Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
  • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
  • D06M13/288—Phosphonic or phosphonous acids or derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/28—Phosphorus compounds with one or more P—C bonds
  • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
  • C07F9/40—Esters thereof
  • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
  • C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
  • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
  • C08K5/5333—Esters of phosphonic acids
  • C08K5/5353—Esters of phosphonic acids containing also nitrogen
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S428/00—Stock material or miscellaneous articles
  • Y10S428/92—Fire or heat protection feature
  • Y10S428/921—Fire or flameproofing
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S521/00—Synthetic resins or natural rubbers -- part of the class 520 series
  • Y10S521/906—Polyurethane cellular product containing unreacted flame-retardant material
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S521/00—Synthetic resins or natural rubbers -- part of the class 520 series
  • Y10S521/907—Nonurethane flameproofed cellular product
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2933—Coated or with bond, impregnation or core
  • Y10T428/2938—Coating on discrete and individual rods, strands or filaments
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
  • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
  • Y10T442/2631—Coating or impregnation provides heat or fire protection
  • Y10T442/2672—Phosphorus containing
  • Y10T442/268—Phosphorus and nitrogen containing compound

Definitions

• R is selected from the group consisting of phenyl, lower alkenyl and halogen substituted and unsubstituted lower alkyl of l-6 carbon atoms
• X is selected from the group consisting of chlorine, bromine and lower alkyl of l-6 carbon atoms
• m is an integer from 1-4
• n is an integer from 0-5, provided that the sum of mand n is not greater than 6 and when m is 1, X is greater than 0.
• This invention relates to novel compounds of the formula wherein R is selected from the group consisting of phenyl, lower alkenyl, and halogen substituted and unsubstituted lower alkyl of 1-6 carbon atoms, X is selected from the group consisting of chlorine, bromine and lower alkyl of l-6 carbon atoms, m is an integer from 1-4 and n is an integer from 0-5, provided that the sum of m and n is not greater than 6 and when m is l, X is greater than 0.
• the invention includes methods of applying the above novel compounds to normally flammable textiles, thermoplastic, thermosetting, and elastomeric resin compositions so as to render them flame retardant.
• Fiber retardant textiles have been producedby depositing metal oxides, within or on the textile fibers, by the successive precipitation of ferric oxides and a mixture of tungstic acid and stannic oxide or by successive deposition of antimony trioxide and titanium dioxide.
• Such posprocesses require plural treatment baths in which strongly acidic solutions are employed thus posing the problem of possible textile degradation.
• metal oxide coatings on textile materials create difiiculties in subsequent dyeing processes which deleteriously atfect the hand of the finished product.
• Another process involves the use of a single processing bath wherein a dispersion of a chlorinated hydrocarbon and finely divided antimony oxide is padded on the textile material.
• antimony oxide will react with hydrogen chloride, generated by degradation of the chlorinated hydrocarbon, to form antimony oxychloride which acts to suppress flame.
• This combination of a chlorinated hydrocarbon and finely divided antimony oxide are not acceptable finishes for closely woven textiles as they deleteriously affect the hand of the finished product.
• a further process for imparting flame resistance to cellulosic materials is by the esterification of the cellulose with diammonium hydrogen orthophosphate. Textile products so treated however are subjected to metathesis reaction with cations during washing, and must be regenerated by reacting the wash product with an ammonium chloride solution.
• thermoplastic, thermosetting, and elastomeric resin compositions which are flame retardant is of considerable commercial importance.
• articles as castings, moldings, foamed or laminated structures and the like are required, or are at least desired, to be resistant to fire and flame and to possess the ability to endure heat without deterioration.
• the use of various materials incorporated into thermoplastic, thermosetting and elasotmeric resins so as to improve the flame retardancy thereof has been known.
• chlorostyrene copolymers chlorinated paraflin wax in admixture with triphenyl styrene, chlorinated paraffins and aliphatic antimonical compounds, as well as antimony oxide-chlorinated hydrocarbon mixtures.
