US3679779A - Phosphonic acid dialkyl esters - Google Patents

Phosphonic acid dialkyl esters Download PDF

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Publication number
US3679779A
US3679779A US5148A US3679779DA US3679779A US 3679779 A US3679779 A US 3679779A US 5148 A US5148 A US 5148A US 3679779D A US3679779D A US 3679779DA US 3679779 A US3679779 A US 3679779A
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US
United States
Prior art keywords
formula
phosphonic acid
acid dialkyl
dialkyl esters
denotes
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Expired - Lifetime
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US5148A
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English (en)
Inventor
Helmut Huber-Emden
Karl Eschle
Arthur Maeder
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Novartis AG
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Ciba Geigy AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C08K5/5333—Esters of phosphonic acids
    • C08K5/5353—Esters of phosphonic acids containing also nitrogen
    • 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

Definitions

  • the subject of the invention is phosphonic acid dialkyl esters of the formula in which R denotes an alkyl radical with one to 18 carbon atoms and n denotes 1 or 2.
  • These phosphonic acid dialkyl esters are used as antioxidants for plastics, especially for polypropylene, polyethylene and polyurethane, and rubber.
  • the combined use of the phosphonic acid dialkyl esters with flameproofing agents may increase the flameproofing action of the flameproofing agent.
  • the use of the compounds according to the invention in combination with other antioxidants also may show advantageous effects.
  • Preferred phosphonic acid dialkyl esters correspond to the Specification 1,571,696- formulas
  • CHFNHfC 1 which is first formed in situ by the addition of metallic sodium.
  • the starting product of formula 13) required for this reac- CwHm tion can be obtained from 2,6-di-tertiary-butylphenol and N- methylol-acrylamide by Tschemiak condensation in glacial acetic acid in the presence of pyrophosphoric acid, as has already been described in French Pat. Specification 1,475,097. 0
  • n denotes 1 or 2, are above all of interest. 50
  • the phosphonic acid dialkyl esters of formula (1) are thus The compounds of formula (13) is obtained in good yields for example dimethyl, diethyl, dibutyl, didodecyl or diocfrom the addition product of formula (15) by splitting ofi l-lCl tadecyl esters. Depending on whether n is 1 or 2, different by means of sodium hydrogen carbonate. starting products are used for the manufacture of these dialkyl
  • the compounds of formulas (2), (3), (4) and (5) with n 2 esters are used for the manufacture of these dialkyl.
  • the phosphonic acid dialkyl esters of formulas (l) to (6) are used as antioxidants for plastics.
  • Possible plastics are polyethylene, polyurethane and above all polypropylene; further, also polyvinyl chloride and rubber.
  • the appropriate procedure is to incorporate into these plastics a small amount, preferably 0.01 to 2 percent relative to the amount of plastic to be protected, of at least one compound offormulas(1)to (6).
  • the compounds of fonnula (1') can for example be worked into the plastics to be protected directly, that is to say by themselves .or together with other additives such as plasticizers, pigments, light protection agents, fluorescent whitening'agents, flameproofing agents or other antioxidants,
  • R denotes a hydrogen atom, an alkyl or aryl residue which is optionally substituted further, or a residue of formula wherein R has the indicated significance and m denotes an integer having a value of at most 2, and n denotes ,an integer h'avinga value of at most 7.
  • Carboxylic acid amides of formula 20), wherein the residue R carries several thioether residues, are preferred.
  • thioethers of formulas 51.5 g of 2,6-di-tertiary-butylphenol and 26.5 g of N- methylolacrylamide are successively dissolved in 50 ml of glacial acetic acid with gentle warming. Thereafter HCl gas is introduced whilststirring, and with exclusion of moisture, until i saturation is reached. The reaction is exothermic; the temperature is kept at 30 C by external cooling.
  • the acrylarnide of formula (13) can also be obtained in almost quantitative yield from the 1:1 addition products by vigorously stirring the latter with excess 2N sodium carbonate solution for several hours and washing the product, after filtering off the sodium carbonate solution, until a neutral reaction is obtained; melting point: 110 to 15 C.
  • the substance is not entirely free of bonded chlorine.
  • chloracetamide are dissolved in 50 ml of dry xylene by warming. 7.22 g of phosphorus acid trimethyl ester are added and the mixture is heated to gentle boiling under reflux. The reaction is complete when the reaction solution contains no further bonded chlorine, which can easily be followed byoccasional sampling and testing by means of the Beilstein reaction. Gentle boiling under reflux for 40 to 45 hours sufl'ices.
  • a larger sample is chromatographically purified on silica gel using an ascending eluent series of benzenechloroforrn, and is then again recrystallized from cyclohexane; melting point: 91 to 92 C.
  • Purification can also be effected by chromatography on silica gel with an ascending eluent series of benzenechloroform-ethyl acetate.
  • EXAMPLE 6 27.6 g of phosphorous acid diethyl ester are dissolved in 150 ml of absolute dioxan. 0.5 g of sodium are added and the mixture is stirred for 15 hours under nitrogen. In the course thereof, the sodium dissolves and a small amount of a flocculent precipitate is produced.
  • EXAMPLE 7 7.76 g of phosphorous acid dibutyl ester are dissolved in 30 ml of absolute dioxan. 0.1 g of sodium are added and the mixture is stirred under nitrogen for 15 hours; in the course thereof, the sodium dissolves and a small amount of a flocculant precipitate is produced. 11.57 g of N-(3,5-di-tertiarybutyl-4hydroxyphenylmethyl)-acrylamide are now added and dissolve rapidly. Thereupon the reaction mixture, contained in a closed vessel, is stirred for 3 days, and is thereafter heated for a further 2 hours to the boil under reflux, in nitrogen.
  • EXAMPLE 8 17.6 g of phosphorous acid dioctadecyl ester are dissolved in ml of absolute l,2-dimethoxyethane whilst warming. 70 mg of sodium are added and the mixture is heated for 18 hours under reflux in nitrogen, while stirring. In the course thereof, the sodium dissolves and a small amount of a flocculant precipitate forms. 8.67 g of N-( 3,S-di-tertiary-butyl-4-hydroxyphenylmethyl)-acrylamide are added thereto; this dissolves rapidly and the mixture is heated for 24 hours under reflux in nitrogen.
  • 1t is also possible to dissolve the crude product in chloroform and then to purify it by chromatography on silica gel.
  • the substance is obtained as a chloroform adduct; melting point 35 to 36 C, the product resolidifies on further heating and finally melts at 72 to 74 C.
  • the chloroform can be eliminated from this adduct by heating in a high vacuum (at 160 C/ 10 minutes/0.001 mm Hg.).
  • EXAMPLE 9 A mixture of 20 percent of the thioether of formula (22) or (23) and 80 percent of the phosphonic acid dialkyl ester of formula (27) is heated with stirring, under a nitrogen atmosphere, for; 1 minute to 130? or 165 C respectively, whereupon cloudy to clear melts are produced. The mixture is then quenched'by cooling with cold water.
  • the sheets aged in this way are comminuted into small chips.
  • the melt index is detennined according to ASTM D-l238-62 T, method E (weight 2.16 kg, temperature 190 C, time 10 minutes). The increase in the melt index and the antioxidant action of the abovementioned compounds can thus be recognized.
  • Table V The results are summarized in table V.
  • a phosphonic acid dialkyl ester of the formula 7 The compound according to claim 1 of the formula 8.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)
US5148A 1969-01-30 1970-01-22 Phosphonic acid dialkyl esters Expired - Lifetime US3679779A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH146069A CH506566A (de) 1969-01-30 1969-01-30 Verfahren zur Herstellung von Phosphonsäuredialkylestern

