US3755323A - Triazinylaminoalkyl phosphonates - Google Patents

Triazinylaminoalkyl phosphonates Download PDF

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US3755323A
US3755323A US00050364A US3755323DA US3755323A US 3755323 A US3755323 A US 3755323A US 00050364 A US00050364 A US 00050364A US 3755323D A US3755323D A US 3755323DA US 3755323 A US3755323 A US 3755323A
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triazinylaminoalkyl
phosphonate
reaction
phosphonates
textile
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E Weil
R Fearing
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Akzo America Inc
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Stauffer Chemical Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
    • 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
    • C07F9/6515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having three nitrogen atoms as the only ring hetero atoms
    • C07F9/6521—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/40—Chemically modified polycondensates
    • 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
    • D06M15/39—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

Definitions

  • ABSTRACT 5 Claims No Drawings TRIAZINYLAMINOALKYL PHOSPI-IONATES BACKGROUND OF THE INVENTION
  • the literature discloses numerous examples of attempts to achieve flame retardant textile finishes based on phosphorus containing triazine or melamine compounds. Early efforts in this area are exemplified by the use of co-condensates of methylol melamines with acidic phosphorus compounds as is taught in U.S. Pat. Nos. 2,582,961; 2,781,281 and 2,711,998.
  • the prior art also discloses flame retardant textile finishes containing phosphoramide or phosphoramidate linkages, i.e.
  • Still another class of flame retardant textile finishes disclosed in the prior art are of the products resulting from the co-condensation of phosphine derivatives with methylolmelamines, e.g. the use of dibutyl phosphine as taught in U.S. Pat. No. 3,050,522 and the use of tetrakis (hydroxymethyl) phosphonium chloride or hydroxide as taught in British Pat. Nos. 882,993 and 884,785 and in U.S. Pat. Nos. 2,722,108; 2,809,941; 2,812,311 and 2,911,322.
  • the prime object of this invention to provide a novel class of phosphorus containing melamine derivatives for use in the preparation of flame retardant textile finishes. It is a further object to provide phosphorus containing melamine derivatives characterized by their low cost and toxicity as well as by their ability to yield highly durable textile finishes which will retain their fire retardant properties after being subjected to repeated launderings.
  • phosphorus containing melamine derivatives characterized by their low cost and toxicity as well as by their ability to yield highly durable textile finishes which will retain their fire retardant properties after being subjected to repeated launderings.
  • triazinylaminoalkyl phosphonates of this invention may be described as those compounds corresponding to the structural formula:
  • A, B, and C are selected from the group consisting of halogen and -NR R groups with at least one of A, B, and C being an -NR'R group, in which R and R are selected from the group consisting of hydrogen, C,C alkyl, C,C hydroxyalkyl, methylene, methyleneoxymethylene methylol, C -C alkoxymethyl and Z, where Z is a phosphonate radical of the structure where n is an integer having a value from 0 to 1, R and R are selected from the group consisting of hydrogen and C -C alkyl, and R and R are selected from the group consisting of alkyl, C C alkoxyalkyl, allyl, C -C 2-haloalkyl, C -C Z-hydroxyalkyl, and aryl, with the proviso that at least one Z group is present in the molecule of said triazinylaminoalkyl phosphonate and that where R and/or R is a methylene or
  • a preferred group of compounds within the above defined triazinylaminoalkyl phosphonates are the melamine N- alkylphosphonic esters wherein all three radi-cals A, B, and C, as defined above, have the structure NRR where R and R are selected from the group consisting of hydrogen, methylol, C -C alkoxymethyl, methylene, methyleneoxymethylene, and 2 where Z is as defined above.
  • each of A, B, and C is a group having the structure NRR wherein R and R are selected from the group consisting of hydrogen, methylol, methylene, methyleneoxymethylene, C C alkoxymethyl, and Z where Z is a phosphonate radical of the structure 0 2 l i o filkynlzv with the proviso that at least one of the R and R groups in the molecule is a Z group and that at least one of the R and R groups in the molecule is a methylol or C -C alkoxymethyl group and that no more than two of the R and R groups in the molecule is hydrogen.
  • the mixtures of the above defined compounds are products of the various processes described hereinbelow wherein precursor triazine compounds containing methylol groups in those positions where Z groups are desired in the final reaction product are reacted in liquid or slurry phases with a (C,C alkyl-O) P reagent until trivalent phosphorus is substantially absent from the re-action mixture.
  • a (C,C alkyl-O) P reagent for example, trivalent phosphorus is substantially absent from the re-action mixture.
  • C -C alkoxymethyl groups, rather than methylol groups are to be conscribed hereinbelow and (2) heating in the liquid phase 55 with a (C,C alkyl-O) PHO reagent until HP- bonds are substantially undetectable in the reaction mixture 60 by the usual mercurometric or infrared analytical methods.
  • This invention comprehends the preparation and use of: 1) mixed products of a typical resinous nature, both the individual components of these mixtures and the mixtures per se being within the scope of the invention and (2) individual molecular species such as can be systematically synthesized as, for example, from cyanuric chloride by means of a process involving the stepwise replacement of the chlorine atoms by reagents containing HNRR groups wherein R and R are as defined above and which may be the same or different.
  • the various processes for the preparation of these triazinylaminoalkyl phosphonates comprise reacting, at from about -200 C., at least one precursor triazine compound selected from the group consisting of polymethylol or methylolated melamines, polyalkoxymethylmelamines, cyanuric chloride, chloromethylmelamine and C,-Cl8 alkoxymethyl melamines and from about 0.3 to 6 moles, per mole of said precursor melamine compound, of at least one phosphorus containing reagent selected from the group consisting of trialkyl phosphites, phosphorus trihalides, dialkyl l-arninoalkyl phosphonates, dialkyl phosphonates and hydroxyalkyl phosphonates.
