DE2656766A1 - NEW PHOSPHITE STABILIZERS - Google Patents

Description

The present invention relates to new single-ended Piperidyl phosphites, a process for their production, their use as stabilizers, and that with their help Stabilized against thermal oxidative and light-induced degradation organic material.

-o ¹ -

It is known, for example from DT-OS 1.929.928 or from GB 1.399.239, to use piperidyl phosphites as stabilizers in synthetic polymers. However, the known compounds are very sensitive to hydrolysis, which leads to poor storage stability and poorly reproducible effectiveness.

709827/1074

It became a class of unsymmetrical aryl-containing ones Piperidyl phosphites 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.

X \\
^R 4 -P- /
V TvT / 6 ■ v » / > —O- E ₅

(D

3-n

or their acid addition salts,

V7orin

η is 1 or 2, and

R,, Ro ₅ Ro are, independently of one another, C, -C ₆ alkyl, and

R / C ₁ -C _n alkyl, phenyl, benzyl or cc-phenylethyl be

H Ly

indicates, or
Ro and R, together are tetramethane} ⁷ len or pentamethylene,

and
Rc and R _fi independently of one another are hydrogen, C 1 -C 4 -alkyl

are and
R ^C l " ^C 12 A ¹ ^ ¹ ' ^C 5 ~ ^C 8 cycloalkyl, C ₅ -C ₉ alkylcyclo-

alkyl, C ₅ -C ₁₀ aryl, C ₇ -C 4 alkaryl or C ₇ -C ₉ aralkyl

is and

Rg hydrogen, chlorine, bromine, CJC ₁₂ alkyl, C ₅ -Cg cycloalkyl, C ₅ -C ₉ alkyl, cycloalkyl, C ₅ -C ₁₀ aryl, C ₇ -C ₁₄

Alkaryl or C ₇ -C ₉ aralkyl, and R _Q if η 1 is hydrogen, chlorine, C _n -C, alkyl or

709827/1074

C ₅ -C ₈ cycloalkyl or C ₆ -C ₉ alkylcycloalkyl means, 'and

R ₉ if η 2 is hydrogen, chlorine, bromine, Ci-C ₁₂ alkyl, C ₅ -C ₈ cycloalkyl, C ₆ -C ₉ alkylcycloalkyl, C ₆ -CJ ₀ aryl, C ₇ -C ₃ ^ alkaryl or C ₇ -C _{9 is} aralkyl, and

X hydrogen, oxyl, C ₁ -C ₁₂ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ^ alkynyl, C ₂ -C ₂₁ alkoxyalkyl, C ₇ -C ₃ aralkyl, 2,3-epoxypropyl, an aliphatic acyl A group with 1-4 carbon atoms or one of the groups -CH ₂ COOR ₁ P, -CH ₂ -CH (R ₁₁ ) -OR ₁₂ , -COOR ₁₃ or -CONHR ₁₃ , in which

R _{10 is} ^C 1 " ^C 8 alkyl, ^C 3 ~ ^C 6 alkenyl, phenyl, C ₇ -C ₃ aralkyl or cyclohexyl, and

R ,, is hydrogen, methyl or phenyl, and

R, 2 denotes hydrogen, an aliphatic or aromatic, an araliphatic or alicyclic acyl group with 1-18 carbon atoms; wherein the aromatic part can optionally be _{substituted with chlorine, C 1} -C, alkyl, C ₁ -C ₃ alkoxy and / or with hydroxy _}

means, and

R ₁₃ ^C l " ^C 12 alkyl j is cyclohexyl, phenyl or benzyl.

R-, R "and R" are alkyl, for example unbranched or branched alkyl with 1-6 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, η-butyl, isobutyl, isopentyl or n-hexyl. Preferred compounds include those in which R and Ro are methyl or ethyl and R _{2 is} methyl.

R ^ as alkyl means, for example, unbranched or branched Alkyl with 1-9 carbon atoms, in particular with 1-6 carbon atoms, and especially with 1 carbon atom, such as methyl, ethyl, isopropyl, n-

709827 / 107A

Butyl, isopentyl, n-hexyl, 2-ethylhexyl or isononyl, in particular Methyl.

R ^ and Rg as C ^ -C ₁ - alkyl are, for example, unbranched or branched alkyl such as methyl, ethyl, isopropyl, isobutyl, n-pentyl. R ₁ - preferably has one carbon atom less than R-, and R, - one carbon atom less than R ~. The preferred meaning of R _r is thus hydrogen or methyl, and of R ^ hydrogen.

As alkyl, R ₇ is, for example, unbranched or branched alkyl with 1-12 C atoms, in particular with 3-9 C acomas. and very particularly with 3-4 carbon atoms such as methyl, ethyl, isopropyl, t-butyl, t-amyl, n-hexyl, t-octyl, t-Non3 ^r l, n-decyl or n-dodecyl, in particular isopropyl or t-butyl.

As C - Cg C3 '"cycloalkyl, R ₇ is, for example, cyclopentyl, cyclohexyl or cyclooctyl, in particular cyclohexyl.

As C ₆ -C 6 alkylcycloalkyl, R ₇ is, for example, l-methylcyclopentyl, l-methylcyclohexyl or 2-ethylcyclohexyl.

As C ₆ -C ₁₀ aryl, R ₇ is, for example, phenyl or α- or / 3-naphthyl, in particular phenyl.

As an alkaryl with 7-14 carbon atoms, in particular with 7-9 carbon atoms, Ry is, for example, α-methy! Phenyl, β- ethy! Phenyl or pn-octylphenyl.

As C ₇ -C ₉ aralkyl, R ₇ is, for example, benzyl, α-phenylethyl or 2-phenj'-1-propyl, in particular ct-phenyl-methyl or 2-phenylpropyl.

