US3895161A - Flame retardant materials - Google Patents
Flame retardant materials Download PDFInfo
- Publication number
- US3895161A US3895161A US39386873A US3895161A US 3895161 A US3895161 A US 3895161A US 39386873 A US39386873 A US 39386873A US 3895161 A US3895161 A US 3895161A
- Authority
- US
- United States
- Prior art keywords
- textile material
- compound
- textile
- flame retardant
- flame
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000463 material Substances 0.000 title claims abstract description 76
- 239000003063 flame retardant Substances 0.000 title claims abstract description 35
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 52
- 239000004753 textile Substances 0.000 claims description 66
- 239000000203 mixture Substances 0.000 claims description 25
- 239000000835 fiber Substances 0.000 claims description 20
- 239000004744 fabric Substances 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 abstract description 9
- 239000000460 chlorine Substances 0.000 abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 abstract description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052794 bromium Inorganic materials 0.000 abstract description 4
- 125000001309 chloro group Chemical group Cl* 0.000 abstract description 4
- 229910052736 halogen Chemical group 0.000 abstract description 4
- 150000002367 halogens Chemical group 0.000 abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 4
- 125000003342 alkenyl group Chemical group 0.000 abstract description 3
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- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
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- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical group O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 2
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- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- HANVTCGOAROXMV-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine;urea Chemical compound O=C.NC(N)=O.NC1=NC(N)=NC(N)=N1 HANVTCGOAROXMV-UHFFFAOYSA-N 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical compound CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229920001702 kydex Polymers 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Chemical compound CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- JFNLZVQOOSMTJK-UHFFFAOYSA-N norbornene Chemical compound C1C2CCC1C=C2 JFNLZVQOOSMTJK-UHFFFAOYSA-N 0.000 description 1
- 239000008601 oleoresin Substances 0.000 description 1
- LIYKJALVRPGQTR-UHFFFAOYSA-M oxostibanylium;chloride Chemical compound [Cl-].[Sb+]=O LIYKJALVRPGQTR-UHFFFAOYSA-M 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 239000003340 retarding agent Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 description 1
- ZWZVWGITAAIFPS-UHFFFAOYSA-N thiophosgene Chemical compound ClC(Cl)=S ZWZVWGITAAIFPS-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- LUVCTYHBTXSAMX-UHFFFAOYSA-N tris(2-chloroethyl) phosphite Chemical compound ClCCOP(OCCCl)OCCCl LUVCTYHBTXSAMX-UHFFFAOYSA-N 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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
- ABSTRACT New flame retardant materials are disclosed having applied thereon compounds of the formula:
- 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 subsequen 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.
- Illustrative examples of compounds of the present invention include, for instance, compounds of the general formula such as Br BrO O D 0 O
- the reaction occurs at elevated temperatures and is continued for about 1 to about 12 hours. Temperatures are generally about C to about 160C. Preferably reaction is continued from about 3 to about 6 hours at a temperature of about 80C to about 120C.
- 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.
- 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.
- 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 methyl derivative, trimethylol melamine, and Zn(NO .6H O and squeezed on a two roll padder to -90% wet weight pick-up.
- the material is dried at 220-270F for l-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 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 manmade fibers.
- cellulosic materials applicant intends to embrace cotton, ravon, 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.
- vinyl chloride vinly butyral, vinyl chloride-acetate copolymer, vinyl pyrrolidone and vinylidene chloride copolymers; polyformaldehyde; polyphenylene oxide; polymers of diallyl phthalates and phthalates; polycarbonates of phosgene or thiophosgene and dihydroxy compounds such as bisphenols phosgene, thermoplastic polymers of bisphenols and epichlorohydrin (trade named Phenoxy polymers); graft copolymers and polymers of unsaturated hydrocarbons and unsaturated monomer, such as graft copolymers of polybutadiene, styrene and acrylonitrile, commonly called ABS resins; ABS polyvinyl chloride polymers, recently introduced under the trade name of Cycovin; and acrylic polyvinyl chloride polymers, known by the trade name Kydex 100.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (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)
Abstract
New flame retardant materials are disclosed having applied thereon 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 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, n is greater than 0.
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, n is greater than 0.
