WO2003072871A1 - Systeme de catalyseur et procede de fabrication de materiaux ignifuges - Google Patents

Systeme de catalyseur et procede de fabrication de materiaux ignifuges Download PDF

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WO2003072871A1
WO2003072871A1 PCT/US2003/005087 US0305087W WO03072871A1 WO 2003072871 A1 WO2003072871 A1 WO 2003072871A1 US 0305087 W US0305087 W US 0305087W WO 03072871 A1 WO03072871 A1 WO 03072871A1
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fabric
treated
tea
cotton
btca
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PCT/US2003/005087
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English (en)
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Charles Q. Yang
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University Of Georgia Research Foundation
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Priority to AU2003215331A priority Critical patent/AU2003215331A1/en
Priority to US10/497,374 priority patent/US20040261191A1/en
Publication of WO2003072871A1 publication Critical patent/WO2003072871A1/fr

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • 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
    • D06M13/322—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 nitrogen
    • D06M13/44—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 nitrogen containing nitrogen and phosphorus
    • 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
    • D06M13/10—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 oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/192—Polycarboxylic acids; Anhydrides, halides or salts 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
    • 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
    • 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
    • D06M13/322—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 nitrogen
    • D06M13/46—Compounds containing quaternary nitrogen atoms
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/667—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing phosphorus in the main chain
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/30—Flame or heat resistance, fire retardancy properties

