zP CHqHNCOHz-CHz-JE-NHCHrPWCHa): 0 5.

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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)
  • Life Sciences & Earth Sciences (AREA)
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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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US05239793 1972-03-30 1972-03-30 N-phosphonomethyl amides Expired - Lifetime US3823206A (en)

Priority Applications (13)

Application Number Priority Date Filing Date Title
US05239784 US3803269A (en) 1972-03-30 1972-03-30 Dialkyl aromatic amidomethyl phosphonates
US05239793 US3823206A (en) 1972-03-30 1972-03-30 N-phosphonomethyl amides
JP3443173A JPS499090A (fr) 1972-03-30 1973-03-26
CA167,354A CA1006171A (en) 1972-03-30 1973-03-28 Phosphorus containing fire retardant additives
GB1518573A GB1432013A (en) 1972-03-30 1973-03-29 Phosphorus containing fire retardant additives
NL7304500A NL7304500A (fr) 1972-03-30 1973-03-30
BE129535A BE797632A (fr) 1972-03-30 1973-03-30 Adjuvants retardateurs d'inflammation contenant du phosphore
DE2316043A DE2316043A1 (de) 1972-03-30 1973-03-30 Phosphonsaeureverbindungen, verfahren zu deren herstellung und deren verwendung als flammschutzmittel fuer textilien und thermoplastische, hitzehaertbare oder elastomere kunstharze
FR7311582A FR2178236B1 (fr) 1972-03-30 1973-03-30
IT2242273A IT982666B (it) 1972-03-30 1973-03-30 Additivi contenenti fosforo atti a ritardare la propagazione del fuoco
US37482673 US3901650A (en) 1972-03-30 1973-06-29 Textile flame retardants
US05393868 US3895161A (en) 1972-03-30 1973-09-04 Flame retardant materials
US05/531,646 US3935162A (en) 1972-03-30 1974-12-11 Dialkyl aromatic amidomethyl phosphonate flame retardants

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US05239784 US3803269A (en) 1972-03-30 1972-03-30 Dialkyl aromatic amidomethyl phosphonates
US05239793 US3823206A (en) 1972-03-30 1972-03-30 N-phosphonomethyl amides
US37482673 US3901650A (en) 1972-03-30 1973-06-29 Textile flame retardants
US05393868 US3895161A (en) 1972-03-30 1973-09-04 Flame retardant materials
US05/531,646 US3935162A (en) 1972-03-30 1974-12-11 Dialkyl aromatic amidomethyl phosphonate flame retardants

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US37482674A Division 1974-06-29 1974-06-29

Publications (1)

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US3823206A true US3823206A (en) 1974-07-09

Family

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Family Applications (5)

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US05239784 Expired - Lifetime US3803269A (en) 1972-03-30 1972-03-30 Dialkyl aromatic amidomethyl phosphonates
US05239793 Expired - Lifetime US3823206A (en) 1972-03-30 1972-03-30 N-phosphonomethyl amides
US37482673 Expired - Lifetime US3901650A (en) 1972-03-30 1973-06-29 Textile flame retardants
US05393868 Expired - Lifetime US3895161A (en) 1972-03-30 1973-09-04 Flame retardant materials
US05/531,646 Expired - Lifetime US3935162A (en) 1972-03-30 1974-12-11 Dialkyl aromatic amidomethyl phosphonate flame retardants

Family Applications Before (1)

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US05239784 Expired - Lifetime US3803269A (en) 1972-03-30 1972-03-30 Dialkyl aromatic amidomethyl phosphonates

Family Applications After (3)

Application Number Title Priority Date Filing Date
US37482673 Expired - Lifetime US3901650A (en) 1972-03-30 1973-06-29 Textile flame retardants
US05393868 Expired - Lifetime US3895161A (en) 1972-03-30 1973-09-04 Flame retardant materials
US05/531,646 Expired - Lifetime US3935162A (en) 1972-03-30 1974-12-11 Dialkyl aromatic amidomethyl phosphonate flame retardants

