DE2656999A1 - NEW PHOSPHITES - Google Patents

Description

New phosphites

The present invention relates to new single-ended Piperidyl-phosphite, e5.n Process for their production, their use as stabilizers, and that with their help stabilized against thermo-oxidative and light-induced degradation organic material,

It is known e.g. from DT-OS 1.929.928 or from GB-PS 1.399.239, Use piperidyl phosphites as stabilizers in synthetic polymers. The known connections are however, it is very sensitive to hydrolysis, which leads to poor storage stability and poorly reproducible effectiveness.

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A class of unsymmetrical aryl-containing piperidyl phosphites has now been found which can be used both as processing stabilizers as well as being particularly suitable as light stabilizers, have good color properties and apart from which have an amazing resistance to hydrolysis.

The new compounds correspond to the general formula I.

^ T (I)

or their acid addition salts,

X is hydrogen, oxyl, C 1 -C ₁₉ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C, alkynyl, C ₂ -C ₂₁ alkoxyalkyl, C ₇ -Cg aralkyl, 2,3-epoxyprcpyl, an aliphatic acyl group with 1-4 carbon atoms or one of the groups -CHpCOOR-, -CH ₂ -CH (R ₂ ) -OR ₃ , -COOR, or -CONHR, wherein

R ₁ ^C l " ^C 12 ^alk y ¹ ' ^C 3" ^C 6 A ^ -keny ¹ * phenyl, C ₇ -C ₃ aralkyl

or cyclohexyl, and
R _{2 is} hydrogen, methyl or phenyl, and

R denotes hydrogen, an aliphatic or aromatic, an araliphatic or alicyclic acyl group with 1-18 C atoms, in which the aromatic part may be _{substituted with chlorine, C 1} -C 4 alkyl, C ₁ -C 6 alkoxy and / or with hydroxyl can, or a group of the formula

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means, and

^C 1 ^'C 12 ^A1 alkyl, cyclohexyl, phenyl or benzyl

means, and

a divalent radical selected from the group

consisting of the remainders of the formulas II, III, IV and V

/ 9

^R 8 ~? \ ^R 10

, ^R 7

(II) (HD

CH "CH,
3 3

(V)

R ₁ -, R ₆ , R ₇ and R _g , independently of one another, are hydrogen, C ₁ -Cg alkyl or C ₁ -C ₅ hydroxyalkyl, and

R _Q and R-ΐΛ »are independently hydrogen, C ₁ -C 6 alkyl, C ₁ -C ₅ hydroxyalkyl or C ₁ -C ^ acyl, or

R _q and R ₁₀ together with the carbon atom to which they are attached form cyclohexyl, cyclohex-3-ene or bicyclo- [2,2, l] -hept-5-ene, and

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Ά ··

R ₁₁ and R ^ 2 ', independently of one another, are hydrogen, C ₁ -C 6 alkyl, C ₅ -C 6 cycloalkyl, or C ₇ -C ₉ aralkyl, and

Y _{1 is} a divalent radical selected from the group

consisting of the residues of the formulas II, III and IV means

_{As C 1} -C ₁₂ alkyl, X is, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl or n-dodecyl. Preferred

are alkyl groups with 1-8 carbon atoms, especially those with 1-4 carbon atoms and especially methyl.

As C 1 -C ₄ alkenyl, X is, for example, allyl, 2-butenyl or 2-hexenyl, in particular allyl.

As C 1 -C 4 alkynyl, X is, for example, propargyl.

If XC ₂ -C ₂₁ alkoxyalkyl, the alkyl part can contain 1-3 C atoms and the alkoxy part can consist of 1-18 C atoms, such as in methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2- n-Butoxyethyl, 3-n-Butoxyäthyl, 2-0ctoxyäthyi or 2-Octadecyloxyäthyl, especially to be mentioned are compounds in which X is an alkoxyalky! group with 2-6 carbon atoms.

_{As C 7} -C 6 aralkyl, X is, for example, benzyl or a-phenylethyl.

X is an aliphatic acyl group with 1-4 carbon atoms, for example Forray1, acetyl, acryloyl or crotonyl, in particular Acetyl.

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26S6999

If X is the group --ClUCOOIt, then R ₁₀ is C ₁ -CJ ₂ alkyl, for example methyl, ethyl, isopropyl, η-butyl, isobutyl, t-butyl, isopentyl, n-octyl, n-decyl or n-dodecyl. Preferred is RC ₁ -C, alkyl. As C ₃ -C ₆ alkenyl, R ₁ is, for example, allyl, 2-butenyl or 2-hexenyl. _{As C 7} -C ₈ aralkyl, R is, for example, benzyl or cc-phenylathy I.