  • the details of these various processes are described herein
  • the derivatives of this invention can be prepared by means of a liquid phase reaction between from about 0.3 to 6, and preferably l-5, moles of a trialkyl phosphite, such as triethyl phosphite, and one mole of a methylolmelamine or of a substituted methylolmelamine having sufficient methylol groups to react with substantially all of the trialkyl phosphite.
  • the reaction may be conducted with pure methylolmelamines which dissolve when phosphonated or with crude methanolic reaction solutions or inert solvent suspensions such as one might directly obtain by means of known prior art procedures from melamine and formaldehyde.
  • the reaction is conducted at temperatures in the range of from about 0 to 200 C.
  • reaction mixture may then be stripped, usually under vacuum, at a temperature of from about 0 to 200 C. yielding the desired triazinylaminoalkyl phosphonate as a residue which may be in the form of a syrup or gummy resin that is soluble in water and in many organic solvents such as alcohols, trichloroethylene and chloroform.
  • These derivatives can be prepared by means of the reaction, in the liquid phase, between one mole of an alkoxymethylmelamine, such as hexamethoxymethylmelamine, about 0.1 to 2 moles of a phosphorus trihalide, such as phosphorus trichloride and from 0.3 to 6 moles of a trialkyl phosphite such as trimethyl phosphite.
  • the latter reagent is first preferably added to the melamine derivative, although premixing with the phosphorus trichloride, as well as other modes of addition, are also permissible.
  • the conversion is a sequence of two exothermic reactions which is carried out at a temperature of from about 20 to 180 C., and preferably at 0l20 C., and for a period of from about 1 minute to 50 hours depending upon the temperature that is utilized.
  • the first reaction in this sequence is a conversion, by PCl of the methoxymethyl groups on the resin intermediate to the form of chloromethyl groups while the second reaction in the sequence is between these chloromethyl groups and the trialkyl phosphite to produce the desired amino methylphosphonic diester groups.
  • dialkyl phosphorochloridite is formed which can react with the resin in a manner which can be represented as a one step overall equation. In either case, the reaction mixture may be heated, after the addition of the trialkyl phosphite, until trivalent phosphorus is no longer detectable, whereupon it is stripped of the alkyl chloride by-product.
  • Triazinylaminoalkyl phosphonates can be prepared by reacting one mole of cyanuric chloride with from about 1 to 3 moles of a dialkyl l-aminoalkylphosphonate, such as diethyl l-aminoisopropylphosphonate, in the optional presence of an equivalent amount ofa base which serves as an HCl acceptor as, for example,,triethylamine, sodium carbonate, pyridine or the like.
  • the dialkyl laminophosphonate may itself serve as the acid acceptor in which case one mole out of each two moles introduced will serve in this capacity while the other will be introduced into the reaction product molecule.
  • This reaction is conducted in the liquid phase, preferably in a solvent for cyanuric chloride, at a temperature of from about 0 to C. until the desired 1 to 3 moles of chloride ion is released.
  • the desired reaction product is generally isolated by evaporation of the solvent, by chilling, or by addition of a non-solvent therefor.
  • This process is especially useful for preparing halotriazinylaminoalkylphosphonates, and specific isomers of the compounds of this invention, since the three chlorine atoms of cyanuric chloride react stepwise, the first very rapidly, the second much less rapidly, and the third quite slowly.
  • compounds can be produced having NR'R groups, as defined above, where at least one of the R or R groups is a phosphonate group.
  • the derivatives of this invention can be prepared by first reacting one mole of an alkoxymethylmelamine with from about 0.3 to 6, preferably 1 to 5, moles of phosgene gas at a temperature of from about to 50 C. for a period of about 1 to 5 hours to obtain a chloromethylmelamine. This reaction is set forth in US. Patent No. 3,317,529.
  • each mole of the residue is slowly reacted with about 0.3 to 6, preferably 1 to 5, moles of a trialkyl phosphite, such as triethyl phosphite, at to 150 C.; the concentration of the latter reagent being equivalent to the number of moles of phosgene used is the prior atep. Distillation yields an alkyl chloride as a by-product leaving the desired triazinylaminoalkyl phosphonate as a residue.
  • a trialkyl phosphite such as triethyl phosphite
  • Process No. 5 These derivatives can be prepared by reacting about 0.3 to 6, preferably 1 to 5, moles ofa dialkyl phosphonate, such as a dimethyl phosphonate, with one mole of an alkoxymethylmelamine, such as hexamethoxymethylmelamine or a fully or partially methylated pentamethyloimelamine at a temperature of from about 20 to 200C. for a period of from about 0.1 to 48 hrs. until substantial completion of the reaction is shown by infra-red, nuclear magnetic resonance or oxidimetric analysis for unreacted dialkyl phosphonate or by distillation of the desired quantity of byproduct alkanol.
  • a dialkyl phosphonate such as a dimethyl phosphonate
  • an alkoxymethylmelamine such as hexamethoxymethylmelamine or a fully or partially methylated pentamethyloimelamine
  • a trialkyl phosphite may also be pres ent in the system in order to scavange any acids formed by side reactions. if desired, the resulting reaction mixture may be used as is or it may first be stripped free of traces of unreacted dialkyl phosphonate and byproduct alkanol.