Definitions

  • the durable flame retardant finishes for cotton and other cellulosic fabrics commonly used by the industry include the tetrakis-(hydroxylmethyl)phosphonium chloride (THPC)- based system with the commercial name of "Proban”, and dimethyl (N- hydroxylmethylcarbamoylethyl) phosphonate and its analog, known as reactive organophosphorous chemicals with the trade name of "Pyrovetax CP" (1-2).
  • THPC tetrakis-(hydroxylmethyl)phosphonium chloride
  • Proban dimethyl (N- hydroxylmethylcarbamoylethyl) phosphonate and its analog, known as reactive organophosphorous chemicals with the trade name of "Pyrovetax CP" (1-2).
  • THPC tetrakis-(hydroxylmethyl)phosphonium chloride
  • Proban dimethyl (N- hydroxylmethylcarbamoylethyl) phosphonate and its analog, known as reactive organophosphorous chemicals with the trade name of
  • the reactive organophosphorous chemicals technology involves the use of a N-methylol phosphorous-containing flame retardant agent and aN-methylol crosslinking agent, and both compounds lead to the emission of high levels of formaldehyde, a known carcinogen, during the application of the finish to cotton fabric as well as during the use of finished cotton products by consumers. Therefore, the flame retardant chemicals for cotton commercially available to the textile industry are very limited.
  • Polycarboxylic acids such as 1,2,3,4-butane-tetracarboxylic acid (BTCA), have been used as nonformaldehyde crosslinking agents for cotton and wood pulp cellulose (4-5).
  • Alkali metal salts of phosphoric, phosphorous and hypophosphorous acids such as sodium dihydrogen phosphate (NaH PO ), sodium phosphite (Na HPO 3 ), and sodium hypophosphite (NaH 2 PO 2 ), have been used as catalysts for the esterification and crosslinking of cellulose by polycarboxylic acids (6-9). In the presence of those catalysts, a polycarboxylic acid molecule esterifies cellulose and forms multiple ester linkages with cellulose, thus crosslinking cellulose and imparting wrinkle resistance to cotton fabrics (10).
  • United States Patent 6,309,565 reports fabric treatments with a formaldehyde-free hydroxylalkyl-functional organophosphorous flame retardant compound (FR) and a cross-linking agent such as 1,2,3,4-butanetetracarboxylic acid (BTCA).
  • BTCA apparently functions as a binding agent between the flame retardant compound and cotton cellulose. It is reported that a catalyst such as NaH 2 PO 2 may be used if adequate cross- linking is to be achieved.
  • the present invention relates to a catalyst system for a nonformaldehyde durable flame retardant finish for fabrics.
  • One preferred flame retardant finish comprises a hydroxylalkyl- functional organophosphorous compound (FR) and a polycarboxylic acid.
  • the new catalyst system comprises (1) hypophosphorous acid (H 3 PO 2 ) or salts thereof and (2) a nitrogen-containing organic base, such as triethanolamine (TEA).
  • the nitrogen-containing organic base reacts with H PO 2 in an aqueous solution to form a salt of hypophosphorous acid (Scheme 1), which functions as the catalyst for the esterification of a carboxylic acid with cellulose and FR.
  • Scheme 1 More specifically, provided is a method of binding a flame retardant compound or composition to cellulose comprising: applying a composition comprising a hydroxyl- functional flame retardant, a polycarboxylic acid, hypophosphorous acid and a nitrogen- containing organic base to a cellulose-containing material. This method may fiirther comprise curing the cellulose-containing material. Also provided is a catalyst system for bonding flame retardants to fabric through a polycarboxylic acid comprising hypophosphorous acid and a nitrogen-containing organic base.
  • polycarboxylic acid includes any organic structure with more than one carboxylic acid functional group.
  • Some examples of polycarboxylic acids include 1,2,3,4-butanetetracarboxylic acid, citric acid, poly(maleic acid), polyritaconic acid), copolymer of maleic acid and itaconic acid, poly(fumaric acid) or mixtures of two or more of these acids.
  • nitrogen containing organic base does not include ammonia and other bases that do not contain carbon.
  • a preferred nitrogen containing organic base is triethanolamine (TEA).
  • compositions and methods of the invention can be treated with the compositions and methods of the invention as long as they contain cellulose.
  • Various salts of hypophosphorous acid may be used, as known in the art.
  • the flame retardant compound is any of a number of flame retardants known in the art, such as a hydroxylalkyl-functionalized organophosphorous compounds.
