EP0000044B1 - Carbamoyloxyalkyl phosphinic acid derivatives, process for their preparation and their use in the preparation of flame-retardant finished materials - Google Patents

Carbamoyloxyalkyl phosphinic acid derivatives, process for their preparation and their use in the preparation of flame-retardant finished materials Download PDF

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EP0000044B1
EP0000044B1 EP78100073A EP78100073A EP0000044B1 EP 0000044 B1 EP0000044 B1 EP 0000044B1 EP 78100073 A EP78100073 A EP 78100073A EP 78100073 A EP78100073 A EP 78100073A EP 0000044 B1 EP0000044 B1 EP 0000044B1
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preparation
carbon atoms
formula
radical
flame
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EP0000044A1 (en
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Hans-Jerg Dr. Kleiner
Fritz Dr. Linke
Walter Dr. Dürsch
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Hoechst 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
    • D06M13/322—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 nitrogen
    • D06M13/44—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 nitrogen containing nitrogen and phosphorus
    • D06M13/453—Phosphates or phosphites containing nitrogen atoms
    • 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
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C07F9/32—Esters thereof
    • C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/3211—Esters of acyclic saturated acids which can have further substituents on alkyl

Definitions

  • FR-A 2 202 100 already discloses phosphinic acid derivatives as flame retardants which contain a carbamoyloxyalkyl ester group.
  • such compounds with a carbamoyloxyalkyl ester group are very sensitive to hydrolysis.
  • DE-A 19 46 574 describes carbamoylalkyl phosphinic acid alkyl esters.
  • these compounds show inadequate durability and only a moderate flame retardant effect in the flame-retardant finishing of pile carpets.
  • the compounds according to the invention can be obtained in good yields from phosphonites of the formula II where Z, R 1 , n have the meanings given above, by reacting the phosphonites of the formula II in the presence of radical formers with olefinically unsaturated carbamates of the formula 111 in which R 3 is an optionally branched alkenyl radical having 2 to 7 carbon atoms and is identical to the radical R Z poorer by one H atom.
  • the carbamates of formula III are known compounds. Examples include: allyl carbamate, methyllylcarbamate, 2-methylbutene- (1) -ylcarbamate, butene- (1) -yl-carbamate, n-hexene- (1) -ylcarbamate. Allyl carbamate is particularly preferred.
  • Any radical generator can be used as a radical generator.
  • the usual organic peroxides are particularly preferred.
  • Di-tert-butyl peroxide is particularly preferred.
  • the free radical generator is used in an amount of 0.5 to 5% by weight, preferably 1 to 2% by weight, based on the amount by weight of the carbamate used.
  • solvents include e.g. in question: alcohols such as B. butanol, hexanol, ether, aromatic hydrocarbons such as e.g. Xylene. In general, no solvent is used.
  • the process can advantageously be carried out under an inert gas atmosphere.
  • the inert gases are e.g. in question argon or nitrogen.
  • the reaction takes place in the temperature range 100 ° -220 ° C.
  • the reaction is particularly preferably carried out at 130 ° -180 ° C.
  • the reaction is expediently carried out in such a way that the phosphonites of the formula II are heated to the desired reaction temperature and then the carbamates of the formula III, mixed with the radical generator, are metered in.
  • the reaction is complete after 2 to 6 hours.
  • the turnover is roughly quantitative.
  • the starting materials can also be reacted by other generally known methods, but the methodology described is preferred.
  • the method can in particular also be carried out continuously.
  • the solvent is distilled off under reduced pressure. If no solvents are used, volatile components can also be distilled off by distillation under reduced pressure. The process products remaining as distillation residues are sufficiently pure for use in technology. The reaction products can often be used directly without special cleaning measures.
  • the substances of the formula can be used very successfully as flame retardants. or used to produce flame retardants.
  • the compounds with formaldehyde can be converted into the corresponding N-methylol compounds, which are then applied to textile material and crosslinked there by methods which are customary in the case of methylol compounds or, as in the case of cotton, react directly with the fiber.
  • Example 6a 184 g of the transesterification product of Example 6a) are heated to 150 ° C. with stirring and under a nitrogen atmosphere. A mixture of 188 g of allyl carbamate and 2 g of di-tert-butyl peroxide is then added dropwise over a period of 2 hours. The mixture is then stirred at 150 ° C for 1 hour. Then it is distilled to an internal temperature of 150 ° C at 1 Torr. About 5 g distill off. About 265 g of a 3-carbamoyloxypropylmethylphosphinic acid ester are obtained, solidification point about 45 ° C. This corresponds to a yield of over 95% of theory. Th.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Description

