JPH05500044A - Aryl-halophosphoramidite, aryse-phosphoramidite, process for producing the same and its use for stabilizing synthetic resins - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Ary-halophonamidino, ary-suphosphonamidino, production thereof Process and its use for the stabilization of synthetic resins The present invention describes novel aryl-halophorous Sphoramidites, monoaryl-bosphonamidites and bis[aryl] ] Diphosphonamidites, their production methods and their use for stabilizing synthetic resins Regarding usage.

Undesirable oxidative, thermal and photochemical effects during the manufacture, kinetics and use of synthetic arresters It is well known that protection against physical damage must be achieved by stabilizers or stabilizer systems. It is knowledge. Such stabilizers include, for example, phenolic antioxidants and one type or Some of them are composed of multiple co-stabilizers that can synergistically reinforce the action of phenolic components. It is.

The most common stabilizers include, for example, phosphorous and phosphonic acid derivatives. Among them, the latter shows very good stability against hydrolysis.

Dihalophosphonites and alcohols in the presence of acid acceptors have been described by various authors. or phosbonamidates by stepwise reaction with phenols and amines. (Houben-Wey 1% Method Chemie, Phosphorver bindungen E+ page 300 (19B2)), achieved with this method. The resulting yield is only about 60-75x.

Similarly, according to European Patent Application No. 0.042.359, poly Monophosphonic amides suitable for use as stabilizers for lukyl- or aryl-dihalophosphonites, e.g. chlorophosphonites and an excess of salts with phenols and amines to help neutralize the resulting hydrochloric acid. It is produced by reacting in the presence of a group. This includes product purity and There is no mention of the yields achieved.

However, the method according to EP 42,359 Due to the difficulty in producing dihalophosphanes required as precursors, This is of course true when considering industrial manufacturing methods. , which is a drawback. For example, among aromatic derivatives, phenyl-dichlorophosphane This is a product that can be used industrially, and this product produces Hensen's phosphorous acid. The only derivative that can be produced manually. This means that European Patent Application Publication No. 42,35 In Specification No. 9, all but one embodiment (not less than 17) contain unsubstituted frames. Confirmed by the fact that it contains a phenyl residue.

In addition to achieving high yields, the stability, potency, low volatility and The phenyl residues were substituted to meet the high demands on the It would be desirable to be able to directly utilize the derivatives of arylphosphonous acids.

However, this utilization by known methods is hitherto not known or economically viable. They fail because they require appropriately substituted precursors that cannot be manufactured. that Therefore, one object of the present invention is to develop a new stabilizer for synthetic resins with improved properties. manufacturing, especially by a method that does not have the disadvantages mentioned above. Ru.

The object of the present invention is the expression ([) [In the formula, R' is a monovalent residue, a phenyl residue having 1 to 3 substituents or , benzyl-5α-methyl, each of which may have 1 to 3 substituents on the nucleus benzyl- or α,α-dimethylbenzyl residue or having 1 to 5 substituents means a naphthyl residue which may be an alkoxy residue or a delkylthio residue having from 8 to 8 carbon atoms, especially from 1 to 6 carbon atoms; is an aryl-ru or aryl atom, each having from 6 to 10 carbon atoms, especially from 6 to 8 carbon atoms. a halogen atom with an atomic number of 9 to 35 and the remaining substituents is a -naphthyl residue, it is exclusively a non-aromatic hydrocarbon residue having 1 to 8 carbon atoms. There is also and R1 as a divalent residue is unsubstituted or has up to 2 carbon atoms. Phenylene residues substituted with non-aromatic hydrocarbon residues or unsubstituted or 1 to 4 non-aromatic hydrocarbon residues each having 1 to 8 carbon atoms as a substituent. means a naphthylene or biphenylene residue which may have a carbon group, and R2 is a carbon a non-aromatic hydrocarbon residue of I to 18 atoms, aryl- or optionally substituted; substituted arylmethyl residues, each aryl residue having 6 to 10 carbon atoms, and R3 is a hydrogen atom, each having 1 to 18 carbon atoms. means an alkoxy- or alkylthio residue or a group listed under R'' and R4 and R5 are each independently an alkyl group having 1 to 22 carbon atoms. oxaalkyl or thiaalkyl having 2 to 21 carbon atoms, 3 to 21 carbon atoms 1'8 alkenyl or -alkynyl, alkoxylic having 3 to 24 carbon atoms Bonylalkyl, cycloalkyl having 5 to 12 carbon atoms, cycloalkyl having 6 to 14 carbon atoms aryl, arylalkyl having 7 to 15 carbon atoms or optionally substituted is a piperidin-4-yl group having 5 to 17 carbon atoms, or R4 and R5 together with the nitrogen atom is a heterogen which is bonded via at least one carbon atom. A ring having 5 to 7 ring atoms which may additionally contain a substituent (0, N or S) system and n is 1 or 2. ] It is expressed as -ru-phosphophonamidite.

In case n-1, the compound is a phosphonamidite and in case n=2 It is a member of the 7-species phosphonine species.

A particularly advantageous group of compounds is a biphenylene residue in which R1 is a biphenylene residue and R1 is a biphenylene residue. 1 and R3 are each branched butyl residues, and R4 and R5 are branched butyl residues. Each is a butyl residue or together with the N-atom forms a morpholide residue. It is.

Another particularly advantageous compound is one in which R' is a trimethyl-phenyl residue and R2oci and R3 are methyl- or branched butyl residues and R4 and R5 are nitrogen together with the atom is a piperidide or morpholide residue or R' is a tertiary- is a butyl-1-phenyl residue, R2 is a tert-butyl residue, and R3 is a methoxybutyl residue. C- or tert-butyl residue and R' and R5 together with the nitrogen atom. It is a morpholide residue.

Furthermore, compounds in which R1 is unsubstituted or substituted naphthyl are particularly preferred. be.

In R1, the substituents may be the same or different. Aromatic residue R1 The alkyl in the substituent is, for example, one of the various hequinol or octyl residues. but particularly preferably carbons bonded to the nucleus optionally via 0 or S 1 to 4 atoms, such as methyl, ethyl or various propyl or butyl It is a type of residue. As non-aromatic hydrocarbon residues, the residues listed for R2 Examples include cycloalkyl having 5 to 8 carbon atoms. In detail, for example, all may have up to two substituents with up to four alkyl carbon atoms, etc. alkyl or naphthyl residues, as well as various biphenyl residues. .

R1 can be a divalent residue, for example unsubstituted or containing one or two carbon atoms. various phenylene residues substituted with alkyl groups having 1 to 8, especially 1 to 3 molecules; or unsubstituted or each having 1 to 4, especially 1 to 3 carbon atoms 8, in particular various naphthylene- or biphelenes substituted with 1 to 3 alkyl groups. Examples include nylene residues.

Of course, the substituent in R1 may be bonded only in such a way that it does not cause steric hindrance. When R- has 3 substituents, 5 or more carbon atoms are present in both ○-positions. For substituted naphthyl residues with more than two substituents, which should not be The substituents are distributed over the two rings.

The residue RZ or R3 is, for example, a non-aromatic hydrocarbon having 1 to 18 carbon atoms. residues, such as alkyl or cycloalkyl, furthermore exclusively aliphatic groups with 6 to 18 Aromatic residues with carbon atoms are suitable. In this case, the number of aromatic ring system parts is 10. It does not have many carbon atoms. 4 to 12 residues R2 or R1, especially 6 to 12 residues Particular preference is given to those containing 10 carbon atoms. Non-aromatic hydrocarbons in detail Examples of elementary residues include: alkyl, such as methyl, ethyl, etc. Noprovir, butyl, pentyl, hexyl, octyl, desole, do Denru, hexadenru, and octadecyl residues and carbon atoms Nocroalkyl, such as cyclopentyl, soclohexyl, ncroheptyl, Hydrogenated henzyl residues and methyl residues clobexyl residue); and aryl and arylmethyl having 6 to 10 carbon atoms However, the concept of aryl also includes alkylaryl in both cases. , having up to 3 substituents as described in R2 and up to 14 carbon atoms including these It has elementary atoms.

When one of the residues R2 or R3 means an alkyl residue, the number of carbon atoms is 4 to 10 tertiary alkyl groups, such as tert-butyl, 2-methyl-2-butyl, 2-methyl Particular preference is given to 2-pentyl, 2-ethyl-2-butyl. another particularly advantageous The compound is such that R2 or R3 is phenyl, benzyl, α-merylbenzyl and α , α-dimethylbenzyl.

R4 and R5 are, for example, the residues mentioned for R'', meaning alkyl In some cases, alkyl radicals having 1 to 12 carbon atoms are particularly preferred.

R' and R5 are oxa- or thiaalkyl having 2 to 21 carbon atoms; , such as methoxymethyl, methylthiamethyl, ethoxymethyl, methylthiaethyl or ethoxyethyl. In particular, alkoxypropyl and alkoxypyl lopyl groups, such as methoxypropyl, ethylthiapropyl, butoxypropyl, Octylthiaprovil, dodecyloxyprovil, octadecylthiapropyl or or octadecyloxypropyl is preferred.

R4 and R5 are alkenyl having 3 to 18 carbon atoms, such as allyl and meta-alkenyl. Lyle, n-hexen-3-yl, n-octen-4-yl, n-undecen-1 O-yl or n-octadecen-17-yl. Allyls and meta-alleles is particularly advantageous.

R4 and R8 are alkynyl having 3 to 18 carbon atoms, such as propargyl, n-butyn-1-yl, n-butyn-2-yl or n-bequinon-l-yl be. 6R4 Alkynyl radicals having 3 to 6 carbon atoms, especially propargyl, are preferred and R5, together with the nitrogen atom to which they are bonded, represent birrolidine-, oxazolidine- Zine, piperidine, morpholine, hexamethyleneimine or piperazine When forming ring rings, these heterocycles contain 1 to 5 members, preferably up to 2 members. It may also be substituted with thyl or ethyl groups. Particularly advantageous are unsubstituted ring systems. It is.