If X is the group -CH ₂ -CH (R) -OR ₃ , R _{2 is} hydrogen, methyl or phenyl, in particular hydrogen. R ₃ is

a3s aliphatic, aromatic, alicyclic or araliphatic Ο, -Ο- «« acyl radical, optionally in the aromatic part with chlorine, C ₁ -C, alkyl wit methyl, ethyl, n-propyl or t-butyl or with C, -Cg alkoxy such as Methoxy, ethoxy, butoxy or octoxy and / or substituted by hydroxy, for example acetyl, propionyl, butyryl, octanoyl, dodecanoyl, stearoyl, acryloyl, benzoyl, chlorobenzoyl, toluoyl, isopropylbenzoyl,

2,4-dichlorobenzoyl, 4-methoxybenzoyl, 3-butoxybenzoyl, 2-hydroxybenzoyl, 3,5-di-t-butyl ~ 4-hydroxybenzoyl, ß- (3,5-dit-butyl-4-hydroxyphenyl) propionyl, Phenylacetyl, cinnamoyl, hexahydrobenzoyl, 1- or 2-naphtho3 ^ 1 or decahydronaphthoyl,

If X is the group -COOR ,, then R ^ is C ₁ -C ₁₂ alkyl, e.g. methyl, ethyl, isobutyl, n-hexyl, n-octyl, n-dedyl or n-dodecyl. Preferred as R 1 are alkyl groups with 1-4 C atoms.

Y means one of the groups II, III, IV or V.

R ₁ -, R _fi $ R ₇ and Rq are alkyl, for example branched or unbranched alkyl with 1-8 carbon atoms, in particular with 1-4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, η-butyl , t-butyl, n-pentyl, n-hexyl, n-octyl, t-octyl, especially methyl or ethyl.

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R ₁ J., Rg, Ry and Rg as C ₁ -Cr hydroxyalkyl are, for example, hydroxymethyl, 2-hydroxyethyl, 3-hydroxybutyl or 4-hydroxypentyl, in particular hydroxymethyl.

In group II, the preferred meaning of Rc, R ^, Ry and Ro is hydrogen, methyl or ethyl; in group III hydrogen, and if Rg and R _{10 are} hydrogen, also methyl.

As C ₁ -C 6 alkyl, R ₉ and R ₁₀ are, for example, methyl, ethyl, n-propyl, isopropyl, η-butyl, n-hexyl or n-octyl, in particular R ₀ and R _{1Q have} 1-4 carbon atoms all mean Rq and methyl.

R _Q and R ₁₀ are hydroxyalkyl with 1-5 carbon atoms, in particular with 1-3 carbon atoms, for example hydroxymethyl, 2-hydroxyethyl, 3-hydrox} i:) utyl or 4-hydroxypentyl.

As C ₁ -C, acyl, Rq and R ₁₀ are, for example, formyl, acetyl, acryloyl or crotonoyl, in particular acetyl.

Rg and R ₁₀ together with the carbon atom to which they are bonded can also form cyclohexyl, cyclohex-3-ene or bicyclo- [2,2,1} -hept-5-ene, in particular cyclohexyl.

R ,, and R _,? denotes as alkyl with 1-9 carbon atoms, and in particular 1-4 carbon atoms, for example methyl, ethyl, isopropyl, n-propyl, t-butyl, η-butyl, iso-amyl, n-hexyl, n-octyl , t-octyl, n-nonyl or t-nonyl.

R ₁₁ and R ₁₂ as C ₅ -C 6 denote cycloalkyl, for example cyclopentyl, cyclohexyl or cyclooctyl, in particular cyclohexyl.

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R ₁₁ and R ₁₂ as C ₇ -C ₉ araikyl, for example benzyl, α-methylbenzyl or in particular α, α-dimethylbenzyl.

Particular emphasis should be placed on compounds of the formula I in which X is hydrogen, oxyl, C ₁ -C 6 alkyl, C ₃ -C 6, alkenyl or alkynyl, C ₂ -C 6 alkoxyalkyl, C 2 -C 6 araicyl, acetyl, acryloyl or crotonoyl, or one of the groups -CH ₂ -COOR ₁ , -CH ₂ -CH (R ₂ ) -OR ₃ , -COOR, or -CONHR, denotes in which

R _{1 is} ^C l ~ ^C 4 alkyl, ^C 3 " ^C 4 alkenyl, phenyl, C ₇ -C ₃ araicyl or cyclohexyl, and ·

R _{2 is} hydrogen, methyl or phenyl, and Ro is hydrogen or an aliphatic, aromatic, alicyclic or araliphatic ^ acyl group with 1-18 C atoms, in which the aromatic part is optionally chlorine, C ₁ -C ^ alkyl, C ₁ - Cg can be substituted by alkoxy and / or hydroxy, means and

R, ^C ] ~ ^C 12 alkyl ^isfc » ^and

Y is one of groups II, III, IV or V, in which R ₅ , R ^, R ₇ and Rg, independently of one another, are hydrogen, C ₁ -C ^

Are alkyl or C ₁ -C ₃ hydroxyalkyl, and R "and Rtq, independently of one another, are hydrogen, C ₁ -C ^ alkyl,

C-, -C. Hydroxyalkyl. Or acetyl, or R ₀ and R ₁₀ together with the carbon atom to which they are attached are cyclohexyl, cyclohex ~ 3-ene or bicyclo- [2,2, I) -

form hept-5-en, and
R ₁₁ and R ₁₉ , independently of one another, _{denote hydrogen, C 1} -C ₉ alkyl, C _n -C 6 cycloalkyl or C ₇ -C ₉ aralkyl.