Description
United States Patent Golborn et al.
FLAME RETARDANT MATERIALS Inventors: Peter Golborn, Lewiston; James J.
Duffy, Buffalo, both of NY.
Assignee: Hooker Chemical & Plastics Corporation, Niagara Falls, NY.
Filed: Sept. 4, 1973 Appl. No.: 393,868
Related US. Application Data Division of Ser. No. 239,784.
US. Cl. 428/289; 428/288; 428/378; 428/921 Int. Cl C09d 5/18 Field of Search 117/136, 138.8 B, 143 R, 117/144, 154, 141; 260/932 References Cited UNITED STATES PATENTS l/l954 Ferguson 117/136 X 8/1957 Erbel et al. 117/136 l/1959 Fon Toy et al. 117/136 [4 1 July 15,1975
Primary ExaminerRa1ph Husack Assistant Examiner-Theodore G. Davis Attorney, Agent, or Firm-Peter F. Casella; Donald C. Studley; William J. Crossetta, Jr.
[5 7] ABSTRACT New flame retardant materials are disclosed having applied thereon compounds of the formula:
(no) 2 P CHZNHC 19 Claims, No Drawings 1 FLAME RETARDANT MATERIALS This is a division of application Ser. No. 239,784, filed Mar. 30, 1972, now US Pat. No. 3,803,269 issued Apr. 9, 1974.
FIELD OF INVENTION This invention relates to novel compounds of the formula R0 P CH LHC wherein R is selected from the group consisting of phenyl, lower altenly, and halogen substituted and unsubstituted lower alkyl of 1-6 carbon atoms, X is selected from the group consisting of chlorine, bromide and lower alkyl of 1-6 carbon atoms, m is an integer from l-4and n is an integer from O-5, provided that the sum of m and n is not greater than 6 and when m is l, X is greater than 0. The invention includes methods of applying the above novel compounds to normally flammable textiles, thermoplastic, thermosetting, and elastomeric resin compositions so as to render them flame retardant.
BACKGROUND OF THE INVENTION Many flame retarding agents and methods of application have been developed in attempts to obtain flame resistant textile materials and thermoplastic, thermosetting, and elastomeric resin compositions.
Flame retardant textiles have been 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 subsequen 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 of considerable commercial importance. For example, such articles as castings, moldings, foamed or laminated scructures and the like are required, or are at least desired, to be resistant to fire and flame and to possess the ability to endure heat without deterioration. The use of various materials incorporated into thermoplastic, thermosetting and elastomeric resins so as to improve the flame retardancy thereof has been known. 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 well 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 addative 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:
o n (no P CHZHHC- wherein R is selected from the group consisting of phenyl, lower alkenyl and halogen substituted and unsubstituted lower alkyl of l-6 carbon atoms, X is selected from the group consisting of chlorine, bromine and lower alkyl of l-6 carbon atoms, m is an integer from I-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.
It is also an object of this invention to provide flame retarding textile materials comprising normally flammable cellulosic, proteinaceous or analogous manmade materials. Another object is to provide a method for treating normally flammable cellulosic, proteinaceous or analogous manmade materials to render them flame retardant. Another object is to provide flame retarding thermoplstic, thermosetting or elastomeric resin compositions comprising normally flammable resin materials. A further object is to provide a process for treating normally flammable thermoplastic, thermosetting or elastomeric resin compositions to render them flame retardant. A particular object is to devise a composition comprising normally flammable cellulosic, proteinaceous or analogous man-made materials and an effective flame retardant amount of the compound represented by the formula wherein R, X, m and n are as above described.
A further particular object is to devise a composition comprising normally flammable thermoplastic, thermosetting or elastomeric polymers and an effective flame retarding amount of the before described novel compound.
These and other objects of the present invention will be obvious from the following description.
