US3374292A - Phosphono carboxamides - Google Patents

Phosphono carboxamides Download PDF

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Publication number
US3374292A
US3374292A US646119A US64611967A US3374292A US 3374292 A US3374292 A US 3374292A US 646119 A US646119 A US 646119A US 64611967 A US64611967 A US 64611967A US 3374292 A US3374292 A US 3374292A
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United States
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solution
mixture
added
propionamide
hydroxymethyl
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US646119A
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Zahir Sheik Abdul-Cader
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BASF Schweiz AG
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Ciba AG
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • 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
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/423—Amino-aldehyde resins
    • D06M15/43—Amino-aldehyde resins modified by phosphorus compounds
    • D06M15/432—Amino-aldehyde resins modified by phosphorus compounds by phosphonic 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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
    • 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
    • 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
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
    • C07F9/657181—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and, at least, one ring oxygen atom being part of a (thio)phosphonic acid derivative
    • 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

Definitions

  • This invention relates to substituted phosphono-amides, to processes for their production, to compositions containing such compounds, and to the use of such compositions to impart flame-resistance to cellulose and cellulosecontaining materials.
  • a known single-bath process involving a metal oxide entails padding a dispersion of a chlorinated hydrocarbon and finely divided antimony oxide on to the fabric and heating to render the finish wash-proof.
  • the active agent in this case is antimony oxychloride which is formed by the interaction of the oxide with the hydrogen chloride liberated from the chlorinated hydrocarbon when flame temperatures are approached.
  • the handle of the finished fabric is deleteriously affected and this is especially so with fine, closely-woven fabrics.
  • Esterification of cellulosic materials with, for instance, diammonium hydrogen orthophosphate has also been used to impart flame resistance. It has the disadvantage that the treated-material is susceptible to ion-exchange in hard water or soap solutions, the inactive calcium or sodium salt being formed. The flame resistance must then be regenerated by steeping the material in ammonium chloride solution.
  • the present invention provides a new class of substituted phosphono-amides which can be used in conjunction with aminoplasts to confer flame-resistance on cellulosic materials by a process which avoids some or all of the disadvantages of known processes.
  • the new substituted phosphono-amides are those of the general Formula I:
  • R represents hydrogen, allyl or alkyl of up to six carbon atoms
  • n is either 1, when X represents hydrogen, methyl or a CH CON-HCH OR group, or zero, when X represents a -CH CONHCH OR group
  • R and R either each represent the same or different alkyl, alkenyl, cycloalkyl, cycloalkenyl, alkoxyalkyl, alkoxyalkenyl, aryl, alkoxyaryl, or alkylene residues, which may be substituted by one or more chlorine and/or bromine atoms, the terminal valency of any such alkylene residue being linked to a group of Formula II:
  • R and R together represent, a polymethylene chain containing from two to six carbon atoms which may be linked to a second polymethylene chain contain ing two to six carbon atoms, via a spiro carbon, which polymethylene chainsmay be substituted by one or more chlorine and/or bromine atoms and/or methyl groups, the terminal valencies of the second polymethylene chain, if such be present, being linked to a group of Formula II.
  • Preferred compounds of Formula I are those wherein R and R either represent identicalalkyl groups, particularly those; containing up to four carbon atoms, or identical alkenyl or alkylene groups, particularly those containing from two to four carbon atoms; or together represent a polymethylene group containing from two to sixcarbon atoms. Also preferred are those compounds wherein R and -R together represent a polymethylene chain containing from two to three carbon atoms linked to a second such polymethylene chain via a spiro-carbon. Further preferred are those compounds of Formula I wherein each of R and R contains up to four chlorine and/ or bromine atoms.
