CA2065406A1

CA2065406A1 - Aryl halophosphoramidites, aryl phosphonamidites, processes for their preparation and their use for the stabilization of plastics

Info

Publication number: CA2065406A1
Application number: CA002065406A
Authority: CA
Inventors: Manfred Boehshar; Hans-Jerg Kleiner; Gerhard Pfahler
Original assignee: Individual
Current assignee: Hoechst AG
Priority date: 1989-08-26
Filing date: 1990-08-18
Publication date: 1991-02-27
Also published as: KR920702366A; WO1991002738A1; EP0489050A1; JPH05500044A

Abstract

Abstract of the disclosure:
Aryl halophosphoramidites, aryl phosphonamidites, proces-ses for their preparation and their use for the stabilization of plastics A process for the preparation of aryl phosphonamidites of the formula (I) (I) in which R1, as a univalent radical, is certain aromatic hydrocar-bon radicals which can carry substituents, in particular a non-aromatic hydrocarbon radical, alkoxy, alkylthio, aryl, aryloxy or halogen, and R1, as a divalent radical, is a phenylene, naphthylene or biphenylene radical which can carry non-aromatic hydrocarbon radicals as substitu-ents, R2 is a non-aromatic hydrocarbon radical, aryl or an optionally substituted arylmethyl radical, R3 is hydrogen, alkoxy or alkylthio or a group mentioned under R2, R4 and R5 are in each case C1-C22-alkyl, C2-C21-oxaalkyl or -thiaalkyl, C3-C18-alkenyl or -alkynyl, C3-C24-alkoxycar-bonylalkyl, C5-C12-cycloalkyl, C6-C14-aryl, C7-C15-arylalkyl or an optionally substituted C5-C17,-piperidin-4-yl qroup, or, together with the nitrogen atom, form a ring system having 5 to 7 ring atoms which can still additionally contain an oxygen, nitrogen or sulfur atom bonded via at least one carbon atom, and n = 1 or 2, in which initially a halide R1(-X)n, in which R1 and n have the abovementioned meaning and X is a halogen having an atomic weight of at least 35, is reacted with mag-nesium to give the corresponding Grignard compounds R1(MgX)n and these are reacted further with aryl halophos-phoramidites of the formula (II) (II) in which R2 to R5 have the meaning mentioned and X is chlorine or bromine, to give the phosphonamidites (I).

The invention further relates to certain compounds of the formulae (I) and (II), to a process for the preparation of compounds of the formula (II), to the use of compounds of the formula (I) alone or in combination with a phenolic antioxidant for the stabilization of plastics and to the plastic molding compositions stabilized in this way.

These molding compositions are distinguished by improved properties compared to those molding compositions which contain phosphonites prepared according to the prior art.

Description

HOECEIST A~CTIENGESELLSCH~FT HOE 89/F 282 K Dr . ZR/ je I)e~criptïon Aryl halophosphoramidites, aryl phosphonamidites, proces-ses for their preparation and their use forthestabiliza-tion of plastics The present invention relates to new aryl halophosphor-amidites, monoaryl phosphonamidites and bis~aryl] diphos-phonamidites, processes for their preparation and their use for the stabilization of plastics.

It is known that synthetic polymers have to be protected by stabilizers or stabilizer systems against undesired oxidative, ~hermal and photochemical damage during preparation, processing and use. Such stabilizers are, for example, composed of a phenolic antioxidant and one or more costabilizers, some of which are also able to reinforce the action of the phenolic ~omponents syner-gistically.

The most used stabilizers include, for ex~mple, phosphor-ous acid and phosphonous acid derivatives, the latter, above all, being distinguished by a ~ery good stability to hydrolysis.

The synthesis of phosphonamidites by stepwise reaction of dihalophonites with alcohols or phenols and amines in the presence of acid acceptors has been described by various authors [Houben-Weyl, Methoden der organischen Chemie (Methods of Organio Chemistry), phosphorus compounds El p. 300 (1982)~. The yields obtained in these processes were only about 60-75%.

In an analogous manner, suitable monophosphonamidites for use as stabilizers for polymers are prepared by reaction of alkyl or aryl dihalophosphonites, for example chloro-phosphonites, with phenols and amines in the presence of excess base, which is used to neutralize the hydrochloric

- 2 ~ t ~
acid formed, according to EP Offenlegunqsschrift 42,359.
Data relating to the purity of the products or ~he yields achieved are not given there.

However, the process of EP Offenlegungsschrift 42,359 can only be carried ou~ to a limited extent because of the difficult preparation of the dihalophosphanes needed as precursors which is, of cour~e/ disadvantageous if industrial production is considered. Thus, for ex2~mple, of the aromatic derivatives, only phenyldichlorophosphane is an industrially available product through which solely derivatives of benzenephosphonous acid are available.
This is confirmed in that in EP Offenlegungsschrift 42,359, except for one, all (no less than 17) ex2~mples contain the unsubstituted phenyl radical.

In addition to the achievement of higher yields, it is desirable for fulfilling the high requirements which are placed on the stability, activity, low volatility and the migration behavior of such stabilizers in practice to have available directly derivatives of aryl phosphonous acids substituted in the phenyl radical. However, their availability by known methods founders on the fact that appropriately substituted precursors are needed for this purpose, which are hitherto unknown or cannot be prepared economically~

It is therefore also an ob~ect of the invention to prepare novel stabilizers for plastics having improved properties, in particular with the aid of processes which do not have such disadvantages.

The present invention relates to aryl phosphon2~midites of the formula ~I) ¦ f ~ ~3 (I) \
~ 5 tl in which:
Rl, as a uniYalent radical, i5 a phenyl radical which carries 1 to 3 substituent~, or a benzyl, ~-methylbenzyl or ~ dLmethylbenzyl radical which in each case can car~y 1 to 3 substituents on the nucleus, or a naphthyl radical which can carry 1 to 5 ~ubstituent~, where at least one of these substituents i~ an alkoxy radical or alkylthio radical in each case havins 1 to 8, preferably 1 to 6, carbon atoms, or an aryl or aryloxy radical in each case having 6 to 10, preferably 6 to 8, carbon atoms or halogen having an atomic number of 9 to 35 and the other substituents - also exclusively in the naphthyl radical - are a non-aromatic hydrocarbon radical having 1 to 8 carbon a~om~, and R~, as a divalent radical, is a phenylene radical which is unsubstituted or substituted by up to 2 non-aroma~ic hydrocarbon radical~ having 1 to 8 carbon atom~, or a naphthylene or biphenylene radical which is unsub~tituted ox can carry 1 to 4 non-aromatic hydrocarbon radicals each having 1 to 8 carbon atoms a~
s~bstituents, R2 i~ a non-~romatic hydrocarbon radical having 1 to 18 carbon atoms, an a~yl or an optionally substituted arylmethyl radical, where the aryl radical in each case contain~ 6 to 10 carbon atom~, R3 i~ hydrogen, an alkoxy or alkylthio radical in each ca e having 1 to 18 carbon atoms or a group mentioned under R2, R' and R5 independently of one a~other in each case are Cl-C22-alkyl, C2-C2l-oxaalkyl or -thiaalkyl, C3-C~8-alkenyl or -alkynyl, C3-C24-alkoxycarbonylalkyl, C5~Cl2~cycloalkyl, C6-Cl4-aryl, C7-Cl5-arylalkyl or an optionally substituted C5-Cl7-piperidin-4-yl group, or R4 and R5, together with the ni~rogen atom, are also a ring system containing 5 to 7 ring atoms which may additional-ly further contain a heteroatom (O, N, S~ bonded via at least one carbon atom and n = 1 or 2.

If n = 1, the compounds are phosphonamidites and if n =
2 the compounds are bis-diphosphonamidites.

A preferred group of compounds are those in which Rl, as a divalent radical, forms a biphenylene radical, R2 and R3 in each case form a branched butyl radical and R4 and R5 in each case form a butyl radical orl together with the nitrogen atom, form ~he morpholide radical.

Other preferred compounds are those in which R1 is the trimethylphenyl radical r R2 and R3 are the methyl radical or a branched butyl radical and R4 and Rs, ~ogether with the nitrogen, are either the piperidide or morpholide radical or in which Rl is ~he tert.-butyl-l-phenyl radi-cal, R2 is the tert.-butyl radical, R~ is the methoxy radical or t~rt.-butyl radical and R4 and R5, together with the nitrogen atom, are the morpholide radical.

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

In R1, the substituents can in each case be identical or different. The alXyl in the substitu0nts of the aromatic radicals Rl is, for e~ample, one of the various hexyl or octyl radicals, but preferably ha~ 1 to 4 carbon atoms and is, for example, methyl, ethyl or one of the various propyl or butyl radicals, which are optionally bonded to the nucleus via O or S. Cs-C~-cycloalkyl may be mentioned as a non-aromatic hydrocarbon radical, like the radicals mentioned further below under R2. In particul~r, for example, the anisyl radicals or naphthyl radicals may be mentioned, which, for example, further carry up to 2 substituents containing altogether up to 4 alkyl carbon atoms, and also the various biphenyl radicals.

For R1 as a divalent radical, the various phenylene radi-cals may, for example, be mentioned which are unsub-stituted or carry 1 to 2 C1-C8-alkyl groups, in particular Cl-C3-alkyl groups, or the various naphthylene radicals and biphenylene radicals which are unsubstituted or substituted by 1 to 4, preferably 1 to 3, Cl-C~-alkyl groups, in particular C1-C3-alkyl groups.

Naturally, the substituents in Rl can only be combined in such a way that no steric hindrance occurs. If R1 contains

3 substituents, no more than 5 carbon atoms should be present in the two o-positions. In substituted naphthyl radicals which c~ntain more than two s~bstituents, these are advantageously distributed on both rings.

Suitable R2 and R3 radicals are, for example, non-aromatic hydrocarbon radicals having 1 to 18 carbon atoms, such as alkyl or cycloalkyl, and furthermore aromatic radicals which have 6-18 carbon atoms including aliphatic groups, where no more than 10 carbon atoms are part of an aroma-tic ring system. Preferably, the radicals R2 and R3 contain 4 to 12 and, in particular, 6 to lO carbon atoms.
In particular, the following may be m~ntioned as non-aromatic hydrocarbon radicals: alkyl, such as methyl, ethyl, the various propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, hexadecyl and octadecyl radicals, and cycloalkyl havin~ 5 to lO carbon atoms such as cyclopen-~yl, cyclohexyl, cycloheptyl and cyclohexylmethyl (i.e.
both the hydrogenated ben~yl radical and the methyl-cyclohexyl radical); C5 C10-aryl and arylmethyl may further be mentioned, where the term aryl in each case includes alkylaryl, carries at most three of the sub-s~ituents mentioned under R2 and, including this, has at 6 ;~5~
most 14 carbon atoms.

