US3746572A - Process for flame retarding fabrics - Google Patents

Process for flame retarding fabrics Download PDF

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US3746572A
US3746572A US00118166A US3746572DA US3746572A US 3746572 A US3746572 A US 3746572A US 00118166 A US00118166 A US 00118166A US 3746572D A US3746572D A US 3746572DA US 3746572 A US3746572 A US 3746572A
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Prior art keywords
textile
fabric
flame
phosphorus
urea
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US00118166A
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E Weil
R Fearing
B Eisenberg
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Akzo America Inc
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Stauffer Chemical Co
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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/423Amino-aldehyde resins
    • D06M15/43Amino-aldehyde resins modified by phosphorus compounds
    • D06M15/432Amino-aldehyde resins modified by phosphorus compounds by phosphonic acids or derivatives thereof
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/92Fire or heat protection feature
    • Y10S428/921Fire or flameproofing
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2631Coating or impregnation provides heat or fire protection
    • Y10T442/2672Phosphorus containing
    • Y10T442/268Phosphorus and nitrogen containing compound

Definitions

  • the present invention provides a process for flame retarding textiles which comprises: (1) applying to a textile an aqueous solution consisting of (a) a phosphonate having at least one carbon-bonded primary alcohol group, (b) dimethyloldihydroxyethylene urea, and (c) a curing catalyst; and (2) curing the phosphonate and urea on the textile and thereby rendering the textile flame retardant.
  • This invention relates to a flame retardant textile finish. More particularly, this invention relates to a process for flame retarding textiles which comprises passing the textile through an aqueous padding solution containing a phosphonate having at least one carbon bonded primary alcohol group, dimethyloldihydroxyethylene urea, and an acid curing catalyst, and curing the treated textile to render the textile flame retardant.
  • the present process is useful for flame retarding various types of textiles especially cellulosic including cotton and polyester-cotton blends, viscose rayon, jute, and products made from wood pulp.
  • textile By textile is meant hereinafter a fabric, filament, staple, or yarn, or products made therefrom, which may be woven or non-woven.
  • the flame retarding of textiles is of importance for improvement of the safety characteristics of apparel, bedding, protective clothing, tent cloth, carpets, home furnishings, aircraft and automobile interior fabrics, and industrial fabrics which may be woven, knitted, tufted and non-woven.
  • the tetrakis (hydroxymethyl) phosphonium chloride finishes have problems with odor (formaldehyde and phosphine-like odors), and stiffness, i.e., a poor hand. Attempts to overcome the hand problem by use of ammonia gas as a curing reagent have required equipment not generally available in textile mills.
  • the phosphonated N-methylolamide finishes have been found in mill practice to have problems of volatility, loss of phosphorus in the pad-dry-cure afterwash cycle, and ultraviolet or thermal stability limitations.
  • Another object of the present invention is to make available finishes useful for cotton-synthetics, especially cotton-polyester blends.
  • Another object of the present invention is to provide a process that can be used with the primary polyol phosphonate to prevent undesirable color development on textiles.
  • Those primary polyol phosphonates such as 0,0- diethyl N,N-bis(2-hydroxyethy1) aminomethyl phosphonate, that may develop some color on curing can be whitened with a prolonged bleaching operation.
  • this whitening process involved bleaching the treated textile for at least 20 minutes in a 5% solution of sodium perborate at F.
  • dimethyloldihydroxyethylene urea provides good reactivity and durability with the above primary polyol phosphonates whereas aminoplasts such as dimethylolethylene urea and methylolated melamines do not.
  • the present invention primarily provides a process for flame retarding most textiles with a finish which can be thermally cured, a finish which is durable when the textile is washed or dry cleaned, and which finish does not cause a color loss or undesired color development to the flame retardant textile.
  • the present flame retarding process comprises applying to a textile an aqueous solution containing a primary polyol phosphonate, dimethyloldihydroxyethylene urea, and an acid or latent acid catalyst.
  • the aqueous bath may also contain optionally other aminoplast resins, softeners, surfactants, and bleaching agents.
  • the solution is dried on the fabric and the primary polyol phosphonate and dimethyloldihydroxyethylene urea are cured on the textile by heating means to render the textile flame retardant.
  • curing is meant the formation of a water-insoluble presumably polymeric finish by the coreaction of the phosphorus alcohol and the dimethyloldihydroxyethylene urea. Where cellulose is the substrate, chemical bonding to the cellulose may also be involved to an unknown degree.
  • the phosphorus reactant to be used in the process of the invention must contain at least one carbon-bonded primary alcohol group plus a pentavalent phosphorus ester group. Secondary alcohol groups do not lead to durable finishes.
  • a carbon-bonded primary alcohol group is meant a (HOCH group attached to a carbon atom, which can be a methylene, methine, or quaternary carbon atom.
  • HOCH group attached to a carbon atom
  • methylol groups attached to nitrogen or phosphorus, which have distinctly different chemistry from the methylol groups on carbon.
  • the alcohol groups required by the process of the invention are those which do not revert to formaldehyde in contrast to the methylol groups such as N-methylol amides or tetrakis (hydroxymethyl) phosphonium salts which are known to be in equilibrium with formaldehyde or which can release formaldehyde.
  • the reactant alcohol compounds as used in the process of the invention do not lead to an undesirable degree of cross-linking of the cellulosic fibers with ensuing stilf hand and loss of abrasion resistance or tear strength.
  • a pentavalent phosphorus ester group is meant a structure of the general formula:
  • R is a hydrocarbyl radical, preferably an aliphatic group of 1 to 20 carbon atoms, which may be unsubstituted or substituted by hydroxy and/or halogen.
  • R and R such, for example, as alkyl and alkoxy which may be unsubstituted or substituted by alkoxy, halogen'or hydroxy groups; hydroxypolyalkyleneoxy; phenyl; halophenyl; amino-substituted alkyl; -O-alkylene-O- or -'O-alkyleneoxyalkylene-O- bonded to the same or to another pentavalent phosphorus ester group; amino; alkyl-substituted amino or hydroxyalkylsubstituted amino, all with the proviso that in at least one of the aforementioned groups there be at least one carbonbonded primary alcohol group.
  • alkyl, alkoxy, or alkylene it is preferred to have no more than eight carbon atoms in the radical, hereinafter designated lower alkyl, lower alkoxy, or lower alkylene.
  • R and R are selected from the group consisting of lower alkyl, halogenated lower alkyl, lower alkoxyalkyl, lower hydroxyalkyl, lower alkoxy, lower hydroxyalkoxy, and halogenated lower alkoxy, hydroxypolyalkyleneoxy; and n is an integer from 1 to 6.
  • n has a value of from abo t 3 to 5.
  • Fyrol HMP Stauffer Chemical Company
  • a particularly useful group of phosphonates having carbon-bonded primary alcohol groups and suitable for the present invention include various phosphorus derivatives of diethanolamine having the general formula:
  • R and R are alkyls, hydroxyalkyls, haloalkyls, alkoxyalkyls or hydroxyalkoxyalkyls of l to 6 carbon atoms, the termini of an alkylene forming a six-membered ring or halogenated analogs, the termini of an alkylene or alkyleneoxyalkylene bonded to a like phosphorus ester group, hydroxypolyoxyalkylene or hydroxysubstituted analogs thereof; R and R are hydrogen, lower alkyls of 1 to 6 carbon atoms; m is an integer from 0 to 2; and n is an integer from 0 to 1. 7
  • Examples of the phosphorus derivatives of this group include the following:
  • a preferred group of pentavalent phosphorus esters because of their unusually favorable color, stability, and flame retardant efficacy, are:
  • R and R can be the same or different and are selected from the group consisting of hydrogen, lower alkyl, lower hydroxyalkyl, lower haloalkyl and hydroxy with the proviso that no more than one of R and R can be hydroxy.
  • the preferred lower alkyl group in the applicable alkyl, hydroxyalkyl or haloalkyl groups is the methyl radical.
  • This class of compounds can be readily prepared by reacting the known cyclic phosphonate of 2,2-dimethylpropane- 1,3-diol, or an appropriately substituted derivative of the latter diol where it is desired to vary R and/or R with diethanolamine and formaldehyde in the manner described in U.S. Pat. No. 3,076,010.
  • diethanolamine and formaldehyde may be replaced in this reaction with hydroxyethyl oxazolidine.
  • the conditions for this reaction involve adding the diethanolamine to the formaldehyde, with agitation, at a temperature in the range of about 20-30 C. Thereafter, the cyclic phosphonate of 2,2-dimethylpropane-1,3-diol, or a substituted derivative thereof, is introduced with agitation at a temperature in the range of from about 2090 C.
  • This reaction is exothermic so that the mixture is held at the latter temperature until all of the phosphonate has reacted.
  • the desired end product is then recovered by removal of water.
  • hydroxyethyl oxazolidine is used in place of the formaldehyde and diethanolamine, it is simply combined with the cyclic phosphonate under the above described reaction conditions.
  • the most preferred phosphonate for use in the present invention because of its excellent flame retardant efiicacy is the compound:
  • the process of the present invention is based upon the findin that dimethyloldihydroxyethylene urea which cocured with a phosphorus compound of the above-defined type, imparts durable flame retardancy to the textile, good tactile quality (hand), and good physical strength properties.
  • DMDHEU dimethyloldihydroxyethylene urea
  • HOCHQN/ NCHzOH HOCHOH--OH (XXV) and is well known in the textile finishing art as a durable press finishing resin.