When R4 or Rs is a piperidin-4-yl group, unsubstituted piperidin-4-yl group or piperidine is substituted with up to 5 alkyl groups. You can stay there. 2. 2. 6. 6-tetramethylbiperidin-4-yl residue is Particularly advantageous.

The object of the present invention is that in formula (1), R1 is a monovalent residue, in addition to the above-mentioned meaning. substituted with phenyl and 1 to 3 non-aromatic hydrocarbon residues having 1 to 8 carbon atoms. phenyl and non-aromatic hydrocarbon residues having 1 to 18 carbon atoms, especially carbon atoms may be alkyl of 1 to 1 days and R'', R3, R' and R5 are as defined above. In the method of producing phosphonamidites, the first step is to Rogenide R' (-X), (wherein R' has the above meaning and n is 1 or 2 and X is a halogen atom with an atomic weight of at least 35). By reacting with very fine magnesium under Grignard conditions, the corresponding Grignard compound R' (MgX), which is then further converted into formula (II) λ in a second step. 2 [wherein R1, R', R' and R5 have the above meanings and X is a chlorine atom or or a bromine atom. ] Phosphonamidine 1 is obtained by reacting with an aryl-halophosphoramidite represented by -(1) is also a distribution method. In the method of the present invention, R1 is e.g.) lylu, dimethylphenyl, trimethylphenyl or tertiary butyl It can also be used for the reaction of compounds of the formula R' (MgX), which are ruphenyl residues. Can be done.

Regarding economical applicability, among compounds (II), those in which X is a chlorine atom are particularly It is advantageous for

The first step of the process of the invention, which can be carried out in any customary manner, consists in preparing an aprotic Organic solvents, such as ethers such as diethyl, dipropyl or diisopropyl Pyl ether, ethylene glycol dimethyl- or -ethyl ether, diethyl Ren glycol dimethyl- or -ethyl ether, methyl-nibutyl ether Particular preference is given to carrying out the reaction in dioxane, dioxane or tetrahydrofuran.

Grignard compounds are sensitive to hydrolysis and oxidation, so do not use them in a protective gas atmosphere. It is expedient to implement it. R2 However, such treatment is necessary for the reaction to be successful. It's not essential. Nitrogen and argon are particularly suitable as protective gases. .

The reaction temperature during the conversion to the Grignard compound is generally between 20 and 125°C, especially at 30°C. ~70°C. Applying ultrasound during this conversion to Grignard compounds is often advantageous.

In order to produce the final product (1), a solution of Grignard reagent or The suspension is preferably dissolved in an inert aprotic solvent, e.g. an aliphatic hydrocarbon fraction. , hexane, cyclohexane, toluene, xylene or one of the above-mentioned ethers halophosphoramidite (m) diluted with Arrange supply. The reaction temperature at this stage is generally -30°C to +50°C, especially -2 It is 0°C to +20°C. This reaction generally proceeds exothermically and therefore the reaction process It may be expedient to control this by cooling. The most favorable result is that the reaction components The chemistry of reactions! This is achieved when used according to the theory. However, the reactive components It is also possible to use an excess of. However, in general, this provides special benefits. Stir until the reaction is complete and then add the precipitated magnesium halide. It is advantageous to separate off the halides. The solvent is removed from the filtrate, generally advantageously by distillation. Therefore, it can be separated by distillation, especially under reduced pressure.

Organometallation, e.g. by reaction of halophosphoramidites with Grignard reagents. The synthesis of phosphoramidites by compounds is based on previously unknown claims. Amino groups and also ester groups bonded to phosphorus can be easily exchanged as is known ( Houben-Weyl, ,Methoden der organische n Chemie, Band 12/1.44 (1963) and El, 30 2 (+982)), so for the reaction between halophosphoramidite and Grignard reagent, side reactions proceed considerably which reduce the yield and thereby reduce the yield of the desired product. There is a clear bias that it should be considered that a reduction in the yield of existed in

Therefore, starting from the readily available halophosphoramidites, the substituted Any aryl-phosphonamidite can be prepared in high yield and purity by the method of the present invention. It's especially amazing what you can get in degrees.

The product (D can be obtained from the crude product by any method, but particularly preferably by crystallization) Can be separated.

The aryl-herophosphoramidifth symbol required as a starting compound is a chlorine atom, R2 is methyl, R″ is a hydrogen atom, and R4 and R5 are each A compound that is ethyl ([zv, A, kad, Nauk, 5SSR, Ser.

Khim, (9), pp. 213]-2133 (1968)) are new. and can likewise be easily produced by the method that is the subject of the invention. However However, these known compounds are of no industrial importance. These are especially It is not suitable as a raw material for stabilizers for

Moreover, the object of the present invention is a method for producing this compound (U), which has the formula (I[l ) is the aryl-dihalophosphinode represented by 2HNR' R5 ([V) in the presence of at least an equimolar amount of an acid binder, with the formulas ■ and ■ In , R'', R'-R' and R5 are described for the manufacturing method of compound (+). and X is a halogen atom with an atomic weight of at least 35. The above method is also characterized by the following. In this method, X is a chlorine atom and R2 is a methyl in which R is a hydrogen atom and R4 and R5 are each ethyl and the Since then, it has also included methods for producing compounds of formula (m) produced by other methods.

This method can be carried out in any conventional manner. In particular, inactive non-pro It is advantageous to carry out the process in a tonic solvent. For this method, hydrocarbons, e.g. Pentane, hexane, hebukun, benzene, luene, xylene, chloroben Zen and ethers such as diethyl, dipropyl, diisopropyl, Ethylene glycol dimethyl- or -ethyl ether is particularly suitable.

The preparation of the compound of formula (It) involves adding an equimolar amount of the amide to a solution of the dihalogenide (III). (■) and an equimolar amount of a base suitable as an acid binder, with vigorous mixing. Added. In this case, the temperature is generally -30 to +30°C, especially -20 to +10'C. give

Mixing takes place, for example, by stirring and is expediently carried out until the reaction is complete. The ammonium salt formed is then separated and removed. The solvent is extracted from the filtrate in the usual way. The separation can be carried out preferably by distillation, preferably under reduced pressure. leave

Bases which are preferably diluted with one of the abovementioned solvents include in particular tertiary amines. , such as triethylamine and pyridine. excess amine HNR4 R8 can also act as an acid binder.

The product (H) obtained by this operation is simply ready for reaction with the Grignard compound. generally occurs in a purity that is sufficient. Therefore, furthermore, e.g. vacuum- or thin-film evaporation Purification by distillation is generally not necessary.

A further object of the present invention is to use the compound of formula (1) alone or in combination with a phenolic antioxidant. In combination with synthetic resins, such as polycarbonates, in particular polymeric synthetic resins, such as polycarbonates, of formula (I) which is also used for stabilizing olefins, especially polypropylene. The compound is added to the synthetic resin in the molding material to improve its resistance to decomposition due to light, oxygen, and heat. gives added stability. However, for this application, the resulting crude reaction product Purity (85-93 χ according to P-NMR) is often sufficient. does not need to be isolated in pure form.

Therefore, the present invention provides thermoplastic or thermosetting synthetic resins and Ratio of (90 to 99.99): (0,01 to 10) It also relates to synthetic resin molding materials contained in

The synthetic resin molding composition according to the invention is a thermoplastic or thermosetting organic polymer, for example: Contains one of the following: 1, heptano and di-olefin polymers remers, such as high-, medium-, or low-density polyethylene (possibly cross-linked) ), polypropylene, polyisobutylene, poly-1-butene, poly Methyl-1-pentene, polyisobutylene or polybutadiene and cyclo- Refin polymers, such as cyclopentene or norbornene polymers.

Mixtures of the polymers mentioned under 2.1), e.g. polypropylene and polyethylene or mixtures with polyisobutylene.

3. Copolymers of mono- and di-olefins with each other or with other vinyl monomers -, for example ethylene-propylene copolymers, propylene-butene-1-copolymers Limer, propylene-isobutylene-copolymer, ethylene-butene-1-copolymer Limer, propylene-butadiene-copolymer, isobutylene-isoprene-copolymer Polymer, ethylene-alkyl acrylate copolymer, ethylene-alkyl methacrylate polymer, ethylene-vinyl acetate copolymer or Ethylene-acrylic acid-copolymers and their salts (ionomers), and ethylene Ren, propylene and dienes such as hexadiene, dicyclopentadiene or is a terpolymer with ethylidene norbornene.

4. Polystyrene.

5. Combination of styrene or α-methylstyrene and dienes or acrylic derivatives Copolymers such as styrene-butadiene, styrene-maleic anhydride, styrene -acrylonitrile, styrene-ethyl methacrylate, styrene-butadiene -ethyl acrylate, styrene-acrylonitrile-methyl acrylate) Copolymers of: styrene-copolymers and other polymers, e.g. polyacrylates , diene-polymer or ethylene-propylene-diene terpolymer. High impact blends with other polymers; as well as block copolymers of styrene, e.g. For example, styrene-butadiene-styrene, styrene-isoprene-styrene, styrene Ren-ethylene/butylene-styrene or styrene-ethylene/propylene- Styrene block copolymer.

6. Graft copolymers of styrene, such as polybutadiene and styrene. Styrene and acrylonitrile to ribtagene (ABS), polybutadiene styrene and maleic anhydride, and styrene and alkyl to polybutadiene. Acrylate or alkyl methacrylate to ethylene-propylene-diene terpolymer with styrene and acrylonitrile, polyalkyl acrylate styrene and acrylonitrile to polyalkyl methacrylate or polyalkyl methacrylate. Graphing styrene and acrylonitrile on acrylate-butadiene copolymer graft copolymers, and 5. With the copolymers listed in Mixtures, such as known ones such as ABS, MBS SASA or AES polymers .

7. Halogen-containing polymers such as polychloroprene, chlorinated bum, chlorinated or or chlorosulfonated polyethylene, shrimp chlorohydrin-homo- and mono- Copolymers, especially polymers made from halogen-containing vinyl compounds, e.g. polyvinyl chloride (pvc), polyvinylidene chloride (PVDC), ribinylfluoride, polyvinylidene fluoride (PVDC); These copolymers, such as vinyl chloride-vinylidene chloride, vinyl Chloride-vinyl acetate- or vinylidene chloride-vinyl acetate tocopolymer.