709827/1074

As alkyl, Ro is, for example, unbranched or branched alkyl with 1-12 carbon atoms, in particular with 1-9 carbon atoms and very particularly with 1-4 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, t-amyl, n-hexyl, t-octyl, t-nonyl, n-decyl or n-dodecyl. Particularly noteworthy are compounds in which Rg is methyl, isopropyl or t-butyl or hydrogen.

_{As C 5} -C 6 cycloalkyl, Rg is, for example, cyclopentyl, cyclohexyl or cyclooctyl, in particular cyclohexyl.

As C ^ -Cq alkylcycloalkyl, R ₀ is, for example, 1-methyleyclopentyl, 1-methylcyclohexyl or 2-ethylhexyl.

Rg is as C _fi -C, ₀ aryl, for example phenyl, or cc- or β-naphthyl, in particular phenyl.

As an alkaryl with 7-14 carbon atoms and in particular with 7-9 carbon atoms, R ₀ is, for example, α-methylphenyl, β-ethylphenyl or pn-octylphenyl.

As C - ^ - Cq aralkyl, Ro is, for example, benzyl, α-phenylethyl or 2 ~ phenylpropyl, especially ot ~ phenylethyl or 2-phenylpropyl.

R ₉ has, if η is 1, is C, -C, alkyl such as methyl, ethyl, _s n-propyl, isopropyl, η-butyl or t-butyl, in particular methyl o.der Isopropj'l · or hydrogen.

R "is, if η is 1, C ^ -Cg cycloalkyl such as cyclopentyl, Cyclohexyl or cyclooctyl, especially cyclohexyl.

709827/1074

Rg is, if η 1 is also C ₆ -C ₉ alkylcycloalkyl such as, for example, 1-methylcycloalkyl, l-methylcyclohex} ⁷ -! or 2-ethylcyclohexyl.

When η is 2, Rg is, for example, unbranched alkyl as alkyl with 1-12 C atoms, in particular 1-4 C atoms and especially 1-3 C atoms, such as methyl, ethyl, isopropyl, t-butyl, t-amyl, n-hexyl, t-octyl, n-nonyl, n-decyl or n-dodecyl, in particular Methyl, ethyl or isopropyl or hydrogen.

If η is 2, Rg denotes, for example, C 1 -C 6 cycloalkyl Cyclopentyl, cyclohexyl or cyclooctyl, especially cyclohexyl.

Rg, if η is 2, denotes as C 1 -C 6 alkylcycloalkyl e.g. 1-methylcyclopentyl, 1-methylcyclohexyl or 2-ethylcyclohexyl.

Rg means for n = 2, as Cg-C-, ~ aryl e.g. phenyl or α- or / 3-naphthyl, especially phenyl.

For n = 2, Rq denotes, as C ₇ -C, alkaryl, for example c-methylphenyl, β-ethylphenyl or pn-octy! Phenyl.

If η is 2, R _{Q denotes, as C 7} -Cg alkaryl, for example benzyl, α-phenylethyl or 2-phenylpropyl.

As C ^ -C ₁₂ alkyl, X is, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl or n-dodecyl. Alkyl groups with 1-8 carbon atoms, in particular those with 1-6 carbon atoms and especially methyl or hydrogen, are preferred.

As C-j-Cg alkenyl, X is, for example, allyl, 2-butenyl or 2-hexenyl, especially allyl.

709827/1074

As Co-C, alkynyl, X is e.g. propargyl.

If X is C ^ -Cp-, alkoxyalkyl, the alkyl part can have 1-3 C atoms and the alkoxy part consists of 1-18 carbon atoms, such as in methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-n-butoxyethyl, 3-n-butoxyethyl, 2-octoxyethyl or 2-octadecyloxyethyl, especially to be mentioned Compounds in which X is an alkoxyalky group with 2-6 carbon atoms means.

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

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

If X is the group -CH ₂ COOR ₁₀ , then R ₁₀ is C ₁ -C ₁₂ alkyl, for example methyl, ethyl, isopropyl, n ~ butyl, isobutyl, t-butyl, isopentyl, n-octyl, n-decyl or n -Dodecyl. _{R 10} is preferably C -C, alkyl. As C ₃ -C ₆ alkenyl, R ₁₀ is, for example, allyl, 2-butenyl or 2-hexenyl. _{As C 7} -Cn aralkyl, R ₁ ^ is, for example, benzyl or (X-phenylethyl.

If X is the group -CH ₂ -CH (R,.,) - OR ₁₂ , R _{11 is} hydrogen, methyl or phenyl, in particular hydrogen. R .. _? is as an aliphatic aromatic, alicyclic or araliphatic C ₁ -C ₁ O acyl radical, optionally in the aromatic part with chlorine, C -C, alkyl with methyl, ethyl, n-propyl or t-butyl or with C 1 -Co 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,

709827/1074

2,4-dichlorobenzoyl, 4 ~ methoxybenzoyl, 3-butoxybenzoyl, 2-hydroxybenzoyl, 3,5-di-t ~ butyl-4-hydroxybenzoyl, / 3 - (3,5-dit-butyl-4-hydroxyphenyl) -propionyl, phenyl-acetyl, cinnamoyl, hexahydrobenzoyl.

.1st X is the group -COOR. ο »so R, g is C ₁ -C ₁₂ alkyl, ^Ζ · ^Β · methyl, ethyl, isobutyl, n-hexyl, n-octyl, n-dedyl or n-dodecyl. Preferred R 1 are alkyl groups with 1-4 C atoms.