  • DMDHEU is synthesized by the reaction of glyoxal with urea followed by methylolation of the resultant dihydroxyethylene urea with formaldehyde. Similar materials such as dimethylolethylene urea exhibit poor durability with the above described primary alcohols.
  • the acid curing catalyst for the process of the present invention may be any compound which affords an acidic reaction at the curing temperature.
  • Such catalysts include mineral acids such as hydrochloric and phosphoric, organic acids such as oxalic, citric, succinic, maleic, glycolic, chloroacetic, and trichloroacetic, toluenesulfonic, alkyl acid phosphates and the like.
  • organic acids such as oxalic, citric, succinic, maleic, glycolic, chloroacetic, and trichloroacetic, toluenesulfonic, alkyl acid phosphates and the like.
  • salts of strong acids With relatively weak bases, for example zinc chloride, magnesium chloride, ammonium chloride, ammonium phosphates, and amine hydrochlorides.
  • amine hydrochlorides include 2-amino-2-methylpropanol hydrochloride, sold under the trade name Catalyst AC, by the Monsanto Chemical Company, and the alkanolamine hydrochloride sold as Catalyst X'RF, by the Millmaster Onyx Corporation.
  • a preferred salt catalyst is a buffered zinc nitrate catalyst, sold under the trade name Catalyst X-4, by the Sun Chemical Company.
  • salts may be viewed as latent acid catalysts, which do not have substantial acid properties at low temperatures but which become acid, by hydrolysis or dissociation, atthe curing temperature of the phosphonate and DMDHEU on the textile.
  • the pH of the padding bath is preferably adjusted to a pH of between about 3 and about 6.7 which in general requires the addition of an acid, such as HCl or preferably H PO which is less corrosive.
  • This acid added to adjust the pH can be considered all or part of the acid catalyst required for the curing reaction.
  • softeners may be, for example, fatty substances such as stearamides, or hydrophobic polymers such as polyethylene emulsions.
  • a surfactant or a wetting agent, to aid wetting and penetration of the fibers.
  • Suitable surfactants include alkyl aryl sulfonates and polyoxyethylene derivatives of alkyl phenols (such as Triton X-100, a product of the Rohm and Haas Company).
  • Another optional ingredient of the padding composition is an additional aminoplast blending ingredient, over and above, but not in place of the requisite amount of DMDHEU.
  • This optional ingredient may be used to increase the degree of durable press character, to impart wet or dry crease angle recovery, and/or to enhance the degree of flame retardancy.
  • Suitable supplementary aminoplast blending ingredients that may be used include methylolureas, methylolmelarnines, methylolurons, methyloltriazones, urea, fatty acid amides, ethylene urea, acetamide, dimethyl hydroxymethylcarbamoylethylphosphomate and the methyl ethers of the above listed methylol compounds.
  • the preferred supplementary animoplast blending ingredients include melamines sold by the American Cyanamid Corporation under the trade names: Aerotex M-3-tris(methoxymethyl) melamine; Aerotex 23 Specia partially methylated pentamethylolmelamine; and Aerotex UM-dimethylol melamine.
  • Another useful supplementary aminoplast blending ingredient is tris- (methylol)melamine sold under the trade name Resloom HU, by the Monsanto Chemical Company.
  • Another optional ingredient of the padding bath is a peroxygen bleach.
  • a peroxygen bleach such as sodium perborate
  • the solvent most commonly employed for the process of the present invention is water, although it is possible to disperse and apply the reactants and curing catalyst in a non-aqueous solvent such as trichloroethylene, perchloroethylene, methylene chloride, methyl chloroform, or the like.
  • a non-aqueous solvent such as trichloroethylene, perchloroethylene, methylene chloride, methyl chloroform, or the like.
  • a non-aqueous solvent it is often found advantageous to employ enough water to swell the cellulosic textile fibers and thus allow efficient uptake of the reactants.
  • the mixtures of reactants, water, and non-aqueous solvent can be rendered homogeneous by the use of an emulsifier.
  • Table I The formulation illustrated below in Table I is representative of the present invention.
  • the specific formulation used in treating textiles will depend on the specific end use performance properties and degree of flame re- 8 tardancy desired. This is illustrated in the subsequent examples with cellulosic fabrics and polyester/cotton blends.
  • the ratio of the primary polyol phosphonate to DMDHEU between about 3:1 and about 1:2.
  • aqueous padding solutions of the present invention are prepared simply by adding the various components together in water. To facilitate solution of the sodium perborate it may be desired to add the perborate to the above formulation already containing the acid for pH control.
  • the aqueous solution is placed in a suitable vessel.
  • the fiame retardant finish is conveniently applied to the fabric by dipping it into, or passing it through the aqueous bath.
  • the excess liquid is removed by pressing the treated fabric through squeeze rolls, and then the fabric is dried, the temperature being a matter of convenience and equipment ranging from ambient up to the curing temperature.
  • the treated fabric is then heated to cure the finish at temperatures from about C. to about 180 C., and preferably from about C. to about C. These temperatures are used with reaction times ranging from a fraction of a minute to a day, or usually from about 1 to about 10 minutes, depending on temperature used.
  • the polyol phosphonate and aminoplast are reacted in situ on the fabric to form a flame retardant finish thereon.
  • the treated samples are first subjected to a hot water wash cycle in a conventional home washing machine with the water at about 140 F. This is to simulate an after wash treatment in a textile mill. In this washing, no soap, detergent, or water hardener is added to the Washing cycle.
  • the samples are subjected to five detergent home laundering cycles in the same washing machine.
  • a strong detergent such as Proctor and Gamble Corporations Tide XK, in the amount of about 50 grams, and 200 parts per million of water hardness (calculated as CaCO and 8 bath towels for ballast.
  • the treated fabric samples may also be tested for their durability by washing them in a boiling aqueous soapsoda solution containing 0.5% soap and 0.2% soda ash (Na CO for about 3 hours.
  • the fabrics are evaluated for flame retardancy using any of the well known test procedures described hereinbelow. Retention of phosphorus is also measured on some fabrics using X-ray fluoroescence. The various flame retardance tests are described below:
  • the Limiting Oxygen Index is a test used for quantitatively measuring the minimum amount of oxygen (in a oxygen-nitrogen mixture) required to sustain combustion. In this test, which is carried out as described in ASTM D-2863, the specimen is ignited from the top, rather than the bottom, and the minimum amount of oxygen required to sustain burning towards the bottom of the specimen is recorded.
  • Modified SPI 45 angle flame test This is another recognized flame testing procedure which is considered more severe than the standard AATCC 33-1966-45 angle test because it entails forced ignition.
  • the fabric sample is placed at a 45 angle but the sample is burned or ignited under conditions of forced ignition rather than using a one second timed ignition.
  • an untreated (65/35%) polyester/cotton fabric will pass the AAT CC 33-1966-45 angle test whereas it fails to pass the Modified SPI 45 angle test. In the latter case the untreated fabric will burn entirely.
  • Add-on (percent)This indicates the percent increase in weight of the dry solids applied to the treated fabric based on the weight of the untreated fabric.
  • OWF This is used with the term percent add-on, and is defined as on the weight of the fabric. For example, add-on OWF is equal to 20% solids applied based on the weight of the fabric.
  • the fabric after being passed through the aqueous bath was dried for 5 minutes at a temperature of about 230 F and cured 5 minutes at about 325 F.
  • the percent dry add-on was calculated to be 27% based on the weight of the untreated fabric. After a one hot water wash, and five detergent Wash cycles, the treated fabric was found to be self-extinguishing when measured by the Modified SPI-45 angle flame test.
  • the same fabric untreated burned completely.
  • the LOI of the fabric after the detergent launderings was 24%.
  • the hand of the fabric was soft and flexible.
  • EXAMPLE 2 A 3.2 oz./yd. cotton print cloth was padded through an aqueous bath containing the following solids or active ingredients: 25 percent of 0,0-diethyl N,N-bis(2-hydroxyethyl aminomethylphosphonate (Fyrol 6), 11.2 percent of DMDHEU, 15 percent Resloom HP, 1 percent part of Catalyst AC, 2.5 percent of phosphoric acid, and 5 percent of sodium perborate.
  • the pH of the aqueous bath was 5.8.
  • Bath A Percent by weight 21.6 DMDHEU 15 Zn(N0 catalyst 2 NaHSO (catalyst) 3 Polyoxyethylene ether (wetting agent) 0.3
  • EXAMPLE 4 A 3.2 oz./yd. cotton print cloth was apdded through anaqueous bath containing the following solids or act1v1ty: 30% 0,0-diethyl N,N-bis(2-hydroxyethyl)aminomethylphosphonate, 12% of dimethylolethylene urea, 1% Catalyst X-4, and 0.5% Titon X-l00 with the pH of the formulation adjusted to 5.1 with HCl. The applied solids was 17.7% OWF.
  • Example 27 Residual color from Example 27 was removed after soaking the sample for 1 minute 14 propanediol and diethyl phosphite are heated at 100 C. over a period of 2 days while removing the ethanol byproduct so as to yield a viscous liquid phosphonate having the formula:
  • Example 29 which was formulated at a pH of 6 f E /CH2BT and cured on the fabric at 150 C., was found to have HP o exgtellienii color, high degree of flame retardancy and a ⁇ OmBr so I n I n I n
  • Table III additional Examples 30 through 10 Th1 lntermcdlate 18 then treated W1th an equimolar 36 are provided to illustrate the durable flame retardant q y 0f py f y yl oxfllolldlne Whlle under aglta' properties with the use of other primary polyol phostron and while bemgmamtalned at a temperature below phonates in combination with dimethyloldihydroxyethyly Yleldlng h Compound Whose formula ene urea (DMDHEU).