Gegenstand der Erfindung sind Carbamoyloxyalkylphosphinsäurederivate oder ihre Gemische der Formel 1

Figure imgb0001
in der Zn einen n-wertigen paraffinischen gesättigten Kohlenwasserstoffrest mit 1 bis 6 Kohlenstoffatomen, R1 eine gegebenenfalls verzweigte Alkylgruppe mit 1 bis 6 Kohlenstoffatomen, die durch ein Halogenatom, vorzugsweise Cl, substituiert sein kann, oder einen Phenylrest, R2 eine gegebenenfalls verzweigte Alkylengruppe mit 2 bis 7 Kohlenstoffatomen bedeutet, n = 1 bis 4 ist.The invention relates to carbamoyloxyalkylphosphinic acid derivatives or their mixtures of the formula 1
Figure imgb0001
 in which Z n is an n-valent paraffinic saturated hydrocarbon radical with 1 to 6 carbon atoms, R 1 is an optionally branched alkyl group with 1 to 6 carbon atoms, which can be substituted by a halogen atom, preferably Cl, or a phenyl radical, R 2 is an optionally branched one Alkylene group having 2 to 7 carbon atoms means n = 1 to 4.

Aus der FR-A 2 202 100 sind bereits Phosphinsäurederivate als Flammhemmittel bekannt, die eine Carbamoyloxyalkylester-Gruppe enthalten. Derartige Verbindungen mit einer Carbamoyloxyalkylester-Gruppe sind aber sehr hydroiyseempfindlich. Die DE-A 19 46 574 beschreibt Carbamoylalkyl-phosphinsäurealkylester. Diese Verbindungen zeigen jedoch im Unterschied zu den nachfolgend beschriebenen Verbindungen bei der flammhemmenden Ausrüstung von Florteppichen eine ungenügende Permanenz und nur einen mäßigen Flammhemmeffekt.FR-A 2 202 100 already discloses phosphinic acid derivatives as flame retardants which contain a carbamoyloxyalkyl ester group. However, such compounds with a carbamoyloxyalkyl ester group are very sensitive to hydrolysis. DE-A 19 46 574 describes carbamoylalkyl phosphinic acid alkyl esters. However, in contrast to the compounds described below, these compounds show inadequate durability and only a moderate flame retardant effect in the flame-retardant finishing of pile carpets.

Die erfindungsgemässen Verbindungen lassen sich in guten Ausbeuten aus Phosphoniten der Formel II

Figure imgb0002
worin Z, Rl, n die oben angegebenen Bedeutungen haben, dadurch herstellen, dass die Phosphonite der Formel II in Gegenwart von Radikalbildnern umgesetzt werden mit olefinisch ungesättigten Carbamaten der Formel 111
Figure imgb0003
worin R3 einen gegebenenfalls verzweigten Alkenylrest mit 2 bis 7 Kohlenstoffatomen bedeutet und identisch ist mit dem um ein H-Atom ärmeren Rest RZ.The compounds according to the invention can be obtained in good yields from phosphonites of the formula II
Figure imgb0002
 where Z, R 1 , n have the meanings given above, by reacting the phosphonites of the formula II in the presence of radical formers with olefinically unsaturated carbamates of the formula 111
Figure imgb0003
 in which R 3 is an optionally branched alkenyl radical having 2 to 7 carbon atoms and is identical to the radical R Z poorer by one H atom.

Die Phosphonite der Formel II sind im Falle n = 1 bekannte Verbindungen. So können z.B. eingesetzt werden: Methanphosphonigsäuremonomethylester, Methanphosphonigsäuremonoäthylester, Methanphosphonigsäuremonoisopropylester, Methanphosphonigsäuremonoisobutylester, Äthanphosphonigsäuremonobutylester, Chlormethylphosphonigsäureisobutylester, Phenylphosphonigsäureisobutylester.The phosphonites of the formula II are known compounds when n = 1. For example, are used: methyl methanephosphonate, monoethyl methanephosphonate, monoisopropyl methanephosphonate, monoisobutyl methanephosphonate, monobutyl ethanephosphonate, isobutylchloromethylphosphonate, isobutyl phenylphosphonate.