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 More specifically, the preferred compounds of the present invention include these compounds wherein R is lower alkyl, alkenyl 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 Br BrO O D 0 O This synthesis of the compositions of the present ina suitable solvent, excess of the phosphite or neat. Typically, the reaction occurs at elevated temperatures and is continued for about 1 to about 12 hours. Temperatures are generally about C to about 160C. Preferably reaction is continued from about 3 to about 6 hours at a temperature of about 80C to about 120C. 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 P. P. HOCH NHuGNHCH OH Br 9. c1 cuacu on o I c uucu ou 5- to cl- 0 CNHCHZOH i gnua-l ou 1 l o o HOCH HNE gm- OH fir 0 2 \K\/ 2 ll o o Cl- 0 -cm-lcu ou HOCHZHNC E Z One or more of the novel compounds of this invention may be applied to textile materials by conventional finishing techniques such as by thermal induced pad curing so as to incorporate into the textile a flame retardant amount thereof. The compounds of this invention have advantages over the flame retardant agents of the prior art in that they may be used on a variety of textile materials of different chemical composition, and
they may be applied by a variety of methods. They may be applied to materials in either the fiber or fabric form to give flame retarding materials with minimum detectable physical changes in the quality or hand of the textile material.
Cellulosic textile materials may be made flame retardant by way of a variety of methods. Products of this invention may be applied to cellulosic materials in several ways to give a durable flame retardant treatment. For example, the products of this invention may be reacted with formaldehyde to give N-hydroxymethyl derivatives which can react with cellulosic materials in a known manner. Alternatively aqueous mixtures of the products with formaldehyde, urea, trimethylol melamine or other known cellulose crosslinking agents may be applied to a cellulose substrated with the aid of an acidic catalyst by a pad dry process.
More preferably the N-hydroxymethyl derivative of the products of this invention prepared by the condensation of the products with formaldehyde, are mixed in an aqueous medium with trimethylol melamine and a Lewis acid catalyst such as NH Cl or Zn(NO .6H O. The cellulosic material is immersed in a aqueous solution of the methyl derivative, trimethylol melamine, and Zn(NO .6H O and squeezed on a two roll padder to -90% wet weight pick-up. The material is dried at 220-270F for l-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 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 manmade fibers. By cellulosic materials, applicant intends to embrace cotton, ravon, 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 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 v Suitable monomers are ethylene, propylene, butene, pentene, hexene, heptene, octene, 2-methylpropene-l, 3-methylbutenel 4-methylpentenel 4-methylhexenel ,S-methylhexene-l bicyclo-(2.2.1 )-2- heptene, butadiene, pentadiene, hexadiene, isoprene, 2,3-dimethylbutadiene-l ,3, Z-methylpentadiene-l ,3, 4-vinylcyclohexene, vinylcyclohexene, cyclopentadiene, styrene and methylstyrene, and the like.
Other polymers in addition to the above-described olefin polymers that are useful in the invention include polyindene, indenecoumarone resins; polymers of acrylate esters and polymers of methacrylate esters, any late 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 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 resorcinol resins such as resorcinol-formaldehyde, resorcinol-furfural, resorcinol-phenol-formaldehyde, resorcinol-polyamide and resorcinol-urea; rubbers such as natural rubber, synthetic polyisoprene, reclaimed rubber, chlorinated rubber, polybutadiene, cyclized rubber, 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, vinly butyral, vinyl chloride-acetate copolymer, vinyl pyrrolidone and vinylidene chloride copolymers; polyformaldehyde; polyphenylene oxide; polymers of diallyl phthalates and phthalates; polycarbonates of phosgene or thiophosgene and dihydroxy compounds such as bisphenols phosgene, thermoplastic polymers of bisphenols and epichlorohydrin (trade named Phenoxy polymers); graft copolymers and polymers of unsaturated hydrocarbons and unsaturated monomer, such as graft copolymers of polybutadiene, styrene and acrylonitrile, commonly called ABS resins; ABS polyvinyl chloride polymers, recently introduced under the trade name of Cycovin; and acrylic polyvinyl chloride polymers, known by the trade name Kydex 100.
The polymers of the invention can be in various physical forms, such as shaped articles, for example, moldings, sheets, rods, and the like; fibers, coatings, films and fabrics, and the like.
The compounds of this invention have been found to have particular utility in ABS resins and in elastomeric materials such as acrylic rubber; acrylonitrilebutadiene 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, 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 sty rene 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 -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:
wherein O is the volumetric flow of oxygen, at the minimal rate and N is the corresponding volumetric flow rate of nitrogen.
