FR2494281A1 - CYCLIC PHOSPHITES OF ALKYLIDENE- OR ARYLIDENE-2,2'-BIS-PHENYLS AND POLYOLS, AND ORGANIC MATERIALS CONTAINING AS STABILIZERS - Google Patents

Abstract

THE OBJECT OF THE INVENTION IS CYCLIC PHOSPHITES OF ALKYLIDENE-2,2-BIS-PHENYL ALKYL, WHICH ARE PREPARED BY REACTION OF 2,2-ALKYLIDENE-BIS-PHENOLS ALKYL WITH PHOSPHORUS TRICHLORIDE IN AN ORGANIC SOLVENT, THEN REACTION WITH A POLYOL OF INTERMEDIATE PHOSPHORO-CHLORIDITY THUS FORMED. THESE PHOSPHITES ARE INTERESTING STABILIZERS FOR PROTECTING ORGANIC POLYMERIC MATERIALS AND LUBRICATING OILS AGAINST DEGRADATION BY OXIDATION AND UNDER THE ACTION OF HEAT OR ACTINIC RADIATION, IN PARTICULAR, DURING TREATMENTS FOR TRANSFORMATION, POLYOXIDATION, ELIMINATION POLYESTERS AND POLYCARBONATES.

Description

Organic polymeric materials, such as

  Plastics and resinous materials, lubricating oils and mineral oils are subject to degradation by heat, light and oxidation. A wide variety of stabilizers are known to protect various materials, the effectiveness of which depends on the cause of the degradation of the substrate to be stabilized, and during

  of this study, stabilizers have been found to be

  most effective anti-oxidants in the long term, are mediocre for the processing of matter

  to protect, that they do not protect against the thermal degradation

  during the short time that the treatment lasts, but which is done at rather high temperatures. Many stabilizers are relatively incompatible with organic substrates, which creates problems during the life of a product and undermines their effectiveness, and some stabilizers are either too volatile or too resistant to

  heat or hydrolysis, so that they can be used in

  dustry. However, the phosphites according to this invention have an exceptional set of interesting characteristics by

  phosphites already known, which makes them stable.

  particularly effective and useful.

  Phosphites are described in several publications

  tions. For example, US Pat. No. 4,196,117 discloses phosphites.

  biphenyl cyclics of which the phosphorus atom bears an O- or S-hydrocarbyl substituent or a second group of cyclic hydrocarbylphosphite of bisphenyl, while Soviet Union Patents Nos. 378,389, Nos. 429,070 and 440,390 describe the stabilization of various polymers with

  organic phosphites or mixtures comprising these phosphors

  phites, which are cyclic phosphites of methylene-bisphenol

  nyle. Other 2,2'-bisphenyl phosphites are described in Chemical Abstracts, 68, 12597s (1968), 73, 15657c (1970).

  and 75, 130242g (1971), and it is stated that these various compounds

  These are stabilizers for various polymeric materials.

  However, the compounds according to the present invention are much more effective as stabilizers for the processing treatments of the materials to be protected, as well as for improving

  improve their resistance to staining and hydrolysis.

  This invention thus has as its first object phosphors

  cyclic phites of bisphenyl which have a better action

  that the phosphites previously known for

processing treatments.

  These compounds are characterized by the general formula

  R 1 wherein R is C 1 -C 18 alkyl; R1, hydrogen or C1-C18 alkyl; R2, alkylene or C1 to C12 arylene;

  R3, a n-valence radical selected from alkylene chain

  straight or branched C2 to C12; alkane-triyls,

  -tetail, -pentayles or -hexayles with a straight chain or

  C3 to C6; C4 to C6 alkenylenes; cyclo-

  C6 to C12 alkylene; the 1,4-cyclohexane-dimethyl radical

  ene; arylenes or arenes-C6 to C10 triols; the radi-

  cal p-xylylene; phenylene-E-phenylene radicals, E

  having a direct bond or -O-, -S- or -NR4-,

  R4 is C1-C18 alkyl; alkylene or alkyl

  C1 to C12 straight or branched chain dienes and cycloalkyl

  C5 or C6 kylidenes; such arylenes and phenylene-E-phenyl-

  substituted with 1 to 4 C 1 to C 8 alkyl groups each, - (CH 2) p X (CH 2) p, p being a number from 2 to 6, dipentaerythrityl and - (CH 2 CHO) z (CH 2 CH-), Y being hydrogen or a group

Y Y

  methyl or ethyl, and z is from 1 to 10; X denotes oxygen or sulfur; and

n, an integer of 2 to 6.

  A preferred subclass of compounds of formula (I) is those in which, on each phenyl ring, R occupies the ortho position with respect to the oxygen atom of the phosphite. The groups R and R 1 are preferably C 4 to C 8 straight or branched chain alkyls, such as n-butyl, sec-butyl, tert-butyl, tert-pentyl, 2-ethylhexyl,

  n-octyl and tert-octyl (1,1,3,3-tetramethylbutyl), the groups

  tert-butyl, tert-pentyl and tert-octyl are particularly

  preferable, and it is also particularly preferable

  group R1 occupies the para position with respect to

  the oxygen of the phosphite, especially if R 1 is a tertiary alkyl.

  If R 1 can be hydrogen or C 1 -C 18 alkyl, it is preferable that it is C 1 -C 8 alkyl, straight or branched chain, and in particular tertiary alkyl in the form of C 1 -C 18 alkyl.

C4 to C8.

