US3875264A - Phosphonous acid esters - Google Patents

Phosphonous acid esters Download PDF

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Publication number
US3875264A
US3875264A US308594A US30859472A US3875264A US 3875264 A US3875264 A US 3875264A US 308594 A US308594 A US 308594A US 30859472 A US30859472 A US 30859472A US 3875264 A US3875264 A US 3875264A
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compound
carbon atoms
alkyl
methyl
formula
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US308594A
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Kurt Hofer
Guenther Tscheulin
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Sandoz AG
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Sandoz AG
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    • 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
    • C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
    • C07F9/4808—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof the acid moiety containing a substituent or structure which is considered as characteristic
    • C07F9/4841—Aromatic acids or derivatives (P-C aromatic linkage)
    • 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
    • C08K5/5393—Phosphonous compounds, e.g. R—P(OR')2
    • 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
    • C08K5/5398—Phosphorus bound to sulfur
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/32—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing two or more of boron, silicon, phosphorus, selenium, tellurium or a metal
    • C09K15/322—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing two or more of boron, silicon, phosphorus, selenium, tellurium or a metal containing only phosphorus
    • C09K15/324—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing two or more of boron, silicon, phosphorus, selenium, tellurium or a metal containing only phosphorus containing phosphorus and sulfur

Definitions

  • C07f 9/08, C07f 9/16 1 2 3 and 4 are or [58] Field of Search 260/932 1, 2 Raiand are hy r r on i l r ng A and B may be substituted by alkyl groups, [56] I References Cited and inorganic salts of compounds in which any of UNITED STATES PATENTS RrRi are hydrogen- 3,707,565 12/1972 Hofer 260/962 19 Claims, No Drawings 1 PHOSPIIONOUS ACll) E-STERS IMPROVEMENTS IN OR RELATING TO ORGANIC COMPOUNDS The present invention relates to phosphonous acid derivatives.
  • Y Y Y and Y which may be the same or different, each signifies O or S.
  • R R R and R which may be the same or different, each signifies a hydrocarbon radical of up to carbon atoms consisting of aromatic and/or saturated aliphatic units,
  • rings A and B may be either further unsubstituted or each further substituted by I or 2 alkyl groups of l to 6 carbon atoms, and inorganic salts of compounds in which any of R to to R is hydrogen.
  • X preferably signifies O and n preferably signifies 1.
  • Y Y Y and Y are preferably the same, and R R R and R, are preferably also the same. In the preferred compounds, the
  • Suitable hydrocarbon radicals for R R R R and R include the following: alkyl radicals, preferably other than tertiary alkyl radicals, of up to 20, preferably up to 12, in particular I to 6 carbon atoms, for example n-alkyl radicals such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecycl and dodecyl, secondary alkyl radicals such as isopropyl, 2- butyl, 3-methyl-2-butyl, 2-pentyl, 2,2-dimethyl-3-butyl, 2-hexyl, 3-hexyl, 2-methyl-3-phenyl, 3 methyl-2- pentyl, 4-methyl-2-pentyl, 2,2-dimethyl-3-pentyl, 2,4-dimethyl-3-pentyl, 2-heptyl, 3 heptyl, 4-heptyl
  • l to 6 carbon atoms such as those alkyl radicals mentioned above and also tertiary alkyl radicals, such as tert. butyl, 2-methyl-2-butyl, 2,3-dimethyl-2-butyl, Z-methyl- Z-pentyl, 3-methyl-3-pentyl, 3-ethyl-3-pentyl, 2,4-dimethyl-2-pentyl, 2-methyl'2-hexyl, 3methyl-3- hexyl, 3,4-dimethyl-3-hexyl, 3,5-dimethyl-3-hexyl, 2-methyl-2-heptyl, 3-methyl-3-heptyl, 4-methyl-4- heptyl, 2,3,4-trimethyl-3-pentyl, 2,4,4-trimethyl-2- pentyl, 3-ethyl-3-heptyl, 2-methyl-2-octyl, 4-methyl-4- octyl, 3,6-dimethyl-3-oct
  • butyl-4-methylphenyl 4-tert.butyl-2- methylphenyl, 6-tert.butyl-3-methylphenyl, 2,4-ditert.butylphenyl, 4-(1',l',3,3-tetramethylbutyl)- phenyl, 2-methyl-4-( l ,l ',33-tetramethylbutyl)- phenyl, 4-nonylphenyl (mixture of isomers), and 2,4-di-terLoctyl-phenyl; aralkyl radicals, such as phenyl or diphenyl alkyl radicals, the alkyl radicals of which suitably contain 1 to 12, particularly 1 to 6 carbon atoms, and the aryl radicals of which may optionally be alkyl substituted as above, including benzyl, land Z-phenyl-ethyl, l-phenyl-l-propyl, l-phenyl-Z- propyl,