  • preferred compounds are N-hydroxymethyl-3-(diethylphosphono) propionamide, N-hydroxymethyl-3-(diallylphosphono) propionatnide,
  • the compound of Formula VII is added to an aqueous solution of formaldehyde, the pH of the reaction mixture being maintained at or above 7.0 by the addition of an alkaline-reacting substance, suitably sodium hydroxide, and to maintain the temperature of the reaction mixture between 40 C. and 60 C.
  • an alkaline-reacting substance suitably sodium hydroxide
  • the solution may be cooled and filtered.
  • the product may be incorporated in the flameproofing compositions hereinafter described as the aqueous solution so obtained.
  • Another preferred method comprises heating a compound of Formula VII with paraformaldehyde in the presence of an alkaline-reacting substance, suitably potassium carbonate or sodium carbonate. Temperatures between about 75 C. and about 150 C., may be employed; if a solvent, such as methanol is added, reaction may be effected at lower temperatures, e.g. about 50 C.
  • an alkaline-reacting substance suitably potassium carbonate or sodium carbonate.
  • R O o R 0 H VIII wherein R and R are as hereinbefore defined except that references to the group P.(CHz)n.(['/HCONIICI.I1OR o X should be understood as references to the group o with acrylamide, methacrylamide, itaconamide, fumaramide or maleamide.
  • a non-acidic condensation catalyst preferably an alkaline catalyst.
  • the latter may be an alkali metal, an alkaline P.CH:CH2C ONHCHzOH metal amide, an alkali metal hydride, a secondary or tertiary amine, an alkali metal salt of the phosphite diesters, a quaternary ammonium hydroxide or basic ionexchange resin, and, especially, a solution or slurry of an alkali metal alkoxide in the corresponding alcohol.
  • a volatile inert solvent particularly a high-boiling liquid, may be added to moderate the reaction. Addition of a solvent is desirable but not essential, when the unsaturated amide is a solid under the reaction conditions.
  • compounds of the general Formula I wherein R denotes an alkyl group containing from one to six carbon atoms are produced by reacting a compound of Formula I in which R is hydrogen with an aliphatic monohydric alcohol containing from one to six carbon atoms, in the presence of an acid.
  • compounds of the general Formula I wherein R denotes an allyl group are produced by reacting a compound of Formula I in which R is hydrogen with allyl alcohol in the presence of an acid.
  • compounds of the general Formula I wherein R denotes an alkyl group containing from one to six carbon atoms or an allyl group are prepared by reacting a compound of Formula VIII with one to two molar proportions of an N-alkoxymethylor N allyloxymethyl 0:,fl unsaturated amide of the Formula X:
  • compositions of utility in imparting flame-resistance to cellulosic materials, which contain at least one compound of the general Formula I having one -CONHCH OR group and an aminoplast, or at least one compound of the general Formula I having two CNHCH OR groups and, optionally, an aminoplast.
  • suc-h compositions also contain a latent acid catalyst to accelerate curing of the aminoplast and cross-linking of the compound of the general Formula I having two CONHCH OR groups.
  • the latent acid catalysts which may be used are well-known in the process of curing aminoplasts on cellulosic materials, and include for example, ammonium chloride, ammonium dihydrogen orthophosphate, magnesium chloride, zinc nitrate, etc.
  • the aminoplast employed may be a condensation product of formaldehyde with urea or a derivative thereof such as ethyleneurea or, preferably, with melamine or a derivative, such as an ether of the said melamineforma-ldehyde condensation product.
  • a process for rendering cellulose-containing materials flame-resistant by treatment with such a composition followed by heating the treated material to cure the said aminoplast, and/or to effect cross-linking of the compound of general Formula I containing two CONHCH OR groups is within the scope of the invention.
  • the propionamide (1440 g.) was then added gradually to formalin (36.5%, 564 g.) at 50 C., the pH of the mixture being maintained at 7.5-8.0 by adding approximately 5 ml. of 40% caustic soda solution. After the mixture had been stirred for 2 hours it was allowed to v6 cool to room temperature and filtered. Approximately 2000 g. of an 82.0% solution of N-hydroxymethyl-3- (diethylphosphono)propionamide was obtained.
  • the infra-red spectrum of the product indicated it to be the required N-hydroxymethyl compound by the presence of the characteristic amide-II band at 1550 cm.- and a broad band at about 3350 cm. due to the hydroxyl group and NH-stretching of the secondary amide.
