US3892578A - Phosphorus containing vinyl ethers - Google Patents

Phosphorus containing vinyl ethers Download PDF

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US3892578A
US3892578A US278506A US27850672A US3892578A US 3892578 A US3892578 A US 3892578A US 278506 A US278506 A US 278506A US 27850672 A US27850672 A US 27850672A US 3892578 A US3892578 A US 3892578A
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compound
textile material
phosphonate
dimethyl
alpha
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US278506A
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Peter Golborn
James L Dever
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Occidental Chemical Corp
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Hooker Chemicals and Plastics Corp
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Priority to GB2012472A priority Critical patent/GB1366456A/en
Priority to CA141,241A priority patent/CA990904A/en
Priority to FR7216371A priority patent/FR2137624B1/fr
Priority to DE19722222489 priority patent/DE2222489A1/en
Priority to BE783162A priority patent/BE783162A/en
Priority to NL7206277A priority patent/NL7206277A/xx
Application filed by Hooker Chemicals and Plastics Corp filed Critical Hooker Chemicals and Plastics Corp
Priority to US278506A priority patent/US3892578A/en
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Priority to CA249,644A priority patent/CA1009245A/en
Assigned to OCCIDENTAL CHEMICAL CORPORATION reassignment OCCIDENTAL CHEMICAL CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE APRIL 1, 1982. Assignors: HOOKER CHEMICALS & PLASTICS CORP.
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    • 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
    • C07F9/4015—Esters of acyclic unsaturated acids
    • 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
    • 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/667—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing phosphorus in the main chain