  • l to 12 in particular 4 to 12 carbon atoms, such as n-butyl or n-dodecyl, and phenyl and diphenyl radicals, optionally substituted by 1 or 2 alkyl radicals of 1 to 4 carbon atoms, preferably tertiary such alkyl radicals, such as 2,4-di-t-butylphenyl, 2-t-butyl-diphenyl, and 2,4'-di-t-butyldiphenyl.
  • the rings A and B may, as indicated, be substituted by l or 2 alkyl groups of up to 6, preferably up to 4 carbon atoms, for example such alkyl groups as mentioned above, but are preferably unsubstituted.
  • the invention also provides a process for the production of compounds of formula I and inorganic salts thereof, characterised by reacting a compound of formula II,
  • R R Y and Y are as defined above, and, where required, converting the resulting product into an inorganic salt.
  • two or more of the compounds III, IV, V and VI may be the same, in which case the molar quantity of the compound is adjusted accordingly.
  • the process of the invention may suitably be carried out in conventional manner, for example as described by K. Sasse, Houben-Weyl (eds.), Methoden der organischen Chemie, fourth impression (1963), Vol. XII/l. pp.3 l 8/ff.
  • the particular conditions employed depend, to an extent, on the particular compounds III, IV, V or VI being employed. For example, in some instances, it may be advisable to apply external cooling to the reaction mixture to restrain the vigorous reaction.
  • any of the compounds III, IV, V and V1 is water
  • the reaction may suitable be carried out at a temperature of from 100 to 150C, in the presence of an acid binding agent such as pyridine or a trialkylamine.
  • VIIa VIIb which are acidic and may be converted into inorganic salts.
  • Suitable salts include alkali metal, e.g. sodium or potassium, al-
  • kaline earth metal e.g. calcium or magnesium, zinc, manganese, aluminium, copper, vanadium, cobalt and nickel salts.
  • the salts may be produced by reaction of the free acid with an inorganic hydroxide or salt, such as calcium hydroxide, zinc oxide, sodium carbonate, potassium bicarbonate, aluminium acetate, borium chloride, nickel acetate and zinc chloride.
  • the reaction of the compounds II with water and production of salts is carried out in a single operation.
  • an excess of water may be provided for hydrolysis of the compound II, and after addition of the appropriate inorganic reagent, the compound II may be slowly added, with stirring, as indicated above.
  • compounds of formula II may be produced by reacting the appropriate diphenylmethane, oxide or sulphide, with a phosphorus trihalide, preferably phosphorus trichloride.
  • a phosphorus trihalide preferably phosphorus trichloride.
  • the process may suitably be effected at an elevated temperature in the gaseous phase, although it is more preferable to react under milder conditions in the presence of a catalyst, e.g. a F riedel-Krafts catalyst, in particular aluminium trichloride. It is preferable to work with phosphorus trichloride at its boiling temperature.
  • any aluminium chloride complex of the compound II may be decomposed, for example with phosphorus oxychloride or pyridine.
  • the resulting compounds of formula Il may be isolated and purified using conventional techniques.
  • the compounds of the invention are useful as stabilisers for organic materials which are sensitive to light, oxygen and heat.
  • they may be incorporated in or applied to form a protective surface film on the organic material.
  • the new compounds by their stabilizing action protect sensitive materials against degradation.
  • plastics materials have a wide area of use in the processing of plastics materials, being suitable, for example, as stabilizers for cellulose acetate, cellulose acetobutyrate, polyethylene, polypropylene, polyvinyl chloride, polyvinyl chloride acetate, polyamides, polystyrene, ethyl cellulose, cellulose nitrate, polyvinyl alcohol, silicon rubber, cellulose propionate, melamine-formaldehyde resins, urea-formaldehyde resins, allyl casting resins, polymethyl methacrylate, polyesters, polyacrylonitrile, and copolymers of these polymers.
  • Thecompounds may also be used for the stabilization of natural products such as rubber, cellulose, wool and silk.
  • the materials for stabilization may suitably be in the form of film or sheet, rods, coatings, panels, tapes, fibres, granules, powders or other processing forms, or as solutions, emulsions or dispersions.
  • the stabilizing compounds may be incorporated in or coated on the materials by conventional methods.
  • An important method of application consists in intimately mixing polymeric material, for example polypropylene granules, with the stabilizer in a kneader or other suitable machine, followed by extrusion. This method ensures homogeneous distribution which is important for good protection.