  R 2 will preferably be an alkylene or an arylene of the formula: R 5 C R 6 R 5 and R 6 each independently of one another;

  hydrogen, C1-C12 alkyl or aryl, with the proviso

  the total number of carbon atoms does not exceed 11,

  representative aryls for these various substituents include

  including phenyl, tolyl, mesityl, xylyl and 1- or 2-naphthyl groups. But it is particularly preferable that R2 be

  a methylene or ethylidene group.

  R3 will preferably be ethylene, hexamethylene, 3-thia-

  pentamethylene or a group of formula:

CH3 -CH-CH CH2-

3 2 2

-H2 + C2 -CH2-C-C -CH3 or C

CH3 -CH21 -CH2 CH2-

  The cyclic phosphites of alkylidene-2,2'-bis-phenol

  alkyls according to this invention may be prepared by

  reaction of an alkylated 2,2'-alkylidene-bisphenol with trichlo-

  phosphorus in a solvent, to form phosphorus

  corresponding chloridite which is then reacted with a polyol in the presence of a proton acceptor, such as an amine

  tertiary, to obtain the desired product.

  The solvent is preferably an aromatic solvent such as benzene, toluene, xylene or the like, and the

  reaction temperature is between the temperature of

  about the temperature and the reflux temperature of the reaction medium

  nel. The tertiary amine may be a trialkyl amine such as

  triethylamine or another tertiary amine such as pyridine

  ridine or substituted pyridine. The synthesis of the present compounds is represented by the following reaction scheme, in which the preferred compounds have been taken: R 1 R 1 R 1 R 1 R 2 O OH R R 1 R. R o-1 P-C 1 + pc 3 B o /

R

R1 Ia II R (XH) n B R3

  B represents a cyclic or acyclic tertiary amine

  proton acceptor and other symbols having

the previous meanings.

  A similar synthetic method consists of replacing

  cer in the reaction scheme above the tertiary amine

  by an alkali metal hydroxide or carbonate. We can do

  carry out these reactions to obtain the desired compounds without

  isolate the intermediate chloridite II.

  The compounds of this invention provide effective protection

  anti-light and / or oxidation a wide variety of organic polymeric materials, including the following: 1. Polymers of monoolefins and di-olefins, for example polyethylene (optionally crosslinked), polypropylene,

  polyisobutylene, polybutene-1, polymethylpentene-1, polyisobutylene

  prene and polybutadiene, as well as cyclo-olefin polymers.

  fine, for example cyclopentene and norbornene.

  2. Polymer mixtures mentioned in 1), for example

  polypropylene with polyethylene or polyisobutylene.

  3. Copolymers of mono-olefins and di-olefins,

  or with other vinyl monomers, eg ethylene / propylene copolymers, propylene / butene-1, propylene /

  isobutylene, ethylene / butene-1, propylene / butadiene, isobutyl-

  ene / isoprene, ethylene / ethyl acrylate, ethylene / methacrylate

  alkyl, ethylene / vinyl acetate or ethylene / acrylic acid and their salts (ionomers), as well as ternary polymers of ethylene with propylene and a diene such as

  hexadiene, dicyclopentadiene or ethylidene norbornene.

4. Polystyrene.

  5. Statistical copolymers (random distribution)

  styrene or c-methylstyrene with dienes or

  acrylic rivets, for example styrene / butadiene copolymers,

  styrene / acrylonitrile, styrene / alkyl methacrylates, styrene

  ne / acrylonitrile / methyl acrylate; copolymer blends of high impact styrene and another polymer such as, for example, a polyacrylate, a diene polymer or a ternary ethylene / propylene / diene polymer; and styrene block copolymers, for example styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butylene / styrene and styrene / ethylene / propylene / styrene. 6. Graft copolymers of styrene, for example styrene

  on polybutadiene, styrene and acrylonitrile on polybutadiene

  diene, styrene and alkyl acrylates or methacrylates

  butadiene, styrene and acrylonitrile on tertiary polymers

  ethylene / propylene / diene, styrene and acrylonitrile on

  polyacrylates or polymethacrylates, styrene and acrylonitrile

  acrylate / butadiene copolymers, as well as their

  with the copolymers indicated above in 5), for example the mixtures known under the names of ABS polymers,

MBS, ASA and AES.

  7. Halogenated polymers, such as polychloroprene,

  chemochlorine, chlorinated or sulphochlorinated polyethylene, polymeric

  resins of halogenated vinyl compounds, for example polyvinyl chloride and fluoride, polyvinylidene chloride and fluoride, and their copolymers, for example vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate

  and vinylidene chloride / vinyl acetate.

  8. Polymers of α, β-unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates, polyacrylamides

and polyacrylonitrile.

  9. Copolymers of the monomers indicated in 8), between them

  or with other unsaturated monomers, for example acrylonitrile

  butadiene, acrylonitrile / alkyl acrylate or acrylonitrile / vinyl chloride, and ternary polymers acrylonitrile /

alkyl methacrylate / butadiene.

  10. Polymers of alcohols and unsaturated amines or of their acyl derivatives or acetals, such as polyvinyl alcohol,

  acetate, stearate, benzoate and polyvinyl maleate, polyvinyl

  nylbutyral, polyallyl phthalate and polyallyl-melamine.

  11. Homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxides and

  polypropylene and copolymers thereof with bis-glycine ethers

dyliques.

  12. Polyacetals such as polyoxymethylene and polyoxymethyl

  thylenes with ethylene oxide as comonomer.