Definitions

  • One process which involves the use of a single processing bath consists of padding a dispersion of a chlorinated hydrocarbon and finely divided antimony oxide on the cellulosic fabric. The fabric is then heated to render the finish wash-proof. Near the combustion temperature, antimony oxide will react with hydrogen chloride, generated by degradation of the chlorinated hydrocarbon, to form antimony oxychloride which suppresses flame.
  • the combination of a chlorinated hydrocarbon and finely divided antimony oxide are not acceptable finishes for closely woven fabrics because they deleteriously effect the hand of the finished product.
  • Flame resistance has been imparted to cellulosic materials by esterification of the cellulose with diammonium hydrogen orthophosphate. Products so treated are subject to metathesis reactions with cations in aqueous solution during washing, the ammonium cation being displaced by calcium, sodium or magnesium. The flame resistance properties of the diammonium orthophosphate ester of the cellulosic material is then regenerated by reacting the washed product with an ammonium chloride solution.
  • R is the methyl or ethyl radicals.
  • the ortho acetate ester is prepared by the alcoholysis of an imino ester hydrochloride which itself is obtained from a nitrile;
  • the compounds of this invention may be applied directly to a textile material by conventional finishing techniques such as by thermal or radiation induced pad curing.
  • the finished textile product whether it is subjected to additional finishing treatments or not, exhibits reasonably durable, flame resistant properties.
  • An application of from about 5 to about 40 percent by weight of fire retardant based upon the textile weight is sufficient to provide protection to the treated material.
  • the flame retarding agents of this invention may be applied to various textiles such as cellulosic materials and proteinaceous materials.
  • cellulosic materials applicants intend to embrace cotton, rayon, regenerated cellulose and cellulose derivatives which retain the cellulose backbone and at least one hydroxyl substituent per repeating glucose unit.
  • proteinaceous material applicants intend to embrace those textile materials which present the functional groups of protein, such as wool, with which the flame retardants are especially durable.
  • the compounds of the instant invention may be polymerized to afford relatively low molecular weight polymers which possess flame retardant characteristics and are suitable for use in the treatment of textile materials.
  • the monomeric compounds of this invention may be copolymerized with olefinically unsaturated compounds such as ethylene, propylene, styrene, butadiene, acrylic acids, acrylonitriles, acrylates, acrylamides, vinyl acetate, vinyl alcohol, vinyl chloride, vinylidene chloride, etc. and mixtures thereof such as acrylonitrile-butadiene-styrene.
  • the copolymers in themselves possess flame retardant properties rendering them suitable for use by incorporation into other polymer blends as well as for direct treatment of a textile material.
  • the polymerization of the monomers of this invention procedes in the presence of a Lewis acid by a cationic mechanism.
  • the copolymerization of the compounds of this invention are readily conducted by conventional techniques employing free radical initiating reagents such as the organic peroxides, azo compounds, and ionizing irradiation.
  • the production of the ortho acetate type compounds is a conventional organic preparation illustrated by S. M. McElvain et a1, .l.A.C.S. 64, 1942 pp. 1825-1827.
  • T he conversion of the ortho acetate to the dialkyl 1,1- d alkoxyethyl phosphonate (111) is a conventional preparation ill strat d by H. Gr ss ct al. .I. Prakt Chem. 311 (1969) 571.
  • the dehyd oalkoxylation reaction of the ins ant in vention employed in the prepa ation of he novel compounds of this invention is a beta elimina ion of an alcohol from an alpha, alpha. diallioxv diall-tyl phosphonate ester performe g nerally at. a tcn-perature from about 90 to 250C. with removal of the alco ol as it is fo med. It is genera ly de red to remove the alcohol as rapidly as po s ble and for this reason the temperatures no mally employed are those in the upper ranqe of opeta ility bet en about 150 o 230 Cfinliflrfltlfi.
  • Th beta elim nation reaction may be hase cataly7ed.
  • the base catalysts employed are sodium carbonate, Sodium bicarbonate, sod um acet e, sodi m methoxide, sodium phenoxide, n-butyl lithium, triethylamine, and the like.
  • the base catalv ts operable in the process o the instant nven ion may he genera ly classifi d as the al al me al sa s of carbonic acid o lower alien-ole acids, the a ka i metal lower all oxdes or plienoxides, the tertiary lowe alkylamines and the lower alkyl organo meta lic deriva ives in which the me al is selected t on: the G oup I, 11, Ill and the transition metas of the Pe iodic Table as presented in the Handbook of Chemistry and Phy ics, 43 d Fditinn, 1?5ll 62, Chemical Rubber Publ shing Co.