  • a total of 224 grams of hydroxyethyl oxazolidine is heated to 60 C. whereupon 274 grams of the cyclic phosphonate of glycerol are slowly added with agitation.
  • the system is cooled to maintain its temperature at 60- 70 C.
  • the reaction is complete after a total of about two hours and the resulting reaction product contained a substantial proportion of the above described compound along with some linear dimers or polyesters thereof.
  • a process for flame retarding textiles which comprises:
  • Rf is a hydrocarbyl radical unsubstituted or substituted by hydroxy and/or a halogen; and R and R are organic radicals selected from the group consisting of alkyl and alkoxy which can be unsubstituted or substituted by alkoxy, halogen or hydroxy; hydroxypolyalkyleneoxy; phenyl; halophenyl; amino-substituted alkyl; or, O-alkylene-O- or O-alkyleneoxyalkylene-O bonded to the same or to another pentavalent phosphorus ester group, amino, alkyl-substituted amino or hydroxyalkyl-substituted amino, with the proviso that in the aforementioned groups there be at least one carbon-bonded primary alcohol group.
  • R and R are selected from the group consisting of lower alkyl, halogenated lower alkyl, lower alkoxyalkyl, lower hydroxyalkyl, lower alkoxy, lower hydroxyalkoxy, hydroxypolyalkyleneoxy and halogenated lower alkoxy; and n is an integer from 1 to 6.
  • R and R are alkyls, hydroxyalkyls, alkoxyalkyls or hydroxyalkoxyalkyls of l to 6 carbon atoms, the termini of an alkylene forming a six-membered ring or a halogenated analog, the termini of an alkylene or alkyleneoxyalkylene bonded to a like phosphorus ester group, hydroxypolyoxyalkylene or a hydroxy substituted analog thereof; R and R are hydrogen, or lower alkyls of 1 to 6 carbon atoms; m is an integer of 0 to 2; and n is an integer from 0 to l.
  • R and R can be the same or difierent and are selected from the group consisting of hydrogen, lower alkyl, lower hydroxyalkyl, lower haloalkyl and hydroxy with the proviso that no more than one of R and R can be hydroxy.
  • a process according to claim 1 wherein the acid curing catalyst is selected from the group consisting of zinc nitrate, 2 amino 2 methylpropanol hydrochloride, zinc chloride and magnesium chloride.
  • a flame retardant textile comprising a textile having cured thereon the reaction product of: (1) a pentavalent phosphorus ester having at least one carbonbonded primary alcohol group; (2) dimethyloldihydroxyethylene urea; and, (3) an acid curing catalyst, wherein said phosphorus ester and said dimethyloldihydroxyethylene urea are present in said reaction product in a ratio of the ester to the urea of between about 3:1 to about 1:2.
  • R is a hydrocarbyl radical unsubstituted or substituted by hydroxy and/or a halogen; and R and R are organic radicals selected from the group consisting of alkyl and alkoxy, which can be unsubstituted or.substituted by alkoxy, halogen or hydroxy; hydroxypolyalkyleneoxy; phenyl; halophenyl; amino-substituted alkyl; or, -O-alkylene-O- or O-alkyleneoxyalkylene-O bonded to the same or to another pentavalent phosphorus ester group, amino, alkyl-substituted amino or hydroxyalkylsubstituted amino, with the proviso that in the aforementioned groups there be at least one carbon-bonded primary alcohol group.
  • R and R are selected from the group consisting of lower alkyl, halogenated lower alkyl, lower alkoxyalkyl, lower alkyleneoxy and halogenated lower alkoxy; and n is an integer from 1 to 6.
  • R and R are alkyls, hydroxyalkyls, alkoxyalkyls or hydroxyalkoxyalkyls of 1 to 6 carbon atoms, the termini of an alkylene forming a six-membered ring or a halogenated analog, the termini of an alkylene or alkyleneoxyalkylene bonded to a like phosphorus ester group, hydroxypolyoxyalkylene or a hydroxy substituted analog thereof; R and R are hydrogen, or lower alkyls of 1 to 6 carbon atoms; m is an integer of to 2; and n is an integer from 0 to 1.
  • R and R can be the same or different and are selected from the group consisting of hydrogen, lower alkyl, lower hydroxyalkyl, lower haloalkyl and hydroxy with the proviso that no more than one of R and R can be hydroxy.

Abstract

THE PRESENT INVENTION A PROCESS FOR FLAME RETARDING TEXTILES WHICH COMPRISES: (1) APPLYING TO A TEXTILE AN AQUEOUS SOLUTION CONSISTING OF (A) A PHOSPHONATE HAVING AT LEAST ONE CARBON-BONDED PRIMARY ALCOHOL GROUP, (B) DIMETHYLOLDIHYDROXYETHYLENE UREA, AND (C) A CURING CATALYST; AND (2) CURING THE PHOSPHONATE AND UREA ON THE TEXTILE AND THEREBY RENDERING THE TEXTILE FLAME RETARDANT.

Description

United States Patent 3,746,572 PROCESS FOR FLAME RETARDING FABRICS Edward D. Weil, Hastings-on-Hudson, Ralph B. Fearing,
Bardonia, and Bernard J. Eisenberg, Nanuet, N.Y., assignors to Stauifer Chemical Company, New York,
.Y. N0 Drawing. Filed Feb. 23, 1971, Ser. No. 118,166 Int. Cl. C09d /18 US. Cl. 117-136 34 Claims ABSTRACT OF THE DISCLOSURE The present invention provides a process for flame retarding textiles which comprises: (1) applying to a textile an aqueous solution consisting of (a) a phosphonate having at least one carbon-bonded primary alcohol group, (b) dimethyloldihydroxyethylene urea, and (c) a curing catalyst; and (2) curing the phosphonate and urea on the textile and thereby rendering the textile flame retardant.
This invention relates to a flame retardant textile finish. More particularly, this invention relates to a process for flame retarding textiles which comprises passing the textile through an aqueous padding solution containing a phosphonate having at least one carbon bonded primary alcohol group, dimethyloldihydroxyethylene urea, and an acid curing catalyst, and curing the treated textile to render the textile flame retardant. The present process is useful for flame retarding various types of textiles especially cellulosic including cotton and polyester-cotton blends, viscose rayon, jute, and products made from wood pulp.
By textile is meant hereinafter a fabric, filament, staple, or yarn, or products made therefrom, which may be woven or non-woven.
The flame retarding of textiles is of importance for improvement of the safety characteristics of apparel, bedding, protective clothing, tent cloth, carpets, home furnishings, aircraft and automobile interior fabrics, and industrial fabrics which may be woven, knitted, tufted and non-woven.
There are various methods known for flame retarding textiles which include the application of chlorinated paraifins with antimony oxide or tris-(dibromopropyl phosphate) plus a resinous binder; Such procedures generally have the disadvantage of requiring the addition of a large amount of solids with a resulting deleterious effect in the quality of the fabric. Furthermore, the resulting finishes are quite limited in their durability to laundering and dry-cleaning. There have been finishes designed to be especially durable for cotton, for example, those based on tetrakis (hydroxymethyl) phosphonium chloride or on phosphonated N-methylolamides, but these have various limitations.
The tetrakis (hydroxymethyl) phosphonium chloride finishes have problems with odor (formaldehyde and phosphine-like odors), and stiffness, i.e., a poor hand. Attempts to overcome the hand problem by use of ammonia gas as a curing reagent have required equipment not generally available in textile mills. The phosphonated N-methylolamide finishes have been found in mill practice to have problems of volatility, loss of phosphorus in the pad-dry-cure afterwash cycle, and ultraviolet or thermal stability limitations.
A further major limitation of the known finishes is their ineffectiveness on cotton-polyester blends, which are fabrics of great commercial importance.
[it is therefore a very important object of the present invention to make available flame retardant finishes which can be used on natural and synthetic textiles and fabrics, especially on cellulosics and cellulosic-synthetic blends, which involves the use of substantially non-toxic, lessvolatile phosphorus compounds, and which leaves the fabric with a soft tactile character (i.e., good hand) and good physical strength properties.
It is a further object to make available textile finishes which are durable to both washing and drycleaning as well as being flame retardant.
Another object of the present invention is to make available finishes useful for cotton-synthetics, especially cotton-polyester blends.
Another object of the present invention is to provide a process that can be used with the primary polyol phosphonate to prevent undesirable color development on textiles. Those primary polyol phosphonates, such as 0,0- diethyl N,N-bis(2-hydroxyethy1) aminomethyl phosphonate, that may develop some color on curing can be whitened with a prolonged bleaching operation. Prior to this invention, this whitening process involved bleaching the treated textile for at least 20 minutes in a 5% solution of sodium perborate at F.
According to the present invention, it has been unexpectedly found that by adding sodium perborate to the padding solution and then padding and curing the solu- .tion on the textile, the color is essentially prevented from forming on the textiles.
Also, according to the present invention, it has been unexpectedly found that dimethyloldihydroxyethylene urea provides good reactivity and durability with the above primary polyol phosphonates whereas aminoplasts such as dimethylolethylene urea and methylolated melamines do not.
