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 PDFInfo
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- 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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- US
- United States
- Prior art keywords
- washing
- formula
- flame
- cellulose fibre
- fibre material
- Prior art date
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- Expired - Lifetime
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- 229920003043 Cellulose fiber Polymers 0.000 title abstract description 8
- 238000000034 method Methods 0.000 title description 25
- 238000005406 washing Methods 0.000 title description 14
- 239000000463 material Substances 0.000 title description 8
- 229920003180 amino resin Polymers 0.000 abstract description 10
- 238000010438 heat treatment Methods 0.000 abstract description 10
- 238000005470 impregnation Methods 0.000 abstract description 8
- 238000009833 condensation Methods 0.000 abstract description 7
- 230000005494 condensation Effects 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 4
- 150000003014 phosphoric acid esters Chemical class 0.000 abstract description 2
- 239000004744 fabric Substances 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 10
- -1 N-hydroxy-methyl-iodoacetamide Chemical compound 0.000 description 10
- 239000004753 textile Substances 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 150000003008 phosphonic acid esters Chemical class 0.000 description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- 229960001040 ammonium chloride Drugs 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002657 fibrous material Substances 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- MJUJXFBTEFXVKU-UHFFFAOYSA-N diethyl phosphonate Chemical compound CCOP(=O)OCC MJUJXFBTEFXVKU-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- AOGYCOYQMAVAFD-UHFFFAOYSA-N chlorocarbonic acid Chemical class OC(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-N 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- YLFBFPXKTIQSSY-UHFFFAOYSA-N dimethoxy(oxo)phosphanium Chemical compound CO[P+](=O)OC YLFBFPXKTIQSSY-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- YHQMSHVVGOSZEW-UHFFFAOYSA-N 1-dimethoxyphosphorylethane Chemical compound CCP(=O)(OC)OC YHQMSHVVGOSZEW-UHFFFAOYSA-N 0.000 description 1
- ZEYUSQVGRCPBPG-UHFFFAOYSA-N 4,5-dihydroxy-1,3-bis(hydroxymethyl)imidazolidin-2-one Chemical compound OCN1C(O)C(O)N(CO)C1=O ZEYUSQVGRCPBPG-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- 101100493710 Caenorhabditis elegans bath-40 gene Proteins 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 238000005654 Michaelis-Arbuzov synthesis reaction Methods 0.000 description 1
- VGGLHLAESQEWCR-UHFFFAOYSA-N N-(hydroxymethyl)urea Chemical compound NC(=O)NCO VGGLHLAESQEWCR-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- USDJGQLNFPZEON-UHFFFAOYSA-N [[4,6-bis(hydroxymethylamino)-1,3,5-triazin-2-yl]amino]methanol Chemical compound OCNC1=NC(NCO)=NC(NCO)=N1 USDJGQLNFPZEON-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JMXMXKRNIYCNRV-UHFFFAOYSA-N bis(hydroxymethyl)phosphanylmethanol Chemical compound OCP(CO)CO JMXMXKRNIYCNRV-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- WRJWRGBVPUUDLA-UHFFFAOYSA-N chlorosulfonyl isocyanate Chemical compound ClS(=O)(=O)N=C=O WRJWRGBVPUUDLA-UHFFFAOYSA-N 0.000 description 1
- 238000004855 creaseproofing Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- RWIGWWBLTJLKMK-UHFFFAOYSA-N diethoxyphosphorylmethanol Chemical compound CCOP(=O)(CO)OCC RWIGWWBLTJLKMK-UHFFFAOYSA-N 0.000 description 1
- WVJOGYWFVNTSAU-UHFFFAOYSA-N dimethylol ethylene urea Chemical compound OCN1CCN(CO)C1=O WVJOGYWFVNTSAU-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical group [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
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)
Abstract
CELLULOSE FIBER MATERIASL ARE RENDERED FLAME PROOF AND FAST TO WASHING BY (A) IMPREGNATION WITH AQUEOUS BATH CONTAINING PHOSPHORIC ACID ESTERS WITH N-METHYLOL GROUPS AND, OPTIONALLY, AMINOPLAST PRECONDENSATES AND/OR AMINOPLAST CONDENSATION CATALYSTS, AND (B) SUBSEQUENT HEAT TREATMENT.
Description
United States Patent 3,690,941 Patented Sept. 12, 1972 US. Cl. 117-136 9 Claims ABSTRACT OF THE DISCLOSURE Cellulose fiber materials are rendered flame proof and fast to washing by (a) impregnation with aqueous bath containing phosphoric acid esters with N-methylol groups and, optionally, aminoplast precondensates and/ or aminoplast condensation catalysts, and (b) a subsequent heat treatment.
