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US3803269A - Dialkyl aromatic amidomethyl phosphonates - Google Patents

Dialkyl aromatic amidomethyl phosphonates Download PDF

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Publication number
US3803269A
US3803269A US23978472A US3803269A US 3803269 A US3803269 A US 3803269A US 23978472 A US23978472 A US 23978472A US 3803269 A US3803269 A US 3803269A
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Prior art keywords
resins
compounds
flame retardant
flame
formula
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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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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Application filed by Hooker Chemical Corp filed Critical Hooker Chemical Corp
Priority to US05239793 priority Critical patent/US3823206A/en
Priority to US05239784 priority patent/US3803269A/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 NL7304500A priority patent/NL7304500A/xx
Priority to FR7311582A priority patent/FR2178236B1/fr
Priority to DE2316043A priority patent/DE2316043A1/en
Priority to BE129535A priority patent/BE797632A/en
Priority to US37482673 priority patent/US3901650A/en
Priority to US05393868 priority patent/US3895161A/en
Application granted granted Critical
Publication of US3803269A publication Critical patent/US3803269A/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 l-6 carbon atoms
  • X is selected from the group consisting of chlorine, bromine and lower alkyl of l-6 carbon atoms
  • m is an integer from 1-4
  • n is an integer from 0-5, provided that the sum of mand n is not greater than 6 and when m is 1, X is greater than 0.
  • This invention relates to novel compounds of the formula wherein R is selected from the group consisting of phenyl, lower alkenyl, and halogen substituted and unsubstituted lower alkyl of 1-6 carbon atoms, X is selected from the group consisting of chlorine, bromine and lower alkyl of l-6 carbon atoms, m is an integer from 1-4 and n is an integer from 0-5, provided that the sum of m and n is not greater than 6 and when m is l, X is greater than 0.
  • the invention includes methods of applying the above novel compounds to normally flammable textiles, thermoplastic, thermosetting, and elastomeric resin compositions so as to render them flame retardant.
  • Fiber retardant textiles have been producedby 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 titanium dioxide.
  • Such posprocesses require plural treatment baths in which strongly acidic solutions are employed thus posing the problem of possible textile degradation.
  • metal oxide coatings on textile materials create difiiculties in subsequent dyeing processes which deleteriously atfect the hand of the finished product.
  • Another process involves the use of a single processing bath wherein a dispersion of a chlorinated hydrocarbon and finely 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 hydrocarbon and finely divided antimony oxide are not acceptable finishes for closely woven textiles as they deleteriously affect 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 elasotmeric resins so as to improve the flame retardancy thereof has been known.
  • chlorostyrene copolymers chlorinated paraflin 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% of additive, must be incorporated into the resin in order to make it sufi'iciently flame retardant.
  • Such large amounts of additive may deleteriously atfect the physical characteristics of the thermoplastic resin, as Well as substantially complicating and increasing the cost of preparation thereof.
  • 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.
  • a particular object is to devise a composition comprising normally flammable cellulosic, proteinaceous or analogous man-made materials and an effective flame retardant amount of the compound represent by the formula 0 noni onmn I DESCRIPTION OF THE INVENTION
  • novel compounds for imparting flame retardancy to textiles and resin materials, of the formula i 3 [(RO): CHrNH Jm I wherein R is selected from the group consisting of phenyl, lower alkenyl and halogen substituted and unsubstituted lower alkyl of 1-6 carbon atoms, X is selected from the group consisting of chlorine, bromine and lower alkyl of 1-6 carbon atoms, m is an integer from 1-4 and n is an integer from 0-5, provided that the sum of m and n is not greater than 6 and when m is 1, X is greater than 0.
  • the preferred compounds of the present invention include these compounds wherein R is lower alkyl, allyl, chlorinated alkyl or phenyl, and X is chlorine, bromine or methyl.
  • Illustrative examples of compounds of the present invention include, for instance, compounds of the general formula such as 0 a @iinnomiwoomwm:
  • compositions of the present invention is accomplished by reacting an N-hydroxymethyl aromatic amides of the formula l-o nnomonl with a trialkyl phosphite of the formula wherein R, m, n and X are as previously described in a suitable solvent, excess of the 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 80 C. to about 120 C.
  • the solvent or other volatiles is thereafter stripped, or otherwise removed from the product.
  • Suitable solvents include benzene, toluene, xylene, glymes, dimethylformamide, aliphatic or aromatic hydrocarbons.
  • Typical N-hydroxymethyl aromatic amides operable as reactants herein include o l; c NHOHzOH o t 01 Nnomon I -hNHoH20H Br o o mNd-@-gnnomon 6 ONHCH2OH or or It or CNHCHOH ll o1 CNHCH2OH Br c o H0CHzNHC@-&NHCH2OH I -dNHoHl0rr Nnomon l 1 JNHCHzOH gNnomorr or or a o HOCHzNH Jinnomorr 0 1% HO GHzHN NHCHzOH HOCH2HN?
  • One or more of the 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.
  • Cellulosic textile materials may be made flame retardant by way of a variety of methods.
  • 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(NO -6H O and squeezed on a two roll padder to 70-90% wet weight pick-up.