The present invention primarily provides a process for flame retarding most textiles with a finish which can be thermally cured, a finish which is durable when the textile is washed or dry cleaned, and which finish does not cause a color loss or undesired color development to the flame retardant textile.
The present flame retarding process comprises applying to a textile an aqueous solution containing a primary polyol phosphonate, dimethyloldihydroxyethylene urea, and an acid or latent acid catalyst. The aqueous bath may also contain optionally other aminoplast resins, softeners, surfactants, and bleaching agents. Then, the solution is dried on the fabric and the primary polyol phosphonate and dimethyloldihydroxyethylene urea are cured on the textile by heating means to render the textile flame retardant. By curing, is meant the formation of a water-insoluble presumably polymeric finish by the coreaction of the phosphorus alcohol and the dimethyloldihydroxyethylene urea. Where cellulose is the substrate, chemical bonding to the cellulose may also be involved to an unknown degree.
The phosphorus reactant to be used in the process of the invention must contain at least one carbon-bonded primary alcohol group plus a pentavalent phosphorus ester group. Secondary alcohol groups do not lead to durable finishes.
By a carbon-bonded primary alcohol group is meant a (HOCH group attached to a carbon atom, which can be a methylene, methine, or quaternary carbon atom. This structure is to be contrasted with methylol groups attached to nitrogen or phosphorus, which have distinctly different chemistry from the methylol groups on carbon.
In particular, the alcohol groups required by the process of the invention are those which do not revert to formaldehyde in contrast to the methylol groups such as N-methylol amides or tetrakis (hydroxymethyl) phosphonium salts which are known to be in equilibrium with formaldehyde or which can release formaldehyde. Not being capable of releasing formaldehyde, the reactant alcohol compounds as used in the process of the invention do not lead to an undesirable degree of cross-linking of the cellulosic fibers with ensuing stilf hand and loss of abrasion resistance or tear strength.
By a pentavalent phosphorus ester group is meant a structure of the general formula:
R: (I) where R is a hydrocarbyl radical, preferably an aliphatic group of 1 to 20 carbon atoms, which may be unsubstituted or substituted by hydroxy and/or halogen. The remaining two valences of the phosphorus are satisfied by other organic radicals R and R such, for example, as alkyl and alkoxy which may be unsubstituted or substituted by alkoxy, halogen'or hydroxy groups; hydroxypolyalkyleneoxy; phenyl; halophenyl; amino-substituted alkyl; -O-alkylene-O- or -'O-alkyleneoxyalkylene-O- bonded to the same or to another pentavalent phosphorus ester group; amino; alkyl-substituted amino or hydroxyalkylsubstituted amino, all with the proviso that in at least one of the aforementioned groups there be at least one carbonbonded primary alcohol group.
It is preferred, for reasons of improved durability, to have two or more carbon-bonded primary alcohol groups in the phosphorus reagent, and for reasons of avoiding excessive cross linking, to have no more than six such groups in the molecule.
Where the term alkyl, alkoxy, or alkylene is employed, it is preferred to have no more than eight carbon atoms in the radical, hereinafter designated lower alkyl, lower alkoxy, or lower alkylene.
The following compounds (Formula II) are examples of a subgroup of useful pentavalent phosphorus esters according to the present invention having the formula:
wherein R and R are selected from the group consisting of lower alkyl, halogenated lower alkyl, lower alkoxyalkyl, lower hydroxyalkyl, lower alkoxy, lower hydroxyalkoxy, and halogenated lower alkoxy, hydroxypolyalkyleneoxy; and n is an integer from 1 to 6.
These compounds have good color and are generally convenient to synthesize from low cost materials such as by reaction of ethylene oxide with acid phosphates, pyrophosphates and phosphoric acid. Compounds of this class include the primary alcohols described in US. Pats. 2,372,244; 3,402,132; 3,474,046; 3,474,047; and 3,487,- 030; and British Pat. 1,082,013; which patents describe the synthesis and other uses for these compounds.
An example of this subgroup of pentavalent phosphorus esters is the compound:
o(CH2CHlo)nH HOCH: (III) where n has a value of from abo t 3 to 5. This compound is sold under the trade name of Fyrol HMP, by the Stauffer Chemical Company.
A particularly useful group of phosphonates having carbon-bonded primary alcohol groups and suitable for the present invention include various phosphorus derivatives of diethanolamine having the general formula:
HoomoH,
HOCH CH, (IV) wherein R and R are alkyls, hydroxyalkyls, haloalkyls, alkoxyalkyls or hydroxyalkoxyalkyls of l to 6 carbon atoms, the termini of an alkylene forming a six-membered ring or halogenated analogs, the termini of an alkylene or alkyleneoxyalkylene bonded to a like phosphorus ester group, hydroxypolyoxyalkylene or hydroxysubstituted analogs thereof; R and R are hydrogen, lower alkyls of 1 to 6 carbon atoms; m is an integer from 0 to 2; and n is an integer from 0 to 1. 7
Examples of the phosphorus derivatives of this group include the following:
HOCH CH; O OCH! N CHrl HOCH CH; OCH; (V) HOCHQOH O OCH(CH N-CHg- HOCIIZCHQ OCH(CH3) (VI) HOCH CH O OCH CHgCl N CH CH,
HOCH CH 0011 011 01 (VII) HOCHzCH: O OCHzCHgBr N C HzCHrd HOCHzCHg OCHzCHzBl (VIII) HOCHgCH: O O 00:11;
C H: C Hl-l HOOHICHI O 01H (IX) HOCHgCH: O O OCzH I ll N 0111-? HOCHQCH, OCgH (X) HOCHgGHg O OCH; CH:
-C Hrll C HOCHzCHr O C a CH:
HOCHzCH: [))OCH:CH2O),H
N CHr-P HOCHICH: (OCHICHI0)|1H (XII) where n is an integer from 11 to 10.
| HOGHzCHaOCHzCHzOflOCHzCHzOCHzCHzOl!O CHzCHzO CHzCHzOH Nwmomon), momomon (XIII) CHI-O O H0---0\ ommomomom,
11 CHz-O (XIV) HOCHzCH: 0 00m CHIOH ll/ N-CH-P\ o HOCH CH. oofi, 011,011 (XV) HOCHQCHQ O OCH;
I HO CHaC/g OCH (XVI) HOCHzCHa O O CzHb l| N-P HOCH: C O H; (XVII) HOCH CH O O CzHs N-CHg- HOCHzCg O CzHs (XVIII) These compounds constitute a preferred subgroup within the invention, since they generally impart a higher degree of flame retardance relative to their phosphorus content, than do the nonamine derived compounds within the broader scope of the invention. Their synthesis and use for other purposes are described in U.S. Pats. 3,076,- 019; 3,457,333; and 3,294,710; and British Pat. 1,178,718.
A narrow preferred subgroup of pentavalent phosphorus esters, because of the ease of their manufacture, stability, and good flame retardant eflicacy is:
HOCH CH (If/ORB N(CH2)m P HO CH CH 0R5 (XX) where m is an integer from 0 to 2 and R and R are defined hereinabove.
A preferred group of pentavalent phosphorus esters, because of their unusually favorable color, stability, and flame retardant efficacy, are:
where R and R can be the same or different and are selected from the group consisting of hydrogen, lower alkyl, lower hydroxyalkyl, lower haloalkyl and hydroxy with the proviso that no more than one of R and R can be hydroxy. The preferred lower alkyl group in the applicable alkyl, hydroxyalkyl or haloalkyl groups is the methyl radical.
This class of compounds, all of which are new compositions of matter, can be readily prepared by reacting the known cyclic phosphonate of 2,2-dimethylpropane- 1,3-diol, or an appropriately substituted derivative of the latter diol where it is desired to vary R and/or R with diethanolamine and formaldehyde in the manner described in U.S. Pat. No. 3,076,010. Alternatively, the diethanolamine and formaldehyde may be replaced in this reaction with hydroxyethyl oxazolidine.
In general, the conditions for this reaction involve adding the diethanolamine to the formaldehyde, with agitation, at a temperature in the range of about 20-30 C. Thereafter, the cyclic phosphonate of 2,2-dimethylpropane-1,3-diol, or a substituted derivative thereof, is introduced with agitation at a temperature in the range of from about 2090 C. This reaction is exothermic so that the mixture is held at the latter temperature until all of the phosphonate has reacted. The desired end product is then recovered by removal of water. Where hydroxyethyl oxazolidine is used in place of the formaldehyde and diethanolamine, it is simply combined with the cyclic phosphonate under the above described reaction conditions.
Exemplary of this preferred group of pentavalent phosphorus esters are the compounds:
11001510111 0 O-CH! (XXII) CHz-O O CHz-O (XXIII) omon CHQOH (XXV) It may also be noted that the above described class of compounds can be used as polyols in the preparation of polyesters and polyurethanes.
The most preferred phosphonate for use in the present invention because of its excellent flame retardant efiicacy is the compound:
0,0-diethyl N,N-bis(2-hydroxy ethyl) aminomethylphosphonate which compound is sold under the trade name Fyrol 6, by the Stautfer Chemical Company.
The process of the present invention is based upon the findin that dimethyloldihydroxyethylene urea which cocured with a phosphorus compound of the above-defined type, imparts durable flame retardancy to the textile, good tactile quality (hand), and good physical strength properties.