  • Process No. 6 Another synthetic route involves the reaction between one mole of an alkoxymethylmelamine, such as heamethoxymethylmelamine, and 0.3 to 6, preferably 1 to 5, moles of a trialkyl phosphite, such as trimethyl phosphite, and from about 0.3 to 6, preferably 1 to 5, moles of a proton donor which may be an organic acid, such as acetic acid, a phenol or an alcohol.
  • This reaction is run at a temperature of from about 20 to 200 C. for a period of from about 0.
  • the resulting reaction mixture may be used as is or it may be stripped free of traces of unreacted trialkyl phosphite and proton donor.
  • the alkylation product of the proton donor such for example as alkyl acetate where acetic acid is used as the proton donor, is also formed as a by-product and may be removed by distillation.
  • Process No. 7 A synthetic route suitable for the preparation of the compounds of this invention where (I -C alkoxymethyl group where the group Z is to be present in the product, with from about 0.3-6 moles of a selected dialkyl l-hydroxyalkyl phosphonate having the structure 0 ll 1100mm 1* 0 run.
  • This reaction is preferably run at about 20-200 C. in the presence of an acid catalyst until substantially one molar equivalent of water (in the case where the precursor melamine compound contains a CH,OH group) or alcohol (in the case where the precursor melamine compound contains a CH o-alkyl group) has been evolved, as determined by means of some suitable analytical technique such as by distillation and collection of the water or alcohol.
  • the resulting product contains -CH,Ol-l groups
  • it is possi ble to subsequently etherify such CH OH groups by the addition of an alcohol, preferably a primary alcohol, in the presence of an acid catalyst.
  • an alcohol preferably a primary alcohol
  • Such etherification processes are, of course, well known in the melamine/formaldehyde resin art.
  • the resulting product contains NH groups
  • Such N(CH Ol-l) groups may then be etherified in the manner described hereinabove.
  • diluents or solvents can be employed with the proviso that they are sufficiently non-reactive towards the respective reagents and reaction products.
  • Suitable diluents include, for example, hydrocarbons, halogenated hydrocarbons such as chloroform, trichloroethylene, and the like. In some cases ketones, alcohols and water can be used provided that the reaction rate of these solvents with the trivalent phosphorus compound are slower than the desired reaction.
  • trimethyl, triethyl, tripropyl, tributyl, trioctyl, trioctadecyl, triallyl, tris-2-chloroethyl, tris-2- chloropropyl, dimethyl ethyl, diethyl propyl, methyl diethyl and ethyl dipropyl phosphite, etc. are all applicable for use as trialkyl phosphites; dimethyl, diethyl, dipropyl, dibutyl, diallyl, bis(2-chloroethyl), dioctyl, methyl ethyl and methyl propyl phosphorochloridite, etc.
  • dialkyl phosphorochloridites dimethyl l-aminomethyl phosphonate, diethyl l-aminomethyl phosphonate, diethyl l-aminoethylphosphonate, dimethyl l-aminoethylephosphonate, diethyl l-ethylaminomethylphosphonate, diisopropyl 1-n-propylaminoisopropylphosphonate, tetraethyliminobis-methylphosphonate and diallyl l-methylamino'm butylphosphonate, etc.
  • dialkyl l-aminoalkylphosphonates dimethyl, diethyl, dipropyl, dibutyl, diallyl, bis(2-chloroethyl), dioctyl, didodecyl, dioctadecyl, methyl ethyl and methyl propyl phosphonate, etc.
  • dialkyl phosphonates are all applicable for use as dialkyl phosphonates; and, dimethylolmelamine, trimethylolmelamine, tetramethylolmelamine, pentamethylolmelamine, hexamethylolmelamine, tetramethylol methylenebismelamine, tris(methoxymethyl)melamine, tetra-, pentaand hexakis(methoxymethyl)melamine, partially methylated tri-, tetra-, pentaand hexamethylolmelamine and, partially or fully ethylated tri-, tetra-, penta-, or hexamethylolmelamine are all applicable for use as alkoxymethylmelamines. Also suitable are methoxymethylated methylene (or methylene oxymethylene) bismelamine dimers and trimers, etc.
  • novel triazinylaminoalltyl phosphonates of this invention may be characterized as colorless viscous liquids or syrups or as readily fusible resins all of which are at least partially soluble in water and in many of the common organic solvents such, for example, as alcohols, ketones, methylene chloride, methyl chloroform, chloroform, ethylene dichloride, trichloroethylene, xylene and perchloroethylene.
  • these compounds generally hydrolyze at a rate of less than about 1 percent, by weight, per hour. They are distinguished from the phosphorus substituted melamine compounds of the prior art since they are non-ionic neither ionizing nor, as noted above, undergoing extensive hydrolysis in water under ordinary conditions of use. And, as will be noted, hereinbelow, these compounds can be cured, by acid catalysis, so as to form insoluble thermoset resins.
  • the triazinylaminoalkyl phosphonates of this invention provide excellent results when utilized as flame proofing finishes for both natural and synthetic textile materials. It is also noteworthy to point out that the finishes derived from these derivatives may also be characterized as durable press finishes since they permit the textiles to which they have been applied to retain their original shape and remain wrinkle-free after being laundered without any need for having them ironed.
  • Textiles may be treated with the derivatives of the invention while the latter are dissolved in an aqueous mediumor, if desired, they may be applied while in the form of organic solvent solutions utilizing such essentially non-polar solvents as methylene chloride, ethylene dichloride, trichloroethene, perchloroethylene, etc. and mixtures thereof.
