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
  • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
  • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
  • C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
  • C07F9/657181—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and, at least, one ring oxygen atom being part of a (thio)phosphonic acid derivative

Definitions

• This invention relates to new derivatives of polyhydric alcohols containing, in the molecule, at least two phosphoric acid groups and at least two carbamoyl groups.
• the invention also relates to a process for the manufacture of said derivatives and to their use in flame-proofing cellulosic textile materials.
• Substances which are used to produce wash-proof finishcs are, for example, metal oxides which are precipitated onto the fibers.
• metal oxides which are precipitated onto the fibers.
• iron(III) oxide and a mixture of tungstic acid and tin(1 V) oxide or, in succession, antimony trioxide and titanium dioxide are precipitated onto the fibers.
• such processes necessitate the use of a plurality of baths. Strong acid solutions and elaborate equipment are therefore very inconvenient.
• a deposit of white metal oxide is formed on the surface of the textile material and this may lead to considerable difiiculties with certain colorations.
• the amount of phosphonium salt and amino resin which must be absorbed toprovide adequate flame resistance is undesirably high and causes a weight increase of the treated textile material of from 20 to 25%.
• This large addition of material causes a considerable change in the handle of the textile material.
• many textiles must be subjected to a special pretreatment in order to render them sufliciently adsorptive and absorptive to accommodate such a large amount of impregnating agent.
• substituent R is always hydroen or alkyl or alkenyl having, preferably, from 4 to 6 carbon atoms.
• the methylol compounds of these dialkyl carbamoylalkanephosphonates are in equilibrium with formalclehyde.
• the free formaldehyde contained in the equilibrium mixtures leads to, odor nuisance; during treatment and also produces a fishy smell on the fabric when ammonium salt catalysts are used at the usual condensation temperatures of from to C.
• That portion of di'alkyl carbamoylalkanephosphonate in the equilibrium mixture which is non-methylolated cannot react with the cellulose fibers and thus constitutes a loss of flame-proofing agent.
• flame-proofing according to the teaching of the above references is carried out using dialkyl methylolor alkoxymethylcarbamoylalkanephosphonates in the presence of amino resin-forming substances.
• a fabric treated in the above maimer meets all demands placed on a flame-proofed textile material, but it has been found that the tensile strength of a fabric thus treated is not always satisfactory, probably on account of the increased use of amino resin-forming substances. Fprthermore, it is often necessary to' re-treat the fabric after not more than 5 or 6 washes," since the wash-fastn'ess of these compounds does not permit a large number of washes. In order to be fully flame-proofed, the fabric must contain a minimum amount of flame-proofing agent. If the amount of said agent in the fabric drops by a only a few percent below the said permissible minimum, the
• R and R each individually denotes alkyl of from 1 to 4 carbon atoms or together form alkylene of from 2 to 3 carbon atoms
• R denotes hydrogen or alkyl of from 1 to 4 carbon atoms
• R can have the same or different meanings in any one molecule and denotes hydrogen, alkyl of from 1 to 3 carbon atoms, methylol, or alkoxymethyl of from 1 to 4 carbon atoms.
• compound of Formula I in which A is the radical of a dihydric alcohol, n is thus 2 and B is a radical of Formula II in which R and R are identical alkyl radicals having 1 or 2 carbon atoms, R is hydrogen and R is hydrogen, methyl or methylol.
• A is the radical of a dihydric alcohol of 2 or 3 carbon atoms, preferably of ethylene glycol or 1,2-propylene glycol.
• a phosphorous acid dialkyl ester of Formula III may be reacted with an unsaturated acid amide of Formula IV, the resulting compound methylolated with formaldehyde and the product then reacted with one of said polyhydric alcohols of Formula V in stoichiometric proportions, i.e., in proportions such that all of the alcoholic groups take part in the reaction.
• the reverse route may be taken, for example, the unsaturated acid amide being methylolated with formaldehyde and the methylolated compound being directly etherified with the polyhydric alcohol and the resulting product then being reacted with the dialkyl phosphite.
• reaction products of unsaturated acid amide, formaldehyde and polyhydric alcohol are already available.
• a representative of such compounds is for example the so-called glycolamol.
• reaction product of the dialkyl phosphite with the methylolated unsaturated acid amide may be available and this can be reacted with the polyhydric alcohol.
• dialkyl phosphites such as are described in German printed application 1,469,281. These are dialkyl phosphites of from 1 to 4 carbon atoms per alkyl radical. We prefer to use those in which the alkyl groups are identical and contain 1 or 2 carbon atoms, i.e., are methyl or ethyl groups.
• Suitable products of this kind are those substituted as defined above. Examplesthereof are acrylamide, methylacrylamide, ethylacrylamide, propyland butyl-acrylamides or their derivatives substituted at the nitrogen atom with C alkyl radicals or optionally etherified methylol radicals.