The compound dimethyloldihydroxyethylene urea, hereinafter known as DMDHEU, has the structure:
HOCHQN/ NCHzOH HOCHOH--OH (XXV) and is well known in the textile finishing art as a durable press finishing resin. DMDHEU is synthesized by the reaction of glyoxal with urea followed by methylolation of the resultant dihydroxyethylene urea with formaldehyde. Similar materials such as dimethylolethylene urea exhibit poor durability with the above described primary alcohols.
The acid curing catalyst for the process of the present invention may be any compound which affords an acidic reaction at the curing temperature. Such catalysts include mineral acids such as hydrochloric and phosphoric, organic acids such as oxalic, citric, succinic, maleic, glycolic, chloroacetic, and trichloroacetic, toluenesulfonic, alkyl acid phosphates and the like. Also included are the salts of strong acids With relatively weak bases, for example zinc chloride, magnesium chloride, ammonium chloride, ammonium phosphates, and amine hydrochlorides. Some typical amine hydrochlorides include 2-amino-2-methylpropanol hydrochloride, sold under the trade name Catalyst AC, by the Monsanto Chemical Company, and the alkanolamine hydrochloride sold as Catalyst X'RF, by the Millmaster Onyx Corporation. A preferred salt catalyst is a buffered zinc nitrate catalyst, sold under the trade name Catalyst X-4, by the Sun Chemical Company.
It is to be understood that the above mentioned salts may be viewed as latent acid catalysts, which do not have substantial acid properties at low temperatures but which become acid, by hydrolysis or dissociation, atthe curing temperature of the phosphonate and DMDHEU on the textile.
The pH of the padding bath is preferably adjusted to a pH of between about 3 and about 6.7 which in general requires the addition of an acid, such as HCl or preferably H PO which is less corrosive. This acid added to adjust the pH can be considered all or part of the acid catalyst required for the curing reaction.
In addition to the three requisite components of the padding bath to be used in the process of the invention, there are optional components which may be added, as is well known in the art of textile finishing, to accomplish particular objectives.
Although the process of the invention affords advantageous tactile qualities (hand), further embellishment may be achieved by the use of softeners. These may be, for example, fatty substances such as stearamides, or hydrophobic polymers such as polyethylene emulsions.
Another optional ingredient of the padding composition is a surfactant, or a wetting agent, to aid wetting and penetration of the fibers. Suitable surfactants include alkyl aryl sulfonates and polyoxyethylene derivatives of alkyl phenols (such as Triton X-100, a product of the Rohm and Haas Company).
Another optional ingredient of the padding composition is an additional aminoplast blending ingredient, over and above, but not in place of the requisite amount of DMDHEU. This optional ingredient may be used to increase the degree of durable press character, to impart wet or dry crease angle recovery, and/or to enhance the degree of flame retardancy. Suitable supplementary aminoplast blending ingredients that may be used include methylolureas, methylolmelarnines, methylolurons, methyloltriazones, urea, fatty acid amides, ethylene urea, acetamide, dimethyl hydroxymethylcarbamoylethylphosphomate and the methyl ethers of the above listed methylol compounds. The preferred supplementary animoplast blending ingredients include melamines sold by the American Cyanamid Corporation under the trade names: Aerotex M-3-tris(methoxymethyl) melamine; Aerotex 23 Specia partially methylated pentamethylolmelamine; and Aerotex UM-dimethylol melamine. Another useful supplementary aminoplast blending ingredient is tris- (methylol)melamine sold under the trade name Resloom HU, by the Monsanto Chemical Company.
Another optional ingredient of the padding bath is a peroxygen bleach. Although the process of the invention, without bleach or with a mild after bleach gives quite acceptable color for many uses, We have discovered that for critical applications where extreme whiteness is required, the inclusion of a peroxygen bleach, such as sodium perborate, in the padding bath is highly advantageous. This is a surprising finding which is not known in customary textile mill practice.
According to the present process it has also been found that for optimum results between color and durability it is desirable to adjust the pH of the padding formulation containing sodium perborate to between about 5.0 and about 6.7. However, for less critical applications where color formation isof no concern we have found that in the absence of the sodium perborate, optimum durability to repeated laundering is achieved by adiusting the pH between 3 and 5.5.
The solvent most commonly employed for the process of the present invention is water, although it is possible to disperse and apply the reactants and curing catalyst in a non-aqueous solvent such as trichloroethylene, perchloroethylene, methylene chloride, methyl chloroform, or the like. When such a non-aqueous solvent is used, it is often found advantageous to employ enough water to swell the cellulosic textile fibers and thus allow efficient uptake of the reactants. The mixtures of reactants, water, and non-aqueous solvent can be rendered homogeneous by the use of an emulsifier.
The average and preferred amounts (in percentages) by weight, of the various components that can make up the aqueous padding solution of the present invention are provided in Table I below.
The formulation illustrated below in Table I is representative of the present invention. The specific formulation used in treating textiles will depend on the specific end use performance properties and degree of flame re- 8 tardancy desired. This is illustrated in the subsequent examples with cellulosic fabrics and polyester/cotton blends.
TABLE I.COMPOSITION OF FLAME RETARDANT AQUEOUS PADDING BATH SOLUTION For optimum results, it is preferred to have the ratio of the primary polyol phosphonate to DMDHEU, between about 3:1 and about 1:2.
Although this formulation provided in Table I above is sufiicient, additional nitrogen containing resins, i.e., an aminoplast resin in the amount of between 0 and about 30% may be added to further improve the flame retardancy, or for increasing the crease recovery properties of the treated material. However these supplementary aminoplasts such as a melamine type may not replace the DMDHEU required for the invention.
The aqueous padding solutions of the present invention are prepared simply by adding the various components together in water. To facilitate solution of the sodium perborate it may be desired to add the perborate to the above formulation already containing the acid for pH control.
The aqueous solution is placed in a suitable vessel. The fiame retardant finish is conveniently applied to the fabric by dipping it into, or passing it through the aqueous bath. The excess liquid is removed by pressing the treated fabric through squeeze rolls, and then the fabric is dried, the temperature being a matter of convenience and equipment ranging from ambient up to the curing temperature. The treated fabric is then heated to cure the finish at temperatures from about C. to about 180 C., and preferably from about C. to about C. These temperatures are used with reaction times ranging from a fraction of a minute to a day, or usually from about 1 to about 10 minutes, depending on temperature used. During the curing of the solution on the fabric, the polyol phosphonate and aminoplast are reacted in situ on the fabric to form a flame retardant finish thereon.
In order to determine the quality and durability of the finish on the fabric, the treated samples are first subjected to a hot water wash cycle in a conventional home washing machine with the water at about 140 F. This is to simulate an after wash treatment in a textile mill. In this washing, no soap, detergent, or water hardener is added to the Washing cycle.
Then, the samples are subjected to five detergent home laundering cycles in the same washing machine. to each of these cycles there is added a strong detergent such as Proctor and Gamble Corporations Tide XK, in the amount of about 50 grams, and 200 parts per million of water hardness (calculated as CaCO and 8 bath towels for ballast.
The treated fabric samples may also be tested for their durability by washing them in a boiling aqueous soapsoda solution containing 0.5% soap and 0.2% soda ash (Na CO for about 3 hours.
After the treated fabric samples have been washed with water, and with detergent, or with a soap and soda ash solution, the fabrics are evaluated for flame retardancy using any of the well known test procedures described hereinbelow. Retention of phosphorus is also measured on some fabrics using X-ray fluoroescence. The various flame retardance tests are described below:
Limiting Oxygen Index (LOI) The Limiting Oxygen Index (LOI) is a test used for quantitatively measuring the minimum amount of oxygen (in a oxygen-nitrogen mixture) required to sustain combustion. In this test, which is carried out as described in ASTM D-2863, the specimen is ignited from the top, rather than the bottom, and the minimum amount of oxygen required to sustain burning towards the bottom of the specimen is recorded.
Most untreated cotton and blend fabrics require a minimum LOI of 17 to 19% O to sustain burning and are considered quite flammable. In general, as reported in Sources & Resources, vol. 2, 1969/5, by R. E. Seaman, increasing the LOI to 21% appears to correlate with fabrics capable of passing the standard horizontal flame test (methenamine pill test) for carpets. Increasing the LOI still further to about 26.5% 0 or greater, represents self-extinguishing properties in air for sample specimens ignited from the bottom in a vertical flame test (i.e. the AATCC 34-1966 flame test described below) which represents the most stringent test conditions commonly used.
In the standard test in air, if the textile is self extinguishing in the vertical position, it is acceptable for the most stringent application. If the textile is self-extinguishing in the position of a 45 angle, it is acceptable for many applications. However, if the textile is only selfextinguishing when in a horizontal position the finish is acceptable for use only in less critical applications.
Modified SPI 45 angle flame test This is another recognized flame testing procedure which is considered more severe than the standard AATCC 33-1966-45 angle test because it entails forced ignition. In this test, like the AATCC 33-1966 flame test, the fabric sample is placed at a 45 angle but the sample is burned or ignited under conditions of forced ignition rather than using a one second timed ignition. For example, an untreated (65/35%) polyester/cotton fabric will pass the AAT CC 33-1966-45 angle test whereas it fails to pass the Modified SPI 45 angle test. In the latter case the untreated fabric will burn entirely.
