SK34095A3 - Process for the preparation of olefin polymers - Google Patents

Abstract

The addition of at least one compound of the series of the hydrotalcites, zeolites or metal oxides that does not release water under the reaction conditions to the polymerisation of olefins with solid supported catalysts effects a strong reduction in the corrosive action of the polymers without adversely affecting the polymerisation itself or the properties of the polymers. Further stabilisers may also be added.

Description

TY

Process for preparing polyolefins

Technical field

The invention relates to a process for the preparation of olefin polymers, in which hydrotalcites, zeolites or metal oxides and optionally stabilizers are added during the polymerization. The invention also relates to polyolefins thus prepared.

BACKGROUND OF THE INVENTION

Low-pressure olefin polymerization using organometallic complexes as catalysts (e.g. Ziegler-Natta catalysts) typically yields polymers in the form of a fine powder, which is extruded before processing. Substances such as stabilizers, corrosion inhibitors, color improver, antistatic agents and other processing agents are used in this granulation. However, this granulation is not always desirable or possible, which is, inter alia, the case of high molecular weight polymers.

Recently, it has been shown that it is possible to prepare spherical granular polymers using solid-supported catalysts which no longer need to be extruded granules and which can be processed directly. Suitable supports for said solid catalysts are, in particular, spherical magnesium halides having a specific particle size, which are described, inter alia, in DE-A-2 641 960. The anhydrous magnesium halide forms insoluble complexes with titanium tetrachloride and an electron donor, which are then activated with alkylene aluminum. Stereospecificity and activity is enhanced by the use of electron donors such as carboxylic acid esters or compounds containing SI-O-C bonds, among others described in EP-A-45 977.

Since the polymers thus obtained no longer need to be granulated, it is desirable to add modifiers that are important for processing and long-term stability during polymerization. However, the addition of many conventional modifiers (e.g., stabilizers) interferes with the polymerization of olefins and causes a change in color of the polymers.

Machines used in the further processing of polymers, such as calenders, are subject to corrosion. The corrosive effect of polymers on metal surfaces is generally attributed to the remainder of the catalysts or the degradation products of the catalyst system. Therefore, up to now, it has not been necessary to add a corrosion inhibiting compound in a separate treatment step.

It is known from EP-A-192 987 or EP-A-0 350 444 that stabilizers based on sterically hindered amines of the polyalkylpiperidine-type do not interfere with said polymerization and thus do not cause a significant color change of the polymer and result in good thermal and oxidative stability.

It is further proposed in EP-A-254 348 to add phosphites or phosphonites as antioxidants.

It is also known to add stabilizers based on spherically hindered amines of the polyalkylpiperidine type in polymerization in combination with organic phosphites or phosphonites (EP-A-0 351 360).

SUMMARY OF THE INVENTION

Surprisingly, it has now been found that the addition of compounds from the group comprising hydrotalcites, zeolites, and metal oxides that do not release water under the reaction conditions, in combination with any stabilizers, does not interfere with olefin polymerization and substantially inhibits corrosion that would otherwise occur during polymerization. the addition of further stabilizers achieves excellent long-term stability.

Accordingly, the invention relates to a process for the preparation of polyolefins by polymerization using transition metal catalysts, characterized in that the polymerization is carried out by adding at least one compound from the group comprising hydrotalcites, zeolites and metal oxides which do not release water under the reaction conditions. .

The polymerization is preferably carried out using a solid supported transition metal catalyst prepared by reacting an aluminum compound bearing at least one alkyl group with a metal compound IV. subgroup of the Periodic System of Elements.

The olefins that are polymerizable in this way are ethylene and alpha-olefins such as propylene, 1-butene, 4-methylpent-1-ene or 5-methylhex-1-ene, as well as olefin mixtures, which are typically ethylene-propylene or propylene in admixture with a minor amount of higher alpha-olefin. Of particular interest is the process of polymerizing and copolymerizing propylene.

The polymerization catalysts are transition metal catalysts. These catalysts are typically formed by a magnesium halide in active form and a titanium compound. Catalysts with other metals IV are also suitable. A subset of the Periodic System of Elements (Zr and magnesium in active form in which the X-ray spectrum is substantially wider than the corresponding line in the spectrum of the inactive magnesium halide.

H). The term halide refers to magnesium halide, the line with the strongest reflection. The magnesium halide may preferably be magnesium chloride or magnesium bromide. The titanium compounds preferably contain at least one thithane halide bond. It is particularly preferred to use titanium tetrachloride.