  • the material can be extruded, for example, as film, tubing or filament, the latter for conversion into textiles.
  • the stabilizer may be incorporated in, for example, the polypropylene prior to textile production.
  • the new stabilizers can also be applied to textile yarns and fabrics from an aqueous medium containing a finely dispersed compound of formula (1). This method is particularly suitable for, e.g. textiles of polyethylene terephthalate and cellulose acetate fibres.
  • Synthetic polymeric materials need not necessarily be in the final form before incorporation of the compounds of the invention.
  • these compounds may be mixed with the monomers or prepolymers prior to the condensation or other polymerization reaction giving the final polymer.
  • the new stabilizers are suitable for application to, for example, clear films and plastics, and are also suitable for stabilizing opaque, semi-opaque and translucent materials having a surface susceptible to degradation by ultra-violet radiation, air or heat.
  • opaque, semi-opaque and translucent materials having a surface susceptible to degradation by ultra-violet radiation, air or heat.
  • the present invention also comprises the sensitive organic materials containing a compound of formula 1 for stabilization.
  • the new compounds can be incorporated in the organic materials at any stage of processing using standard methods.
  • the amounts of stabilizer employed may vary within wide limits, for example from 0.01 to 5% or preferably from 0.05 to 1% in relation to the weight of the material.
  • the stabilized organic materials may contain compounds of formula I alone, or together with further additives, for example ultra-violet absorbers and other stabilizers against degradation by heat and oxygen.
  • suitable stabilizers are those belonging to different chemical classes to the compounds of formula I, for example organic compounds of sulphur, tin and pentavalent phosphorus, sterically hindered phenols, 2- hydroxy-benzophenones and hydroxybenzotriazoles. Often, notably high stabilization may be obtained with such mixtures since they may have a synergistic action.
  • EXAMPLE 2 At 5, a solution of 33.4 parts of the diphenylether dichloro-phosphine of formula l la, above, in 50 parts of toluene is added to 50.7 parts of 2,4-ditert.butylphenol and parts of triethylamine in 200 parts of toluene in the absence of moisture. The solution is allowed to react overnight at the precipitated product filtered, the filtrate evaporated under vacuum, and the residue crystallized from ether/methanol. m.p. 8889..
  • EXAMPLE 4 A solution of parts of 4,4-diphenylether-(bischlorophosphine) in parts of toluene is added, at
  • EXAMPLE 6 A solution of 12.5 parts of 4,4-diphenylether-(bisdichlorophosphine) in 50 parts of toluene is added at and the residue triturated with methanol and crystal- 5 99 parts of butane] and 14 parts of triethylam lized from benzene. m.p. 7780.
  • Y Y Y and Y which may be the same or different, each signifies -O or -S,
  • R R R and R which may be the same or different, each signifies a hydrocarbon radical of up to 20 carbon atoms selected from the group consisting of alkyl; cycloalkyl which may be substituted by up to 3 alkyl groups; cycloalkylalkyl; phenyl which may be substituted by up to 3 alkyl or alkylcycloalkyl groups; diphenyl which may be substituted by up to 3 alkyl or alkylcycloalkyl groups; and phenyl 3.
  • R,, R R and R each signifies an alkyl radical of l to 12 carbon atoms, a cycloalkyl radical of 3 to 12 carbon atoms, which may be substituted by l, 2 or 3 alkyl groups of l to 4 carbon atoms, a cycloalkylalkyl radical in which the cycloalkyl portion contains 5 to 12 carbon atoms and the alkyl portion l to 6 carbon atoms, or a phenyl or diphenyl radical which may be substituted by l, 2 or 3 alkyl radicals of l to 12 carbon atoms.
  • R R R and R each signifies an alkyl radical of l to 6 carbon atoms, a cycloalkyl radical of 5 to 8 carbon atoms, which may be substituted by l, 2 or 3 alkyl groups of l to 4 carbon atoms, a cycloalkylalkyl radical in which the cycloalkyl portion contains 5 to 8 carbon atoms and the alkyl portion contains 1 to 4 carbon atoms, or a phenyl or diphenyl radical which may be substituted by 1, 2 or 3 alkyl radicals of l to 6 carbon atoms.
  • R, R R and R each signifies an alkyl radical of 4 to 12 carbon atoms, or phenyl or diphenyl radical, which may be substituted by l or 2 alkyl radicals of l to 4 carbon atoms.
  • R R R and R each signifies n-butyl, n-dodecyl, 2,4-di-tbutylphenyl, 2-t-butylphenyl, or 2,4-di-t-butyldiphenyl.
  • a compound f l i 12 i hi h R 12,, R and l to 6 carbon atoms. R are the same.
  • X signifies 16' The compound of claim 1 of f ul --O.

