US3627784A - Heterocyclic phosphorus compounds and process for their manufacture - Google Patents
Heterocyclic phosphorus compounds and process for their manufacture Download PDFInfo
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- US3627784A US3627784A US883627A US3627784DA US3627784A US 3627784 A US3627784 A US 3627784A US 883627 A US883627 A US 883627A US 3627784D A US3627784D A US 3627784DA US 3627784 A US3627784 A US 3627784A
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- -1 Heterocyclic phosphorus compounds Chemical class 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 238000000034 method Methods 0.000 title claims description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- VNVRRNRPVIZREH-UHFFFAOYSA-N carbamoylphosphonic acid Chemical compound NC(=O)P(O)(O)=O VNVRRNRPVIZREH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003377 acid catalyst Substances 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 17
- 239000011574 phosphorus Substances 0.000 claims description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000004965 chloroalkyl group Chemical group 0.000 claims description 3
- 239000001257 hydrogen Chemical group 0.000 claims description 3
- 229910052739 hydrogen Chemical group 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 23
- 229920003180 amino resin Polymers 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 10
- 229920002678 cellulose Polymers 0.000 abstract description 7
- 239000001913 cellulose Substances 0.000 abstract description 7
- 239000004753 textile Substances 0.000 abstract description 6
- 238000004855 creaseproofing Methods 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical class [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 abstract description 2
- 125000004430 oxygen atom Chemical group O* 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 52
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 238000002360 preparation method Methods 0.000 description 17
- 239000000047 product Substances 0.000 description 14
- 229930040373 Paraformaldehyde Natural products 0.000 description 12
- 239000004744 fabric Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 229920002866 paraformaldehyde Polymers 0.000 description 12
- 239000007795 chemical reaction product Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 9
- 150000003018 phosphorus compounds Chemical class 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000002657 fibrous material Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- LSCSYJWMZUCJDW-UHFFFAOYSA-N 3-dimethoxyphosphorylpropanamide Chemical compound COP(=O)(OC)CCC(N)=O LSCSYJWMZUCJDW-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 235000011007 phosphoric acid Nutrition 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000006188 syrup Substances 0.000 description 3
- 235000020357 syrup Nutrition 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine powder Natural products NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- NQPJDJVGBDHCAD-UHFFFAOYSA-N 1,3-diazinan-2-one Chemical compound OC1=NCCCN1 NQPJDJVGBDHCAD-UHFFFAOYSA-N 0.000 description 1
- CVKGSDYWCFQOKU-UHFFFAOYSA-N 2-n-butyl-1,3,5-triazine-2,4,6-triamine Chemical compound CCCCNC1=NC(N)=NC(N)=N1 CVKGSDYWCFQOKU-UHFFFAOYSA-N 0.000 description 1
- QKVNMODHEHRIMX-UHFFFAOYSA-N 3-dibutoxyphosphorylpropanamide Chemical compound CCCCOP(=O)(CCC(N)=O)OCCCC QKVNMODHEHRIMX-UHFFFAOYSA-N 0.000 description 1
- NNTWKXKLHMTGBU-UHFFFAOYSA-N 4,5-dihydroxyimidazolidin-2-one Chemical compound OC1NC(=O)NC1O NNTWKXKLHMTGBU-UHFFFAOYSA-N 0.000 description 1
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical class CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- NJYZCEFQAIUHSD-UHFFFAOYSA-N acetoguanamine Chemical compound CC1=NC(N)=NC(N)=N1 NJYZCEFQAIUHSD-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- MASBWURJQFFLOO-UHFFFAOYSA-N ammeline Chemical compound NC1=NC(N)=NC(O)=N1 MASBWURJQFFLOO-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229940077445 dimethyl ether Drugs 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- VPVSTMAPERLKKM-UHFFFAOYSA-N glycoluril Chemical compound N1C(=O)NC2NC(=O)NC21 VPVSTMAPERLKKM-UHFFFAOYSA-N 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical compound NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000008096 xylene Substances 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6527—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and oxygen atoms as the only ring hetero atoms
Definitions
- These compounds are manufactured by reacting 2 mols of at least one phosphonocarboxylic acid amide with at least 4 mols of anhydrous formaldehyde in the presence of an acid catalyst and in the absence of water.
- the phosphorous compounds are used for flameproofing and creaseproofing cellulose-containing textile material. They may be optionally used together with an aminoplast precondensate.