  • 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 5 to about 40% and preferably about 10 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 and analogous man-made fibers.
  • cellulosic materials applicant intends to embrace cotton, rayon, paper, regenerated cellulose and cellulose derivatives which retaina 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 thermoplastic, thermosetting or elastomeric 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, Z-methylpropene-l, S-methylbutene-l, 4-methylpentene-l, 4-methyl-hexene-1, S-methylhexene-l, bicyclo-(2.2.1)-2-heptene, butadiene, pentadiene, hexadiene, isoprene, 2,3-dimethylbutadiene-l,3, 2- methylpentadiene-l,3, 4-vinylcyclohexene vinylcyclohexene, cyclopentadiene, styrene and methylstyrene, and the like.
  • Suitable monomers are ethylene, propylene, butene, pen
  • 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 cellu lose acetate, cellulose acetate butyrate, cellulose nitrate, ethyl cellulose, hydroxyethyl cellulose, methyl cellulose and sodium carboxymethyl cellulose; epoxy resins; furan resins (furfuryl alcohol or furfural-ketone); hydrocarbon resins from petroleum; isobutylene resins (polyisobutylene); isocyanate resins (polyurethanes);
  • 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-acrylonitrile 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, b'utadiene rubbers, e.g., styrene-butadiene rubber, isobutylene polymers, polybutadiene polymers, polyisobutylene 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 supporting cylindrical test specimens 70-150 mm. x 8.0 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:
  • 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 plastic samples of -200 mm. x 8 mm. 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 samples 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.
  • thermometer thermometer, and reflux condenser.
  • the mixture was warmed to and maintained at about 130 C. for about five hours. After cooling the mixture was stripped, at 120 C. and 2 mm. Hg, to remove phenol and other volatile material.
  • the stripped product was identified by elemental analysis as N-(diphenylphosphonomethyl)-p-toluamide and was obtained in 85.3 yield.
  • EXAMPLE X Preparation of EXAMPLE XI Forty parts of N-dimethylphosphonomethy1-2,4-dichlorobenzamide was mixed with 60 parts of polypropylene and dry blended for about five minutes. This mixture was then heated to a melt and mixed well in the molten state for about fifteen minutes. The mixture was then allowed to cool to room temperature and the plastic composition was cut into small pieces. These pieces were placed slowly into a glass tube (9 mm.) immeresd in a hot metal bath, the temperature of the bath being maintained above the melt temperature of the plastic composition. Pieces of the composition were added until the melt had a depth of approximately 200 mm. A metal rod was then placed in the tube with a. weight attached and the tube cooled to solidify the composition. The composition was then removed from the tube and tested by ASTM tests 132863-70 and D635-68. The results of the testing are contained in Table I.
  • EXAMPLE XXX N-dimethyl phosphonomethyl-p-toluamide (25 g.) was mixed with 40% formalin solution (37.5 g.) and stirred overnight at pH 10. The pH was adjusted to 7.0 with hydrochloric acid and 3.1 g. of ammonium chloride and 14.0 g. of a solution of a methylolated melamine added. 5.0 oz. sq. yd. cotton sheeting was immersed in the solution and the excess squeezed from the cloth by passing through a two roll laboratory pa-dder at lb. gauge pressure, to a wet pick-up of about The sheeting was then dried at about 250 F. for about 2 minutes and cured at about 340 F. for about 5 minutes in a circulating air oven. The sheeting was then washed by hand for about 5 minutes in a detergent (Tide) water mixture and tumble dried. A resin pick-up of 23.7% was calculated.
  • the then treated sheeting was thereafter subjected to ASTM test D2863-70 and AATCC test 34- 1969 with initial results as indicated in Table II.
  • the cotton sheeting was thereafter subjected to four additional hand washes, as above described, and tested under AATCC test 34- 1969.
  • EXAMPLE XXXIV Rayon staple fiber was immersed in the solution described in Example XXX and squeezed on a two roll laboratory padder at about 60 lb. gauge pressure to a wet pick-up of about 100%. The fiber was then dried for about 3 minutes at about 250 F. and cured for about minutes at about 350 F. in a circulating air oven. The fiber was then washed by hand for about 5 minutes in a hot detergent (Tide) water mixture and dried in the circulating air oven resulting in an add-on of about 13.8%. The fiber was then tested for flammability by holding one end of a treated sample in a benson flame for about 2 sec. and then removing and observing the sample. Treated samples self-extinguish immediately untreated samples are completely consumed.
  • Tide hot detergent
  • the fiber was then further tested for durability by subjecting it to a 5 complete wash cycles in a standard, home type automatic washer using Tide detergent. There after the fiber was tested for flammability as previously described. The results of testing is tabulated in Table II.
  • XXXIIL do Same as above.. Y 18. 6 B B 16 TABL-E II-Continued Flammability tesling Percent OI 6 home Example Textile Compound add-on initial Initial washes XXXIV.. Rayon (staple) (11]) 13. 8 23 SE SE oH,-@-ANHCH,P OGH,
  • a compound of claim 1 of the formula 1 A compound of the formula XI 0 f nnomi womorbcnm (ROhl CHINH -I I 25 wherein R is selected from the group consisting of phenyl, lower alkenyl and halogen substituted and unsubstituted lower alkyl of 1-6 carbon atoms, X is selected (3H, from the group consisting of chlorine, bromine and lower alkyl of 1-6 carbon atoms, in is an integer from 1-4 and n is an integer from 0-5, provided that the sum m and n A compound of 01mm 1 of the formula is not greater than 6 and when m is 1, X is greater than 0.
  • a om d of claim 1 of the formula c pouno 9.

