US3901650A - Textile flame retardants - Google Patents

Textile flame retardants Download PDF

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Publication number
US3901650A
US3901650A US37482673A US3901650A US 3901650 A US3901650 A US 3901650A US 37482673 A US37482673 A US 37482673A US 3901650 A US3901650 A US 3901650A
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Prior art keywords
compound
article
textile
flame
flame retardant
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Peter Golborn
James J Duffy
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Occidental Chemical Corp
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Hooker Chemicals and Plastics Corp
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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 BE129535A priority patent/BE797632A/en
Priority to DE2316043A priority patent/DE2316043A1/en
Priority to NL7304500A priority patent/NL7304500A/xx
Priority to FR7311582A priority patent/FR2178236B1/fr
Application filed by Hooker Chemicals and Plastics Corp filed Critical Hooker Chemicals and Plastics Corp
Priority to US37482673 priority patent/US3901650A/en
Priority to US05393868 priority patent/US3895161A/en
Priority to US05/531,646 priority patent/US3935162A/en
Application granted granted Critical
Publication of US3901650A publication Critical patent/US3901650A/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.
  • v is an integer from 1-2 provided that when y is l.
  • 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.
  • the invention includes methods of applying the above novel compounds to normally flammable textiles and thermoplastic, thermosetting and elastomeric resin compositions so as to render them flame retardant.
  • 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 titanium dioxide.
  • Such processes 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 difficulties in subsequent dyeing processes which deleteriously affect 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 combustion temperature antimony oxide will react with hydrogen chloride generated by degradation of the chlorinated hydrocarbon.
  • 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 ofconsiderable commercial importance.
  • articles as castings, moldings. foamed or laminated structures and the like are required, or are at 2 least desired, to be resistant to fire and flame and to possess-the ability to endure heat without deterioration.
  • thermoplastic thermosetting and elastomeric resins so as to improve the flame retardancy thereof has been known.
  • Many compounds have been commercially available for such use. among them being chlorostyrene copolymers. chlorinated paraffin wax in admixture with triphenyl styrene. chlorinated paraffins and aliphatic antimonical compounds. as wel as antimony oxidechlorinated hydrocarbon mixtures.
  • chlorostyrene copolymers chlorinated paraffin wax in admixture with triphenyl styrene.
  • chlorinated paraffins and aliphatic antimonical compounds as wel as antimony oxidechlorinated 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 sufficiently flame retardant. Such large amounts of additive may deliteriously affect the physical characteristics of the thermoplastic resin.
  • the present invention relates to a group of compounds which may be added to thermoplastic resins in relatively small amounts and still produce satisfactory flame retardant compositions which will not crystallize nor oil out of the resin after incorporation therein.
  • R is selected from the group consisting of phenyl. lower alkenyl and halogen substituted and unsubstituted lower alkyl of l6 carbon atom.
  • y is an integer from l2 provided that when y is l.
  • R is selected from the group consisting of hydrogen. lower alkyl of 2-8 carbon atoms. benzyl. dialkylph osphonalkyl and phenoxymethylene and when y is 2.
  • R is lower alkylene of l4 carbon atoms.
  • thermo- DESCRIPTION OF THE INVENTION there are provided novel compounds, for imparting flame retardancy to textiles and resin materials.
  • novel compounds for imparting flame retardancy to textiles and resin materials.
  • of the formula compounds of the present invention include these compounds wherein R is lower alkyl of l-6 carbon atoms.
  • Illustrative examples of compounds of the present invention include. for instance. compounds of the general formula such as O O 0 ll ll ll
  • the synthesis of the compositions of the present in- ⁇ CflllOH is accomplished by reacting a N- hydroxymethyl amide of the formula ll RCNHCH OH with a trialkyl phosphite of the formula wherein R and R are as previously described in a suitable solvent an excess of phosphite or neat. Typically. the reaction occurs at elevated temperatures and is continued for about 1 to about 12 hours. Temperatures are generally about 5()C to about 160C. 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.
  • Suitable solvents include benzene. toluene. xylene. glymes. I dimethyl formamide. aliphatic or aromatic hydrocarbons.
  • Typical N-hydroxymethyl amides operable as reactants herein include ll CH CH -CH CH CN HCH- OH o i ll
  • 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 retardent 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 ofdifferent 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 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 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 catalyst such as NH Cl or Zn(NO,,) 6H O.
  • the cellulosic material is immersed in a aqueous solution of the methylol derivative. trimethylol melamine. and Zn(NO 6H O and squeezed on a two roll padder to 70-9071 wet weight pick-up.
  • the material is dried at 22()27()F for 1-3 minutes and cured at 3()()37()F for l6 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 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 ofcellulosic or proteinaceous materials with analogous manmade fibers.
  • eellulosic 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 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
  • the compounds of this invention may be incorporated into the thermoplastic resin in flame-retarding amounts. i.e. generally amounts ranging from about 571 by weight. to about 5071 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. octene. Z-methylpropene-l. 3- methylbutene-l. 4-methylpentene-l. 4-methylhexenel.5-methylhexene-l. bicyclo-(2.2.l )-2-heptene. butadiene. pentadiene. hexadiene. isoprene. 2.3- dimethylbutadiene-l.3. 2-methylpentadiene-l.3. 4- vinylcyclohexene. vinyleyclohexene. 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 ofaerylate esters and polymers of methacrylate esters. acrylate and methacrylate resins such as ethyl acrylate. nbutyl methacrylate. isobutyl methacrylate. ethyl methacrylate and methyl methacrylate; alkyd resins and pain vehicles. such as bodied linseed oil; cellulose derivatives such as cellulose acetate. cellulose acetate butyrate. cellulose nitrate. ethyl cellulose.