The titanium compound can be used in combination with an electron donor, which is typically a carboxylic acid ester as described in EP-A-45 977.

After reacting the magnesium halide with the titanium compound and optionally with an electron donor, the excess titanium compound and the excess electron donor are suitably eluted with an inert solvent, such as typically hexane or heptane.

The catalyst thus prepared is then activated by reaction with an aluminum compound which carries at least one alkyl group and which is preferably used as a solution in an alkane. Examples of suitable aluminum alkyls are Al (C ₂ H _{s), and} or Al (C ₄ H _g). An electron donor, which is suitably an organosilicon compound containing at least one Si-OC bond and described in EP-A-45 977, can be used as a co-activator. Typical examples of such silicon compounds or ethyltrimethoxysilane.

Other transition metal catalysts are typically composed of a solid supported chromium compound such as alumina or silica or mixtures thereof. Examples of such catalysts, also referred to as Phillips catalysts, can be found in US-A-2,825,721.

The polymerization using these catalysts can be carried out by known liquid or gas phase methods. The liquid phase may suitably be an aliphatic hydrocarbon or liquid monomer itself.

Compounds from the group consisting of hydrotalcites, zeolites and metal oxides that do not release water under the reaction conditions are added to the polymerization mixture at the beginning of the polymerization, during the polymerization and at the end of the polymerization.

Said compounds from the group comprising hydrotalcites, zeolites and metal oxides are either naturally occurring substances or synthetically prepared compounds.

The compounds of the hydrotalcite group are illustrated by formula (I)

Μ ²⁺ μχ · Μ ³ x x ((OH) ₂ * (Α ^η -) _χ · πτΉ ₂ Ο (I) in which

M ² * means M ³ * means A ⁿ means n means x means m means A means

Mg, Ca, Sr, Ba, Z; Al, B or Bi, anion with a valence number from 1 to 4, a number from 0 to 0.5 a number from 0 to 2, and

Sn or / and Ni,

OH, d, Br, 1 ', C10 /, HCO ₃ ', CH ₃ COO ·, C ₆ H ₅ COO-, CO ₃ ² -, SO ² -, cooCOO-, (CHOHCOOH ² -, (CHOH) 4 CH ² OHCOO-. (COO) 2 ', (CH 2 COO) 2 ² ', CH ₃ CHOHCOO-, SiO ₃ ² ', SiOA Fe (CN) 6 ³ -, Fe (CNV, HPO ^{4 2} ').

Other hydrotalcites which are suitably used in the above-described process are compounds of formula Ia

-mH ₂ O;

wherein M ² * represents at least one metal from the group consisting of Mg and Zn, the preferred metal being Mg, A represents an anion from the set / co ° | = comprising CO ₃ ² , CO ² , OH and S ² , and n represents the valence of these anions, m represents a positive number, preferably a number from 0.5 to 5, and x and z are positive numbers, x preferably being 2 to 6 and less as 2.

Preferred compounds of the hydrotalcite group are those of formula I '(OH) ₂ ' (A-) _x · mH ₂ O ₍ j).

4i wherein M ² * represents Mg or represents a solid solution of Mg and Zn, A ^- represents CO ₃ ^2- , x represents a number from 0 to 0.5 and m represents a number from 0 to 2.

Particularly preferred hydrotalcites are those of the formulas

Al ₂ O ₃ -6MgO-CO ₂ - 12H ₂ O

Mg 4 J ₅ Al ₂ (OH) ₁₃ -CO ₃ -3,5H ₂ O,

4MgO-Al ₂ O ₃ -CO ₂ -9H ₂ O

4MgO-Al ₂ O ₃ -CO ₂ -6H ₂ O

ZnO-3MgO-Al ₂ O ₃ -CO ₂ -8-9H ₂ O

ZnO-3MgO-Al ₂ O ₃ -CO ₂ -5-6H ₂ O.

Zeolites of formula X can also be used in the present invention

M ^ KMO ^ SiO ^ yJ-wE ^ O ^(x >

where n is the charge of cation M,

M represents an element of the first or second main group

Periodic system of elements, y: x stands for a number of 0.8 to 1.2 a

W is from 0.5 to 10.

Preferably, the known zeolites which can be used in the above process have a mean pore diameter of 3 to 5 A (0.3 to 0.5 nm), including NaA type zeolites having a mean effective pore diameter of 4 A (0.4 nm). ) and are therefore referred to as zeolites 4A.