8. Polymers derived from α,β-unsaturated acids and their derivatives, e.g. Acrylates and polymethacrylates, polyacrylamides and polymethacrylates, Acrylonitrile.

Copolymers of the monomers listed under 9.8) with each other or with other unsaturated monomers , for example acrylonitrile-butadiene copolymer, acrylonitrile Kylacrylate copolymer, acrylonitrile alkoxy acrylate copolymer, acrylonitrile-vinyl halide-copolymer or acrylic Ronitrile-alkyl methacrylate-butadiene-terpolymer.

10. Unsaturated alcohols and amines or their acyl derivatives or aceters Polymers derived from polyvinyl alcohols, polyvinyl aceters, etc. Polyvinyl stearard, Polyvinyl benzoate, Polyvinyl maleate , polyvinyl butyral, polyallyl phthalate and bo-11 allyl, melami homopolymers and copolymers of specific cyclic ethers, such as polyethylene Recalls, polyethylene oxide, polypropylene oxide or the like and bisgrindyl ether.

12. Polyacecules, such as polyoxymethylene and also comonomers, For example, polyoxymethylenes containing ethylene oxide.

13. Polyphenylene oxide and polyphenylene sulfide.

14. Polyether, polyester and polybutadiene with terminal hydroxyl groups are combined into one Polyurethane on the one hand and an aliphatic or aromatic polyisocyanate on the other hand compounds and their precursors (polyisocyanate-polyol-brepolymer).

15, from diamines and dicarboxylic acids and/or aminocarboxylic acids or Polyamides and copolyamides derived from the corresponding lactams, e.g. Mido-4, Polyamide-6, Polyamide-6/6, Polyamide-6/]0, Polyamide Amide-11, polyamide-12, poly-2,4,4-)limethylhexamethylene -m-terephthalamide, poly-m-phenylene-isophthalamide, and and polyethers, such as polyethylene glycol, polypropylene glycol or a copolymer with polytetramethyllene-glycol.

16. Polyureas, polyimides and polyamide-imides.

17. From dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, e.g. polyethylene- Terephthalate, polybutylene terephthalate, poly-1,4-dimethylol Cyclohexane terephthalate, poly(2,2-bis(4-hydroxy-phthalate) phenyl)-propane) terephthalate, polyhydroxybenzoate and Derived from polyethylene, dialcohols and dicarboxylic acids with terminal hydroxyl groups Block-polyether-ester.

18, polycarbonate (pc).

19. Polysulfones and polyethersulfones.

20, an aldehyde on one side and a phenol, urea or melamine on the other. cross-linked polymers derived as methods, such as phenol-formaldehyde trees. fats, urea-formaldehyde resins and melamine-formaldehyde resins.

21. Drying alkyd resin and non-drying alkyd resin.

22. Copolyesters of saturated and unsaturated dicarboxylic acids and polyhydric alcohols and unsaturated polyester resins derived from vinyl compounds as crosslinking agents and Also halogen-containing flame-retardant modified products.

23. Crosslinkable acrylic resins derived from substituted acrylic esters, e.g. e.g. epoxy acrylate, urethane-acrylate or polyester acrylate A crosslinkable acrylic resin derived from a resin.

24. Crosslinked with melamine resin, urea resin, polyisocyanate or epoxy resin alkyd resins, polyester resins and acrylate resins.

25, crosslinked epoxy resins derived from polyepoxides, e.g. Crosslinked resins derived from cidyl ethers or cycloaliphatic dieboxides.

26. Natural polymers such as cellulose, natural rubber, gelatin and their like Chemically similar derivatives of chemically converted polymers, e.g. Cetates, -propionates, and -butycetes and cellulose acetate esters, such as methylcellulose.

27. Mixtures of the above polymers, e.g. P P/E P DM, polyamide-6 /EPDMt or ABS, PVC/ABS, PVC/MBS, PC/ABS, P BTP/ABS, PC/ASA-PC/PBT, PVC/CPE, PVD/7ri IJ rate, POM/thermoplastic PUR, POM/acrylate, POM/MBS , PPE/HI PS, PPE/Polyamide-6,6 and copolymer, P A /HD PE, PA/PP, PA/PPE.

28. Naturally occurring organic substances that are pure monomers or monomer mixtures and Synthetic organic substances, such as mineral oils, animal and vegetable fats, waxes, or or oils, fats and waxes based on synthetic esters or these substances. blend.

29. Aqueous dispersions of natural or synthetic rubbers.

Among these polymers, polyolefins, especially polypropylene, are particularly preferred.

The proportion of polymer in the molding material of the invention is from 90 to 99.99, in particular from 98 to 99.98. Weight%.

The molding compound contains two (+) aryl-phosphonamidites and, in some cases, as a stabilizer. Therefore, it contains phenolic antioxidants.

Phenolic antioxidants include, for example, formula (V) [wherein m is 1 or 2]. R' means an alkyl residue having 1 to 12 carbon atoms when m=1; When =2, it is an alkylene residue having 1 to 12 carbon atoms. ] 3,3-bis-(3′-tert-butyl-4′-hydroxyphenyl)- Contains butanoic acid. R" is an alkylene residue having 2 to 4 carbon atoms, especially 2 carbon atoms is preferably an alkylene residue.

However, phenolic antioxidants are β-(3゜5-di Even if it is an ester of tert-butyl-4-hydroxyphenyl)-propionic acid Frequently, the alcohol component is monovalent and / or polyhydric, especially monohydric to pentahydric alcohols, such as methanol, diethylene glycol Recall, octadecanol, triethylene glycol, 1,6-hexanedio alcohol, pentaerythritol, neopentyl glycol, tris-hydroxyethyl di-isocyanurate, thiodiethylene glycol, di-hydroxyethyl-ol There is xalic acid diamide.

The novel stabilizers are incorporated into organic polymers in a generally conventional manner. This contamination is , for example by adding stabilizers before or during polymerization, polycondensation or polyaddition reactions. Therefore, this compound and possibly other additives may be added before or during molding. This can be done by mixing it into the melt. Dissolved or dispersed directly or by applying the compound to the polymer, or in a solution of the polymer, mixing with the suspension or emulsion and optionally then evaporating the solvent It can be carried out by The amount that should be added to the polymer is the amount that should be stabilized. 0.01 to 10, especially 0.025 to 5, especially 0.05 to 1.0 weight based on quality The amount is %.

The novel compounds can be prepared by adding these compounds to a concentration of, for example, 1 to 50, in particular 2.5 to 20, 1z It may be added to the polymer to be stabilized in the form of a masterbatch containing .

Furthermore, the molding material of the present invention may contain other antioxidants: 1. monophenols such as 2,6-di-tert-butyl-4-methylphenol , 2-tert-butyl-4,6-dimethylphenol, 2,5-di-tert-butyl-4 -ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2 ．． 6-di-tert-butyl-4-i-butylphenol, 2,6-di-cyclobenzene -4-methylphenol, 2-(α-methylcyclohexyl)-4,6-cyme Tylphenol, 2.6-di-octadecyl-4-methylphenol, 2.4. 6-) Dicyclohexylphenol, 2,6-di-tert-butyl-4-methoxy Methylphenol.

2. Alkylated hydroquinones, such as 2,6-di-tert-butyl-4-meth xyphenol, 2.5-di-tertiary butyl-hydroquinone, 2.5-di-tertiary Amyl-hydroquinone, 2,6-diphenyl-4-octadecyloxypheno Rules.

3. Hydroxylated thiodiphenyl ethers, e.g. 2,2'-thio- Bis-(6-tert-butyl-4-methylphenol), 2.2゛-thio-bis-( 4-octylphenol), 4.4°-thio-bis-(6-tert-butyl-3-methyl methylphenol), 4.4″-thio-bis-(6-tert-butyl-2-methylphenol) Nord).

4. Alkylidene-bisphenols, such as 2.2"-tyrene-bis-(6 -tert-butyl-4-methylphenol), 2,2'-methylene-bis-(6-tert-butyl-4-methylphenol), 3-butyl-4-ethylphenol), 2.2"-methylene-bis-[4-methyl -6-(α-methylcyclohexyl)-phenol.

2.2'-methylene-bis-(4-methyl-6-cyclohexylphenol), 2.2"-methylene-bis-(6-nonyl-4-methylphenol), 2.2' -methylene-bissube4.6-di-tert-butylphenol), 2.2'-tylide nbis=(4,6-di-tert-butylphenol), 2.2°-tylidenebis =(6-tert-butyl-4-isobutylphenol)), 2,2'-methylene- bis-(6-(α-methylhensyl)-4-nonylphenol), 2.2'-methylene-bis-(6-(α,α-dimethylbenzyl)-4-nonyl phenol], 4.4"-methylene-bis-(2,6-di-tert-butylphenol), 4.4" -methylene-bis-(6-tert-butyl-2-methylphenol), 1,1-his -(5-inickel-4-hydroxy-2-methylphenyl)-butane, 2.6-di(34-tributyl-5-methyl-2-hydroxybenzyl)-4=meth tilphenol, 1, 1. 3-tris-(5-tert-butyl-4-hydroxy-2-methylphenylene) nil)-butane, 1.1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3 -n-dodenlumerkabutane, Di(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopene Tagen, Di[2-(3'-tert-butyl-2"-hydroxy-5°-methylbenzyl) -6-tert-butyl-4-methylphenyl]-terephthalate.

5. Benzyl compounds, e.g. 1, 3. 5-4 lis-(3,5-di-tert-butyl-4-hydroxybenzyl )-2,4,6-1-dimethylbenzene, di(3,5-di-tert-butyl-4- Hydroxyhensyl)-sulfide, isooctyl-3,5-di-tert-butyl- 4-hydroxybenzyl-mercaptoacetate, Bis-(4-tert-butyl-3-hydroxy-2,6-dimethylhensyl)-dithi All-terephthalate, 1.3.5-4lis=(3,5-di-tert-butyl-4-hydroxybenzyl)- isocyanurate, 1, 3. 5-1-Lis-(4-tert-butyl-3-hydroxy-2,6-dime chirhensyl)-isocyanurate, Dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzyl-phosphona tort, Mono-ethyl-3,5-di-tert-butyl-4-hydroxybenzyl-phosphoner calcium salts.