If one of the radicals R2 or R3 is an alkyl r~dical, tertiary alkyl groups containing 4-10 carbon atoms, such as tert.-butyl, 2-methyl-2-butyl, 2-methyl-2-pentyl and 2-ethyl-2-butyl are particularly preferred. Other pre-ferred compounds are those in which R2 or R3 is phenyl, benzyl, ~-methylbenzyl and ~,~-dimethylbenzyl.

R4 and R5 are, for example, the radicals indicated for R2.
If they are alkyl, Cl-Cl2-alkyl groups are preferred.

R4 and R5, as C2-C21-oxa- or thiaalkyl, are, for example, methoxymethyl, methylthiamethyl, ethoxymethyl, methyl-thiaethyl or ethoxyethyl. Alkoxypropyl and slkylthia-propyl groups are preferred, such as methoxypropyl, ethylthiapropyl, butoxypropyl, octylthiapropyl, dodecyl-lS oxypropyl, octadecylthiapropyl or octadecyloxypropyl.

R4 and R5 are, as C3-C18-alkenyl, for example allyl, methallyl, n-hexen-3-yI, n-octen-4-yl, n-undecen-10-yl or n-octadecen-17-yl. Allyl and methallyl are preferred.

R4 and R5, as C3-C1~-alkynyl are, for example, propargyl, n-butyn-l-yl, n-butyn-2-yl or n-hexyn-l-yl. Alkynyl groups having 3-6 carbon atoms are preferred, in par-ticular propargyl.

If R4 and R5, together with the nitrogen atom to which they are bonded, form a pyrrolidine, oxazolidine, piperi-dine, morpholine, hexamethyleneimine or piperazine ring,these heterocycles can be substituted by 1 to 5, ad-vantageously at most 2, methyl or ethyl groups. Ring systems of this type are preferably unsubstituted.

If R4 and R5 are piperidin-4-yl groups, they may be unsubstituted piperidin-4-yl, or the piperidine may be substituted by up to 5 alkyl groups. The 2,2,6,6-tetra-methylpiperidin-4-yl radical is particularly preferred.

The invention also relates to a process for the prepara-tion of phosphonamidites of the formula ~I) in which Rl, as a univalent radical, in addition to the abovementioned meaning can also be phenyl and a phenyl substituted by 1 to 3 non-aromatic hydrocarbon radicals having 1 to 8 carbon atoms, and a non-aromatic hydrocarbon radical having 1 to 18 carbon a~oms, preferably Cl-Cl8-alkyl, and R2, R3, R4 and R5 have the abovemention d meaning, which comprises initially reacting in a first step a halide Rl(-X)n in which Rl has the abovementioned meaning, n = 1 or 2 and X is a halogen having an atomic weight of at least 35, preferably chlorine or bromine, under Grignard conditions, i.e. advantageously with intimate mixing, with finely particulate magnesium to give the corresponding Grignard compounds R1(MgX)n and reacting these in a second step with aryl halophosphoramidites of the formula (II) ~2 O ~ ~3 X--N

in which R2 R3, R4 and Rs have the abovementioned meaning and X is chlori.ne or bromine, to give the phosphonamid-ites (I). The process according to the invention is thus also utilizable for the reaction of those compounds of the formula R1(MgX)n in which Rl, for example, is the tolyl, dimethylphenyl, trimethylphenyl or tert.-butyl-phenyl radical.

With respect to economic accessibility~ those of thecompounds (II) where ~ = chlorine are particularly preferred.

The first step of the process according to the invention which can be carried out in any customary manner, i5 preferably carried out in an aprotic organic solvent, such as an ether, for example diethyl, dipropyl or diisopropyl ether, ethylene glycol dimethyl ether or ethylene glycol diethyl ether, diethylene glycol dLmethyl ether or diethylene glycol diethyl ether, methyl tert.~
butyl ether, dioxane or tetrahydrofuran.

As the Grignard compounds are sensitive to hydrolysis and oxidation, it is advantageous to work under a protective gas atmosphere, however, such a process is not compulsory for the success of the reaction. Nitrogen and argon are particularly suitable as protective gases.

The reaction temperature during the conversion into a Grignard compound is in general between 20 and 125C, preferably between 30 and 70C. The effect of ultrasound during the conversion into a Grignard compound is some-times advantageous.

In order to prepare the final product (I), the solution ox suspension of the Grignard reagent in the second step is metered into the halophosphoramidite (II) which is advantageously diluted with an inert, aprotic solvent~
for example an aliphatic hydrocarkon fraction, hexane, cyclohexane, toluene, xylene or one of the abovementioned ethers, advantageously at a temperature below 0C. The reaction temperature in this step is in general between 30C and +50C, but preferably between -20C and +20C.
As a rule, the reaction proceeds exothermically; accord-ingly it may be expedient to control the course of the reaction by cooling. The most favorable results are achieved if the reaction components are employed accord-ing to the reacti.on stoichiometry. However, it is also possible to employ one reaction component in excess;
however, in general there are no particular advantages associated with this. The mixture is expediently stirred until the reaction i~ complete, and precipitated mag-nesium halide is subssquently separated off. The solvents ;~?~
g can be removed from the filtrate in a customary manner, advantageously by distillation, in particular under reduced pressure.

The synthesis of phosphonamidites with the aid of organo-metallic compounds, for example by reaction of halo-phosphoramidites with Grignard reagents, was hitherto unknown. Ob~iously, owing to the known easy replaceabil-ity of amino groups and also ester groups bonded to the phosphorus by nucleophiles [Houben-Weyl, Methoden der organischen Chemie (Methods of Organic Chemistry), volume 12/1, 44, (1963) and E 1,302 (1982)], a prejudice existed in this respect in that in th~ reaction of halophosphor-amidites with Grignard reagents, to a high extent side reactions reducing the yield with its progress and a still lower yield of desired product ca~sed as a result may have to be taken into account.

It is therefore particularly surprising that, starting from easily accessible halophosphoramidites, any sub-stituted phosphonamidites can be obtained in such a high 2Q yield and purity according to the proces~ of the present invention.

The products (I) can be separated from the crude products ~y any desired processess, but preferably by crystalliza-tion.

The halophosphoramidites (II) required as starting compounds, which are new except for that compound in which X is chlorine, R2 is methyl, R3 is hydrogen and R4 and R5 are in each case ethyl [Izv. Akad. Nauk. SSSR, Ser.
Khim., (9), 2131~2133 (1968)], can be prepared in a simple manner by a process to which the invention also relates. However, this known compound has achieved no industrial Lmportance. It is particularly unsuitable as a starting material for stabilizers fox polymers.

The invention thus also relates to a process for the lo- 2~5~
preparstion of these compound~ (II), which comprises reactinq an aryl dihalopho~phite of the formula ~III) p _ 0 ~ 3 (III) with an amine of the formula XNR~R5 (IY) in the presence S of at least an equimolar amount of an acid-binding agent, where, in the formulae (III) and (IV), R2, R3, R~ and R5 have the meanings which are indicated for the process for the preparation of the compounds (I) and X is a halogen having an atomic weight of at least 35. The process thus also extends to the preparation of the compound of the formula (II) in which X is chlorine, R2 is methyl, R3 is hydrogen and R4 and R5 are in each case ethyl, which has hitherto been prepared in another manner.

This process can be carried out per se in any customary lS manner. It is preferably carried out in an inert aprotic solvent. Hydrocarbons such as pentane, hexane, heptane, benzene, toluene, xylene, chlorobenzene and ethers such as diethyl ether, dipropyl ether, diisopropyl ether, ethylene glycol dimethyl ether or ethylene glycol diethyl ether are particularly suitable for this purpose.

The compound~ of the formula (II) are expediently prepar-ed by adding an equimolar amount of the amine (IV) and an equimolar amount of a base suitable as an acid-binding agent to the solution of the dihalide (III) with vigorous mixing. In this case the reaction i~ in general carried out between -30 and +30-C, preferably between -20 and ~lO-C. The mixing is carried out, for exampIe, by stir-ring and, expediently, until the reaction i8 complete.
~he precipitated ammonium ~alt i~ then separated off. The solvents can be removed from the filtrate in a customary .. . .

~: ,' ' '- . ' , : . : ~ . .

:, ~ , . .

d ? :, s d manner t preferably by distillation, the solvents ex-pediently being distilled under reduced pressure.

Suitable bases, which are advantageously dil~l-ted with one of the abovementioned solven~s, are, above all, tertiary amines, such as trie~hylamine and pyridine. An excess of amine HNR4R5 can also act as an acid-binding agent.

The products (II) obtained in this procedure are usually obtained in a purity which is easily sufficient for reaction with the Grignard compounds. A further purifica-tion, for example by vacuum or thin-layer distillation, is therefore as a rule unnecessary.

The invention finally relates to the use of the compounds of the formula (I) alone or in combination with a pheno-lic antioxidant for the stabilization of plastics, such as polycarbonates, preferably polymerization plastics such as polyolefins, in particul~r polypropylene. The compounds of the formula (I) impart an Lmproved stability against degradation by light, oxygen and heat to the plastics in the molding compositions. However, the purity of the crude reaction product obtained (85-93% according to 31P-NMR) iS frequently sufficient for this use. Isola-tion in a pure form is then unnecessary.

The present invention thus also relates to a plastic molding composition, containing a thermoplastic or thermoset material and an aryl phosphonamidite of the formula (I) in the ratio of (90 to 99.99):(0.01 to 10).

The plastic molding composition according to the inven-tion contains a thermoplastic or thermoset organic polymer, for example one of the following:

1. Polymers of mono- and diolefins,forexample polyethyl-ene of high, medium or low density (which, if desired, can b~ crosslinked), pol~ypropylene, polyisobutylene, poly-1-butene, polymethyl-1-pentene~ polyisoprene or polybutadiene and polymers of cycloolefins, such as, for example, cyclopentene or norbornene.

2. Mixtures of the polymers mentioned under l), for example mixtures of polypropylene with polyethylene or with polyisobutyl~ne.