Particular emphasis should be given to compounds of the formula I in which

η is 1 or 2, and

RJ ₁ R ₂₅ Ro and R ^, independently of one another, are C-, -Cr alkyl, and R- and R, together form tetramethylene or pentaraethylene,

and
R ₁ - and R ^ independently of one another are hydrogen, CJC ₁ - alkyl

mean, and

R-, ^C 1 " ^C 12 A ¹¹ *? ¹ » ^C 5 " ^C 8 ^c y ^cioalkyl ·, ^C ß" ^C 9 alkylcycloalkyl, phenyl, C ₇ -C ₉ alkaryl or C ₇ -C ₉ aralkyl

is and
R ₈ hydrogen, chlorine, C ₁ -C ₉ alkyl, C ₅ -C ₃ cycloalkyl,

C ₆ -C ₉ alkylcycloalkyl, phenyl, C ₇ -C ₉ alkaryl or

C ₇ -C ₉ aralkyl, and R ₉ if η is 1,

Hydrogen, chlorine, C ₁ -C ₃ alkyl, C ₅ -C ₅ cycloalkyl

or C ₆ -C ₇ alkylcycloalkyl, and R ₉ , if η is 2,

Hydrogen, chlorine, C ₁ -C, alkyl, C ₅ -C ₆ cycloalkyl, C ₆ -C ₇ alkylcycloalkyl, phenyl, C ₇ -C ₉ alkaryl or

C ₇ -C ₉ aralkyl, and X denotes hydrogen, oxyl, C ₁ -C 6 alkyl, C ₃ -C, alkenyl or C ₃ -C ₄ alkynyl, C ₂ -C ₅ alkoxyalkyl, C ₇ -C ₃ aralkyl, acetyl,

709827/1074

Is acryloyl or crotonoyl, or one of the groups -CH ₂ -COOR ₁₀ , -Cl ₂ -CH (R ₁₁ ) -OR ₁₂ , -COOR ₁₃ or -CONHR ₁₃ , in which
R ₁₀ ^C 1 ~ ^C 4 alkyl, ^C 3 ~ ^C 4 alkenyl, phenyl, C ₇ -C ₈ era Iky 1

or cyclohexyl, and

R _{11 is} hydrogen, methyl or phenyl, and R-. 2 denotes hydrogen or an aliphatic, aromatic, alicyclic or araliphatic ^ acyl group with 1-18 carbon atoms, vzorin the aromatic part can optionally be substituted with chlorine, C-, -C, alkyl, C.-Cp alkoxy and / or hydroxy , means, and

^R 13 ^{is C} l ^"G 12 ^is alkyl ·

Preference is given to compounds of the formula I in which η is 1 or 2, and R 1 and R 1 are methyl or ethyl, and R ₂ and R 1 are methyl, and

R ₅ if R _{1 is} methyl, hydrogen, and if R ₁

Is ethyl, is methyl, and Rß is hydrogen, and
R ₇ ^C 3 ~ ^C Q alkyl, C ₁ -C. Cycloalkyl, Cg-C ₇ alkylcycloalkyl,

Phenyl or Cq-Cq aralkyl, and R ₈ denotes hydrogen, chlorine, C ₁ -C ₉ alkyl, C ₅ -C ₆ cycloalkyl, C ₆ -C ₇ alkylcycloalkyl, phenyl or C ₅ -C ₉ aralkyl

is and
R _{0 is} hydrogen, chlorine, C ₁ -C ₃ alkyl or cyclohexyl,

and
X hydrogen, C ^ -C ^ alkyl, allyl, propargyl, C ₂ ~ C ₆

Is alkoxyalkyl, acetyl, acryloyl or crotonoyl, or one of the groups -CH ₂ -COOR ₁₀ , -CH ₂ -CH (R ₁₁ ) -OR ₃₉

-COOR ₁₃ , or -CONHR ₁₃ , wherein

709827/1 07A

^R 10 C ₁ -C ₄ alkyl is and R ₁₁ hydrogen or methyl and ^R 12 hydrogen means, and R ₁₃ C ₁ -C ₄ alkyl is.

Particularly preferred are compounds of the formula I in which

η is 1 or 2,

R ₁ and R _{3 are} methyl or ethyl, and R2 and R _{4 are} methyl, and

R ₅ , if R _{1 is} methyl, hydrogen, and if R,

Aethyl is methyl, and Rr is hydrogen, and

Ry is isopropyl, t-butyl or cyclohexyl, and Rg is hydrogen, CJC ₄ alkyl or cyclohexyl, and Rq is hydrogen, methyl or isopropyl, and X is hydrogen, methyl, allyl, propargyl or acetyl

is.

Compounds of the formula I in which

η is 1 or 2, and R _15, R _99, Ro and R, are methyl, and R ₁ . and R, denotes hydrogen, and Ry is isopropyl or t-butyl, and Rg is hydrogen, methyl or isopropyl,

and
R is hydrogen, methyl, ethyl or isopropyl,

and X is hydrogen or methyl.

In the above-mentioned compounds of the formula I, in addition to the meanings otherwise given, is also special preferably X benzyl, hydrogen, C .. -C, - alkyl, allyl, propargyl or acetyl.

709827/1074

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 diphenyl phosphoric acid, Methanephosphonic acid or diphenylphosphinic acid.