  • organic solvent solutions utilizing such essentially non-polar solvents as methylene chloride, ethylene dichloride, trichloroethene, perchloroethylene, etc. and mixtures thereof.
  • the solutions may be applied to textiles by the use of any desired procedure. It is merely necessary to have the triazinylaminoalkyl phosphonate absorbed throughout the mass of the textile and/or to apply it to at least one surface thereof by means of any convenient procedure. Thus, they may be applied by being sprayed onto one or both surfaces of the textile or, as is more frequently the case, the textile may be passed or padded through the solution while the latter is being held in a tank or other suitable container. Such a process is commonly referred to as a padding technique with the solution being referred to as a padding bath" or padding solution.
  • the concentration of the triazinylaminoalkyl phosphonate within the padding bath, or other applicable solution, will be dependent upon a number of factors including the nature of the fibers which comprise the textile, the weight and weave of the textile, the degree of flameproofing that is desired in the finished textile, as well as other technical and economic considerations known and understood by those skilled in the art.
  • the padding bath should contain from about 5 to percent, by weight, of one or more of the triazinylaminoalkyl phosphonate; the latter concentration being sufficient to deposit a finish upon the textile which will contain from about 5 to 75 percent, by weight of the textile, of the triazinylaminoalkyl phosphonate which, in turn, will provide the thus treated textile with about 0.2 to 7.5 percent, by weight of the textile, of phosphorus.
  • the latter limits are merely illustrative and may be varied so as to provide a textile finish having any desired degree of flame retardancy.
  • the triazinylaminoalkyl phosphonates contained within the padding solution may be cured, or crosslinked, so as to yield a highly durable, fire retardant finish.
  • This curing operation may be accomplished by maintaining the treated fabric for a period of from about 1 hour to 10 days at ambient temperatures, or, a more rapid cure may be affected by the application of heat at temperatures of up to about 200 C. Under the latter conditions, a curing time as short as only about one second may be required. Additional control of the curing rate may be achieved by the optional presence in the padding solution of various adjuvants including pH controlling substances such as acid releasing salts which accelerate or catalyze the rate of cure or basic substances which will, on the other hand, retard the cure rate.
  • pH controlling substances such as acid releasing salts which accelerate or catalyze the rate of cure or basic substances which will, on the other hand, retard the cure rate.
  • Rate retarding substances include, for example, alkali metal hydroxides, such as sodium hydroxide, and alkali metal bicarbonates and carbonates such as sodium bicarbonate and sodium carbonate.
  • Cure accelerators, or catalysts are exemplified by ammonium, alkaline earth and transition metal salts such as ammonium chloride, magnesium chloride, zinc chloride and zinc nitrate; amine hydrochlorides such as diethanolamine hydrochloride triethylamine hydrochloride; and, organic and inorganic acids such as acetic, oxalic, maleic, malic, citric, trichloroacetic, hydrochloric and phosphoric acids and alkyl acid phosphates.
  • curing rate retarders and accelerators may, respectively, be used alone or in combination with one another in a concentration which is sufficient to attain the cure rate desired by the practitioner.
  • An exception to the foregoing discussion regarding catalysts and retarders comprises the compositions of this invention wherein A, B, or C are halogen.
  • alkaline substances are accelerators of the desired reaction for the attachment of these special reagents to a cellulosic textile substrate while acid substances retard this reaction.
  • co-reactants are materials which will undergo a reaction with the triazinylaminoalkyl phosphonate and which are used for various purposes such as to control the crosslink density of the finish, to improve the hand and durability of the finished textile as well as its durability, flame retardance, durable press, laundering and crease resistance properties.
  • aminoplast forming reagents such, for example, as urea; condensation products of urea-formaldehyde, urea-glyoxal or urea-glyoxal-formaldehyde; melamine; melamineformaldehyde condensation products; N-methylolated O-alkyl carbamates; ammonia, and formaldehyde.
  • urea condensation products of urea-formaldehyde, urea-glyoxal or urea-glyoxal-formaldehyde
  • melamine melamineformaldehyde condensation products
  • N-methylolated O-alkyl carbamates ammonia, and formaldehyde.
  • urea is meant to include within its scope various cyclic ureas such, for example, as ethyleneurea, propyleneurea, uron, triazones, glyoxaldiurein and isocyanuric acid.
  • co-reactants include forrnamide, acetamide, propionamide, dialkoxyphosphonopropionamide or the N-methylol derivatives thereof, tetrakis(- hydroxymethyl) phosphonium chloride or hydroxide, trimethylolphosphine, aminated phosphonitrilic chloride, phosphoric triamide and thermal condensation products thereof, ammonium phosphates, glycols such as the phosphorus-containing glycols and the hydroxyalkyl esters of all phosphorus acids.
  • Particularly useful as coreactants are the novel ureidoalkylphosphonates disclosed in copending application Ser. No. 50,304 filed June 26, 1970.
  • the triazinylaminoalkyl phosphonate finishing reagents of this invention can be made to condense during the above described curing process with co-reactant compounds having either Ol-I, -NH, -NCH OH or N-Cl-l OCI-I groups and the proper and oil-repellents such as polyfluoroalkyl compounds, silicones, acrylic acid copolymers, and the like; abrasion resistance agents such as polyacrylates, polyurethanes, and the like; colorants and color-modifying agents such as dyes, pigments, bleaches, anti-fading agents, ultraviolet screening agents and the like; antistatic agents such as quaternary ammonium compounds; humectants; bonding agents; antimicrobial agents which will supplement the inherent rotresistance and antimicrobial action of the triazinylaminoalkyl phosphonate containing finishes of this invention; and, pH modifying agents.