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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)
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  • Fireproofing Substances (AREA)

Abstract

NEW COMPOUNDS ARE DISCLOSED OF THE FORMULA:

((R-O-)2-P(=O)-CH2-NH-CO-)M,(X)N-BENZENE

WHEREIN R IS SELECTED FROM THE GROUP CONSISTING OF PHENYL, LOWER ALKENYL AND HALOGEN SUBSTITUTED AND UNSUBSTITUTED LOWER ALKYL OF 1-6 CARBON ATOMS, X IS SELECTED FROM THE GROUP CONSISTING OF CHLORINE, BROMINE AND LOWER ALKYL OF 1-6 CARBON ATOMS, M IS AN INTEGER FROM 1-4 AND N IS AN INTEGER FROM 0-5, PROVIDED THAT THE SUM OF M AND N IS NOT GREATER THAN 6 AND WHEN M IS 1, X IS GREATER THAN O. THE COMPOUNDS OF THIS INVENTION ARE USEFUL AS FLAME RETARDANT AGENTS FOR TEXTILE MATERIALS AND IN THE PRODUCTION OF POLYMERS AND COPOLYMERS WHICH POSSESS FLAME RETARDANT PROPERTIES.

Description

United States Patent 3,803,269 DIALKYL AROMATIC AMIDOMETHYL PHOSPHONATES Peter Golborn, Lewiston, and James J. Dufiy, Butfalo, N.Y., assignors to Hooker Chemical Corporation, Niagara Falls, N.Y. No Drawing. Filed Mar. 30, 1972, Ser. No. 239,784 Int. Cl. C07f 9/40; C08f 45/58 US. Cl. 260- 932 11 Claims ABSTRACT OF THE DISCLOSURE New compounds are disclosed of the formula:
l: ll
wherein R is selected from the group consisting of phenyl, lower alkenyl and halogen substituted and unsubstituted lower alkyl of l-6 carbon atoms, X is selected from the group consisting of chlorine, bromine and lower alkyl of l-6 carbon atoms, m is an integer from 1-4 and n is an integer from 0-5, provided that the sum of mand n is not greater than 6 and when m is 1, X is greater than 0. The compounds of this invention are useful as flame retardant agents for textile materials and in the production of polymers and copolymers which possess flame retardant properties.
FIELD OF INVENTION This invention relates to novel compounds of the formula wherein R is selected from the group consisting of phenyl, lower alkenyl, and halogen substituted and unsubstituted lower alkyl of 1-6 carbon atoms, X is selected from the group consisting of chlorine, bromine and lower alkyl of l-6 carbon atoms, m is an integer from 1-4 and n is an integer from 0-5, provided that the sum of m and n is not greater than 6 and when m is l, X is greater than 0. The invention includes methods of applying the above novel compounds to normally flammable textiles, thermoplastic, thermosetting, and elastomeric resin compositions so as to render them flame retardant.
BACKGROUND OF THE INVENTION Many flame retarding agents and methods of application have been developed in attempts to obtain flame resistant textile materials and thermoplastic, thermosetting, and elastomeric resin compositions.
=Flame retardant textiles have been producedby 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 titanium dioxide. Such posprocesses require plural treatment baths in which strongly acidic solutions are employed thus posing the problem of possible textile degradation. Furthermore, metal oxide coatings on textile materials create difiiculties in subsequent dyeing processes which deleteriously atfect the hand of the finished product. Another process involves the use of a single processing bath wherein a dispersion of a chlorinated hydrocarbon and finely divided antimony oxide is padded on the textile material. Near the textile ice combustion temperature 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 hydrocarbon and finely divided antimony oxide are not acceptable finishes for closely woven textiles as they deleteriously affect 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.
The production of thermoplastic, thermosetting, and elastomeric resin compositions which are flame retardant is of considerable commercial importance. For example, such 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 elasotmeric 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 paraflin 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% of additive, must be incorporated into the resin in order to make it sufi'iciently flame retardant. Such large amounts of additive may deleteriously atfect 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.
OBJECTS OF THE INVENTION It is, therefore, a principal object of this invention to provide novel compounds of the formula:
I 0 O [(R Ohi CHzNH wherein R is selected from the group consisting of phenyl, lower ralkenyl and halogen substituted and unsubstituted lower alkyl of 1-6 carbon atoms, X is selected from the group consisting of chlorine, bromine and lower alkyl of 1-6 carbon atoms, m is an integer fiom 14 and n is an integer from 0-5, provided that the sum of m and n is not greater than 6 and when m is l, X is greater than 0.