  • EXAMPLE 2 198 g. (1.0 mole) dimethyl-l,1(dimethoxy)-ethyl phosphonate, 2.5 g. sodium bicarbonate and 2.5 g. hydroquinone were placed in a round bottomed flask. The reaction mixture was heated and over the temperature range 158 to 200C. methanol was removed from the reaction flask by distillation. 39 g. distillate was collected in 2.5 hours. After cooling, the reaction mixture was distilled to give 126.4 g. dimethyl methoxyvinyl phosphonate, boiling at to 84C. under a pressure of 0.6 to 0.9 millimeters of mercury.
  • EXAMPLE 3 In a round bottomed flask fitted with a thermometer, mechanical stirrer, distillation head cooled with dry ice and acetone and a heating mantle was placed 198 g. (1.0 mole) dimethyl-1,1-(dimethoxy)-ethyl phosphonate, 2.5 g. anhydrous sodium acetate and 2.5 g. hydroquinone. The reaction mixture was heated and at about C. methanol was formed and was removed from the reaction vessel by distillation. 39.5 g. distillate was collected in 3.5 hours and during the distillation, the temperature of the reaction mixture increased to C. The reaction mixture was cooled and distilled to yie d 1 10.7 g. dimethyl methoxyvinyl phosphonate, boiling at 69 to 75C. under a pressure of 0.2 to 0.6 millimeters of mercury.
  • EXAMPLE 4 In a round bottomed flask equipped with a thermometer, mechanical stirrer, distillation head cooled with dry ice and ac tone and a heating mantle, was placed 127 g. (0.5 mo e) diethyl-l,l(dicthoxy)-ethyl phosphonate, 2 g. sodium methoxide and 2.5 g. hydroquinone. The reacti n mixture was heated under nitrogen and at about 158C. ethanol was formed and was removed hy distillation. 26.5 g. ethanol was collected over 3.25 hours and during the dis illation the temperature of the reaction mixture rose to 210C. Reaction mixture was cooled and dist lled to gi e 78.3 g. diethyl ethoxyvinyl phosphonate, boiling at 60 to 67C. under a pres ure of 0.2 millimeters mercury, 11 1.4 10.
  • EXAMPLE 7 In a round bottomed flask fitted with a thermometer, mechanical stirrer, distillation head cooled with dry ice and acetone and a heating mantle, was placed 198 g. (1.0 mole) dimethyl-1,l-(dimethoxy)-ethyl phosphonate. 5 ml. triethylamine and 2.5 g. hydroquinone. The reaction mixture was heated under nitrogen and at about 140C methanol was ormed and was removed by istilla ion. 36 g. methanol was collected over 2.5 hours and during this time the temperature of the reaction mixture rose to 180C. The reaction mixture was cooled and vacuum distilled at 90 to 100C under 0.9 to 2.6 millimeters mercury pressure to g e 122.5 g. dimethyl methoxyvinyl phosphouate, 11 1.4 45.
  • EXAMPLE 9 utes.
  • the sample- was then immersed in a solution con-- taining 50 g. diethyl ethoxyvinyl phosphonate and 50 g. methanol for 10 minutes and squeezed to remove excess solution.
  • the sample was then held at 330F. for 2.5 minutes, then rinsed in hot water and dried.
  • EXAMPLE 10 A sample of cotton sheeting. 5.0 ounces per square yard was impregnated with an aqueous solution containing 15 g. solium hydroxide per 100 g. of solution and squeezed to about 80% wetpick up. The impregnated fabric was then dried at 250F for 2 minutes. The resulting fabric was then impregnated with a methanolic solution containing 50 g. diethyl ethoxyvinyl phosphonate per 100 g. of solution and squeezed to about 100% wet weight pick up. This impregnated fabric was cured for 2.5 minutes at 330F, then washed in hot water and dried. The treated cotton sheeting had a char length of 6.5 inches as measured by AATCC Method 34-1966.
  • EXAMPLE 1 l A sample of rayon staple fiber was immersed in a solution of 63 g. dimethyl methoxyvinyl phosphonate, 37 g. maleic anyhydride, 2 g. azo-bis-isobutyronitrile and 100 ml. benzene for 1.5 hours and then squeezed to about 80% wet pick up and held at C for 12 hours. The fiber was twisted tightly and held in a bunsen flame. Upon removal, the material was selfextinguish ng. A sample not treated by the procedure described was completely cons med by he bunsen fla'ne.
  • a sample of wool oedford cord of approximately 8.0 ounces per square ya d was immersed in a solution of 63 g. dimethyl methoxyvinyl phosphonate, 37 g. maleic anhydride, 2 g. azo-bis-isoh'.ityronitrile and 100 ml. benzene for 1.5 hours. After squeezing the fabric to about wet pick up, it was cured at 75C. for 12 hours. The treated fabric showed an initial char of about 1.0 inches and about 2.0 nches after 5 home washes.
  • a process for imparting flame resistance to a textile material comprising combining, from 5 to 40 percent by weight of textile material, a compound of the formula R O O CH 1 II n 2 P COR wherein R R and R are lower alkyl radica s independently containing from 1 to 8 carbon atoms, with a textile material selected from the group consisting of cellulosic material and proteinaceous material.
  • said textile material is selected from the group consisting of rayon, cotton and wool.
  • a composition comprising a textile material selected from the. group consisting of a celiulosic material and a proteinaceous material and from 5 to 0 percent,
  • composition of claim wherein said compound is diethyl (alpha-ethoxy) vinyl phosphonate.