  13. Oxides and sulfides of polyphenylene.

  14. Polyurethanes from polyethers, polyesters

  or polybutadienes with terminal hydroxyl

  aliphatic or aromatic isocyanates and their

  sliders. 15. Polyamides and copolyamides of diamines and acids

  dicarboxylic acids and / or aminocarboxylic acids or lac-

  corresponding sheets, for example polyamide 4, polyamide 6, polyamide 6/6, polyamide 6/10, polyamide 11, polyamide 12,

  poly-2,4,4-trimethylhexamethylene terephthalamide and poly-m-

  phenylene isophthalamide, as well as their copolymers with

  polyethers such as polyethylene glycol, polypropylene gly-

  col or polytetramethylene glycols.

  16. Polyureas, polyimides and polyamide-imides.

  17. Polyesters of dicarboxylic acids and glycols

  and / or hydroxycarboxylic acids or lactones corresponding thereto.

  dantes, for example polyethylene terephthalate, terephthalate

  of polybutylene, terephthalate and polyhydroxybenzoates of

  1,4-dimethylol-cyclohexane, as well as the copolyether-esters

  sequenced polyethers with hydroxyl terminal groups

lic.

18. Polycarbonates.

  19. Polysulfones and polyether sulfones.

  20. Cross-linked polymers of aldehydes and phenols, ureas or melamines, for example phenol / formaldehyde resins, urea

  formaldehyde and melamine / formaldehyde.

  21. Drying and drying non-drying alkyd resins.

  22. Unsaturated polyester resins from copoly-

  esters and saturated and unsaturated dicarboxylic acids with polyols and vinyl compounds as crosslinking agents,

  as well as their flame-retarded halogenated derivatives.

  23. Thermosetting acrylic acrylate ester resins

  substituted, for example epoxy-acrylates, urethanes-

acrylates or polyester acrylates.

  24. Alkyd resins, polyester resins and acrylate resins mixed with melamine or urea resins,

  polyisocyanates or epoxy resins as crosslinking agents

culants.

  25. Crosslinked epoxy resins from polyepoxyses

  for example bis-glycidyl ethers or cycloaliphatic diepoxides.

  26. Natural polymers, eg cellulose, rubber

  rubber, gelatin and their chemically modified derivatives in

  homologous polymers, for example acetates, propionates and

  cellulose tyrates, or cellulose ethers such as methyl-

cellulose.

  27. Organic materials of natural or synthetic origin

  which are pure monomeric compounds or mixtures of these compounds, for example mineral oils, fats, oils and waxes of animal or vegetable origin, or oils, greases and waxes based on synthetic esters (for example phthalates, adipates, phosphates or trimellitates) as well as mixtures of synthetic esters with mineral oils in any weight ratios, which may be employed as plasticizers for polymers or as oils for spinning

  textiles, as well as aqueous emulsions of these materials.

  28. Aqueous emulsions of natural rubber or synthetic

  ticks, for example natural latex or copolymer latex

carboxylated styrene / butadiene.

  The compounds according to this invention are also shown

  particularly effective for stabilizing liquids

  synthetic or synthetic oils such as lubricating oil, circulating oils, etc. However, these compounds are particularly useful for protecting polyolefins, for example polyethylene, polypropylene, polyisobutylene, polybutene-1, poly (pentene-1), poly (3-methylbutene-1), poly (4-methylpentene) and the like. 1), and various ethylene-propylene copolymers, etc.

  Other substrates in which the present compounds

  are particularly useful are polystyrene, including

  high-impact polystyrene, ABS resins, SBR rubbers and polyisoprene, and natural rubber, polyesters including polyethylene terephthalate and polybutylene terephthalate, including

  copolymers, and polyurethanes can also be stabilized.

  nes, polycarbonates, polyamides such as nylon 6, nylon 6/6

  and others, as well as copolyamides and polysulfones.

  The present compounds can be used alone, as sole stabilizer mainly having a function either antioxidant or light stabilizing, or combining these two functions, or they can be used together with

  phenolic antioxidants, lubricants such as stearate

  calcium spleen, pigments and dyes, absorbing

  ultraviolet light, photo-stabilizers such as hindered amines, metal deactivators, talc and other fillers, etc. In general, the stabilizers according to this invention are used in a proportion of about 0.01 to 5% by weight.

  stabilized composition, although the proportions can be

  vary with the particular substrate and the application

  read, but an advantageous range is of the order of 0.05 to 2%,

  in particular from about 0.1 to 1%.

  The present compounds protect the polymeric materials

  particularly in the course of their treatment at

  erations, and only then

  relatively weak colors, even if the material is

  several extrusions, and among the polymers for

  this characteristic is particularly obvious, include polypropylene, polyethylene, copolymers of

  styrene such as ABS copolymer, polyethylene terephthalates

  ethylene and polybutylene, polycarbonates, natural rubber and synthetic rubbers such as rubber

  SBR. While many compounds that have been used as

  stabilizers do not show themselves sufficiently

  ficaces for poly-olefin processing treatments in the presence of co-stabilizers such as antioxidants

  phenolic compounds, the compounds of this invention are effectively

  these also without phenolic antioxidants, and many

  they associate stabilization during treatments with the ability to protect the polymer against light, which

  is particularly important in the case of fibers, for

  which treatment temperatures are among the highest

  and stability to actinic radiation constitutes a

first requirement.

  A particularly important property for stabilizers which are trivalent phosphorus esters is

  the absence of hygroscopic character and the resistance to hy-

  drolysis in a humid atmosphere during storage under ambient conditions, especially during the summer and in the tropics. A hygroscopic nature often causes difficulties to incorporate the stabilizer of a

  homogeneous way in the polymer, which causes adhesions

  and blockages during mixing, while hydro-

  lysis of the stabilizer during storage frequently

  formation of compounds that are less effective.