3. Copolymers of mono- and diolefins with one another or wi~hother vinyl monomers, such as, for example, ethylene-propylene copolymers, propylene-l-butene copolymers, propylene-isobutylene copolymers, ethylene-l-butene copolymers, propylene-butadiene copolymers, isobutylene-isoprene copolymers, ethylene-alkyl acryla~e copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers or ethylene-acrylic acid copolymers and salts ~hereof tionomers) and terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclo-pentadien~ or ethylidenenorbornene.

4. Polystyrene.

5. Copolymers of styrene or ~-methylstyrene with dienes or acrylic derivatives, such as, for example, styrene-butadiene, styrene-maleic anhydride, styrene-acrylonitrile, styrene-ethyl methacrylate, styrene-butadi~ne-ethyl acrylate, styrene-acrylonitrile-methyl acrylate; mixtures of high impact strength and composed of styrene copolymers and one other polymer, such as, for example, a polyacrylate, a diene polymer or an ethylene-propylene-diene terpolymer; and block copolymers of styrene, ~uch a~, for example, styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene/butylene-styrene or styrene-ethylene/propylene-styrene.

6. Graft copolymers of styrene, such as, for example, styrene onto polybutadiene, styrene and acrylonitrile onto polybutadiene, styrene and maleic anhydride onto polybutadiene, styrene and alkyl acrylates or alkyl methacrylates onto polybutadiene, styrene and acrylo-- 13 - v~ qf~
nitrile on~o ethylene-propylene-diene terpolymers, styrene and acryloni~rile onto poly(alkyl acrylates) or poly(alkyl me~hacrylates), styrene and acrylonitrile onto acrylate-butadiene copolymers, and mixtures thereof with the copolymers mentioned under 5~, which are known, for example, as so-called A~S, MBS, ASA or AES polymers.

7 Halogen-containing polymers, such as, for example, polychloroprenP, chlorinated rubber, chlorinated or chlorosulfonated polyethylene, epichlorohydrin homo- and copolymers, in particular polymers of halogen-containing vinyl compounds, such as, for example, polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride; and their copolymers such as vinyl chloride-vinyliden~ chloride, vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate.

8. Polymers derived from ~ unsa~urated acids and derivatives thereof, such as polyacrylates and polymeth-acrylates, polyacrylamides and polyacrylonitriles.

9. Copolymers of the mcnomers mentioned under 8) with one another or with other un~aturated monomers, such as, for example, acrylonitrile-butadiene copolymers, acrylonitrile-a:Lkyl acrylate copolymers, acrylonitrile-alkoxyacrylate copoiymers, acrylonitrile-vinyl halide copolymer~ or ac:rylonitrile-alkyl methacryla~e-butadiene terpolymers.

10. Polymers derived from unsaturated alcohols and amines or acyl derivatives or acetals thereof, such as polyvinyl alcohol, polyvinyl acetate, stearate, benzoate, maleate, poly~inylbutyral, polyallyl phthalate, polyallylmelamine.

11. Homo- and copolymers of cyclic ethers, such as polyethylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethex6.

12. Polyacetals, such a~ polyoxymethylene, and tho~e J '~ f ~r3 polyoxymethylenes containing comonomers, such as, for example, ethylene oxide.

13. Polyphenylene oxides and sulfides.

14. Polyurethanes derived on the one hand from poly-ethers, polyesters and polybutadienes having terminalhydro~y groups and on ~he other hand from aliphatic or aromatic polyisocyanates and precursors thereof (polyisocyanates-polyols prepolymers).

15. Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corr~sponding lactams, such as nylon-4, nylon-6, nylon-6,6, nylon-6,10, nylon-11, nylon-12, poly-2,4,4-trimethylhexamethyleneterephthalamide, poly-m-phenylene-isophthalamide, and copolmers thereof with polyethers, such as, for example, with polyethylene glycol, poly-propylene glycol or polytetramethylene glycol.

15. Polyureas, polyLmides and polyamidoimides.

17. Polyesters derived from dicarboxylic acids and diols and/or hydroxycarboxylic acids or the corresponding lactones, such as polyethy~ene terephthalate,polybutylene terephthalate, poly-1,4-dLmethylolcyclohexane terephtha-late, poly-(2,2-bis(4-hydroxyphenyl)propane) tereph-thalate, polyhydroxybenzoates, and block polyether esters derived from polyethylene having terminal hydroxy groups, dialcohols and dicarboxylic acids.

18. Polycarbonates.

19. Polysulfones and polye~her sulfones.

20. Crosslinked polymers derived on the one hand from aldehydes and on the other hand frcm phenols, urea or melamine, such as phenol-foxmaldehyde, urea-formaldehyde and melamine-formaldehyde resins.

- 15 - 2~
21. Drying and non-drying alkyd resins.

22. Unsaturated polyester resins derived from copoly-esters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols, and vinyl compounds as cross-linking agents, as well as their halogen-containing non-flammable modifications.

23. Crosslinkable acrylic resins derived from substituted acrylic esters such as, for example, from epoxy acrylates, urethane acrylates or polyester acrylates.

24. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, polyiso-cyanates or epoxy resins.

25. Crosslinked epoxy resins derived from polyepoxides, for example from bis(glycidyl) ethers or from cyclo-aliphatic diepoxides.

26. Natural polymers, such as cellulose, natural rubber, gelatin and polymer-homologous chemically modified derivatives thereof, such as cellulose acetates, propio-nates and butyrates, and the cellulose ethers, such as methylcellulose.

27. Mixtures of the abovementioned polymers, such as, for example, PP/EPDM, nylon-6/EPDM or ABS, PVC/EVA, PVC~ABS, PVC/MBS, PC~ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVD/acrylate, POM/thermoplastic PUR, POM/acrylate, POM/MBS, PPE/HIPS, PPE/nylon-6,6 and copolymers, PA/HDPE, PA/PP, PA/PPE.

28. Naturally occurring and synthetic organic materials which are pure monomers or mixtures of monomers, such as, for example, mineral oils, animal and vegetable fats, oils and waxes, or oils, fats and waxes based on syn-thetic esters or mixtures of these substances.

- 16 ~
29. Aqueous dispersions of natural or synthetic rubber.

The polymer is preferably a polyolefin, in particular polypropylene. The amount of the polymer in the molding composition according to the invention is 90 to 9g.99, S preferably 98 to 99.98%, by weight.

The molding composition contains a~ stabilizer an aryl phosphonamidite of the formula I and, if necessary, a phenolic antioxidant.

The phenolic antioxidant is an ester of 3,3-bis(3~-t-butyl-4'-hydroxyphenyl)butanoic acid of the formula (V) OH
~ t-~4~;

CH3 - C - CH2 - C ~ - - R6 (V) ~\
t-C4Hg OH
L m in which R~ is a Cl-Cl2-alkyl radical or a Cl-Cl2-alkylene radical and m i8 1 or 2. R5 is prefer~bly a C2-C~-alkylene radical, in particular a C2-alkylene radical.

However, the phenolic antLoxidant can also be an eqter of ~-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid of the formula (VI) t-C4Hg HO- ~ -cH2-cH2-c-oH

t-C4Hg (VI) . ~, '' . , : , ~ ;

, ,

- 17 ;~I?~
in which the alcohol component is a mono- or polyhydric alcohol having 1 to ..., preferably 1 to ..., carbons atoms, such as, for example, methanol diethylene glycol octadecanol triethylene glycol 1,6-hexanediol pentaerythritol neopentyl glycol tris(hydroxyethyl) isocyanurate thiodiethylene glycol di-(hydroxyethyl)oxalamide.

The new stabilizers are incorporated in the organic polymers by generally customary methods. They can be incorporated, for example, by adding the stabilizers before or during the polymerization, polycondensation or polyaddition, or by admixing the compounds and, if necessary, further additives to the melt before or during the molding. They can also be incorporated by applying the dissolved or dispersed compounds directly to the polymer or admixing to a solution, suspension or emulsion of the polymer, if appropriate then allowing the solvent to evaporate. The amount to be added to the polymer is 0.01 to 10, preferably 0.025 to 5, in particular 0.05 to 1.0, % by weight, relative to the m~terial to be stabil-ized.

The new compounds can also be added in the form of a ma~ter batch containing these compounds, for example, in a concentration of 1 to 50, preferably 2.5 to 20 %, by weight, to the polymers which are to be stabilized.

In addition, the organic polymers to be stabilized can also contain the following antioxidants, such as, for example:

1. Alkylated monophenols, for example 2,6-di-t-butyl-4-methylphenol, 2-t-butyl-4,6-dimethylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-n-butylphenol, 2,6-di-t-butyl-4-i-butylphenol, 2,6-di-cyclopentyl-4~methylphenol, ~
2-~-methylcyclohexyl)-4,6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol, 2,6-di-t-butyl-4-methoxymethylphenol.

2. Alkylated hyd~oquinone~, for example 2 t 6-di-t-butyl-4-methoxyphenol, 2,5-di-t-butyl hydroquinone, 2,5-di-t-amyl hydroquinone, 2,6-diphenyl-4-octadecyloxyphenol.

3. Hydroxylated thiodiphenyl ethers, for example 2,2'-thio-bis(6-t-butyl-4-methylphenol), 2,2'-thio-bis(4-octylphenol), 4,4'-thio-bis(6-t-butyl-3-methylphenol), 4,4~-thio-bis~6-t-butyl-2 methylphenol).

4. Alkylidene bisphenols, for example 2,2'-methylene-bis(6-t-butyl-4-methylphenol), 2,2'-methylene-bis(6-t-butyl-4-ethylphenol), 2,2'-mathylene-bis[4~methyl-6-(~-methylcyclohexyl)-phenol~, 2,2'-methylene-bis(4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis~6-nonyl-4-methylphenol), 2,2'-methylene-bi~(4,6 di-t-butylphenol), 2,2'-ethylidene-bis(4,6-di-t-butylphenol), 2,2'-ethylidene-bis(6-t-butyl-4-isobutylphenol), 2,2'-methylene-bis[6-(~-methylbenzyl)-4~nonylphenol], 2,2'-methy:Lene-bis[6-(~ dimethylbenzyl)-4-nonylphenol]~
4,4'-methylene-bis(2,6-di-t-butylphenol), 4,4~-methylene-bis(6-t-butyl-2-methylphensl), 1,1-bis(5-t-butyl-4-hydroxy-2-methylphenyl)-butane, 2,6-di-(3-t-butyl-5~methyl-2-hydroxybenzyl)-4-methyl-phenol, 1,1,3-tris(5-t-butyl-4-hydroxy-2-methylphenyl)-butane, 1,1-bis(5-t-hutyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, - 19 - ~?65~
di-(3-l-butyl-4-hydroxy-5-methylphenyl)-dicyclo-pentadiene, di-~2-(3~-t-butyl-2~-hydroxy-5~-methyl-benzyl)-6-t-butyl-4-methyl-phenyl] terephthalate.