This application is a continuation-in-part application of our copending application Ser. No. 43,192, filed June 3, 1970.
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. These compounds, however, have some drawbacks: they are obtained only in a risky and dangerous manner from hydrogen phosphide, the access to which is very dittficult, further, they have an unfavorable influence on the shades of several textile dyeings.
In other known processes, 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. The drawbacks of these phosphoric compounds are: they can be prepared only by very lengthy synthesis and they have only a limited stability under normal temperatures.
Further, there have been used condensates from phosphoric acid or phosphonic acids and urea in order to produce a fiameproof finish fast to Washing on cellulose textiles, which, however, damage the ultimate tensile strength of the textiles. These finishes also behave towards anion active detergents as ion exchangers which, as a result of a washing process, considerably reduces the flame-proofness. High textile tear strength losses of the textiles result when finishes with phosphorus nitrilamido-methyl esters are used.
There has further been suggested to react cellulose with N-hydroxy-methyl-iodoacetamide and to convert the iodoacetamido-methylcellulose compound of the general formula by further reaction according to the Arbuzov reaction excess trialkylphosphites and thus converting these to the corresponding phosphonic esters of the general formula This process requires a special equipment for the recovery of the phosphites and it cannot be carried out on the finishing machines usual in industrial practice. Moreover, all of these processes are odoriferous, the odor elimination of which can be ensured only by expensive apparatuses.
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. In this process, tear strength losses and feel deterioration of the cellulosic fibre as well as alteration of the shades are eliminated, and good flame-proof effects fast to washing are obtained. Also, an odoriferous emission does not occur.
As compounds corresponding to Formula I those are preferred in which 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.
As starting products for the preparation of the compounds of Formula I used in the process of the invention there may be used for example 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:
In Formula V, R, R and A are as defined above.
Thereafter, 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.
In the process of the invention, 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. Further, 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%. Then, 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. Finally, the fibrous material may be subjected to an alka line washing, for example with a 0.2%-aqueous sodium carbonate solution.
Further known 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.
The following examples illustrate 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 2 When working as described in Example 1 but using 33 0 g. of (N,N-dimethylol)-urethanomethyl phosphonic acid diethyl ester of the formula C H O) P( 0) CH OCON (CI-I OH) Instead of the 250 g. of the monomethyl compound and adding to the impregnation bath 50 g. of 1,3-dimethylol- 4,5-dihydroxyimidazolidinone 2 and 8 g. of magnesium chloride the so-obtained fabric showed after the condensation at 170 C. a burning length of 11.0 cm. only. The other properties of the fabric remained essentially unchanged. After washing the fabric for 15 minutes at 95 C. with a 0.2% aqueous sodium carbonate solution the burning length was 10.5 cm. After a washing for 3 hours in a bath containing 5 g./l. of soap and 3 g./l. of sodium carbonate in an open beaker at the boil the burning length was, likewise, 10.5 cm.
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.
5 Analysis.Calculated 16.9% C1. Found 16.4% C1.
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.
Analysis.C H N P (197): Calculated 30.5% C, 6.0% H, 7.0% N, 15.7% P, 31.5% CH O. Found: 30.3% C, 6.1% H, 7.5% N, 15.6% P, 31.4% CH O.
0.55 mol of the so-obtained urethane was dissolved in 1.1 mol of 37% formaline at 50 C. while stirring and this temperature maintained for a further hour. The initial pH value of 4 was raised to 8.4 by means of 13 cc. of 2 N NaOH and maintained at this value.
There was found by means of alkaline iodine solution 17.3% of HCHO (theoretically: 17.0% with hydroxylamine, however, only 4.3% of free HCHO was found. These values indicate that a mixture of at least 50 molpercent the dimethylol compound and of at most 50 molpercent of the monomethylol compound was present.
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.
We claim:
1. In a process for flame proofing fibrous materials of cellulose, the improvement of which comprises impregnating said material in an aqueous bath comprising a phosphonic acid ester of the formula in which R and R' are lower alkyl, A is straight-chain or branched alkylene of l to 5 carbon atoms each and Y is hydrogen or CH 0H, and heating said impregnated material at a temperature from C. to 200 C.
2. The process as claimed in claim 1, wherein the impregnated goods are predried at about 80 to C., and finally subjected to a heating at a temperature up to 200 C.
3. The process as claimed in claim 1, wherein heating is at a temperature above about 110 C. and below 200 C.
4. The process as claimed in claim 1, wherein the heating is at a temperature from C. to C.
5. The process as claimed in claim 1, wherein the impregnating aqueous bath consists essentially of about 50 to 400 g. per liter of the phosphonic acid ester.