  • 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 resoreinol resins such as resorcinolformaldehyde. resorcinol-furfural. resorcinol-phenol-formaldehyde. resorcinolpolyamide and resoreinol-urea; rubbers such as natural rubber. synthetic polyisoprene. reclaimed rubber. chlorinated rubber. polybutadienc. cyclized rubber. butadieneacrylonitrile rubber.
  • 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 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; acrylonitrilebutadiene styrene terpolymers; butadiene-acrylonitrile copolymers; butyl rubber; chlorinated rubbers. e.g.. polyvinyl chloride resins, chloroprcne rubber. chlorosulfonated polyethylene; ethylene polymers. e.g.. ethylene-propylene copolymers. ethylene-propylene terpolymers: fluorinated rubbers. butadiene rubbers. e.g.. styrene-butadiene rubber. isobutylene polymers.
  • polystyrene polymers polysobutylene rubbers. polyisoprene rubbers; polysulfide rubbers; silicon rubbers; urethane rubbers; high styrene resins latices. high styrene resins. vinyl resins; sponge rubber; and the like.
  • 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 70150 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:
  • 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 D63568 used in accordance with the following examples. generally provides for the comparison of burning rates. selfextinguishment and non-burning characteristics of plastics in the form of sheets. bars. plates or panels.
  • the procedure encompasses preparing cylindrical plastic samples of l50200 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 angle in a controlled burner flame (1 inch flame length) for two 30 second attempts. The movement ofthe flame up the length of the sample through the two points is measured for rate of burning. non-burning or selfextinguishing characteristics.
  • a sample is rated SE(selfextinguishing) ifthe 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.
  • 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 determined the average tear length as representing the char 8 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.
  • Nhydroxymethyl formamide (0.5 mole) was mixed with trimethyl phosphite (0.5 mole) in a round bottomed. there necked flask fitted with a thermometer. reflux condenser with take off and a magnetic stirrer. The mixture was heated slowly to about 100C and distillate collected for about two hours. The distillate was identified by infrared analysis as methanol. After the distillate ceased the reaction mixture was heated to about 120C and held at that temperature for about 9% hour. The mixture was then stripped on a rotary evaporator at about 80C and 5 mm Hg. for about 1 hour to remove all volatiles. The resulting product was identified as N-dimethylphosphonomcthyl formamide and was obtained in 98% yield.
  • the structure was confirmed by elemental analysis and infrared and nuclear magnetic resonance spectroscopy to be N,NBis(dimethylphosphonomethyl) succinamide.
  • the product structure was confirmed by elemental analysis and infrared and nuclear magnetic resonance spectroscopy to diethylphosphonoacetamide.
  • Trimcthyl phosphite (62g 0.5 mole) was heated to about C in a round bottomed flask.
  • hydroxymethylphenoxyacetamide 54g, 03 mole was added over a 5.0 minute time period and the mixture heated at about 92 for about 2 hours. After the heating period the mixture was stripped, at 100C and 0.5 mm pressure. to give a 90% of the desired product.
  • N-diphenyl phosphonomethyl propionamide was prepared in 82.2% yield by heating N- 1 1 hydroxymethylpropionamide (0.2 mole) and triphenyl phosphite (0.2 mole) at about 130 for about hours. After the heating period was complete phenol was removed under reduced pressure (2 mm Hg) at 120. The product structure was confirmed by infrared and nuclear magnetic resonance spectroscopy.
  • the sheeting was squeezed to a wet pick-up by means of a two roll laboratory padder. and thereafter dried at about 250F 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 AATCC test method 34-1969 had a calculated char length of 5.5 inches.
  • wool Bedford cord was padded through the solution of Example XXVll and squeezed to 60% wet pick-up. After drying curing and washing as in Example XXVll 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 detergent 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 XXVlI and squeezed to weight gain. The sample was dried for 5 minutes at 240F and cured 10 minutes at 340F, washed in hot tap water. and dried to give a 32% add-on.
  • a treated sample is self-extinguishing if ignited is 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 ac etamide (0.2 mole) and 38% formalin solution (0.2 mole) in 50 g of water was refluxed about 1 hour at a pH of 9 and then stirred on additional 3 hours at room temperature. The pH was adjusted to 7.0 and 20g of trimethylolmelamine and 5g of magnesium chloride hexahydrate added. 5.0 02. cotton sheeting was padded through the solution and squeezed to a wet pick-up of on a two roll laboratory padder. The sheeting was then dried at about 240F for about 2 minutes and cured at about 350F 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.
  • EXAMPLE XXXl N.N'-bis-dimethylphosphonomethyl succinamide (40g) was mixed with 40% formalin solution (60g) and stirred overnight at a pH of 10. The pH was then adjusted to 7.0 with hydrochloric acid and 23g of a 50% solution of a methylolated melamine and 5g of ammonium chloride added.
  • treated wool was then dried at about 250F for about 2 minutes and cured at about 350F for about 4 minutes in a circulating air oven. The treated wool was then washed by hand for about five minutes using Tide de- 14 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 self-extinguishing characand found to have a calculated char length of 3.0 ter is maintained after live but water. hand washings.
  • 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.
  • a process for rendering textiles flame retardant which comprises applying to said textile a flame retardant amount of a compound of the formula wherein R is selected from the group consisting of phenyl, lower alkenyl and halogen substituted and unsubstituted lower alkyl of l6 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, lower dialkylphosphonoalkyl and phenoxymethylene and when y is 2.
  • R is lower alkylene of 1-4 carbon atoms.
  • acid textile is selected from the group consisting of cellulosic fibers, proteinaceous fibers and blends thereof.
  • An article comprising a textile selected from the group consisting of ccllulosic fibers. proteinaceous l'ibers and blends thereof and a flame retardant amount of a compound of the formula O 1
  • the article of claim 6 wherein said compound is 9.
  • the article of claim 6 wherein said compound is l ll ll (Cl h Ol PCH:NHC(.H CH:CNHCH PKX'HM 10.
  • the article of claim 6 wherein said compound is 11.
  • said compound is ll ll 13.
  • the article of claim 6 wherein said compound is 14.
  • the article of claim 6 wherein said compound is 15.
  • the article of claim 6 wherein said compound is 17.