A modification of ASTM Test D635-68 used in accordance with the following'examples, generally provides for the comparison of burning rates, selfextinguishment and non-burning characteristics of plastics in the form of sheets, bars, plates or panels. The
procedure encompasses preparing plastic samples of 1 -200 mm X 8 mm with and without the subject flame 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 self-extinguishing characteristics. A sample is rated SE(self-extinguishing) if the flame burns through the first point but extinguishes before reaching the second point. A sample is rated NB(nonburning) 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 control tearing tests, using tabulated weights, to determine the average tear length as representing the char length of the fabric. In addition, samples which are wholly consumed by the flame are rated (B) and samples which do not burn are rated (NB). For comparison purposes, it should be noted that untreated samples of the fabrics used in the examples of this case would be consumed for this test.
In all the examples of the application, the following general procedure was used except when otherwise specifically noted. Padding was done on a standard two EXAMPLE 1 Preparation of A 500 ml. flask was changed with 124g. (1.0 mole) of trimethyl phosphite and was heated to about 100C. 57.5g. (0.25 mole) of 3-bromo-N-hydroxymethyl benzamide was then added to the reaction flask over a period of minutes. The reaction mixture was then refluxed at about 95 for about 3 hours then stripped at 100C under a vacuum of 0.5 mm mercury to give 81g of a colorless, viscous oil which by elemental analysis was confirmed to be the desired product.
EXAMPLE 11 Preparation of Following the procedure described in Example I 69g. (0.3 mole) of 3-bromo-N-hydroxymethyl benzamide was refluxed with 80g. (0.35 mole) of tri-n-butyl phosphite for about 5 hours at about 125C. n-Butanol and excess tri-n-butyl phosphite were removed by stripping the reaction mixture at 1 C under a vacuum of 0.5 mm mercury. After stripping 121g. of a pale yellow viscous liquid was obtained which was confirmed, by elemental analysis to be the desired product.
EXAMPLE "I Preparation of A 500 ml. flask, fitted with a reflux condenser, mechanical stirrer and thermometer, was charged with 124g. 1.0 mole) of trimethyl phosphite and was heated to about 100C. 61.8g. (0.3 mole) of 2,4-dichloro-N- hydroxymethyl benzamide was added to the trimethyl phosphite, over a period of about 5 minutes. The homogeneous reaction mixture was then refluxed at about 93C for 3 hours and thereafter stripped, under a reduced pressure of about 0.5 mm Hg. at about 10C, to give 93g. ofa tacky solid. Recrystallization of the solid from benzene of cyclohexane (1:1) gave 828g. of dimethyl 2,4-dichlorobenzamidomethyl phosphonate.
EXAMPLE 1V 5 Preparation of c1 ct A 250 ml. flask was charged with 62g. (0.5 mole) of trimethyl phosphite and was heated to about 100C. 29g. (0.1 mole) of bis-N,N-hydroxymethyl tetrachloroterephthalamide was added to the flask and the reaction mixture was refluxed for about 6 hours and then cooled to room temperature. Unreacted solids were filtered off and the filtrate was stripped, at 70C under 2 mm. mercury of reduced pressure, to give 12.0g. of a tacky solid product which was found, by infrared and nuclear magnetic resonance spectroscopy to be substantially pure desired product.
EXAMPLE V Preparation of 0 y o CNHCH P(OCH CH Cl) A 250 ml. flask was charged with 21.9g. (0.1 mole) of 2,4-dichloro-N-hydroxymethyl benzamide and 27g. (0.1 mole) of tris-2-chloroethyl phosphite. This reaction mixture was heated at about 130C for about 4 hours then stripped, at 100C under a vacuum of 1.3 mm mercury, to give 41 grams of a white solid. The product was proven, by elemental and infrared and nu clear magnetic resonance spectroscopy, to be substan tially pure desired product.
EXAMPLE VI Preparation of 0 0 45 ll ll CNHCH2P(OCH?CH-CH2)2 A 250 ml. flask was charged with 16.5g. (0.1 mole) of N-hydroxymethyl-p-toluamide and 40.2g. (0.2 mole) of triallyl phosphite and this reaction mixture was heated at about 130C for about 4 hours. Excess triallyl phosphite and allyl alcohol were removed by stripping, at 100C under a vacuum of 2 mm mercury, to yield a thick yellow oil product. The product was confirmed by infrared and nuclear magnetic resonance spectroscopy and elemental analyses.
