US3690941A - Process for providing cellulose fibre material with a flame-proof finish fast to washing - Google Patents

Process for providing cellulose fibre material with a flame-proof finish fast to washing Download PDF

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Publication number
US3690941A
US3690941A US96286A US3690941DA US3690941A US 3690941 A US3690941 A US 3690941A US 96286 A US96286 A US 96286A US 3690941D A US3690941D A US 3690941DA US 3690941 A US3690941 A US 3690941A
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United States
Prior art keywords
washing
formula
flame
cellulose fibre
fibre material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US96286A
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English (en)
Inventor
Martin Reuter
Claus Beermann
Fritz Linke
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Hoechst AG
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Hoechst AG
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D06M13/288—Phosphonic or phosphonous acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/92—Fire or heat protection feature
    • Y10S428/921—Fire or flameproofing

Definitions

  • a number of processes are known for providing cellulose fibre materials, especially textiles, with a flame-proof finish fast to washing by using condensation products of organophosphoric compounds.
  • Processes are mostly used in which condensates of methylol-phosphoric compounds, especially of quaternization products of the tris-hydroxymethylphosphine, for example of tetrahydroxy-methylphosphonium-hydroxide and its salts, are produced on the textiles, partly with addition of aminoplast forming agents, partly cross-linking with gaseous ammonia.
  • condensation products of phosphoryl or phosphonyl-ethylene-imides of the type are produced on the textiles, in which R stands for an aliphatic radical or signifies the radical NC H of the very toxic ethylene-imine.
  • R stands for an aliphatic radical or signifies the radical NC H of the very toxic ethylene-imine.
  • the present invention relates to a process for providing cellulose fibre material with a flame-proof finish fast to washing by means of condensates of organophosphoric compounds, in which the aforementioned drawbacks are eliminated.
  • the object of the invention is a process for providing cellulose fibre material with a flame-proof finish fast to washing, wherein the fibrous material is treated with an aqueous impregnation bath which contains a phosphonic acid ester having N-methylol groups of the Formula I in which R and R represent lower alkyl having preferably from 1 to 4 carbon atoms, A is straight-chain or branched alkylene of 1 to 5 carbon atoms and Y stands for hydrogen or the radical CH OH, and, preferably, aminoplast precondensates and/or aminoplast condensation catalysts, and subsequently is subjected to a heat-treatment.
  • aqueous impregnation bath which contains a phosphonic acid ester having N-methylol groups of the Formula I in which R and R represent lower alkyl having preferably from 1 to 4 carbon atoms, A is straight-chain or branched alkylene of 1 to 5 carbon atoms and Y stands for hydrogen or the radical CH OH, and, preferably, aminoplast precon
  • A stands for methylene, 1,1-ethylene or 1,1-propylene, i.e. compounds in which A represents a bridge-member of the formula in which A stands for hydrogen, methyl or ethyl.
  • urethano-alkyl-phosphonic esters of the Formula II in which n is an integer of l to 4 and Hal is halogen, especially chlorine, with dior trialkylphosphites.
  • the compounds of Formula II are, furthermore, obtained by reacting the known hydroxyal'kyl phosphonic ac id-esters (cf. Houben-Weyl, Methoden der organischen Chemie, 4th Edition, vol. 12/1, page 478) of the formula O;P-A--OlI RO (m') in which R, R and A are as defined above, in known manner, with phosgene and reacting the so-obtained chlorocarbonic acid esters of the formula O PAOC0-Cl RO (1V) in which R, R and A are as defined above, with ammonia.
  • the urethano-a1kyl-phosphonic esters of Formula II may also be obtained by reaction of the hydroxyalkylphosphonic acid esters of Formula III with chlorosulfonyl isocyanate according to the following formula equations:
  • R, R and A are as defined above.
  • these urethano-alkyl-phosphonic esters of the Formula II are converted according to known methods into the N-monomethylol or N-dimethylol compounds of Formula I to be used in the process of the invention by reaction with 1 to 2 mols of aqueous formaldehyde or with paraformaldehyde at temperatures of from about to 70 C., preferably in the alkaline pH range, for example at pH 8 to 9.
  • Preferred examples of such phosphonic acid esters containing N-methylol groups used in the process of the invention are: N-mono-methylol-urethanoethyl-phosphonic acid diethyl ester N-monomethylol urethano ethyl phosphonic acid dimethyl ester (CH O) P(O)CH OCONHCH or the corresponding N-dimethylol compounds.
  • the cellulose fibre materials are preferably treated with aqueous solutions or dispersions which contain per litre about 50 to 400 g. of the phosphonic acid esters of Formula I.
  • aqueous solutions or dispersions which contain per litre about 50 to 400 g. of the phosphonic acid esters of Formula I.
  • about to 200 g./l. of known aminopl ast precondensates for example N-methylol-urea, NN dimethylol-cycloethylene-urea, trimethylolmelamine, penta-methylolmelamine trimethyl ether or other such substances are preferably added, as well as known acid forming condensation catalysts, for example ammonium chloride or magnesium chloride.