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (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)
  • Fireproofing Substances (AREA)

Abstract

New flame retardant textile compositions and a process for the production thereof are disclosed wherein a compound 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, 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, lower dialkylphosphonoalkyl and phenoxymethylene and when y is 2, R is lower alkylene of 1-4 carbon atoms is applied to said textile.

Description

Uite States Golborn et a1.
atent [191 Aug. 26, 1975 1 TEXTILE FLAME RETARDANTS [75] Inventors: Peter Golborn, Lewiston; James J.
Duffy, Buffalo, both of N.Y.
[73] Assignee: Hooker Chemicals and Plastics Corporation, Niagra Falls, NY.
[22] Filed: June 29, 1973 [21] Appl. No.: 374,826
Related US. Application Data [62] Division of Scr. No. 239,793, March 30, 1972, Pat.
[52] US. Cl. 8/115.7; 8/116 P; 8/l27.5 A; 117/136; 252/8.1
[51] Int. Cl. D06m l/OO; D06m 3/00 [58] Field of Search 8/116 P, 127.5; 117/136, 117/1 15.7; 252/8.1
[56] References Cited UNITED STATES PATENTS 3,579.532 5/1971 Nacbur et a]. 260/932 X Primary ExuminerDonald Levy Attorney, Agent, or FirmPeter F. Casella; William J. Crossetta, Jr.
[ 5 7 ABSTRACT New flame retardant textile compositions and a process for the production thereof are disclosed wherein a compound of the formula 18 Claims, No Drawings TEXTILE FLAIWE RETARDANTS This is a division. of application Ser. No. 239.793, filed Mar. 30. I972 now US. Pat. No. 3.823.206. issued July 9. 1974.
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. v is an integer from 1-2 provided that when y is l. 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. The invention includes methods of applying the above novel compounds to normally flammable textiles and thermoplastic, thermosetting and elastomeric resin compositions so as to render them flame retardant.
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, thermo setting and elastomeric resin compositions.
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 titanium dioxide. Such processes 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 difficulties in subsequent dyeing processes which deleteriously affect 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 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 ofconsiderable commercial importance. For example. such articles as castings, moldings. foamed or laminated structures and the like are required, or are at 2 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. Many compounds have been commercially available for such use. among them being chlorostyrene copolymers. chlorinated paraffin wax in admixture with triphenyl styrene. chlorinated paraffins and aliphatic antimonical compounds. as wel as antimony oxidechlorinated 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 sufficiently flame retardant. Such large amounts of additive may deliteriously affect the physical characteristics of the thermoplastic resin. as well as substantially complicating and increasing the cost of preparation thereof. A further problem is that these prior art additives tend to crystallize or oil out of the resin after a relatively short time of incorporation. The present invention relates to a group of compounds which may be added to thermoplastic resins in relatively small amounts and still produce satisfactory flame retardant compositions which will not crystallize nor oil out of the resin after incorporation therein.
OBJECTS OF THE INVENTION It is. therefore. a principal object of this invention to provide 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 l6 carbon atom. y is an integer from l2 provided that when y is l. R is selected from the group consisting of hydrogen. lower alkyl of 2-8 carbon atoms. benzyl. dialkylph osphonalkyl and phenoxymethylene and when y is 2. R is lower alkylene of l4 carbon atoms.
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 analogeous man-made materials to render them flame retardant. Another object is to provide flame retarding thermoplastic, thermosetting or elastomeric resin compositions comprising normally flamma' ble 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 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. thermo- 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 compounds of the present invention include these compounds wherein R is lower alkyl of l-6 carbon atoms.