6. Acylaminophenols, such as 4-hydroxy-lauranilide, 4-hydroxy stearanilide, 2.4-bis-octamercap! --6-(3,5-di-tert-butyl-4-hydro loxianilino)-s-1-lyazine, octyl-N-(3,5-di-tert-butyl (4-hydroxyphenyl)-hydralhamate.

7, β-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propyl dionic acids and monohydric or polyhydric alcohols, e.g. methanol, octadecanol , 1. 6-hexanediol, neopentyl glycol, thiodiethylene glycol Recall, diethyl glycol, triethylene glycol, penquelisol Toll, tris-hydroxyethyl-isocyanurate, di-hydroxyethyl Esters with ruoxamide etc.

8, β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propion Amides of acids, e.g. N, N'-di(3,5-di-tert-butyl-4-hydroxyphenylpropio) nyl)-hexamethylene diamine, N, N'-di(3,5-di-tert-butyl-4-hydroxyphenylpropio) nil)-trimethylenediamine, N, N'-di(3,5-di-tert-butyl-4-droxyphenylpropio) )-hydrazine.

Furthermore, the molding composition according to the invention may contain further additives, such as: ): 14 Ultraviolet absorber and light stabilizer 1.1 2-(2”-hydroxyphenyl)-benzotriazoles, e.g. 5 '-Methyl-13°, 5'-di-tert-butyl-15°-tert-butyl-15'-( 1,1,3,3-tetramethylbutyl)-15-chloro-3',5'-di-tertiary Butyl-25-chloro-3″-tert-butyl-5°-methyl-53″-sec-butyl -5°-tert-butyl-14"-octoxy-13',5"-G tertiary amyl- 23',5'-bis-(α1α-dimethylhensyl) derivative.

1.22-Hydroquinobenzophenones, such as 4-hydroxo-14-methoxy Nor-14-octoxy-24-decyloxy, 4-dodecyloxo-14-be ndyloxy, 4,2°, 4'-1-lihydroxy, 2°-hydroxy-4 , 4'-dimethokino derivative.

1.3 Optionally substituted esters of benzoic acid, e.g. 4-tert-butyl- Phenyl-saltylar 1, phenyl-saltylate, octylphenylusal tyrate, di-\nzoylresorcinol, bis-(4-tert-butylhenduyl) )-resorcinol, benzoylresorcinol, 2.4-di-tert-butylphene Nyl-3,5=tert-butyl-4-hydroxy-benzoate, hexadecyl-3 , 5-di-tert-butyl-4-hydroxybenzoate.

1.4 Acrylates, e.g. Ethyl-α-cyano-β, β-diphenylacrylate and isooctyl-α -cyano-β, β-diphenylacrylate, ethyl-α-carpomethoxy annamate, methyl-α-cysoano-β-methyl-p-methoxycinnamate and and butyl-α-cyano-β-methyl-p-methoxyphenol, methyl=α=ka Rubomethoxy p-methoxycinnamate and N-(β-carbomethoxy-β- Cyano-vinyl)-2-methyl-indoline.

1.5 Nickel compounds, e.g. 2.2'-thio-bis-[t-(1,1,3,3-tetramethyl-butyl)-ph Nickel complex salts of phenols, e.g. optionally with additional ligands, e.g. Thylamine, triethanolamine or N-cyclohexyl-jethanol tit- or 1:2-tit salts with amines, alkylnickel-dithiocarba mates, monoalkyl-4-hydroxy-3,5-di-tert-butyl-benzyl nickel salts of phosphonates, such as those of the methyl- or ethyl esters; Nickel complex salts of ketooximes, e.g. 2-hydroxy-4-methylphenyl- those of undecyl-ketoocytum, 1-phenyl-4-lauroyl-5-hydro; Nickel complex salts of roxypyrazole, optionally with additional ligands and 2 - Nickel salts of human'roxy 4-alkoxybenzophenones.

1.6 Sterically hindered amines, e.g. 1.6.1 bis-(2,2,6,6-tetramethylbiveridyl)-sebacate, bis-(+, 2. 2. 6. 6-pentamethylpiperidyl)-sebacate, Bis=(2,2,6,6-tetramethylbibelinol)-glutarate, bis-( 1,2,2,6,6-pentamethylpiperidyl)-glutarate bis-(2,2 ,6,6-tetramethylbiperidyl)-sufucina-1.,bis-(1,2,2, 6,6-pentamethylpiperidyl)-sufucina-1.,4-stearyloxy- 2,2,6,6-tetramethylbiveridine, 4-stearyloxy-1,2,2 , 6,6-pentamethylpiperidine, 4-stearoyloxy-2,2,6,6 -tetramethylbiveridine, 4-stearoyloxy-1,2,2,6,6- Pentamethylpiperidine, 2, 2. 6. 6-titramethylpiveridyl-be Henart, 1, 2. 2. 6. 6-hentamethyl biperidyl behenate , 2, 2. 4. 4-tetramethyl-7-oxa-3,20-diazadisbi rho(5,1,11,2)-heneicosan-21-one, 2, 2. 3.　 4. 4-pentamethyl-7-oxa-3,20-diazadisbillow 5. 1. 11. 2')-heneicosan-21-one, 2, 2. 4. 4-Tet lamethyl-3-acetyl-7-oxa-3,20-diazadisbirow C5,1, 11,2)-heneicosan-21-one, 2, 2. 4. 4-tetramethy -7-oxa-3,20-diaza-20-(β-lauryloxycarbonyl edi )-2''-oxa-disbilow (5,1゜11.2)-heneicosane, 2, 2. 3. 4. 4-pentamethyl-7-oxa-3,20-diaza- 20-(β-lauryloxylponylethyl)-21-oxa-dispiro~[5 ゜1, 11.2) - Heneikosan, 2, 2. 4. 4-tetramethyl-3-7cetyl-7-oxer 3.20- Diaza-20-(β-laurylquinocarponylethyl)-21-oxa disbi Rho (5,1,H,2)-heneikosan, 1.1", 3. 3', 5. 5 '-hexahydro-2,2'', 4.4'', 6.6°-to, hexaaza-2,2°, 6. 6'-bismethano-7,8-dioki-4゜4゛-bis-(1,2,2 ,6,6-pentamethyl-4-piperidyl)-biphenyl, N, N", N", N1-tetrakis-(2,4-bis, -CN-(2,2,5 ゜6-Tetramethyl-4-piperidyl)-butylamino)-1,3,5-)ria Zin-6=yl l-47-diazadecane-1,10-diamine, N, N', N ゝ,N″゛-tetrakis-(2,4-bis-(N-(1,2,2゜6.6-pen) tamethyl-4-piperidyl)-butylamino]-1,3,5-triazine-6 -yl14.7-cyazadecane-1. io-diamine, N, N’, N”, N″° -Tetrakis-C2,4-bis-! N-(2,2,6゜6-tetramethyl-4- piperidyl)-methoxypropylamino]-1,3゜5-triazin-6-yl l-4,7-cyazadecane-1,10-diamine, N, N', N'', N''-te Trakis-(2,4-bis-[N-(1,2,2゜6.6-bentamethyl-4- piperidyl)-methoxypropylamino]-1゜3.5-)riazin-6-yl )-4,7-cyazadecane-1,10-diamine, Bis~(1,2,2,6,6-pentamethylpiperidyl)-n-butyl-3゜5 -di-tert-butyl-4-hydroxybenzyl-malonate, tris-(2,2, 6,6-tetramethyl-4-piperidyl)-nitrilotriacetate, Tetrakis-(2,2,6,6-tetramethyl-4-piperidyl-1,2゜3 ．． 4-butanetetracarboxylic acid, 1.1°-(1,2-ethanediyl)-bis-(3,3,5,5-tetramethyl - piperazinone).

1.6.2. Poly N, N'-bis-(2,2,6,6-tetramethyl-4- piperidyl)-1,8-diazadecane, 1-(2-hydrogynethyl)-2,2,6,6-tetramethyl-4-hydro Condensation product of xy-piperidine and succinic acid, N,N'-bis-(2,2,6, 6-Tetramethyl-4-piperidyl)-hexamethylenediamine and 4-tertiary octane Condensation product of thylamino-2,6-dichloro-1,3,5-triazine 7, N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-hexa Methylenediamine and 4-morpholino-2,6-dichloro-1,3,5-)riazi condensation product with

In many cases, a compound of the invention and 1. 6. The combination with the compounds listed in 1. Particularly advantageous.

1.7 Oxalamides, e.g. 4.4"-di-octyloxy-oxanilide, 2,2"-di-octyloxy C-5,5'-di-tert-butyl-oxanilide, 2,2'-didodecyloxy- 5,5°-di-tert-butyl-oxanilide, 2-ethoxy-2′-ethyl-oxanilide Sanilide, N,N″-bis-(3-dimethylaminopropyl)-oxamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its combination with 2-ethyl oxanilide mixture with toxy-2°-ethyl-5,4-di-tert-butyl-oxanilide, or Mixtures of tho- and para-methoxy substituted oxanilides and. - and p -Mixture of ethoxy-disubstituted oxanilides.

2. Metal deactivators, e.g. N,N'-diphenyloxalamide, hesa r) nariru N"-zarytyloyl -Hydrazine, N, N"-bis-salicyloyl-hydrazine, N, N"-bis -(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydra Zine, 3-salicyloyl-amino-1,2,3-1 lyazole, bis-benzyly zono oxalic acid dihi;'・5 sites.

3. Phosphites and bosphoninotes, such as triphenyl-phosphites , diphenyl-alkyl-phosphite, phenyl-dialkylphosphinode, trisnonylphenyl-phosphinode, trilauryl-phosphite, trioc Tadecyl phosphite, distearyl pentaerythrityl diphosphinot , tris-(2,4-di-tert-butylphenyl)phosphite, diisodecyl- Pentaerythrityl-diphosphinto, bis-(2,4-di-tert-butylphenyl) ) Pentaerythrityl diphosphite, tristearyl sol phosphate Lisphosphindo, tetrakis-(2,4-di-tert-butylphenyl)-4,4 “-biphenylene-diphosphonitrate, 3.9-bis-(2,4-di-tert-butyl phenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro( 5,5)-undecane, tris-(2-tert-butyl-4-thio-(2”-methenyl) -4°-hydroxy-5'-tert-butyl)-phenyl-5-methenyl)-phenyl Nyl-phosphinide.