  • the padding bath may also contain adjuvants intended to directly facilitate the padding operation
  • All types of textiles may be treated by means of the process of this invention so as to provide them with durable, fire retardant finishes.
  • textiles derived from natural fibers such as cotton, wool, silk, sisal, jute, hemp and linen and from synthetic fibers including nylon and other polyamides; polyolefins such as polypropylene; polyesters such as polyethylene terephthalate; cellulosics such as rayon, cellulose acetate and triacetate; fiber glass; acrylics and modacrylics, i.e. fibers based on acrylonitrile copolymers; saran fibers, i.e. fibers based on vinylidene chloride copolymers; nytril fibers, i.e.
  • Textiles derived from blends of any of the above listed natural and/or synthetic fibers may also be treated by means of the process of this selection of such co-reactants in order to achieve a deinvention sired modification of crosslink density, crease resistance, durable press, and flame retardant properties will be evident to those skilled in the art.
  • dimethylolmela- As used in this disclosure, the term textile or textiles is meant to encompass woven or knitted fabrics as well as non-woven fabrics which consist of continuous or discontinuous fibers bonded so as to form a fabmifle; Uimelhylolmelamine; dimethylol y y ric by mechanical entanglement, thermal interfiber thyleneurea; trismethoxymethylmelamine; dimethyloluron; dimethylolethyleneurea; dimethylolpropyleneurea; N,N-dimethylol methyl carbamate; N,N-dimethylolethylcarbamate, N,N-dimethylol 2-hydroxyethylcarbamate; N,N-dimethylol methoxyethylcarbamate; urea methylolurea; dimethylolurea;
  • the padding bath containing the triazinylaminoalkyl phosphonates of this invention, and the textile finishes derived therefrom may contain other ingredients in order to modify the finish in accordance with practices known to those skilled in the art of textile finishings.
  • non-woven fabrics may contain a certain percentage of wood pulp as well as conventional textile fibers in which case part of the bonding process is achieved by means of hydrogen bonding between the cellulosic pulp fibers.
  • the finishing agents of this invention can serve not only as flame retardant finishes but can also contribute to .the interfiber bonding mechanism by serving as all or part of the adhesive or bonding resin component. This dual role can also be played by the finishing agents of'this invention in fabric laminates where the finishing agent can at the same time serve as the interlaminar bonding agent and as the flame retardant. In both of these systems, i.e.
  • finishing agents of this invention can also be blended with the usual bonding agents such, for example, as acrylic emulsion polymers, vinyl acetate, homoand copolymer emulsions, styrene-butadiene rubber emulsions, urethane resin emulsions, polyvinylchloride emulsions, polyvinylchloride acrylate emulsions, polyacrylates modified by vinylcarboxylic acid comonomers and the like.
  • bonding agents such, for example, as acrylic emulsion polymers, vinyl acetate, homoand copolymer emulsions, styrene-butadiene rubber emulsions, urethane resin emulsions, polyvinylchloride emulsions, polyvinylchloride acrylate emulsions, polyacrylates modified by vinylcarboxylic acid comonomers and the like.
  • novel triazinylaminoalkyl phosphonates of the invention may also be used in various other applications in which their flame retarding properties are advantageous. These include their being cured into thermoset resins which may be employed for the preparation of molded objects and coatings or for laminating or impregnating paper or wood. When used in molding resins, the novel compositions of this invention may be compounded with other thermosetting resins as well as with various tillers such as wood flours, clays, mica and the like.
  • the uncured or thermoset resins of this invention may also be used as flame retardant additives for other resins. For example, they may be employed to crosslink hydroxyl containing polymers such, for example, as alkyds and curable acrylic polymers so as to form coatings and laminates.
  • triazinylaminoalkyl phosphonates display useful biological properties which include, for example, their ability to function as preemergence herbicides especially in those compounds of this invention where A and/or B is halogen. 1n the latter use, these compounds need merely be applied to the locus of the weeds, i.e. the soil, the weeds per se or to the water in the case of aquatic weeds, in a phytotoxic concentration such, for example as from 0.5 to 50 pounds per acre depending upon the weed species, soil type, duration of control required and similar factors.
  • EXAMPLE I This example illustrates the preparation of one of the novel triazinylaminoalkyl phosphonates of this invention by means of reaction process No. 1 as described hereinabove.
  • EXAMPLE II This example illustrates the use of one of the novel triazinylaminoalkyl phosphonate derivatives of this invention as a therrnoset coating and as part of an epoxy resin system.
  • Part A An aqueous solution containing 20 parts of water, 10 parts of the derivative whose preparation is described in Example 1, hereinabove, and 0.2 parts of zinc nitrate was allowed to dry on the surface of a wooden board and was then heated for 12 hours at 95 C. the resultant cured coating was hard, infusible, clear, and completely resisted attach by water or aqueous sodium carbonate. When exposed to flame, this coating intumesced yielding a foamy char which affords fire protection to the underlying flammable substrate.
  • Parts B A mixture of 2.8 parts of the triazinylaminoalkyl phosphonate derivative whose preparation was described in Example 1, hereinabove, and 3.4 parts of Epon 828" (a commercial epoxy resin solid by the Shell Chemical Company which is mainly the diglycidyl ether of bis-phenol A) was heated to C. and stirred to obtain a clear melt which has degassed under vacuum and then allowed to cure over 10 hrs. at 95 C. The cooled resin was clear, had a Barcol hardness of 37, and was self-extinguishing when ignited by means of a Bunsen burner.