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Preferred compounds of the formula I are those in which hydrogen, C -C, alkyl, allyl, propargyl, C _? -C _{r is} alkoxyalkyl, acetyl, acryloyl or crotonoyl, or one of the groups -CH ₂ -COOR ₁ , -CH ₂ -CH (R ₂ ) -OR

-COOR, or -CONHR, where 4 4 *

R _{2 is} hydrogen or methyl and Ro is hydrogen, and

R ^ ^c i " ^c 4 Aiky ^{1 is} > ^and

Y is one of the groups II, III, IV or V, in which R _r , Rg, R., And Rg, independently of one another, are hydrogen, C, -C,

Alkyl or hydroxymethyl, and R "and R ₁ Q, independently of one another hydrogen or C -, - C,

Alkyl, hydroxymethyl. or acetyl, or R _q and R-.Q together with the carbon atom to which they are attached, cyclohexyl, cyclohex-3-ene or bicyclo- [2.2 _f 1] -

form hept-5-en, and
R ₁₁ and R _{2 are} hydrogen, C 1 -C, alkyl, cyclohexyl or α, α-dimethylbenzyl.

Particularly preferred are compounds of the formula I in which X is hydrogen, methyl, allyl, propargine} ^! or acetyl is and

Y is a group II, III, IV or V, in which

Rr »Rg. R ₇ »Rg. Rn ^{and R} xo * ^{υη £ ΐ1) ηΙίη} ^ 8 of one another are hydrogen, methyl, ethyl or hydroxymethyl, or

R _Q and R, _{fi are} additionally acetyl, or R _Q and R ₁ -. together with the carbon atom to which they are bound cyclohexyl, cyclohex-3-ene or bicyclo- [2,2,1] -

form hept-5-en, and
R ₁₁ and R ₁₂ , independently of one another, are hydrogen or C ₁ -C ^ alkyl.

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Compounds of the formula I in which

X is hydrogen or methyl, and Y is one of the groups II, ItI, IV or V, in which R _r , R _fi> R ₇ and R "in group II, independently of one another, are hydrogen or methyl, and

R ₅ , R ₆ , R ₇ and R _g in group III are hydrogen, or, if R _Q and R _{10 are} hydrogen, hydrogen or methyl, and

Rq and R., ^ Independently of one another are hydrogen, methyl or Are ethyl, and.

^R 31 ^{and R} j2 ^'una ^ ^Naen gig the other hydrogen or C, -C, alkyl.

Also preferred are those compounds of the formula I which are emphasized above as being preferred, in which Ro a group of the formula

wherein Y- is one of the groups II, III or IV.

The present invention also includes the salts of compounds of the formula I, which by addition of acids in a maximum the piperidine groups are formed in equivalent amounts. Such acids can be inorganic acids, such as sulfur-salt or phosphoric acid, organic carboxylic acids such as formic, acetic, oxalic, maleic, benzene or salicylic acid, organic Sulphonic acids such as methane or p-toluenesulphonic acid or organic Phosphorus acids such as dipheny / phosphoric acid, methane phosphonic acid or dipheny / phosphinic acid.

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Compounds of the formula I are for example:

4,4-dimethyl-2f2,2,6,6-tetraraethyl-4-piperidinyl) -1,3,2-dioxaphospholane

4-ethyl-2 [2,2,6,6-tetraniethyl-4-piperidinyl] -1,3,2-dioxaphospholane

4 _f 4,5-triethyl-2 [1,2,2,6,6-pentamethyl-4-piperidinyl] -1,3,2-dioxaphospholane

4, 5-dimethyl-2 [2,2,6,6-tetramethyl-4-piperidinyl thyl-l-acetyl] -1,3,2-dioxaphospholane

4-methyl ~ 2 [2,2,6, 6-tetraraethyl-4-piperidiriyl ~ l-but5 ^T Royl] 1,3,2-dioxaphospholane

5,5-Dimethyl 1-2 [2,2,6,6-tetramethyl 1-4-piperidinyl-1- propargyl] -1,3,2-dioxaphosphorinane

4,4,6-trimethyl-2 [2,2,6,6-tetramethyl-4-piperidinyl-1-acetyl] -1,3,2-dioxaphosphorinane

5,5-di-hydroxymethyl-2 [2,2,6,6-tetraraethyl-4-piperidinyl] -1,3,2-dioxaphosphorinane

5-ethyl-5-hydroxyraethyl-2 [1,2,2,6,6-pentaraethyl-4-piperidinyl-3-1,3,2-dioxaphosphorinane

4-propyl-6-raethyl-2 [2,2,6,6, -tetramethyl-1-acryloylj-1,3,2-dioxaphosphorinane

4-propyl-2 [2,2,6,6-tetramethyl-4-piperidinyl-1-acetyl] -1,3,2-dioxaphosphorinane.