  • Monomeric, oligomeric (which generally contain from about two to ten repeat units) and polymeric (which generally contain over about ten repeat units) hydroxyalkyl- functional organophosphorus flame retardant additives are intended for use herein.
  • a preferred embodiment has the following structure:
  • Ri is independently selected from methyl and hydroxyethyl
  • R 2 is independently selected from methyl, methoxy, and hydroxyethoxy
  • n is equal to or greater than 1.
  • This embodiment is made by a multistep process from dimethyl methylphosphonate, phosphorus pentoxide, ethylene glycol, and ethylene oxide and is available under the registered trademark FYROL® 51 from Akzo Nobel Chemicals Inc.
  • the endgroups are principally hydroxyl groups.
  • Another class of materials for use herein includes water soluble oligomeric alkenylphosphonate materials, examples of which are described in U.S. Pat. Nos. 3,855,359 and 4,017,257, both to E. D. Weil.
  • alkenyl substituents in these materials provide an additional mechanism for permanence utilizing free radical curing conditions (described in the patents above).
  • a preferred species of this type is available under the trademark PYROL® 76 from Akzo Nobel Chemicals Inc. and is produced by reacting bis(2- chloroethyl) vinylphosphonate and dimethyl methylphosphonate with the substantial elimination of methyl chloride.
  • hydroxyalkyl- functional organophosphorus flame retardant that can be employed are oligomeric phosphoric acid esters that carry hydroxyalkoxy groups as described in U.S. Pat. Nos. 2,909,559, 3,099,676, 3,228,998, 3,309,427, 3,472,919, 3,767,732, 3,850,859, 4,244,893, 4,382,042, 4,458,035, 4,697,030, 4,820,854, 4,886,895, 5,117,033, and 5,608,100.
  • the nitrogen- containing organic base is bound to cotton through its esterification with the polycarboxylic acid. It also has the following functions:
  • Figure 7 The ester carbonyl band intensity of the cotton fabric treated with 24% FR, 9.6% BTCA, %H 3 PO in combination with different concentrations of TEA, and cured at 185 ° C for 2 min as a function of the TEA concentration.
  • Figure 8 The calcium concentration on the cotton fabric treated with 24%) FR, 9.6% BTCA,7 %H 3 PO 2 in combination with TEA of different concentrations, and cured at 185°C for 2 min, and finally treated with 0.5M CaCl 2 for 30 min as a function of the TEA concentration.
  • Figure 9 The LOI (%)of the cotton fabric treated with 24% FR, 9.6% BTCA, 7%H 3 PO 2 in combination with TEA of different concentrations, and cured at 185° C for 2 min and finally subjected to 5 HLWD cycles as a function of the TEA concentration.
  • DETAILED DESCRIPTION OF THE INVENTION The following nonlimiting examples will assist in understanding the invention.
  • the fabrics used in the investigation include: (1) a dark brown 100% cotton twill weave fabric weighing 246 g/m 2 ; (2) a white 60/40 cotton/polyester blend plain weave fabric weighing 136g/m 2 .
  • the flame retardant agent (FR) was a hydroxyl-functional organophosphorous oligomer with the trade name of Fyrol 51 supplied by Akzo Nobel Chemical Corporation, New York.
  • BTCA hypophosphorous acid
  • TAA triethanolamine
  • NaH 2 PO 2 sodium hypophosphite
  • the melamine-formaldehyde crosslinker with the trade name of Ecco Rez M-300 was supplied by Eastern Color & Chemical Company, Greenville, South Carolina.
  • the fabric was first immersed in a finish solution containing FR, BTCA, and the catalyst, then passed through a laboratory padder with two dips and two nips, dried at 90°C for 3 min, and finally cured in a Mathis curing oven at a specified temperature. All the concentrations presented here are based on weight (w/w, %>). The wet pick-up of the cotton and cotton/polyester blend fabrics was approximately 85 and 80%, respectively. After curing, the treated fabric was first subjected to a washing/drying cycle without use of a detergent (specified here as "water wash") to remove FR and BTCA not bound to cotton and the catalyst. The home laundering wash/dry process was done according to AATCC Test Method 124-1996 (Appearance of Fabrics After Repeated Home Laundering). The detergent used was a commercial Tide detergent without bleach. The water temperature was approximately 45°C.
  • the fabric sample thus treated is dried at 80°C for 5 min.
  • the fabric sample was finely ground in a Wiley mill to form a powder before infrared spectroscopy analysis.
  • the ester carbonyl band intensity in the infrared spectra was normalized against the 1318 cm "1 band associated with a C-H bending mode of cellulose.
  • the sample thus prepared was analyzed with a Thermo-Farrell-Ash Model 965 induced current plasma atomic emission spectrometer (ICP/AES) to determine the % concentrations of phosphorous and calcium. Formation of Calcium Salt on the Cotton Fabric Treated with BTCA