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

Abstract

Compounds of the formula:

IN WHICH R1, R2 and R3 are lower alkyl radicals are produced by the dehydroalkoxylation of the corresponding dialkyl 1,1dialkoxyethyl phosphonates. The vinyl ether phosphonates are useful as flame retarding agents for textile materials and in the production of polymers and copolymers which possess flame retardant properties.

Description

Golborn et a1.
July 1, 1975 EZ ISEEISIORUS CONTAINING VINYL OTHER PUBLICATIONS M k et 1., Chem. Ab 68 1968 3973lt d [75] Inventors: Peter Golborn; James L. Dever, a S pp an both of Lewiston, NY.
[73] Assignee: Hooker Chemicals & Plastics Primary Examiner-Harry Wong, Jr.
Corporation, Niagara Falls, NY. Attorney, Agent, or FirmPeter F. Casella; Donald C. Filed: g 1972 Studley; W1l11am J. Crossetta, Jr.
[2]] App]. No.: 278,506 57 ABSTRACT Related US. Application Data Compounds of the formula: [62] Division of Ser. No. 142,075, May 10, 1971,
abandoned. R O 0 CH 1 II II 2 [52] US. Cl 106/16; 106/15 FP; 117/140; -0R
260/855 ZA; 260/857; 260/875 G; 2
260/877; 260/881 R; 260/881 PE; 260/91.1 R; 260/968 [51] Int. Cl C09k 3/28 in which R R and R are lower alkyl radicals are produced by the dehydroalkoxylation of the correl Field of Search 106/15 FP, P sponding dialkyl 1,1-dialkoxyethyl phosphonates. The vinyl ether phosphonates are useful as flame retarding References Cited agents for textile materials and in the production of UNITED STATES PATENTS polymers and copolymers which possess flame retar- 2,5l6,l68 7/1950 Woodstock 260/45.7 dant propernes' 2,934,507 4/1960 Chadwick et al. 260/45.7
3,669,610 6/1972 Friedman 106/15 PF 10 Clams Drawmgs .r w R a 1 PHOSPHORUS CONTAINING VINYL ETHERS This is a division of application Ser. No. 142,075, filed May 10, 1971, now abandoned.
BACKGROUND OF THE INVENTION Many flame retarding agents and methods of application have been developed in attempts to obtain flame resistant textile materials. For example, mixtures of ammonium dihydrogen orthophosphate or boric acid with borax have been used to retard flame in cellulosic materials. Wash-proof finishes have been produced by depositing metal oxides within or on the fibers of cellulose by the successive precipitation of ferric oxide 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. These strongly acidic solutions are both inconvenient to use and pose the problems of possible degradation of the cellulose. Furthermore, the presence of a metal oxide coating on cellulosic textile materials creates difficulties in some subsequent dyeing processes.
One process which involves the use of a single processing bath consists of padding a dispersion of a chlorinated hydrocarbon and finely divided antimony oxide on the cellulosic fabric. The fabric is then heated to render the finish wash-proof. Near the combustion temperature, antimony oxide will react with hydrogen chloride, generated by degradation of the chlorinated hydrocarbon, to form antimony oxychloride which suppresses flame. The combination of a chlorinated hydrocarbon and finely divided antimony oxide are not acceptable finishes for closely woven fabrics because they deleteriously effect the hand of the finished product.
Flame resistance has been imparted to cellulosic materials by esterification of the cellulose with diammonium hydrogen orthophosphate. Products so treated are subject to metathesis reactions with cations in aqueous solution during washing, the ammonium cation being displaced by calcium, sodium or magnesium. The flame resistance properties of the diammonium orthophosphate ester of the cellulosic material is then regenerated by reacting the washed product with an ammonium chloride solution.
BRIEF DESCRIPTION OF THE INVENTION In accordance with this invention, there is provided a novel group of flame retardants for textile materials which are dialkyl (alpha-alkoxy) vinyl phosphonates of the formula:
CH n
The latter compounds being prepared by the reaction of a trialkyl ortho acetate with a tertiary phosphite and PCl in accordance with known procedures. For example,
in which R is the methyl or ethyl radicals.
The ortho acetate ester is prepared by the alcoholysis of an imino ester hydrochloride which itself is obtained from a nitrile;
DC H5 The compounds of this invention may be applied directly to a textile material by conventional finishing techniques such as by thermal or radiation induced pad curing. The finished textile product whether it is subjected to additional finishing treatments or not, exhibits reasonably durable, flame resistant properties. An application of from about 5 to about 40 percent by weight of fire retardant based upon the textile weight is sufficient to provide protection to the treated material.
The flame retarding agents of this invention may be applied to various textiles such as cellulosic materials and proteinaceous materials. By cellulosic materials, applicants intend to embrace cotton, rayon, regenerated cellulose and cellulose derivatives which retain the cellulose backbone and at least one hydroxyl substituent per repeating glucose unit. By proteinaceous material applicants intend to embrace those textile materials which present the functional groups of protein, such as wool, with which the flame retardants are especially durable.