Compounds of the formula I are for example:

Bis-2,2,6,6-tetramethyl-4-piperidinyl - (2,4-isopropyl-6-methylphenyl) phosphite

709827/1074

Bis-1,2,2,6,6-pentamethyl-4-pipei: idinyl ~ (2,4,6-tri-isopropyl- • phenyl) phosphite

Bis-2,2,6, δ-tetramethyl-1-piperidinyl-1-acetyl- (2-tert-butyl-4,6-dimethyl-phenyl) -phosphite

Bis-2, 3,6-trimethyl-2,6-di ~ ethyl-4-piperidinyl ~ (2-tert. Arnyl-G-raethj'-l-phenyl) -phosphite

Bis-2,2,6,6-tetramethyl-4-piperidinyl- (2-tert-butyl-4-chlorophenyl) phosphite

Bis-2,4-isopropyl-6-methyl-phenyl- (2,2,6,6-tetramethyl-4-pipcridinyl) -phosphite

Bis-2,4-di-tert-amyl-phenyl- (1,2,2,6,6-pentamethyl-4-piperidinyl) -phosphite

Bis-2-cyclohexyl-5-methyl-phenyl- (2,2,6,6-tetramethyl-4 ~ piperidinyl-1-acryloyl) phosphite

Bis-2-tert-octyl-A-raethyl-phenyl- (2,3,6-trimethyl-2,6-di-2 ethyl 4-piperidinyl-1-oxyl) phosphite

Bis-2,4-di-tert-butyl-phenyl- (2,2,6,6-tetramethyl-4-piperidinyl-1-butyroyl) --phosphite

Bis-2-tert-butyl-4-chloro-phenyl- (2,2,6,6-tetraroethyl-4-piperidinyl) -phosphite

Bis-2-tert-amyl-4-methyl-6-chlorophenyl (1,2,2,6,6-pentauiethyl 4-piperidinyl) phosphite.

The compounds of the general formula I can be prepared by reacting about η moles of a piperidine of the formula II

OH (II)

with about one mole of a phosphorous acid ester dihalide or a phosphorous acid diester halide of the formula III

² V Λ > - X-N
γ \
^E 5 \
^E 4

709827/1074

(III)

getting produced. In the formulas II and III, the symbols n, R, -Rq and X have the same meaning as in formula I. In formula III, shark is preferably chlorine.

The reaction is advantageously carried out in an apolar solvent such as toluene, xylene or ligroin in the presence of a base carried out. The medium is used for 1-12 hours. Room temperature held and then for 5-20 hours heated at reflux temperature. As bases are above all organic tertiary nitrogen bases, such as triethylamine, N, K-diethylaniline or pyridine suitable. It is also possible to use the 4-hydroxypiperidine of the formula II itself as the base.

Some of the 4-hydroxypiperidines are known substances and, starting from the corresponding 4-oxopiperidines, can Formula IV

709827 / 1Π7Λ

X, Λ \
/ Χ — Ν N
\
^Ε 4 R. / 6

by reduction, e.g. catalytic hydrogenation over Raney nickel.

The 4-oxopiperidines of the formula IV, in which X is hydrogen, can be produced by various processes.

For example, W. Traube in Chem. Ber. t ± L, 777 (1908) the reaction of an aliphatic ketone with ammonia described ben.

4-oxopiperidines of the formula IV, in which X is hydrogen, can also be prepared analogously to the process described in US Pat. No. 3,513,170. It is an alkyl-substituted Tetrahydropyrimidine rearranged hydrolytically in the presence of an acidic catalyst.

N-H compounds of the formula IV, which in the 2- and 6-position Have various substituents can be prepared by reacting a ketone of the formula R, -CO-R ^ with ammonia will. The pyrimidine formed is, as in HeIv. Chiüi. Acta _3_0, 114 (1947), to an aminoketone of formula V hydrolyzed.

- C - CH - CO - CH ₂ R ₆ (V)

709827/1074

The compounds of formula V are used in a second process step with ammonia and a ketone R ,, - CO-R, reacted, as it e.g. in monthly Chemie 88 ^ 464 (1957) is. The compounds of the formula IV in which X is hydrogen can be obtained from the pyrimidine thus obtained by hydrolysis be won.

Compounds of the formula IV in which X is not hydrogen can be obtained by substitution from the corresponding N-H compounds getting produced. These are the usual substitution reactions for secondary amines, though due to the steric hindrance caused by the residues R-J-R, these run more slowly. The N-H connections can e.g. with alkyl, alkenyl, aralkyl or alkoxyalkyl halides, with dialkyl sulfates, with epichlorohydrins, with esters of chlorocarboxylic acids such as chloroacetic acid esters or with acid chlorides or anhydrides are implemented.

The group -CH ₂ -CH (R,,) - OR, ₂ can be obtained by reacting the NH-piperidines with an epoxide of the formula R, ..- CH-CHj and

subsequent acylation with an acyl chloride of the formula.

The phosphorous acid ester dihalides and phosphorous acid diester halides of formula III are known substances and can be prepared, for example, by methods described in Houben-Weyl, XII, 2, page 12ff and 45ff (1964) are.

Even when added in small amounts, the compounds of the formula I protect organic polymers against light-induced aging

709827/1 07

tion. 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 by the inventive Compounds of the formula I is delayed or prevented, for example, the following classes relevant in technology: Polymers that are made up of mono- or doubly unsaturated Derive hydrocarbons. Halogen-containing vinyl polyols, such as polyvinyl chloride. Polyraere, which differ from a, / 5-unsaturated Acids and their derivatives, such as polyacrylates and polymethacrylates, polyacrylamides and polyacrylonitrile. Polymers derived from unsaturated alcohols or their acyl derivatives or acetals. Gay and Copolymers derived from epoxies such as polyethylene oxide. Polyacetals, polyphenylene oxides, polyurethanes and polyureas, Polycarbonates, polysulfones. Polyamides and copolyamides which are different from diamines and dicarboxylic acids and / or derived from aminocarboxylic acids or the corresponding lactams. Polyester, which is different from dicarboxylic acids and dialcohols and / or derived from hydroxycarboxylic acids or the corresponding lactones. Networked Polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other. Alkyd resins. Unsaturated polyester resins, which are derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols, as well as vinyl compounds as crosslinking agents, as well as their halogen-containing, flame-retardant modifications. Natural po ^ mers, like

709827/1074

Cellulose, rubber, as well as their polymer homologous chemical modified: e derivatives, vie cellulose acetate ^, -propionate and -butyrate, or. the cellulose ethers such as methyl cellulose.