• the methylol radicals may be etherified, for example, with alkyl groups containing from 1 to 4 carbon atoms.
• the preferred compounds are acrylamide, methacrylamide and N-methylolacrylamide.
• the polyhydric alcohols which may be used as starting materials for the compounds of the invention and which form the main feature of the invention, are represented by alcohols of from 2 to not more than 6 hydroxyl groups in the molecule and containing from 2 to 6 carbon atoms.
• Suitable representatives are, for example, glycol, glycerol, propylene glycol, 1,2- and 1,3-butyl glycols, polyhydric alcohols bridged by oxygen atoms such as butyl diglycol and lower polyalkylene oxides having not more than 6 carbon atoms, pentitols, hexitols, sorbitol and spatially branched alcohols such as pentaerythritol.
• Preferred on a commercial scale are glycol and 1,2-propylene glycol, although very favorable results are also obtained using sorbitol or pentaerythritol.
• the compounds of the invention may be manufactured for example as follows: a glycolamol of the following formula:
• A, R and R have the meanings given for Formula I, may be reacted with a dialkyl phosphite.
• This reaction proceeds readily in, for example, alkaline medium in the presence of, say, alcoholates or any other desired alkaline substance. Since this reaction is known in the art, it requires no further explanation in this description.
• dialkyl phosphite prepared in known manner by reacting dialkyl phosphite with one of said unsaturated acid amides, e.g. acrylamide, followed by methylolation with formaldehyde.
• the etherification proceeds in known manner in the presence of acid catalysts such as sulfuric acid, boron fluoride etherate and other Lewis acids.
• acid catalysts such as sulfuric acid, boron fluoride etherate and other Lewis acids.
• the compounds may be further methylolated at the nitrogen atoms and these methylolated compounds further etherified with one of the usual etherifying agents.
• the materials of Formula I may be used with great success as flame-proofing agents for textile materials, particularly those consisting of or containing natural or regenerated cellulose.
• textile materials particularly those consisting of or containing natural or regenerated cellulose.
• Particularly suitable textile materials, to which the materials of the invention may be applied, are for example cotton and regenerated cellulose.
• Fabrics finished with the materials of the invention are distinguished by a very soft handle, excellent wash fastness and the complete absence of odorous substances.
• the textile material to be treated is impregnated with one or more materials of Formula I and is then reacted therewith in the presence of at least one acidic and/or potentially acidic catalyst. It is preferred to use the materials of Formula I in the form of aqueous baths. The concentration of materials of Formula I in said baths is generally between 200 and 600 g./l.
• the impregnated textile material may, for example, be dried and then heated to a temperature of up to 200 C. and preferably of from 130 to 170 C. in the presence of acidic or potentially acidic catalysts. Under these conditions the reaction is generally complete in from 1 to 6 minutes.
• Acidic or potentially acidic catalysts for use in this type of treatment are Well known.
• Suitable compounds are, for example, inorganic or organic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, boric acid, oxalic acid and their acid-reacting salts or compounds capable of forming acids during use, for example due to the action of heat and/or hydrolysis, for example ammonium or amine salts, and also Lewis acids such as magnesium chloride, zinc chloride and zinc nitrate. Particularly good flame-proofing effects are achieved when using monoor di-ammonium phosphates.
• the reaction of the materials of Formula I is carried out in the presence of such catalysts.
• This may be effected by applying the catalysts, preferably in the form of aqueous solutions, to the textile material immediately after it has been impregnated with the novel substances.
• the catalysts are added directly to the bath con taining the materials of Formula I.
• Catalyst concentra tions in said baths of from 1 to 40 g./l. have been found to be convenient.
• Fabrics which have been rendered flame-proof in this manner are distinguished by excellent properties in respect of handle, tensile strength and flame resistance. It is possible to add to the baths, in addition to the mate rials of Formula I, other finishing agents such as nitrogen-free hydroxylmethyl or alkoxymethyl compounds, polyethylene glycol formals andcompounds containing epoxy groups such as glycol diglycidyl ether. Finally, amino resin-forming materials may also be used without the addition of plasticizers being essential, as hitherto necessary with prior art flame-proofing agents. In addition, conventional water-repellent, softening, leveling, wetting and finishing agents may be used if desired.
• suitable water-repellent finishes are aluminum-containing or zirconium-containing paraffin wax emulsions, siliconcontaining compositions and perfluorinated aliphatic compounds.
• Typical softeners are, for example, ethoxylation products of high molecular weight fatty acids. fatty alcohols or fatty acid amides; high molecular weight polyglycol ethers and esters thereof; high molecular Weight fatty acids; fatty alcohol sulfonates, stearyl-N,N-ethylene urea; and stearylamidomethylpyridinium chloride.