In addition, the compounds of the instant invention may be polymerized to afford relatively low molecular weight polymers which possess flame retardant characteristics and are suitable for use in the treatment of textile materials. Likewise, the monomeric compounds of this invention may be copolymerized with olefinically unsaturated compounds such as ethylene, propylene, styrene, butadiene, acrylic acids, acrylonitriles, acrylates, acrylamides, vinyl acetate, vinyl alcohol, vinyl chloride, vinylidene chloride, etc. and mixtures thereof such as acrylonitrile-butadiene-styrene. The copolymers in themselves possess flame retardant properties rendering them suitable for use by incorporation into other polymer blends as well as for direct treatment of a textile material. The polymerization of the monomers of this invention procedes in the presence of a Lewis acid by a cationic mechanism. The copolymerization of the compounds of this invention are readily conducted by conventional techniques employing free radical initiating reagents such as the organic peroxides, azo compounds, and ionizing irradiation.
DETAILED DESCRIPTION OF THE INVENTION The compounds of this invention are prepared by the reaction sequence:
(m) CH OCH 3 llil 2 III-?(RO) PCOR ROH or P-COR ROH base cat. I1I- A (R01 where R is methyl or ethyl.
The production of the ortho acetate type compounds is a conventional organic preparation illustrated by S. M. McElvain et a1, .l.A.C.S. 64, 1942 pp. 1825-1827. T he conversion of the ortho acetate to the dialkyl 1,1- d alkoxyethyl phosphonate (111) is a conventional preparation ill strat d by H. Gr ss ct al. .I. Prakt Chem. 311 (1969) 571.
The dehyd oalkoxylation reaction of the ins ant in vention employed in the prepa ation of he novel compounds of this invention is a beta elimina ion of an alcohol from an alpha, alpha. diallioxv diall-tyl phosphonate ester performe g nerally at. a tcn-perature from about 90 to 250C. with removal of the alco ol as it is fo med. It is genera ly de red to remove the alcohol as rapidly as po s ble and for this reason the temperatures no mally employed are those in the upper ranqe of opeta ility bet en about 150 o 230 Cfinliflrfltlfi. Th beta elim nation reaction may be hase cataly7ed. Am ng the base catalysts employed are sodium carbonate, Sodium bicarbonate, sod um acet e, sodi m methoxide, sodium phenoxide, n-butyl lithium, triethylamine, and the like. Therefore, the base catalv ts operable in the process o the instant nven ion may he genera ly classifi d as the al al me al sa s of carbonic acid o lower alien-ole acids, the a ka i metal lower all oxdes or plienoxides, the tertiary lowe alkylamines and the lower alkyl organo meta lic deriva ives in which the me al is selected t on: the G oup I, 11, Ill and the transition metas of the Pe iodic Table as presented in the Handbook of Chemistry and Phy ics, 43 d Fditinn, 1?5ll 62, Chemical Rubber Publ shing Co.
As monomers f r the production o homoand co' polymers, t e alpha-alkoxyviny ol osohonate es ers of this in enti n afhrd i T-e r p p t s t e polymer w ich rende s it especially useful in ca tingi s for use in the construcmo di qs, foams and la n stry in t re fo -a of wall cove inqs and p nels :c system conduits and ca ti gs s well as in the is often of p a ticn i:
or el ct: texti e industry v!ere1. vne retard mount mportance.
190 g. (0.75 mole) diethy l .l-t yly p osphonete, 2.5 g sodium carbo ate and 2.5 y ou not e was placed in a round. bottomed flask. The reac on m xture was hea ed ar d over the temperature range 1 0" to 223C. etlzaccl wa distilled rom the reaction flask. A total of 39 g. distillate was collected in 3 hours. The reaction mixture was cooled and vacuum distilled at 69 to 84C. under 0.3 millimeters mercury pressure to yield 105.3 g. diethyl ethoxyvinyl phosphonate.
Calculated: C, 46.2; H, 8.2; P, 14.9.
Found: C, 45.2; H, 8.8; P, 14.4.
EXAMPLE 2 198 g. (1.0 mole) dimethyl-l,1(dimethoxy)-ethyl phosphonate, 2.5 g. sodium bicarbonate and 2.5 g. hydroquinone were placed in a round bottomed flask. The reaction mixture was heated and over the temperature range 158 to 200C. methanol was removed from the reaction flask by distillation. 39 g. distillate was collected in 2.5 hours. After cooling, the reaction mixture was distilled to give 126.4 g. dimethyl methoxyvinyl phosphonate, boiling at to 84C. under a pressure of 0.6 to 0.9 millimeters of mercury.
Calculated C, 36.2; H, 6.7; P, 18.6.
Found C, 34.9; H, 6.8; P, 18.9.
EXAMPLE 3 In a round bottomed flask fitted with a thermometer, mechanical stirrer, distillation head cooled with dry ice and acetone and a heating mantle was placed 198 g. (1.0 mole) dimethyl-1,1-(dimethoxy)-ethyl phosphonate, 2.5 g. anhydrous sodium acetate and 2.5 g. hydroquinone. The reaction mixture was heated and at about C. methanol was formed and was removed from the reaction vessel by distillation. 39.5 g. distillate was collected in 3.5 hours and during the distillation, the temperature of the reaction mixture increased to C. The reaction mixture was cooled and distilled to yie d 1 10.7 g. dimethyl methoxyvinyl phosphonate, boiling at 69 to 75C. under a pressure of 0.2 to 0.6 millimeters of mercury.
Calculated C, 36.2;1-1, 6.7; P, 18.6
Found C, 34.9: H, 7.1; P, 18.5.
EXAMPLE 4 In a round bottomed flask equipped with a thermometer, mechanical stirrer, distillation head cooled with dry ice and ac tone and a heating mantle, was placed 127 g. (0.5 mo e) diethyl-l,l(dicthoxy)-ethyl phosphonate, 2 g. sodium methoxide and 2.5 g. hydroquinone. The reacti n mixture was heated under nitrogen and at about 158C. ethanol was formed and was removed hy distillation. 26.5 g. ethanol was collected over 3.25 hours and during the dis illation the temperature of the reaction mixture rose to 210C. Reaction mixture was cooled and dist lled to gi e 78.3 g. diethyl ethoxyvinyl phosphonate, boiling at 60 to 67C. under a pres ure of 0.2 millimeters mercury, 11 1.4 10.
Calcul ted C, 46.2: H, 8.2; P, 14.9.
Found c, 46.0; H, 8.6; P, 148.