Vertical flame testAATCC 34-1966 In this test, the fabric is suspended vertically with the base of the fabric in. above a bunsen burner having a flame height of 1% inches. The flame is held under the sample for 12 seconds and then withdrawn. Char length is then measured in a standard manner. Char length is the length in inches of charred fabric measured from the base of the fabric upward. Accordingly, a short char length of 5 to 7 inches indicates a good flame retardancy; Whereas a char length of to inches indicates a lower degree of flame retardancy of the treated fabric and is not acceptable for most applications.
The present invention will be more fully and completely understood by the following examples.
The following terms, as used herein and in the examples have the following meanings:
5 DWThe fabric sample has been given one hot water wash cycle, and five detergent wash cycles.
3.2 oz./yd. -This is a light weight material weighing 3.2 ounces per square yard. Light weight fabrics are generally more difiicult to flame retard than heavier weight fabrics.
8 oz./yd. This is a heavier weight material weighing 8 ounces per square yard.
Add-on (percent)This indicates the percent increase in weight of the dry solids applied to the treated fabric based on the weight of the untreated fabric.
OWFThis is used with the term percent add-on, and is defined as on the weight of the fabric. For example, add-on OWF is equal to 20% solids applied based on the weight of the fabric.
The components utilized in the following examples and tables are set forth in quantities by weight percent of solids or active ingredients.
10 EXAMPLE 1 A 2.6 ounce per square yard polyester/cotton (65/ 35%) fabric was padded through an aqueous bath containing the following solids or active ingredients: 30 percent of 0,0-diethyl N,N-'bis-(2-hydroxyethyl) aminomethylphosphonate (Fyrol 6), 13.5 percent of dimethyloldihydroxyethyleneurea (DMDHEU), 1 percent of a softener, a polyethylene emulsion, and 1 percent of zinc nitrate (Catalyst X-4). The pH of the aqueous bath was adjusted to about 5.0 with HCl.
The fabric after being passed through the aqueous bath, was dried for 5 minutes at a temperature of about 230 F and cured 5 minutes at about 325 F.
The percent dry add-on was calculated to be 27% based on the weight of the untreated fabric. After a one hot water wash, and five detergent Wash cycles, the treated fabric was found to be self-extinguishing when measured by the Modified SPI-45 angle flame test.
The same fabric untreated burned completely. The LOI of the fabric after the detergent launderings was 24%. The hand of the fabric was soft and flexible.
EXAMPLE 2 A 3.2 oz./yd. cotton print cloth was padded through an aqueous bath containing the following solids or active ingredients: 25 percent of 0,0-diethyl N,N-bis(2-hydroxyethyl aminomethylphosphonate (Fyrol 6), 11.2 percent of DMDHEU, 15 percent Resloom HP, 1 percent part of Catalyst AC, 2.5 percent of phosphoric acid, and 5 percent of sodium perborate. The pH of the aqueous bath was 5.8. The dry add-on after drying 5 minutes at 230 F. and curing 5 minutes at 300 F., was 40% OWF.
Flame retardancy as measured by the vertical flame test (AATCC 34-1966) showed the treated fabric to be selfextinguishing with a 6 inch char length before and after 5 detergent washes.
No apparent discoloration of the treated fabric was evident.
EXAMPLE 3 To compare the durability to laundering of finishes containing DMDHEU relative to a finish containing another aminoplast resin such as trimethylolmelamine, two aqueiaus padding baths were made up of compositions as folows:
Bath A: Percent by weight 21.6 DMDHEU 15 Zn(N0 catalyst 2 NaHSO (catalyst) 3 Polyoxyethylene ether (wetting agent) 0.3
Formula:
Bath B was similar but the DMDHEU was replaced by trimethylolmelamine.
Eight-ounce cotton cloth samples were padded in each bath, dried cured at and washed with water. Accelerated laundering was performed by boiling the swatches for 3 hours in a 0.2% soda, 0.5% soap solution. The swatch treated with bath composition (A) was found to have 0.9% phosphorus and was self extinguishing, whereas the swatch treated with bath composition (B had only 0.27% phosphorus.
EXAMPLE 4 A 3.2 oz./yd. cotton print cloth was apdded through anaqueous bath containing the following solids or act1v1ty: 30% 0,0-diethyl N,N-bis(2-hydroxyethyl)aminomethylphosphonate, 12% of dimethylolethylene urea, 1% Catalyst X-4, and 0.5% Titon X-l00 with the pH of the formulation adjusted to 5.1 with HCl. The applied solids was 17.7% OWF.
parts of sodium perborate, the color was improved considerably and essentially non-existent at the higher pH of 6.6, as in Example 27. Residual color from Example 27 was removed after soaking the sample for 1 minute 14 propanediol and diethyl phosphite are heated at 100 C. over a period of 2 days while removing the ethanol byproduct so as to yield a viscous liquid phosphonate having the formula:
in a 5% solution of sodium perborate at 180 F. 5
Example 29, which was formulated at a pH of 6 f E /CH2BT and cured on the fabric at 150 C., was found to have HP o exgtellienii color, high degree of flame retardancy and a \OmBr so I n I n I n In Table III below, additional Examples 30 through 10 Th1 lntermcdlate 18 then treated W1th an equimolar 36 are provided to illustrate the durable flame retardant q y 0f py f y yl oxfllolldlne Whlle under aglta' properties with the use of other primary polyol phostron and while bemgmamtalned at a temperature below phonates in combination with dimethyloldihydroxyethyly Yleldlng h Compound Whose formula ene urea (DMDHEU). As in Examples 6 through 29 of depicted hereinabove. This end product had the follow- Table II, the examples in Table II contain about 0.5 15 g Y Found! part of active Triton X-100 wetting agent. Theoretical: Br=36.8%, N=3.22%, P=7.13%.
TABLE III Examples 30 31 32 a3 34 as HO PONCHOH1 30 o dnioiiznsgzdmdrioionimozrnomz 30 so 30 [(OH;)2CHO];P(O)CHZN(C2H4OH)Z (czgsfprg(g)ggzg%g?rg%g;onu 30 i rirfini ir 2 z 4 13.5 13.5 13.5 13.5 13.5 13.5 13.5 Tn's(methoxymethyb 8 8 Catalyst (ii-M 1 1 1 1 1 1 233 H01 H01 HCl H01 HC1H3PO4 H01 p 5.5 5.0 5.0 5.0 6.0 5 5 grion (percent 31 28.6 21 27.6 27.6 40 40 26.3 23.3 29.0 27.5 27.5 fiiififil'iivlfiii'.23123111111111:111212111111: 253 29. 8 23.1 25.6 23.4 26.4 25.8
To illustrate the connection in flame retardancy be- EXAMPLE 38 tween LOI and vertical char length, some samples were This example illustrates the preparation of: also tested by the vertical flame test, AATCC 34-1966, 0 HOCH CH 0 O CH CH before and after 5 detergent washings. The char length 1 of samples of the various Examples tabulated below in N H= /O\ Table IV, further illustrates the relationship described HOCHZCH, O CHl CH hereinabove.
As can be seen from the results of these various examples the retention of the char length after washing is not greatly affected.
In addition to providing flame retardancy, durability and good color of treated textiles, it is also intended to provide a soft hand. Primary polyol phosphonates reacted with 12 parts of a melamine type resin result in a rather firm hand. However, similar fabrics containing 13.5 parts of DMDHEU or a blend of about 11 to 13.5 parts of DMDHEU and a melamine resin as in Example 29 result in finished fabrics with a soft hand.
EXAMPLE 37 This example illustrates the preparation of:
HOCH CH, O-CH, CH Br NCH HOCH G,
Equimolar proportions of 2,2-bis-bromomethyl-l,3-
A total of 234 grams of hydroxyethyl oxazolidine is placed into a reactor to which there is then slowly added, under agitation, a total of 310 grams of the cyclic phosphonate of 2,2-dimethylpropane-1,3-diol. The system reached a temperature of 53-54 C. and the reaction was complete ,in 2 /2 hours. The resulting product is obtained in a purity of about and has a refractive index n 1=1.4900.
EXAMPLE 39 This example illustrates the preparation of:
HO GHzCHz O O-CH: OH
A total of 224 grams of hydroxyethyl oxazolidine is heated to 60 C. whereupon 274 grams of the cyclic phosphonate of glycerol are slowly added with agitation. The system is cooled to maintain its temperature at 60- 70 C. The reaction is complete after a total of about two hours and the resulting reaction product contained a substantial proportion of the above described compound along with some linear dimers or polyesters thereof.
It is apparent that many modifications and variations of the invention as hereinbefore set forth may be made without departing from the spirit and scope thereof; and therefore, only such limitations should be imposed as are indicated in the appended claims.
What is claimed is:
1. A process for flame retarding textiles which comprises:
(a) applying on a textile, an aqueous solution containing 1) a pentavalent phosphorus ester having at least one carbon-bonded primary alcohol group, (2) dimethyloldihydroxyethylene urea, and (3) an acid curing catalyst; wherein the phosphorus ester and dimethyloldihydroxyethylene urea are included in said aqueous solution in a ratio of the ester to the urea of between about 3:1 to about 1:2, and (b) curing the pentavalent phosphorus ester and said dirnethylolhydroxyethylene urea on said textile so as to effect the curing of the ester and the dimethylolhydroxyethylene urea with one another in situ on said textile to render the fabric flame retardant.
2. A process according to claim 1 wherein the phosphorus ester is: 0,0-diethyl N,N-bis(2-hydroxyethyl) aminomethyl phosphonate.