Illustrative examples of compounds of the present invention include. for instance. compounds of the general formula such as O O 0 ll ll ll The synthesis of the compositions of the present in- \CflllOH is accomplished by reacting a N- hydroxymethyl amide of the formula ll RCNHCH OH with a trialkyl phosphite of the formula wherein R and R are as previously described in a suitable solvent an excess of phosphite or neat. Typically. the reaction occurs at elevated temperatures and is continued for about 1 to about 12 hours. Temperatures are generally about 5()C to about 160C. 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. I dimethyl formamide. aliphatic or aromatic hydrocarbons. Typical N-hydroxymethyl amides operable as reactants herein include ll CH CH -CH CH CN HCH- OH o i ll 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 retardent 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 ofdifferent 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 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 cellulose substrate with the aid of an acidic catalyst by a padding 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 Cl or Zn(NO,,) 6H O. The cellulosic material is immersed in a aqueous solution of the methylol derivative. trimethylol melamine. and Zn(NO 6H O and squeezed on a two roll padder to 70-9071 wet weight pick-up. The material is dried at 22()27()F for 1-3 minutes and cured at 3()()37()F for l6 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 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 ofcellulosic or proteinaceous materials with analogous manmade fibers. By eellulosic 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. 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 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 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 571 by weight. to about 5071 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. octene. Z-methylpropene-l. 3- methylbutene-l. 4-methylpentene-l. 4-methylhexenel.5-methylhexene-l. bicyclo-(2.2.l )-2-heptene. butadiene. pentadiene. hexadiene. isoprene. 2.3- dimethylbutadiene-l.3. 2-methylpentadiene-l.3. 4- vinylcyclohexene. vinyleyclohexene. 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 ofaerylate esters and polymers of methacrylate esters. acrylate and methacrylate resins such as ethyl acrylate. nbutyl methacrylate. isobutyl methacrylate. ethyl methacrylate and methyl methacrylate; alkyd resins and pain vehicles. such as bodied linseed oil; cellulose derivatives such as cellulose acetate. cellulose acetate butyrate. cellulose nitrate. ethyl cellulose. hydroxyethyl cellulose..methyl cellulose and sodium carboxymethyl cellulose; epoxy resins; furan resins (furfuryl alcohol or furfuralketone); hydrocarbon resins from petroleum; isobutylene resins (polyisobutylene); isocyanate resins (polyurethanes); melamine resins such as melamineformaldehyde and melamine-urea-formaldehyde; oleoresins; phenolic resins such as phenol-formaldehyde. phenolic-elastomer. phenolic-epoxy. phenolicpolyamide. 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 resoreinol resins such as resorcinolformaldehyde. resorcinol-furfural. resorcinol-phenol-formaldehyde. resorcinolpolyamide and resoreinol-urea; rubbers such as natural rubber. synthetic polyisoprene. reclaimed rubber. chlorinated rubber. polybutadienc. cyclized rubber. butadieneacrylonitrile 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 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; acrylonitrilebutadiene styrene terpolymers; butadiene-acrylonitrile copolymers; butyl rubber; chlorinated rubbers. e.g.. polyvinyl chloride resins, chloroprcne 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. polysobutylene 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 70150 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:
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 D63568 used in accordance with the following examples. generally provides for the comparison of burning rates. selfextinguishment and non-burning characteristics of plastics in the form of sheets. bars. plates or panels. The procedure encompasses preparing cylindrical plastic samples of l50200 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 angle in a controlled burner flame (1 inch flame length) for two 30 second attempts. The movement ofthe flame up the length of the sample through the two points is measured for rate of burning. non-burning or selfextinguishing characteristics. A sample is rated SE(selfextinguishing) ifthe 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 determined the average tear length as representing the char 8 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.