5. ~enzyl compounds, for example 1,3,5-tri-(3,5-di-t-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, di-(3,S-di-t-butyl-4-hydroxybenzyl) sulfide, isooctyl 3,5-di-t-butyl-4-hydroxybenzylmercapto-acetate, bis (4-t-butyl-3-hydroxy-2, 6-dimethylbenzyl) dithioterephthalate, 1, 3, 5-tris ( 3, 5-di-t-butyl-4-hydroxybenzyl ) isocyanurate, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, dioctadecyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate, calcium monoethyl 3,5-di-t-butyl-4-hydroxybenzyl-phosphonate.

6. Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, 2,4-bis(octylmercapto)-6-(3,5-di-t-butyl-4-hydroxy-anilino~-s-triazine, octyl N-(3,5-di-t-butyl-4-hydroxyphenyl)-carbamate.

7. Esters of ~-~S-t-butyl-4-hydroy-3-methylphenyl)-propionic acid with mono- or polyhydric alcohols, such as, for example, with methanol, diethylene glycol, octadecanol, triethylene glycol, 1,6-hexanediol, pentaerythritol, neopentylglycol, tris ( hydroxyethyl ) isocyanurate, thiodiethylene glycol, di-(hydroxyethyl) oxalamide.

- . -`

'. :~ . .
- ~

` - 20 - 2~
8. Amides of ~-(3,5-di-t-butyl-4-hydro~yphenyl)propionic acid, such as, for example N,N'-di-(3,5-di-t-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine, N,N'-di-(3,5-di-t-butyl-4-hydroxyphenylpropionyl)-trimethylenediamine, N,N'-di-(3,5-di-t-butyl-4-hydroxyphenylpropionyl)-hydrazine.

Apart from these, the polymers to be stabilized can additionally contain further additives, such as, for example:

1. W absorbers and light stabilizers 1.1 2-(2'-Rydroxyphenyl)-benzotriazoles, such as, for example, the 5'-methyl, 3',5'-di-t-butyl, 5'-t-butyl, 5'-(1,1,3,3-tetramethylbutyl), 5-chloro-3',5'-di-t-butyl, 5-chloro-3~-t-butyl-5~-methyl, 3~-sec.-butyl-5~-t-butyl, 4'-octoxy, 3~,5~-di-t-amyl, 3',5'-bis-(~
dimethylbenzyl) derivative.

1.2 2-~ydro~ybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dode-cyloxy, 4-benzyloxy, 4,2',4'-trihydroxy, 2'-hydroxy-4,4'-dimethoxy derivative.

1.3 ~sters of substituted or un~ubstituted benzoic acids, for example 4-t-butylphenyl salicylate, phenyl salicylate, octyl-phenyl salicyalate (sic), dibenzoylresorcinol, bis(4-t-butylbenzoyl)resorcinol,benzoylresorcinol,2,4-di-t-butylphenyl 3,5-di-t-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-t-butyl-4-hydroxybenzoate.

1.4 A!crylates, for example ethyl or isooctyl ~-cyano-~,~-diphenylacrylate, methyl ~-carbomethoxycinnamate, methyl or butyl ~-cyano-~-methyl-p-methoxycinnamate, methyl ~-carbo-methoxy-p-methoxycinnamste, N-(~-carbomethoxy-~-cyanovinyl)-2-methylindoline.

1.5 Nickel compounds, for example nickel complexes of 2,2'-thio-bis[4-(1,1,3,3-tetra-methylbutyl)phenol], such as the 1:1 or 1:2 complex, if appropriate containing additional ligands, such as n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine, nickel alkyl dithiocarbamates, nickel salts of monoalkyl (methyl or ethyl) 4-hydroxy-3,5-di-t-butylbenzylphosphonates, nickel complexes of ketoximes, such as 2-hydroxy-4-methylphenyl undecyl ketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, if appropriate with additional ligands, nickel salts of 2-hydroxy-4-alkoxy-benzophenones.

1.6 Sterically hindered amines, for example 1.6.1 bis(2,2,6,6-tetramethylpiperidyl) sebacate, bis(l,2,2,6,6-pentamethylpiperidyl) sebacate, bis(2,2,6,6-tetramethylpiperidyl) glutarate, bis(l,2,2,6,6-pentamethylpiperidyl) glutarate, bis(2,2,6,6-tetramethylpiperidyl) succinate, bis(l,2,2,6,6-pentamethylpiperidyl) succinate, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-1,2,2,6,6-pentamethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-1,2,2,6,6-pentamethylpiperidine, 2,2,6,6-tetramethylpiperidyl behenate, 1,2,2,6,6-pentamethylpiperidyl behenate, 2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro-t5.1.11.2]-heneicosan-21-one, 2,2,3,4,4-pentamethyl-7-oxa-3,20-diazadispiro-[5.1.11.2]-heneicosan-21-one, 2,2,4,4-tetramethyl-3-acetyl-7-oxa-3,20-diaza-dispiro[5.1.11.2]-heneicosan-21-one, 2~2~4~4-tetramethyl-7-oxa-3~2o-diaza-2o-(~ aur ..
..
, . . .
;

- 22 ~?`~
oxyca~bonylethyl~-21-oxodispiro[5.1.11.2]-heneicosane, 2,2,3,4,4-pentamethyl 7 oxa~3,20-dia~a-20-(~-lauryloxycarbonylethyl)-21-oxodispiro-[5.1.11.2]-heneicosane, 2,2,4,4-tetramethyl-3-S acetyl-7-oxa-3,20-diaza-20-(~-laurylo~ycarbonyl-ethyl)-21-oxodispiro-[5.1.11.2]-heneicosane, 1,1',3,3',5,5'-hexahydro-2,2',4,4',6,6'-hexaaza-2,2',6,6'-bismethano-7,~-dioxo-4,4'-bis(1,2,2,6,6-pentamethyl-4-piperidyl)-biphenyl, NN'N"N"'-tetrakis{2,4-bis[N-(2,2,6,6-tetramethyl-4-piperidyl~-butylamino]-1,3,5-triazin-6-yl}-4,7-diazadecane-1,10-diamine, NN~N~N"'-tetrakis-{2,4-bis E N-(1,2,2,6,6-pentamethyl-4-piperidyl)-butylamino]-1,3,5-triazin-6-yl}-4,7-diazadecane-l,10-diamine, NN'N"N"'-tetrakis-{2,4-bis[N-(2~2,6,6-tetramethyl-4-piperidyl)-methoxypropyl-amino]-1,3,5-triazin-6-yl}-4,7-diazadecane-1,10-diamine, NN'N"N"~-tetrakis-{2,4-bis[N-(1,2,2,6,6-pentamethyl-4-piperidyl)-methoxypropylamino]-1,3,5-triazin-6-yl}-4,7-diazadecane-1,10-diamine, bis-(1,2,2,6,6-pentamethylpiperidyl)-n-butyl-3,5-di-tert.-kutyl-4-hydroxybenzylmalonate, tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetra-kis-(2,2,6,6-tetramethyl-4 piperidyl)-1,2,3,4-butanetetracarboxylic acid, 1,1'-(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone)~

1.6.2 Poly-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,8-diazadecylene, condensation product from 1-(2-hydroxyethyl)-2,2,6,6-totramethyl-4-hydroxypiperi-dine and succinic acid, condensation product from N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl~hexa-methylenediamine and 4-tert.-octylamino-2,6-dichloro-1,3,5-triazine, condensation product from N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexa-methylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine.

In many cases, a combination of th~ compounds according to the invention with the compounds mentioned und~r 1.6.1 is particularly advantageous.

1.7 Oxalamides, for example 4,4'-di-octyloxyoxan~lide, 2,2'-di-octyloxy-5,5'-di-t-butyloxanilide, 2,2'-didodecyloxy-5,5'-di-t-butyl~
oxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dLmethyl~minopropyl)oxalamide, 2-ethoxy-5-t-butyl-2~-e~hyloxanilide and its mixture with 2-etho~y-2~-ethyl-5,4-di-t-butyloxanilide, mixtures of ortho- and para-methoxy- and of o~ and p-ethoxy-di-substituted oxanilide~.

2. Metal deactivators, for example N,N'-diphenyloxalamide, N-salicylyl-N'-salicyloyl-hydra~.ine, N,N'-bis(salicyloyl)hydrazine, N,N' bis-(3,5-di-t-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,3-triazole, bis(benzylidene)-oxaldihydrazide.

3. Phosphites and phosphonites, for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialhyl phosphites, tris~nonylphenyl) phosphite, trilauryl phosphite, tri-(octadecyl) phosphite, distearyl pentaerythrityl diphosphite, tris(2,4-di-t-butylphenyl3 phosphite, di-(isodecyl) pentaerythrityl diphosphite,bis(2,4-di-t-butylphenyl)pentaerythrityl diphosphite~ tristearyl sorbityl triphosphite, tetrakis(2,4--di-~-butylphenyl) 4,4'-diphenylenediphos-phonite, 3,9-bis(2,4-di-t-butylphenoxy) 2,4,8,10-tetraoxa-3,9-diphosphaspiro(5.5)undecane, trist2-t-butyl-4-thio(2'-methenyl-4~-hydroxy-5'-t-butyl)phenyl-5-methenyl)phenyl phosphite.

4. Pero~ide-de~troying compounds, for example es~ers of ~-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl ester, m~rcap~obenzimidazole, the zlnc salt of 2-mercapto-b~nzLmidazole, zinc alkyldithiocarbamate~, dioctadecyl s~

disulfide, dioctadecyl monosulfide, tetraXis(~-dodecylmercapto)pentaerythritol propionate.

5. Basic costabilizers, for example melamine, polyvinylpyrrolidone, dicyandiamide, tri-allyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamines, polyurethanes, alkali metal and alkaline earth metal salts of higher fatty acids or phenolates, for example Ca stearate, Zn stearate, Mg stearate, Na ricinoleate, K palmitate, antimony pyrocatecholate or tin pyrocatecholate, hydroxides and oxides of alkaline earth metals or aluminum, for example CaO, Mg~, ZnO.