  • Epon 828 a commercial epoxy resin solid by the Shell Chemical Company which is mainly the diglycidyl ether of bis-phenol A
  • Phosphorus trichloride (27.5 grams, 0.2 mole) was mixed with 200 grams of trimethyl phosphite and maintained at 150-40 C. for three hours so as to obtain redistribution to a mixture estimated as containing up to 0.6 mole of dimethyl phosphorochloridite and 1.2 moles of excess trimethyl phosphite. This was then slowly added at 50 C. to 156 grams of hexamethoxymethylmelarnine (0.4 moles). The exothermic reaction period was followed by an additional 1% hours of heating (6575 C).
  • EXAMPLE IV This example illustrates the use of one of the novel triazinylaminoalkyl phosphonate derivatives in the preparation of a durable, flame retardant textile finish.
  • each of the curved or semi-circular mounted textile samples is oriented at various positions ranging from vertical to horizontal and a flame is ignited at its lower edge. If the textile is self-extinguishing in the vertical position, it is acceptable for use in all applications. If self-extinguishing when positioned at a 45 angle but not selfextinguishing in a vertical position, it is acceptable for use is less critical applications. However, if the treated textile is only self-extinguishing when in a horizontal position, the finish is only marginally acceptable and should be used only in non-critical applications. At the lowest add-on, i.e. 21 percent, the cloth did not maintain a flame, with only a 1% inch char length resulting at the near-vertical end of the curved test strip.
  • EXAMPLE V This example illustrates the preparation of two more the hydrochloride of diethyl l-aminoisopropylphosphonate.
  • the filtrate was evaporated and the gummy residue triturated with water to remove more hydrochloride.
  • the residual material was taken up in ether and chilled to obtain successive crops comprising two compounds.
  • the less soluble was a colorless crystalline solid, m.p. l52-l52.5 C. having the correct analysis (Cl calcd. 21.6, C1 found 21.7) for N N l NJ NHC(CH Reaction of this product with ethylamine affords the corresponding phosphonate which is an effective pre-emergence herbicide.
  • the more soluble compound derived from the residual material was a colorless crystalline solid, m.p.
  • this compound When applied to weed-infested soil pre-emergence at 20 lbs/acre, this compound substantially prevented the 65 growth of annual grassy weeds.
  • cyanuric chloride is reacted with ethylamine and then with diethyl l-aminoethylphosethylaminochlorotriazinylisopropyl phonate in order to obtain 2-chloro-4-ethylamino-6-( l- [diethoxyphosphino]ethylamino) -5-triazine which also functions as a pre-emergence herbicide.
  • EXAMPLE VI This example illustrates the preparation of another of the novel triazinylaminoalkyl phosphonate derivatives of this invention, the procedure utilized in this case being reaction process No. 4 as described hereinabove.
  • EXAMPLE VII This example again illustrates the use of another of the novel triazinylaminoalkyl phosphonates of this invention in the finishing of textiles.
  • the resulting formulation was then diluted to 10 grams by the addition of water.
  • the preparation of the latter formulation was then repeated with the addition, in this instance, of 1.0 grams of a co-reactant comprising a 50 percent aqueous solution of a partially methylated polymethylolmelamine and a dimethylolated ethyleneurea.
  • orig. P ori P LO1 Limiting oxygen lndex as determined by the procedure described by Fenimore and Martin in the November, 1966, issue of Medern Plastics.
  • this procedure directly relates flame retardancy to a measurement of the minimum percentage concentration of oxygen in a oxygenznitrogen mixture which pennits the sample to burn the LOI being calculated as follows:
  • EXAMPLE VlIl This example illustrates the preparation, on a large scale, of a triazinylaminoalkyl phosphonate by the use of reaction process No. 2.
  • EXAMPLE IX This example illustrates the preparation of a 10 triazinylaminoalkyl phosphonate by means of reaction process No. 5 as described hereinabove.
  • a mixture of 330 g. (3 moles) of dimethyl phosphonate and 390 g. 1 mole) of hexamethoxymethylmelamine was heated at l-l60 C. over a period of 5 15 hours while allowing 88 g. of distillate, primarily methanol, to distill off at a vapor temperature which did not exceed the boiling point of methanol.
  • the residual reaction mixture was then stripped free of unreacted dimethyl phosphonate and about 45 g. of volatile byleaving the desired phosphonated triazinylaminoalkyl reaction product as a colorless viscous syrup.
  • the thus treated cloth was then subjected to five laundry cycles, using 100 grams of detergent to 16 gallons of water (200 ppm. hardness expressed as CaCO with 10 towels, as ballast, in a Maytag washer. When dry, the cloth had an LOI of 28.0.
  • Another padding bath was prepared in which the concentration of the above described reaction product was reduced to 25 percent, by weight. However, it contained 5 percent, on a solids basis, of a dimethylolethyleneurea. A cured cloth which had been padded in this bath had a 16.2 percent dry add-on of this composltion.
  • the warm reaction product was diluted with methanol to an concentration.
  • the resultant easily-pourable liquid was then diluted with water to a concentation of 30 percent in which form it was suitable for application to textiles.
  • EXAMPLE XI This example illustrates the use, in a textile finishing operation, of the triazinylaminoalkyl phosphonate whose preparation was described in Example X hereinabove.
  • EXAMPLE XII This example illustrates the preparation of a triazinylaminoalkyl phosphonate by means of a reaction process No. 5 as described hereinabove.