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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)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)
US308594A 1971-11-24 1972-11-21 Phosphonous acid esters Expired - Lifetime US3875264A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US455597A US3903208A (en) 1971-11-24 1974-03-28 Phosphonous and thiophosphonous acid esters

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH1712971A CH557389A (de) 1971-11-24 1971-11-24 Verfahren zur herstellung von neuen diphenylmethan-, diphenyloxid- und diphenylsulfid-phosphonig und-thiophosphonigsaeuren, deren ester und thioester.

Related Child Applications (1)

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US05/575,524 Continuation-In-Part US4107138A (en) 1971-11-24 1975-05-08 Phosphonous and thiophosphonous acid ethers as stabilizers for organic materials

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US3875264A true US3875264A (en) 1975-04-01

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US (1) US3875264A (pt)
JP (1) JPS5645919B2 (pt)
AT (1) AT327944B (pt)
BE (1) BE791767A (pt)
BR (1) BR7208256D0 (pt)
CA (1) CA989414A (pt)
CH (1) CH557389A (pt)
DE (1) DE2256783C2 (pt)
ES (1) ES408865A1 (pt)
FR (1) FR2161052B1 (pt)
GB (1) GB1415532A (pt)
IT (1) IT971154B (pt)
NL (1) NL7215623A (pt)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2701638A1 (de) * 1976-01-16 1977-07-21 Raychem Corp Phosphorverbindungen enthaltende isoliermassen
US4219607A (en) * 1978-01-13 1980-08-26 Raychem Corporation High voltage insulating compositions containing phosphorus compounds
US4223071A (en) * 1978-01-13 1980-09-16 Raychem Corporation High voltage insulating compositions containing phosphorus compounds
US4263230A (en) * 1979-10-11 1981-04-21 Stauffer Chemical Company Bisphosphonites
EP0158501A2 (en) * 1984-04-02 1985-10-16 Polyplastics Co. Ltd. Method of preparation of polyester
US4551527A (en) * 1981-07-02 1985-11-05 Borg-Warner Chemicals, Inc. Salts of 5,5-bis-(bromomethyl)-2-hydroxy-2-oxo-1,3,2-dioxaphosphorinane and process for preparing same
US5298541A (en) * 1989-05-20 1994-03-29 Hoechst Aktiengesellschaft Aryl phosphonites, a process for their production and their use for stabilizing plastics
US5342869A (en) * 1991-07-03 1994-08-30 Sandoz Ltd. Stabilized polymeric compositions