  • the cotton fabric treated with 9.6% BTCA and 4.8%NaH 2 P0 2 was cured at 185°C for 2 min.
  • the treated fabric was first washed in water to remove the catalyst and BTCA not bound to cotton, then treated in CaCl 2 solutions of different concentrations at room temperature for 30 min.
  • the calcium concentration of the CaCl solutions ranged from 0J0 to 4.00%).
  • the cotton fabric thus treated was thoroughly washed in deionized water for 30 min to remove any residual calcium ions not bound to the fabric, and finally dried.
  • the calcium concentration on the cotton fabric determined by ICP/AES is plotted against the calcium concentration of the CaCl 2 solutions used to treat the fabric ( Figure 1).
  • the calcium concentration on the fabric reached approximately 0.3% when the calcium concentration of the solution was increased to 1.00%), and it stabilized at the 0.3%> level as the calcium concentration of the solution increased further ( Figure 1).
  • the data indicate that the calcium cations form salt with the free carboxylic acid group on the fabric, which has low solubility in water (Scheme 3).
  • the formation of calcium salt on the treated cotton fabric reached saturation when the calcium concentration in the solution was increased to 1.00% as shown in Figure 1.
  • the calcium concentration on the cotton fabric is plotted against the number of the home laundering washing/drying (HLWD) cycles ( Figure 2).
  • HLWD home laundering washing/drying
  • the data show that the calcium cations of the tap water form salt with the free carboxylic acid group bound to the treated cotton fabric.
  • 0J g of the powder sample was suspended in 50 ml distilled water, and then titrated with a 0J0 M CaCl 2 solution.
  • the pH of the fiber/water mixture was plotted against the volume of the CaCl solution added to the mixture ( Figure 3).
  • the pH of the fiber/water mixture decreased as the volume of the added CaCl 2 solution increased.
  • the steady decline in pH value was evidently a result of the formation of calcium salt on the fiber as shown in Scheme 3, which liberated the proton from the carboxylic acid groups on the fabric.
  • the pH value stabilized at approximately 4.65 when the volume of the CaCl solution was increased to 14.0 ml, indicating the formation of calcium salt on the fiber reached saturation. All the data demonstrated that calcium cation reacts with the free carboxylic acid bound to the cotton fabric to form insoluble salt.
  • the cotton fabric was treated with 16% FR and BTCA of different concentrations.
  • the fabric thus treated was subject to 10 HLWD cycles, followed by thoroughly rinsing in deionized water for 30 min to remove the calcium physically absorbed on the fabric.
  • the calcium concentration on the treated cotton fabric before and after 10 HLWD cycles are presented in Table 1.
  • the calcium concentration on the fabric before washing is insignificant, and it became substantially larger after 10 HLWD cycles.
  • larger number of carboxylic acid groups on the cotton fabric as a result of higher BTCA concentration used to treat the fabric led to the increased calcium concentration after home laundering.
  • the cotton fabric was treated with 24% FR, 9.6% BTCA and 4.8%NaH 2 PO 2 , cured at 185°C for 2 min, then subjected to different number of HLWD cycles.
  • the LOI, char length, percent phosphorous retention, and calcium concentration of the fabric thus treated is shown in Table 2.
  • the char length exceeded 300 mm and LOI also decreased significantly.
  • the calcium concentration increased from 0.008% to 0.110% after 3 HLWD cycles ( Figure 5).
  • the diminished flame resistance of the treated cotton fabric is due to the formation of calcium salt of carboxylic acid on the fabric during the laundering process.
  • New Catalyst System NaH 2 PO 2 has been the most effective catalyst for esterification and crosslinking of cotton by a polycarboxylic acid.
  • the combination of H 3 P0 2 and TEA was used as a new catalyst system to replace NaH 2 PO 2 .
  • 20 ml of a 0.30 M H 3 PO 2 was titrated with 0.30 M TEA.
  • the pH of H 3 PO 2 is presented as a function of the volume of TEA added ( Figure 6).
  • H 3 PO is a relatively strong acid with K a value of 5.9xl0 "2 whereas TEA is a weak base with K value of 5.75xl0 "7 .
  • the original pH of H 3 PO 2 was 1.56 before the titration was started.
  • H 3 PO was neutralized to form TEA salt as TEA was gradually added as shown in Scheme 1.
  • the esterification of cotton cellulose by a polycarboxylic acid proceeds in two steps: formation of a 5-membered cyclic anhydride intermediate by dehydration of two adjacent carboxylic acid groups, and the reaction between cellulose and the anhydride intermediate to form ester (12-13).