  • EXAMPLE XIII This example illustrates the use of reaction process No. 1 for the preparation of a triazinylaminoalkyl phosphonate employing, in this instance, 50 percent aqueous solution of a partially methylated polymethylolmelamine and a dimethylolated ethyleneurea as the starting reagent.
  • the starting reagent was stripped of its water, then 96 grams of the resulting residue was mixed with 111 grams of trimethyl phosphite (0.89 moles); the latter concentration being roughly calculated to produce a trisubstituted melamine.
  • the stripped residue was warmed with twice its weight of methanol at a pH of 4 whereupon it was neutralized and stripped. The latter operation converted any free N-methylo1 groups to methoxymethyl groups, thereby increasing the pourability of the product.
  • the yield of mixed melamine N-methylphosphonic ester represented about 2.4 phosphonate groups per melamine molecule.
  • EXAMPLE XIV This example illustrates the use, in a textile finishing operation, of the triazinylaminoalkyl phosphonate whose preparation was described in Example XIII hereinabove.
  • the cured fabric contained 1.6 percent, by weight, of phosphorus and produced an L.O.I. of 28.
  • the treated fabric Upon subjecting the treated fabric to one detergent-free hot water wash cycle in a washing machine, the fabric was found to have retained 1.2 percent of phosphorus. The latter concentration was also retained after subjecting additional samples of this treated fabric to 5 repeated detergent wash cycles with 10 bath towels present as ballast.
  • EXAMPLE XV This example illustrates the preparation of a triazinylaminoalkyl phosphonate by means of reaction process No. 5 as described hereinabove.
  • a total of 210 grams of a polymethoxymethylmelamine which was approximately pentasubstituted with CH OCH groups was heated to l43l65C/1- 30-250mm. together with grams of dimethyl phosphite and 24 grams of trimethyl phosphite, the latter reagent being present to scavenge acidity, for a period of 6 hours so as to yield 43 grams of a slightly contaminated methanol by-product. Heating in a hot water bath, under 0.1 mm. pressure, then yielded 34 grams of unreacted dimethyl phosphite along with a residue which weighed 306 grams, thereby indicating incorporation of 1.23 phosphonate groups in the desired reaction product. Thus, about 40 percent of all of the available methoxymethyl groups were converted to methylenephosphonic ester groups.
  • EXAMPLE XVI This example illustrates the use for the finishing of textiles of the derivative whose preparation was described in Example XV hereinabove.
  • EXAMPLE XVlI This example illustrates the preparation of a triazinylaminoalkyl phosphonate by means of reaction process No. l as described hereinabove.
  • A, B and C are NRR wherein R and R are the same or different and are selected from the group consisting of hydrogen, C C alkyl, C,C hydroxyalkyl, methylene, methyleneoxymethylene, C -C alkoxymethyl and Z where Z is a phosphonate radical of the structure myfmz it group where Z is as defined above and R is C,C, alkoxymethyl and that where R and/or R is a methylene or methyleneoxymethylene group the remaining valence thereof is attached to another triazine nucleus as here defined; and mixtures thereof.
  • R and R are the same or different and are selected from the group consisting of hydrogen, methylol, C,C alkoxymethyl, methyleneoxymethylene, and Z, wherein Z is as defined in claim 1 and R is C,-C alkoxymethyl; and mixtures thereof.
  • a process for the preparation of triazinylaminoalkyl phosphonates which comprises reacting a methylolmelamine with a trialkyl phosphite.

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Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4013813A (en) * 1975-02-27 1977-03-22 Leblanc Research Corporation Aminoalkylphosphonic acid ester-based textile fire retardants
US4043987A (en) * 1974-12-10 1977-08-23 Encoat Chemicals Limited Substituted ammonium polyphosphate composition
US4052158A (en) * 1973-11-12 1977-10-04 Stauffer Chemical Company Textile finishing process
US4061605A (en) * 1976-03-03 1977-12-06 Eli Simon Reaction products of benzenephosphonic acid and melamine as flame-retardant additives
US4072633A (en) * 1975-05-21 1978-02-07 S.A. Texaco Belgium N.V. Novel process
US4085283A (en) * 1975-04-19 1978-04-18 Stamicarbon, B.V. Phosphonate-isocyanurates
US4140856A (en) * 1978-02-22 1979-02-20 Phillips Petroleum Company Color stabilization of intumescent flame retardant
US5534573A (en) * 1991-12-18 1996-07-09 Courtaulds Plc Aminotriazine phosphonates in plastics
US6277482B1 (en) * 1998-10-01 2001-08-21 Fred J. Amundson Fire retarding adhesives