4. Peroxide decomposers, e.g. Esters of β-thio-dipropionic acid, such as lauryl, stearyl, mi Listyl- or tridecyl-esters, mercaptobenzimidazole, 2 - Zinc salts of mercaptobenzimidazole, alkylzinc-dithiocarbamates , dioctadecyl sulfide, pentaerythritol tetrakis (β- dodecyl mercapto)-propionate.

5. Basic co-stabilizers, e.g. Melamine, polyvinylpyrrolidone, dicyandiamine, triallyl-cyanuride , urea derivatives, hydrazine derivatives, amines, polyamines, polyurethanes , alkali metal and alkaline earth metal salts of higher fatty acids, or phenolates such as calcium stearate, zinc stearate, magnesium stearate. um, sodium ricinoleate, potassium palmitate, antimony-virocate cholate or tin-bilocatecholate, alkaline earth metal or aluminum hydroxides and oxides such as CaOlMgO, Zn0°6, nucleating agents such as 4-tertiary butenzoic acid, adipic acid, diphenylacetic acid, sobenzilic acid Rubitol.

γ, fillers and reinforcing agents, e.g. Calcium carbonate, silicate, glass fiber, Ashes 1-, talc, kaolin, mi mosquito, barium sulfate, metal oxides and monohydroxides, carbon black, grapha It.

8. Other additives, e.g. Plasticizers, lubricants, emulsifiers, pigments, optical brighteners, flame retardants, antistatic agents, blowing agents.

Various additional additives within groups 1 to 6 above may be added to the polymer to be stabilized. An amount of 0.01 to 10% by weight, in particular 0.01 to 5% by weight, based on the total weight of the material. Add with The amount of additives in groups 7 and 8 is 1% based on the total amount of molding material. ~80% by weight, especially 10-50% by weight.

The organic polymers stabilized according to the invention can be used in various forms, e.g. films, fibers. , as tapes, profiles or as a binder for paints, adhesives or plasters. can be used.

Before the examples illustrating the invention, the preparation of the starting compound (I[[), some of which is known, will be described. Explain the law. If these compounds are not yet known, they may be Similarly to the compound, it can be easily produced from PXz (X=CLBr) and the corresponding phenol. Can be built. Phenols and amines used as starting materials HNR' R' (TV) are mostly known compounds. If not, it can be manufactured using the same method. Wear.

TIU's aryl-dichlorophosphine 11. and 650 mmol (=89.3 g) of phosphorus chloride (I[[ ), a spatula tip amount (about 100 mg) of p-dimethylaminopyridine, and 500 mmol of the corresponding phenols are combined. Cool this solution and Starts generating HCl. For 60 to 90 minutes, slowly boil for 90 to 90 minutes while stirring vigorously. Heat to 100°C and keep the mixture at this temperature for 2 hours until the reaction is complete. Ru.

The low-boiling components are then distilled off at 50° C. under reduced pressure with a water pump. arylji The content of chlorophosphite was measured by 31P-NMR-spectroscopy. Established. It was generally 70-92χ.

Health, Earth Niji 3-butyl phenyl-dichlorophosph: 91.7χ ("P- NMR: δCDCl, = 184.7 ppm: crude product containing the title compound 129 g of a yellowish oil with a boiling point of 104-105 °C and 10.05 mbar were distilled from can get.

C,,H,,CI□OP Calculated value: 54.13″1C16,89χH510,0 8χP(307,20)ile fixed straight: 54.9χC16,7’LH,10,2 ZPB 2-Tributyl phenyl dichlorophosphite Tomy 84″1 [Co’ P-NMR: δCDClff-185, 1 ppm) Distillation of the product yielded 94 g of a colorless oil with a boiling point of 74-76°C10, O1 mbar. can get.

C,,H,,CI 20P Calculated value: 47.83χC15,21ZH,12,3 3χP(251,09) Measured value: 47.4ZC25,1XH112,0ZPC 24-dimethylphenyl-dichlorophon 374-1-nia 5χ [Co-NMR: Distillation of the crude product containing the title compound of δCDC1, = 180.9 ppm) 72 g of a colorless oil with a boiling point of 58-60 DEG C. and 10.05 mbar are obtained.

C, H,'c L OP Calculated value: 43.08χC14,06χH,13,88 χP(223,03) Measured value: 42.7 IC13,9χH113,6χPD 2-Tributyl-4-methoxyphenyl-dichlorophosphite: Crude product Distillation yields 110 g of a colorless oil with a boiling point of 108-110 °C and 10,05 mbar. It will be done.

C,,H,, CIt　ox　P calculation value: 46.99χC15, 37χH, 11, 01χP(281,11) Measured value: 46. 7 IC, 5, 5XH, 10, 7 ZPE 24-dinibutylphenyl-dichlorophosphite: 71χ (”P -NMR: Crude product containing the title compound of δCDCIz-182,3ppm) Distillation of gives 93 g of a colorless oil with a boiling point of 108° C. 10.05 mbar.

C,,H! Ic1. OP calculated value: 54.73XC, 6,89$H, 10,08 χP(307,20) Measured value 754.5’1C16,1’tH110,0XP F　2-　nibutylphenyl-dichlorophosphite:78χ　[Go'P-NM Distillation of the crude product containing the title compound of R: δCDCl5-182.3 ppm) This gives 83 g of a colorless oil with a boiling point of 92 DEG -93 DEG C. and 10.1 mbar.

C1゜H,, C1, OP Calculation Direct: 41.83χ C15,2lχ　H,12 , 33χ P(251,09) Measured value: 41.4 IC14, 9χH112, 0χPH1-12-arylk tetralophosphoramidine I! General for mold manufacturing target prescription Dissolve 500 mmol of aryl-dichlorophosphite in 400 ml of toluene. 500 mmo+ of amine H was added to a solution stirred in a nitrogen atmosphere at -10°C. NR' R' and 500 mmo I (=50.6 g) of triethylamine was dissolved in 100 ml of toluene for 30 to 40 minutes until the internal temperature reached O' C was metered in such a way that it did not exceed After-stir at warm temperature. Crude chloroamidite after filtration and distillation of the solvent under reduced pressure generally remains as a yellow oil. For further reaction with Grignard reagent, Generally, no further purification is necessary.

J124-di-tributylphenyl-chlorophosphine-morpholide: 153, 6 g of 2,4-di-tert-butylphenyl-dichlorophosphite and 43,6 g starting from morpholine with a melting point of about 70"C and 94χ [31P- NMR: 165 with the title compound purity of δCDCIs = 156.9 ppm) g of a colorless solid was obtained.

C. , H. , CINO□P Calculated values: 60.41χC, 8,17χH, 8.65 χP (357.86) Measured value: SO. 1 IC, 8.4 XH, 8,3 χP 2 2 4-Di-3-butyl phenyl-chlorophosphite-d-n-butyl amide Upper two 153, 6 g of 2,4-di-butylphenyl-dichlorophosphite and 6 4. Starting from 62 g of di-n-butylamine, 94χ [”P’-NMR : δCDCIff = 162.3 ppm) with a purity of about 190 g of yellow oil was obtained.

CtxHs*C I No P Calculation i: 66, osx c, 9, R 2’t H. ,7. 74X P (399.99) Measured value: 66.42C, 9 ．． 6ZH, 7.7$P2- 3-butyl phenyl with a strong odor. Ch'tylamide: 125, 54 g of 2-tert-butylphenyl-dichlorophosphine and 64,62 g of di-n-butylamine, 89χ (“P -NMR: δCDCli=16]. 1 with a purity of the above compound (8 ppm) 65 g of yellow oil were obtained.

C. , H3. CINOP (343.87) λ1 22 tert-butylphenyl -Chlorophosphinotopiveridide: -153, 6g of 2,4-di-tert-butylph Starting from phenyl-dichlorophosphite and 42,57 g of piperidine, 88χ ("P-NMR: δCDCI.

Approximately 170 g of a yellow oil was obtained with a purity of the above compound of = 157.7 ppm). Ta.

C,, H,, CINOP (355.89) 5 2 4-di 3-butylphenyl -Chlorophosphinodo-N--r3nia'-)/Lz7壬冱eni 153, 6 g of 2,4-di-tert-butylphenyl-dichlorophosphite and 7 Starting from 4.6 g of N-n-butylaniline, 89χ ("P-NMR: Approximately 200 g of yellow with a purity of the above compound of δCDCI+-156.6 ppm) of oil was obtained.

Cz4HzsCINOP (419.97)6 2 4-di 3-butylphenyl -N2 153, 6 g of 2,4-di-tert-butylphenyl-dichlorophosphite and 4 Starting from 9.58 g of hexamethyleneimine (also called homopiperidine) Wow, 87! l:”P-NMR: δCDCIs (sic) = 163.9 ppm ]+7) Approximately 1.76 g of yellow oil with the above compound purity was obtained.

C2. Hj. CINOP (369.91) engineered suede tertiary butylphenyl -Jishikdo plan' Jirukuro Himself Water Fire Ayuno l-Upwork 153, 6 g of 2,4-di-tert-butylphenyl-dichlorophosphite and 9 Starting from 0.65 g of dicyclohexylamine, the reaction was completed at 60"C, 84! ["P-NMR: δCDC1.-166, 0 ppm) of the above compound purity Approximately 205 g of yellow resin was obtained.

CthHayuClN0P (452,05) fllLJ tributyl-4: mexo Phenyl-chlorophosphite tomorpholide: 140.56 g of 2-tert-butyl -4-methoxyphenyl-dichlorophosphine and 43.6 g of morpholine Starting from about 152 g of colorless oil are obtained which solidifies at room temperature.