6. Nucleating agents, for example 4-t-butylbenzoic acid, adipic acid, diphenylacetic acid, dibenzylidenesorbitol.

7. Fillers and reinforcing agents, for example calcium carbonate, silicates, glass fibers, asbestos, talcum, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite.
0 8. Other additives, for example plasticizers, lubricants, emulsifiers, pigments, optical brighteners, fireproofing agents, anti~tatics, blowing agents.

The various additional additives of the abovementioned groups 1 to 6 are added to the polymers to be stabilized in an amount of 0.01 to 10, preferably 0.01 to 5, % by weight, relative to the total weight of the molding composition. The relative amount of the additives of groups 7 and 8 is 1 to 80, preferably 10 to 50, % by weight, relative to the entire molding composition.

The organic polymers stabilized according to the inven-tion can be used in a wide range of forms, for example as sheets, fibers, ribbons, profiles or as binders for paints, adhesives or cements.

Before the examples illustrating the invention, the preparation of the starting materials (III), which are known in some cases, is described. If these compounds are still unknown, they can be prepared easily from PX3 (X=C1, Br) and the phenol concerned in analogy to known com-pounds (for example EP-PS 158,300). The phenols and amines HNR4R5 (~V) used as starting materials are mo~tly known compounds; otherwise they can be prepar~d by analogous processes.

I) G~neral procedure for the preparation of the precur-sors A2yl dichlorophosphites tIII) 650 mmol (= 89.3 g) of phosphorus (III~ chloride, a spatula tip-full (about 100 mg) of p-dimethylaminopyri-dine and 500 mmol of the phenol concerned were added together with the exclusion of air and moisture. The solution cooled and evolution of HCl commenced. The mixture was slowly heated to 90-100C with vigorous stirring in the course of 60-90 min and was held at this temperature for 2 hours in order to complete the reac-tion. The low-boiling constituents were then stripped off at 50C in the vacuum of the water ~e~ pump. The purity f aryl dichlorophosphites was determined by means of 31p_ NMR spectroscopy and was in general between 70 and 92%.

A) 2,4-di-tert.-butylphenyl dichlorophosphiteO
Distillation of the crude product having a purity of 91.7% [31P-NMR: ~CDCl3 = 184.7 ppm] of the above compound yielded 129 g of yellowish oil of b.p. 104-105C/0.05 mbar.
C14H21Cl2OP Calc.: 54.73 % C, 6.89 % H, 10.08 % P
(307.20) Found: 54.9 % C, 6.7 ~ H, 10.2 % P.

B) 2-~ert.-butylphenyl dichlorophosphite:
Distillation of the crude product having a purity of 84%

- 26 - 2~5~
[31P-NMR: ~CDCl3 = 185.1 ppm] of the above compound yielded 94 g of colorless oil of b.p. 74-76~C/0.01 mbar.
CloHl3C12OP Calc.: 47.83 % C, 5.21 % H, 12.33 ~ P
(251.09) Found: 47.4 % C, 5.1 % H, 12.0 % P.

C) 2,4-dimethylphenyl dichlorophosphite:
Distillation of the crude product having a purity of 75%
t3lP-NMR: ~CDCl3 = 180.9 ppm] of the above compound yielded 72 g of colorless oil of b.p. 58-60C/0.05 mbar.
C~HgCl2OP Calc.: 43.08 % C, 4.06 % H, 13.88 % P
(223.03) Found: 42.7 % C, 3.9 % H, 13.6 % P.

D) 2-tert.-butyl-4-metho~yphenyl dichlorophosphite:
Distillation of the crude product yield 110 g of color-less oil of b.p. 108-110C/0.05 mbar.
C11Hl5Cl2O2P Calc.: 46.99 % C, 5.37 % H, 11.01 % P
(281.11) Found: 46.7 % C, 5.5 % H, 10.7 % P.

E) 2,4-di-sec.-butylphenyl dichlorophosphite:
Distillation of the crude product having a purity of 71%
[3lP-NMR: ~CDCl3 = 182.3 ppm] of the above compound yielded 93 g of colorless oil of b.p. 108C/0.05 mbar.
C14H2lCl2OP Calc.: 54.73 % C, 6.89 % H, 10.08 % P
(307.20) Found: 54.5 % C, 6.7 % H, 10.0 % P.

F) 2-sec.-butylphenyl dichlorophosphite:
Distillation of the crude product having a purity of 78%
t31P-NNR: ~CDCl3 = 182.3 ppm] yielded 83 g of colorles~
oil of b.p. 92-93-C/0.1 mbar.
CloH13Cl2OP Calc.s 47.83 % C, 5.21 % H, 12.33 % P
(251.09) Found: 47.4 % C, 4.9 % H, 12.0 % P.

II) ~ample~ 1 to 12 - aryl chlorophosphoramidites (II) General procedure for preparation A solution of 500 mmol of the amine HNR4R5 and 500 mmol (= 50.6 g) of triethylamine in 100 ml of toluene was metered in the course of 30-40 minutes into a 601ution of 500 mmol of aryl dichlorophosphite in 400 ml of toluene - 27 ~ S~ {j which was stirxed 2t -10C under nitrogen in such a way that the internal temperature did not exceed 0C. The mixture was subsequently stirred at room temperatuxe for a further 2 hours in order to complete the reaction.
After filtration and removal of the solven~ by distil-lation in vacuo, the crude chloroamidites usually remained as yellow oils. A further purification is in general not necessary for further reaction with Grignard reagents.

1) 2,4-di-tert.-butylphenyl chloropho6phite morpholide:
Starting from 153.6 g of 2,4-di-tert.-butylphenyl di-chlorophosphite and 43.6 g of morpholine, 165 g of a colorless solid of mOp. about 70C and a purity of 94%
[31P-NMR: ~CDCl3 = 156.9 ppm] of the above compound were obtained.
C13H29ClNO2P Calc.: 60.41 % C, 8.17 % H, 8.65 % P
l357.86) Found: 6D.1 ~ C, 8.4 % H, 8.3 % P.

2) 2,4-di-tert.-butylphenyl ~hlorophosphite di-n-butyl-amide: Starting from 153.6 g of 2,4-di-tert.-butylphenyl dichlorophosphite and 64.62 g of di-n-butylamine, about 190 g of a yellow oil having a purity of 94% [31P-NMR:
~CDCl3 = 162.3 ppm~ of the above compound were obtained.
C2zH29ClNOP Calc.: 66.06 % Ct 9.82 ~ H, 7.74 % P
(399.99) Found: 66.4 % C, 9.6 % H, 7.7 ~ P.

3) 2-tert.-butylphe~yl chlorophosphite di-n-butylamide:
Starting from 125.54 g of 2-tert.-butylphenyl dichloro-phosphite and 64.62 g of di-n-butylamine, about 165 g of a yellow oil having a purity of 89% [3lP-NMR: ~CDCl3 =
161.8 ppm] of the above compound were obtained.
C1aH31ClNOP (343.87) 4) 2,4~di-tert.-butylphenyl ~hlorophosphite piperidide Starting from 153.6 g of 2,4-di-tert.-butylphenyl di-chlorophosphite and 42.57 g of piperidine, about 170 g of a yellow oil having a purity of 88~ [31p_NMR: ~CDC13 =
157.7 ppm] of the above compound were obtained.

28 - Z ~
-ClgH31ClNOP (355.89) 5) 2,4-di-tert.-butylphenyl chlorophosphite N-n-butylani-lide: Starting from 153.6 g of 2,4-di-tert.-butylphenyl dichlorophosphite and 74.6 g of N-n-butylaniline, about 200 g of a yellow oil having a purity of 89% t3lP-NMR:
~CDCl3 = 156.6 ppm] were obtained.
C24H3sClNP (419.97) 6)2,4-di-tert.-butylphenylN-(hesamethyleneimino)chloro-phosphoramidite: Starting from 153.6 g of 2,4-di-tert.-butylphenyl dichlorophosphite and 49.58 g of hexamethyl-eneimine (also called homopiperidine)l about 176 g of a yellow oil having a purity of 87% t3lP-NMR: ~CDC13 (sic) =
163.9 ppm] of the above compound were obtained.
C20H33ClNOP (369.91) 7) 2,-4-di-tert.-butylphenyl dicyclohexylchlorophosphor-amidite: Starting from 153.6 g of 2,4-di-tert.-butyl-phenyl dichlorophosphite and 90.65 g of dicyclohexyl-amine, the reaction being completed at 60C, about 205 g of a yellow resin having a purity of 84% t3lP-NMR: ~CDCl3 = 166.0 ppm] of the above compound were obtained.
C26H43ClNOP (452.05) 8) 2-tert.-butyl-4-aethosyphenyl chlorophosphite mor-pholide: Starting from 140.56 g of 2-tert.-butyl-4-methoxyphenyl dichloropho~phite and 43.6 g of morpholine, about 152 g of colorless oil were obtained which solidified at room temperature.
Cl5H23ClNO3P Calc.: 54.30 % C, 6.98 % H, 9.33 ~ P
(331.77) Found: 54.0 % C, 6.7 % H, 8.9 % P.

9) 2,4-di-sec.-butylphenyl chlorophosphite morpholide:
Starting from 153.6 g of di-sec.-butylphenyl dichloro-phosphite and 43.6 g of morpholine, about 160 g of a yellow oil having a purity of 80% t3lP-NMR: ~CDC13 = 159.8 ppm] of the above compound were obtained.
Cl8H29ClNO2P (357.86) - ~9 -10) 2,4-dLmethylphsnyl chlorophosphite morpholide: Start-ing fxom 111.52 g of 2,4-dimethylphenyl dichlorophosphite and 43.6 g of morpholine, about 120 g of a yellow oil having a puri~y of 90% [31p_NMR: SCDC13 = 160.7 ppm] were 5 obtained. The distillation yielded a colorless oil of b.p. = 148-150C/0.05 mbar C1zHl7ClNO2P Calc: 52.66 % C, 6.26 % H, 11.31 % P
~273.70~ Found: 51.9 ~ C, 5.9 % H, 11.5 % P.