Die Carbamate der Formel III sind bekannte Verbindungen. Beispielsweise kommen in Frage: Allylcarbamat, Methyllylcarbamat, 2-Methylbuten-(1)-ylcarbamat, Buten-(1)-yl-carbamat, n-Hexen-(1)-ylcarbamat. Besonders bevorzugt ist Allylcarbamat.The carbamates of formula III are known compounds. Examples include: allyl carbamate, methyllylcarbamate, 2-methylbutene- (1) -ylcarbamate, butene- (1) -yl-carbamate, n-hexene- (1) -ylcarbamate. Allyl carbamate is particularly preferred.

Als Radikalbildner kommen beliebige Radikalbildner in Frage. Besonders bevorzugt kommen die üblichen organischen Peroxide in Frage. Im einzelnen seien z.B. genannt: Di-tert.-butyl-peroxid, tert.-Butylperoxybenzoat, 2,5-Dimethyl-bis-2,5-(peroxybenzoat), tert.-Butylhydroperoxid, Dicumylperoxid, Benzoylperoxid. Besonders bevorzugt ist Di-tert.-butylperoxid. Der Radikalbildner wird zwechmässig in einer Menge von 0,5 bis 5 Gew.-%, vorzugsweise 1 bis 2 Gew.-%, bezogen auf die Gewichtsmenge des eingesetzten Carbamats, eingesetzt.Any radical generator can be used as a radical generator. The usual organic peroxides are particularly preferred. In particular, for example called: di-tert-butyl peroxide, tert-butyl peroxybenzoate, 2,5-dimethyl-bis-2,5- (peroxybenzoate), tert-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide. Di-tert-butyl peroxide is particularly preferred. The free radical generator is used in an amount of 0.5 to 5% by weight, preferably 1 to 2% by weight, based on the amount by weight of the carbamate used.

Der Zusatz von inerten Lösungsmitteln kann zweckmässig sein. Als derartige Lösungsmittel kommen z.B. in Frage: Alkohole wie z. B. Butanol, Hexanol, Äther, aromatische Kohlenwasserstoffe wie z.B. Xylol. Im allgemeinen wird ohne Lösungsmittel gearbeitet.The addition of inert solvents can be expedient. Such solvents include e.g. in question: alcohols such as B. butanol, hexanol, ether, aromatic hydrocarbons such as e.g. Xylene. In general, no solvent is used.

Das Verfahren kann vorteilhaft unter Inertgasatmosphäre durchgeführt werden. Als Inertgase kommen z.B. in Frage Argon oder Stickstoff.The process can advantageously be carried out under an inert gas atmosphere. The inert gases are e.g. in question argon or nitrogen.

Die Umsetzung erfolgt im Temperaturbereich 100°-220°C. Besonders bevorzugt wird die Umsetzung bei 130°-180°C durchgeführt.The reaction takes place in the temperature range 100 ° -220 ° C. The reaction is particularly preferably carried out at 130 ° -180 ° C.

Die Umsetzung wird zweckmässig derart durchgeführt, dass die Phosphonite der Formel II auf die gewünschte Reaktionstemperatur erhitzt werden und dann die Carbamate der Formel III, vermischt mit dem Radikalbildner, zudosiert werden. Die Umsetzung ist nach 2 bis 6 Stunden beendet. Der Umsatz ist etwa quantitativ. Die Ausgangsstoffe können auch nach anderen allgemein bekannten Methoden zur Umsetzung gebracht werden, jedoch ist die beschriebene Verfahrensmethodik bevorzugt. Das Verfahren kann insbesondere auch kontinuierlich durchgeführt werden.The reaction is expediently carried out in such a way that the phosphonites of the formula II are heated to the desired reaction temperature and then the carbamates of the formula III, mixed with the radical generator, are metered in. The reaction is complete after 2 to 6 hours. The turnover is roughly quantitative. The starting materials can also be reacted by other generally known methods, but the methodology described is preferred. The method can in particular also be carried out continuously.