- dehyde is here used in the form of paraformaldehyde.
- Preferred compounds are symmetrical phosphorus compounds of formula preferably used.
- phosphorus compounds'of formula wherein R represents a methyl or ethyl residue Acompound which has above all proved valuable is the phosphorus compound of formula
- the reaction is advantageously carried out at elevated temperature, preferably 80 to 150C.
- the phosphorus compounds of formula l are appropriately manufactured by reacting (a) 2 mols of atleast one phosphonocarboxylic acid amide of formula CH2]CHCO-NH2 X Y RFO acid or especially p-toluenesulfonic acid are used as .acid catalysts required for this reaction.
- reaction in the presence of a solvent'which is inert towards the reagents,-such as forexample benzene, toluene, xylene or methanol.
- a solvent' which is inert towards the reagents,-such as forexample benzene, toluene, xylene or methanol.
- the reaction can also be carried out in the melt, .thatis' to say without solvents.
- the p'hosphonocarboxylic acid amides of formula (5) used for the manufacture of the phosphorus compounds of formula (1) to (4) are in themselves known and can be manufactured according to kncwnmethods.
- phosphorus compounds of forguanamines for example benzoguanamine.
- acetoguanamine mulas (l) to (4) it is also possible to proceed by starting from or also diguanamines may be mentioned.
- Further possible sub- 2 mols of the dimethylolated compounds of formula (5), disstances are: alkylureas or arylureas and alkylthioureas or solving these in an inert organic solventand effecting the ring arylthioureas, alkyleneureas'or alkylenediureas, for example closure between two molecules of the dimethylol compounds ethyleneurea, propyleneurea, acetylenediurea, or especially at a time at elevated temperature in the presence of an acid 4,5-dihydroxyimidazolidone-Z and derivatives thereof, for excatalyst and with water being split off.
- the invention also relates to a process for the flameproofmg and greaseproofing of cellulose-containing fiber materials characterized in that an aqueous preparation which contains at least one phosphorus compound of one of the formulas (l) to (4) and optionally a curable aminoplastic precondensate to these materials, thereafter drying the materials and subjecting them to a treatment at elevated temperature.
- the phosphorus compounds of formula (I) are used for flameproofing and creaseproofing cellulose-containing textile material.
- Phosphorus compounds of formulas (2) and (3) are preferred, and the process for flameproofing and creaseprooftng is of very particular interest if the compound of formula (4) is used.
- the pH value of the aqueous preparations containing the compounds of formula (1) is advantageously less than 5, in particular less than 3.
- mineral acids such as sulfuric acid, nitric acid, orthophosphoric acid or hydrochloric acid are added to the preparations.
- acids themselves, especially hydrochloric acid, it is also possible to use compounds from which the corresponding acids are easily, for example even without warming, formed in water by hydrolysis.
- phosphorus trichloride phosphorus pentachloride, phosphorus oxychloride, thionyl chloride, sulfuryl chloride, cyanuryl chloride, acetyl chloride and chloracetyl chloride.
- the preparations for flameproofing and creaseproofing can also contain a latent acid catalyst for accelerating the cure of the aminoplast precondensate which is optionally present and for cross-linking the compounds of formula l
- latent acid catalysts it is possible to use the catalysts which are known for curing aminoplasts on cellulose-containing material, for example ammonium chloride, ammonium dihydrogen orthophosphate, magnesium chloride, zinc nitrate and others.
- the preparations to be used according to the invention can contain yet further substances.
- An addition of aminoplast precondensates is advantageous for achieving a good wash-resistant flameproof finish, but is not necessary.
- aminoplast precondensates there are understood addition products of formaldehyde to nitrogen compounds which can be methylolated.
- 1,3,5-Amino-triazines such as N-substituted melarnines, for example N-butylmelamine, N- trihalogenomethylmelamines, as well as ammeline,
- Suitable aminoplast precondensates areboth predominantly monomolecular and also more highly precondensed aminoplasts.
- ethers of these aminoplast precondensates together withthe compounds of formula (l
- Advantageous compounds are for example the ethers of alkanols such as methanol, ethanol, n-propanol, isopropanol, nbutanol or pentanols. It is however appropriate for these aminoplast precondensates to be water soluble, as for example pentamethylolmelamine-dimethyl-ether.