  • This product (271.5 g., 1.5 moles) was added in portions to 36.5% formalin solution (123 g., 1.5 moles) at 55-60 C.
  • the pH of the mixture was maintained at 8.0 by the addition of 40% caustic soda solution, about 1 m1. being required.
  • the reaction mixture was stirred for 1 hour at 60 C., cooled and filtered to give a solution of the desired product.
  • This compound (119 g.) was similarly hydroxymethylated with 36.5% formalin solution (41 g.) at 55- 60 C. and a solution of the desired productobtained, as described in Example I.
  • This intermediate (237 g.) was treated with 36.5% formalin solution (82 g.) at 5560 0., about 0.2 ml. of 40% caustic soda solution being added.
  • the reaction mixture was stirred for 2 hours at 60 C., cooled and filtered to give a solution of the desired product.
  • the intermediate (11.05 g., 0.05 mole), paraformaldehyde (1.5 g., 0.05 mole) and methanol (25 ml.) were heated at 50 C. for 1 hour, the mixture being kept at pH 8.0 by addition of a few drops of concentrated methanolic sodium methoxide solution.
  • the hydroxymethyl derivative remained as a clear, resinous liquid on evaporation of the solvent.
  • Pentaerythritol (68 g., 0.5 mole) was transesterified with diethyl phosphite (276 g., 2 moles) in the presence of concentrated ethanolic sodium ethoxide solution (5 ml.), g. of ethanol being collected over 2 hours. Unchanged diethyl phosphite was then distilled off. The viscous, colourless residue (105.2 g.) set to a glassy solid on cooling.
  • the intermediate was reacted with acrylamide (64.5 g.) in dimethyl formamide (200 ml.) as described above, 40 ml. of 4.4 M-methanolic sodium methoxide solution being added. After distilling off the solvents, 185 g. of a resinous material remained. This was then reacted with 36.5% formalin (27.2 g.) as previously described.
  • This intermediate (23.9 g., 0.1 mole), paraformaldehyde (3.1 g.) and anhydrous potassium carbonate (0.2 g.) were heated at C. for 2 hours to yield the desired product as a yellow, viscous resin.
  • Ammonia gas was passed into a mixture of the ester (687.3 g.) and methanol (3 litres) for about six hours, i.e. until the mixture was saturated. The mixture was allowed to stand at room temperature for one week, and
  • the succinamide (26.6 g.) was dissolved in methanol .(100 ml.), and paraformaldehyde (6.0 g.) was added, followed by a few drops of methanolic sodium methoxide solution to adjust the pH of the mixture to 9.0. The mixture was then stirred at 50 C. for 3 hours.
  • Product E Product F. Ammonium d ydrogen orthophospha Magnesium chloride hcxahydrate Amonium chloride EXAMPLE XIX 30 Product D was a 75% aqueous solution of a highly NNLbh th I l etherified polymethylolmelamine.
  • Product F was a commercially-available nonionic wetting agent derived from ethylene oxide.
  • Samples of a bleached cotton fabric and of a bleached spun viscose material with raised woven effects were padded to a weight increase of 80% (cotton) or 100% (spun viscose), dried at 80 C., cured for 4.5 minutes at l55160 C., and rinsed for minutes with cold soft water.
  • Product B was a conventional flame-proofing agent con- 1 0 taining ammonium pyrophosphate.
  • N-(hydroxymethyl) 3 (diethylphosphono)-propionamide was incorporated (as an aqueous solution) into decorative paper-melamine formaldehyde laminates.
  • Product C was a commercially-available water-soluble F1 ofi properties were evaluated by the Su f Condensation Product of melamine and o aldehyde. Spread of Flame Test (British Standard Specification No.
  • Bleached cotton fabric was padded with each solution 7r 476, Part I, 1953).
  • the resin employed was used as a to give a weight increase of 85%, dried at 80 C., and 0 50% aqueous solution and prepared by the reaction of melamine (1 part by weight) with formaldehyde (2.45 quirements of British Standard Specification No. 3120 parts by weight, as an aqueous solution); it was cured at (1959). 145 C.
  • Cotton flannelette was padded with an aqueous solution N'hydroxymethyl 3 (blswmmomchlommethyl' i l)phosphono)propionamide. containlng, per litre, 300 g. of N-methoxymethyl-3-(d1- Propy ethylphosphono)Propionarnide, 140 g. of Product D and 40 N'auyloxymethyl 3 (diethylp hosp homo) p mp 10H- 5 g. of ammonium chloride. The impregnated fabric was amlde' dried and then heated at 150 C. for 5 minutes. The The compound of theformula: treated fabric met the requirements of British Standard (limo 0 Specification NO. 3119 (1959). RUECHCONHCHOH EXAMPLE XXV CaHaO dmoonnomon Cotton flannelette was padded with an aqueous sol-u- The compound of the formula:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
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US646119A 1963-05-03 1967-06-14 Phosphono carboxamides Expired - Lifetime US3374292A (en)