The compounds of general formula I, by the reaction of about one mole of a 4-Rydroxypiperidins Formula VI-.

(VI)

with about one mole of a phosphite of the formula VII

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Z — P Y (VII)

O
getting produced.

The symbols X and Y have the same meaning as in formula I. Z means C, -C, alkoxy or halogen.

a) If Z is C.-C, alkoxy, such as methoxy, ethoxy or butoxy, the reaction is catalyzed by strong bases such as lithium amide, sodium amide, sodium ethanolate or sodium hydride. The reaction can without solvent at 70-180 ⁰ C, preferably 80-150 ⁰ C, carried out at atmospheric pressure or under vacuum. However, an inert organic solvent can also be used. The reaction temperature is preferably 120-150 ⁰ C.

Suitable solvents are all organic solvents which are not compatible with the reactants of formulas VI and VII react, such as aromatic such as toluene or xylene, cycloaliphatic such as decalin, amides such as dimethylformamide or hexamethylphosphoric triamide. The same basic catalysts mentioned above can be used.

b) When Z is halogen, such as chlorine, the reaction is preferably carried out at -10 to '+20 ⁰ C in the presence of a base in a solvent. Particularly suitable bases are tertiary nitrogen bases, such as triethylamine or diethylaniline. It is also possible to use the piperidine of the formula VI as the base. The solvents used are ethers such as dioxane, tetrahydrofuran or diethyl ether; aromatic hydrocarbons such as benzene, toluene or xylene; amides such as dimethyl

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- YES '-

formamide or hexametal, phosphoric acid triamide, or aliphatic Hydrocarbons such as hexane in question.

The 4-hydroxypiperidines of the formula VI can be prepared according to known Methods from the corresponding 4-oxopiperidines of formula VIII

(VIII)

by reduction, e.g. catalytic ^ hydrogenation via Raney nickel getting produced.

The piperidine of formula VIII, in which X is hydrogen, 2,2,6,6 "tetrane; ethyl-4-oxopiperidine is prepared, for example, by the process described in US Pat. No. 3,513,170. In this case, 2,2,4,6 , 6 - Pentamethyl-2 _i 3.4,5-tetrah \ '' drO "P3 ^r ? R5.raidin hydrolytically converted in the presence of an acidic catalyst. It is also known, for example from German Offenlegungsschrift 2,429,937, to produce 2,2,6,6-tetramethyl-4-oxopiperidine directly from ammonia and acetone in the presence of an acidic catalyst.

Compounds of the formula VIII in which X is not hydrogen can be obtained by substitution from 4,4,6,6-tetramethyl-4-oxopiperidine "These are the usual substitution reactions for secondary amines, although these are slower due to the steric hindrance caused by the 4 methyl groups in the 2- or 6-position. The N-H compound can, for example, with alkyl, alkenyl, aralkyl or alkoxyalky! Halides, with dialkyl sulfates, with epichlorohydric

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inside, with esters of chlorocarboxylic acids such as chloroacetic acid esters or acid chlorides or anhydrides are reacted.

The group —CH ₉ —CH (R ₉ ) —OR— can be obtained by reacting the NH piperidines with an epoxide of the formula R ₉ —CH — CH ₉ and

subsequent acylation with an acyl chloride of the formula RoCl are introduced.

The phosphites of the formula VII are known substances and can be produced, for example, by methods that are described in Houben-Weyl, XII, 2, page 46ff (1964) are described.

Even when added in small amounts, the compounds of the formula I protect organic polymers against light-induced aging. The light aging of organic polymers can, on the one hand, lead to degradation and associated deterioration mechanical properties and, on the other hand, lead to discoloration of the polymers, both of which are aging phenomena can occur side by side. Amazingly, the compounds of formula I are also useful as processing stabilizers suitable.

Polymers whose light aging is delayed or prevented by the compounds of the formula I according to the invention are, for example, the following classes ^{which are relevant in technology: Pol3 T} mers which are derived from mono- or doubly unsaturated hydrocarbons. Halogen-containing vinyl polymers, such as polyvinyl chloride. Polymers derived from ct.ß-unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates, polyacrylate and polyacrylonitrile.

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Polymers that differ from unsaturated alcohols or their Derive acyl derivatives or acetals. Homo- and copolymers. derived from epoxy, such as polyethylene oxide. Polyacetals, Polyphenylene oxides, polyurethanes and polyureas, polycarbonates, polysulfones. Polyamines and! Copolyamides die from diamines and dicarboxylic acids and / or from aminocarboxylic acids or the corresponding lactams derive. Polyesters that are derived from dicarboxylic acids lind dialcohols and / or from hydroxycarboxylic acids or the corresponding Lactonen ableiter .. Crosslinked polymers, which differ from aldehydes on the one hand and phenols, ureas and melamines on the other hand. Alkyd resins. Unsaturated polyester resins, derived from Kopolyc! Stern of saturated and unsaturated dicarboxylic acids with polyhydric alcohols, as well as vinyl compounds as Verriet zungsmitt a derive, as well as their halogen-containing flame-retardant modifications. Natural polymers j like Cellulose, rubber, and their polymer-homologous chemically modified derivatives, such as cellulose acetates and cellulose propionates and butyrates, or the cellulose ethers, such as "Methy! cellulose, . ■.