  The present stabilizers can be easily incorporated into organic polymers by the techniques

  at any convenient stage prior to the manufacture of articles

  cles. The stabilizer may for example be mixed with the

  dry powder polymer, or a suspension can be mixed

  or an emulsion of the stabilizer with a solution, a

  suspension or emulsion of the polymeric material. The components

  The stabilized polymer compositions of this invention may optionally also contain various customary additives such as the following: 1. Antioxidants

  1.1. 2,6-Dialkylphenols, for example 2,6-di-

  tert.-butyl-4-methylphenol, 2-tert.-butyl-4,6-dimethylphenol,

  2,6-di-tert-butyl-4-methoxymethylphenol and 2,6-di-octadecyl-

4-methyl phenol.

  1.2. Derivatives of alkyl-hydroquinones, for example 2.5-

  di-tert-butyl-hydroquinone, 2,5-di-tert.-amyl hydroquinone,

  2,6-di-tert.-butyl-hydroquinone, 2,5-di-tert-butyl-4-hydroxy-

  anisole, 3,5-di-tert-butyl-4-hydroxy-anisole, phosphite

  tris- (3,5-di-tert.-butyl-4-hydroxyphenyl), 3,5-di-stearate

  tert.-butyl-4-hydroxyphenyl and bis (3,5-di-tertiary) adipate

  butyl-4-hydroxyphenyl). 1.3. Hydroxy thiodiphenyl ethers, for example

  2,2'-thio-bis- (6-tert-butyl-4-methylphenol), 2,2'-thio-bis-

  (4-octylphenol), 4,4'-thio-bis- (6-tert-butyl-3-methylphenol),

  4,4'-thio-bis- (3,6-di-sec-amylphenol), 4,4'-thio-bis- (6-tert);

  butyl-2-methylphenol) and 4,4'-bis- (2,6-dimethyl) disulfide

4-hydroxyphenyl).

  1.4. Alkylidene bisphenols, for example 2,2'-methylene

  bis- (6-tert-butyl-4-methylphenol), 2,2'-methylene-bis- (6-tert)

  butyl-4-ethylphenol), 4,4'-methylene-bis- (6-tert-butyl) -2-

  methylphenol), 4,4'-methylene-bis- (2,6-di-tert-butylphenol), 2,6-di- (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4- methylphenol, 2,2'-methylene-bis [4-methyl-6- (α-methylcyclohexyl) phenol],

  1,1-bis- (3,5-dimethyl-2-hydroxyphenyl) butane, 1,1-bis- (5-tert)

  butyl-4-hydroxy-2-methylphenyl) butane, 2,2-bis (3,5-di-tert)

  butyl-4-hydroxyphenyl) -propane, 1,1,3-tris- (5-tert.-butyl) -4-

* hydroxy-2-methylphenyl) -butane, 2,2-bis- (5-tert-butyl-4-hy-

  droxy-2-methylphenyl) -4-n-dodecylmercapto-butane, 1,1,5,5-

  tetra- (5-tert.-butyl-4-hydroxy-2-methylphenyl) -pentane and bis-

  Ethyl [3,3-bis- (3'-tert-butyl-4'-hydroxyphenyl) -butyrate]

no glycol.

  1.5. O-, N- or S-benzyl compounds, for example 3,3 ', 5,5'-tetrater-butyl-4,4'-dihydroxydibenzyl ether, 4-hydroxy-3,5-dimethylbenzylmercaptoacetate octadecyl

  tris- (3,5-di-tert.-butyl-4-hydroxybenzyl) -amine and di-

  bis (4-tert.-butyl-3-yl) -hydroxy-2,6-dimethyl-thioephthalate

benzyl)

  1.6. Hydroxybenzylated Mlalonates, for example 2,2-bis-

  Dioctadecyl (3,6-di-tert-butyl-2-hydroxybenzyl) -malonate,

  2- (3-tert.-butyl-4-hydroxy-5-methylbenzyl) -malonate of di-

  octadecyl, 2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) -

  di-dodecylmercapto-ethyl malonate and 2,2-bis- (3,5-di-

  tert.-butyl-4-hydroxybenzyl) -malonate of di [4- (1,1,3,3-tetra-

  methylbutyl) phenyl] .d. 1.7. Hydroxybenzyl aromatic compounds, for example

  1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-tri

  methyl-benzene, 1,4-di- (3,5-di-tert-butyl-4-hydroxybenzyl) -

  2,3,5,6-tetramethylbenzene and 2,4,6-tris- (3,5-di-tert);

butyl-4-hydroxy-benzyl) -phenol.

  1.8. S-triazine compounds, for example 2,4-bis-

  octylmercapto-6- (3,5-di-tert-butyl-4-hydroxy-anilino) -s

  triazine, 2-octylmercapto-4,6-bis- (3,5-di-tert.-butyl-4-hydroxy)

  xy-anilino) -s-triazine, 2-octylmercapto-4,6-bis- (3,5-di-tert)

  butyl-4-hydroxyphenoxy) -s-triazine, 2,4,6-tris- (3,5-di-tert)

  butyl-4-hydroxyphenoxy) -s-triazine, 2,4,6-tris- (3,5-di-tert)

  butyl-4-hydroxyphenylethyl) -s-triazine and 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate.