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0005447B1 (de) * 1978-04-20 1982-05-05 Ciba-Geigy Ag Orthoalkylierte Phenylphosphonite, Verfahren zu ihrer Herstellung und stabilisierte Massen
CA1276344C (en) * 1980-12-17 1990-11-13 Markus Matzner Processing of heat stabilized polyarylates
JPS5813653A (ja) * 1981-07-17 1983-01-26 Teijin Ltd 樹脂組成物
JPS638453A (ja) * 1986-06-27 1988-01-14 Polyplastics Co 熱可塑性ポリエステル樹脂組成物
JPS63105053A (ja) * 1986-10-20 1988-05-10 Kuraray Co Ltd 耐光性に優れたポリエステル樹脂
GB8901517D0 (en) * 1989-01-24 1989-03-15 Sandoz Ltd Improvements in or relating to organic compounds
JPH02287165A (ja) * 1989-04-27 1990-11-27 Nec Kansai Ltd 半導体集積回路装置の電気的特性測定方法
KR100563947B1 (ko) * 1998-09-01 2006-03-29 클라리언트 파이넌스 (비브이아이)리미티드 유기 인 화합물의 제조 방법

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3707565A (en) * 1968-08-28 1972-12-26 Sandoz Ltd Phenol sulfide derivatives

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3707565A (en) * 1968-08-28 1972-12-26 Sandoz Ltd Phenol sulfide derivatives

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2338555A1 (fr) * 1976-01-16 1977-08-12 Raychem Corp Compositions isolantes contenant des composes phosphores
US4100089A (en) * 1976-01-16 1978-07-11 Raychem Corporation High-voltage insulating material comprising anti-tracking and erosion inhibiting compounds with insulating polymers
DE2701638A1 (de) * 1976-01-16 1977-07-21 Raychem Corp Phosphorverbindungen enthaltende isoliermassen
US4219607A (en) * 1978-01-13 1980-08-26 Raychem Corporation High voltage insulating compositions containing phosphorus compounds
US4223071A (en) * 1978-01-13 1980-09-16 Raychem Corporation High voltage insulating compositions containing phosphorus compounds
US4263230A (en) * 1979-10-11 1981-04-21 Stauffer Chemical Company Bisphosphonites
US4551527A (en) * 1981-07-02 1985-11-05 Borg-Warner Chemicals, Inc. Salts of 5,5-bis-(bromomethyl)-2-hydroxy-2-oxo-1,3,2-dioxaphosphorinane and process for preparing same
EP0158501A2 (en) * 1984-04-02 1985-10-16 Polyplastics Co. Ltd. Method of preparation of polyester
JPS60208325A (ja) * 1984-04-02 1985-10-19 Polyplastics Co ポリエステルの製造方法
EP0158501A3 (en) * 1984-04-02 1986-10-08 Polyplastics Co. Ltd. Method of preparation of polyester
JPH0341091B2 (pt) * 1984-04-02 1991-06-21
US5298541A (en) * 1989-05-20 1994-03-29 Hoechst Aktiengesellschaft Aryl phosphonites, a process for their production and their use for stabilizing plastics
US5342869A (en) * 1991-07-03 1994-08-30 Sandoz Ltd. Stabilized polymeric compositions

Also Published As

Publication number Publication date
GB1415532A (en) 1975-11-26
BE791767A (fr) 1973-05-22
DE2256783A1 (de) 1973-05-30
ATA997272A (de) 1975-05-15
DE2256783C2 (de) 1982-04-01
ES408865A1 (es) 1976-03-16
FR2161052A1 (pt) 1973-07-06
AT327944B (de) 1976-02-25
CH557389A (de) 1974-12-31
NL7215623A (pt) 1973-05-28
FR2161052B1 (pt) 1977-12-23
JPS5645919B2 (pt) 1981-10-29
IT971154B (it) 1974-04-30
CA989414A (en) 1976-05-18
BR7208256D0 (pt) 1973-08-23
JPS4862741A (pt) 1973-09-01

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