Preferred polymers are high and low density polyethylene, polypropylene, polybutadiene, polyurethanes, polyvinyl chloride, Polystyrene and its copolymers, and mixtures thereof.

Examples of polymers, which by the invention Connections protected against light aging can be v / earthed, are listed in DT-OS 2.427.853, pages 15-17.

The new compounds are added to the substrates in a concentration "Tration of 0.005 to 5% by weight calculated on the too stable! -

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sizing material, added. Preferred prices are 0.01 to 1.0, particularly preferably 0.05 to 0.5% by weight of the compounds, calculated on the material to be stabilized, incorporated into it. _t

The incorporation can take place after the polymerization, for example by mixing the compounds and, if necessary, further additives into the melt according to those in the art customary methods, before or during the shaping, or by applying the dissolved or dispersed compounds on the polymer, optionally with subsequent evaporation of the solvent.

The new compounds can also be in the form of a masterbatch containing these compounds, for example in one concentration from 2.5 to 25 wt .-%, are added to the polymers to be stabilized.

In the case of agitated polyethylene, the connections attached before networking.

The compounds according to the invention can also be used with other additives, with synergistic mixtures can be formed.

As further additives with which together the according to the invention Usable stabilizers can be used, for example: · ·.

Antioxidants such as simple 2,6-dialkylphenols, derivatives of alkylated hydroquinones, hydroxylated thiodipheiiyl ethers,

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Alkylidene bisphenols, 0-, N- and S-Benzy! Compounds, Hydroxybenzylated Kalonester, Hydroxybenzyl-Aroir.aten, s-triazine compounds, amides of /5-(3,5~ditert.-butyl-4-hydroxyphenyl) propionic acid, Ester of /J-(3,5-di-tert.-butyl-4-hydroxyphenyl)- propionic acid, Ester of /S-(5-Tert.-butyl-4-hydroxy-3-methylphenyl)- propionic acid, Ester of 3,5-di-tert-butyl-4-hydroxyphynyl acetic acid, Acy! Aminophenols, benzyl phosphonates, aminoaryl derivatives, UV absorbers and light stabilizers, such as 2- (2'-hydroxyphenyl) -benztriazoles, 2,4-bis- (2'-hydroxyphenyl) -6-alkyl-s-triazines, 2-hydroxybenzophenones, 1,3-bis- (2'-hydroxybenzoyl) -benzenes, esters of optionally substituted benzoic acids, acrylates, furthermore kickel compounds, sterically hindered amines, oxalic acid diamides, Metal deactivators, phosphites, psroxide-destroying agents Compounds, polyamide stabilizers, basic carbon stabilizers, PVC stabilizers, nucleating agents or other additives such as plasticizers, lubricants, emulsifiers, fillers, soot, asbestos, kaolin, talc, glass fibers, Pigments, optical brighteners, flame retardants, antistatic agents.

Examples of further additives with which together the invention Usable stabilizers can be found in DT-OS 2.427.853 on pages 18-24.

The invention is described in more detail in the following examples:

Unless otherwise noted, the examples are percentages by weight and parts by weight.

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Example i

To 35.6 parts of 5,5-dimethyl-2-ethoxy-l, 3,2 ~ dioxaphosphorinane and 34.0 parts of 1,2,2,6,6-pentamethyl-4-hydroxy-piperidine were reacted at 80 ⁰ C 0 , 3 parts of lithium amide were added. Thereafter, the mixture was heated to 130-140 ⁰ C. After 2 -hour the temperature for a further 4 hours at 150 ⁰ C was increased off and the resulting ethanol under vacuum. By distillation at 0.06 Torr and 98-100 ⁰ C was 5,5-Dimethy1-2- (I, 2,2,6,6-pentame thy 1-piperidin-4-yl) -1,3,2- dioxaphosphorinane obtained. (Stabilizer No. 1).

Example-1 2. ■ ■.

In otherwise the same procedure as in Example 1, equimolar Amounts of 2-ethoxy-l, 3,2-dioxaphosphorinane and 2,2,6,6-tetramethyl-4-hydroxypiperidine implemented. The product 2- (2,2,6,6-tetramethyl-piperidiii-4-yl) -1,3,2-dioxaphosphorine axi has a boiling point of 83 ° C at 0.05 torr. (Stabilizer No. 2).

Example 3

In otherwise the same procedure as in Example 1, 5-methyl-5-ethyl-2-ethoxy-1,3,2-dioxaphosphorinane was reacted with 2,2,6,6-tetra-methyl-4-hydroxypiperidine. The product 5-methyl--5-ethyl-2- (2, 2, o ^ -tetramethyl-piperidin ^ -yl) -1,3,2-dioxaibDS. phoriiian has a boiling point of 101-105 ⁰ C at 0.04 torr (stabilizer no. 3).