Illustrative examples of suitable zeolites are the compounds:

Na ₁₂ [(AlO ₂ ) i ₂ (SiO ₂ ) i ₂ ] · 12Η ₂ Ο

Ca ₄₅ Na ₃ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] -30H ₂ O

K ₉ Na ₃ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] -27H ₂ O

Metal oxides can also be used in the process of the invention. Preferred metal oxides are divalent metal oxides. Particularly preferred metal oxides are the metal oxides of the second main group or subgroup of the Periodic Table of the Elements, the most preferred metal oxides being zinc oxide or magnesium oxide.

The novel compounds are dried to remove unbound or only separably bound water to a temperature of 50 to 800 ° C, preferably to a temperature of 80 to 400 ° C, provided that the compounds are not sufficiently dry and that they are not stored in a moisture-free environment. This drying may be carried out under vacuum or under an inert gas atmosphere. The surface of said materials may be treated with surfactants such as carboxylic acids or linear alcohols having 8 or more carbon atoms, suitably stearic acid.

Compounds from the group consisting of hydrotalcites, zeolites and metal oxides or similar synthetically prepared compounds which do not release water under the reaction conditions are normally added in an amount of 0.005 to 5.0% by weight, preferably in an amount of 0.01 to 1% by weight, based on polymer weight.

The above process is preferably carried out using additional stabilizers.

In a particularly preferred embodiment of the process according to the invention, said process is carried out with a further addition of a compound containing at least one 2,2,6,6-tetramethylpiperidine group and having a molecular weight of more than 500, or with a further addition of a trivalent phosphorus compound. Especially preferred is the use of said 2,2,6,6-tetramethylpiperidine compound with a trivalent phosphorus compound.

Sterically hindered amines, preferably piperidines, are known as light-stabilizers, and also act as antioxidants, meaning that the polymers provide thermal oxidation stability. These compounds contain one or more groups of formula I

These compounds may be oligomeric or polymeric compounds.

Particularly important stabilizers are the following classes of tetramethylpiperidines:

(a) compounds of formula II

wherein n is a number from 1 to 4, preferably 1 or 2,

R ¹ is hydrogen, oxyl, C? -C? -Alkyl, C ₃ -C _s -alkenyl, C ₃ -C -alkynyl _and C ^ C ^^ - _aralkyl, C -C _g alkanoyl group, a C ₃ -C _s -alkenoylovú group, glycidyl or a group CH ₃ CH (OH) -Z, in which

Z represents a hydrogen atom, a methyl group or a phenyl group, wherein

R ^{1 is} preferably C 1 -C 4 -alkyl, allyl, benzyl, acetyl or acryloyl, and

R ^2, if n is 1, is hydrogen, C? -C? -Alkyl which may be interrupted by one or more than one oxygen atom, cyanoethyl, benzyl, glycidyl, monovalent radical of an aliphatic, cycloaliphatic, an araliphatic, unsaturated or aromatic carboxylic acid, carbamic acid or phosphorus-containing acid, or a monovalent silyl group, preferably a C 2 -C 18 aliphatic carboxylic acid group, a C 7 -C 15 cycloaliphatic carboxylic acid, alpha, beta unsaturated carboxylic acid containing 3 to 5 carbon atoms or an aromatic carboxylic acid containing 7 to 15 carbon atoms, and

R ² when n = 2 represents a C 1 -C 4 -alkylene group, a C ₄ -C ₁₂ -alkenylene group, a xylylene group, a bivalent group of an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, dicarbamic acid or an acid containing phosphorus or a divalent silyl group, preferably an aliphatic dicarboxylic acid group having 2 to 36 carbon atoms, a cycloaliphatic or aromatic dicarboxylic acid having 8 to 14 carbon atoms or an aliphatic, cycloaliphatic or aromatic dicarbamic acid having 8 to 14 carbon atoms, and

R ^2, if n = 3, is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, of an aromatic tricarbamic acid or a phosphorus-containing acid or a trivalent silyl radical, and

R ² when n = 4 represents a four-valency group of aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.

Substituents defined as _i -C _i2 alkyl group may typically be methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

And ^C '' ^C ^ x and ^{Alk nominal} groups that of R ² may be the aforementioned groups, to which may be added .tridecylová n, n-tetradecyl, nhexadecylová or n-octadecyl.

C ₃ -C _{-alkenyl, and} that R ¹ R may typically be 1-propenyl, allyl, methallyl, 2-butenyl, 2pentenylová, 2-hexenyl, 2-octenyl, 4-tert. butyl-2-butenyl group.