3. A process according to claim 1 wherein the phosphorus ester has the structure:
i=-OR Rf wherein R is a hydrocarbyl radical unsubstituted or substituted by hydroxy and/or a halogen; and R and R are organic radicals selected from the group consisting of alkyl and alkoxy which can be unsubstituted or substituted by alkoxy, halogen or hydroxy; hydroxypolyalkyleneoxy; phenyl; halophenyl; amino-substituted alkyl; or, O-alkylene-O- or O-alkyleneoxyalkylene-O bonded to the same or to another pentavalent phosphorus ester group, amino, alkyl-substituted amino or hydroxyalkyl-substituted amino, with the proviso that in the aforementioned groups there be at least one carbon-bonded primary alcohol group.
4. A process according to claim 1 wherein the phosphorus ester has the structure:
wherein R and R are selected from the group consisting of lower alkyl, halogenated lower alkyl, lower alkoxyalkyl, lower hydroxyalkyl, lower alkoxy, lower hydroxyalkoxy, hydroxypolyalkyleneoxy and halogenated lower alkoxy; and n is an integer from 1 to 6.
5. A process according to claim 1 wherein the phosphorus ester has the structure:
HO 011,03; R1 (")/OR| N PG HOCHzC Rs in 0R5 wherein R and R are alkyls, hydroxyalkyls, alkoxyalkyls or hydroxyalkoxyalkyls of l to 6 carbon atoms, the termini of an alkylene forming a six-membered ring or a halogenated analog, the termini of an alkylene or alkyleneoxyalkylene bonded to a like phosphorus ester group, hydroxypolyoxyalkylene or a hydroxy substituted analog thereof; R and R are hydrogen, or lower alkyls of 1 to 6 carbon atoms; m is an integer of 0 to 2; and n is an integer from 0 to l.
6. A process according to claim 1 wherein the phosphorus ester has the structure:
HO CHzCHfl N(CH2)m1 HOCHiOH,
ORI
HOCH, O O 02 NCH HOCH, 0 CI I 8. A process according to claim 1 wherein the phosphorus ester has the structure:
HOCH CH OI/OCE: R
N-CHa-i\ /C\ HOCH OH, OCH, Rm
where R and R can be the same or difierent and are selected from the group consisting of hydrogen, lower alkyl, lower hydroxyalkyl, lower haloalkyl and hydroxy with the proviso that no more than one of R and R can be hydroxy.
9. A process according to claim 1 wherein the phosphorus ester has the structure:
10. A process according to claim 1 wherein the phos phorus ester has the structure:
11. A process according to claim 1 wherein the phosphorus ester has the structure:
12. A process according to claim 1 wherein the phosphorus ester has the structure:
13. A process according to claim 1 wherein said aqueous solution also contains sodium perborate.
14. A process according to claim 1 wherein the acid curing catalyst is selected from the group consisting of zinc nitrate, 2 amino 2 methylpropanol hydrochloride, zinc chloride and magnesium chloride.
15. A process according to claim 1 wherein the phosphorus ester and dimethyloldihydroxyethylene urea are cured at a temperature ranging between 200 and 400 F. for a period of about 3 to about 10 minutes.
16. A process according to claim 1 wherein a sufiicient amount of said acid curing catalyst is added to the aqueous solution to adjust the pH thereof to between about 3 and about 6%.
17. A process according to claim 8 wherein the phosphorus ester has the structure:
18. The process of claim 14, wherein said acid catalyst is zinc nitrate.
19. A flame retardant textile comprising a textile having cured thereon the reaction product of: (1) a pentavalent phosphorus ester having at least one carbonbonded primary alcohol group; (2) dimethyloldihydroxyethylene urea; and, (3) an acid curing catalyst, wherein said phosphorus ester and said dimethyloldihydroxyethylene urea are present in said reaction product in a ratio of the ester to the urea of between about 3:1 to about 1:2.
20. The textile of claim 19, wherein said phosphorus ester is: 0,0-diethyl N,N-bis(2-hydroxyethyl) aminomethyl phosphonate.
21. The textile of claim 19, wherein the phosphorus ester has the structure:
wherein R is a hydrocarbyl radical unsubstituted or substituted by hydroxy and/or a halogen; and R and R are organic radicals selected from the group consisting of alkyl and alkoxy, which can be unsubstituted or.substituted by alkoxy, halogen or hydroxy; hydroxypolyalkyleneoxy; phenyl; halophenyl; amino-substituted alkyl; or, -O-alkylene-O- or O-alkyleneoxyalkylene-O bonded to the same or to another pentavalent phosphorus ester group, amino, alkyl-substituted amino or hydroxyalkylsubstituted amino, with the proviso that in the aforementioned groups there be at least one carbon-bonded primary alcohol group.
22. The textile of claim 19, wherein the phosphorus ester has the structure:
wherein R and R are selected from the group consisting of lower alkyl, halogenated lower alkyl, lower alkoxyalkyl, lower alkyleneoxy and halogenated lower alkoxy; and n is an integer from 1 to 6.
23. The textile of claim 19, wherein the phosphorus ester has the structure:
wherein R and R are alkyls, hydroxyalkyls, alkoxyalkyls or hydroxyalkoxyalkyls of 1 to 6 carbon atoms, the termini of an alkylene forming a six-membered ring or a halogenated analog, the termini of an alkylene or alkyleneoxyalkylene bonded to a like phosphorus ester group, hydroxypolyoxyalkylene or a hydroxy substituted analog thereof; R and R are hydrogen, or lower alkyls of 1 to 6 carbon atoms; m is an integer of to 2; and n is an integer from 0 to 1.
24. The textile of claim 19, wherein the phosphorus ester has the structure:
HOCHZCH] fl) 0R0 N(CHz)m-P HOCHzC 1 5 0 CzHs HOCH CH, O OCH; R;
HOGH C OCH: R10
where R and R can be the same or different and are selected from the group consisting of hydrogen, lower alkyl, lower hydroxyalkyl, lower haloalkyl and hydroxy with the proviso that no more than one of R and R can be hydroxy.
27. The textile of claim 19, wherein the phosphorus ester has the structure:
28. The textile of claim 19, wherein the phosphorus ester has the structure:
29. The textile of claim 19, wherein the phosphorus ester has the structure:
30. The textile of claim 19, wherein the phosphorus ester has the structure:
31. The textile of claim 26, wherein the phosphorus ester has the structure:
r-cH Nw flloH),
32. The textile of claim 20, wherein sodium perborate residues are also present in said reaction product.
33. The textile of claim 20, wherein said acid catalyst is selected from the group consisting of zinc nitrate, 2- amino-Z-methylpropanol hydrochloride, zinc chloride and magnesium chloride.
34. The textile of claim 33, wherein said catalyst is zinc nitrate.
References Cited UNITED STATES PATENTS 3,179,522 4/1965 Temin 117-136 X 3,459,716 8/1969 Schaefer et a1. 117-143 R 3,076,010 1/ 1963 Beck et al 260945 3,294,710 12/1966 Rosenberg et a1. 260-970 UX 3,457,333 7/1969 Price 260-945 3,220,869 11/1965 Ruemens et a1. 117139.4 X 3,192,242 6/1965 Birum 117-136 X 3,420,702 1/ 1969 Spangler 117139.4
WILLIAM D. MARTIN, Primary Examiner T. G. DAVIS, Assistant Examiner US. Cl. X.R. 117138.8 F, 143 A 33331 111mm) S'lA'iEZS lwim'z. OFFICE CER'LHZCA'US OF CORREC'JLION Patent 130, 3:7 :57 Dated y 7:
Inventor) Edward D, Weil, Ralph B. Fearing & Bernard J. Eisenberg .It is certified that error appears in the ahoveddcntified.patent and that said Letters Patent are hereby corrected as shown below:
golumn 5, line 20, the number "019'" should read O1O- Column 6, line 5, FORMULA XXIV should appear as follows:
- HOCHZCHZ 0 o- CH2 11 3]:
" Hocn cn 0-" CH 4 'fCH Br .Column 10, ll, [line 69, .the Word 'fap'dded" should a read padded line 73, the word "Titon" should 'read --.'Tri ton.--.