Cl5HzxCI NOzP Calculated value: 54.30χC16, 98χH19, 33χP (331,77) Measured value: 54.0”tC26,7ZH18,9XP 1st work soil 2nd nib 1st and Z enil black machimaru otto Z work upper 2nd todo length upper 2 153. 6 g of di-butylphenyl-dichlorophosphite and 43°6 g mole Starting from Hollin, 80χ ("P-NMR: δCDC1, = 159.8pp Approximately 160 g of yellow oil were obtained with a purity of the above compound of m).

C, IIH,, CI No□P (357,86) Engineering f112-To 2 2 Kaku 42 Wang Sanxi: rioo # Starting from phenyl-dichlorophosphite and 43.6 g of morpholine, The purity of 90χ ("P-NMR: δCDCI s = 160.7 ppm)" 120 g of yellow oil were obtained. Boiling point 148-150°C10,05mb by distillation A colorless oil of ar is obtained.

C1□H,, ClN0h P calculated value: 52.66χC16,26χH-11,3 ]χP(273,70) Measured value: 51. 9 XC, 5,9χH, 11,5X P1124-dimethylphenyl-chlorophosphin...11],52 g of 2,4-dimethylphenyl-dichlorophosphite and 42.6 g (7) Starting from biheridine, 892 ("P-NMR: δCDCl3-161. 121 g of yellow oil were obtained with a purity of the compound (3 ppm). boiled by distillation A colorless oil having a temperature of 134-135°C and 10,05 mbar is obtained.

C, H,, CI No. P Calculated value: 57.46χC17,04χH,11,3 9χP(271,72) Measurement value: 57.1 χC56, 9χH, 11°2 χ P224-dimethylphenyl-di-n-buty2v4o phosphoramidite = 1 2,4-dimethylphenyl-dichlorophosphite at 11.52 and 64.6 Starting from g of di-n-butylamine, 86χ ("P-NMR: δCDCL 143 g of a yellow oil were obtained with a purity of the above compound (=167.7 ppm).

Distillation gives a colorless oil with a boiling point of 148°C and 10.05 mbar.

C,, H2tCI　No　P　Calculated value: 60.84χC18, 61χH, 9,8 0IP (315,82) Measured value 260.5$C28,4zH19,9χPm~ 33-Aryluho to Maru Zen [1) Ti mouth] General manufacturing recipe A suitable Grignard compound is mixed with 250 mmol of an organic bromide compound and 250 mmol of an organic bromide compound. f (6° 1.g) of magnesium section in 170 ml of tetrahydrofuran. Produced under nitrogen cloud surroundings with exclusion of moisture. Of the organometallic compounds obtained? 8f! ! , or the suspension was then dissolved in 120 ml of tetrahydrofuran and the corresponding under vigorous stirring into a solution of 250 mmol of chlorophosphoramidite (II). 6. Place and feed for 30 to 40 minutes at an internal temperature of -20 to -10 °C. The reaction mixture was further stirred for 2.5 hours to complete the reaction. precipitated magnesium After filtration of the salt, the solvent is distilled first under reduced pressure in a water jet pump and then at high pressure. Distill under reduced pressure and pulverize the colorless or pale beige residue. Dry under pressure.

The content of the desired product in the crude material was determined by “P-NMR-spectroscopy. Ta. In the case of monophosphonamidites, it generally ranges from 80 (total P) to It is between 94χ. In the case of those listed, a crude mixture is used to characterize the product. The product was crystallized from an acetonitrile/acetone mixture.

”32゛　4″-di-tributylphenyl 2　4　6-drimethyl-1-2 王三 Raw earth sutomeyu l--hihe') site: 49.7 g of bromomesitylene and 89 ．． From 0 g of 2,4-di-tert-butylphenyl-chlorophosphite-piperidide Starting from about 1 with a softening point of about 80°C and with a purity of the compound of 86χ 08 g of a beige substance is obtained ('IP-NMR: δCDC1, -132 ,7ppm).

CzaH4zNOP Calculated value: 76.49zC, 9,632H, 7,042P (439, 62) Measured value near 6, OχC19, 5χH56, 7χP top Lr, Eny 2 tertiary butylphenyl 24.6-)suj length 4-1-fukojinoσ2 14 steps Nit-morpho-historical 49.7 g of bromomesitylene and 89.47 g of Starting from 2,4-di-tert-butylphenyl-chlorophosphinode-morpholide , about 110 with a melting point of 70-80 °C and a purity of the above compound of 902 g of colorless substance is obtained ("P-NMR: δCDC1, = 132.4 ppm) .

C,, H4゜NO2P Calculation Directly 73. 43′t C, 9, 13χ Hl 7.01χ P(441,60) Measured value near 3. l　χC19,5χH16 , 6χP15) 2 “Yo” Nini’; Lou 1 - Hue 7 Shao and 夾 5 9 nt morpholide: 49.7g bromomesitylene and 68.43g 2,4-dimethylphenyl - Starting from chlorophosphinode-morpholide with a softening point of 90-95°C Approximately 90 g of yellowish material is obtained with a purity of the compound of 91x. "P-NMR: δCDC1, = 135.1 ppm).

Cz+HzsNOzP Calculated value near 0.56XC17,89XH18,66X P(357,44) Measured value: 69.9 χC18, 1χH18, 2χPp2' ``Yu'' Ninny J1 = Tetenta Eo Jinshiba 1 Work'' Work 6-Tokime Lu 1-Phenyl Ho Sukhoni - Morpholide: 49.7 g of bromomesitylene and 89.46 g of 2,4-di-butylphenyl Starting from nyl-chlorophosphite-morpholide, the purity of the above compound of 86χ Approximately 108 g of yellowish oil with 34.3 and 135 P F m (diaswo rheomer)].

C,,H,. NO, P (441,60) 172゛ 4°-di-tributylpheny Le 1 work 45 days L1 spirit 2 years 2 times 5 days 49.7a 5-bromo-], 2. 4-) Limethylbenzene and 89.4 From 6 g of 2,4-di-tert-butylphenyl-chlorophosphine-morpholide Approximately 100 g of colorless resin with a purity of the above compound of 93χ is obtained. 31P-NMR: δCDCl, = 120.9 ppm), crystallized in acetonitrile Colorless crystals with a melting point of 130 to 132"C are obtained upon chemical treatment.

C27H4゜NO,P Calculated value +73.43χC59,13χH27,01χP (441,6) Measured value near 3.2 χC59, 4χH16, 8χPL Tsuji Y Mataji "-di-nibutyl-hue et al. 1-,, = 3rd-butyl-ru 17 jade master 49 stop 9 = tsu Tormorpholide: 53.5 g of p-bromo-tert-butylbenzene and 89.46 g of 2,4-di Starting from nibutylphenyl-phosphiso-1 (sic) morpholide, 85χ Approximately 110 g of colorless resin are obtained with a purity of the above compound ("P-NMR: δCDCl, = 126.3 ppm), acetonitrile/acetonitrile (1:1) Colorless crystals with a melting point of 106-108"C are obtained.

Upper l and λ22 male three butyl 4゛-methoxy 2 stop ball J1℃ (second; butyl-Z Tamashiri Suhonisotomorphorito 1 53.3 g p-bromo-tert-butylbenzene and 82.95 g 2-tert-butylbenzene Starting from thyl-4-methoxyphenyl-chlorophosphindo-morpholide, about 103 g having a softening point of about 70"C and a purity of the above compound of 82 χ A beige substance is obtained (P-NMR: δCDC13 = 126.7 ppm ), CzsHsaNOsP (429,54)202°4'-dinibutyl Phenyl-4-bisphenylphenyl-4-bisphenol 58.3 g of 4-bromobiphenyl and 89.46 g of 2,4-di-tert-butyl Starting from phenyl-chlorophosphite-morpholide, 88 of the above compounds Approximately 114 g of colorless material is obtained with purity ("P-NMR: δCDCl5 = 125.3 ppm), melting point of 124-125 °C after crystallization treatment with acetone colorless crystals are obtained.

C1゜H3,NO□P Calculated value near 5.76χC18,05χH,6,5+χP (475°61) Measurement (if; 75.9 χC18, 35χH, 6,3χP2 12° 4゛-diphenyl-4-methoxy-1 cuff ball 452 phosphoni , tone-n-butylamide: 46.75 g of 4-bromoanisole and 10 0 g of 2,4-di-tert-butylphenyl-chlorophosphite-di-n-butyl acetate Starting from the mido, about 110 g of yellow resin with a purity of the above compound of 90 (P-NMR: δCDCl, = 1.27.9 ppm).

C,,H4,NO,P　(471,67)iυ"Shu"2nijil壬○Paddy Ishiki Ze Kanji 1-Naphthylphosphoni, tomorpholide: 51.8 g of 1-bromonaphthalene and 89.46 g of 2,4-di-tert-butyl Starting from phenyl-chlorophosphine-morpholide, about 100-105°C about 112 g of a colorless substance having a softening point of and a purity of the above compound of 87 χ is obtained ("P-NMR: δCDCl3 = 120.8 ppm).

CzsH3sNOz　P Calculated value near 4.8XC28,07$H16,88$P (449,58) Measured value near 4.2ZC28, 1XH36, 4ZP] ,] 4゛-Schiff 3 Butylphenite Tuesday 2nd day 297 Chiruphosphoninotoni Heaven, Four, and Earth 1.8 g of 2-bromonaphthalene and 89.46 g of 2,4-di-tert-butyl Starting from phenyl-chlorophosphine-morpholide, a softening point of about 100°C Approximately 110 g of colorless material were obtained having a purity of 92× and a purity of the above compound of ("P-NMR: δCDCl, -125.0 ppm), 12 with acetonitrile Colorless crystals with a melting point of 0° C. are obtained.

CtsHxbNO□P Calculated value near 4.80χC, 8,07χH16, 88χP (449,58) Measured value near 4.5 χC28, 3ZH16, 9χP and soil L Nie' death two Gods day = butyl phenyl 1-naf nine fire two um Lord three first two to foundation l top knee 51,. 8 g of 1-bromonaphthalene and 89.46 g of 2,4-dibutylene Starting from ruphenyl-chlorophosphite-morpholide, 80χ (3'P -NMR: δCDC1, = 121.2 and 121.6 ppm (diastereomeric -)] Approximately 116 g of plastic resin having the above-mentioned compound purity is obtained.

