Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
  • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
  • D06M13/288—Phosphonic or phosphonous acids or derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/28—Phosphorus compounds with one or more P—C bonds
  • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
  • C07F9/40—Esters thereof
  • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
  • C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
  • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
  • C08K5/5333—Esters of phosphonic acids
  • C08K5/5353—Esters of phosphonic acids containing also nitrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
  • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
  • C08K5/5333—Esters of phosphonic acids
  • C08K5/5373—Esters of phosphonic acids containing heterocyclic rings not representing cyclic esters of phosphonic acids

Definitions

• ABSTRACT New compounds are disclosed of the formula:
• R is selected from the group consisting of lower alkyl of 1-6 carbon atoms, phenyl and alkyl substituted phenyl and R is selected from the group consisting of phenyl, lower alkenyl and halogen substituted and unsubstituted lower alkyl of 1-6 carbon atoms.
• the compounds of this invention are useful as flame retarding agents for textile materials and in the production of polymers and copolymers which possess flame retardant properties 6 Claims, No Drawings DIALKYL ALKYL AND AROMATIC SULFONAMIDOMETHYL PHOSPHONATES FIELD OF INVENTION
• This invention relates to novel compounds of the formula wherein R is selected from the group consisting of lower alkyl of l-6 carbon atoms, phenyl and alkyl substituted phenyl and R is selected from the group consisting of phenyl, lower alkenyl and halogen substituted and unsubstituted lower alkyl of 1-6 carbon atoms.
• the invention includes methods of applying the above novel compounds to normally flammable textiles and thermoplastic or thermosetting 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.
• 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 resin compositions which are flame retardant are of considerable commercial importance.
• articles as castings I
• 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 lower alkyl of 1-6 carbon atoms, phenyl and alkyl substituted phenyl and R is selected from the group consisting of phenyl, lower alkenyl and halogen substituted and unsubstituted lower alkyl of l-6 carbon atoms.
• novel compounds for imparting flame retardancy to textiles and thermoplastic or thermosetting resin materials, of the formula II R s OzNHCHgP (o R):
• R is selected from the group consisting of lower alkyl of l-6 carbon atoms, phenyl and alkyl substituted phenyl and R is selected from the group consisting of phenyl, lower alkenyl and halogen substituted and unsubstituted lower alkyl of l-6 carbon atoms. More specifically, the preferred compounds of the present invention include these compounds wherein R and R are lower alkyl of 1-6 carbon atoms.
• Illustrative examples of compounds of the present invention include, for instance, compounds of the general formula such as H on? s Oz-NII-CHz-P 0 GHQ-CH3);
• compositions of the present invention is accomplished by reacting an N- hydroxymethyl sulfonamide of the formula R SO NHCH OH with a trialkyl phosphite of the formula wherein R and R are as previously described in a suitable solvent. with an excess of the phosphite. or without solvent. Typically. the reaction is continued for about 1 to about l2 hours. Temperatures are generally about 50C to about 160C. Preferably reaction is continued from about 3 to about 6 hours at a temperature CHzBr 2
• One or more of the novel compounds of this invention may be applied to textile materials by conventional finishing techniques such as by thermal 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 retardantby way of a variety of methods.
• the cellulose 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 orother known cellulose cross linking agents may be applied to a cellulose substrate with the acid of an acidic catalyst by pad dry process.
• N-hydroxymethyl derivative of the products of this invention prepared by the condensation of the products with formaldehyde, are mixedin 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 70-90 percent wet weight pick-up.
• the material is dried at 220-270F for 1-3 minutes and cured at 300-370F for l-6 minutes in a circulating air oven.
• the samples are then washed in hot water and dried.
• the finishedsamples have a flame retardant add-on of about 5 to about 40 percent and preferably about 10 to about 25 percent 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.
• cellulosic materials applicant intends to embrace cotton, rayon, paper, regenerated cellulose and cellulose derivatives which retain a cellulose backbone of at least one hydroxy substituent per repeating glucose unit.
• proteinaceous material applicant intends to embrace those textile materials comprising the functional groups of proteins such as the various animal wools, hairs and furs.
• the flame retardant compounds or additives of the invention may be incorporated into thermoplastic or thermosetting resin compositions by any known method.
• 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 polymer-- have been found sufficient.
• thermoplastic resin embraced within the scope of this invention include the homopolymers and copolymers of unsaturated aliphatic, alicyclic, and aromatic hydrocarbons. Suitable monomers are ethylene, propylene, butene, pentene, hexene, heptene, octene, Z-methylpropene-l, 3-methylbutene-l, 4-methylpentene-l, 4-methylhexene-l,5-methylhexene-l, bicyclo- (2.2.l)-2-heptene, butadiene, pentadiene, hexadiene, isoprene, 2,3-dimethylbutadiene-1,3, 2-methylpentadien-l,3 4-vinylcyclohexene, vinylcyclohexene, cyclopentadiene, styrene and methylstyrene, and the like.