  • the cellulose fibre material impregnated in known manner on a foulard is subsequently squeezed off; the resulting increase in weight (squeezing effect) being preferably of from 60 to 100%.
  • the goods are dried in known-manner and subjected to a further heat-treatment.
  • the drying is advantageously carried out at about 80 to 120 C., preferably up to a residual moisture content of about 4 to 8 percent by weight.
  • the subsequently heattreatment is carried out at a temperature in excess of 110 C. and up to about 200 C., preferably for about 1 to 10 minutes at 130 C. and up to about 180 C.
  • the fibrous material may be subjected to an alka line washing, for example with a 0.2%-aqueous sodium carbonate solution.
  • textile auxiliaries such as plasticizers, crease-proofing or hydrophobizing agents, may be added to the impregnation solutions to be used in the process of the invention.
  • EXAMPLE 1 A cotton-moleskin fabric (200 g./m. was impregnated on a foulard at about C. with an aqueous solution which contained per litre 250 g. of N-methylolurethanomethyl-phosphonic acid diethyl ester of the formula further 50 g. of pentamethylolmelamine trimethyl ether and 4 g. of ammonium chloride.
  • the N-mcthylol-uretlranomethyl-phosphonic acid diethyl ester was prepared from hydroxymethyl-phosphonic acid diethyl ester and phosgene and by the action of ammonia on the so-obtained chlorocarbonic acid ester of the formula followed by known methylolization with formaldehyde. During the impregnation a squeezing effect of was maintained.
  • the fabric was predried at 100 C. so that it contained a residual moisture of about 8% by weight, and subsequently heated for 4 minutes at 170 C. for condensation purposes.
  • the fabric so finished had a pleasant full feel (hand), showed no damage in its tear strength and showed in the vertical flame-proof test according to DIN 53 906 (German Industrial Standards, equivalent to the Framed Vertical Strip CCCT-l9 l b Method 5902, cf. M. J. Koroskys, American Dyestuff Reporter, Mar. 24, 1969, page 15 et seq., especially page 19, col. 3) a burning length of 18.0 cm. These properties were maintained also after a washing of 15 minutes at C. with a 0.2%- aqueous sodium carbonate solution.
  • EXAMPLE 3 A cotton moleskin fabric (200 g./m. was padded at 25 C. on a foulard with an aqueous solution containing 250 g./l. of (N,N-dimethylol) 1 urethanoethyl-phosphonic acid dimethyl ester of the formula 50 g./l. of pentamethylolmelamine trimethyl ether and 4 g./l. of ammonium chloride.
  • the impregnated fabric was squeezed between rollers until the increase in weight, referred to dry fabric, was 80%.
  • the padded fabric was dried at C. until the moisture content was about 8% and, subsequently, heated to effect condensation for 4 minutes to C.
  • the so-obtained fabric showed a pleasant soft handle and was not impaired in respect to tear strength.
  • the burning length according to DIN 53 906 was 8.0 cm. These properties were maintained after a washing for 15 minutes at 95 C. with an 0.2% aqueous sodium carbonate solution.
  • the (N,N-dimethylol)-1-urethanoethyl dimethyl phosphonate mentioned above was prepared as follows: 1 mol of l-hydroxyethyl-l-phosphonic acid dimethyl ester of the formula (known from Houben-Weyl, Methoden der organischen Chemie, 4th Edition, vol. 12/1, page 478) was added dropwise at 0 C. to 2 moles of phosgene. After distilling off the hydrogen chloride and the surplus phosgene at 10 to 20 C. the oily chloro-carbonic acid ester of the formu a (CH O) 1 (0) CH(CH )0COCl was obtained in 95% yield.
  • the chlorocarbonic acid ester was addded dropwise to the five-fold amount by volume of chloroform, in which 2 mols of ammonia was bubbled in.
  • the ammonium chlo ride formed as by-product was removed by filtration with suction and washed with chloroform for several times. From the combined chloroform filtrates the chloroform was distilled off in vacuo at about 40 C. There remained the urethane of the formula in 80% yield as a crystalline solid, melting point 98 C, after recrystallization from hot acetone 108 C.
  • EXAMPLE 4 When impregnating a cotton moleskin fabric as described in Example 3, but adding, furthermore, to the impregnation bath 40 g./l. of l,3-dimethylol-4,S-dihydroxyimidazolidinone-2 and 8 g. /l. of magnesium chloride a flame-proof fabric was obtained the burning length of which was 8 cm., which was maintained after a washing at the boil with a bath containing 5 g./l. of soap and 3 g./l. of sodium carbonate for 3 hours.
  • EXAMPLE 5 When impregnating a cotton moleskin fabric as described in Example 3, but using instead of the (N,N-dimethylol)-1-urethanoethyl phosphonic acid dimethyl ester the same amount of (N,N-dimethylol)-1-urethanopropyl phosphonic acid diethyl ester of the formula (C H O) P(O)CH(C H )--0CON(CH OH) substantially the same results were obtained as given in Example 3.
  • the (N,N-dimethylol) 1 urethanopropyl-phosphonic acid dimethylester was obtained as folows: 1 hydroxypropyl 1 phosphonic acid diethyl ester (known from Houben-Weyl, 4th Ed., vol. 12/1, p. 478) was reacted as described in Example 3 with phosgene, and, subsequently with ammonia to yield the urethane of the formula (melting point 80 C.) and reacting said urethane finally with 2 mols of formaline.
  • heating is at a temperature above about 110 C. and below 200 C.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
US96286A 1970-08-29 1970-12-08 Process for providing cellulose fibre material with a flame-proof finish fast to washing Expired - Lifetime US3690941A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE2042949A DE2042949C3 (de) 1970-08-29 1970-08-29 Verfahren zum waschbeständigen Flammfestausriisten von Cellulosefasergut