• a problem associated with these compounds has been however, the fact that generally a large amount, i.e. upwards of 35% of additive, must be incorporated into the resin in order to make it sufi'iciently flame retardant.
• Such large amounts of additive may deleteriously atfect the physical characteristics of the thermoplastic resin, as Well as substantially complicating and increasing the cost of preparation thereof.
• the present invention relates to a group of compounds which may be added to thermoplastic resins in relatively small amounts and still produce satisfactory flame retardant compositions which will not crystallize nor oil out of the resin after incorporation therein.
• a particular object is to devise a composition comprising normally flammable cellulosic, proteinaceous or analogous man-made materials and an effective flame retardant amount of the compound represent by the formula 0 noni onmn I DESCRIPTION OF THE INVENTION
• novel compounds for imparting flame retardancy to textiles and resin materials, of the formula i 3 [(RO): CHrNH Jm I wherein R is selected from the group consisting of phenyl, lower alkenyl and halogen substituted and unsubstituted lower alkyl of 1-6 carbon atoms, X is selected from the group consisting of chlorine, bromine and lower alkyl of 1-6 carbon atoms, m is an integer from 1-4 and n is an integer from 0-5, provided that the sum of m and n is not greater than 6 and when m is 1, X is greater than 0.
• the preferred compounds of the present invention include these compounds wherein R is lower alkyl, allyl, chlorinated alkyl or phenyl, and X is chlorine, bromine or methyl.
• Illustrative examples of compounds of the present invention include, for instance, compounds of the general formula such as 0 a @iinnomiwoomwm:
• compositions of the present invention is accomplished by reacting an N-hydroxymethyl aromatic amides of the formula l-o nnomonl with a trialkyl phosphite of the formula wherein R, m, n and X are as previously described in a suitable solvent, excess of the phosphite or neat.
• the reaction occurs at elevated temperatures and is continued for about 1 to about 12 hours. Temperatures are generally about 50 C. to about 160 C. Preferably reaction is continued from about 3 to about 6 hours at a temperature of about 80 C. to about 120 C.
• the solvent or other volatiles is thereafter stripped, or otherwise removed from the product.
• Suitable solvents include benzene, toluene, xylene, glymes, dimethylformamide, aliphatic or aromatic hydrocarbons.
• Typical N-hydroxymethyl aromatic amides operable as reactants herein include o l; c NHOHzOH o t 01 Nnomon I -hNHoH20H Br o o mNd-@-gnnomon 6 ONHCH2OH or or It or CNHCHOH ll o1 CNHCH2OH Br c o H0CHzNHC@-&NHCH2OH I -dNHoHl0rr Nnomon l 1 JNHCHzOH gNnomorr or or a o HOCHzNH Jinnomorr 0 1% HO GHzHN NHCHzOH HOCH2HN?
• One or more of the novel compounds of this invention may be applied to textile materials by conventional finishing techniques such as by thermal induced pad curing so as to incorporate into the textile a flame retardant amount thereof.
• the compounds of this invention have advantages over the flame retardant agents of the prior art in that they may be used on a variety of textile materials of different chemical composition, and they may be applied by a variety of methods. They may be applied to materials in either the fiber or fabric form to give flame retarding materials with minimum detectable physical changes in the quality or hand of the textile material.
• Cellulosic textile materials may be made flame retardant by way of a variety of methods.
• Products of this invention may be applied to cellulosic materials in several ways to give a durable flame retardant treatment.
• the products of this invention may be reacted with formaldehyde to give N-hydroxymethyl derivatives which can react with cellulosic materials in a known manner.
• aqueous mixtures of the products with formaldehyde, urea, trimethylol melamine or other known cellulose crosslinking agents may be applied to a cellulose substrate with the aid of an acidic catalyst by a pad dry process.