1n 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. A Hooker Boil (HE) is done in a standard. center post. wringer washer fitted with internal steam coils. The sample to be treated is washed and agitated therein for 45 minutes in a solution containing 88 pounds of water. grams of sodium carbonate. 100 grams of Ivory soap and 10 grams ofTidedetergent at a temperature of about 200 to about 210 Fahrenheit. The washer is then drained. the sample squeezed through the wringer and again washed and agitated therein for 15 minutes in about 88 pounds of water at about to about Fahrenheit.
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 1 Preparation of I I HCNHCH HOCHM;
Nhydroxymethyl formamide (0.5 mole) was mixed with trimethyl phosphite (0.5 mole) in a round bottomed. there necked flask fitted with a thermometer. reflux condenser with take off and a magnetic stirrer. The mixture was heated slowly to about 100C and distillate collected for about two hours. The distillate was identified by infrared analysis as methanol. After the distillate ceased the reaction mixture was heated to about 120C and held at that temperature for about 9% hour. The mixture was then stripped on a rotary evaporator at about 80C and 5 mm Hg. for about 1 hour to remove all volatiles. The resulting product was identified as N-dimethylphosphonomcthyl formamide and was obtained in 98% yield.
EXAMPLE 11 Preparation of In a 500 ml. round bottomed flask was placed 81.9g (0.70 mole) of N-hydroxymethylbutyrlamide and 124g 1.0 mole) of trimethyl phosphite. The mixture heated to reflux and held at that temperature for about 6 hours. The reaction was then cooled stripped. at 100C and 2 mm Hg pressure. to remove any volatiles. Infrared and nuclear magnetic resonance spectroscopy identified the product as essentially pure N- 9 dimethylphosphonomethylbutyrlamide in 76.7% yield.
EXAMPLE 111 A flask. fitted with reflux condenser. stirrer and thermometer. was charged with 88g (0.5 mole) N.N-bis hydroxymethyl succinamide and 186g (1.5 mole) tri methyl phosphite and was refluxed at about 92 for about 4 hours. 100 mls. of toluene was added to the reaction and reflux was continued for 25 hours. The reaction mixture was cooled and solidified by addition of 500 mls. acetone. The reaction mixture was then filtered to give 12g solid (mp 236245). lnfrared spectra and elemental analysis indicated the solid was succinamide.
The filtrate was then stripped. under 10 mm Hg vacuum at 70C to give 182g of amber liquid. This liquid was further distilled under vacuum to remove excess trimethyl phosphite. After distillation 144g of amber liquid liquid remained.
The structure was confirmed by elemental analysis and infrared and nuclear magnetic resonance spectroscopy to be N,NBis(dimethylphosphonomethyl) succinamide.
EXAMPLE [V A 1 liter flask was fitted with reflux condenser, stirrer and thermometer. The flask was charged with 430g. (1.86 mole) of N-hydroxymethyl diethylphosphonoacetamide and 248g (2.0 mole) of trimethyl phosphite. The reaction mixture was heated for about 13 hours at about 105C. Excess trimethyl phosphite was removed by vacuum distillation to give 528.5g of a thick yellow liquid.
The product structure was confirmed by elemental analysis and infrared and nuclear magnetic resonance spectroscopy to diethylphosphonoacetamide.
EXAMPLE V Preparation of Trimethyl phosphite (2.0 mole) was mixed with N- hydroxymethyl-3-dimethylphosphonopropionamide (1.0 mole) in a 1 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.
After the heating period. when no more methanol was evident in the distillate. the excess phosphite was removed under reduced pressure. The product, a clear viscous oil. was obtained in 95% yield and was the structure N-dimethylphosphonomethyl-3-dimethyl phosphonopropionamide which was confirmed by elemental analysis and infrared spectroscopy.
EXAMPLE V1 Preparation of u it cmcmicn pux'nun EXAMPLE VII Preparation of g 0 ll OCH CNH(H. P(()CH;.)
Trimcthyl phosphite (62g 0.5 mole) was heated to about C in a round bottomed flask. N-
hydroxymethylphenoxyacetamide (54g, 03 mole) was added over a 5.0 minute time period and the mixture heated at about 92 for about 2 hours. After the heating period the mixture was stripped, at 100C and 0.5 mm pressure. to give a 90% of the desired product.