Nach beendeter Umsetzung wird (im Falle eines Einsatzes) das Lösungsmittel unter vermindertem Druck abdestilliert. Werden keine Lösungsmittel verwendet, so können ebenfalls durch Andestillieren unter vermindertem Druck leichtflüchtige Anteile abdestilliert werden. Die als Destillationsrückstand verbleibenden Verfahrensprodukte sind für den Einsatz in der Technik genügend rein. Häufig können die Umsetzungsprodukte ohne besondere Reinigungsmassnahmen direkt eingesetzt werden.After the reaction has ended (in the case of use), the solvent is distilled off under reduced pressure. If no solvents are used, volatile components can also be distilled off by distillation under reduced pressure. The process products remaining as distillation residues are sufficiently pure for use in technology. The reaction products can often be used directly without special cleaning measures.

Die Stoffe der Formel können mit sehr gutem Erfolg als Mittel zur Flammhemmung . bzw. zur Herstellung von flammhemmenden Mitteln verwendet werden.The substances of the formula can be used very successfully as flame retardants. or used to produce flame retardants.

So lassen sich die Verbindungen mit Formaldehyd in die entsprechenden N-Methylolverbindungen überführen, die dann nach Verfahren, wie sie bei Methylolverbindungen üblich sind, auf Textilmaterial appliziert und dort vernetzt werden oder, wie bei Baumwolle, direkt mit der Faser reagieren.In this way, the compounds with formaldehyde can be converted into the corresponding N-methylol compounds, which are then applied to textile material and crosslinked there by methods which are customary in the case of methylol compounds or, as in the case of cotton, react directly with the fiber.

Beispiel 1example 1

108 g Methanphosphonigsäuremonoäthylester werden unter Rühren und unter Stickstoffatmosphäre auf 150°C erhitzt. Nun wird während 2,5 Stunden ein Gemisch von 101 g Allyl-carbamat und 1 g Di-tert.-butylperoxid eingetropft. Es wird 1 Stunde bei dieser Temperatur nachgerührt. Anschliessend wird gekühlt und bei 0,2 Torr bis zu einer Innentemperatur von 140°C andestilliert. Es destillieren 9 g ab. Als Rückstand verbleiben ca. 205 g 3-Carbamoyloxypropylmethylphosphinsäureäthylester, nD 21: 1,4765. Das entspricht einer Ausbeute von ca. 95% d. Th.108 g of methyl methanephosphonate are heated to 150 ° C. with stirring and under a nitrogen atmosphere. A mixture of 101 g of allyl carbamate and 1 g of di-tert-butyl peroxide is then added dropwise over a period of 2.5 hours. The mixture is stirred at this temperature for 1 hour. It is then cooled and distilled at 0.2 torr to an internal temperature of 140 ° C. 9 g distill off. The residue remaining about 205 grams of 3-Carbamoyloxypropylmethylphosphinsäureäthylester, n D 21: 1.4765. This corresponds to a yield of approx. 95% of theory. Th.

Figure imgb0004
Figure imgb0004

Beispiel 2Example 2

136 g Methanphosphonigsäuremono-n-butylester werden unter Rühren und in einer Inertgasatmosphäre auf 150°C erhitzt. Nun wird während 2 Stunden ein Gemisch von 101 g Allylcarbamat und 1 g Di-tert.-butylperoxid eingetropft. Dann wird 1 Stunde bei dieser Temperatur nachgerührt. Anschliessend wird gekühlt. Bis zu einer Innentemperatur von 120°C wird bei 0,5 Torr der Versuch einer Andestillation unternommen. Es wird kein Destillat erhalten. Es verbleiben 237 g 3-Carbamoyloxypropylmethylphosphinsäure-n-butylester, Fp. 56°-57°C. Das Produkt kann bei 0,6 Torr und 220°C im Dünnschichtverdampfer destilliert werden.136 g of mono-n-butyl methanephosphonate are heated to 150 ° C. with stirring and in an inert gas atmosphere. A mixture of 101 g of allyl carbamate and 1 g of di-tert-butyl peroxide is then added dropwise over a period of 2 hours. The mixture is then stirred at this temperature for 1 hour. It is then cooled. Up to an internal temperature of 120 ° C, an attempt at distillation is made at 0.5 Torr. No distillate is obtained. 237 g of n-butyl 3-carbamoyloxypropylmethylphosphinate remain, mp. 56 ° -57 ° C. The product can be distilled at 0.6 Torr and 220 ° C in a thin film evaporator.