EXAMPLE V11 Preparation of CMlCH P(0CH A 500 ml. flask, equipped with mechanical stirrer, thermometer and reflux condenser, was charged with 66g (0.4 mole) of N-hydroxymethyl p-toluamide and 124 g (1.0 mole of trimethyl phosphite. This reaction mixture was refluxed for about 4 hours then stripped, at 70C under 0.2 mm mercury vacuum, to give 95g of a low melting solid. Elemental analysis with infrared and nuclear magnetic resonance spectroscopy confirmed the structure of the product.
EXAMPLE VIII Preparation of EXAMPLE IX Preparation of A mixture of 44.8g (0.2 mole) of N,N'-bishydroxyphenyl terephthalamide and 124 g (1.0 mole) of trimethyl phosphite was refluxed for about 6 hours. After the completion of the reaction the mixture was stripped, at 120C and 1 mm Hg, to remove excess phosphite and other volatiles. The product was confirmed by infrared and nuclearmagnetic resonance spectroscopy.
atile materials. A yellow liquid, which weighed 62.0g, was isolated and confirmed as the desired product by spectroscopic and elemental analyses.
EXAMPLE XI Forty parts of N-dimethylphosphenomethyl-Z,4- dichlorobenzamide was mixed with 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 15 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) immersed 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 D2863- and D635-68. The results of the testing are contained in Table l.
EXAMPLES XII-XXIX Various additive compounds were mixed and treated with various resins according to the method of Example XI. Table l tabulates the results of testing by ASTM tests D2863-70 and D635-68 for Examples XII-XXIX.
EXAMPLE XXX N-Dimethyl phosphonomethyl-p-toluamide (25g) was mixed with 40% formalin solution (37.5g) and stirred overnight at pH 10. The pH was adjusted to 7.0 with hydrochloric acid and 3. lg of ammonium chloride and 14.0g of a 50% 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 padder at 60 lb. gauge pressure, to a wet pick-up of about The sheeting was then dried at about 250F for about 2 minutes and cured at about 340F for about 5 minutes in a circulating air oven. The sheeting was then washed by hand for about 5 minutes in a detergent EXAMPLE X (Tide) water mixture and tumble dried. A resin pick-up Prepfl UOfl 0f 55 of 23.7% was calculated.
r A a l. t I ercent Flafl-nabi Ii ty Tests Example Polymer Additive wa Q; 3. 35
O 0 II II x1 Polypropylene cl @-c. ll-lcli l (ocll 19- SE 9. 9. xx! Nylon @CNHCH2P(0CH3)2 30 26.6 NB
9. 9 I XIII Polyethylene @CNHCH P(OCH O 28 NB Tcrcphthalate 2 3 2 3 T A B L E I-Continued Fle -ability mt-ts Examnlc Polymer Additive Q; 3.535
9. 9. XIV ASS CNHCH2P(0CH3)2 30 2h NB XV Nylon ditto 3O 25 N8 XVI Polyethylene ditto 3O 36 NB Terephthalate 9. P. XVI! Ass CNHCt-l P(OCH CH CH CH +0 22.3 $5
xvtn Nylon g ditto 26 NB XIX Epoxy ditto 3O 29 NB 9. 9. XX st rene CH @-CNHCH P(0CH 30 23.3 SE
T A B L E (continued) Pderpqnt Flammability Tests Example Polymer Additive il E Fn 01 -5 0 0 II II XXI Polyethylene CH -@-CNHGl P(OCl-l CH=Cl-l '40 29A NB Terephthalate P. P. 'xxu Epoxy CHJ-@-CNHG-I P-(O-@)2 3 SE o o o 0 II II I II xxnx Epoxy (H cO )PcH HNC-@-CNrio-i P(0cH 30 28 SE XXIV Polyethylene ditto 3 7-5 Terephthalate xxv ABS ditto E P. 9. 9. 9. xxv: Polystyrene (H C=CHCH 0)PCH HNC-@-CNHCl-l P(0Cl-l CH=CH b0 SE xxvzt Ass ditto 30 2 4-3 9. 9. xxvm Polystyrene Cl-@ C-NHCH HOCH CH CU no 23- xxtx ssa ditto 30 2 4.1 SE
test 34-1969.