It is also an object of this invention to provide flame retarding textile materials comprising normally flammable cellulosic, proteinaceous or analogous man-made materials. Another object is to provide a method for treating normally flammable cellulosic, proteinaceous or analogous man-made materials to render them flame retardant. Another object is to provide flame retarding thermoplastic, thermosetting or elastomeric resin compositions comprisnormally flammable resin materials. A further object is to provide a process for treating normally flammable thermoplastic, thermosetting or elastomeric resin compositions to render them flame retardant. A particular object is to devise a composition comprising normally flammable cellulosic, proteinaceous or analogous man-made materials and an effective flame retardant amount of the compound represent by the formula 0 noni onmn I DESCRIPTION OF THE INVENTION In accordance with this invention there are provided novel compounds, for imparting flame retardancy to textiles and resin materials, of the formula i 3 [(RO): CHrNH Jm I wherein R is selected from the group consisting of phenyl, lower alkenyl and halogen substituted and unsubstituted lower alkyl of 1-6 carbon atoms, X is selected from the group consisting of chlorine, bromine and lower alkyl of 1-6 carbon atoms, m is an integer from 1-4 and n is an integer from 0-5, provided that the sum of m and n is not greater than 6 and when m is 1, X is greater than 0.
More specifically, the preferred compounds of the present invention include these compounds wherein R is lower alkyl, allyl, chlorinated alkyl or phenyl, and X is chlorine, bromine or methyl.
Illustrative examples of compounds of the present invention include, for instance, compounds of the general formula such as 0 a @iinnomiwoomwm:
o @bnnomr o omcmem I'tr Br Br Br Br 0 0 Br( LNHCHzIi (O omon=onm 0 l BQANHCHQPMCHZCHDI (F-NHCHr-P (O CHzCHs)! H -@i ama).
Br Br 0 O NH-OHg-IH (OCH:CH= CH2):
ONE-CHz-P (O CHzCH=CH2h The synthesis of the compositions of the present invention is accomplished by reacting an N-hydroxymethyl aromatic amides of the formula l-o nnomonl with a trialkyl phosphite of the formula wherein R, m, n and X are as previously described in a suitable solvent, excess of the phosphite or neat. Typically, 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 80 C. to about 120 C. The solvent or other volatiles is thereafter stripped, or otherwise removed from the product. Suitable solvents include benzene, toluene, xylene, glymes, dimethylformamide, aliphatic or aromatic hydrocarbons. Typical N-hydroxymethyl aromatic amides operable as reactants herein include o l; c NHOHzOH o t 01 Nnomon I -hNHoH20H Br o o mNd-@-gnnomon 6 ONHCH2OH or or It or CNHCHOH ll o1 CNHCH2OH Br c o H0CHzNHC@-&NHCH2OH I -dNHoHl0rr Nnomon l 1 JNHCHzOH gNnomorr or or a o HOCHzNH Jinnomorr 0 1% HO GHzHN NHCHzOH HOCH2HN? One or more of the 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.
Cellulosic textile materials may be made flame retardant by way of a variety of methods. Products of this invention may be applied to cellulosic materials in several ways to give a durable flame retardant treatment. For example, 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. Alternatively 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.
More preferably the 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(NO -6H O and squeezed on a two roll padder to 70-90% wet weight pick-up. 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 5 to about 40% and preferably about 10 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 and analogous man-made fibers. By cellulosic materials, applicant intends to embrace cotton, rayon, paper, regenerated cellulose and cellulose derivatives which retaina cellulose backbone of at least one hydroxy substituent per repeating glucose unit. By 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, thermosetting or elastomeric 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. Generally, 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, Z-methylpropene-l, S-methylbutene-l, 4-methylpentene-l, 4-methyl-hexene-1, S-methylhexene-l, bicyclo-(2.2.1)-2-heptene, butadiene, pentadiene, hexadiene, isoprene, 2,3-dimethylbutadiene-l,3, 2- methylpentadiene-l,3, 4-vinylcyclohexene vinylcyclohexene, cyclopentadiene, styrene and methylstyrene, and the like.
Other 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 cellu lose acetate, cellulose acetate butyrate, cellulose nitrate, ethyl cellulose, hydroxyethyl cellulose, methyl cellulose and sodium carboxymethyl cellulose; epoxy resins; furan resins (furfuryl alcohol or furfural-ketone); hydrocarbon resins from petroleum; isobutylene resins (polyisobutylene); isocyanate resins (polyurethanes); melamine resins such as melamine-formaldehyde and melamine-ureaformaldehyde; oleo-resins phenolic resins such as phenolformaldehyde, phenolic elastomer, phenolic-epoxy, phenolic-polyamide, and phenolic-vinyl acetals; polyamide polymers, such as polyamides, polyamide-epoxy and particularly long chain synthetic polymeric amides containing recurring carbonamide groups as an integral part of the main polymer chain; polyester resins such as unsaturated polyesters of dibasic acids and dihydroxy compounds, and polyester elastomer and resorcinol resins such as resorcinol-formaldehyde, resorcinol furfural, resorcinol-phenol-formaldehyde, resorcinol-polyamide and resorcinol-urea; rubbers such as natural rubber, synthetic polyisoprene, reclaimed rubber, chlorinated rubber, polybutadiene, cyclized rubber, butadiene-acrylonitrile rubber, butadiene-styrene rubber, and butyl