• N-hydroxymethyl derivative of the products of this invention prepared by the condensation of the products with formaldehyde, are mixed in an aqueous medium with trimethylol melamine and a Lewis acid catalyst such as NH CI or Zn(NO -6H O.
• the cellulosic material is immersed in an aqueous solution of the methylol derivative, trimethylol melamine, and Zn(NO -6H O and squeezed on a two roll padder to 70-90% wet weight pick-up.
• the material is dried at 220-270 F. for 1-3 minutes and cured at 300370 F. for 1-6 minutes in a circulating air oven.
• the samples are then washed in hot water and dried.
• the finished samples have a flame retardant add on of about 5 to about 40% and preferably about 10 to about 25% by weight.
• the flame retardant agents of this invention may be applied to various textiles such as cellulosic materials, proteinaceous materials and blends of cellulosic or proteinaceous materials and analogous man-made fibers.
• cellulosic materials applicant intends to embrace cotton, rayon, paper, regenerated cellulose and cellulose derivatives which retaina cellulose backbone of at least one hydroxy substituent per repeating glucose unit.
• proteinaceous material applicant intends to embrace those textile materials comprising the functional groups of proteins such as the various animal wools, hairs and furs.
• the flame retardant compounds or additives of the invention may be incorporated into thermoplastic, thermosetting or elastomeric resin compositions by any known method. That is to say, the flame retardant additive may be added to the resin by milling the resin and the additive on, for example, a two-roll mill, or in a Banbury mixer etc., or it may be added by molding or extruding the additive and resin simultaneously, or by merely blending it with the resin in powder form and thereafter forming the desired article. Additionally, the flame-retardant may be added during the resin manufacture, i.e., during the polymerization procedure by which the resin is made, provided the catalysts etc. and other ingredients of the polymerization system are inert thereto.
• the compounds of this invention may be incorporated into the thermoplastic resin in flame-retarding amounts, i.e. generally amounts ranging from about 5% by weight, to about 50% by weight, preferably from about 20% by weight, to about 40% by weight, based on the weight of the polymer, have been found sufficient.
• Resins embraced within the scope of this invention include the homopolymers and copolymers of unsaturated aliphatic, alicyclic, and aromatic hydrocarbons. Suitable monomers are ethylene, propylene, butene, pentene, hexene, heptene, octene, Z-methylpropene-l, S-methylbutene-l, 4-methylpentene-l, 4-methyl-hexene-1, S-methylhexene-l, bicyclo-(2.2.1)-2-heptene, butadiene, pentadiene, hexadiene, isoprene, 2,3-dimethylbutadiene-l,3, 2- methylpentadiene-l,3, 4-vinylcyclohexene vinylcyclohexene, cyclopentadiene, styrene and methylstyrene, and the like.
• Suitable monomers are ethylene, propylene, butene, pen
• polymers in addition to the above-described olefin polymers that are useful in the invention include polyindene, indenecoumarone resins; polymers of acrylate esters and polymers of methacrylate esters, acrylate and methacrylate resins such as ethyl acrylate, n-butyl methacrylate, isobutyl methacrylate, ethyl methacrylate and methyl methacrylate; alkyd resins and paint vehicles, such as bodied linseed oil; cellulose derivatives such as cellu lose acetate, cellulose acetate butyrate, cellulose nitrate, ethyl cellulose, hydroxyethyl cellulose, methyl cellulose and sodium carboxymethyl cellulose; epoxy resins; furan resins (furfuryl alcohol or furfural-ketone); hydrocarbon resins from petroleum; isobutylene resins (polyisobutylene); isocyanate resins (polyurethanes);
• the polymers of the invention can be in various physical forms, such as shaped articles, for example, moldings, sheets, rods, and the like; fibers, coatings, films and fabrics, and the like.