EXAMPLE V111 Preparation of N-hydroxymethyl phenyl acetamide 14.0g 0.085 mole)was heated with triphenyl phosphite (27g 0.085 mole) at 124C for about five hours in a round bottomed flask. The reaction mixture was then stripped. at 120C and 2 mm pressure. to remove phenol and other volatile material to give the desired product (29.4g). The product was confirmed by infrared and nuclear magnetic resonance spectroscopy.
EXAMPLE IX Preparation of In a 250 ml round bottomed flask 17.6g of N.N'-bis hydroxymethyl succinamide and 62g of triphenyl phosphite were heated at about C for about 5 hours. Upon completion of the heating the reaction mixture was stripped, at 120C and 2 mm Hg. to remove phenol and other volatile material. The product was a thick yellow semi solid and was obtained in 89.3% yield. The structure of the desired product was confirmed by spectroscopic and elemental analyses.
EXAMPLE X Preparation of 0 1| 1| CH:,CH2CNHCH2P(O)-,
N-diphenyl phosphonomethyl propionamide, was prepared in 82.2% yield by heating N- 1 1 hydroxymethylpropionamide (0.2 mole) and triphenyl phosphite (0.2 mole) at about 130 for about hours. After the heating period was complete phenol was removed under reduced pressure (2 mm Hg) at 120. The product structure was confirmed by infrared and nuclear magnetic resonance spectroscopy.
EXAMPLE Xl Preparation of Triallyl phosphite (40.2g 0.2 mole) was mixed with N-hydroxymethyl butyramide (23.4g 0.2 mole) in a round bottomed flask and heated about 4 hours at about 125C. At the end of this time the reaction mixture was stripped at about 125C and 2 mm pressure. The product obtained was a red-brown liquid and its structure was confirmed by a elemental analysis and infrared and nuclear magnetic resonance spectroscopy.
EXAMPLE XlI Preparation of A mixture of tris-2-chloroethyl phosphite (0.2 mole) and N,N-bis-hydroxymethyl succinamide (0.1 mole) was heated in a round bottomed flask at about 130C for about 6 hours. The reaction mixture was then stripped, at 100C and 2 mm Hg pressure. to remove any volatile material. 43 grams of N.N-bis-(2- chloroethyl)phosphonomethyl succinamide was obtained as a brown wax.
EXAMPLE Xlll EXAMPLES XIV-XXVI Using the procedure of Example 13. various plastic compositions were prepared and tested containing various flame retardants. The results are set forth in Table EXAMPLE XXVll 5.0 oz. cotton sheeting was padded through a solution containing 30 parts of N- dimethylphosphonomethyl-3- dimethylphosphonopropionamide. 10 parts of trimethylolmelamine, parts of 40% formalin solution. 25 parts of water and 5 parts of Zn(NO 6H O.
The sheeting was squeezed to a wet pick-up by means of a two roll laboratory padder. and thereafter dried at about 250F 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 AATCC test method 34-1969 had a calculated char length of 5.5 inches.
EXAMPLE XXVlll 8.0 oz. per sq. yd. wool Bedford cord was padded through the solution of Example XXVll and squeezed to 60% wet pick-up. After drying curing and washing as in Example XXVll 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 detergent 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 XXVlI and squeezed to weight gain. The sample was dried for 5 minutes at 240F and cured 10 minutes at 340F, washed in hot tap water. and dried to give a 32% add-on.
A treated sample is self-extinguishing if ignited is 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 ac etamide (0.2 mole) and 38% formalin solution (0.2 mole) in 50 g of water was refluxed about 1 hour at a pH of 9 and then stirred on additional 3 hours at room temperature. The pH was adjusted to 7.0 and 20g of trimethylolmelamine and 5g of magnesium chloride hexahydrate added. 5.0 02. cotton sheeting was padded through the solution and squeezed to a wet pick-up of on a two roll laboratory padder. The sheeting was then dried at about 240F for about 2 minutes and cured at about 350F 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.
EXAMPLE XXXl N.N'-bis-dimethylphosphonomethyl succinamide (40g) was mixed with 40% formalin solution (60g) and stirred overnight at a pH of 10. The pH was then adjusted to 7.0 with hydrochloric acid and 23g of a 50% solution of a methylolated melamine and 5g of ammonium chloride added.
6.0 oz. sq. yd. wool sample was padded through the solution and squeezed to about wet pick-up on a two roll laboratory padder at 60 lb. gauge pressure. The
13 treated wool was then dried at about 250F for about 2 minutes and cured at about 350F for about 4 minutes in a circulating air oven. The treated wool was then washed by hand for about five minutes using Tide de- 14 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 tergent and tumble dried. A resin add-on of 4192 and samples self-extinguished when a Bunsen flame was apoxygen index of 28 was calculated. The thus treated plied for 2 seconds and removed while untreated samwool was then subjected to AATCC method 34-1969 ples burned completely. The self-extinguishing characand found to have a calculated char length of 3.0 ter is maintained after live but water. hand washings.