EXAMPLES XXXI-XXXlll Using the method of Example 30, 5 oz. per sq. yard cotton sheeting was treated with various compounds and subjected to ASTM test D2863-70 and AATCC test 34-1969. The results therefore are indicated in Table 11.
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 The fiber was then dried for about 3 minutes at about 250F and cured for about 10 minites at about 350F 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 while untreated samples are completely consumed.
The fiber was then further tested for durability by We claim: y
l. A fire retardant textile material comprising a textile selected from-the group consisting of cellulosic fibers proteinaceous fibers and blends thereof and a SubjeCtlng it to a Complete Wash cycles in a Standard, 5 flame retardant amount of a compound of the formula: home type automatic washer using Tide detergent. Thereafter the fiber was tested for flammability as previously described. The results of testing is tabulated in X 0 ,0 r1 Table 11. I
EXAMPLES XXXV-XXXVI P CHZNHC Using the method of Example XXXlV, rayon staple m fiber was treated with various compounds and sub jected to ASTM test D2863-7O and AATCC test 34-1969. The results are shown in Table I1.
wherein R is selected from the group consisting of phe- EXAMPLE XXXVH my], lower alkenyl and halogen substituted and unsub- N-Diallyl phosphonomethyl-p-toluam d g) was stituted lower alkyl of 1-6 carbon atoms, X is selected m d with 40% formalin Solution g) and Stirred from the group consisting of chlorine, bromine and overnight at pH 10. The pH was brought to 7.0 with hy-' lower alkyl of 1-6 carbon atoms, m is an integer from dr ChI C a nd ammonium g) and a and n is an integer from O5, provided that the sum 50% Solution Of a methylolated mfllamine g) of m and n is not greater than 6 and when m is l, X is added. greater than 0.
6.0 02. sq. yd. wool was immersed in the above solu- 2. The textile material of claim 1 wherein said textile tion. squeezed on a 2 roll laboratory padder to a wet is a blend of cellulosic and proteinaceous fibers. pick-up of about 100% dried for about 2 minutes at 3. The textile material of claim 1 wherein said textile about 250F and cured for about 5 minutes at about is 66111110516 fibers- 350F in a circulating air oven. The was h 4. The textile material of claim 1 wherein said comwashed for one wash cycle using Tide, in a standard, Pound is? home type, automatic washer and tumble dried. Theresin add-on was calculated as 25.3%. 0 0
The thus treated wool was thereafter subjected to ASTM test D2863-70 and AATCC test 34-1969. The CNll(.l-l P(0Cl-l wool was then subjected to four additional one cycle 35 l washings in a standard home type automatic washer, as above described, and thereafter tested by AATCC test 34-1969. Test results are tabulated in Table 11. r
- T A I 1. E 11 T I 3 l i 7 "ram: 1 V l EXI' 'TI'. futile Add-on In tial Jalflal mm I 0 -0 g xxx cm. (s n.) cn,-@ cmn vtm,) 2 1 1 xxx! 111m .@-CI1O P(0Cfl 5 27- 1.0 3.1 v 1 11 9. 1. xxxtt ditto (11 co )rc11 1mc-@-cmu1 r(ccn 20.2 21. m 5.0 xxxnr ditto mic i 18.6 is I i xxxzv 11 m (staple) m -@-cmu1 r(uc11 1 I 13.5 s: s;
xxxv m:- .tca ql-cu n rcu mccmas rtaa uwuqp 19.13v 12.7 s: st
xxxvt am." am. I l i 18.9 a I 5. The textile material of claim 1 wherein said com- 10. The textile material of claim 1 wherein said compound is: pound is:
0 o o [in S 'I '7 CNHCl-l P OCH cNncn P(ocH cn cH cH 2 3 CH3 6. The textile material of claim 1 wherein said compound is:
11. The textile material of claim 1 wherein said com- 9 H pound is: I 2 3 )2 O 0 C CNHCH P- o 7. The textile material of claim 1 wherein said com- 3 pound'is: 12. The textile material of claim 1 wherein said compound is:
9 o 0 0' (H3C0)2PCH2HN' 1 v1 'r v H CO PCH NHC CNHCH P OCH Thefextile material of claim 1 wherein Said 13. The textile material of claim 1 wherein said compound pound is:
14. The fire retardant textile material of claim 1 HCHZHQCHZCH=CHZ )2 wherein about 5 to about 40% by weight of said compound has been added on.