Preferred polymers are polyethylene higher and lower Density, polypropylene, polyurethanes, polybutadiene, polyvinyl chloride, polystyrene and its copolymers, as well. Mixtures of that,

Examples of polymers, which by the erfindungsgomässen Connections that can be protected against light aging are listed in DT-OS 2.427.853, page 15-17.

The new compounds are added to the substrates in a concentration of 0.005 to 5% by weight, calculated on the material to be stabilized. Preferably 0.01 to 1.0, particularly preferably 0.05 to 0.5% by weight _{, of} the compounds, calculated on the material to be stabilized, are incorporated into it.

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., if necessary under * afterwards Evaporation of the solvent.

The new compounds can also be in the form of a masterbatch, which contains these compounds, for example, in a concentration of 2.5 to 25% by weight, the one to be stabilized Polymers are added.

709827 / 107A

In the case of networked! Polyethylene becomes the joints attached before networking.

The compounds according to the invention can also be used with others Additives are used, with synergistic mixtures can be formed.

As further additives with which the invention Usable stabilizers can be used, for example:

Antioxidants such as simple 2,6-dialkylphenols, derivatives of alkylated hydroquinones, hydroxylated thiodiphenyl ethers, Alkylidene bisphenols, 0-, N- and S-benzyl compounds, hydroxybenzylated maleic esters, hydroxybenzyl aromatics, s-triazine compounds, amides of /3~(3,5-di-tert.-butyl-4-hydroxyphenyl) propionic acid, Ester of / 3- (3,5-di-tert-butyl-4-hydroxypheny]) propionic acid, Ester of /3~(5-Tert.-butyl-4-hydi-oxy-3-metlrylphenyl) -propionic acid, ester of 3,5-Ditert. -butyl ~ 4-lrydroxypheny! acetic acid, acylarainophenols, 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-HydroxybenzophenoneCj 1, 3-bis- (2'-hydroxybenzoyl) -benzenes, esters of optionally substituted benzoic acids, acrylates, further nickel compounds, sterically hindered amines, oxalic acid diamides, Metal deactivators, phosphites, peroxide-destroying compounds, polyamide stabilizers, basic co-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.

709827/1074

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.

709827/1074

example 1

To a solution of 16.7 parts of bis (2,4-di-t-buty! Phenyl) chlorophosphite in 100 parts by volume of xylene, 11.0 parts of 4-hydroxy 2.2 6,6-tetri [riethylpiperidine added. The reaction mixture was stirred and finally presented vrarde refluxed gently for 8 hours at 25 ⁰ C for one hour. After cooling, the hydrochloride salt of the base was filtered off and the solvent was distilled off in vacuo. The product is a pale yellow, viscous oil. The yield is 48% of theory. The bis (2,4-di-t-butylphenyl) -2,2,6,6-tetramethylpiperidinyl phosphite thus obtained showed the following elemental analysis: (in X)

C. H N P. target
gef, 75.5
74.5 10.3
10.0 2.3
2.4 4.6
'5.2

Example 2

A mixture consisting of 9.82 parts of bis (2-methyl-6-t-butylphenyl) chlorophosphite, 4.88 parts of 4-hydroxy-2,3,6-trimethyl-2, δ-diethylpiperidine and 3.5 parts by volume of triethylamine in 100 parts by volume of toluene was added under a nitrogen atmosphere Stirred at room temperature for 5 hours and then refluxed for 16 hours. The base was used as the hydrochloride salt filtered off and toluene distilled off under vacuum. The yield of bis (2-methyl-6-t-buty! Phenyl) -2,3,6-trimethyl-2,6-diethylpiperidinyl-phosphite was 78.3%. The pale yellow, viscous oil showed the following elemental analysis (in%.)

709827/1074

should be

Example 3

In example 2, the 4-hydroxy-2,3,6-trimethyl-2,6 ™ is replaced diethyl piperidine by 4.98 parts of N - acetyl ~ 4 - hydroxy ~ 2, 2, 6,6-tetramethyl-piperidine is obtained with otherwise the same Process 12.9 parts (92.7%) bis (2 »rcethyl-6-t-butylphenyl) K-acetyl-2,2,6,6-tetramethylpipcridinyl-pho.sphit as a pale yellow, viscous oil with the following El enieritaranilyse (in%)

C. H N P. target
found 70.1
71.3 9.1
9.1 2.3
2.5 5 ₅ 2
5.6

Example 4

A mixture of 1.2 parts of N-acetyl-4-hydroxy-2,2, ojo-tetramethj ^ lpiperidine and 0.8 parts of triethylamine were added. In the otherwise same procedure as in Example 2, 3.6 parts (94%) of bis (2,4-di-t-butylpheivyl) N-acetyl-2,2,6,6-tetrameth) ⁷ l-piperidinyl Phosphite obtained as a thick oil with the following elemental analysis (in%):

709827/1074

- STL -

η H N P. target
ge f. 73.8
73.2 9.9
9.8 2.2
2.2 3.9
4.8

Example 5

To a solution of 10 parts of 2-methyl-6-t-butylphenyl dichlorophosphite in 200 parts by volume of xylene there were 23.6 parts of 4-hydroxy-2,2,6,6-tetramethylpiperidine at room temperature and added under a nitrogen atmosphere. I'm otherwise the same Procedure as in Example 1, 16.8 parts (88.2%) of 2-methyl-6-t-butylphenyl-bis- (2,2,6,6-tetramethyl-piperidinyl) phosphate as a pale yellow viscous oil with the following Elemental analysis (in%) obtained:

• c H N P. target
found 70.4
68.7 10.2
10.1 5.2
5.5 4.8
6.1

709827/1074

Example 6

To 15.4 parts of 2,4-di-t-butylphenyl ~ di-chlorophosphite in 50 parts by volume of toluene was a mixture of 15.7 parts of 4-hydroxy-2,2,6,6-tetramethylpiperidine and 13.9 parts Triethylamine added at room temperature and under a nitrogen atmosphere. In otherwise the same procedure as in Example 5 were 19.9 parts of 2,4-di-t-butylphenyl bis (2,2,6,6-tetramethylpiperinyl) phosphite obtained as a pale yellow viscous oil with the following elemental analysis (in%):

C. H N P. target
found 69.91
70.0 10.63
• S, 3 5.10
4.6 5.63
5.4

Example 7

A mixture consisting of 10.1 parts of bis- (2,4,6-tri-isopropyl phenyl) chlorophosphite, 3.4 parts of 4-hydroxy-N-methyl-2,2,6,6-tetramethylpiperidine and 2.75 parts by volume of triethylamine in 100 parts by volume of toluene was added under a nitrogen atmosphere Maintained room temperature for 5 hours and then for 16 hours under reflux. The hydrochloride salt of Base was filtered off and the toluene was distilled off under vacuum. The product is a pale yellow, viscous one OeI. Yield 7.4 parts.

709827/1 07

The bis (2,4,6-tri-isopropylphenyl) -N-methyl-2,2,6j6-tetramethylpiperidinyl-phosphite thus obtained showed the following elemental analysis (in%):

C. H ■ N P. target
found 75.07
74.8 10.4
10.1 2.19
1.4 4.84
5.0

Example 8

If the 4-hydroxyl-2,2,6,6-tetramethylpiperidine in Example 6 is replaced by 6.1 parts of 4-H3'drox} ' ^r IN-methyl-2,2,6,6-tetramethylpiperidine, 5.5 is obtained with otherwise the same procedure Parts of 2,4-di-t-butylphenyl-bis (N-methy1-2,2,6,6-tetramethylpiperidinyl) phosphite as a yellow viscous oil with the following elemental analysis (in%).

C. H N P. target
found 70.79
71.3 10.66
10.5 4.4 5.37
5.5

Example 9

To a solution of 8.4 parts of bis (2,6-di-isopropylphenyl) ' chlorophosphite and 2.7 parts by volume of triethylamine in 100 parts by volume of toluene were 3.4 parts of 4-hydroxy-N-methyl-2,2,6,6-tetramethylpiperidine at room temperature and below

709827/107 *

Given a nitrogen atmosphere. Otherwise in the same procedure as in Example 7, 8.3 parts of bis (2,6-di-isopropylphenyl) -N-methyl-2 , 2,6,6-tefcramethylpiperidiriyl-phosphite as weak yellow viscous oil with the following elemental analysis (in 7o) won:

C. H N P. target
found 73.48
73.2 9.79
9.8 2.52
2.2 5.57
5.1

Example 10

A mixture of 3.15 parts was added to 8.4 parts of bis (2,6-di-isopropylphenyl) chlorophosphite in 150 parts by volume of toluene 4-hydroxy-2,2,6,6-tetramethyl 1-piperidine and 2.8 parts by volume Triethylamine added. Otherwise in the same procedure as in Example 7 were 6.1 parts of bis (2,6-di-isopropylphenyl) -2,2,6,6-tetramethylpiperidinyl phosphite, obtained as viscous oil with the following elementary analysis (in%):

C. H N P. target
found 73.48
72.9 9.79
9.4 2.52
1.9 5.57
5.9

Example 11

In Example 3, the 4-hydroxy-N-acetyl-2,2,6,6-tetramethylpiperidine is replaced by 2.98 parts of 4-hydroxy-2,2,6,6-

709827/1074

tetramethylpiperidine, one obtains otherwise with the same Process 9.9 parts (96.3%) bis (2-methyl-6-t-butylphenyl) 2.2,6jo-tctramethylpiperidiriyl-phosphite as a pale yellow, viscous oil with the following elemental analysis (in%):

C. H N P. target
found 72.48
71.9 9.42
9.1 2.73
2.2 6.03
5.0

Example 12

A mixture of 17.1 parts was added to 13.9 parts of 2,6-di-iso-propylphenyl-di-chlorophosphite in 150 parts by volume of toluene 4-hydroxy-N-methyl-2.2,6,6-tetramethyl-piperidine and 10.9 Share triethylamine at room temperature and under a nitrogen atmosphere given. In otherwise the same procedure as in Example 6, 21.9 parts of 2,4-di-iso-propylphenyl-bis (N-raethyl-2,2,6,6-tetramethyl-piperidinyl) -phosphite were obtained as viscous oil with the following elemental analysis (in%):

C. H N P. target
found April 70
70.41 10.47
10.12 5.10
4.51 5.64
5.36

709827/107

Example 13

Stabilization of Polypro pylene ge gene thermo-ο κΐ dative A BBAU b ei proces un t n gsbediiigimge

The stabilizers listed in Table 1 are mixed homogeneously in a concentration of 0.1% with polypropylene powder from ICI ("Propathen HF 20" type) and 5 times in a single-screw extruder at a maximum of 260 ° C. and 100 rpm granulated. In each case after the l. _{In the} 3rd and 5th extrusions, the melt index (MI) of the material is measured (2160 g load at 230 ° C.; g / 10 minutes). A breakdown of the polymer manifests itself in a rapid increase in the melt index.