- a copolymer obtainable by polymerization in aqueous emulsion, of (a) 0.25 to 10 percent of an alkaline earth salt of an afi-ethylenically unsaturated monocarboxylic acid, (b) 0.25 to 30 percent of a N-methylolamide .or N-methylolamideether of an a,B-ethylenically unsaturated monocarboxylic or dicarboxylic acid and (c) 99.5 to60 percent of at least one other copolymerizable compound.
- copolymers and their manufacture are also known.
- the tear resistance and scouring resistance of the treated fiber material can be advantageously influenced by the conjoint use of such a copolymer.
- a plasticizing dressing for example an aqueous polyethylene emulsion or ethylene copolymer emulsion.
- emulsifier for example a nonionic emulsifier, to the preparations.
- the content of compound of formula (1) in the aqueous preparation is appropriately such that 10 to 28 percent is applied to the material to be treated.
- the commercially available textile materials of native or regenerated cellulose can take up between 50 and 120 percent of an aqueous preparation.
- the aqueous preparations contain to 500 g./l. preferably 250 to 400 g./l., of phosphorus compound of formula l
- the amount of the additive required to adjust the hydrogen ion concentration to a value of less than 5 depends on the selected value itself and on the nature of the additive, though in any case it is not possible to go below a certain minimum. A certain excess above this minimum amount is generally to be recommended. Large excesses offer no advantages and can even prove harmful.
- the preparations are now applied to the cellulose-containing fiber materials, for example linen, cotton, acetate rayon, viscose rayon or fiber mixtures of such materials and others such as wool, polyamide or polyester fibers, and this can be carried out in a manner which is in itself known.
- piece goods are used and these are impregnated on a padder of the usual construction which is fed with the preparation at room temperature.
- the fiber material impregnated in this way must now be dried, and this is appropriately done at temperatures of up to 100 C. Thereafter it is subjected to a dry heat treatment at temperatures above 100 C., for example between 130 and 200 C., and preferably between 150 and 180 C., the duration of which can be the shorter, the higher the temperature. This duration of warming is for example 2 to 6 minutes at temperatures of l50to 180 C I WWMM W H Rinsing with an acid-binding agent, preferably with aqueous sodium carbonate solution, for example at 40 C. to boiling temperature, and for 3 to 10 minutes, is advisable in the case of a strongly acid reaction medium.
- an acid-binding agent preferably with aqueous sodium carbonate solution, for example at 40 C. to boiling temperature, and for 3 to 10 minutes
- a particular advantage of the present process is the fact that the treated cellulose-containing fiber materials are simultaneously flameproof and creaseproof, even without the conjoint use of aminoplast precondensates.
- the wet creaseproof properties of the treated fiber materials are significantly improved.
- a distinct improvement in the dry creasing angle can also be observed.
- the phosphorus compounds of formula (1) into the spinning composition, for example of cellulose-Zlzacetate, provided they exhibit adequate solubility in organic solvents such as acetone.
- the incorporation is simple, the spinning poses no difficulties, and fabrics manufactured therefrom are thus flameproofed in a simple manner.
- the reaction product corresponds to formula (4).
- the reaction product is diluted with the same volume of water. Thereafter it is extracted with n-hexane for 72 hours, in the course of which mainly thecompound of formula (5) is extracted.
- the reaction product is distilled, with the main fraction being collected between 252 and 260 C.
- the structure of formula (4) can be confirmed by means of mass spectroscopy and infrared spectroscopy.
- the compounds of examples 2 to 7 can also be purified and identified in an analogous manner.
- EXAMPLE-3 1,357.5 parts (7.5 mols) of 3-(dimethylphosphono)- propionic acid amide, 922.5 parts (30 mols) of 97.5 percent strength Paraformaldehyde and 6.75 parts of p-toluenesulfonic acid, monohydrate in 1,500 parts of toluene are stirred for 3 hours at reflux temperature (100 C.) in a 5,000 parts by volume stirred flask equipped with a condenser and thermometer. Thereafter the mixture is cooled to 60 C., the toluene is decanted, 1,500 parts 'of methanol are added, the whole is cooled to 15 C. with rapid stirring, and free paraformaldehyde is filtered off. The methanol is then removed in vacuo.