  • the cotton fabric was treated with 24% FR, 9.6% BTCA, 7% H 3 P0 2 in combination with different concentrations, of TEA.
  • the pH of all the finish solutions was adjusted to 3.0 using either NaOH or HC1 solutions.
  • the fabric was cured at 185°C for 2 min, and washed in deionized water to remove any FR, BTCA and TEA not bound to cotton.
  • the samples were treated with 0J M NaOH to convert the free carboxylic acid groups to carboxylate anions so that the ester carbonyl band was not overlapped by the carboxylic carbonyl, therefore could be measured quantitatively (15).
  • the ester carbonyl of the cotton fabric thus treated is plotted against the TEA concentration in Figure 7.
  • the amount of ester formed on the treated cotton fabric increased notably as the TEA concentration was increased, and the ester carbonyl band intensity reached its maximum when the TEA concentration was increased to 8%.
  • the infrared spectroscopy data evidently show that addition of TEA to the finish system resulted in esterification of BTCA with TEA during the curing process, thus increasing the total amount of ester formed on cotton.
  • a further increase in the TEA concentration from 8% to 14% reduces the ester carbonyl band intensity (Figure 7).
  • the calcium concentration of the cotton fabric treated with 24% FR, 9.6%> BTCA, 7%oH 3 PO 2 in combination with different concentrations of TEA and cured at 185°C for 2 min was treated in a 0.5 M CaCl 2 solution for 30 mins.
  • the calcium concentration of the fabric thus treated is plotted against the TEA concentration ( Figure 8).
  • Figure 8 One observes a significant decrease in calcium concentration as the TEA concentration was increased, and the calcium concentration reached its minimum when the TEA concentration was increased to 8%>. Previously, it was found that ester formation reached its maximum when TEA concentration was increased to 8%>.
  • the LOI (%) for the cotton fabric treated with FR, BTCA and H 3 P0 2 without the presence of TEA was only 24. L It increased to 30.7 when 5% TEA was presented in the finish and it reached its maximum (31.1) when TEA concentration was 10%. The same trend remained after the treated cotton fabric was subject to different number of home laundering cycles.
  • the LOI (%) of the treated cotton fabric after 5 laundering cycles is presented as a function of the TEA concentration in the finish system ( Figure 9).
  • the increased LOI is attributed to two factors: the reduction in calcium concentration as shown in Figure 8 and the increase in nitrogen concentration as a result of more TEA bonding to cotton through its esterification with BTCA.
  • the data also indicate that a further increase to 12% in TEA concentration reduced the LOI (Figure 9). This is consistent with the change in ester carbonyl band intensity as demonstrated in Figures 7.
  • the TEA added to the finish system esterifies the free carboxylic acid group, thus reducing the calcium concentration on the treated fabric.
  • the TEA bound to cotton through its esterification with cellulose also provides phosphorous-nitrogen synergism. Consequently, the H 3 PO 2 /TEA catalyst system significantly enhances the flame retardant properties of the treated cotton fabric.
  • the cotton fabric was treated with 28% FR, 14% BTCA and 7% H 3 PO 2 in combination with TEA of different concentrations.
  • the pH of the finish solutions was adjusted to 3.0 using either NaOH or HCl solutions.
  • the treated fabric was cured at 185°C for 2 min.
  • the calcium concentration and LOI of the fabric treated with different TEA concentrations are presented in Table 4. The data show that calcium concentration increased as the number of laundering cycles were increased. When TEA is present, however, the calcium concentration on the fabric was drastically reduced and LOI was increased. One also observes that TEA concentration at 8-10% resulted in the highest LOI. This is consistent with the data presented in Figures 9.
  • the performance of the FR/BTCA finish with different catalysts was compared.
  • the cotton fabric was treated with 28% FR and 14% BTCA in the presence of two different catalysts: (1) 7% H 3 P0 2 in combination of 10% TEA and (2) 7% NaH 2 PO 2 .
  • the fabric was then cured at 185°C for 2 min.
  • the calcium concentration, LOI, and char length of the cotton fabric thus treated are presented in Tables 6, 1, and 8, respectively.
  • the calcium concentration on the fabric after 5 HLWD cycles was increased to 0J96%> whenNaH 2 P0 2 was used as the catalyst, whereas it was only 0.045%> when H 3 PO 2 /TEA was used.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