11) 2,4-dimethylphenyl chloropho6phite pip~ridide:
Starting from 111.52 g of 2,4-dimethylphenyl dichloro-phosphite and 42.6 g of piperidine, 121 g of a yellow oil having a purity of 89% [3lP-NMR: ~CDCl3 = 161.3 ppm] of the above compound were obtained. The distillation yielded a colorless oil of b.p. = 134-135C/0.05 mbar Cl3HlgClNOP Calc: 57.46 ~ C, 7.04 % H, 11.39 % P
(271.72) Found: 57.1 ~ C, 6.9 % H, I1.2 % P.

12) 2,4-dimethylphenyl di-n-butylchlorophosphoramidite:
Starting from 111.52 g of 2,4-dimethylphenyldichlorophos-phite and 64.6 g of di-n-butylamine, 143 g of a yellow oil having a purity of 86% [3lP-NMR: ~CDC13 = 167.7 ppm]
of the above compound were obtained. The distillation yielded a colorless oil of b.p. = 148C/0.05 mbar Cl6H27ClNOP Calc: 60.84 ~ C, 8.61 ~ H, 9.80 % P
(315.82) Found: 60.5 ~ C, 8.4 % H, 9.9 % P.

III) ~amples 13 to 33 - aryl pho~phonamidites (I) General procedure for preparation The corresponding Grignard compound was prepared from 250 mmol of organobromine compound and 250 mmol (= 6.1 g) of magnesium turnings in 170 ml of tetrahydrofuran under a nitrogen atmosphere and with exclusion of moi~ture. The resulting solution or suspension of the organometallic compound was subsequently metered into a solution of 250 mmol of the chlorophosphoramidite (II) concerned in 120 ml of tetrahydrofuran with vigorous ~tirring at an internal temperature of -20 to -lO~C in the course of 30 - 30 ~ ?~r~
- 40 minutes. The reaction mixture was then allowed to come to room temperature and was stirred for a furthex 2.5 hours in order to complete the reaction. After filtration of the precipitated magnesium salt, the solvent was remo~ed by distillation first in the vacuum of the water jet pump and then in a high vacuum and the colorless or pale-beige residue was pulverized and dried in a high vaouum.

The purity of desired product in the crude materials was determined by 3lP-NMR spectroscopy. In the case of the monophosphonamidites it was in general between 80 and 94%
(of the total P). In th cases indicated, the crude mixture was crystallized from acetonitrile/acetone mixtures in order to characterize the product.

13) 2',4'-di-tert.-butylphenyl ~2,4,6-trimethyl-1-phenyl)phosphonite piperidide: Starting from 49.7 g of bromomesitylene and 89.0 g of 2,4-di-tert.-butylphenyl chlorophosphite piperidide, about 108 g of beige material of softening point about 30C and a purity of 86~ of the above compound were obtained [31P-NMR: ~CDCl3 = 132.7 ppm].
C2BH42NOP Calc: 76.49 ~ C, 9.63 % H, 7.04 ~ P
(439.62) Found:76.0 % C, 9.5 % H, 6.7 % P.

14~ 2',4'--cli-tert. butylphenyl (2,4,6-trimethyl-1-phe~yl)phosphomite morpholides Starting from 49.7 g of bromomesitylene and 8g.47 g of 2,4-di-tert.-butylphenyl chlorophosphite: morpholide, about 110 g of coLorles~
material of m.p. 70-80C and a purity of 90% of the above compound were obtained [31P-NMR: ~CDCl3 = 132.4 ppm~.
C27H40NOzP Calc: 73.43 % C, 9.13 ~ H, 7.01 % P
(441.60) Found: 73.1 % C, 9.5 ~ H, 6.5 % P.

15) 2',-4'-dLmethylphen~l (2,4,6-trimethyl-1-phenyl3-pho~phonite morpholide Starting from 49.7 g of bromome-sitylene and 68.43 g of 2,4-dimethylphenyl chlorophos-phite morpholide, about 90 g of yellowish material of softening point 90-95C and a purity of 91~ of the aboYe compound were obtained [3lP-NMR: ~CDC13 = 135.1 ppm].
C21H23NO2P Calc: 70.56 % C, 7.89 % H, 8.66 % P
(357.44) Found: 69.9 % C, 8.1 % H, 8.2 % P.

16) 2',4'-di-secO-butylphenyl (2,4,6-trimethyl-1-phenyl)phosphonite morpholide: Star~ing from 49.7 g of bromomesitylene and ~9.46 g of 2,4~ sec.-butylphenyl chlorophosphite morpholide, about 108 g of yellowish oil having a purity of 86% of the above compound were ob-tained [3lP-NMR: ~CDC13 = 134.3 ~nd 135 ppm (diastereo-mers)].
C27H40NO~p (441.60~

17) 2~,4'-di-tert.-butylphenyl (2,4,5-trLmethyl-l-phenyl)phosphonite morph~lide: Starting from 49.7 g of lS 5-bromo-1,2,4-trimethylbenæene and 89.46 g of 2,4-di-tert.-butylphenyl chlorophosphite moxpholide, about 100 g of colorless resin having a purity of 93% of the above compound were obtained [31P-NMR: ~CDC13 = 120.9 ppm].
Crystallization from acetonitrile yielded colorless crystals of m.p. 130 - 132C.
C27H40NO2P Calc: 73.43 % C, 9.13 % H, 7.01 % P
(441.6) Found: 73.2 % C, 9.4 % H, 6.8 % P.

18) 2',4'-di-tert.-butylphenyl (4-~ert~-butyl-1-phenyl)-phosphonite mo~pholide: Starting from 53.5 g of p-bromo-tertO-butylbenzene and 89.46 y of 2,4-di-tert.-butyl-phenyl phosphit~ (sic~ morpholide, about 110 g of color-less resi.n having a purîty of 85% of the above compound [31P-NMR: ~CDCl3 = 126.3 ppm] were obtained. Crystalliza-tion from acetone/acetonitrile (1~1) yielded colorless crystals of m.p. 106 - 108C.

19) 2'-tert.-butyl-4'-methoxyphenyl (4-tert.-butyl-l-phenyl)pho~phonite morpholide: Staxting from 53.3 g of p-bromo-tert~-butylbenzene and 82.95 g of 2-tert.-butyl-4-methoxyphenyl chlorophosphite morpholide, about 10~ g of beîge material of softening point about 70C and a purity 5 1~

of 82% of the above compound were obtained [31p_NNR:
~CDCl3 = 126.7 ppm].
C25H36NO3P t429.54).

20) 2~,4~-di-tert.-butylphenyl 4-biphenylphosphonite morpholide: Starting from 58.3 g of 4-bromobiphenyl and 89.46 g of 2,4-di-tert.-butylphenyl chlorophosphite morpholide, about 114 g of colorless material having a purity of 88% of the above compound were obtained [31p_ NMR: 6CDC13 = 125.3 ppm]. CrystallizatiOn from acetone yielded colorless crystals of m.p. 124 - 125C.
C30H3~NO2P Calc.: 75.76 % C, 8.05 % H, 6.51 % P
(475.61) Found: 75.9 % C, 8.35 % H, 6.3 % P.

21) 2',4'-di-tert.-butylphenyl (4-metho y-l-phenyl)-phosphonite di-n-butyl~mide: Starting from 46.75 g of 4-bromoanisole and 100 g of 2,4-di-tert.-butylphenyl chlorophosphite di-n-butylamide, about 110 g of yellow resin having a purity of 90% of the above compound were obtained t3lP-NNR: ~CDCl3 = 127.9 ppm].
C29H46NO2P (471.67).

22) 2~,4~-di-tert.-butylphenyl l-naphthylphosphonite morpholide: Starting from 51.8 g of l-bromonaphthalene and 89.46 g of 2,4-di-tert.-butylphenyl chlorophosphite morpholide, about 112 g of colorless material of soften-ing point about 100-105C and a purity of 87% of the above compound were obtained t3lP-NMRs CCDCl3 - 120.8 ppml. C2~H36NO2P Calc.: 74.8 % C, 8.07 % H, 6.88 % P
(449.58) Found: 74.2 % C, 8.1 % H, 6.4 % P.

23) 2',4'-di-tert.-butylphenyl 2-naphthylpho~phonite morpholide: Starting from 51.8 g of 2-bromonaphthalene and 89.46 g of 2,4-di-tert.-butylphenyl chlorophosphite morpholide, about 110 g of colorless material of soften-ing point about 100-C and a purity of 92% of the above compound were obtained t3lP-NMR: 6CDCl3 = 125.0 ppm].
Colorless crystals of m.p. 120C were obtained from acetonitrile.

2 ~ , A l$ >
Cz8H36NO2P Calc .: 74.80 % C, 8.07 ~ H, 6.88 ~ P
(449.58) Found: 74.5 % C, 8.3 % H, 6.9 % P.

24) 2~,4~-di-sec.-butylphenyl l-naphthylphosphonite morpholide: Starting from 51.8 g of l-bromonaphthalene and 89.46 g of 2,4-di-sec.-butylphenyl chlorophosphite morpholide, about 116 g of ductile resin having a purity of 80% of the above compound were obtained [3lP-NMR:
~CDCl3 = 121.2 and 121.6 ppm (diastereomers)~.
C28H36NO2P (449.58)-

25) 2',4'-dimethylphenyl l-naphthylphosphonite mor-pholide: Starting from 51.8 g of 1-bromonaphthalene and 68.43 g of 2,4-dLmethylphenyl chlorophosphite morpholide, about 91 g of colorless material of softening point 78 -80C and having a purity of 89% of the above compound [31P-NMR: 6CDCl3 = 121.6 ppm] were obtsined.
C22H24NO2P Calc.: 72.31 % C, 6.62 % H, 8.47 % P
(365.41) Pound: 71.9 % C, 6.4 % H, 8.1 % P.

26) 2',4'-di-tert.-butylphenyl (4-methyl-1-naphthyl)-phosphonite morpholide: Starting from 55.27 g of 1-bromo-4-methylnaphthalene and 89.46 g of 2,4-di-tert.-butyl-phenyl chlorophosphite morpholide, about 113 g of beige material of softening point about 90C and a purity of 88% of the above compound were obtsined t3lP-NMR:
~CDCl3 = 121.4 ppm~. A colorless powder of m.p. 110C was obtained from acetonitrile.
C2~H38NO2P Calc.: 75.13 % C, 8.26 % H, 6.68 % P
(463.59) Found: 74.7 % C, 8.0 % H, 6.5 % P.