C,,H,,NO□P　(449,58)252゛゛　4゛-dimethylph and triluni Earth: Phthyruphosphonye - 1-bromonaphthalene and 51.88 and 68.43 g of 2,4-dimethylphenyl-chlorophosphinodo-morpholide. Starting from Approximately 91 g of colorless material is obtained ("P-NMR: δCDC1t-121. 6ppm).

C2□)(,,NO□P Calculated value: 12.31χC16,62χH,8,47χ P (365, 41) Measured value near 1.9 χC26, 4χH28, l χP21 Σ-2H-, 4', -7n 2nd F] Nine-sho F'' Regular Uni 1± Roux 1-Length Tenka Y2 soil sulfoninotomorpholide: 55.27 g of 1-bromo-4-methylnaphthalene and 89.46 g of 2°4 Starting from -di-tert-butylphenyl-chlorophosphite-morpholide, about 9 Approximately 113 g of base having a softening point of 0°C and a purity of the above compound of 88χ A dichroic substance is obtained ("P-NMR: δCDClx = 121. 4P pm) - A colorless powder with a melting point of 110° C. is obtained in acetonitrile.

C,, H3, NO, P Calculated value near 5.13XC18,26! H16,68ZP (463,59) Measured value near 4.7 χC18, 0χH16, 5χP272゛ 4'-Di-3-butylphenyl--λ-, <-B so and two, LJ-Otori ni Suho Nittomorpholide: 55.3 g of 1-bromo-2-methylnaphthalene and 89. '2.4 of 46g - starting from di-tert-butylphenyl-chlorophosphite-morpholide, about 7 Approximately 108 g of almost pure substance having a softening point of 0°C and a purity of the above compound of 83χ A colored substance is obtained ("P-NMR: δCDCIz-131,8ppm1. Colorless needle-shaped crystals with a melting point of 115 DEG -118 DEG C. are obtained with tonitrile.

C,, H,, NO, P calculation (linear 5.13χ C, 8, 26χ Hl 6. 68χ P (463,59) Measured value near 5.6XC18,5XH26,3χP 51.8 g of 1-bromonaphthalene and 92.48 g of 2,4-di-tert-butyl Starting from phenyl-chlorophosphinedo-homopiperidide (see Example 6) , about 110 g of colorless plastic material are obtained with a purity of the above compound of 88z. 3 years P-NMR: δCDC1, = 122.9 ppm). Acetonitrile (+. :1) gives colorless crystals with a melting point of 112-113°C.

C. ,H,,NOP Calculated value near 8.05zC, 873χH, 6.70! P( 46]. 62) Measured value 71B. 2 χC, 8.5 χH, 6,5 χP29) 2"　Euni2tert-butylphenyl-6-methoxy-2p22tmi,=3,2 Shake 1 mi. Three oxen, Nijiro one □ and 12 = = - Te no Mishi guide Bini self 1 Me IJ□□J go -3=59, 3g of 2-bromo-6-medquinnaphthalene and 89.46g 2.

Derived from 4-di-tert-butylphenyl-phenyl-chlorophosphite-morpholide about 100 ml, having a softening point of about 45° C. and a purity of the compound of 94 χ. 7, (7) Colorless @lJ quality is obtained (P-NMR: δCDCI* = 125 ．． 7ppm].

C29H sIIN O, +P Calculated value near 2.62χC, 7.98χH , 6.45χP (479.60) Measured value near 2.2 χC, 8. 3 χH , 6, 1 Suhoni Tomorho 1: By changing the general prescription, 250 mmol (-78 g) of 4,4°-dibromobi 500 mmol (=12.2 g) of phenyl and 500 mmol of magnesium fragments ml of tetrahydrofuran under the action of ultrasound (40 kHz). 5 was converted to Nyar compound and dissolved in 200 ml of tetrahydrofuran. 00 mmol (-136.9 g) of 2,4-dimethylphenyl-chloro React with phosphonite. Approximately 150 g yellowish with a purity of the above compound of 63 m A colored plastic resin is obtained (P-NMR: δCDC1.=126.7 ppm) .

C36H4□N. O. P. (628.68) m vertical 1 C machining 1 branch 2 2nd; Butyl Fueni Street 2nd floor Fuenire Otsu Ward ± Suhonitto Morhoyu Kamijo By changing the general prescription, 250 mmol (=78 g) of 4,4' - Dibromohif. 2 Jlz to 500 mmol (=1 2.2 g) magnet Ultrasonic waves (40kHz) were applied in silium fragments and 500rr+1 tetrahydrofuran. to the Grignard compound and add 200 ml of tetrahydrogen. 19 g of 17E in Dorofuran react with t-morpholide. It has a softening point of 103-105 °C and 70 χ (“P-NMR: δCDCI.

Approximately 200 g of a yellowish powder was obtained with a purity of the above compound (-125.0 ppm). It will be done.

C,,H66N20,P. (797.00) 11 Le-kun Ichiro--Koujiji man; bu±15 yakuto and 2 4゛biphenylene 2 sulfoninoto)-n-butyl acetate By changing the general prescription, 250 mmol (-78 g) of 4 , 500 mmol (=12.2 g) of 4°-dibromobiphenyl Action of ultrasonic waves (40kHz) in 500ml of tetrahydrofuran with sium fragments 200 ml of tetrahydrofuric acid. 500m during the run. mol (=200g) of 2,4-dibutylphenyluk React with oral phosphoni, tozy n-butylamide. The above compound of 73′1 Approximately 210 g of yellow plastic resin with physical purity is obtained ("P-NMR: δC DC1. -126.9ppm).

Cs6HsiNz　Oz　Pt　(88　1.27) 1 Lord 9 for 3 times” Meng-J Ni Butilum! Ze and Y Uni King Niya Z 2 = 14-2 naninto world cry wataru""ko"- By changing the general prescription, 250 mmol (=58.97 g) of 1,4-dibro Mohenzen 600mm! (=14.6g) of Magneum fragments and 300 ml of tetrahydrofuran under the action of ultrasound (40 kHz). Converted to Niard compound and firstly diluted with 500 mm in 200 ml of tetrahydrofuran. ol (=178.9g) of 2,4-di-tert-butylphenyl-chlorophosphonite -React with morpholide. Approximately 170 g of almost colorless resin is obtained. acetone C''P-NMR: δC to obtain colorless crystals with a softening point of 230°C. DC I! = 124.6 ppm).

C. , H. ,N. O. P. Calculated values: 69.97XC, 8.66ZH, 8.59 ! P (720.90) Measured value: 69.52C, 8.9$H, 8.3XPM eight flights thoughts The aryl-phosphonamidine (1) of the present invention listed below is used in the experiment. ) 2°, 4°-di-tert-butylphenyl (2,4,6-)limethyl-1-phenylphenyl )-phosphonite-morpholide b) 2',4'-di-tert-butylphenyl (2,4,5-trimethyl-1-phenylphenyl) Nyl)-phosphonite-morpholide c) 2',4'-di-butylphenyl-4-bipheniJ rephosphonintomo Ruhorid d) 2°, 4°-di-butylphenyl-1-naphthylphosphonine tomol Horid e) 2',4'-di-tert-butylphenyl-1-naphthylphosphonite-homo Piperizide f) 2',4'-di-tert-butylphenyl-(5-methoxy-2-naphthyl) -phosphonite-morpholide g) Bis(2",4"-di-tert-butylphenyl)-phenylene-1,4-dipho sufonitomorpholide Implementation [4 and　''　A-C 100.0 parts by weight of unstabilized polypropylene powder (density: 0.903 g/cm3 ; melt flow index MF123015: 4 g/10 min) with acid acceptor. 0.1 part by weight of calcium stearate as Mix with the ingredients and use a laboratory extruder (Short Combridge Town Zone). Screw, screw diameter: 20mm, length = 20D, vertical length of nozzle J = 30mm, nozzle diameter: 2mm, rotation speed = 125 rotations/min, temperature program ram: 200/230/230°C). 1 time, 5 After extruding once and ten times, a sample of the granules is taken and DIN 53,735 Melt Flow Index according to and yellow according to ASTM D 1925-70 Used to measure yellowness as degree I. Furthermore, the granules extruded once were It was used to produce extruded plates with dimensions of 0x60x1mm and the yellowness was determined. Chini and Hot Storage II! (7 days at 100″C) before measurement.

The results are listed in Tables 1.2a and 2b.

35 and　″D-F 100.0 parts by weight of unstabilized polypropylene powder (density: 0.903 g/cm) ; melt flow index MF123015: 4 g/10 min) with acid acceptor. 0.1 parts by weight of calcium stearate and 0.05 parts by weight of ethylene. Glycol-bis(3,3-bis(3゛　-tert-butyl-4　-hydroxyph) phenyl)butylar L(sic) and the amount of phosphorus compound listed in the table. laboratory extruder (short compression zone screw, Nozzle diameter: 20mm, length: 20D, vertical length of nozzle: 30mm, nozzle diameter: 2mm, rotation speed: 125 rotations/min, temperature program: 200/23 0/230'C). 1, 5 and 10 extrusions After that, take a sample of the granules and check the melt flow according to DIN 5'3,735. Yellow as index and yellowness index according to ASTM D 1925-70 used to measure degrees. Furthermore, the granules extruded once are 60X60X+, mm used to manufacture extruded plates of dimensions and yellowness immediately and during hot storage. Measure after storage (7 days at 100°C).

The results are listed in Tables 3.4a and 4b.