On utilise actuellement des acides carboxyliques multifonctions tels que l'acide 1,2,3,4-butanetétracarboxylique (BTCA) pour lier un oligomère organo-phosphoré à fonctionnalité hydroxyle à un tissu en coton en présence d'un catalyseur tel que l'hypophosphite de sodium (NaH2PO2). Cependant, les groupes libres d'acide carboxylique liés à un tissu en coton forment pendant le lavage machine à domicile un sel de calcium, ce qui réduit les propriétés ignifuges du tissu en coton traité. L'invention concerne un nouveau système de catalyseur constitué d'acide hypophosphorique (H3PO2) et d'une base organique contenant l'azote telle que la triéthanolamine (TEA). Lorsque le système de catalyseur est conjugué à un acide polycarboxylique, la triéthanolamine estérifie les groupes acides carboxyliques libres dans des conditions de polymérisation et réduit ainsi la concentration du calcium sur le tissu pendant le lavage à domicile. L'invention concerne aussi une synergie azote - phosphore pour améliorer la capacité ignifuge du composé organo-phosphoré. Le tissu en coton traité au BTCA et oligomère à organo-phosphoré à fonctionnalité hydroxyle en présence de ce nouveau catalyseur manifeste des propriétés ignifuges supérieures à celles obtenues par le traitement au NaH2PO2 utilisé comme catalyseur.
PCT/US2003/005087 2002-02-22 2003-02-20 Systeme de catalyseur et procede de fabrication de materiaux ignifuges WO2003072871A1 (fr)