4-Methyl-2,6-di ~ t-butylphenol is used as a comparison substance (BHT) used.

The granules obtained after the 1st, 3rd and 5th extrusion are also ^{pressed in a plate press at 260 °} C. for 10 minutes to give 1 mm thick plates and assessed visually for their discoloration. Experience has shown that pressing the plate out of the granulate does not cause any further discoloration. An empirical color scale is used, in which grade 5 signifies colorlessness, 4 a just perceptible slight discoloration and 3-1 signifies increasingly clearly perceptible discoloration. The values after the 5th extrusion are important in practice.

709827/1074

TABLE I.

STABILIZER MI / 2160 g at 230 ⁰ G in g / 10
Min. After multiple text ms ion 3x ' 5x Color notes of the plates according to
More fac hextru si on 3x 5x without addition Ix 25.7 60.5 Ix 5 5 BHT (0.10% BHT)
as comparison 9.1 4.6 6.2 5 3 3 Example 5 3.2 4.8 6.7 3 5 5 Example 11 3.3 4.7 7.6 5 3.2

Example 14

100 parts of polypropylene powder (Moplen, Fiber grade, from Montedison) are mixed with 0.2 parts of ß- (3,5-di ~ tert-butyl-4-hydroxyphen3 ^r l) propionic acid - octadecyl ester and 0.25 parts of a Stabilizer of the following Table 2 is ^{homogenized in the Brabender plastograph at 200 °} C. for 10 minutes. The mass obtained in this way is removed from the kneader as quickly as possible and pressed into a 2-3 mm thick plate in a toggle press. Part of the raw pressed part obtained is cut out and pressed between two high-gloss hard aluminum foils with a hand-hydraulic laboratory press for 6 minutes at 260 ° C. and 12 tons of pressure to form a 0.5 mm thick foil, which is immediately quenched in cold water. The 0.1 mm thick test film is produced from this 0.5 mm film under exactly the same conditions. Sections of 60 × 44 mm each are then punched out of this and exposed in the Xenotest 150. These test specimens are removed from the exposure apparatus at regular intervals and checked for their carbon content in an IR spectrophotometer. The increase in the carbonyl extinction upon exposure is a measure of the photoxidative degradation of the polymer (see L. Balaban et al., J. Polymer Sci. Part C, 22, 1059-1071 (1969); JF Heacock, J. Polymer Sci . Part AI, 2_2, 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 Achieve a carbon extinction of approx. 0.3 at which the comparison film is brittle.

The protective effect of the stabilizers according to the invention is can be seen from the following table 2:

709827/1074

TABLE 2

STABILIZER Hours to carbonyl
extinction 0.300 Protection factor NO 980 1.0 Example 3 1470 1.5 Example 2 1568 1.6 Example 5 4900 5.0 Example 11 1960 2.0

709827/1074

Claims (11)