• the compounds of this invention have been found to have particular utility in ABS resins and in elastomeric materials such as acrylic rubber; acrylonitrile butadiene styrene terpolymers; butadiene-acrylonitrile copolymers; butyl rubber; chlorinated rubbers, e.g., polyvinyl chloride resins, chloroprene rubber, chlorosulfonated polyethylene; ethylene polymers, e.g., ethylene-propylene copolymers, ethylene-propylene terpolymers; fluorinated rubbers, b'utadiene rubbers, e.g., styrene-butadiene rubber, isobutylene polymers, polybutadiene polymers, polyisobutylene rubbers, polyisoprene rubbers; polysulfide rubbers; silicon rubbers; urethane rubbers; high styrene resins latices, high styrene resins
• ASTM Test D2863-70 used in accordance with the following examples, generally provides for the comparison of relative flammability of self-supporting plastics by measuring the minimum concentration of oxygen in a slowly rising mixture of oxygen and nitrogen that will support combustion.
• the procedure encompasses supporting cylindrical test specimens 70-150 mm. x 8.0 mm. vertically in a glass tube fitted with controlled upward oxygen/nitrogen gas flow. The top of the specimen is ignited and oxygen flow is adjusted until it reaches that minimum rate at which the specimen is extinguished before burning 3 minutes or 50 mm. whichever happens first.
• the oxygen index (n) is then calculated as follows:
• a modification of ASTM Test D635-68 used in accordance with the following examples, generally provides for the comparison of burning rates, self-extinguishment and non-burning characteristics of plastics in the form of sheets, bars, plates or panels.
• the procedure encompasses preparing plastic samples of -200 mm. x 8 mm. with and without the subject flame retardant additive. Each sample is marked at points 1 inch and 4 inches from its end and held, marked end in the flame, at a 45 degree angle in a controlled burner flame (1 inch flame length) for two 30 second attempts. The movement of the flame up the length of the sample through the two points is measured for rate of burning, non-burning or self-extinguishing characteristics.
• a sample is rated SE (self-extinguishing) if the flame burns through the first point but extinguishes before reaching the second point.
• SE self-extinguishing
• NB non-burning
• AATCC test method 34-1969 The Vertical Char Test, used in accordance with the following examples, generally provides for the comparison of relative flammability of 2% inch x 10 inch fabric test specimens when exposed to a controlled burner flame, under controlled conditions, for periods of 12.0 and 3.0 seconds. Charred specimens are thereafter subjected to controlled tearing tests, using tabulated weights, to determine the average tear length as representing the char length of the fabric. In addition, samples which are wholly consumed by the flame are rated (B) and samples which do not burn are rated (NB). For comparison purposes, it should be noted that untreated samples of the fabrics used in the examples of this case would be consumed for this test.
• thermometer thermometer, and reflux condenser.
• the mixture was warmed to and maintained at about 130 C. for about five hours. After cooling the mixture was stripped, at 120 C. and 2 mm. Hg, to remove phenol and other volatile material.
• the stripped product was identified by elemental analysis as N-(diphenylphosphonomethyl)-p-toluamide and was obtained in 85.3 yield.
• EXAMPLE X Preparation of EXAMPLE XI Forty parts of N-dimethylphosphonomethy1-2,4-dichlorobenzamide was mixed with 60 parts of polypropylene and dry blended for about five minutes. This mixture was then heated to a melt and mixed well in the molten state for about fifteen minutes. The mixture was then allowed to cool to room temperature and the plastic composition was cut into small pieces. These pieces were placed slowly into a glass tube (9 mm.) immeresd in a hot metal bath, the temperature of the bath being maintained above the melt temperature of the plastic composition. Pieces of the composition were added until the melt had a depth of approximately 200 mm. A metal rod was then placed in the tube with a. weight attached and the tube cooled to solidify the composition. The composition was then removed from the tube and tested by ASTM tests 132863-70 and D635-68. The results of the testing are contained in Table I.