- EXAMPLE 4 One hundred and eighty-one parts (1 mol) of 3- (dimethylphosphon0)-propionic acid amide are mixed with 96 parts (3 mols) of 97.5 percent strength paraformaldehyde and 0.6 parts of magnesium oxide in a stirred flask of 500 volumes capacity, equipped with a thermometer and reflux condenser, and kept at 100 C. internal temperature for 30 minutes while stirring. After this time the content of bonded formaldehyde is 48.4 parts, corresponding to an percent formation of the dimethylol compound. The total CH O found is parts and the free C14 0 found is 41.6 parts.
- EXAMPLE 5 One hundred and thirty-nine parts (0.5 mol) of (bis-2- chlorethyl)-phosphonopropionic acid amide are mixed with 61.5 parts of 97.5 percent strength paraformaldehyde (2 mols), 0.5 parts of p-toluenesulfonic acid monohydrate and 200 parts of toluene in a stirred flask of 200 volumes capacity equipped with a thermometer and reflux condenser, and are treated for 5 hours at 100 C. internal temperature. Thereafter the mixture is cooled, the toluene is separated off and the reaction product is stirred with 250 parts of methanol. Excess paraformaldehyde is filtered off and the methanol is removed in vacuo at 45 C.
- EXAMPLE 6 116.6 parts (0.5 mol) of diallylphosphonopropionic acid amide, 61.5 parts (2 mols) of 97.5 percent strength paraformaldehyde, 0.2 part of hydroquinone, 0.5 part of ptoluenesulfonic acid monohydrate and 200. parts of toluene are mixed in a stirred flask of 500 volumes capacity equipped with a thermometer and reflux condenser, and the mixture treated at 100 C. internal temperature for 10 hours. Thereafter it is cooled, the toluene is separated off, and the reaction product is stirred with 250 parts of methanol. Excess formaldehyde is filtered off and the methanol removed in vacuo at 45 C.
- creasing rating 1: poor freedom from creasing.
- EXAMPLE 9 A cotton fabric is padded with one of the aqueous liquors E to l of table ll below. The liquor uptake is 80 percent. The fabric is dried at 80 C. and curing is then carried out for 4 minutes at 160 C. The fabric is now post-washed for minutes at the boil in a solution which per liter of water contains 2 g. of anhydrous sodium carbonate, rinsed and dried.
- concentrations of preparations E to l are so chosen that 44.5 g./l. of phosphorus is in each case contained in the bath.
- R is alkyl, chloroalkyl or allyl with at most four carbon atoms each and X is methyl or hydrogen.
- a phosphorus compound according to claim 2 of the formula 6.
- a phosphorus compound according to claim 2 of the formula 7 A phosphorus compound according to claim 1 of the formula l v 12 011 0 RL-O 0 /P ⁇ CHzOHzC l v CH'3O CHzCH C O-N /N-OC Ri-0 ClIa----(
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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)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH1891868A CH501094A (de) | 1968-12-18 | 1968-12-18 | Verwendung heterocyclischer Phosphorverbindungen zum Flammfest- und Knitterfestmachen von cellulosehaltigem Textilmaterial |
Publications (1)
Publication Number | Publication Date |
---|---|
US3627784A true US3627784A (en) | 1971-12-14 |
Family
ID=4436118
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US883627A Expired - Lifetime US3627784A (en) | 1968-12-18 | 1969-12-09 | Heterocyclic phosphorus compounds and process for their manufacture |
Country Status (18)
Country | Link |
---|---|
US (1) | US3627784A (no) |
JP (1) | JPS4821116B1 (no) |
AT (1) | AT299890B (no) |
BE (1) | BE743297A (no) |
BR (1) | BR6915214D0 (no) |
CH (2) | CH1891868A4 (no) |
CS (1) | CS152342B2 (no) |
DE (1) | DE1961884C3 (no) |
FI (1) | FI47998C (no) |