EX AM PLE 5 198 g. (1.0 mole) dimcthvl-l,l (dimethoxy)-ethyl phosphona e, 2.5 g. sodium phenoxide and 2.5 g. hydroquinone were placed in a round bottomed flask. The reaction mixture was heated under ni rogen and over the temperature range 140 to 200C. methanol was removed fr m the reaction vessel by distillation. 42 g. distillate was collected over a period of 5.5 hours. Reactive mixture was cooled and vacuum distilled at 80 to 0 C. under 0.4 to 1.0 mil meters mercury pressure to yield 105 g. dimethyl methoxyyinyl phospho-- nate, n ,,1.4434. p f
Calculated C, 36.2; H, 6.7; P, 18.6. Found C, 34.0; H, 7.1; P, 18.6. I
EXAMPLE 6 Dimethyl-l,1-(dimethoxy)-ethy1. ph osphonate 198 g. 1.0 mole) and hydroquinone (2.5 g.) was placed in a round bottomed flask fitted with a thermometer, dropping funnel,mechanicalstirrer, distillation head and a heating mantle. n--butyl lithium (2 g.) in hexane (20 ml.) was added over 5 minutes to the reaction mixture which was then heated and methanol and hexane was removed by distillation. 5 g. distilla e was collected over 3.5 hours ard he temperature of the reaction mixture increased during this period of time from 92 to 200C. After cooling, the reaction mixture was vacuum distilled at 95 to 108C. under 2.8 to 3.8 millimeters mercury pressure to yield 54 g. dimethyl methoxyvinyl phosphonate, n 1.4420.
Calculated C, 36.2; H, 6.7; P, 18.6.
Found C. 34.8; H, 6.7; P. 18.0.
EXAMPLE 7 In a round bottomed flask fitted with a thermometer, mechanical stirrer, distillation head cooled with dry ice and acetone and a heating mantle, was placed 198 g. (1.0 mole) dimethyl-1,l-(dimethoxy)-ethyl phosphonate. 5 ml. triethylamine and 2.5 g. hydroquinone. The reaction mixture was heated under nitrogen and at about 140C methanol was ormed and was removed by istilla ion. 36 g. methanol was collected over 2.5 hours and during this time the temperature of the reaction mixture rose to 180C. The reaction mixture was cooled and vacuum distilled at 90 to 100C under 0.9 to 2.6 millimeters mercury pressure to g e 122.5 g. dimethyl methoxyvinyl phosphouate, 11 1.4 45.
Calculated C, 36.2; H, 6.7; P, 18.6.
Found C, 34.6; H, 6.9: P, 18.6.
EXAMELE 8 Dimethyl-l,l-(dimethoxy)-ethyl phosphor a e (198 g. 1.0 mole) and hydroquinone (2.5 g) was placed in a round bottomed flask, fitted with a thermometer, mechanical st rrer, distillation head cooled with C 'jy ice and acetone and a heating mantle. The reaction mixture was heated under nitrogen and methanol was removed by distillation as it was formed. 64 g. distillate was collected over 5 hours and the temperature of the reaction mixture increased from 197 to 220C. The reaction mixture was cooled and vacuum distilled at 74 to 80C under 0.8 to 1.0 millimeters mercury a isolute to yield 98.1 g. dimethyl methoxyvinyl phosphonate n 1. 437.
Calculated C, 36.2; H, 6.7; P, 18.6.
Found C, 34.6; H, 7.0; P, 18.6.
EXAMPLE 9 utes. The sample-was then immersed in a solution con-- taining 50 g. diethyl ethoxyvinyl phosphonate and 50 g. methanol for 10 minutes and squeezed to remove excess solution. The sample was then held at 330F. for 2.5 minutes, then rinsed in hot water and dried. The
a fiber was twisted tightly and held in a bunscn flame. Upon removal, the material was self-extinguishing. A sample not treated by the procedure described was completely consumed by the bunsen flame.
EXAMPLE 10 A sample of cotton sheeting. 5.0 ounces per square yard was impregnated with an aqueous solution containing 15 g. solium hydroxide per 100 g. of solution and squeezed to about 80% wetpick up. The impregnated fabric was then dried at 250F for 2 minutes. The resulting fabric was then impregnated with a methanolic solution containing 50 g. diethyl ethoxyvinyl phosphonate per 100 g. of solution and squeezed to about 100% wet weight pick up. This impregnated fabric was cured for 2.5 minutes at 330F, then washed in hot water and dried. The treated cotton sheeting had a char length of 6.5 inches as measured by AATCC Method 34-1966.
EXAMPLE 1 l A sample of rayon staple fiber was immersed in a solution of 63 g. dimethyl methoxyvinyl phosphonate, 37 g. maleic anyhydride, 2 g. azo-bis-isobutyronitrile and 100 ml. benzene for 1.5 hours and then squeezed to about 80% wet pick up and held at C for 12 hours. The fiber was twisted tightly and held in a bunsen flame. Upon removal, the material was selfextinguish ng. A sample not treated by the procedure described was completely cons med by he bunsen fla'ne.
EXAMPLE 1?.
A sample of wool oedford cord of approximately 8.0 ounces per square ya d was immersed in a solution of 63 g. dimethyl methoxyvinyl phosphonate, 37 g. maleic anhydride, 2 g. azo-bis-isoh'.ityronitrile and 100 ml. benzene for 1.5 hours. After squeezing the fabric to about wet pick up, it was cured at 75C. for 12 hours. The treated fabric showed an initial char of about 1.0 inches and about 2.0 nches after 5 home washes.
What is claimed is:
1. A process for imparting flame resistance to a textile material comprising combining, from 5 to 40 percent by weight of textile material, a compound of the formula R O O CH 1 II n 2 P COR wherein R R and R are lower alkyl radica s independently containing from 1 to 8 carbon atoms, with a textile material selected from the group consisting of cellulosic material and proteinaceous material.
2. The process of claim 1 wherein said compound is diethyl (alpha-ethoxy) vinyl phosphonate.
3. The process of claim 1 wh rein said compound is dimethyl (alplna-metlioxy) v nyl phosphonate.
4. The process of claim 1 wherein said textile material is selected from the group consisting of rayon, cotton and wool.
5. A composition comprising a textile material selected from the. group consisting of a celiulosic material and a proteinaceous material and from 5 to 0 percent,
by weight of textile material, of a compound of the formula wherein R R and R are lower alkyl radicals independently containing from 1 to 8 carbon atoms.
6. The composition of claim wherein said compound is diethyl (alpha-ethoxy) vinyl phosphonate.
pound.