15. The fire retardant textile material of claim 1 wherein about 10 to about 25% by weight of said compound has been added on.
3 16. The fire retardant textile material of claim 1 wherein said compound is applied by padding.
9. The textile material of claim 1 wherein said com- The fire retardant textile material of claim 1 Pound is? wherein said compound is applied to thermal induced R R pad curing.
NHCH P(OCH CH C1) 18. The fire retardant textile material of claim 1 1 wherein said compound is applied to the textile material while in the fiber form.
19. The fire retardant textile material of claim 1 wherein said compound is applied to the textile mate rial in fabric form.
Claims (19)
1. A FIRE RETARDANT TEXTILE MATERIAL COMPRISING A TEXTILE SELECTED FROM THE GORUP CONSISTING OF CELLULOSIC FIBERS PROTEINACEOUS FIBERS AND BLEND THEREOF AND A FLAME RETARDANT AMOUNT OF A COMPOUND OF THE FORMULA:
2. The textile material of claim 1 wherein said textile is a blend of cellulosic and proteinaceous fibers.
3. The textile material of claim 1 wherein said textile is cellulosic fibers.
4. The textile material of claim 1 wherein said compound is:
5. The textile material of claim 1 wherein said compound is:
6. The textile material of claim 1 wherein said compound is:
7. The textile material of claim 1 wherein said compound is:
8. The textile material of claim 1 wherein said compound is:
9. The textile material of claim 1 wherein said compound is:
10. The textile material of claim 1 wherein said compound is:
11. The textile material of claim 1 wherein said compound is:
12. The textile material of claim 1 wherein said compound is:
13. The textile material of claim 1 wherein said compound is:
14. The fire retardant textile material of claim 1 wherein about 5 to about 40% by weight of said compound has been added on.
15. The fire retardant textile material of claim 1 wherein about 10 to about 25% by weight of said compound has been added on.
16. The fire retardant textile material of claim 1 wherein said compound is applied by padding.
17. The fire retardant textile material of claim 1 wherein said compound is applied to thermal induced pad curing.
18. The fire retardant textile material of claim 1 wherein said compound is applied to the textile material while in the fiber form.
19. The fire retardant textile material of claim 1 wherein said compound is applied to the textile material in fabric form.
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 |
BE129535A BE797632A (en) | 1972-03-30 | 1973-03-30 | FLAMMATION-DELAYING ADDITIVES CONTAINING PHOSPHORUS |
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 |
FR7311582A FR2178236B1 (en) | 1972-03-30 | 1973-03-30 | |
NL7304500A NL7304500A (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 |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US05239784 Division US3803269A (en) | 1972-03-30 | 1972-03-30 | Dialkyl aromatic amidomethyl phosphonates |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US05/531,646 Division US3935162A (en) | 1972-03-30 | 1974-12-11 | Dialkyl aromatic amidomethyl phosphonate flame retardants |
Publications (1)
Publication Number | Publication Date |
---|---|
US3895161A true US3895161A (en) | 1975-07-15 |
Family
ID=27540127
Family Applications (5)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US05239793 Expired - Lifetime US3823206A (en) | 1972-03-30 | 1972-03-30 | N-phosphonomethyl amides |
US05239784 Expired - Lifetime US3803269A (en) | 1972-03-30 | 1972-03-30 | Dialkyl aromatic amidomethyl phosphonates |
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 (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US05239793 Expired - Lifetime US3823206A (en) | 1972-03-30 | 1972-03-30 | N-phosphonomethyl amides |
US05239784 Expired - Lifetime US3803269A (en) | 1972-03-30 | 1972-03-30 | Dialkyl aromatic amidomethyl phosphonates |