rubber; neoprene rubber (polychloroprene); polysulfides (Thiokol); terpene resins; urea resins; vinyl resins such as polymers of vinyl acetal, vinyl acetate or vinyl alcohol-acetate copolymer, vinyl alcohol, vinyl chloride, vinyl butyral, vinyl chloride-acetate copolymer, vinyl pyrrolidone and vinylidene chloride copolymers; polyformaldehyde; polyphenylene oxide; polymers of diallyl phthalates and phthalates; polycarbonates of phosgene or thiophosgene and dihydroxy compounds such as =bisphenols, phosgene, thermoplastic polymers of bisphenols and epichlorohydrin (trade named Phenoxy polymers); graft copolymers and polymers of unsaturated hydrocarbons and unsaturated monomer, such as graft copolymers of polybutadiene, styrene and acrylonitrile, commonly called ABS resins; ABS polyvinyl chloride polymers, recently introduced under the trade name of Cycovin; and acrylic polyvinyl chloride polymers, known by the trade name Kydex 100.
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-acrylonitrile 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, b'utadiene rubbers, e.g., styrene-butadiene rubber, isobutylene polymers, polybutadiene polymers, polyisobutylene rubbers, polyisoprene rubbers; polysulfide rubbers; silicon rubbers; urethane rubbers; high styrene resins latices, high styrene resins, vinyl resins; sponge rubber; and the like.
It should be noted that it is also within the scope of the present invention to incorporate such ingredients as plasticizers, dyes, pigments, stabilizers, antioxidants, antistatic agents and the like to the novel composition.
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 8.0 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:
It, percent: (x0 K ri- 2) 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 plastic samples of -200 mm. x 8 mm. 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. A sample is rated NB(non-burning) if, upon ignition it does not burn to the first point.
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 samples 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.
In all the examples of the application, the following general procedure was used except when otherwise specifically noted. Padding was done on a standard two roll laboratory padder at a gauge pressure of about 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 a standard, home, top loading, automatic washer and dryer. The following examples are set forth for purposes of illustration only and are not to be construed as limitations of the present invention except as set forth in the appended claims. All parts and percentages are by weight unless otherwise specified.
EXAMPLE I Preparation of EXAMPLE II Preparation of II (l3NHOHzP(O CHzCHzCHzCHa):
Following the procedure described in Example I 69 g. (0.3 mole) of 3-bromo-N-hydroxymethyl benzamide was refluxed with 80 g. (0.35 mole) of tri-n-butyl phosphite for about 5 hours at about 125 C. n-Butanol and excess tri-n-butyl phosphite were removed by stripping the reaction mixture at 115 C. under a vacuum of 0.5 mm. mercury. After stripping 121 g. of a pale yellow viscous liquid was obtained which was confirmed, by elemental analysis to be the desired product.
EXAMPLE III Preparation of C-NHCHrIi (O CHQM A 500 m1. flask, fitted with a reflux condenser, mechanical stirrer and thermometer, was charged with 124 g. 1.0 mole) of trimethyl phosphite and Was heated to about 100 C. 61.8 g. (0.3 mole) of 2,4-dichloro-N-hydroxymethyl benzamide was added to the trimethyl phosphite, over a period of about 5 minutes. The homogeneous reaction mixture was then refluxed at about 93 C. for 3 hours and thereafter stripped, under a reduced pressure of about 0.5 mm. Hg at about C., to give 93 g. of a tacky solid. Recrystallization of the solid from benzene of cyclohexane (1:1) gave 828 g. of dimethyl 2,4-dichlorobenzamidomethyl phosphonate.
EXAMPLE IV Preparation of i i? i i (HzCO)zPCHzHNC CNHCH2P OCH3 Q A 250 ml. flask was charged with 62 g. (0.5 mole) of trimethyl phosphite and was heated to about 100 C. 29 g. (0.1 mole) of bis-N,N-hydroxymethyl tetrachloroterephthalamide was added to the flask and the reaction mixture was refluxed for about 6 hours and then cooled to room temperature. Unreacted solids were filtered ofl and the filtrate was stripped, at 70 C. under 2 mm. mercury of reduced pressure, to give 12.0 g. of a tacky solid prodnot which was found, by infrared and nuclear magnetic resonance spectroscopy to be substantially pure desired product.
10 EXAMPLE V Preparation of A 250 ml. flask was charged with 21.9 g. (0.1 mole) of 2,4-dichloro-N-hydroxymethyl benzamide and 27 g. (0.1 mole) of tris-Z-chloroethyl phosphite. This reaction mixture was heated at about 130 C. for about 4 hours then stripped, at C. under a vacuum of 1.3 mm. mercury, to give 41 grams of a white solid. The product was proven, by elemental and infrared and nuclear magnetic resonance spectroscopy, to be substantially pure desired product.