6. The process as claimed in claim 1, wherein the impregnating bath additionally contains an aminoplast precondensate.
7. The process as claimed in claim 1, wherein the impregnation bath additionally contains about 20 to 200 g. per liter of an aminoplast precondensate.
8. The process as claimed in claim 1, wherein the impregnated goods are squeezed to yield an increase in weight of about 60 to 100%, referred to dry goods.
9. The process as claimed in claim 1, wherein the heating lasts from 1 to 10 minutes at a temperature from 130 C. to 180 C.
References Cited UNITED STATES PATENTS 3,423,369 1/1969 Nachbur et a1 117-136 X 2,781,281 2/1957 Berger 117136 3,351,617 11/1967 Jaeger et al. 1l7136 X 2,494,283 1/1950 Cassaday et a1 260-940 2,998,347 8/ 1961 Fancher et a1 260-938 X 3,183,258 5/1965 Schuler et al. 260938 3,219,478 11/1965 Wagner 117136 3,579,532 5/ 1971 Nachbur et al. 117136 X WILLIAM D. MARTIN, Primary Examiner H. I. GWINNELL, Assistant Examiner US. Cl. X.R.
l17139.5 CQ, 143 R; 2528.1
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent 3.6900 11 Dated September 12. 1972 Inventor(s) Martin Reuter et a1.
It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
In theHeading:
"Application Germany" should read --applications German June 1 1, 1969, P 19 50 508.5 and-.
Signed and sealed this 13th day of February 1973.
(SEAL) Attest:
EDWARD l I.FI .1'l'(.IIER,JR ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents FORM Po-1050 (10-69) USCOMM-DC 60376-P69 \LS. GOVERNMENY PRINTING OFFHIE: I959 0-365-334,
UNITED STATES PATENT OFFICE v CERTIFICATE OF CORRECTION Patent 3.6QO.Q Ll Dated September 12. 1972 Inventor(s) Martin Reuter et a1.
It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
In. theHeading:
"Application Germany" should read --applications German June 11%, 1969; P 19 50 508.5 and.
Signed and sealed this 13th day of February 1973.
(SEAL) Attcst:
EDWARD M.FIII'I'CIIER,JR ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents 1 FORM (10459) I USCOMM-DC 60376-P69 R U.S. GOVERNMENT PRINTING OFFICE 1 I959 0-356'33,
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2042949A DE2042949C3 (en) | 1970-08-29 | 1970-08-29 | Process for the wash-resistant, flame-retardant finish of cellulose fiber material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3690941A true US3690941A (en) | 1972-09-12 |
Family
ID=5781075
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US96286A Expired - Lifetime US3690941A (en) | 1970-08-29 | 1970-12-08 | Process for providing cellulose fibre material with a flame-proof finish fast to washing |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US3690941A (en) |
| BE (1) | BE771893R (en) |
| CA (1) | CA960921A (en) |
| DE (1) | DE2042949C3 (en) |
| FR (1) | FR2104890B4 (en) |
| GB (1) | GB1364700A (en) |
| IT (1) | IT987553B (en) |
| NL (1) | NL7111620A (en) |
Cited By (5)
| 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 |
-
1970
- 1970-08-29 DE DE2042949A patent/DE2042949C3/en not_active Expired
- 1970-12-08 US US96286A patent/US3690941A/en not_active Expired - Lifetime
-
1971
- 1971-08-24 NL NL7111620A patent/NL7111620A/xx unknown
- 1971-08-25 GB GB3984671A patent/GB1364700A/en not_active Expired
- 1971-08-27 CA CA121,549A patent/CA960921A/en not_active Expired
- 1971-08-27 BE BE771893A patent/BE771893R/en active
- 1971-08-27 FR FR717131133A patent/FR2104890B4/fr not_active Expired
- 1971-08-27 IT IT27961/71A patent/IT987553B/en active
Cited By (5)
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CA960921A (en) | 1975-01-14 |
| GB1364700A (en) | 1974-08-29 |
| DE2042949B2 (en) | 1977-11-24 |
| DE2042949C3 (en) | 1978-08-10 |
| NL7111620A (en) | 1972-03-02 |
| IT987553B (en) | 1975-03-20 |
| BE771893R (en) | 1972-02-28 |
| FR2104890B4 (en) | 1973-05-25 |
| FR2104890A8 (en) | 1972-04-21 |
| DE2042949A1 (en) | 1972-03-02 |
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