Claims (10)

1. A PROCESS FOR IMPARTING FLAME RESISTANCE TO A TEXTILE MATERIAL COMPRISING COMBINING, FROM 5 TO 40 PERCENT BY WEIGHT OF TEXTILE MATERIAL, A COMPOUND OF THE FORMULA
2. The process of claim 1 wherein said compound is diethyl (alpha-ethoxy) vinyl phosphonate.
3. The process of claim 1 wherein said compound is dimethyl (alpha-methoxy) vinyl phosphonate.
4. The process of claim 1 wherein said textile material is selected from the group consisting of rayon, cotton and wool.
5. A composition comprising a textile material selected from the group consisting of a cellulosic material and a proteinaceous material and from 5 to 40 percent, by weight of textile material, of a compound of the formula
6. The composition of claim 5 wherein said compound is diethyl (alpha-ethoxy) vinyl phosphonate.
7. The composition of claim 5 wherein said compound is dimethyl (alpha-methoxy) vinyl phosphonate.
8. The composition of claim 5 wherein said textile material is selected from the group consisting of rayon, cotton and wool.
9. The process of claim 1 wherein the textile material is immersed in said compound and thereafter squeezed to about 80% wet pickup.
10. The procEss of claim 1 wherein the textile is immersed in an aqueous solution of sodium hydroxide, squeezed, dried, and thereafter immersed in said compound.
US278506A 1971-05-10 1972-08-07 Phosphorus containing vinyl ethers Expired - Lifetime US3892578A (en)