  1.9. Amides of the acid - (3,5-di-tert.-butyl-4-hydro-

  xyphenyl) -propionic acid, for example 1,3,5-tris- (3,5-di-tert)

  butyl-4-hydroxyphenylpropionyl) -hexahydro-s-triazine, N,

  N'-di- (3,5-di-tert-butyl-4-hydroxyphenyl-propionyl) -hexamé-

  thylene diamine and N, N'-bis- (3,5-di-t-butyl-4-hydroxy)

phenyl) -propionyl-hydrazine.

  1.10 Esters of f- (3,5-di-tert.-butyl-4-hydroxyethyl)

  xyphenyl) -propionic with monoalcohols or polyalcohols such as, for example, methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, the

  1,2-propanediol, diethylene glycol, thiodiethylene gly-

  col, neopentyl glycol, pentaerythritol, 3-thia-undec

  canol, 3-thia-pentadecanol, trimethyl hexanediol, trimethylol ethane, trimethylol propane, isocyanurate

  tris-hydroxyethyl and 4-hydroxymethyl-1-phospha-2,6,7-tri

oxabicyclo [2,2,2] octane.

  1.11 Esters of f- (5-tert.-butyl-4-hydroxy-3-)

  methyl-phenyl) -propionic with mono-alcohols or poly-

  alcohols such as, for example, methanol, ethanol, octa-

  decanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,

  1,2-propanediol, diethylene glycol, thiodiethyl-

  glycol, neopentyl glycol, pentaerythritol, 3-thia-

  undecanol, 3-thia-pentadecanol, trimethyl hexanediol, trimethylol ethane, trimethylolpropane, isocyanurate

  of tris-hydroxyethyl and 4-hydroxymethyl-1-phospha-2,6,7-

trioxabicyclo [2,2,2] octane.

  1.12 Esters of 3,5-di-tert.-butyl-4-hydroxy-acid

  phenyl-acetic acid with monoalcohols or polyalcohols

  that, for example, methanol, ethanol, octadecanol, 1,6-

  hexanediol, 1,9-nonanediol, ethylene glycol, 1,2

  panediol, diethylene glycol, thiodiglycol, neopentyl

  glycol, pentaerythritol, 3-thia-undecanol, 3-thia-

  pentadecanol, trimethylol hexanediol, trimethylol ethane, trimethylol propane, tris-hydroxyethyl isocyanurate

  and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] -

  octane, especially the pentaerythritol tetra-bis ester.

  1.13 Benzylphosphonates, for example 3,5-di-tert.-

  dimethyl butyl-4-hydroxybenzyl phosphonate, 3,5-di-tert.-

  butyl-4-hydroxybenzyl diethyl phosphonate, 3,5-di-tert.-

  dioctadecyl butyl-4-hydroxybenzylphosphonate and 5-di-

  dioctadecyl tert.-butyl-4-hydroxy-3-methylbenzyl phosphonate.

  The following compounds may be exemplified as other additives which may be employed in conjunction with the present stabilizers and antioxidants:

  1. Aminoaryl derivatives, for example phenyl-1

  naphthylamine, phenyl-2-naphthylamine, N, N'-di-phenyl-p-phenylene

  diamine, N, N'-di-2-naphthyl-p-phenylenediamine, N, N'-di-2-naphthyl-

  p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, 6-

  ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, 6-dodecyl-2,2,4-

  trimethyl-1,2-dihydroquinol.etin, mono- and dioctyliminodiben

  Zyl, 2,2,4-trimethyl-1,2-dihydroquinoline polymerized, octyl-

  diphenylamine, nonyl-diphenylamine, N-phenyl-N'-cyclohexyl-p-

  phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine,

  N, N'-di-sec-octyl-p-phenylenediamine, N, N'-di- (1,4-dimethyl)

  pentyl) -p-phenylenediamine, N, N'-dimethyl-N, N'-di- (sec-octyl) D-

  p-phenylenediamine, 2,6-dimethyl-4-methoxyaniline, 4-ethoxy-N-

  sec.-butylaniline, di-phenylamine-acetyl condensation product

  Tone, aldol-1-naphthylamine and phenothiazine.

  The effects of alteration must be taken into

  color ration when using the antioxidants above.

  2. Ultraviolet Absorbent Body and Protective Agents

  against light 2.1. 2- (2'-Hydroxyphenyl) -benzotriazoles, for example the 5'-methyl, 3 ', 5'-di-tert-butyl, 5'-tert.-butyl derivatives (1,1,3,3 tetramethylbutyl, 5-chloro-3 ', 5'-di-tert-butyl, -chloro-3'-tert-butyl-5'-methyl, 3'-sec-butyl-5'-tert-butyl, 3'-emethylbenzyl-5'-methyl, 3'-a-methylbenzyl-5'-

  methyl-5-chloro, 4'-hydroxy, 4'-methoxy, 4'-octoxy, 3 ', 5'-di-

  tert.-amyl, 3'-methyl-5'-carbomethoxyethyl and 5-chloro-3 ', -di-tert.amyl. 2.2. 2,4-bis- (2'-Hydroxyphenyl) -6-alkyl-s-triazines,

  for example the 6-ethyl, 6-heptadecyl and 6-

  undecyl. 2.3. 2-Hydroxybenzophenones, for example derivatives

  4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy.

  2.4. 1,3-bis- (2'-Hydroxybenzoyl) benzenes, e.g.

  1,3-bis (2'-hydroxy-4'-hexyloxy-benzoyl) benzene, the

  1,3-bis- (2'-hydroxy-4'-octyloxy-benzoyl) -benzene and 1,3-

  bis- (2'-hydroxy-4'-dodecyloxy-benzoyl) -benzene.