EXAMPLE VI Preparation of II II ONHCHaP(OCH2CH=OHz)a A 250 ml. flask was charged with 16.5 g. (0.1 mole) of N-hydroxymethyl-p-toluamide and 40.2 g. (0.2 mole) of triallyl phosphite and this reaction mixture was heated at about C. for about 4 hours. Excess triallyl phosphite and allyl alcohol were removed by stripping, at 100 C. under a vacuum of 2 mm. mercury, to yield a thick yellow oil product. The product was confirmed by infrared and nuclear magnetic resonance spectroscopy and elemental analyses.
EXAMPLE VII Preparation of O iNHCHzi fl) CHa):
I OH;
A 500 ml. flask, equipped with mechanical stirrer, thermometer and reflux condenser, was charged with 66 g. (0.4 mole) of N-hydroxymethyl p-toluamide and 124 g. (1.0 mole) of trimethyl phosphite. This reaction mixture was refluxed for about 4 hours then stripped, at 70 C. under 0.2 mm. mercury vacuum, to give 95 g. of a low melting solid. Elemental analysis with infrared and nuclear magnetic resonance spectroscopy confirmed the structure of the product.
EXAMPLE VIII Preparation of (3H3 Triphenyl phosphite (62 g., 0.2 mole), was mixed with N-hydroxymethyl-p-toluamide in a 250 ml. round bottomed three necked flask fitted with mechanical stirrer,
thermometer, and reflux condenser. The mixture was warmed to and maintained at about 130 C. for about five hours. After cooling the mixture was stripped, at 120 C. and 2 mm. Hg, to remove phenol and other volatile material. The stripped product was identified by elemental analysis as N-(diphenylphosphonomethyl)-p-toluamide and was obtained in 85.3 yield.
EXAMPLE IX Preparation of A mixture of 44.8 g. (0.2 mole) of N,N-bis-hydroxymethyl terephthalamide and 124 g. (1.0 mole) of trimethyl phosphite was refluxed for about 6 hours. After the completion of the reaction the mixture was stripped, at 120 C. and 1 mm. Hg, to remove excess phosphite and other volatiles. The product was confirmed by infrared and nuclearmagnetic resonance spectroscopy.
EXAMPLE X Preparation of EXAMPLE XI Forty parts of N-dimethylphosphonomethy1-2,4-dichlorobenzamide was mixed with 60 parts of polypropylene and dry blended for about five minutes. This mixture was then heated to a melt and mixed well in the molten state for about fifteen minutes. The mixture was then allowed to cool to room temperature and the plastic composition was cut into small pieces. These pieces were placed slowly into a glass tube (9 mm.) immeresd in a hot metal bath, the temperature of the bath being maintained above the melt temperature of the plastic composition. Pieces of the composition were added until the melt had a depth of approximately 200 mm. A metal rod was then placed in the tube with a. weight attached and the tube cooled to solidify the composition. The composition was then removed from the tube and tested by ASTM tests 132863-70 and D635-68. The results of the testing are contained in Table I.
EXAMPLES X-H-XXIX Various additive compounds were mixed and treated with various resins according to the method of Example XI. Table I tabulates the results of testing by ASTM tests D2863-70 and 'D635-68 for Examples XIIXXIX.
EXAMPLE XXX N-dimethyl phosphonomethyl-p-toluamide (25 g.) was mixed with 40% formalin solution (37.5 g.) and stirred overnight at pH 10. The pH was adjusted to 7.0 with hydrochloric acid and 3.1 g. of ammonium chloride and 14.0 g. of a solution of a methylolated melamine added. 5.0 oz. sq. yd. cotton sheeting was immersed in the solution and the excess squeezed from the cloth by passing through a two roll laboratory pa-dder at lb. gauge pressure, to a wet pick-up of about The sheeting was then dried at about 250 F. for about 2 minutes and cured at about 340 F. for about 5 minutes in a circulating air oven. The sheeting was then washed by hand for about 5 minutes in a detergent (Tide) water mixture and tumble dried. A resin pick-up of 23.7% was calculated.
TABLE I Flammability Percent tests additive Example Polymer Additive (by weight) OI D-635 XI Polypropylene-.-.. (a ('1' 40 19.8 SE
mQ-onnommoomn XII. Nylon (a n 30 26.6 NB
@omzromriocnm XIII Polyethylene 0 O 30 28 NB terephthalate. II
, NHCHaP(OCHz)2 XIV ABS (1? n 30 24 NB @ormommoom V N lon Same as abov 30 25 NB VI. Pglyethylene do 30 36 NB terephthalate.
XVII ABS. 8 l? 40 22.3 SE
@ounomiwoomomomomn B e b n 40 26 NB a?! amdflasa w an 29 NB XX Polystyrene (a t: 30 23.3 5E
om-@-onnomr oomh xxx; Polyethylene o to 29.4 NB
terephthalete; ll
TABLE I-Continued Flammability Pegging; tests a Example Polymer Additive (by weigh t) OI D-635 XXII Epoxy O 30 24.7 SE
II H CH3 CNHCHP O- XXIII --d0 i) (H) (I? (H) 30 28 SE (H3002)rename-@ormommocnm XXIV Polyethylene Same as above 30 27.5
terephthalate.
XXV ABS do 40 SE XXVI Polystyrene (i (d (I). 3 40 SE mo=o11omo P camera-@omaomr (0 ornon=om XXVII ABS Same as above 80 24.3
XXVIII.--. Polystyrene (II; 1" 40 23.8
(ll-@O-NHCHA (0 crncmoi XXIX SBR Same as above 30 24.1 SE
The then treated sheeting was thereafter subjected to ASTM test D2863-70 and AATCC test 34- 1969 with initial results as indicated in Table II. The cotton sheeting was thereafter subjected to four additional hand washes, as above described, and tested under AATCC test 34- 1969.
EXAMPLES XXXI-XXXIII Using the method of Example 30, oz. per sq. yard cotton sheeting was treated with various compounds and subjected to ASTM test D286370 and AATCC test 34- 1969. The results therefore are indicated in Table II.