US20020037410A1 (en) * 2000-08-04 2002-03-28 Christian Criegee Flameproof finishing of cellulose, fibers and articles containing them
US6617028B1 (en) * 1999-11-05 2003-09-09 Chang Chun Plastics Co., Ltd. Phosphorus and nitrogen containing resin hardener and a flame retarding resin composition containing said hardener
US20050011015A1 (en) * 2001-11-09 2005-01-20 Manfred Schmidt Method of flameproofing cellulose fibers
CN103980313A (zh) * 2014-05-23 2014-08-13 厦门大学 一种磷氮协同阻燃多元醇及其制备方法
CN110283207A (zh) * 2019-05-31 2019-09-27 北京理工大学 一种磷—氮协同阻燃聚醚多元醇及其制备方法
CN111285990A (zh) * 2020-02-07 2020-06-16 山东理工大学 含三聚氰环的三膦酸及其衍生物复配的高性能反应型聚氨酯阻燃剂的制备
CN112538094A (zh) * 2020-12-15 2021-03-23 江苏长能节能新材料科技有限公司 三聚氰胺烷基磷酸酯及其制备方法与应用
CN112592514A (zh) * 2020-12-15 2021-04-02 江苏长能节能新材料科技有限公司 磷氮阻燃剂及其制备方法与应用
CN113956484A (zh) * 2021-11-17 2022-01-21 南京工业大学 一种三聚氰胺氰尿酸盐衍生物共价三嗪框架阻燃剂及其制备方法和应用
CN115785626A (zh) * 2022-11-15 2023-03-14 马鞍山水木方舟新材料科技有限公司 一种改性塑料粒子及其制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT329511B (de) * 1972-05-25 1976-05-10 Schill & Seilacher Verfahren zur wasch- und chemischreinigungsbestandigen flammfestausrustung von textilmaterialien
SE462421B (sv) * 1988-11-04 1990-06-25 Boliden Contech Ab Anordning vid vaatelektrofilter
EP2528995B1 (fr) 2010-01-27 2015-01-07 Ecoatech GmbH Sel de n-méthyl-mélamine de l'ester d'acide monométhyl-méthane-phosphonique servant d'agent ignifugeant
CN103275127B (zh) * 2013-06-04 2015-04-15 南昌航空大学 一种三嗪基磷酸丙烯酸酯光固化膨胀阻燃剂的制备方法
CN103965237A (zh) * 2014-05-27 2014-08-06 中北大学 一种含N-Si或N-P的三嗪类衍生物及其制备方法
CN111211350B (zh) * 2020-01-11 2023-02-10 山东理工大学 含三聚氰环的易溶于有机溶剂的阻燃电解质的制备方法

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US3551422A (en) * 1968-03-27 1970-12-29 Stevens & Co Inc J P N-(oxymethyl) derivatives of phosphonopolyamino-s-triazines

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Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4052158A (en) * 1973-11-12 1977-10-04 Stauffer Chemical Company Textile finishing process
US4043987A (en) * 1974-12-10 1977-08-23 Encoat Chemicals Limited Substituted ammonium polyphosphate composition
US4013813A (en) * 1975-02-27 1977-03-22 Leblanc Research Corporation Aminoalkylphosphonic acid ester-based textile fire retardants
US4085283A (en) * 1975-04-19 1978-04-18 Stamicarbon, B.V. Phosphonate-isocyanurates
US4072633A (en) * 1975-05-21 1978-02-07 S.A. Texaco Belgium N.V. Novel process
US4061605A (en) * 1976-03-03 1977-12-06 Eli Simon Reaction products of benzenephosphonic acid and melamine as flame-retardant additives
US4107145A (en) * 1976-03-03 1978-08-15 Eli Simon Salts of benzenephosphonic acid and melamine as reactive additives to flammable epoxy monomers to reduce flammability of the cured reaction products
US4140856A (en) * 1978-02-22 1979-02-20 Phillips Petroleum Company Color stabilization of intumescent flame retardant
US5534573A (en) * 1991-12-18 1996-07-09 Courtaulds Plc Aminotriazine phosphonates in plastics
US6277482B1 (en) * 1998-10-01 2001-08-21 Fred J. Amundson Fire retarding adhesives
US20040044168A1 (en) * 1999-11-05 2004-03-04 Chang Chun Plastics Co., Ltd. Phosphorus- and nitrogen-containing resin hardener and a flame retarding resin composition containing said hardener
US6617028B1 (en) * 1999-11-05 2003-09-09 Chang Chun Plastics Co., Ltd. Phosphorus and nitrogen containing resin hardener and a flame retarding resin composition containing said hardener
US20020037410A1 (en) * 2000-08-04 2002-03-28 Christian Criegee Flameproof finishing of cellulose, fibers and articles containing them
US20050011015A1 (en) * 2001-11-09 2005-01-20 Manfred Schmidt Method of flameproofing cellulose fibers
US8177859B2 (en) * 2001-11-09 2012-05-15 Evonik Degussa Gmbh Method of flameproofing cellulose fibers
CN103980313A (zh) * 2014-05-23 2014-08-13 厦门大学 一种磷氮协同阻燃多元醇及其制备方法
CN110283207A (zh) * 2019-05-31 2019-09-27 北京理工大学 一种磷—氮协同阻燃聚醚多元醇及其制备方法
CN111285990A (zh) * 2020-02-07 2020-06-16 山东理工大学 含三聚氰环的三膦酸及其衍生物复配的高性能反应型聚氨酯阻燃剂的制备
CN112538094A (zh) * 2020-12-15 2021-03-23 江苏长能节能新材料科技有限公司 三聚氰胺烷基磷酸酯及其制备方法与应用
CN112592514A (zh) * 2020-12-15 2021-04-02 江苏长能节能新材料科技有限公司 磷氮阻燃剂及其制备方法与应用
CN113956484A (zh) * 2021-11-17 2022-01-21 南京工业大学 一种三聚氰胺氰尿酸盐衍生物共价三嗪框架阻燃剂及其制备方法和应用
CN115785626A (zh) * 2022-11-15 2023-03-14 马鞍山水木方舟新材料科技有限公司 一种改性塑料粒子及其制备方法
CN115785626B (zh) * 2022-11-15 2024-03-12 嘉禾伍丰(河北)包装科技有限公司 一种改性塑料粒子及其制备方法

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US3832227A (en) 1974-08-27
FR2099972A5 (fr) 1972-03-17
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DE2131040A1 (de) 1972-01-27
GB1346464A (en) 1974-02-13
CH553875A (fr) 1974-09-13
NL7108583A (fr) 1971-12-28

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