FR (1) | FR2026447A1 (no) |
GB (1) | GB1241926A (no) |
IL (1) | IL33494A (no) |
NL (1) | NL158863B (no) |
NO (1) | NO128916B (no) |
PL (1) | PL82736B1 (no) |
SE (1) | SE359588B (no) |
SU (1) | SU383320A3 (no) |
YU (1) | YU33297B (no) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3906136A (en) * | 1971-04-30 | 1975-09-16 | Stauffer Chemical Co | Process of flame retarding substrates by applying hexahydratriazine phosphonate derivatives |
US4237056A (en) * | 1979-07-26 | 1980-12-02 | Velsicol Chemical Corporation | Cyclic acetal-methyl-carbamoyl-methyl esters of phosphonic and phosphoric acid |
US4314840A (en) * | 1979-07-26 | 1982-02-09 | Velsicol Chemical Corporation | Cyclic acetal-methyl-carbamoyl-methyl esters of phosphonic and phosphoric acids, as herbicides |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3381062A (en) * | 1963-05-03 | 1968-04-30 | Ciba Ltd | Cyclic diphosphono-carboxylic amides |
-
1968
- 1968-12-18 CH CH1891868D patent/CH1891868A4/xx unknown
- 1968-12-18 CH CH1891868A patent/CH501094A/de not_active IP Right Cessation
-
1969
- 1969-11-19 SE SE15883/69A patent/SE359588B/xx unknown
- 1969-12-05 PL PL1969137349A patent/PL82736B1/pl unknown
- 1969-12-08 IL IL33494A patent/IL33494A/xx unknown
- 1969-12-09 US US883627A patent/US3627784A/en not_active Expired - Lifetime
- 1969-12-10 DE DE1961884A patent/DE1961884C3/de not_active Expired
- 1969-12-10 GB GB60379/69A patent/GB1241926A/en not_active Expired
- 1969-12-11 SU SU1385370A patent/SU383320A3/ru active
- 1969-12-15 FI FI693626A patent/FI47998C/fi active
- 1969-12-16 FR FR6943583A patent/FR2026447A1/fr not_active Withdrawn
- 1969-12-16 CS CS8284A patent/CS152342B2/cs unknown
- 1969-12-16 BR BR215214/69A patent/BR6915214D0/pt unknown
- 1969-12-17 AT AT1173869A patent/AT299890B/de not_active IP Right Cessation
- 1969-12-17 BE BE743297D patent/BE743297A/xx unknown
- 1969-12-17 YU YU3159/69A patent/YU33297B/xx unknown
- 1969-12-17 NL NL6918938.A patent/NL158863B/xx unknown
- 1969-12-17 NO NO04977/69A patent/NO128916B/no unknown
-
1971
- 1971-09-09 JP JP46069335A patent/JPS4821116B1/ja active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3381062A (en) * | 1963-05-03 | 1968-04-30 | Ciba Ltd | Cyclic diphosphono-carboxylic amides |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3906136A (en) * | 1971-04-30 | 1975-09-16 | Stauffer Chemical Co | Process of flame retarding substrates by applying hexahydratriazine phosphonate derivatives |
US4237056A (en) * | 1979-07-26 | 1980-12-02 | Velsicol Chemical Corporation | Cyclic acetal-methyl-carbamoyl-methyl esters of phosphonic and phosphoric acid |
US4314840A (en) * | 1979-07-26 | 1982-02-09 | Velsicol Chemical Corporation | Cyclic acetal-methyl-carbamoyl-methyl esters of phosphonic and phosphoric acids, as herbicides |
Also Published As
Publication number | Publication date |
---|---|
BR6915214D0 (pt) | 1973-01-04 |
SE359588B (no) | 1973-09-03 |
GB1241926A (en) | 1971-08-04 |
YU315969A (en) | 1976-03-31 |
YU33297B (en) | 1976-08-31 |
NL6918938A (no) | 1970-06-22 |
SU383320A3 (no) | 1973-05-25 |
CH501094A (de) | 1970-08-14 |
NO128916B (no) | 1974-01-28 |
FI47998B (no) | 1974-01-31 |
DE1961884A1 (de) | 1970-07-09 |
BE743297A (no) | 1970-06-17 |
NL158863B (nl) | 1978-12-15 |
IL33494A (en) | 1972-07-26 |
FI47998C (fi) | 1974-05-10 |
CH1891868A4 (no) | 1970-08-14 |
CS152342B2 (no) | 1973-12-19 |
FR2026447A1 (no) | 1970-09-18 |
DE1961884C3 (de) | 1978-06-15 |
PL82736B1 (no) | 1975-10-31 |
IL33494A0 (en) | 1970-02-19 |
AT299890B (de) | 1972-07-10 |
DE1961884B2 (de) | 1977-10-20 |
JPS4821116B1 (no) | 1973-06-26 |
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