Column 12, TABLE 11, line 15', the word "Add-1n" should read Addn line 18', under Example l, th numher "B l-.7" should read '24.?
line 18, under Example 17, .thenumber "26.9"
should read 26.8 line 21, under Example 6,;the number "0.5" should read 1-05,
Column 15, TABLE .111, line 14, the word "(percent' should t a read (percent)- .1-
Column 15, Claim 1, line 9, the word "ylolhydroxyethylene" should read yloldihydroxyethylene -line 10;
the Word "dimethylolhyw" should read dimethyloldihy- Claim 5, line 27, the word "O-alkyl-" should read -O-alkyl- 4 ro-wso 5 v m T I CER'lil* LCA i I; OF CUliRlsC l LON Patent No. 5,746,572 Dated July 1975 1 Well, ph Fearlng & Bernard J. 'Elsenberg Page 2 I It is certified that error appears in the above-identifiedpatent and that said Letters Patent are hereby corrected as shown below:
in Column 1?, Claim 22, line 20, after "lower" (first Occurrence) inser hydrox'yal'kyl, lower alkoxy, lower hydroxyalkoxy, hydroxypolyalkyleneoxy line 20, delete the word "alkyleneoxy" 4 1 Column 18, Claim 32, line; 58, the number "20"- sh oul'd read "l9 Claim 55,- line 40, .the number "20' should read 19 Signed and. sealed thie 19th day O E 'Y M- ($EAL) z I I v Attes't: 1 I H EDWARD MLFLETCHERJR. c. MARSHALL 'DANN 'Attesting Officer Commissloner of Patents
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Cited By (22)

* Cited by examiner, † Cited by third party
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US3859124A (en) * 1972-09-25 1975-01-07 Proctor Chemical Company Inc Durable fire retardant textile materials by anhydrous solvent finishing process
US4034141A (en) * 1974-12-31 1977-07-05 Hooker Chemicals & Plastics Corporation Brominated phosphoramidates
US4084027A (en) * 1977-05-06 1978-04-11 The United States Of America As Represented By The Secretary Of Agriculture Process for imparting durable flame-retardancy to cotton-polyester blended textiles
JPS5476528A (en) * 1977-11-11 1979-06-19 Bayer Ag Manufacture of n*nnbiss*22hydroxyalkyl** aminomethane phosphoric acid dimethyl ester
US4196260A (en) * 1977-03-03 1980-04-01 Ciba-Geigy Corporation Process for flameproofing cellulosic fibrous material
US4404313A (en) * 1981-08-31 1983-09-13 Stauffer Chemical Company Flame retardant-smolder resistant textile backcoating
US4444831A (en) * 1981-08-31 1984-04-24 Stauffer Chemical Company Flame retardant-smolder resistant textile backcoating
US6491727B1 (en) 1999-06-09 2002-12-10 Cotton Incorporated Methods for reducing the flammability of cellulosic substrates
US20050272838A1 (en) * 2002-06-20 2005-12-08 Charles Yang Durable flame retardant finish for cellulosic materials
US20060202175A1 (en) * 2005-03-10 2006-09-14 Yang Charles Q Flame retarding system for nylon fabrics
US20080245998A1 (en) * 2005-09-22 2008-10-09 Basf Coatings Ag Use of Phosphonic and Diphosphonic Diesters, and Thermally Curable Mixtures Comprising Phosponic and Diphosphonic Diesters
US20080245999A1 (en) * 2005-09-22 2008-10-09 Basf Coatings Ag Use of Phosphonic and Diphosphonic Diesters, and Silane-Functional, Curable Mixtures Comprising Phosphonic and Diphosphonic Diesters
US20090223631A1 (en) * 2006-05-29 2009-09-10 Basf Coatings Ag Use of curable mixtures comprising silane compounds and also phosphonic diesters or diphosphonic diesters as coupling agents
US20100120952A1 (en) * 2007-03-23 2010-05-13 Basf Coatings Ag Phosphonate containing two-component coating system and the production and use thereof
WO2014056138A1 (en) 2012-10-08 2014-04-17 Dow Global Technologies Llc Organophosphorus compounds for flame retardant polyurethane foams
WO2015101312A1 (en) * 2013-12-31 2015-07-09 广东德美精细化工股份有限公司 Flame retardant working solution and flame retardant finishing method for pure cotton fabrics and/or cotton-polyester blend fabrics
US9523195B2 (en) 2014-06-09 2016-12-20 Johns Manville Wall insulation boards with non-halogenated fire retardant and insulated wall systems
US9528269B2 (en) 2014-06-09 2016-12-27 Johns Manville Roofing systems and roofing boards with non-halogenated fire retardant
CN106757481A (en) * 2016-12-27 2017-05-31 燕山大学 Environment-friendly type negative ion far-infrared flame retardant polyester staple fibre and preparation method
US9815966B2 (en) 2014-07-18 2017-11-14 Johns Manville Spray foams containing non-halogenated fire retardants
US9815256B2 (en) 2014-06-09 2017-11-14 Johns Manville Foam boards including non-halogenated fire retardants
CN112898348A (en) * 2021-01-22 2021-06-04 中国科学院福建物质结构研究所 Phosphorus-nitrogen-containing polyether polyol compound, and preparation method and application thereof

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* Cited by examiner, † Cited by third party
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US3859124A (en) * 1972-09-25 1975-01-07 Proctor Chemical Company Inc Durable fire retardant textile materials by anhydrous solvent finishing process
US4034141A (en) * 1974-12-31 1977-07-05 Hooker Chemicals & Plastics Corporation Brominated phosphoramidates
US4196260A (en) * 1977-03-03 1980-04-01 Ciba-Geigy Corporation Process for flameproofing cellulosic fibrous material
US4084027A (en) * 1977-05-06 1978-04-11 The United States Of America As Represented By The Secretary Of Agriculture Process for imparting durable flame-retardancy to cotton-polyester blended textiles
JPS5476528A (en) * 1977-11-11 1979-06-19 Bayer Ag Manufacture of n*nnbiss*22hydroxyalkyl** aminomethane phosphoric acid dimethyl ester
JPS6145998B2 (en) * 1977-11-11 1986-10-11 Bayer Ag
US4404313A (en) * 1981-08-31 1983-09-13 Stauffer Chemical Company Flame retardant-smolder resistant textile backcoating
US4444831A (en) * 1981-08-31 1984-04-24 Stauffer Chemical Company Flame retardant-smolder resistant textile backcoating
US6491727B1 (en) 1999-06-09 2002-12-10 Cotton Incorporated Methods for reducing the flammability of cellulosic substrates
US20050272838A1 (en) * 2002-06-20 2005-12-08 Charles Yang Durable flame retardant finish for cellulosic materials
US20060202175A1 (en) * 2005-03-10 2006-09-14 Yang Charles Q Flame retarding system for nylon fabrics
US20080245998A1 (en) * 2005-09-22 2008-10-09 Basf Coatings Ag Use of Phosphonic and Diphosphonic Diesters, and Thermally Curable Mixtures Comprising Phosponic and Diphosphonic Diesters
US20080245999A1 (en) * 2005-09-22 2008-10-09 Basf Coatings Ag Use of Phosphonic and Diphosphonic Diesters, and Silane-Functional, Curable Mixtures Comprising Phosphonic and Diphosphonic Diesters
US10294389B2 (en) * 2005-09-22 2019-05-21 Basf Coatings Gmbh Use of phosphonic acid diesters and diphosphonic acid diesters and thermally curable mixtures containing phosphonic acid diesters and diphosphonic acid diesters
US8013099B2 (en) 2005-09-22 2011-09-06 Basf Coatings Ag Use of phosphonic acid diesters and diphosphonic acid diesters and silane group containing, curable mixtures containing phosphonic acid diesters and diphosphonic acid diesters
US20090223631A1 (en) * 2006-05-29 2009-09-10 Basf Coatings Ag Use of curable mixtures comprising silane compounds and also phosphonic diesters or diphosphonic diesters as coupling agents
US9018330B2 (en) 2006-05-29 2015-04-28 Basf Coatings Gmbh Use of curable mixtures comprising silane group-containing compounds and phosphonic acid diester or diphosphonic acid diester as adhesives
US8138249B2 (en) 2007-03-23 2012-03-20 Basf Coatings Japan Ltd. Phosphonate-containing two-component coating system and the production and use thereof
US20100120952A1 (en) * 2007-03-23 2010-05-13 Basf Coatings Ag Phosphonate containing two-component coating system and the production and use thereof
WO2014056138A1 (en) 2012-10-08 2014-04-17 Dow Global Technologies Llc Organophosphorus compounds for flame retardant polyurethane foams
CN104936967A (en) * 2012-10-08 2015-09-23 陶氏环球技术有限责任公司 Organophosphorus compounds for flame retardant polyurethane foams
JP2016500663A (en) * 2012-10-08 2016-01-14 ダウ グローバル テクノロジーズ エルエルシー Organophosphorus compounds for flame retardant polyurethane foam
EP2903994A4 (en) * 2012-10-08 2016-07-06 Dow Global Technologies Llc Organophosphorus compounds for flame retardant polyurethane foams
CN104936967B (en) * 2012-10-08 2017-09-29 陶氏环球技术有限责任公司 Organic phosphorus compound for fire retardant polyurethane foam
US9738766B2 (en) 2012-10-08 2017-08-22 Dow Global Technologies Llc Organophosphorus compounds for flame retardant polyurethane foams
WO2015101312A1 (en) * 2013-12-31 2015-07-09 广东德美精细化工股份有限公司 Flame retardant working solution and flame retardant finishing method for pure cotton fabrics and/or cotton-polyester blend fabrics
US9739063B2 (en) 2014-06-09 2017-08-22 Johns Manville Roofing systems and roofing boards with non-halogenated fire retardant
US9528269B2 (en) 2014-06-09 2016-12-27 Johns Manville Roofing systems and roofing boards with non-halogenated fire retardant
US9815256B2 (en) 2014-06-09 2017-11-14 Johns Manville Foam boards including non-halogenated fire retardants
US9523195B2 (en) 2014-06-09 2016-12-20 Johns Manville Wall insulation boards with non-halogenated fire retardant and insulated wall systems
US9815966B2 (en) 2014-07-18 2017-11-14 Johns Manville Spray foams containing non-halogenated fire retardants
US10870984B2 (en) 2014-07-18 2020-12-22 Johns Manville Spray foams containing non-halogenated fire retardants
CN106757481A (en) * 2016-12-27 2017-05-31 燕山大学 Environment-friendly type negative ion far-infrared flame retardant polyester staple fibre and preparation method
CN112898348A (en) * 2021-01-22 2021-06-04 中国科学院福建物质结构研究所 Phosphorus-nitrogen-containing polyether polyol compound, and preparation method and application thereof

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