27) 2~,4'-di-tert.-butylphenyl (2-methyl-1-naphthyl)-pho~phonite rpholide: Starting from 55.3 g of l-bromo-2-methylnaphthalene and 89.46 g of 2,4-di-tert.-butyl-phenyl chlorophosphite morpholide, about 108 g of nearly colorless material of softening point about 70C and a purity of 83% of the above compound were obtained t31P-NMR: ~CDCl3 = 131.8 ppm]. Colorless needles of m.p. 115 -118C were obtained from acetonitrile.

.

2~

C25,H38NO2P Calc.: 75.13 9~i C, 8.26 % H, 6.68 % P
(463.59) Found: 75.6 9c C, 8.5 % H, 6.3 % P.

28) 2~,4~-di-tert.-butylphenyl l-napthylphosphonite homopiperidide: Starting from 51.8 g of l-bromonaphthal-ene, and 92.48 g of 2,4-di-tert.-butylphenyl chloro-phosphite homopiperidide (see Example 6), about 110 g of colorless, ductile resin having a purity of 88% t3lP-NMR:
6CDCl3 = 122.9 ppm] of the above compound were obtained.
Colorless crystals of m.p. 112 - 113-C were obtained from acetonitrile/acetone (1:1).
C30H40NOP Calc.: 78.05 % C, 8.73 9~ H, 6.70 % P
(461.62) Found: 78.2 % C, 8.5 % H, 6.5 % P.

29) 2~,4'-di_tert.-butylphenyl ~6-metho~q-2-naphthyl) phosphonite morpholides Starting from 59.3 g of 2-bromo-6-methoxynaphthalene and 89.46 g of 2,4-di-tert.-butyl-phenyl chlorophosphite morpholide, about 107 g of color-less material of softening point about 45C and a purity of 94% of the above compound were obtained [3lP-NMR:
~CDCl3 = 125-7 ppm]
C29H3,lNO3P Calc.: 72.62 96 C, 7.98 % H, 6.45 % P
(479.60) Found: 72.2 % C, 8.3 % H, 6.1 % P.

30) Bist2,4,-dimethylphenyl) 4,4~-biphenylenediphosphon-ite morpholide]s Differing from the general procedure, 250 mmol (- .78 g) of 4,4'-dibromobiphenyl were converted into a Grignard compound with 500 mmol (- 12.2 g) of magnesium turnings in 500 ml of tetrahydrofuran under the action of ultrasound (40 kHz) and reacted with 500 mmol (= 136.9 g) of 2,4-dimethylphenyl chloropho~phite which was dissolved in 200 ml of tetrahydrofuran. About lS0 g of yellowish, ductile resin having a purity of 63% of the above compound wereobtained ~31p_NMR: ~CDCl3 = 126.7 ppm].
C36H42N2O4P2 (628.68)

31) Bist(2,4,-di-tert.-butylphenyl) 4,4'-biphenylenedi-phosphonite morpholide]: Differing from the general procedure, 250 mmol (= 78 g) of 4,4'-dibromobiphenyl were - 35 ~
converted into a ~rignard compound with 500 mmol (= 12.2 g) of magnesium turnings in 500 ml of tetrahydro-furan under the action of ultrasound (40 kHz) then and reacted wi~h 178.9 g of 2,4-di-~art.-butylphenyl chloro-phosphite morpholide in 200 ml of tetrahydrofuran. About200 g of yellowish powder of softening point 103 - 105C
and a purity of 70~ of the above compound were obtained [31p_NMR: ~CDCl3 = 125.0 pp~.
C 4 8H66N204P2 (797-00)

32) Bis[(2,4,-di-tert.-butylphenyl) 4~4r-biphenylenedi-phosphonite di-n-butylamide~: Differing from the general procedure, 250 mmol (= 78 g) of 4,4'-dibromobiphenyl were converted into a Grignard compound with 500 mmol (= 12.2 g) of magnesium turnings in 500 ml of tetrahydro-furan under the action of ultraso~tnd (40 kHz) and then reacted with 500 mmol (= 200 g) of 2,4-di-tert.~butyl-phenyl chlorophosphite di-n-butylamide in 200 ml of tetrahydrofuran. About 210 g of a ductile, yellow resin having a purity of 73% of the above compound were obtained [3lP-NMR: ~CDCl3 = 126.g ppm].
Cs6Ha6N202P2 (881.27)

33)Bist(2'4'-di-tert.-butylphenyl)phenylene-1,4-diphos-phonite morpholide]: Differing from the general proced-ure, 250 mmol (= 58.97 g) of 1,4~dibromobenzene were converted into a Grignard compound with 600 mmol (= 14.6 g) of magnesi~n turnings in 300 ml of tetrahydrofuran under the action of ultrasound (40 kHz) and then re~cted with 500 mmol (= 17809 g) of 2,4 di-tert.-butylphenyl chlorophosphite morpholide in 200 ml of tetrahydrofuran.
About 170 g of an almost colorless resin were obtained.
Colorless crystals of softening point 230C were obtained from acetone [31P-NMR ~CDCl3 = 124.6 ppm].
C42H62N204P2 Calc.: 69.97 ~ C, 8.66 ~ H, 8.59 % P
(720.90) Found: 69.5 % C~ 8.9 % H, 8.3 % P.

IV) ~xamples of use The aryl phosphonamidites (I) according to the invention listed below were employed for the experiments:

a) 2~,4~-di-tert.-butylphenyl (2~4~6-trimethyl-I-phenyl)-phosphonite morpholide b) 2',4'-di-tert.-butylphenyl (2,4,5-trimethyl-1-phenyl)-phosphonite morpholide c) 2',4'-di-tert.-butylphenyl 4-biphenylphosphonite morpholide 0 d) 2~,4~-di-tert.-butylphenyl l-naphthylphosphonite morpholide e) 2',4'-di-tert.-butylphenyl 1-naphthylphosphonite homopiperidide f) 2',4'-di-tert.-butylphenyl ~S-methoxy-2-naphthyl)-phosphonite morpholide g) bis(2~4~-di-tert.-butylphenyl) phenylene-1,4-diphosphonite morpholide Example 34 and Comparative E~amples A to C

100.0 psrts by weight of unstabilized polypropylene powder (density: 0.903 g/cm3; melt flow index MFI 230/5:
4 q/10 min) were mixed with 0.1 part by weight of Ca stearate as acid acceptor and the amounts of phosphorus compound listed in the tables and extruded repeatsdly by means of a laboratory extruder (short-compression zone screw, diameter of screw: 20 mm; length 20 D, length of nozzle 30 mm, diameter 2 mm; number of revolutions:
125 rpm; temperature program: 200/230/230C). After the 1st, 5th and 10th pass, samples were taken from the granules and used to measure the melt flow index Z~6~

accordinq to DIN 53 735 and the yellowness as yellowness index according to ASTM D 1925-70. In addition, the granules of the 1st pass were used to produce extruded sheets of the dimensions 60 x 60 x 1 mm, and the yellow-ness was measured immediately and after hot storage (7days at 100C).

The results are listed in Tables 1, 2a and 2b.

Esample 35 and Comparative Examples D to F

100.0 parts by weight of unstabilized polypropylene powder (density: 0.903 g/cm3; me}t flow index MFI 230/5:
4 g/10 min) were mixed with 0.1 part by weight of Ca stearate as acid acceptor and 0.05 part by weight of ethylene.glycol bis(3,3-bis(3't-butyl-4'-hydroxyphenyl)-butyrate (sic) and the amounts of phosphorus compound listed in the tables and extruded repeatedly by means of a laboratory extruder (short-compression zone screw, diameter of screw: 20 mm; length 20 D, length of nozzle 30 mm, diameter 2 mm; number of revolutions: 125 rpm;
temperature program: 200/230/230C). After the 1st, 5th and 10th pass, samples were taken from the granules and used to measure the melt flow index according to DIN 53 735 and the yellowness as yellowness index according to ASTM D 1925-70. In addition, the granules of the l~t pass were used to produce extruded sheets of the dimension~ 60 x 60 x 1 mm, and the yellowness was measured immediately and after hot storage ~7 days at 100C).

The results are listed in Tables 3, 4a and 4b.

,. . : .
.. ,~, ~ .

. ' .

~ ~r~

Table l: The effect of phosphorus compounds on the proce~sing stability of polypropylene. Melt flow index MFI 230~5 after multiple granula-tion. (MFI in g/10 ~in) ~ ~ _ . _ Example Phosphorus compound MFI after _ _ _ _ 1st _5th 10th qranulation Comp Ex. A none 10.5 19.0 34.0 Comp. 0.1 part by weight 6.4 7.0 10.5 Ex. h of tris(2,4-di-t~
butylphenyl) phosphite Comp. 0.1 part by weight 5.5 5.7 7.8 Ex. C of commercial phosphonite ) 34a 0.1 part by weight 5.6 6.1 7.5 of (phosphonite according to the invention) 34b ~ 1.0 1.0 1.3 34c " 6.1 6.3 11.3 34d ~ 5.4 5.5 6.0 34e ~ 1.0 1.3 2.0 34f " 1.1 1.1 1.7 34g " 1.~ 1.4 1.6 .
Tetrakis(2,4 di-t-butylphenyl) 4,4'-biphenylenediphos-phonite Table 2a: Coloration (yellowness index according to ASTM
D 1925-70) after multiple granulation of polypropylene.
_ _ Example Phosphorus compound YI after 1st 5th10th aranulation Comp.
Ex. A none 18.7 25.7 27.7 Comp. 0.1 part by weight 13.9 23.0 30.4 Ex. B of tris(2,4-di-t-butylphenyl) phosphite Comp. 0.1 part by weight 12.8 21.0 26.1 Ex. C of commercial phosphonite~) 34a 0.1 part by weight 8.2 15.5 22.8 of (phosphonite according to the invention) 34b " 2.5 2.6 7.7 34c ~' 16.3 20.4 33.2 34d " 14.5 15.0 18.8 34e ll 3.7 6.5 13.8 34f " 6.1 7.9 16.1 34g " 2.2 2.6 5.8 _ .
) Tetrakis(2,4-di-t-butylphenyl) 4,4'-biphenylenediphos-phonite Table 2b: Coloration of 1 mm extruded sheets immediately after production and after heat treatment (7 days at 100C) YI immediately YI after 7 days/100C
Comp. Ex. A 4.2 10.1 Comp. Ex. B 3.4 13.0 Comp. Ex. C 4.5 12.5 34a 2.5 11.1 34b 1.6 5.4 34c 4.7 9.3 34d 3.9 8.7 34e 1.5 5.5 34f 1.8 8.5 34g 1.0 4.5 t, J' !, Table 3~ The effect of phosphorus compounds on the processing stability of polypropylene. Melt flow index MFI 230/5 after mul~ipl~ granula-tion. (MFI in g/10 min) Example Phosphorus compound MFI after _ __ _ 1st 5th 10th qranulation See D none 13.4 19.0 23.8 See E 0.01 part by weight7.1 7.8 8.8 of tris(2,4~di-t-butylphenyl) phosphite See F 0.01 part by weight5.8 6.4 8.9 of commercial phosphonite ) 35a 0.01 part by weight5.0 4.8 5.4 of ~phosphonite according to the invention) 35b " 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 35f " 5.8 7A3 8.4 35g " 5.0 6.6 8.0 ... . ~
) Tetrakis(2,4-di-t-butylphenyl) 4,4~-biphenylenediphos-phonite - 41 - 2~
Table 4a: Coloration (yellowness index according to ASTM
D 1925-70) after multiple granulation of polypropylene.