C ₃ -C -alkynyl _and that R R ^x is preferably propargyl.

The C 1 -C 6 Aralkyl group of R ¹ is preferably a phenethyl group, and more preferably a benzyl group.

_A C ~ C _and Alkanoyl in the definition of the substituent R ¹ is typically formyl, propionyl, butyryl, octanoyl, the preferred group is acetyl and C ₃ -C preferred -alkenoylovou _the group is acryloyl.

The monovalent carboxylic acid group R ² is typically acetic acid, caproic acid, stearic acid, acrylic acid, methacrylic acid, benzoic acid or beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid. .

The divalent carboxylic acid group D ² is typically malonic acid, succinic acid, glutaric acid, adipic acid, corkic acid, sebacic acid, maleic acid, phthalic acid, dibutylmalonic acid, dibenzylmalonic acid, butyl- (3,5 di-tert-butyl-4-hydroxybenzyl) malonic acid or bicycloheptenedicarboxylic acid.

The trivalent carboxylic acid tricarboxylic acid group R ² is typically trimellitic acid or nitriloacetic acid.

Tetravalent radical of a tetracarboxylic acid, in the definition of substituent R ² is typically a tetravalent radical of a butane-1,2,3,4-tetracarboxylic acid or of pyromellitic acid.

A divalent radical of a dicarbamic acid that R is a group R ² of hexametyléndikarbamovej or a 2,4-toluylenedicarbamic acid.

b) Compounds of formula III

wherein n is 1 or 2,

R ¹ is as defined under a),

R ³ is H, C? -C? -Alkyl, ^C 2 ^'C hydroxyalkyl, C _s -C ₇ -cycloalkyl

C ₇ -C _e -aralkylovTi group, a C ₂ -C _s alkanoyl group, a C ₃ -C _s -alkenoylovú or benzoyl, and

R ^4, if n = l, is H, C _{x and} C _x -alkyl, C ₃ -C _e -alkenyl, C? -C? -Cycloalkyl, C _x -C ₄ alkyl group, which is substituted by hydroxyl, cyano, alkoxycarbonyl or carbamido, glycidyl, -CH ₂ -CH (OH) -Z or -CONH-Z, wherein Z is hydrogen, methyl or phenyl or

R ^4, if n is 2, is C ₂ -C _x2 -alkylene group, C -C -arylénovú group, a xylylene group, a group -CH ₂ -CH (OH) -CH ₂ or -CH ₂ CH ( OH) -CH -ODO-, wherein D is C ₂ -C _xo ~ alkylene, C ₆ -C _xs -arylénovú group, a C _s -C _i2 -cycloalkylene radical, or

R ⁴ , provided that R ^{3 is} not an alkanoyl, alkenoyl or benzoyl group, is also a bivalent group of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid, or -CO- or

R ³ and R ⁴ when n = 1 together represent a bivalent aliphatic, cycloaliphatic or aromatic 1,2- or 1,3-dicarboxylic acid group.

Substituents defined as C _x -C _x2 ~ alkyl or

C _{they and} C _x -alkyl are as already mentioned in a).

C _s -C ₇ -cycloalkyl group is preferably cyclohexyl.

C ₇ -C -aralkyl _{group, and} that R ³ R is preferably phenylethyl or, most preferably, benzyl. C ₂ -C _s group is preferably -hydroxyalkylovou

2-hydroxyethyl or 2-hydroxypropyl.

C ₂ -C _{i and} alkanoyl groups that sub13 of substituents R ³ is typically propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl, octadecanoyl, the preferred group is acetyl, and C ₃ -C _s -alkenoylovou the group is preferably an acryloyl group.

C ₂ -C _{-alkenyl, and} that R ⁴ R is typically allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl.

C 1 -C 4 -alkyl substituted by hydroxyl, cyano, alkoxycarbonyl or carbamide as R ⁴ is typically 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl a 2-aminocarbonylpropyl or 2- (dimethylcarbamoyl) ethyl group.

The substituents defined as C 1 -C 4 -alkylene may typically be ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

Substituents defined as C _{6 is} -arylénová group may be, typically, o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-biphenylene.

C ₆ -C _x2 -cycloalkylen that R D is preferably cyclohexylene.