TABLE I '7, Compound Example Polymer Compound in Mixture Ol D635 0 0 ll ll X111 Polystyrene CH lCHg cNHCH- PtOCH 30 Sl-I ll ll Xl\' Polypropylene CH;;(CH2)- -CNHCH2P( OCH2CH=CH) 40 SE 0 0 ll ll xv Epoxy CH CH CNHCH P o(-@ 1s SF.
0 O 0 II II I] H 25.5 NB X\'1 Polyethylene (C1CH2CH2O)2PCH2NHCCH2CH2CNHCH2P(OCH2CH2CU2 O O O 0 II II ll ll xvll Epoxy ld ()J PCH NHCCH CH CNHCH P(Oda): 23.5
O O ll ll X\'ll1 Nylon b CH-:CNHCH- P(Oda) 30 24.9 NB
0 ll ll xlx Polystyrene d CH- .CNHCH- P(OCH 40 19.4
O 0 ll ll xx Polyslyrene tbocH CNHcH P(oCH ,l. 40 20.5 XXI ABS ditto 40 20 O O O 0 ll ll ll ll X'Xll ABS ((H O) PCH NHC-CH CH C-NHCH P(OCH;,) 40 24.6 X'Xlll Nylon ditto 40 25.0 XXIV Polyethylene ditto 40 34 NB 'lcrephthalate XXV SBR ditto 30 "0." SE
0 O O O 11 11 ll ll XXVI Polypropylene (ClCll CH O) PCH NHCCH CH CNHCH P(CICH CH O) 30 3.5 SF.
inches. The treated wool was then subjected to 4 additional hand washes. on above described, and after testing by method 34-1969 had a char length of4.0 inches.
EXAMPLE XXXll A padding solution was prepared as in Example XXXI using N dimethylphosphonomethylbutyramide as the phosphorus containing species.
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 XXXlll We claim:
1. A process for rendering textiles flame retardant which comprises applying to said textile a flame retardant amount of a compound of the formula wherein R is selected from the group consisting of phenyl, lower alkenyl and halogen substituted and unsubstituted lower alkyl of l6 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, lower dialkylphosphonoalkyl and phenoxymethylene and when y is 2. R is lower alkylene of 1-4 carbon atoms.
2. The process of claim 1 wherein acid textile is selected from the group consisting of cellulosic fibers, proteinaceous fibers and blends thereof.
3. The process of claim 1 wherein about 5 to about 40% by weight compound is added on the textile.
4. The process of claim 3 wherein about 10 to about 25% by weight compound is added on the textile.
5. The process of claim 1 wherein the compound is mixed in an aqueous medium with trimethylol melamine and a Lewis acid catalyst and applied to the textile.
- 15 6. An article comprising a textile selected from the group consisting of ccllulosic fibers. proteinaceous l'ibers and blends thereof and a flame retardant amount of a compound of the formula O 1| ll HCNHCH HOCHM 8. The article of claim 6 wherein said compound is 9. The article of claim 6 wherein said compound is l ll ll (Cl h Ol PCH:NHC(.H CH:CNHCH PKX'HM 10. The article of claim 6 wherein said compound is 11. The article of claim 6 wherein said compound is 12. The article of claim 6 wherein said compound is ll ll 13. The article of claim 6 wherein said compound is 14. The article of claim 6 wherein said compound is 15. The article of claim 6 wherein said compound is l6. The article of claim 6 wherein said compound is 17. The article of claim 6 wherein said compound is l I CH CH CH CNHCH ltOCH CH=CH:)
18. The article of claim 6 wherein said compound is UNITED STATES PATENT OFFICE CERTIFICATE OF CGRRECTION PATENT NO. 3,901,650 DATED August 26, 1975 tNVENTOR($) 1 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:
In the 1t s tract R-- CNHCl-I P(0R') y should read R--CNH'CH2P(OR')2 y Column 6, line 13, "hexene, octane" should ead ---hexene, heptene, octene--- Table 1, Columns 13 and 14 the formula should read XVI Polyethylene Terephthalate HCNHCH P(OCH Signed and Sealed this A ttes t.
RUTH C. MASON C. MARSHALL DANN Allesting Officer Commissioner ofPatents and Trademarks UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION O PATENT NO. 3,901,650
DATED August 26, 1975 |N\/ENTOR(5) Peter Golborn and James J. Duffy it is certified that error appears in the above-identified patent and that said Letters Patent q are hereby corrected as shown below:
In the AQgtract II II II II I u CNHCH P(OR y should read Pc- CNHCH P(OR y Column 6, line 13, "hexene, octane" should read ---hexene, heptene, octene--- Table 1, Columns l3 and 14 the formula should read 0 O o n H XVI Polyethylene Terephthalate HCNI-ICH P(OCH ---a Signed and Scaled this y-Seventh D y f January 1976 [SEAL] Arrest:
m M c. MARSHALL DANN ff Commissioner ofParents and Trademarks