5 Example Phosphorus compound YI after 1st 5th 10th aranulation See D none 8.0 23.4 28.0 See E 0.05 part by weight 9.5 12.3 15.1 of tris(2~4-di-t-butylphenyl) phosphite See F 0.05 part by weight 12.5 16.5 20.8 of commercial phosphonite ) 35a 0.05 part by weight 3.3 5.6 9.5 of (phosphonite according to the invention) 35b ~ 11.1 9.4 12.9 35c ~ 7.0 12.1 15.7 35d ~ 10.4 23.4 31.3 35e ~ 11.1 15.6 19.5 35f ~ 12.1 20.9 26.6 35g ~ 8.7 29.9 32.0 ) Tetrakis(2,4-di-t-butylphenyl) 4,4~-biphenylenediphos-phonite Table 4b: Coloration of 1 mm extruded sheets immediately after production and after heat treatment (7 days at 100C) YI immediatelyYI after 7 days/lOO~C
See D 3.9 7.7 See E 2.3 5.0 See P 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 35f 3.9 6.3 35g 2.7 2.9

Claims

Patent Claims:

1. A phosphonamidite of the formula (I) (I) in which:
R1, as a univalent radical, is a phenyl radical which carries 1 to 3 substituents, or a benzyl, .alpha.-methylbenzyl or .alpha.,.alpha.-dimethylbenzyl radical which in each case can carry 1 to 3 substituents on the nucleus, or a naphthyl radical which can carry 1 to 5 substituents, where at least one of these substituents is an alkoxy radical or alkylthio radical in each case having 1 to 8 carbon atoms, or an aryl or aryloxy radical in each case having 6 to 10 carbon atoms or halogen having an atomic number of 9 to 35 and the other substituents - also exclusively in the naphthyl radical - are a non-aromatic hydrocarbon radical having 1 to 8 carbon atoms, and R1, as a divalent radical, is a phenylene radical which is unsubstituted or substituted by up to 2 non-aromatic hydrocarbon radicals having 1 to 8 carbon atoms, or a naphthylene or biphe-nylene radical which is unsubstituted or can carry 1 to 4 non-aromatic hydrocarbon radicals each having 1 to 8 carbon atoms as substituents, R2 is a non-aromatic hydrocarbon radical having 1 to 18 carbon atoms an aryl or an optionally substituted arylmethyl radical, where the aryl radical in each case contains 6 to 10 carbon atoms, R3 is hydrogen, an alkoxy or alkylthio radical in each case having 1 to 18 carbon atoms or a group mentioned under R2, R4 and R5 independen~ly of one another in each case are C1-C22 alkyl, C2-C21-oxaalkyl or -thiaalkyl, C3-C18-alkenyl or -alkynyl, C3-C24-alkoxycarbonylalkyl, C5-C12-cycloalkyl, C6-C14-aryl, C7-C15-arylalkyl or an optionally substituted C5-C17-piperidin-4-yl group, or R4 and R5, together with the nitrogen atom, are also a ring system containing 5 to 7 ring atoms which may additionally further contain an oxygen, nitrogen or sulfur atom bonded via at least one carbon atom and n = 1 or 2.

2. A compound as claimed in claim 1, wherein R1, as a divalent radical, forms a biphenylene radical, R2 and R3 in each case form a branched butyl radical and R4 and R5 in each case form a butyl radical or, together with the nitrogen atom, form the morpholide radical.

3. A compound as claimed in claim 1, wherein R1 is unsubstituted naphthyl.

4. A compound of the formula (I), as shown in claim 1, wherein R1 is the trimethylphenyl radical, R2 and R3 are the methyl radical or a branched butyl radical and R4 and R5, together with the nitrogen, are either the piperidide or morpholide radical.

5. A compound of the formula (I), as shown in claim 1, wherein R1 is the tert.-butyl-1-phenyl radical, R2 is the tert.-butyl radical, R3 is the methoxy radical or tert.-butyl radical and R4 and R5, together with the nitrogen atom, are the morpholide radical.

6. A process for the preparation of phosphonamidites of the formula (I) as shown in claim 1, in which R1, as a univalent radical, is a non-aromatic hydrocarbon radical having 1 to 18 carbon atoms or a phenyl, benzyl, .alpha.-methylbenzyl or .alpha.,.alpha.-dimethylbenzyl radical, where these radicals in each case can carry 1 to 3 substituents on the nucleus, or a naphthyl radical which can carry 1 to 5 substituents, where the substituents are a non-aromatic hydrocarbon radical, alkoxy radical or alkylthio radical in each case having 1 - 8 carbon atoms, or an aryl or aryloxy radical in each case having 6 to 10 carbon atoms or halogen having an atomic number of 9 to 35 and R1, as a divalent radical, is a phenylene radical which is unsubstituted or substituted by up to 2 non-aromatic hydrocarbon radicals having 1 to 8 carbon atoms, or a naphthylene radical or biphenylene radical which is unsubstituted or can carry 1 to 4 non-aromatic hydrocar-bon radicals each having 1 to 8 carbon atoms as sub-stituents, R2 is a non-aromatic hydrocarbon radical having 1 to 18 carbon atoms, or an aryl radical or an optionally sub-stituted arylmethyl radical, where the aryl radical in each case contains 6 to 10 carbon atoms, R3 is hydrogen, an alkoxy radical or alkylthio radical in each case having 1 to 18 carbon atoms or a group men-tioned under R2, R4 and R5 independently of one another in each case are C1-C22-alkyl, C2-C21-oxaalkyl or -thiaalkyl, C3-C18-alkenyl or -alkynyl, C3-C24-alkoxycarbonylalkyl, C5-C12-cycloalkyl, C6-C14-aryl, C7-C15-arylalkyl or an optionally substituted C5-C17-piperidine-4-yl group, or R4 and R5, together with the nitrogen atom, form a ring system containing 5 to 7 ring atoms which can still additionally contain an oxygen, nitrogen or sulfur atom bonded via at least 1 carbon atom and n is 1 or 2, which comprises; initially reacting in a first step a halide R1(-X)n, in which R1 and n have the abovementioned meaning and X is a halogen having an atomic weight of at least 35, under Grignard conditions with finely divided magnesium to give the corresponding Grignard compounds R1(MgX)n and then reacting these further in a second step with halophosphoramidites of the formula (II) (II) in which R2, R3, R4 and R5 have the abovementioned meaning and X is chlorine or bromine, to give the phosphonamid-ites (I).

7. The process as claimed in claim 6, wherein the reaction in the first step is carried out between 20 and 125°C, preferably between 30 and 70°C.

8. The process as claimed in claims 6 or 7, wherein the reaction of the first step is carried out under the action of ultrasound.

9. The process as claimed in one or more of clai ms 6 to 8, wherein the reaction in the second step is carried out at a temperature between -30 and +50°C, preferably between -20°C and +20°C.

10. The use of compounds of the formula (I), as claimed in one or more of claims 1 to 5, alone or in combination with a phenolic antioxidant for the stabilization of plastics, in particular polymerization plastics.

11. An aryl halophosphoramidite of the formula (II) in which R2, R3, R4 and R5 have the meaning indicated in claim 6 and X is chlorine or bromine, excluding the compound in which X is chlorine, R2 is methyl, R3 is hydrogen and R4 and R5 are in each case ethyl.

12. A process for the preparation of compounds as claimed in claim 11, which comprises reacting an aryl dihalophosphite of the formula (III) (III) with an amine of the formula HNR4R5 (IV) in the presence of at least an equimolar amount of an acid-binding agent, where in the formulae III and IV R2, R3, R4 and R5 have the meaning indicated in claim 6 and X is a halogen having an atomic weight of at least 35.

13. The process as claimed in claim 12, wherein the reaction is carried out at a temperature of -30 to +30°C, preferably -20 to +10°C.

14. A plastic molding composition, consisting of a) 90 to 99.99% by weight of a thermoplastic or thermoset plastic and b) 0.01 to 10% by weight of an aryl phosphonamidite of the formula (I) (I) in which R1 to R5 and n have the meaning as claimed in claim 1.

15. A plastic molding composition as claimed in claim 14, wherein the plastic is a polyolefin.

16. A plastic molding composition as claimed in claims 14 or 15, which comprises a) 90 to 99.98% by weight of a thermoplastic or thermoset plastic, b) 0.01 to 5% by weight of the said aryl phosphonamidite (I) and c) 0.01 to 5% by weight of an ester from the group comprising c1) 3,3-bis(3'-t-butyl-4'-hydroxyphenyl)butanoic acid of the formula (V) (V) in which m is 1 or 2 and R6 iB a C1-C12-alkyl radical if m = 1, or is a C1 to C12-alkylene radical if n (sic) = 2, and/or c2) an ester of .beta.-(3,5-di-t-butyl-4-hydroxyphenyl)propio-nic acid of the formula (VI) (VI) with a monohydric or polyhydric alcohol.

17. A plastic molding composition according to one or more of claims 14 to 16, wherein it additionally contains additives from the group comprising antioxidants, UV
absorbers, light stabilizers, metal deactivators, peroxide-destroying compounds, basic costabilizers, nucleating agents, fillers, reinforcing agents, plasti-cizers, lubricants, emulsifiers, pigments, optical brighteners, fireproofing agents, antistatics and/or blowing agents.