Comparative Example A No additives 10.5+, 9.0 34. ．． 034b 1.0 1. O L3 34c 6.1 6.3 11.3 34d 5.4 5.5 6.0 34e 1.0 1.3 2.0 *) Tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene Diphosphoninoto Table 2a: Color change after granulating polypropylene multiple times (ASTM-D 192 yellowness index according to 5-70) Comparative Example A No additives 18.7 25°7 27.734b 2.5 2.6 2 ．． 7 34c 16.3 20.4 33.234d 14.5 15.0 18.8 34e 3.7 6.5 13.8 34f 6. ], 7.9 16. 134g 2.2 2.6 5.8 *) Tetrakis(2,4-di-tert-butylphenyl)-4,4°-biphenylenedi Yellowness index immediately after production Yellowness index after heat treatment (7 days at 100°C) Comparative example A 4.2 10.1 Comparative example B 3.4 13.0 Comparative example C4,512,5 Comparative Example D No additives 1.3.4 19.0 23.835b 5.4 5.4 7.9 35c 4.6 5.4 5.5 35d 4.6 5.9 7. 1 35e 5.8 5.9 5.5 35r5.8 7.38.4 35g 5.0 6.6 8.0 *) Tetrakis(2,4-di-tert-butylphenyl)-4,4°-biphenylenedi phosphonit Comparative Example D Additive-free 8.0 23.4 28.035b 11.1 9.4 1 2.9 35c 7.0 12.1 15.7 35d 10.4 23.4 31.335e 11.1 15.6 19.5 35f 12.1 20.9 26.635g 8.7 29.9 32.0 Book) Tetrakis(2,4-di-tert-butylphenyl)-4,4°-biphenylene Yellowness index immediately after production Yellowness index after heat treatment (7 days at 100°C) Comparative example D 3. 9 7. 7 Comparative example E 2. 3 5. 0 Comparative example F 2. 8 4. 5 35a 1,8 11.2 35b 2.7 3.0 35c 2.3 2.8 35d 3. 5 4. 2 35e 2.9 4.5 34M 3.9 6.3 35g 2.7 2.9 Quiet inspection report international search report PCT/EP 90101361 S^　39259 Bits rO beast uP6an 1

Claims (1)

[Claims] 1) Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R1 is a monovalent residue, 1 Phenyl residues with ~3 substituents or each with 1 to 3 substituents in the nucleus benzyl-, α-methylbenzyl- or α,α-dimethylbenzyl which may be means a zyl residue or a naphthyl residue which may have 1 to 5 substituents, In this case, at least one of the substituents is an alcoholic group having 1 to 8 carbon atoms or is an alkylthio residue or an aryl or aryl group having 6 to 10 carbon atoms, respectively. A lyloxy residue or a halogen atom with an atomic number of 9 to 35 and the remainder When the substituent of It is also a hydrogen residue and R1 as a divalent residue is unsubstituted or has up to 2 carbon atoms. Phenyhin residue substituted with a non-aromatic hydrocarbon residue or unsubstituted or 1 to 4 non-aromatic hydrocarbon residues each having 1 to 8 carbon atoms as a substituent. means a naphthylene or biphenylene residue which may have a carbon group, and R2 is a carbon a non-aromatic hydrocarbon residue of 1 to 18 atoms, aryl or optionally substituted; substituted arylmethyl residues, each aryl residue having 6 to 10 carbon atoms, and R3 is a hydrogen atom, each having 1 to 18 carbon atoms. means an alkoxy or alkylthio residue or a group listed under R2 and R4 and R5 are each independently an alkyl group having 1 to 22 carbon atoms. oxaalkyl or thiaalkyl having 2 to 21 carbon atoms, 3 to 21 carbon atoms 18 alkenyl or -alkynyl, alkoxycarboxylic acid having 3 to 24 carbon atoms Nylalkyl, cycloalkyl having 5 to 12 carbon atoms, alkyl having 6 to 14 carbon atoms aryl, arylalkyl having 7 to 15 carbon atoms or optionally substituted is a piperidin-4-yl group having 5 to 17 carbon atoms, or R4 and R5 together with the nitrogen atom, O-, N- or or a ring system having 5 to 7 ring members which may additionally contain an S-atom. and n is 1 or 2. ] An aryl-phosphonamidite represented by 2) R1 is a biphenylene residue as a divalent residue, and R2 and R3 are biphenylene residues. each is a branched butyl residue, and R4 and R5 are each a butyl residue. or together with the N-atom to form a morpholide residue. thing. 3) The compound according to claim 1, wherein R1 is unsubstituted or substituted naphthyl. . 4) R1 is a trimethyl-phenyl residue, R2 and R3 are methyl- or is a branched butyl residue and R4 and R5 together with the nitrogen atom are piperidide. A compound of formula (I) according to claim 1 which is a residue or a morpholide residue. 5) R1 is a tert-butyl-1-phenyl residue, and R2 is a tert-butyl residue. and R3 is a methoxy- or tert-butyl residue and R4 and R5 are nitrogen 2. A compound of formula (I) according to claim 1, which together with the atoms forms a morpholide residue. 6) R1 as a monovalent residue is a non-aromatic hydrocarbon residue having 1 to 18 carbon atoms or is phenyl-, benzyl-, α-thylbenzyl- or α,α-dimethylbenzyl - each of these residues may have 1 to 3 substituents on the ring. Naphthyl residue optionally having - or 1 to 5 substituents, provided that These substituents are non-aromatic hydrocarbon residues, each having from 1 to 8 carbon atoms. alkoxy or alkylthio residues, or 6 to 10 carbon atoms each an aryl- or aryloxy residue, or a halogen with an atomic number of 9 to 35 and R1, as a divalent residue, is unsubstituted or contains up to two Phenylene residues substituted with non-aromatic hydrocarbon residues having 1 to 8 carbon atoms or is unsubstituted or has 1 to 4 substituents each having 1 to 8 carbon atoms. Naphthylene- or biphenylene residues optionally having non-aromatic hydrocarbon residues , R2 is a non-aromatic hydrocarbon residue having 1 to 18 carbon atoms, or aryl - or optionally substituted arylmethyl residues, in which case the aryl methyl residue R3 residues each have 6 to 10 carbon atoms, R3 is a hydrogen atom, each means an alkoxy or alkylthio residue having 1 to 18 carbon atoms; means the group listed for R2, and R4 and R5 are each a carbon group independently of each other. Alkyl having 1 to 22 atoms, oxaalkyl having 2 to 21 carbon atoms or thiaa Alkyl, alkenyl having 3 to 18 carbon atoms or -alkynyl, having 3 to 18 carbon atoms 24 alkoxycarbonylalkyl, cycloalkyl having 5 to 12 carbon atoms, Aryl having 6 to 14 carbon atoms, arylalkyl having 7 to 15 carbon atoms, or an optionally substituted piperidin-4-yl group having 5 to 17 carbon atoms; or R4 and R5 together with the nitrogen atom through at least one carbon atom. ring members which may additionally contain O-, N- or S-atoms bonded to Forms a ring system with 5 to 7 children and n is 1 or 2. ] A method for producing a phosphonamidite of formula (I) shown in claim 1, represented by In the first step, the halide R1(-X)n (wherein R1 and n are and X is a halogen atom with an atomic weight of at least 35) is reacted with finely divided magnesium under Grignard conditions to form the corresponding Grignard. compound R1(MgX)n which is then further converted in a second step to the formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) [In the formula, R2, R3, R4 and R 5 has the meaning given above and X is a chlorine or bromine atom. ] Phosphonamidite by reacting with aryl-halophosphoramidite represented by (I) The above method. 7) A claim in which the first stage reaction is carried out at 20-125°C, preferably 30-70°C. The method described in Section 6. 8) The method according to claim 6 or 7, wherein the first step reaction is carried out under the action of ultrasound. . 9) The second stage reaction is carried out at a temperature of -30 to +50°C, preferably -20 to +20°C. A method according to one or more of claims 1 to 3 for carrying out. 10) A compound of formula (I) according to one or more of claims 1 to 5, alone or in combination. Used in combination with phenyl antioxidants to stabilize synthetic resins, especially polymerized synthetic resins. To be there. 11) Formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) [In the formula, R2, R3, R4 and R 5 has the meaning given in claim 6 and X means a chlorine atom or a bromine atom . ] Aryl-halophosphoramidite. However, X is a chlorine atom, and R 2 is methyl, R3 is hydrogen atom, and R4 and R5 are each ethyl Excludes compounds. 12) A method for producing a compound according to claim 11, wherein formula (III) ▲ formula, There are chemical formulas, tables, etc.▼Aryl-dihalophosphite represented by (III) in the presence of an amine of formula HNR4R5(IV) and at least an equimolar amount of an acid binder. wherein in formulas III and IV R2, R3, R4 and R5 are halogen having the meaning as defined in claim 6 and where X has an atomic weight of at least 35 The above method, characterized in that it is atomic. 13) The reaction is carried out at a temperature of -30 to +30°C, preferably -20 to +20°C 13. The method according to claim 12. 14) a) 90-99.99% by weight of thermoplastic or thermosetting synthetic resins and b) 0.01-10% by weight of formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R1 to R5 and n are has the meaning set forth in 1. ] Consisting of aryl-phosphonamidite represented by Synthetic resin molding material. 15) According to claim 14, the synthetic resin is polyolemine, especially polypropylene. synthetic resin molding materials. 16) a) 90-99.98% by weight of thermoplastic or thermosetting synthetic resin, b) 0.01-5% by weight of the aforementioned aryl-phosphonamidites (I) and c)0 ．． 01-5% by weight, c1) Formula (V) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (V) [In the formula, m is 1 or 2, and R6 has 1 to 1 carbon atoms when m=1 2 alkyl residue, and when m=2, it means an alkyl residue having 1 to 12 carbon atoms. It is a residue. ] 3,3-bis-(3'-tert-butyl-4'-hydroxyphenyl)- butanoic acid and/or c2) Formula (VI) ▲There are mathematical formulas, chemical formulas, tables, etc.▼β-(3,5-ditertiary block represented by (VI)) methyl-4-hydroxy-phenyl)-propionic acid and esters from the group consisting of esters of monohydric or polyhydric alcohols. A synthetic resin molding material according to claim 14 or 15. 17) Antioxidant, ultraviolet absorber, light stabilizer, metal deactivator, peroxide decomposition agent Compounds, basic co-stabilizers, nucleating agents, fillers, reinforcing agents, plasticizers, lubricants, emulsifiers , pigments, optical brighteners, flame retardants, antistatic agents and/or blowing agents. A synthetic resin molding material according to one or more of claims 1 to 3, which contains an additive.