Illustrative examples of polyalkylpiperidine compounds of this class are:

N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) -N, N ' dibutyladipamid,

N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) -N, N'-cyclohexyl-2-hydroxypropylene-1,3-diamine and a compound of the formula

CH _{3 y} CH ₃

C "H,

4 * '9

CH.

ch ₃ ch ₃

CH ₃ . ^CH 3

N-CH ₂ -CH (OH) -CH ₂ -o

N-CH ₂ -CH (OH) -CH 2

CHt - - CH <

c) A compound of formula IV

wherein n is 1 or 2,

R ¹ is as defined under a) and

^R, if n is 1, is C ₂ -C _e -alkylene or C ₂ -C _s -hydroxyalkylénovú group or C? -C? -Acyloxyalkylénovú; and

R ⁵ when n = 2 is (-CH ₂ ) ₂ C (CH ₂ -).

C __- _C -alkylene or C ₂ -C -hydroxyalkylénovou _of groups that R ^with may be ethylene, 1-methylethylene, propylene, 2-ethylpropylene or 2-ethyl-2-hydroxymethylpropylene group.

C? -C? -Acyloxyalkylénovou group in the definition of substituent ^R may be 2-ethyl-2-acetoxymetylpropylénová group.

d) Compounds of formulas VA, VB and VC

(VA) (VB) (VC) where n is 1 or 2,

R ¹ is as defined under a),

R ^a is H, C? -C? Alkyl, allyl, benzyl, glycidyl or C ₂ -C _e -alkoxyalkylovú; and

R ^7, if n is 1, is hydrogen, C? -C? -Alkyl, C ₃ -C _s -alkenyl, C ₇ -C _g -aralkyl group, a C _s -C ₇ -cycloalkyl, A C 1 -C 6 -hydroxyalkyl group, a C ₂ -C ₆ -alkoxyalkyl group, a C ₆ -C ₁₀ -aryl group, a glycidyl group or a group of the formula - (CH ₃ ) 4 -COO-Q or of the formula - (CH ₂ ) - O-CO-Q, wherein p is 1 or 2 and Q is C _x -C ₄ alkyl or phenyl, or

R ^7, if n is 2, is C ₂ -C _x2 -alkylene, C ₄ -C _x2 -alkenylene, C ₆ -C -arylénovú _{X 2} group, a -CH ₂ -CH (0H) -CH ₂ -0-D-0-CH ₂ -CH (OH) -CH ₂ wherein D is _C2-xQ -alkylene, C ₆ -C _xs -arylénovú group, a C ₆ -C _x2 -cycloalkylene group, or is a group of formula

-CH ₂ CH (OZ ') _CH2 - _(OCH2 --CH (OZ') _{CH2) 2} -, wherein Z is H, C _{x with x} -C alkyl, allyl, bezylovú group, a C ₂ -C _{x 2} -alkanoyl or benzoyl,

_Τ χ and T ₂ each independently of the other represents a hydrogen atom or a C _e -C _xo -aryl or C ₇ -C ₉ ~ aralkyl group which may be substituted by halogen or C _x -C ₄ -alkyl, or T _x and T ₂ together with the carbon atom to which they are attached, _a C-C _x2 -cykloalkánovú group.

Substituents defined as C _x -C _x2 alkyl group may typically be methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

Substituents defined as C _x-x alkyl group may be the above group, and may additionally include n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

Substituents defined as _C2-C6 -alkoxyalkylová sku17 pina may typically be methoxymethyl, ethoxymethyl, propoxymethyl, t-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl group, terc.butoxyetylová group, isopropoxyethyl or propoxypropyl .

C ₃ -C _s alkenoyl group in the definition of substituent R ⁷ may be 1-propenyl, allyl, methallyl, 2-butenyl or 2-pentenyl.

C-C _{in g} -aralkyl group in the definition of the radicals R ^7, T and T ₂ are preferably phenethyl or, most preferably, benzyl. The cycloalkane ring formed by T and T ₂ together with the carbon atom to which they are attached may be a cyclopentane ring, a cyclohexane ring, a cyclooctane ring or a cyclododecane ring.

The C 1 -C 4 -hydroxyalkyl group represented by the general substituent R ⁷ may be 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

The C ₆ -C ₁₀ -Aryl group _as defined by the general substituents T and T ₂ is preferably a phenyl group, an alpha- or beta-naphthyl group which is substituted by a halogen atom or a C 1 -C 6 -alkyl group.

The C ₂ -C ₁₂ -alkylene group represented by the general substituent R ⁷ may typically be an ethylene group, a propylene group, a 2,2-dimethylpropylene group, a tetramethylene group, a hexamethylene group, an octamethylene group, a decamethylene group or a dodecamethylene group.