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Example 4 _¥ H

In the otherwise same process V7ie in Example 1, equimolar amounts of 5-methyl-S-ethyl-Z-ethoxy-1,3,2-dioxaphosphorinane and 1,2,2,6,6-penta-ethyl-4-hydroxypiperidine were reacted. The product 5-methyl-5-ethyl-2- (l ₅ 2,2 _> 6,6-pentamethyl-pipsrljdm ^ i.-yl). 1,3 ^ -dioxaphosphorinane has a boiling point of 111 ° C at 0.04 Torr. (Stabilizer Kr. 4).

Example 5

In otherwise the same procedure as in Example 1, equivalent amounts of 5-1,5-dimethyl-2-ethoxy-1,3,2-dioxaphosphorinane and 2,2,6,6-tetramethyl-4-hydroxypiperidine are converted. The product 5,5-dimethyl-2 - (2,2,6,6 -1 etramethyX-piperidin-4-yl) -1,3 -Jl dioxaphosphorinane has a. Melting point of 90 ^° C. (stabilizer no. 5).

Example 6

In the otherwise same procedure as in Example 1, equirolar amounts of 4,4,6-trimethyl-2-ethoxy-1 _s 3j2-dioxaphosphorinane and 2,2,6 _> 6-tetramethyl-4-hydroxypiperidine were reacted. The product 4,4,6 -Trimethyl-2- (2,2,6,6 -tetramethyl-piperidin-4-yl) -1,3,2 "dioxaphosphorinane has a boiling point of 95-96 ° C at 0.3 Torr. (Stabilizer No. 6).

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Example 7 * ^ *

In otherwise the same procedure as in Example 1, equimolar amounts of 4,4,6-trimethyl-2-ethoxy-1,3,2-dioxapbosphorinane and 1,2,2,6,6-pentamethyl-4-hydroxypiperidine were reacted. The product 4,4,6-trimethyl-2- (1,2,2,6,6-pentamethyl-piperidin.-4-yl) -1,3,2-dioxaphosphorinane has a boiling point of 106-108 ⁰ C in 0.3 torr. (Stabilizer No. 7).

Example 8

In otherwise the same procedure as in Example 1, 1 mole of 4,9-diethoxy ~ 3,5,8,10 ~ tetraoxa ~ 4,9-diphospha-15,5] -undecane with 2 moles of 2,2,6,6 ~ Tetramethyl "4-hydroxypiperidine reacted. The product 4,9-bis- (2,2,6,6-tetramethyl-piperMin.4-yl) -3.5 ₅ 8> 10-tetraoxa-4,9-diphospha Spiro [5.5] undecane (Stabilizer No. 8) has a boiling point of 152 ~ 154 ° C at 0.1 torr.

Example 9

In otherwise the same procedure as in Example 1, 21.0 parts of 2-methoxy-1,3,2-dioxaphospholane and 27.0 parts of 2,2,6,6-tetraroethyl-4-hydroxypiperidine were used implemented in the presence of 0.1 part of lithium amide. The product 2- (2,2,6,6 ~ tetramethyl-piperidin ~ 4-yl) «* - 1,3,2-dioxaphospholane has a boiling point from 84-88 ° C at 0.02 torr. (Stabilizer No. 9).

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Example 10 _/

In the same way as in Example 1, the product is obtained from 4,4,5,5-tetramethyl-2-methoxy-1,3,2-dio: iaphospholane and 2,2,6,6-tetramethyl-4-hydroxypiperidine 4,4,5,5 · - Tetramethyl-2- (2,2,6,6-tetrainethyl-piperidin.-4-yl) _{-1 3} 3,2.-dioxaphospholane. (Stabilizer Kr. 10).

Example 11

In the same way as in Example 1, 5,5-dimethyl-2-ethoxy-1,3,2-dioxaphosphorinane is obtained and 1-ethyl-2,2,6,6-tetra-methyl-4-hydroxypiperidine 5,5-dimethyl- ^ (1-acetyl-2,2,6,6-tetramethyl-piperidin-4-yl) -1,3,2-dlxaphosphorinane of m.p. 152-154 ° C (Stabilizer No. I).

Example 12

100 parts of polypropylene powder (copies, fiber grade, from Montedison) are mixed with 0.2 parts of /5-(3.5-D5.~tert.butyl-4-hyeroxyphenyl )prcpionsä"ure-octadecy!ester and 0, 25 parts of a stabilizer from Table I below are ^{homogenized for 10 minutes in a Brabender plastograph at 200 °} C. The mass obtained in this way is removed from the kneader as quickly as possible and pressed in a toggle press to form a sheet 2 ~ 3 nm thick pressed between two high-gloss hard aluminum foils with a hand-hydraulic laboratory press for 6 minutes at 260 ° and 12 tons of pressure to form a 0.5 mm thick foil, which is immediately quenched in cold water Test film 0.1 min thick is produced from which sections of 60 × 44 min each are punched out and exposed in the Xenotest 150. At regular time intervals

709825/1044

these test specimens were removed from the exposure apparatus and tested for their carbon content in an IR spectrophotometer. The increase in carbon extinction at 5.85μ during exposure is a measure of the photo-oxidative degradation of the polymer

(see L. Blaban et al., J. Polymer Sci. Part C, 22.> 1059-1071 (1969); JF Heacock, J. Polymer Sci. Part Λ-1, 22_, 2921-34 (1969); DJ Carlsson and DM. Wiles, Macromolecules _2, 587-606 (1969)) and experience has shown that it is associated with a decrease in the mechanical properties of the polymer. For example, the film is completely brittle when a carbon extinction of approx. 0.3 is reached.