Figure imgb0005
Figure imgb0005

Beispiel 3Example 3

100 g Methanphosphonigsäuremono-n-butylester werden unter Rühren und unter einer Stickstoffatmosphäre auf 140°C erhitzt. Nun wird während 2 Stunden ein Gemisch von 85 g Methallylcarbamat und 3,7 g tert.-Butylperbenzoat eingetropft. Dann wird 1 Stunde bei 135°C nachgerührt. Anschliessend wird bei 0,8 Torr bis zu einer Innentemperatur von 140°C andestilliert. Es destillieren ca. 5 g ab. Es ver- . bleiben 180 g (3-Carbamoyloxy-2-methyl-propyl)-methylphosphinsäure-n-butylester, n, 23: 1,4725. Das entspricht einer Ausbeute von ca. 95% d. Th.

Figure imgb0006
100 g of mono-n-butyl methanephosphonate are heated to 140 ° C. with stirring and under a nitrogen atmosphere. A mixture of 85 g of methallyl carbamate and 3.7 g of tert-butyl perbenzoate is then added dropwise over a period of 2 hours. The mixture is then stirred at 135 ° C for 1 hour. The mixture is then distilled at 0.8 torr up to an internal temperature of 140 ° C. About 5 g distill off. It ver. 180 g of (3-carbamoyloxy-2-methylpropyl) methylphosphinic acid n-butyl ester remain, n, 23 : 1.4725. This corresponds to a yield of approx. 95% of theory. Th.
Figure imgb0006

Beispiel 4Example 4

70 g Methanphosphonigsäuremonoisobutylester werden unter Rühren und unter einer Inertgasatmosphäre auf 150°C erhitzt. Nun wird während 2 Stunden ein Gemisch von 66,5 g 2-Methylbuten-(1)-yl-4-carbamat und 1,2 g Di-tert.-butylperoxid eingetropft. Es wird 1 Stunde bei 150°C nachgerührt. Anschliessend wird gekühlt. Dann wird bis zu einer Innentemperatur von 150°C bei 0,5 Torr andestilliert. Es destillieren 1 g ab. Es verbleiben 136 g (4-Carbamoyloxy-2-methylbutyl)-methyl- phosphinsäureisobutylester, no23: 1,4720. Das entspricht einer Ausbeute von mehr als 95% d. Th.70 g of monoisobutyl methanephosphonate are heated to 150 ° C. with stirring and under an inert gas atmosphere. A mixture of 66.5 g of 2-methylbutene- (1) -yl-4-carbamate and 1.2 g of di-tert-butyl peroxide is then added dropwise over 2 hours. The mixture is stirred at 150 ° C for 1 hour. It is then cooled. The mixture is then distilled to an internal temperature of 150 ° C. at 0.5 torr. 1 g distill off. 136 g (4-carbamoyloxy-2-methylbutyl) methylphosphinic acid isobutyl ester, no 2 3 : 1.4720, remain. This corresponds to a yield of more than 95% of theory. Th.

Figure imgb0007
Figure imgb0007

Beispiel 5Example 5 a) Umesterungsprodukt von Methanphosphonigsäuremonoisobutylester mit Hexandiol-1,6 im Molverhältnis 2:1a) Transesterification product of monoisobutyl methanephosphonate with 1,6-hexanediol in a molar ratio of 2: 1

408 g Methanphosphonigsäuremonoisobutylester, 177 g Hexandiol-1,6 und 6 g Soda werden im Wasserstrahlvakuum bei 100 bis 20 Torr 3 Stunden auf 100°-120°C erhitzt. Dabei destillieren über eine Kolonne 220 g Isobutanol ab. Der Rückstand wird abgesaugt. Man erhält 360 g einer farblosen Flüssigleit, nD 20: 1,4649. Die Ausbeute beträgt mehr als 95% d. Th.408 g of monoisobutyl methanephosphonate, 177 g of 1,6-hexanediol and 6 g of soda are heated to 100 ° -120 ° C. in a water jet vacuum at 100 to 20 torr for 3 hours. 220 g of isobutanol distill off from a column. The residue is suctioned off. 360 g of a colorless liquid line, n D 20 : 1.4649, are obtained. The yield is more than 95% of theory. Th.

