US3627784A - Heterocyclic phosphorus compounds and process for their manufacture - Google Patents

Heterocyclic phosphorus compounds and process for their manufacture Download PDF

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Publication number
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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formula
parts
compounds
acid
mols
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US883627A
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Hermann Nachbur
Joerg Kern
Arthur Maeder
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BASF Schweiz AG
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Ciba AG
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    • 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)
US883627A 1968-12-18 1969-12-09 Heterocyclic phosphorus compounds and process for their manufacture Expired - Lifetime US3627784A (en)

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

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US3627784A true US3627784A (en) 1971-12-14

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US (1) US3627784A (ru)
JP (1) JPS4821116B1 (ru)
AT (1) AT299890B (ru)
BE (1) BE743297A (ru)
BR (1) BR6915214D0 (ru)
CH (2) CH1891868A4 (ru)
CS (1) CS152342B2 (ru)
DE (1) DE1961884C3 (ru)
FI (1) FI47998C (ru)
FR (1) FR2026447A1 (ru)
GB (1) GB1241926A (ru)
IL (1) IL33494A (ru)
NL (1) NL158863B (ru)
NO (1) NO128916B (ru)
PL (1) PL82736B1 (ru)
SE (1) SE359588B (ru)
SU (1) SU383320A3 (ru)
YU (1) YU33297B (ru)

Cited By (3)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3381062A (en) * 1963-05-03 1968-04-30 Ciba Ltd Cyclic diphosphono-carboxylic amides

Patent Citations (1)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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

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Publication number Publication date
BR6915214D0 (pt) 1973-01-04
SE359588B (ru) 1973-09-03
GB1241926A (en) 1971-08-04
YU315969A (en) 1976-03-31
YU33297B (en) 1976-08-31
NL6918938A (ru) 1970-06-22
SU383320A3 (ru) 1973-05-25
CH501094A (de) 1970-08-14
NO128916B (ru) 1974-01-28
FI47998B (ru) 1974-01-31
DE1961884A1 (de) 1970-07-09
BE743297A (ru) 1970-06-17
NL158863B (nl) 1978-12-15
IL33494A (en) 1972-07-26
FI47998C (fi) 1974-05-10
CH1891868A4 (ru) 1970-08-14
CS152342B2 (ru) 1973-12-19
FR2026447A1 (ru) 1970-09-18
DE1961884C3 (de) 1978-06-15
PL82736B1 (ru) 1975-10-31
IL33494A0 (en) 1970-02-19
AT299890B (de) 1972-07-10
DE1961884B2 (de) 1977-10-20
JPS4821116B1 (ru) 1973-06-26

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