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AU2003215331A AU2003215331A1 (en) 2002-02-22 2003-02-20 Catalyst system andmethod for preparing flame resistant materials
US10/497,374 US20040261191A1 (en) 2002-02-22 2003-02-20 Catalyst system and method for preparing flame resistant materials

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US35893802P 2002-02-22 2002-02-22
US60/358,938 2002-02-22

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015179426A1 (fr) * 2014-05-19 2015-11-26 MegaMatter Inc. Retardateurs de flamme polymériques à grandes molécules

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9228093B2 (en) 2013-10-18 2016-01-05 Weyerhaeuser Nr Company Colored water-repellant and crocking-resistant compositions
CN107025379B (zh) * 2017-04-17 2020-02-07 东南大学 一种基于余弦函数的海洋潮汐区干湿循环参数等效方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6309565B1 (en) * 1999-09-27 2001-10-30 Akzo Nobel Nv Formaldehyde-free flame retardant treatment for cellulose-containing materials
US6372811B2 (en) * 1997-07-25 2002-04-16 Sachchida N. Singh Flame resistant rigid polyurethane foams blown with hydrofluorocarbons

Family Cites Families (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2909559A (en) * 1958-02-03 1959-10-20 Union Carbide Corp Polymeric phosphate esters and their production
US3228998A (en) * 1960-10-17 1966-01-11 Union Oil Co Liquid polyphosphate esters
US3099676A (en) * 1961-11-03 1963-07-30 Union Carbide Corp Hydroxyalkyl polyphosphates
US3309427A (en) * 1963-01-15 1967-03-14 Atlas Chemicals Ind Inc Polyhydroxy phosphate esters
FR1411875A (fr) * 1964-08-13 1965-09-24 Kuhlmann Ets Nouveaux polyols phosphorés, leur procédé de préparation et leurs applications
US3695925A (en) * 1970-03-27 1972-10-03 Stauffer Chemical Co Process for flameproofing textiles
BE789815A (fr) * 1970-03-27 1973-04-06 Stauffer Chemical Co Vinylphosphonates copolycondenses et leur utilisation comme agents retardant l'inflammation
GB1323381A (en) * 1970-07-23 1973-07-11 Knapsack Ag Polyols containing halogen and phosphorus and process for making them
US3850859A (en) * 1970-07-23 1974-11-26 Hoechst Ag Difficultly inflammable polyurethanes and process for making them
US4017257A (en) * 1974-09-11 1977-04-12 Stauffer Chemical Company Textiles fire-retardant treated with copolycondensed vinylphosphonates and process
DE2726478A1 (de) * 1977-06-11 1978-12-14 Hoechst Ag Phosphor enthaltende polyaddukte und verfahren zu deren herstellung
US4382042A (en) * 1978-04-03 1983-05-03 Stauffer Chemical Company Method of preparing oligomeric phosphate esters
US4268633A (en) * 1978-04-20 1981-05-19 Stauffer Chemical Company Polyurethanes containing a poly (oxyorganophosphate/phosphonate) flame retardant
US4199534A (en) * 1978-04-20 1980-04-22 Stauffer Chemical Company Poly (oxyorganophosphate/phosphonate) and process for preparing
US4335178A (en) * 1979-09-10 1982-06-15 Stauffer Chemical Company Textiles containing a poly(oxyorganophosphate/phosphonate) flame retardant
US4458035A (en) * 1981-11-04 1984-07-03 Stauffer Chemical Company Polyurethane foam having a flame retardant oligomeric phosphate ester
US4886895A (en) * 1985-05-23 1989-12-12 Akzo America Inc. Phosphate-containing and phosphonate-containing phosphate esters
US4697030A (en) * 1985-05-23 1987-09-29 Stauffer Chemical Company Phosphate-containing and phosphonate-containing phosphate esters
US5117033A (en) * 1985-05-23 1992-05-26 Akzo America Inc. Phosphate-containing and phosphonate-containing phosphate esters
US5221285A (en) * 1988-06-16 1993-06-22 The United States Of America As Represented By The Secretary Of Agriculture Catalysts and processes for formaldehyde-free durable press finishing of cotton textiles with polycarboxylic acids, and textiles made therewith
US4820307A (en) * 1988-06-16 1989-04-11 The United States Of America As Represented By The Secretary Of Agriculture Catalysts and processes for formaldehyde-free durable press finishing of cotton textiles with polycarboxylic acids
US4936865A (en) * 1988-06-16 1990-06-26 The United States Of America As Represented By The Secretary Of Agriculture Catalysts and processes for formaldehyde-free durable press finishing of cotton textiles with polycarboxylic acids
US5496476A (en) * 1992-12-21 1996-03-05 Ppg Indutstries, Inc. Non-formaldehyde durable press finishing for cellulosic textiles with phosphonoalkylpolycarboxylic acid
US5695528A (en) * 1994-07-13 1997-12-09 Nippon Chemical Industrial Co., Ltd. Treating agent for cellulosic textile material and process for treating cellulosic textile material
US5608100A (en) * 1993-12-16 1997-03-04 Hoechst Aktiengesellschaft Oligomeric phosphoric acid esters which carry hydroxyalkoxy groups, their preparation and their use
US6165919A (en) * 1997-01-14 2000-12-26 University Of Georgia Research Foundation, Inc. Crosslinking agents of cellulosic fabrics
US6221275B1 (en) * 1997-11-24 2001-04-24 University Of Chicago Enhanced heat transfer using nanofluids
US6329058B1 (en) * 1998-07-30 2001-12-11 3M Innovative Properties Company Nanosize metal oxide particles for producing transparent metal oxide colloids and ceramers
US6166170A (en) * 1999-12-02 2000-12-26 E. I. Du Pont De Nemours And Company Esterification catalysts and processes therefor and therewith

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6372811B2 (en) * 1997-07-25 2002-04-16 Sachchida N. Singh Flame resistant rigid polyurethane foams blown with hydrofluorocarbons
US6309565B1 (en) * 1999-09-27 2001-10-30 Akzo Nobel Nv Formaldehyde-free flame retardant treatment for cellulose-containing materials

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015179426A1 (fr) * 2014-05-19 2015-11-26 MegaMatter Inc. Retardateurs de flamme polymériques à grandes molécules
US9975841B2 (en) 2014-05-19 2018-05-22 Megamatter, Inc. Large molecule and polymer flame retardants

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