Figure imgb0008
Figure imgb0008

b) Anlagerungsprodukt von Allylcarbamat an das Produkt von Beispiel 5a)b) adduct of allyl carbamate with the product of Example 5a)

360 g Umesterungsproduktes des Beispiels 5a) werden unter Rühren und unter einer Stickstoffatmosphäre auf 150°C erhitzt. Nun wird während 3;5 Stunden ein Gemisch von 283 g Allylcarbamat und 5 g Di-tert.-butylperoxid eingetropft. Anschliessend wird 1 Stunde bei 150°C nachgerührt. Dann wird gekühlt und bis zu einer Innentemperatur von 140°C bei 1 Torr andestilliert. Es destillieren ca. 5 g ab. Man erhält ca. 630 g eines 3-Carbamoyloxypropylmethylphosphinsäureesters, nD 21: 1,4930. Das entspricht einer Ausbeute von mehr als 95% d. Th.360 g of the transesterification product of Example 5a) are heated to 150 ° C. with stirring and under a nitrogen atmosphere. A mixture of 283 g of allyl carbamate and 5 g of di-tert-butyl peroxide is then added dropwise over the course of 3 and 5 hours. The mixture is then stirred at 150 ° C for 1 hour. It is then cooled and distilled to an internal temperature of 140 ° C. at 1 torr. About 5 g distill off. Man receives about 630 g of a 3-carbamoyloxypropylmethylphosphinic acid ester, n D 21 : 1.4930. This corresponds to a yield of more than 95% of theory. Th.

Figure imgb0009
Figure imgb0009

Beispiel 6Example 6 a) Umesterungsprodukt von Methanphosphonigsäuremonoisobutylester mit Pantaerythrit im Molverhältnis 4:1a) Transesterification product of methanephosphonous monoisobutyl ester with pantaerythritol in a molar ratio of 4: 1

272 g Methanphosphonigsäuremonoisobutylester, 68 g Pentaerythrit und 3 g Soda werden im Wasserstrahlvakuum bei 80 bis 30 Torr 5 Stunden auf 80° bis 130°C erhitzt. Über eine Kolonne destillieren dabei 146 g Isobutanol ab. Der Rückstand wird abgesaugt. Es resultieren 190 g einesfarblosen Öls, nD 20: 1,4926. Die Ausbeute beträgt ca. 95% d. Th.

Figure imgb0010
272 g of monoisobutyl methanephosphonate, 68 g of pentaerythritol and 3 g of soda are heated in a water jet vacuum at 80 to 30 torr at 80 ° to 130 ° C. for 5 hours. 146 g of isobutanol are distilled off over a column. The residue is suctioned off. The result is 190 g of a colorless oil, n D 20 : 1.4926. The yield is about 95% of theory. Th.
Figure imgb0010

b) Anlagerungsprodukt von Allylcarbamat an das Produkt von Beispiel 6a)b) adduct of allyl carbamate with the product of Example 6a)

184 g des Umesterungsproduktes des Beispiels 6a) werden unter Rühren und einer Stickstoffatmosphäre auf 150°C erhitzt. Nun wird während 2 Stunden ein Gemisch von 188 g Allylcarbamat und 2 g Di-tert.-butylperoxid eingetropft. Anschliessend wird 1 Stunde bei 150°C nachgerührt. Dann wird andestilliert bis zu einer Innentemperatur von 150°C bei 1 Torr. Es destillieren ca. 5 g ab. Man erhält ca. 265 g eines 3-Carbamoyloxypropylmethylphosphinsäureesters, Erstarrungspunkt ca. 45°C. Das entspricht einer Ausbeute von über 95% d. Th.