EXAMPLE XXXIV Rayon staple fiber was immersed in the solution described in Example XXX and squeezed on a two roll laboratory padder at about 60 lb. gauge pressure to a wet pick-up of about 100%. The fiber was then dried for about 3 minutes at about 250 F. and cured for about minutes at about 350 F. in a circulating air oven. The fiber was then washed by hand for about 5 minutes in a hot detergent (Tide) water mixture and dried in the circulating air oven resulting in an add-on of about 13.8%. The fiber was then tested for flammability by holding one end of a treated sample in a benson flame for about 2 sec. and then removing and observing the sample. Treated samples self-extinguish immediately untreated samples are completely consumed.
The fiber was then further tested for durability by subjecting it to a 5 complete wash cycles in a standard, home type automatic washer using Tide detergent. There after the fiber was tested for flammability as previously described. The results of testing is tabulated in Table II.
EXAMPLES XXXV-XXXIV Using the method of Example XXXIV, rayon staple fiber was treated with various compounds and subjected to ASTM test D2863- and AATCC test 34-1969. The results are shown in Table II.
EXAMPLE XXXVII N-diallyl phosphonomethyl-p-toluamide (19 g.) was mixed with 40% formalin solution (28.5 g.) and stirred overnight at pH 10. The pH was brought to 7.0 with hydrochloric acid and ammonium chloride (2.4 g.) and a 50% solution of a methylolated melamine (10.9 g.) added.
6.0 oz. sq. yd. wool was immersed in the above solution, squeezed on a 2 roll laboratory padder to a wet pick-up of about dried for about 2 minutes at about 250 F. and cured for about 5 minutes at about 350 F. in a circulating air oven. The wool was then Washed for one wash cycle using Tide, in a standard, home type, automatic washer and tumble dried. The resin add-on was calculated as 25.3%.
The thus treated wool was thereafter subjected to ASTM test D2863-70 and AATCC test 34-1969. The wool was then subjected to four additional one cycle washings in a standard home type automatic washer, as above described, and thereafter tested by AATCC test 34-1969. Test results are tabulated in Table II.
TABLE II Flammability testing Percent OI 5 home Example Textile Compound add-on initial Initial washes XXX Cotton (5 oz.) (H) (H) 23. 7 22. 2 4. 9 6. 0
era-@omromr 0 cm).
XXXI...-. do (I? 54 27 1. 0 3. 1
@onnomr 0 cm):
XXXII do (III! (I) O (I? 20. 2 21. 9 4. 1 5. 0
(H O 0;)1 CHzHN-@(%NHCH|P (0 CH):
XXXIIL: do Same as above.. Y 18. 6 B B 16 TABL-E II-Continued Flammability tesling Percent OI 6 home Example Textile Compound add-on initial Initial washes XXXIV.. Rayon (staple) (11]) 13. 8 23 SE SE oH,-@-ANHCH,P OGH,
XXXV do f 0 o (I? 19.8 22.7 SE SE (0H,=cH-cH,0),POH,NH&@ANHCH;P(00H=GH=0H):
XXXVI ..do Sameasab0ve Y 18.9 B B XXXVII. Wool (6 oz.).....; 0 3 25.3 5.0 5. 0
cnp rmcmmoomorr=om We claim: 7. A compound of claim 1 of the formula 1. A compound of the formula XI 0 f nnomi womorbcnm (ROhl CHINH -I I 25 wherein R is selected from the group consisting of phenyl, lower alkenyl and halogen substituted and unsubstituted lower alkyl of 1-6 carbon atoms, X is selected (3H, from the group consisting of chlorine, bromine and lower alkyl of 1-6 carbon atoms, in is an integer from 1-4 and n is an integer from 0-5, provided that the sum m and n A compound of 01mm 1 of the formula is not greater than 6 and when m is 1, X is greater than 0.
2. A compound of claim 1 of the formula 0 0 O NHCHzPUJCHI):
nnomi wcm Br 40 S 3. A om d of claim 1 of the formula c pouno 9. A compound of clam 1 of the formula NHCHaIQWOCHzCHzCHaCE)! O o NHCHal !-(O@) 4. A compound of claim 1 of the formula 0 0 5 l JNHCHr-(0CH;):
c1 10. A compound of claim 1 of the formula 0 0 O 0 (H300): CHgNH NHCHzP(0CHa)s l 5. A co and of cl im 1 of the formula mp0 a c1 01 6o 11. A compound of claim 1 of the formula u i 3 i0 o mmnno nnomiuoonn, f
:(momnommi CH,NHt -@-GNHCH= (oomcmomn l l 6. A compound of claim 1 of the formula 0 0 ENHOHA (O CHzCH Cl);
References Cited ANTON H. SUTTO, Primary Examiner US. Cl. X.R.
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 1 3 03 2 9 DATED April 9, 1974 r (5) Peter Golborn and James J. Duffy It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column 1, line 25, change "X" to ---n---; line -48, change "X" to ---n--. Column 2, line 61, change "X" to --n---. Column 3, line 36, change "X" to ---n--- Column 15, line 32, change "X" to ---n--- Signed and Scaled this ninth Day of September 1975 [SEAL] Arrest:
RUTH C. MASON C. MARSHALL DANN Arresting Officer (rmrmr'sxr'rmer oj'lalems and Trademarks UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 03,2 9 t Hated April 9, 1974 I Peter Golborn et a]..
It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
1 Column 2, linevv 69, "compris'-" should read comprising Column 3, line 12, "obj cet" should read object Column 10, line 66, that portion of the formula reading should read Signed and sealed this 3rd day of September 1974 (SEAL) Attest:
MCCOY 1 1. GIBSON, JR. v c. MARSHALL DANN Attesting Officer Commissioner of Patents
US05239784 1972-03-30 1972-03-30 Dialkyl aromatic amidomethyl phosphonates Expired - Lifetime US3803269A (en)