The protective effect of the stabilizers according to the invention is off can be seen in the following table I:

Table I.

stabilizer
Example no. Exposure time in hours
until CO extinction = 0 _f 3 comparison 1050 1
4th
7th
10 7600
4630
5550
. 3650

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Example 13

100 parts of polypropylene "Propathen HF 20" of ICI are the table below IY homogeneously mixed with 0.1 parts of stabilizers and 5 times in a single screw extruder at max. 260 ^c C and 100 UPCI consecutively granulated "each case after the 1st, 3rd and 5. Extrusion, the Schraelzindcx (MI) of the material is measured. The load is 2160 g at 230 ^° C. ₁ the MI is given in g / 10 min.

The granules obtained after the 1st, 3rd and 5th extrusion are assessed visually for their discoloration. For the color judgment of Table IV is an empirical color scale j 2 was used in which 5 colorlessness, l \ a just noticeable slight discoloration, 3, 1 represents a successively greater discoloration.

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None

stabilizer

Table II

Pen taerythri t-1et ra
[3- (3,5-di-t-butyl ·
^ -hydroxyphenyl) propionate]

i-Ma thy 1-2,6-di -
t-butylphenol

MI in g / 10 rain na cli E χ t r ii s i ο η

.1

11.6

4.3

4.1

4.4

27.6

50.8

6.3

10.7

7.9

COLOR RULING of the panels after extrusion

3 5

Table II shows the excellent color properties of the Phosphite j compared with the conventional phenol! Antioxidants.

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Claims (11)