US37482673 Expired - Lifetime US3901650A (en) | 1972-03-30 | 1973-06-29 | Textile flame retardants |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
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) | US3823206A (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) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US4606853A (en) * | 1983-08-11 | 1986-08-19 | Imperial Chemical Industries Plc | Fire retardant polyamide compositions |
US20090255039A1 (en) * | 2008-04-10 | 2009-10-15 | Pontus Danielsson | Chemical protective garment with added flash fire protection |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3823206A (en) * | 1972-03-30 | 1974-07-09 | Hooker Chemical Corp | N-phosphonomethyl amides |
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 |
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US2666078A (en) * | 1952-05-16 | 1954-01-12 | Arvey Corp | Bis-trichloroethyl benzene phosphonate |
US2803562A (en) * | 1955-05-26 | 1957-08-20 | Dow Chemical Co | Treatment of cellulosic materials to impart flame resistance thereto |
US2867547A (en) * | 1953-09-22 | 1959-01-06 | Victor Chemical Works | Method of flameproofing fibers, compositions used therein and the resulting products |
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GB1197591A (en) * | 1967-07-28 | 1970-07-08 | Ciba Ltd | Phosphorus-Containing Reaction Products, processes for their production and their Application |
US3823206A (en) * | 1972-03-30 | 1974-07-09 | Hooker Chemical Corp | N-phosphonomethyl amides |
-
1972
- 1972-03-30 US US05239793 patent/US3823206A/en not_active Expired - Lifetime
- 1972-03-30 US US05239784 patent/US3803269A/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 FR FR7311582A patent/FR2178236B1/fr not_active Expired
- 1973-03-30 BE BE129535A patent/BE797632A/en unknown
- 1973-03-30 DE DE2316043A patent/DE2316043A1/en active Pending
- 1973-03-30 NL NL7304500A patent/NL7304500A/xx unknown
- 1973-06-29 US US37482673 patent/US3901650A/en not_active Expired - Lifetime
- 1973-09-04 US US05393868 patent/US3895161A/en not_active Expired - Lifetime
-
1974
- 1974-12-11 US US05/531,646 patent/US3935162A/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US2666078A (en) * | 1952-05-16 | 1954-01-12 | Arvey Corp | Bis-trichloroethyl benzene phosphonate |
US2867547A (en) * | 1953-09-22 | 1959-01-06 | Victor Chemical Works | Method of flameproofing fibers, compositions used therein and the resulting products |
US2803562A (en) * | 1955-05-26 | 1957-08-20 | Dow Chemical Co | Treatment of cellulosic materials to impart flame resistance thereto |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4606853A (en) * | 1983-08-11 | 1986-08-19 | Imperial Chemical Industries Plc | Fire retardant polyamide compositions |
US20090255039A1 (en) * | 2008-04-10 | 2009-10-15 | Pontus Danielsson | Chemical protective garment with added flash fire protection |
US8247077B2 (en) * | 2008-04-10 | 2012-08-21 | Ansell Protective Solutions Ab | Chemical protective garment with added flash fire protection |
US8268451B2 (en) | 2008-04-10 | 2012-09-18 | Ansell Protective Solutions Ab | Chemical protective garment with added flash fire protection |
Also Published As
Publication number | Publication date |
---|---|
BE797632A (en) | 1973-10-01 |
FR2178236A1 (en) | 1973-11-09 |
FR2178236B1 (en) | 1976-09-10 |
GB1432013A (en) | 1976-04-14 |
JPS499090A (en) | 1974-01-26 |
NL7304500A (en) | 1973-10-02 |
US3935162A (en) | 1976-01-27 |
US3901650A (en) | 1975-08-26 |
DE2316043A1 (en) | 1973-10-18 |
US3803269A (en) | 1974-04-09 |
CA1006171A (en) | 1977-03-01 |
US3823206A (en) | 1974-07-09 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: OCCIDENTAL CHEMICAL CORPORATION Free format text: CHANGE OF NAME;ASSIGNOR:HOOKER CHEMICALS & PLASTICS CORP.;REEL/FRAME:004109/0487 Effective date: 19820330 |