Figure imgb0011
184 g of the transesterification product of Example 6a) are heated to 150 ° C. with stirring and under a nitrogen atmosphere. A mixture of 188 g of allyl carbamate and 2 g of di-tert-butyl peroxide is then added dropwise over a period of 2 hours. The mixture is then stirred at 150 ° C for 1 hour. Then it is distilled to an internal temperature of 150 ° C at 1 Torr. About 5 g distill off. About 265 g of a 3-carbamoyloxypropylmethylphosphinic acid ester are obtained, solidification point about 45 ° C. This corresponds to a yield of over 95% of theory. Th.
Figure imgb0011

Beispiel 7Example 7

122 g Methanphosphonigsäuremonoisopropylester werden unter Rühren und unter Stickstoffatmosphäre auf 150°-160°C erhitzt. Nun wird während 1,25 Stunden ein Gemisch von 101 g Allylcarbamat und 1,5 g Di-tert.-butylperoxid eingetropft. 30 Minuten wird bei dieser Temperatur nachgerührt. Anschliessend wird gekühlt und bei 0,3 Torr bis zu einer Innentemperatur von 140°C andestilliert. Es destillieren 4,5 g ab. Als Rückstand verbleiben ca. 215 g 3-Carbamoyloxypropylmethylphosphinsäureisopropylester, nD 20: 1,4728. Das entspricht einer Ausbeute von mehr als 95% d. Th.

Figure imgb0012
122 g of monoisopropyl methanephosphonate are heated to 150 ° -160 ° C. with stirring and under a nitrogen atmosphere. A mixture of 101 g of allyl carbamate and 1.5 g of di-tert-butyl peroxide is then added dropwise over a period of 1.25 hours. The mixture is stirred at this temperature for 30 minutes. It is then cooled and distilled at 0.3 torr up to an internal temperature of 140 ° C. Distill off 4.5 g. The residue remaining approximately 215 g of 3-Carbamoyloxypropylmethylphosphinsäureisopropylester, n D 20: 1.4728. This corresponds to a yield of more than 95% of theory. Th.
Figure imgb0012

Claims (5)

1. Compounds of the formula
Figure imgb0018
in which
Zn is an n-valent, saturated hydrocarbon radical having from 1 to 6 carbon atoms,
R1 is an optionally branched alkyl group having from 1 to 6 carbon atoms, which alkyl group may be substituted by a halogen atom, preferably chlorine, or a phenyl radical,
R2 is an optionally branched alkylene group having from 2 to 7 carbon atoms and
n is in the range of from 1 to 4; and the mixtures thereof.
2. A compound of the formula I
Figure imgb0019
in which
R, is methyl or ethyl
R2 is ethylene or
Figure imgb0020
Zn is an n-valent aliphatic, saturated hydrocarbon radical having from 1 to 6 carbon atoms and n is in the range of from 1 to 4.
3. Process for preparing a compound as claimed in claim 1, wherein a phosphonite of the formula II
Figure imgb0021
in which Z, R1 and n have the meaning as defined in claim 1 is reacted, in the presence of radical-forming agents, with an olefinically unsaturated carbamate of the formula III
Figure imgb0022
in which R3 is an optionally branched alkylene radical having from 2 to 7 carbon atoms.
4. The process as claimed in claim 3, wherein the reaction is carried out in an inert gas.
5. Method of using a compound as claimed in claim 1 for the preparation of a flame-retardant finish.
EP78100073A 1977-06-10 1978-06-01 Carbamoyloxyalkyl phosphinic acid derivatives, process for their preparation and their use in the preparation of flame-retardant finished materials Expired EP0000044B1 (en)

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CH719277 1977-06-10
CH7192/77 1977-06-10

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EP0000044A1 EP0000044A1 (en) 1978-12-20
EP0000044B1 true EP0000044B1 (en) 1980-07-23

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2957931A (en) * 1949-07-28 1960-10-25 Socony Mobil Oil Co Inc Synthesis of compounds having a carbonphosphorus linkage
NL7008521A (en) * 1969-06-14 1970-12-16
DE2024280A1 (en) * 1970-05-19 1971-12-09 Badische Anilin- & Soda-Fabrik Ag, 6700 Ludwigshafen Anti-flame agent for textile material - com prising dialkoxyphos - phonoalkyl-carbamates
US3758554A (en) * 1971-06-18 1973-09-11 Stevens & Co Inc J P Phosphorus-containing carbamates
CH567145A (en) * 1972-10-07 1975-09-30

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US4173601A (en) 1979-11-06
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IT1098316B (en) 1985-09-07
IT7824358A0 (en) 1978-06-08

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