  2.5. Esters of benzoic acid, which may be

  such as phenyl salicylate, octyl salicylate

  phenyl, dibenzoylresorcin, bis- (4-tert.-butylbenzoyl) resor

  benzoylresorcin and 3,5-di-tert.-butyl-4-hydroxybenzoate

  2,4-di-tert.-butylphenyl, octadecyl or 2-methyl-

4,6-di-tert-butyl.

  2.6. Acrylates, for example α-cyano-B, β-diphenylacryl-

  ethyl or isooctylate, methyl-carbomethoxy-cinnamate, methyl acyano-3-methyl-p-methoxy-cinnamate or

  butyl or N- (c-carbomethoxyvinyl) -2-methylindoline.

  2.7. Amines with steric hindrance, e.g.

  4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyl-

  oxy-2,2,6,6-tetramethylpiperidine, bis (2,2,6) sebacate,

  6-tetramethylpiperidyl) and 3-n-octyl-7,7,9,9-tetramethyl-3-yl

  1,3,8-triaza-spiro [4.5] decane-2,4-dione.

  2.8. Diamides of oxalic acid, for example 4,4'-

  di-octyloxy-oxanilide, 2,2'-dioctyloxy-5,5'-di-tert.-butyl-

  oxanilide, 2,2'-di-dodecyloxy-5,5'-di-tert.-butyl-oxanilide,

  2-ethoxy-2'-ethyl-oxanilide, N, N'-bis (3-dimethylaminopropyl) -

  oxalamide, 2-ethoxy-5-tert.-butyl-2'-ethyl-oxanilide or its

  mixture with 2-ethoxy-2'-ethyl-4,5'-di-tert.-butyloxani-

  lide, as well as mixtures of ortho- and para-methoxy-oxa-

  nilides or ortho- and para-ethoxy-oxanilides.

  3. Metal deactivators, for example oxanilide, isophthalic acid dihydrazide, bis-phenylhydrazide

  sebacic acid, bis-benzylidene acid dihydrazide

  oxalic acid, dihydrazide of N, N'-diacetal-adipic acid, di-

  N, N'-bis-salicyloyl-oxalic acid hydrazide, N, N'-bis-

  salycyloyl-hydrazine, N, N'-bis- (3,5-di-tert-butyl-4-hydroxypropyl);

  xyphenylpropionyl) -hydrazine, N-salicyloyl-N'-salicylalhydrate

  zine, 3-salicyloyl-amino-1,2,4-triazole and dihydrazide of the

  N, N'-bis-salicyloyl-thio-propionic acid.

  4. Basic co-stabilizers, for example metal salts

  alkaline or alkaline-earth levels of higher fatty acids

  such as calcium or zinc stearate, magnesium behenate

  sium, sodium ricinoleate or potassium palmitate.

  5. Nucleating agents, for example 4-tert.-acid

  butylbenzoic acid, adipic acid and diphenylacetic acid.

  6. Phosphites, for example triphenyl, diphenyl

  nylalkyls, phenyldialkyls, tri- (nonylphenyl), tri-

  trioctadecyl lauryl, as well as 3,9-isodecyloxy-2,4,8, -tetraoxa3,9-diphospha- [5,5] -undecane and the phosphite of tri- (4-hydroxy-3,5-ditert) . -butylphenyl). Other additives that can be further incorporated into the stabilized compositions are synergistic agents

  thio group such as thiodipropionate dilauryl or di-

  starylene, lubricants such as stearyl alcohol,

  gums, lampblack, asbestos, kaolin, talc, fiberglass, pigments, optical brighteners, flame retardants and

antistatic agents.

  If the phosphites according to this invention can be

  employees with advantage as stabilizers for a great deal of

  Many materials, especially in polyolefins, both alone and in combination with other co-additives, combine with sterically hindered phenolic antioxidants to give such substrates enhanced and particularly effective protection, and antioxidants. phénoliquesqui

  have been especially useful in this regard are 2,6-

  di-tert-butyl-4-methylphenol, 4,4'-thio-bis- (6-tert.-butyl)

  3-methylphenol), 2,2'-methylene-bis- (6-tert-butyl-4-methylphenol), 4,4'-methylene-bis- (2,6-di-tert) butylphenol), 1,1,3-tris- (5-tert.butyl-4-hydroxy-2-methylphenyl) -butane,

  1,3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethyl

  thylbenzene, 2-octylthio-4,6-bis- (3,5-di-tert.butyl-4-hydroxy)

  xyanilino) -s-triazine, 3,5-di-tert-butyl-4-hydroxyhydrocin

  n-octadecyl namate, tetrakis- (3,5-di-tert-butyl-4-hy-

  droxyhydrocinnamate) of neopentane-tetrail, isocyanurate

  1,3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl), bis-

  di-tert.-butyl-4-hydroxyhydrocinnamate) of thiodiethylene and

  the tris (2-hydroxyethyl) -isocyanate ester of 3- (3,5-

  di-tert-butyl-4-hydroxyphenyl) -propionic acid. The present compositions thus comprise (a) a

  substrate, preferably a polyolefin such as polypropylene.

  (b) about 0.01 to 5% of the weight of the composition, preferably about 0.025 to 2% and more preferably 0.025 to 1%, of one or more phosphites according to the invention, and the case

  (c) one or more phenolic antioxidants selected

  in the above group, also in a proportion of 0.01 to 5%, preferably 0.05 to 1%, of the weight of the

composition.