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US3690941A true US3690941A (en) 1972-09-12

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US (1) US3690941A (show.php)
BE (1) BE771893R (show.php)
CA (1) CA960921A (show.php)
DE (1) DE2042949C3 (show.php)
FR (1) FR2104890B4 (show.php)
GB (1) GB1364700A (show.php)
IT (1) IT987553B (show.php)
NL (1) NL7111620A (show.php)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3859124A (en) * 1972-09-25 1975-01-07 Proctor Chemical Company Inc Durable fire retardant textile materials by anhydrous solvent finishing process
US3874911A (en) * 1972-01-14 1975-04-01 Ciba Geigy Ag Process for the manufacture of phosphorus-containing condensation products, the products and their use as flameproofing agents
US3901985A (en) * 1971-09-10 1975-08-26 Ciba Geigy Ag Process for the manufacture of condensation products containing phosphorus, the products and their use as flameproofing agents
US4026808A (en) * 1972-03-30 1977-05-31 Hooker Chemicals & Plastics Corporation Flame retardant textile finishes
US4077964A (en) * 1974-10-17 1978-03-07 Societe Nationale Des Poudres Et Explosifs Carbamate-phosphonates, and process of preparation
CN120967672A (zh) * 2025-10-20 2025-11-18 浙江梅盛新材料有限公司 一种三聚氰胺原位超分子自组装阻燃整理液及其制备方法和应用、阻燃仿麂皮织物及其制备方法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3901985A (en) * 1971-09-10 1975-08-26 Ciba Geigy Ag Process for the manufacture of condensation products containing phosphorus, the products and their use as flameproofing agents
US3874911A (en) * 1972-01-14 1975-04-01 Ciba Geigy Ag Process for the manufacture of phosphorus-containing condensation products, the products and their use as flameproofing agents
US4026808A (en) * 1972-03-30 1977-05-31 Hooker Chemicals & Plastics Corporation Flame retardant textile finishes
US3859124A (en) * 1972-09-25 1975-01-07 Proctor Chemical Company Inc Durable fire retardant textile materials by anhydrous solvent finishing process
US4077964A (en) * 1974-10-17 1978-03-07 Societe Nationale Des Poudres Et Explosifs Carbamate-phosphonates, and process of preparation
CN120967672A (zh) * 2025-10-20 2025-11-18 浙江梅盛新材料有限公司 一种三聚氰胺原位超分子自组装阻燃整理液及其制备方法和应用、阻燃仿麂皮织物及其制备方法

Also Published As

Publication number Publication date
DE2042949A1 (de) 1972-03-02
FR2104890B4 (show.php) 1973-05-25
IT987553B (it) 1975-03-20
GB1364700A (en) 1974-08-29
BE771893R (fr) 1972-02-28
NL7111620A (show.php) 1972-03-02
FR2104890A8 (show.php) 1972-04-21
DE2042949B2 (de) 1977-11-24
CA960921A (en) 1975-01-14
DE2042949C3 (de) 1978-08-10

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