Priority Applications (12)

Application Number Priority Date Filing Date Title
US05239793 US3823206A (en) 1972-03-30 1972-03-30 N-phosphonomethyl amides
US05239784 US3803269A (en) 1972-03-30 1972-03-30 Dialkyl aromatic amidomethyl phosphonates
JP3443173A JPS499090A (en) 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
FR7311582A FR2178236B1 (en) 1972-03-30 1973-03-30
NL7304500A NL7304500A (en) 1972-03-30 1973-03-30
DE2316043A DE2316043A1 (en) 1972-03-30 1973-03-30 PHOSPHONIC ACID COMPOUNDS, PROCESS FOR THEIR PRODUCTION AND THEIR USE AS FLAME PROTECTION AGENTS FOR TEXTILES AND THERMOPLASTIC, HEAT-CURABLE OR ELASTOMERIC RESINS
BE129535A BE797632A (en) 1972-03-30 1973-03-30 FLAMMATION-DELAYING ADDITIVES CONTAINING PHOSPHORUS
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
US05239793 US3823206A (en) 1972-03-30 1972-03-30 N-phosphonomethyl amides
US05239784 US3803269A (en) 1972-03-30 1972-03-30 Dialkyl aromatic amidomethyl phosphonates
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

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US05393868 Division US3895161A (en) 1972-03-30 1973-09-04 Flame retardant materials

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US3803269A true US3803269A (en) 1974-04-09

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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

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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

Country Status (8)

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

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US3935162A (en) * 1972-03-30 1976-01-27 Hooker Chemicals & Plastics Corporation Dialkyl aromatic amidomethyl phosphonate flame retardants
US3954860A (en) * 1973-08-06 1976-05-04 Monsanto Company Phosphorous compounds

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IT1019221B (en) * 1973-09-11 1977-11-10 Sumitomo Bakelite Co COMPOSITION OF NON-FLAMMABLE THERMOINDURENT RESIN AND PROCEDURE TO PRODUCE IT
DE2351295A1 (en) * 1973-10-12 1975-04-24 Bayer Ag N, N-BIS- (PHOSPHONOMETHYL) -ACRYLAMIDE
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 (en) * 1976-05-28 1982-08-20 Montedison Spa SELF-EXTINGUISHING POLYMERIC COMPOSITIONS
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 (en) * 2000-12-29 2004-02-20 Nylstar Sa PROCESS FOR PRODUCING STABILIZED POLYAMIDE COMPOSITIONS
ITMI20020734A1 (en) * 2002-04-08 2003-10-08 Eurotecnica Dev & Licensing S AROMATIC GLYCOLS AND PLIOLS PREPARATION PROCEDURE AND THEIR USE AS MONOMERS
US8247077B2 (en) 2008-04-10 2012-08-21 Ansell Protective Solutions Ab Chemical protective garment with added flash fire protection

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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
US3935162A (en) * 1972-03-30 1976-01-27 Hooker Chemicals & Plastics Corporation Dialkyl aromatic amidomethyl phosphonate flame retardants
US3954860A (en) * 1973-08-06 1976-05-04 Monsanto Company Phosphorous compounds

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Publication number Publication date
US3895161A (en) 1975-07-15
FR2178236B1 (en) 1976-09-10
JPS499090A (en) 1974-01-26
GB1432013A (en) 1976-04-14
DE2316043A1 (en) 1973-10-18
US3901650A (en) 1975-08-26
BE797632A (en) 1973-10-01
NL7304500A (en) 1973-10-02
CA1006171A (en) 1977-03-01
US3823206A (en) 1974-07-09
US3935162A (en) 1976-01-27
FR2178236A1 (en) 1973-11-09

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