Claims (18)

1. A PROCESS FOR RENDERING TEXTILE FLAME RETARDANT WHICH COMPRISES APPLYING TO SAID TEXTILE A FLAME RETARDANT AMOUNT OF A COMPOUND OF THE FORMULA
2. The process of claim 1 wherein acid textile is selected from the group consisting of cellulosic fibers, proteinaceous fibers and blends thereof.
3. The process of claim 1 wherein about 5 to about 40% by weight compound is added on the textile.
4. The process of claim 3 wherein about 10 to about 25% by weight compound is added on the textile.
5. The process of claim 1 wherein the compound is mixed in an aqueous medium with trimethylol melamine and a Lewis acid catalyst and applied to the textile.
6. An article comprising a textile selected from the group consisting of cellulosic fibers, proteinaceous fibers and blends thereof and a flame retardant amount of a compound of the formula
7. The article of claim 6 wherein said compound is
8. The article of claim 6 wherein said compound is
9. The article of claim 6 wherein said compound is
10. The article of claim 6 wherein said compound is
11. The article of claim 6 wherein said compound is
12. The article of claim 6 wherein said compound is
13. The article of claim 6 wherein said compound is
14. The article of claim 6 wherein said compound is
15. The article of claim 6 wherein said compound is
16. The article of claim 6 wherein said compound is
17. The article of claim 6 wherein said compound is
18. The article of claim 6 wherein said compound is
US37482673 1972-03-30 1973-06-29 Textile flame retardants Expired - Lifetime US3901650A (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
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
NL7304500A NL7304500A (en) 1972-03-30 1973-03-30
FR7311582A FR2178236B1 (en) 1972-03-30 1973-03-30
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

Publications (1)

Publication Number Publication Date
US3901650A true US3901650A (en) 1975-08-26

Family

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Family Applications (5)

Application Number Title Priority Date Filing Date
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 (2)

Application Number Title Priority Date Filing Date
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

Family Applications After (2)

Application Number Title Priority Date Filing Date
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 (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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US4606853A (en) * 1983-08-11 1986-08-19 Imperial Chemical Industries Plc Fire retardant polyamide compositions

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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
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
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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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
US3803269A (en) * 1972-03-30 1974-04-09 Hooker Chemical Corp Dialkyl aromatic amidomethyl phosphonates

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Publication number Priority date Publication date Assignee Title
US4606853A (en) * 1983-08-11 1986-08-19 Imperial Chemical Industries Plc Fire retardant polyamide compositions

Also Published As

Publication number Publication date
US3895161A (en) 1975-07-15
JPS499090A (en) 1974-01-26
FR2178236A1 (en) 1973-11-09
FR2178236B1 (en) 1976-09-10
GB1432013A (en) 1976-04-14
US3935162A (en) 1976-01-27
BE797632A (en) 1973-10-01
US3803269A (en) 1974-04-09
US3823206A (en) 1974-07-09
CA1006171A (en) 1977-03-01
NL7304500A (en) 1973-10-02
DE2316043A1 (en) 1973-10-18

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