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GB17563/63A GB1011572A (en) 1963-05-03 1963-05-03 Phosphorus-containing carboxylic acid amides

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BE (1) BE647376A (cs)
CH (2) CH474605A (cs)
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GB (1) GB1011572A (cs)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3699192A (en) * 1970-10-20 1972-10-17 U S Oil Co Inc Phosphonium compounds
US3765837A (en) * 1971-09-03 1973-10-16 Burlington Industries Inc Flame retardant finish for polyester/cotton blends
US3772068A (en) * 1970-04-27 1973-11-13 Ciba Geigy Ag Process for flameproofing fibre materials of polyesters and cellulose
US3894122A (en) * 1972-11-02 1975-07-08 Hoechst Ag Phosphorus compounds containing amide groups
US3903337A (en) * 1974-04-04 1975-09-02 Mitsui Toatsu Chemicals Method for processing cellulose containing material to impart flame resistance
US4007318A (en) * 1975-05-21 1977-02-08 General Electric Company Phosphorylated polystyrene and method for forming same
US4017462A (en) * 1974-08-22 1977-04-12 The United States Of America As Represented By The Secretary Of Agriculture Treatment of organic textiles with adduct polymers and phenols
US4162279A (en) * 1977-09-28 1979-07-24 Stauffer Chemical Company Phosphonoxycarboxamides
US4577013A (en) * 1983-12-22 1986-03-18 Ciba-Geigy Corporation Ionically modified cellulose material, its preparation and its use
US5320785A (en) * 1990-08-03 1994-06-14 Ciba-Geigy Corporation Compositions containing phosphono compounds and organic acids as flameproofing agents
EP2133461A1 (de) 2008-06-12 2009-12-16 Huntsman Textile Effects (Germany) GmbH Zusammensetzung für die Behandlung von Fasermaterialien, insbesondere mittels Ausziehverfahren
US20100044653A1 (en) * 2006-12-20 2010-02-25 Salman Dermeik Composition for treating fiber materials

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6211792A (ja) * 1985-02-27 1987-01-20 Dainippon Ink & Chem Inc 難燃剤及び難燃木質物
DE3682906D1 (de) * 1986-08-20 1992-01-23 Dainippon Ink & Chemicals Feuerhemmendes mittel fuer holzartige stoffe.
GB9004633D0 (en) * 1990-03-01 1990-04-25 Albright & Wilson Flame retardant composition and method of use

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3772068A (en) * 1970-04-27 1973-11-13 Ciba Geigy Ag Process for flameproofing fibre materials of polyesters and cellulose
US3699192A (en) * 1970-10-20 1972-10-17 U S Oil Co Inc Phosphonium compounds
US3765837A (en) * 1971-09-03 1973-10-16 Burlington Industries Inc Flame retardant finish for polyester/cotton blends
US3894122A (en) * 1972-11-02 1975-07-08 Hoechst Ag Phosphorus compounds containing amide groups
US3903337A (en) * 1974-04-04 1975-09-02 Mitsui Toatsu Chemicals Method for processing cellulose containing material to impart flame resistance
US4017462A (en) * 1974-08-22 1977-04-12 The United States Of America As Represented By The Secretary Of Agriculture Treatment of organic textiles with adduct polymers and phenols
US4007318A (en) * 1975-05-21 1977-02-08 General Electric Company Phosphorylated polystyrene and method for forming same
US4162279A (en) * 1977-09-28 1979-07-24 Stauffer Chemical Company Phosphonoxycarboxamides
US4577013A (en) * 1983-12-22 1986-03-18 Ciba-Geigy Corporation Ionically modified cellulose material, its preparation and its use
US5320785A (en) * 1990-08-03 1994-06-14 Ciba-Geigy Corporation Compositions containing phosphono compounds and organic acids as flameproofing agents
US20100044653A1 (en) * 2006-12-20 2010-02-25 Salman Dermeik Composition for treating fiber materials
EP2133461A1 (de) 2008-06-12 2009-12-16 Huntsman Textile Effects (Germany) GmbH Zusammensetzung für die Behandlung von Fasermaterialien, insbesondere mittels Ausziehverfahren
US20110114904A1 (en) * 2008-06-12 2011-05-19 Huntsman Textile Effects (Germany) Gmbh Composition for treatment of fiber materials by exhaust method in particular
US8303835B2 (en) 2008-06-12 2012-11-06 Huntsman Textile Effects (Germany) Gmbh Composition for treatment of fiber materials by exhaust method in particular

Also Published As

Publication number Publication date
CH474540A (de) 1969-06-30
DE1469281A1 (de) 1969-05-08
CH474605A (de) 1969-08-15
CH297667A4 (cs) 1969-03-14
DE1469281C3 (de) 1973-11-22
DE1469281B2 (de) 1973-04-26
BE647376A (cs)
GB1011572A (en) 1965-12-01

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