Publications (1)

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US3679779A true US3679779A (en) 1972-07-25

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Country Status (12)

Country Link
US (1) US3679779A (de)
JP (2) JPS4819308B1 (de)
AT (2) AT303068B (de)
BE (1) BE745119A (de)
BR (1) BR7016481D0 (de)
CH (2) CH511899A (de)
DE (1) DE2002729A1 (de)
FR (1) FR2029669A1 (de)
GB (1) GB1265121A (de)
IL (1) IL33729A (de)
NL (1) NL7001286A (de)
SE (1) SE360083B (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4104287A (en) * 1973-02-24 1978-08-01 Basf Aktiengesellschaft 4-M,M'-Di-t-butyl-p-hydroxyphenyl) butyl-2 compounds
US4192796A (en) * 1979-03-26 1980-03-11 American Cyanamid Company Polymers stabilized with organo-phosphorus compounds

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4148747A (en) * 1973-10-11 1979-04-10 Raychem Corporation Antioxidant comprising a hydroxy aromatic compound containing sulfur and an organic phosphonate
JPS5267715U (de) * 1975-11-15 1977-05-19
JPS536019U (de) * 1976-06-30 1978-01-19
JPS536018U (de) * 1976-06-30 1978-01-19
JPS5314924A (en) * 1976-07-27 1978-02-10 Matsushita Electric Works Ltd Sheet material for roof backing
US4098760A (en) * 1977-01-13 1978-07-04 Uniroyal, Inc. Substituted haloacetamide antioxidants for elastomers and plastic polymers
JPS53106022U (de) * 1977-01-31 1978-08-25

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2875232A (en) * 1956-02-14 1959-02-24 Eastman Kodak Co Phosphonoalkanamides prepared from phosphites and lactams
US2908605A (en) * 1955-11-03 1959-10-13 Ciba Ltd New organic phosphorus compounds and process for their manufacture

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2908605A (en) * 1955-11-03 1959-10-13 Ciba Ltd New organic phosphorus compounds and process for their manufacture
US2875232A (en) * 1956-02-14 1959-02-24 Eastman Kodak Co Phosphonoalkanamides prepared from phosphites and lactams

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4104287A (en) * 1973-02-24 1978-08-01 Basf Aktiengesellschaft 4-M,M'-Di-t-butyl-p-hydroxyphenyl) butyl-2 compounds
US4192796A (en) * 1979-03-26 1980-03-11 American Cyanamid Company Polymers stabilized with organo-phosphorus compounds

Also Published As

Publication number Publication date
GB1265121A (de) 1972-03-01
NL7001286A (de) 1970-08-03
BR7016481D0 (pt) 1973-04-05
CH511899A (de) 1971-08-31
BE745119A (fr) 1970-07-29
FR2029669A1 (de) 1970-10-23
JPS4819308B1 (de) 1973-06-12
AT303068B (de) 1972-11-10
DE2002729A1 (de) 1970-08-13
AT302363B (de) 1972-10-10
SE360083B (de) 1973-09-17
JPS492115B1 (de) 1974-01-18
IL33729A (en) 1973-02-28
CH506566A (de) 1971-04-30
IL33729A0 (en) 1970-03-22

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