• EXAMPLE XXX N-dimethyl phosphonomethyl-p-toluamide (25 g.) was mixed with 40% formalin solution (37.5 g.) and stirred overnight at pH 10. The pH was adjusted to 7.0 with hydrochloric acid and 3.1 g. of ammonium chloride and 14.0 g. of a solution of a methylolated melamine added. 5.0 oz. sq. yd. cotton sheeting was immersed in the solution and the excess squeezed from the cloth by passing through a two roll laboratory pa-dder at lb. gauge pressure, to a wet pick-up of about The sheeting was then dried at about 250 F. for about 2 minutes and cured at about 340 F. for about 5 minutes in a circulating air oven. The sheeting was then washed by hand for about 5 minutes in a detergent (Tide) water mixture and tumble dried. A resin pick-up of 23.7% was calculated.
• the then treated sheeting was thereafter subjected to ASTM test D2863-70 and AATCC test 34- 1969 with initial results as indicated in Table II.
• the cotton sheeting was thereafter subjected to four additional hand washes, as above described, and tested under AATCC test 34- 1969.
• EXAMPLE XXXIV Rayon staple fiber was immersed in the solution described in Example XXX and squeezed on a two roll laboratory padder at about 60 lb. gauge pressure to a wet pick-up of about 100%. The fiber was then dried for about 3 minutes at about 250 F. and cured for about minutes at about 350 F. in a circulating air oven. The fiber was then washed by hand for about 5 minutes in a hot detergent (Tide) water mixture and dried in the circulating air oven resulting in an add-on of about 13.8%. The fiber was then tested for flammability by holding one end of a treated sample in a benson flame for about 2 sec. and then removing and observing the sample. Treated samples self-extinguish immediately untreated samples are completely consumed.
• Tide hot detergent
• the fiber was then further tested for durability by subjecting it to a 5 complete wash cycles in a standard, home type automatic washer using Tide detergent. There after the fiber was tested for flammability as previously described. The results of testing is tabulated in Table II.
• XXXIIL do Same as above.. Y 18. 6 B B 16 TABL-E II-Continued Flammability tesling Percent OI 6 home Example Textile Compound add-on initial Initial washes XXXIV.. Rayon (staple) (11]) 13. 8 23 SE SE oH,-@-ANHCH,P OGH,
• a compound of claim 1 of the formula 1 A compound of the formula XI 0 f nnomi womorbcnm (ROhl CHINH -I I 25 wherein R is selected from the group consisting of phenyl, lower alkenyl and halogen substituted and unsubstituted lower alkyl of 1-6 carbon atoms, X is selected (3H, from the group consisting of chlorine, bromine and lower alkyl of 1-6 carbon atoms, in is an integer from 1-4 and n is an integer from 0-5, provided that the sum m and n A compound of 01mm 1 of the formula is not greater than 6 and when m is 1, X is greater than 0.
• a om d of claim 1 of the formula c pouno 9.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Polymers & Plastics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• General Health & Medical Sciences (AREA)
• Molecular Biology (AREA)
• Biochemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Fireproofing Substances (AREA)

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• 1972
  • 1972-03-30 US US05239784 patent/US3803269A/en not_active Expired - Lifetime
  • 1972-03-30 US US05239793 patent/US3823206A/en not_active Expired - Lifetime
• 1973
  • 1973-03-26 JP JP3443173A patent/JPS499090A/ja active Pending
  • 1973-03-28 CA CA167,354A patent/CA1006171A/en not_active Expired
  • 1973-03-29 GB GB1518573A patent/GB1432013A/en not_active Expired
  • 1973-03-30 DE DE2316043A patent/DE2316043A1/de active Pending
  • 1973-03-30 BE BE129535A patent/BE797632A/xx unknown
  • 1973-03-30 NL NL7304500A patent/NL7304500A/xx unknown
  • 1973-03-30 FR FR7311582A patent/FR2178236B1/fr not_active Expired
  • 1973-06-29 US US37482673 patent/US3901650A/en not_active Expired - Lifetime
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• 1974
  • 1974-12-11 US US05/531,646 patent/US3935162A/en not_active Expired - Lifetime

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