• Suitable leveling agents are water-soluble salts of acid esters of polybasic acids with ethylene oxide adducts or propylene oxide adducts of longer chain alkoxylated substances.
• wetting agents are salts of alkyl naphthalene sulfonic acid, the alkali metal salts of sulfonated dioctyl succinate and addition products of alkylene oxides with fatty alcohols, all-:yl phenols, fatty amines. etc.
• synthetic polymers such as polyethylene
• the textile material After reacting with the materials of Formula I and, where applicable, with any of the aforementioned additives, the textile material possesses excellent flame-proof properties which are very fast to hydrolysis and washing and which are accompanied by complete absence of odor.
• the flame-proofing properties are always realized whether or not the aforementioned additives are used. Only specific uses of the fabric can justify the inclusion of said addi tives, although this does not in any way influence the re sults obtained by the present invention.
• Parts by weight relate to parts by volume as do kilograms to liters.
• EXAMPLE 2 A mixture of 724 parts of dimethyl Z-carbamoylethane phosphate, 300 parts of 40% formaldehyde solution and 60 parts of 25% caustic soda solution is stirred for 2 hours at 50 C. The reaction mixture is then reduced to about 870 parts by evaporation under reduced pressure. To the sirupy residue there are added 124 parts of ethylene glycol and 20 parts of phthalic acid, and the mixture is heated at 50 C. for 3 hours. The mixture is neutralized with caustic soda solution and cooled to room temperature. The reaction product crystallizes after standing for 1 day. The yield of crude product is 790 g., equivalent to 88% of theory. The crude product may be recrystallized from a mixture of acetone and methanol. The results of paper chromatography and the mixed melting point show that the product is identical to that produced in Example 1.
• bamoylethane phosphonate 225 parts of butanediol-1,4 and 25 parts of phthalic acid is heated for 3 hours at from 60 to 65 C. in a stirred vessel.
• the mixture is neutralized with caustic soda and the reaction product crystallizes on standing for a short period at room temperature. There are obtained 860 parts, equivalent to 72% of theory.
• EXAMPLE 5 25 parts of a 30% methanolic soduim methoxide solu tion are added dropwise to a mixture of 228 parts of glycolamol and 276 parts of diethyl phosphite with stir ring at from to C. The reaction is controlled at 85 C. by cooling. The mixture is then heated at 80 C. for a further hour. There are obtained 475 parts of prod uct, equivalent to 94% of theory. Its formula is as follows:
• PCHaCH C ONH-CHz-OCHaCI-I: O---- CH; O
• EXAMPLE 7 A piece of cotton twill weighing 170 g./m. is added 320 parts of the compound of the formula: with an aqueous bath containing 325 parts of the follow Omo 0 mg -on,orr,oorzn-oH
• P-CHrCI-I C ONi-CHs- -OCHgCHsO EN 0 0 Q HICHH 11 omo H.011 0cm 0 com i are dissolved in about 500 parts of water. 20 parts of C r-HNQ0CHlCHl* 85% phosphoric acid are then added and the solution is stirred well and made up to 1 liter with water. A piece and 17 parts of monoammonium phosphate per liter of solution, so that a wet pick-up of abo'ut90% is achieved.
• the fabric is dried at 110 C. and treated onatenter for 5 minutes at 165 C. After storage under standard conditions for 24 hours, the rate of application is found to be 22% of the dry weight of the textile material. The fabric is then washed with a 0.2% soda solution for 2 minutes at 70 C. The fabric is rinsed until neutral and then redried.
• CH1 0 HIOH and 18 parts of monoammonium phosphate are dissolved in water and made up to 1 liter of solution.
• the weight of the poplin is 350 g./m.
• the material is dried at 100 C.
• the rate of application is found to be 23% of the dry Weight of the textile material.
• the fabric is treated with'a 0.2% aqueous soda solution for 2 minutes at 70 C. in-a washing machine and then rinsed until neutral arid'finally dried.
• A is the radical of an n-hydric aliphatic alcohol with 2 to 6 carbon atoms
• n is a whole number from 2 to 6
• R and R denote alkyl of from 1 to 4 carbon atoms or together form an alkylene radical of 2 to 3 carbon atoms, denotes hydrogen or alkyl of from 1 to 4 carbon atoms
• R denotes the same or different radicals selected from hydrogen atoms, alkyl of from 1 to 3 carbon atoms, methylol or alkoxymethyl of from 1 to 4 carbon atoms.

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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)
• Fireproofing Substances (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=5802788

Family Applications (1)

Country Status (10)

Cited By (5)

• 1971
  • 1971-03-26 DE DE19712114610 patent/DE2114610A1/de active Pending
• 1972
  • 1972-03-17 FR FR7209367A patent/FR2130369B1/fr not_active Expired
  • 1972-03-20 US US00236203A patent/US3808292A/en not_active Expired - Lifetime
  • 1972-03-22 CA CA137,842A patent/CA989412A/en not_active Expired
  • 1972-03-23 BE BE781146A patent/BE781146A/xx unknown
  • 1972-03-24 NL NL7204002A patent/NL7204002A/xx unknown
  • 1972-03-24 GB GB1382572A patent/GB1378962A/en not_active Expired
  • 1972-03-24 AT AT257272A patent/AT312554B/de not_active IP Right Cessation
  • 1972-03-24 ZA ZA722028A patent/ZA722028B/xx unknown
  • 1972-03-25 IT IT49247/72A patent/IT952401B/it active

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