Country Status (8)

Country Link
US (5) US3803269A (fr)
JP (1) JPS499090A (fr)
BE (1) BE797632A (fr)
CA (1) CA1006171A (fr)
DE (1) DE2316043A1 (fr)
FR (1) FR2178236B1 (fr)
GB (1) GB1432013A (fr)
NL (1) NL7304500A (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3989772A (en) * 1973-10-12 1976-11-02 Bayer Aktiengesellschaft N,N-bis-(phosphonomethyl)-acrylamides
US3998789A (en) * 1973-09-11 1976-12-21 Sumitomo Bakelite Company, Limited Flame resistant thermosetting resin composition and method for preparing same

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3803269A (en) * 1972-03-30 1974-04-09 Hooker Chemical Corp Dialkyl aromatic amidomethyl phosphonates
US3954860A (en) * 1973-08-06 1976-05-04 Monsanto Company Phosphorous compounds
US4113671A (en) * 1974-10-17 1978-09-12 Societe Nationale Des Poudres Et Explosifs Carbamate-phosphonates as flame-proofing agents in polyurethane foam
US4003862A (en) * 1975-10-23 1977-01-18 Michigan Chemical Corporation N-substituted tetrahalophthalimides as flame retardants
IT1060705B (it) * 1976-05-28 1982-08-20 Montedison Spa Composizioni polimeriche autoestinguenti
GB8321643D0 (en) * 1983-08-11 1983-09-14 Ici Plc Fire retardant polyamide compositions
US4753972A (en) * 1985-12-16 1988-06-28 Ciba-Geigy Corporation Substituted aminoxyethyl phosphonates
GB8617861D0 (en) * 1986-07-22 1986-08-28 Ciba Geigy Ag Flame retardant compositions
FR2818985B1 (fr) * 2000-12-29 2004-02-20 Nylstar Sa Procede de fabrication de compositions stabilisees a base de polyamide
ITMI20020734A1 (it) * 2002-04-08 2003-10-08 Eurotecnica Dev & Licensing S Glicoli e plioli aromatici procedimento di preparazione e loro uso quali monomeri
US8247077B2 (en) 2008-04-10 2012-08-21 Ansell Protective Solutions Ab Chemical protective garment with added flash fire protection

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Publication number Priority date Publication date Assignee Title
US2666078A (en) * 1952-05-16 1954-01-12 Arvey Corp Bis-trichloroethyl benzene phosphonate
US2867547A (en) * 1953-09-22 1959-01-06 Victor Chemical Works Method of flameproofing fibers, compositions used therein and the resulting products
US2803562A (en) * 1955-05-26 1957-08-20 Dow Chemical Co Treatment of cellulosic materials to impart flame resistance thereto
GB1197591A (en) * 1967-07-28 1970-07-08 Ciba Ltd Phosphorus-Containing Reaction Products, processes for their production and their Application
US3803269A (en) * 1972-03-30 1974-04-09 Hooker Chemical Corp Dialkyl aromatic amidomethyl phosphonates

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3998789A (en) * 1973-09-11 1976-12-21 Sumitomo Bakelite Company, Limited Flame resistant thermosetting resin composition and method for preparing same
US3989772A (en) * 1973-10-12 1976-11-02 Bayer Aktiengesellschaft N,N-bis-(phosphonomethyl)-acrylamides

Also Published As

Publication number Publication date
US3803269A (en) 1974-04-09
GB1432013A (en) 1976-04-14
US3935162A (en) 1976-01-27
DE2316043A1 (de) 1973-10-18
US3901650A (en) 1975-08-26
NL7304500A (fr) 1973-10-02
US3895161A (en) 1975-07-15
CA1006171A (en) 1977-03-01
FR2178236A1 (fr) 1973-11-09
FR2178236B1 (fr) 1976-09-10
JPS499090A (fr) 1974-01-26
BE797632A (fr) 1973-10-01

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