  Similarly, the light-protecting agents below are preferably used, alone or in combination with the indicated phenolic antioxidants, as additives with

  the present stabilizers in the substrates mentioned: 2- (2'-

  hydroxy-5'-methylphenyl) benzotriazole; 2- (3 ', 5'-di-tert

  butyl-2'-hydroxyphenyl) benzotriazole; 2- (2'-hydroxy-3 ', 5'-

  di-tert-amylphenyl) benzotriazole; bis [O-ethyl- (3,5-di-tert

  butyl-4-hydroxybenzyl)] nickel phosphonate; 2-n-butyl-2-

  (Bis (1,2,3-di-tert-butyl-4-hydroxybenzyl) -malonate

  6,6-phentaméthyl-4-piperidyl); sebacate of bis- (2,2,6,6-

  tetramethyl-4-piperidyl); dimethylsuccinate polymer with

  4-hydroxy-2,2,6,6-tetramethyl-1-piperidinethanol; and poly-

  mother of 2,4-dichloro-6-octylamino-s-triazine with N '- (2,

  2,6,6-tetramethyl-4-piperidyl) -hexamethylenediamine.

  The following examples illustrate the modes of

  of the present invention, examples in the following

  which, unless otherwise indicated, all parts of materials indicated are by weight.

EXAMPLE A

  ol, o2-r2,2'-methylene-bis- (4,6-di-tert-butylphenyl)] phospho-

  ro-chloridite In a 500 ml flask dried with flame, or put under nitrogen 6.87 g of phosphorus trichloride and 100 ml of toluene, and while maintaining the temperature between 10 and 15 C,

  a solution of 21.27 g of 2,2'-methyl is added over 15 minutes.

  lene-bis- (4,6-di-tert.-butylphenol) and 10.1 g of triethyl

  amine. Stir at room temperature until there is no more bisphenol, as shown by the IR spectrum and

  thin layer chromatography (TLC), then filter, evaluate

  pore on a rotary evaporator and the remaining material is recrystallized from heptane to give 11 g of crystals

white, melting at 207-217 C.

  Analysis: Calculated: C, 71.22; H, 8.66. Found: C, 71.44;

H, 8.62.

  In a similar way phosphor

following chloridites:

  O1.0 2- [2,2'-ethylidene-bis (4,6-di-tert-butylphenyl) phosphon

ro-chloridite. ::

  Ol, 02- [2,2'-methylene-bis- (4,6-di-tert-amylphenyl)] phosphorodithioate

chloridite.x

  O, O2- [2,2'-methylene-bis- (4-methyl-6-tert-butylphenyl)] phos-

phoro-ch] .oridite. ::

  ol, 02- [2,2'-butylidene-bis- (4,6-di-tert-butylphenyl)] phosphonate

ro-chloridite .:

  O, O2- [2,2 '- (2-hexylidene) -bis- (4,6-di-tert-butylphenyl)] phos-

phoro-chloridite.

  l, 02- [2,2'-dodécylidène-bis- (4,6-di-tert-butylphenyl)] phos-

phoro-chloridite.

  O, O2- [2,2'-methylene-bis- (4,6-di-tert-octylphenyl)] phosphonate

ro-chloridite.

  :: characterized by IR spectra.

  01,02- [2,2'-methylene-bis- (4-tert.-butyl-6-n-octadécylphényl)] -

phosphoro-chloridite.

  O1,02- [2,2'-ethylidene-bis- (4,6-di-tert-amylphenyl)] phosphonate

  ro-chloridite .: :: characterized by IR spectra.

EXAMPLE 1

  O, O'-Hexamethylene-bis-O1, O21 -2,2'-methylene-bis- (4,6-di-tert)

  butylphenyl) -phosphite] In a flamed 1-liter flask, 18.75 g of phosphorus trichloride and 200 ml of toluene are added under nitrogen while keeping the temperature between 10 and 15 C,

  a solution of 58 g of 2,2'-methylene-bis (4,6-di-

  tert.-butylphenol) and 27.64 g of triethylamine in 250 ml of toluene. The mixture is stirred at room temperature until there is no more bisphenol on examination by the IR spectrum and the TLC, then a solution of 8.07 g of 1 is added at a temperature of 10 ° C. 6-hexanediol in 13.82 g of triethylamine is stirred at room temperature until the reaction is complete.

  the IR spectrum and the TLC are complete.

  The mixture is evaporated on a rotary evaporator and the remaining material is recrystallized from a mixture of toluene and acetone.

  which gives 46.1 g of a white powder melting at 259-267 C.

  Analysis: Calculated: C, 75.11; H, 9.46. Found: C, 75.33;

H, 9.06.

  Following the procedure of this Example 1, the other compounds according to the invention, which are grouped in

Table 1 below.

TABLE 1

EXAMPLES 2 to 17

  R3 P.F. C Form Recrystallization solvent 2 4,4'-t-butyl 3 4,4'-tbutyl

t-b, utyle -CH2-

t-butyl, CH (CH2) 2-al3 CH

2 0 -CH2 - H2-

CH3 2 0 CH i3

-CH2-C -CH2-

  CH3 Ch3 253-256 white crystals 254-256 white crystals 4,4'-t-butyl tbutyl CH (CH2) 2-CH3

- (CH2) 6-

  270-276 white crystals trituration with 4,4'-t-butyl n-heptane

t-butyl -CH2-

-CH / CH2 -

2 \ "2

4 0 / C

-CH2 CH2-

187-95 white crystals 2-butanone

4,4'-t-butyl. t-butyl -CH2-

CH

4,4'-t-butyl t-butyl-CH-

CH2

O -CH 2-C-CH 2 -CH 3

2 2

-CH2 CH

2 0 -CH 2 -CH 2

  CH3 176-182 white crystals 297-308 white crystals 2-butanone 2-butanone

EX R1

  RR n XR z - 3 n-heptane n-heptane O -methyl-% EX R1 8 4,4'-t-butyl 9 4,4'-t-butyl 4,4'-t-butyl 11 4 4'-t-amyl 12 4,4'-t-amyl 13 4,4'-t-amyl 14,4,4'-t-octyl