Claims Compounds of the general formula I H7 R. Br 3 4 5 0 —P— R, (D 3-n or their acid addition salts, in which η is 1 or 2, and R 1, R 25 Ro independently of one another is C 1 -C 4 -alkyl mean, and R, Cl "C9 Alk> Tl» means phenyl, benzyl or α-phenylethyl, or R-, and R, together mean tetramethylene or pentamethylene and R1- and R ^ - independently of one another hydrogen, C-, ~ Cr alkyl and Cl is "C] 2 alkyl, C5" CS is cycloalkyl, C5-C9 alkylcycloalkyl, Cg-C10 aryl, C7-C1, alkaryl or C7-C9 aralkyl, and is hydrogen, chlorine, bromine, C ^ -C- jo alkyl, C ^ -Co cycloalkyl, C6-C9 alkylcycloalkyl, C5-C10 aryl, C7-C34 allcaryl or C7-C9 aralkyl, and if η 1 is hydrogen, chlorine, C1-C ^ alkyl or C5-Co cycloalkyl or C ^ -Cg means alkylcycloalkyl, and "if η 2 is hydrogen, chlorine, bromine, C, -C ^ alkyl, Cr-Cg cycloalkyl, C6-C9-alkylcycloalkyl, 709827/1074 C6-C] 0 aryl, C7-C14 alkaryl or C7-C9 aralkyl, and hydrogen, oxyl, C1-C12 alkyl, C3-C5 alkenyl, C ~-C4 alkynyl, C2-C2 1 alkoxyalkyl, C7-C3 aralkyl, 2,3-epoxypropyl, an aliphatic acyl group with 1-4 C-Atoincη or one of the groups -CH2COOR, .., ₁ ) -OR ₁₂ , -COOR ₁₃ or -CONHR ₁₃ means in which R ₁₀ is ^C l ^"C 8 ^{Alk> r1 'C} 3 ~ ^C 6 ^alkene y ^1' is phenyl, C ₇ -C ₃ aralkyl or cyclohexyl, and R _{11 is} hydrogen, methyl or phenyl, and R, ρ denotes hydrogen, an aliphatic or aromatic, an araliphatic or alicyclic acyl group with 1-18 C atoms, in which the aromatic part is optionally _{substituted with chlorine, C 1} -C, alkyl, C ₁ -Cg alkoxy and / or with hydroxy can be, means, and Γί, ~ ^] * " ^C ] 2 alk-yl» means cyclohexyl, phenyl or benzyl. 2. Compounds of formula I according to claim 1, wherein η is 1 or 2, and R ₁ ) R ₂₅ R ₃ and R, independently of one another, are Cj-Cg alkyl, and Ro and R, together form tetramethylene or pentaraethylene, and
Rc and R ^ independently of one another are hydrogen, C-, -C. Alkyl mean, and R ₇ ^C l " ^C 3 2 ^alk y ^{1 >>} - ^C 5" ^C 8 ^c y cloalk 3 ^r l, ^C 6 " ^C 9 alkylcycioalkyl, phenyl, C ₇ -C ₉ alkaryl or C ₇ -C ₉ aralkyl is and
Rg hydrogen, chlorine, C ₁ -C ₉ alkyl, C ₅ -Cg cycloalkyl, C ₆ -C ₉ alkylcycloalkyl, phenyl, C ₇ -C ₉ alkaryl, C ₇ - C ₉ Araik} * -! means, and 709827/1074 R. _Q if η is 1, Is hydrogen, chlorine, C ₃ -C ₃ alkyl, C ₅ -C ₅ cycloalkyl or C ₅ -C ₇ alkylcycloalkyl, and R ₉ , if η is 2, Denotes hydrogen, chlorine, C ₃ -C ^ ₁ alkyl _{, C 1 -C 6} cycloalkyl, C ₅ -C ₇ alkylcycloalkyl, phenyl, C ₇ -C ₉ alkaryl or C ₇ -C ₉ aralkyl, and X is hydrogen, oxyl, C ₃ -C 6 alkyl, C ₃ -C ₄ AlkOiTyI or C ₃ -C ₄ alkynyl, C ₂ -C ₅ alkoxyalkyl, C ₇ -C ₈ aralkyl, acetyl, acryloyl or crotonoyl, or one of the groups -Cl ₂ -COOR-J ₀ , -CH ₂ -CH (R ₁₁ ) -OR ₁₉₅ -COOR ₁₃ or -CONHR-, means, in which R _{10 is} C ₃ -C ₄ AIkVl, C ₃ -C ₄ AIkCHyI, phenyl, C ₇ -Cg aralkyl or cyclohexyl, and R _{11 is} hydrogen, methyl or phenyl, and RJ _{9 is} hydrogen or an aliphatic, aromatic, alicyclic or araliphatic ^ acyl group with 1-18 carbon atoms, in which the aromatic part optionally with chlorine, C-. -C ^ alkyl, C _n -C ^ alkoxy and / or hydroxy can be substituted, means, and R, _{o is} C _n -C ₁₀ alkyl. JLj X J_Z 3. Compounds of formula I according to claim 1, wherein η is 1 or 2, and R ₁ and Ro are methyl or ethyl, and R ₉ and R _{4 are} methyl, and R if R- is methyl., 'Is hydrogen, and if R _{1 is} ethyl is, means methyl, and
R, means hydrogen, and
R ^C 3 ~ ^C Q ^Α1ι \> ^7ΐ > ^C 5 ~ ^C 6 cycloalkyl, C ₅ -C ₇ alkylcycloalkyl, Denotes phenyl or Cg-C ₉ aralkyl, and 709827/1074 Rg is hydrogen, chlorine, C ₁ -C ₉ alkyl, C ₅ -C ₆ cycloalkyl, C ₆ -C ₇ alkylcycloalkyl, phenyl or C _g -C aralkyl, and Ro is hydrogen, chlorine, C ₁ -C ₃ alkyl or cyclohexyl, and X hydrogen, C ₁ -C ₄ alkyl, allyl, propargyl, C _? ~ C _f alkoxyalkyl, acetyl, acryloyl 'which is crotonoyl, or one of the groups -CH ₂ -COOR ₁₀ , -CH ₂ -CH (R ₁₁ ) -OE- ₉ , -COOR ₁₃ or -CONHPv ₁₃ , wherein R ,, · hydrogen or methyl and R _{19 is} hydrogen, and R _{13 is} ^C 1 ~ ^C 4 ^Alk > ^rl - 4. Compounds of formula I according to claim 1, wherein η is 1 or 2, R ₁ and R ^ are methyl or ethyl, and R ₉ and R ^ are methyl, and R _rj if R _{1 is} methyl, hydrogen, and if R _{1 is} ethyl is methyl, and R ^ is hydrogen, and R _{7 is} isopropyl, t-butyl or cyclohexyl, and R _{ß is} hydrogen, C -, - C, alkyl or C} ^T clohexyl, and R _{Q is} hydrogen, methyl or isopropyl, and X is hydrogen, methyl, allyl, propargyl or Acetyl is. 5. Compounds of formula I, according to claim 1, wherein η is 1 or 2, and R ₁ , R ₂ , Pv ₃ and R, are methyl, and 709827/1074 R ₁ - and IL. Are hydrogen, and R _{7 is} isopropyl or t-butyl, and Rn is hydrogen, methyl, isopropyl or t-butyl, and R _{0 is} hydrogen, methyl or isopropyl, and X is hydrogen or methyl. 6. Compounds of formula I according to one of claims 3 to 5, xrorin X is benzyl, hydrogen, G ₁ -C ₆ alkyl, allyl, propargyl or acetyl. 7. Compound of formula I according to claim 1, Bis- (2,4-di-t-buty! Phenyl) -2,2,6,6-tetramethylpiperidinylphosphito 8. Compound of formula I according to claim 1, Bis- (2-methy1-6-t-buty! Phenyl) -N-acetyl-2,2,6,6-tetraraethylpiperidinyl phosphite. 9. Process for the preparation of compounds of the general formula I according to claim 1, characterized in that that, a piperidine of the formula II X / ¹ OH (II) with a phosphorous acid ester dihalide or a phos phosphoric acid diester mono halide of the formula III 709827/1074 (HaI) _n (HI) is implemented, in which the symbols n, R -, - R ₀ and X have the same meaning as in formula I. 10. Use of the compounds of the formula I according to Claim 1 for stabilizing organic material. 11. The organic material containing a compound of the formula I, according to claim 1. 709827/1074