• polymers in addition to the above-described olefin polymers that are useful in the invention include polyindene, indenecoumarone resins; polymers of acrylate esters and polymers of methacrylate esters, acrylate and methacrylate resins such as ethyl acrylate, nbutyl methacrylate, isobutyl methacrylate, ethyl methacrylate and methyl methacrylate; alkyd resins and paint vehicles, such as bodied linseed oil; cellulose derivatives such as cellulose acetate, cellulose'acetate butyrate, cellulose nitrate, ethyl cellulose, hydroxyethyl cellulose, methyl cellulose and sodium carboxymethyl celurated polyesters of dibasic acids and dihydroxy compounds, and polyester elastomer and resorcinol resins such as resorcinol-formaldehyde, resorcinol-furfural, resorcinol-
• the polymers ofthe 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; butadieneacrylonitrile copolymers; butyl rubber; chlorinated rubbers, e.g., polyvinyl chloride resins, chloroprene rubber, chlorosulfonated polyethylene; ethylene polymers, e.g., ethylene-propylene copolymers, ethylene-propylene terpolymers; fluorinated rubbers, butadiene rubbers, e.g., 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;
• 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 in length X 8.0 mm in diameter 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 D635-68 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 150200 mm X 8 mm cylindrical plastic test samples with an 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 of the 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) 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.
• the vertical Char Test used in accordance with the following examples, generally provides for the comparison of relative flammability of 2% inch X l 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.
• reaction solution was heated at reflux for 15 hours and then cooled to room temperature. On standing, colorless crystals separated from the solution. The crystals were filtered off the solution and dried resulting in a yield of 179g. A further concentration of the mother liquor, after filtration, yielded a further 40g. ofcrystalline material. Total yield of product was 219g. of a colorless cyrstallinc solid analyzed as essentially pure N-dimethyl phosphonomethyl-p-toluene sulfonamide.
• EXAMPLE VI A padding solution was prepared by mixing N- dimethylphosphonomethyl-p-toluenesulfonamide. (400g) with 60.0g of 40 percent formalin solution of a pH of 9-10 and stirring overnight. The pH was adjusted to 7.0 with hydrochloric acid and 23g. of a 50 l was added to the hydroxymethyl compound 201g. percentsolutipln oga ntijejthdylolated melamine and g of (0 1 mole) in a round bottomed flask and warmed to ammonium c on e a e d It b t 125C f i h Th 6.0 oz. sq. yd.
• wool textile material was padded f d I b or a 3 through the above mixture and the excess squeezed out f f gf, en fi g by means ofa two roll laboratory padder at 60 lb. gauge 34 s fi 1 f f g pressure to a wet pickup ofabout 130 percent.
• the texuc i or ebb lqul w Ose h S tile'material was dried at about 250F for about 2 mineonflrmed by mtrared and nuclear magnetic resonance 0 I I utes, and cured at about 350 F for about 4 minutes in spectroscopy and elemental analysis to be that of the claimed mduct a circulating an oven.
• N-Hydroxymethyl-p-toluene sulfonamide was pre- Cloth 9 qy was "h with the abofle pared as in Example I.
• Example VI wlth 20.1g. (0.1 mole) was then added to 27g. (0.! mole) of results 88 lndlcaled Table ltris-Z-chloroethyl phosphite and warmed to 120C.
• the reaction mixture was held at 120C for two hours and EXAMPLE VIII then stripped at 100C and 0.5 mm Hg to give the de- 6.0 02. sq. yd. wool textile material was treated and sired product.
• a viscous yellow liquid was obtained in quantitative yield. with elemental ples thereof in a controlled burner flame for 2 seconds then removing and observing for self-extinguishment (SE).
• SE self-extinguishment
• EXAMPLE X 30 parts of N-dimethyl phosphonomethyl-p-toluene sulfonamide was mixed with 70 parts of polypropylene and dry blended for about minutes. This composition was then heated to a melt and mixed in the molten state for about 15 minutes. The composition was allowed to cool and solidify after which it was cut into small pieces. These small composition pieces were then 2.
• a compound of claim 1 of the formula II 5 om-@-sogNucul 1 001m;
• lower alkyl of l-6 carbon atoms phenyl and alkyl substituted phenyl and R is selected from the group consisting of phenyl, lower alkenyl and halogen substituted and unsubstituted lower alkyl of 1-6 carbon atoms.
• a compound of claim 1 of the formula 1.

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• Polymers & Plastics (AREA)
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• Molecular Biology (AREA)
• Biochemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Fireproofing Substances (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)

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• 1972
  • 1972-03-30 US US239757A patent/US3870771A/en not_active Expired - Lifetime
  • 1972-03-30 US US00239799A patent/US3812218A/en not_active Expired - Lifetime
• 1973
  • 1973-03-22 GB GB1390773A patent/GB1418775A/en not_active Expired
  • 1973-03-27 FR FR7310953A patent/FR2187802B1/fr not_active Expired
  • 1973-03-28 CA CA167,352A patent/CA1004227A/en not_active Expired
  • 1973-03-28 DE DE2315493A patent/DE2315493A1/de active Pending
  • 1973-03-28 BE BE129396A patent/BE797476A/xx unknown
  • 1973-03-30 NL NL7304503A patent/NL7304503A/xx unknown
  • 1973-03-30 JP JP48036575A patent/JPS4916735A/ja active Pending
  • 1973-03-30 IT IT22420/73A patent/IT982664B/it active
  • 1973-09-18 FR FR7333434A patent/FR2196341B1/fr not_active Expired

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