4,4'-n-

octadecyl 16 4,4'-t-butyl

17 3,3'-CH3

  R t -butyl t-butyl t-butyl t-amyl t-amyl t-amyl t-octyl t-butyl tbutyl t-butyl H3-CH-CH2-CH-CH-CH3-CH-CH 3 CH2 CH2 CH2 CH2 CH2 X X R3 CH2

CH2-C-CH2-CH3

* -CH2

-CH2CH2-S-CH2CH2-

-CHH

-CH2CH2-S-CH2CH2-

-CH2CH2-S-CH2CH2-

2 0 -H2'2so2H2

2 0 - (CH 2) 6-

2 0 - (CH 2) 6-

2 0 -CH2CH2-

-CH2- (CH) -4-CH2-

2 5 -CH2CH2-

-CH 2 (CH 2) 10 CH 2

P.F. OC Form

285-295

239-247

257-75

157-165

189-209

  -178 white crystals white crystals white crystals white crystals white crystals white crystals Recrystallization solvent acetonitrile trituration with acetone toluene-n-heptane 2-butanone 2-butanone toluene acrylonitrile Co co

EXAMPLE 18

  STABILITY OF POLYPROPYLENE DURING TREATMENTS

OF TRANSFORMATION

  Basic formula: Polypropylene'x Calcium Stearate

Tetrakis [3- (3,5-di-tert

butyl-4-hydroxyphenyl)] -

  pentaerythrityl propionate parts

0.10 "

0.10 l!

  :: Profax 6801 from Hercules Chemical.

  The stabilizers are mixed in solution in

  methylene chloride with polypropylene, and after removing the solvent by evaporation under reduced pressure, the resin is extruded under the following conditions: Cylinder n 1 Cylinder n 2 Cylinder n 3 Matrix n 1 Matrix n 2 Matrix n 3 Rev / min Temperature (C)

  During extrusion (after the first, the third

  second and fifth extrusions), the internal pressure of

  the extruder is measured by a pressure transducer.

TABLE 2 -

  Extrusion temperature 260 C Phosphite None

0.05% EX. 1

0.05% EX. 6

0.05% EX. 9

  Pressure after extrusion n (MPa) 1.015 1.12 1.12 1.26 0.945 1.05 1.12 1.26 0.805 1.05 1.015 1.19

Claims (13)

1. Compound of general formula: R R   wherein R is C1-C18 alkyl; R1, hydrogen or C1-C18 alkyl; R2 is C1-C12 alkylene or arylene;   R3, a n-valence radical selected from alkylene chain   straight or branched C2 to C12; alkane-triyls,   -tetail, -pentayles or -hexayles with a straight chain or   C3 to C6; C4 to C6 alkenylenes; cyclo-   C6 to C12 alkylene; the 1,4-cyclohexane-dimethyl radical   ene; arylenes or arenes-C6 to C10 triols; the p-xylylene radical; phenylene-E-phenylenes, where E is a direct bond or -O-, -S- or 4_ 4   -NR -, R being C1-C18 alkyl; alkylenes or alkylidenes with a straight or branched C1 to C12 chain and   C 5 or C 6 cycloalkylidenes; such arylenes and   nylene-E-phenylenes substituted with 1 to 4 C 1 to C 8 alkyl groups each, - (CH 2) pX (CH 2) p, where p is a number of 2   at 6, dipentaerythrityl and - (CH2CHO) z (CH2CH-), Y represent Y Y   both hydrogen or a methyl or ethyl crystal, and a number of 1 to 10; X denotes oxygen or sulfur; and nr, an integer from 2 to 6.   2. A compound according to claim 1, wherein, on each phenyl ring, R occupies the ortho position with respect to the phosphite group.   3. Compound according to claim 1 or 2 in the which R is a C4 to C8 alkyl.   4. Compound according to claim 1 or 2 in the   which R is tert.-butyl, tert.-pentyl or 1,1,3,3- tetramethylbutyl.   5. Compound according to any one of the claims   1-4, wherein R1 is C1-C8 alkyl.   6. Compound according to any one of the claims   1 to 5, wherein R2 is an alkylene or arylene of formula   the: C R6 R5 and R6 each representing, independently of one another,   hydrogen, C 1 -C 12 alkyl or aryl, with the proviso that   that the total number of carbon atoms does not exceed 11.   7. Compound according to any one of the claims   1 to 5, wherein R2 is methylene or ethylidene.   8. A compound according to any one of the claims   1 to 7, in which R 3 is an ethylene, hexamethylene, 3-thiapentamethylene group or a group of formula: CH f 3 CH2 - CH2 CH3 -CH2 -CH2-C-CH2-CH3 -CH2 CH 2- C 'or -CH2   9. Composition comprising an organic matter   oxidizes and / or degrades under the action of heat or actinic radiation, stabilized with one or more   compounds according to any one of the preceding claims. s s CH2-   10. Composition according to claim 9, in which   the organic matter is a synthetic polymer material than.   11. Composition according to claim 10, in which   the polymer is a polyolefin or a copolyolefin.   12. Composition according to any one of the   cations 9 to 11, also containing a phenolic antioxidant.   13. Composition according to any one of the   9 to 12, also containing a protective agent against the light.