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GB2012472A GB1366456A (en) 1971-05-10 1972-05-01 Phosphorus containing vinyl ethers
CA141,241A CA990904A (en) 1971-05-10 1972-05-03 Phosphorus containing vinyl ethers
DE19722222489 DE2222489A1 (en) 1971-05-10 1972-05-08 Phosphorus-containing vinyl ethers and processes for their preparation
BE783162A BE783162A (en) 1971-05-10 1972-05-08 VINYL ETHERS CONTAINING PHOSPHORUS
FR7216371A FR2137624B1 (en) 1971-05-10 1972-05-08
NL7206277A NL7206277A (en) 1971-05-10 1972-05-09
US278506A US3892578A (en) 1971-05-10 1972-08-07 Phosphorus containing vinyl ethers
CA249,644A CA1009245A (en) 1971-05-10 1976-04-06 Phosphorus containing vinyl ethers

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US14207571A 1971-05-10 1971-05-10
US278506A US3892578A (en) 1971-05-10 1972-08-07 Phosphorus containing vinyl ethers

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4098986A (en) * 1976-03-31 1978-07-04 Chas. S. Tanner Co. Copolymerizable monoethylenically unsaturated phosphonates and fire retardant copolymers containing the same
US4822861A (en) * 1988-03-15 1989-04-18 Polychrome Corporation Method for the preparation of polyvinyl phosphonic acid
US4851490A (en) * 1983-10-26 1989-07-25 Betz Laboratories, Inc. Water soluble phosphonated polymers

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2516168A (en) * 1947-10-17 1950-07-25 Victor Chemical Works Aryl and alkyl alkenylphosphonates
US2934507A (en) * 1954-06-18 1960-04-26 Monsanto Chemicals Polyvinyl chloride resins stabilized with mixtures of phosphonate esters, epoxy compounds and metallic salts of fatty acids
US3669610A (en) * 1970-02-12 1972-06-13 Us Agriculture Flame-resistant wool

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2516168A (en) * 1947-10-17 1950-07-25 Victor Chemical Works Aryl and alkyl alkenylphosphonates
US2934507A (en) * 1954-06-18 1960-04-26 Monsanto Chemicals Polyvinyl chloride resins stabilized with mixtures of phosphonate esters, epoxy compounds and metallic salts of fatty acids
US3669610A (en) * 1970-02-12 1972-06-13 Us Agriculture Flame-resistant wool

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4098986A (en) * 1976-03-31 1978-07-04 Chas. S. Tanner Co. Copolymerizable monoethylenically unsaturated phosphonates and fire retardant copolymers containing the same
US4851490A (en) * 1983-10-26 1989-07-25 Betz Laboratories, Inc. Water soluble phosphonated polymers
US4822861A (en) * 1988-03-15 1989-04-18 Polychrome Corporation Method for the preparation of polyvinyl phosphonic acid

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FR2137624B1 (en) 1977-12-23
GB1366456A (en) 1974-09-11
NL7206277A (en) 1972-11-14
DE2222489A1 (en) 1972-11-23
BE783162A (en) 1972-11-08
FR2137624A1 (en) 1972-12-29
CA990904A (en) 1976-06-15

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