Compounds of the general formula I (D or their SMur addition salts, wherein X hydrogen, oxyl, C ₁ -C ₁₂ alkyl, C ₃ -C ₆ alkenyl, • Co-C, alkynyl, C ₂ -C ₂ -, alkoxyalkyl, Cy- ¹ Cg era Iky 1, 2,3-epoxypropyl, an aliphatic acyl group with 1--4 carbon atoms or one of the groups -CH ₂ COOR ₁ , -CH ₀ -CH (R ₀ ) -OR ₀ , -COOR ₇ or -CONHR, where ZZJ q η- R ₁ C ₁ -C ₁₀ alkyl, C ₀ -C _c alkenyl, phenyl, C ₇ -C ₀ era1 X. -L iZ JD / O or cyclohexyl, and
Ro is hydrogen, methyl or phenyl, and R ~ is hydrogen, an aliphatic or aromatic, araliphatic or alicyclic acyl group having 1-18 C atoms, wherein the aromatic moiety is optionally substituted by chlorine, C _ß be alkoxy / or substituted by hydroxy and ₁ to C ^ alkyl, Cj -C can, or a group of the formula JX ^(ia) means, and
R. C ₁ -CJ ₀ alkyl, cyclohexyl, phenyl or benzyl means tet, and
. a divalent radical selected from the group consisting of the radicals of the formulas II, III, IV and V 709825 / 104A. original inspected (H) ι ⁵ Λ ^R Q \ κ ⁹ σ / \ R. ok A ^R 7 R ₈ 7 (III) (IV) (V) wori-ϊΐ and Ε. ~, independently of one another, are hydrogen, C-Cp-alkyl or C ₁ -C ₅ -hydroxyalkyl, and ₀ , independently of one another, are hydrogen, Cj-Cg-alkyl, C-j-C ^ Hj ^ droxyalk} '! or C-i ~ C, acyl, or and R, ^ »together with the carbon atom to which they are attached are, cyclohexyl j. Cyclohex-3-ene or bicycloi2,2,1] -hept-5-ene form, and and R-IO 'are independently hydrogen, CJ ^- -Cq alkyl, Cv-Cg cycloalkyl, or C ₇ -C ₉ aralkyl. denotes a divalent radical selected from the group consisting of the radicals of the formulas II, III and IV. 709825/1044 2. Compounds of formula I according to claim 1, wherein X. Is hydrogen, oxyl, C ₁ -C 6 alkyl, C ₃ -C ₄ alkenyl or alkynyl, C ₂ -C 4 alkoxyalkyl, C ₇ -C 6 aralkyl, acetyl, acryloyl or crotonoyl, or one of the groups -CH ₂ -CH (R ₂ ) -OR ₃ , -COOR ₄ or -CONHR ₂ ) -OR ₃ , -COOR ₄ or -CONHR, means,
wherein R ₁ ^C 1 ~ ^C 4 alkyl, ^C 3 " ^C 4 alkenyl, phenyl, C ₇ -Cg aralkyl or cyclohexyl is _f and R _? Is hydrogen, methyl or phenyl, and. R ₃ denotes hydrogen or an aliphatic, aromatic, alicyclic or araliphatic acyl group with 1-18 carbon atoms, in which the aromatic part can optionally be _{substituted with chlorine, C 1} -C, alkyl, C 1 -C 6 alkoxy and / or hydroxy , means, and " R, ^C 1 ~ ^C 12 ^{alkyl "and} Y is one of the groups II, III, IV or V, in which Rc, Rf, R ₇ and Rg, independently of one another, are hydrogen, C ₁ -C, Alkj'l or C-, -C ₃ hydroxyalkyl, and Rq and R ₁₀ , independently of one another, are hydrogen, C ₁ -C, alkyl, C ₁ -Co hydroxyalkyl or acetyl, or Rq and R, ₀ together with the C atom to which they are bonded are cyclohexyl, cyclohex-3-ene or bicyclo- [2,2,1] - form hept-5-en, and
and R-jο », independently of one another, denote hydrogen Cj-Cg alkyl, Cc-Cg cycloalkyl or C ₇ -C ₉ aralkyl. 709 825/1044 • τ 3. Connections of form ?. I, according to claim 1, wherein X is hydrogen, C ₃ -C, alkyl, allyl, propargyl, C ₃ -C ₆ alkoxyalkyl, acetyl, acryloyl or crotonoyl,. Or one of the groups "CH ₂ -COOR ₁ , -CH ₂ -CH (R ₂ ) - OR ₃ -ΟΟΟΡγ or -CONHR ^, wherein R, ^C ] ~ ^C 4 A ¹¹ ^ ^{1 is} * ^un . ^d R _{2 is} hydrogen or methyl and IL is hydrogen, and
E., ^C 1 ~ ^C 4 ^Α1 ^ Α , and Y denotes one of the groups II, III, IV or V, in front of R, -, R .., R ₇ and Rp, independently of one another hydrogen, C-, -C, Alkyl or hydroxymethyl, and R _Q and R-ΐΛ, independently of one another hydrogen or C -.- C, Alkyl, Hydroxj'tnethyl or acetyl mean, or Rq and R * ~ together with the C atom to which they are bound, Cyclohexyl, cyclohex-3-ene or Bicycle- [2,2, Ij - form hept-5-en, and
R ,, and R.J2 are hydrogen, C -, - Cy alkyl, cyclohexyl or - cc, cc ~ dimethylben2} ^r l. 4. Compounds of formula I, according to claim 1, wherein X is hydrogen, methyl, allyl, propargyl or acetyl, and Y is a group II, III, IV or V, in which R ^ ₅ Rg, R ₇ , RgiRq and R-jq, independently of one another, are hydrogen, Methyl, ethyl or hydroxymethyl, or Rq and R, r, are also acetyl, or Rg and R ^ Q together with the carbon atom to which they are bonded are cyclohexyl, cyclohex-3-ene or bicyclo- [2,2j1 ] -hept-5-ene form, and R-j-j and Rio »independently of one another hydrogen or C, ~ C, • "mean alkyl. 709825/1044 ¹ * ' 5. Compounds of formula I according to claim 1, wherein X - is hydrogen or methyl, and Y. . is one of groups II, III, IV or V, wherein Rt-.R ^ -, R ^ and R "in group II ·, independently of one another hydrogen or methyl, and Rr ₁ R ^ ₁ R-, and R ₀ in group III are hydrogen, or, if R _g and R _{10 are} hydrogen, hydrogen or methyl, and R _q and R _{10 are} independently hydrogen, methyl or ethyl, and. R ₁₁ and Ri ο »independently of one another are hydrogen or CJC ₁ ,,. 6. A compound of the formula I, geffiäss any one of the preceding claims 1-5, wherein R _{3 is} a group of the formula -P wherein Y _{1 is} a divalent radical selected from the group consisting of the radicals of the formulas II, III and IV. 7. The compound 5,5-dimethyl - ^ - (1,2,2,6,6-pentamethyl-piperidin-4-yl) -1,3,2-dioxaphosphorinane, according to claim 1, 8. The compound 5,5-dimethyl-2- (1-acetyl-2,2,6,6-tetrainethyl-piperidin-4-yl) -1,3 _} 2-dioxaphosphorinane, according to claim 1. 709825/1044 9. Process for the preparation of compounds of the general formula I, characterized in that a 4 ~ Hydroxypiperidine of formula VI CIL,
5 X — IT> —OH (VI) CH ₇ CH ₃
with a phosphate from Forrael VII Z — P X (YII) is reacted, wherein X and Y have the same meaning as in formula I and Z is C -, - C, alkoxy or halogen. 10. Use.der of the compounds of the formula T according to claim 1 to stabilize against organic material. 11. The organic material containing a compound of the formula I according to claim 1. 709825/1044