The C-C 1-6 alkenylene group, preferably R ^7, is preferably a 2-butenylene group, a 2-pentenylene group or a 3-hexenylene group.

C ₆ ~ C _x2 -Arylénovou groups that substi18 Tuenti R ⁷ is typically o-, n- or p-phenylene, 1,4naftylénová, or 4,4'-biphenylene.

The C ₂ -C ₁₂ -Alkanoyl group represented by the general substituent Z 1 may be a propionyl group, a butyryl group, an octanoyl group, a dodecanoyl group, but the preferred group is an acetyl group.

_C2-io alkylene group, a C ₆ -C -arylénová, or _is C ₆ -C _i2 that R D are as defined in b).

Illustrated examples of polyalkylpiperidines of this class of compounds are the following compounds:

ch ₃

HN ch ₃

CH ₃ CH ₃

about

e) Compounds of formula VI

wherein n is 1 or 2 and

R 8 represents a group of the general formula

in which

R ¹ is as defined under a),

E represents -O- or -NR ¹¹ -,

A represents a C ₂ -C ₆ -alkylene group or group

- (CH) -O-, and x is 0 or 1,

R ⁹ has the meaning of the substituent R®, or is -NR ¹¹ R ^12, -OR ^13, -NHCH ^ OR ¹³ or -N (CH 2 OR ¹³⁾ 2,

R ¹⁰ when n = 1 has the meaning of the general substituent R ⁸ or R ⁹ , and

R ¹⁰ when n = 2 represents a group -EBE- in which B represents a C ₂ -C ₆ -alkylene group which may be disturbed by the group -N (R ^XX ) -, where

R ^xx represents a C 1 -C 4 -alkyl group, a cyclohexyl group, a benzyl group or a C 1 -C 4 -hydroxyalkyl group or a group of the general formula

R ¹² is a C _x -C _i2 alkyl, cyclohexyl, benzyl, C -C -hydroxyalkylovú; and

R ¹³ represents a hydrogen atom, a C 1 -C 4 -alkyl group or a phenyl group;

R ¹¹ and R ¹² together are C ₄ -C _s alkylene or ~ C-C -oxaalkylénovú group, typically having

-ch ₂ ch ₂

-ch ₂ ch ₂ or represents a group of the formula

-ch ₂ ch ₂

-ch ₂ ch ₂

N — R ¹ r 1 or

R ^xx and R ¹² each also represent a group of the formula

CH ₃ CH ₃

HN

NH-ACH ₃ ch ₃

H

CH ₃ CH ₃ CH ₃

The substituents defined as C1-C4-alkyl are typically methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, -ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

The substituents defined as C1-C4-hydroxyalkyl may typically be 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

C ₂ -C ₆ alkylene group that R A may be ethylene, propylene, 2,2dimetylpropylénová, tetramethylene or hexamethylene.

C ₄ -C _s alkylene group which can be represented by R ^X1 and R ^X2 can be tetramethylene, pentamethylene or 3-oxypentametylénová group.

Illustrative examples of polyalkylpiperidines of this compound group are compounds of the following formulas:

N (C ₄ H 8) 2

^H 3 ^C CH ₃

R = -NH-CH ₂ CH ₂ CH ₂ -O n -ch ₃

H ₃ C ^CH 3 ^CH 3 CH ₃

In CH ₃ CH ₃ CH ₂ CH ₂ NH ·

r24

75)

R =

R-NH- (CH ₂ ) ₃ -N- (CH ₂ ) ₂ -N- (CH ₂ ) ₃ -NH-R

76)

R =

R R

I I

R-NH- (CH ₂ ) ₃ -N- (CH ₂ ) ₂ -N- (CH ₂ ) ₃ -NH-R

77) ch ₃ yy

I I I

RN - (CH ₂ ) ₃ - N - (CH ₂ ) ₂ - N - (CH ₂ ) ₃ · ch ₃

I

N -

80)

f) Oligomeric or polymeric compounds whose structural repeating unit contains one or more than one 2,2,6,6, -tetraalkylpiperidine group of formula I, preferably polyesters, polyethers, polyamides, polyamines, polyurethanes, polyureas, polyaminotriazines, poly ( meth) acrylates, polysiloxanes, poly (meth) acrylamides and their copolymers containing the above group.

Illustrative examples of 2,2,6,6-polyalkylpiperidine light stabilizers of this group are the compounds of the following formulas wherein m is an integer from 2 to 200.

82)

CH ₃ ch ₃ ^/ oo _to ii U

N-CH ₂ -CH-C _5-O (CH _{2) 4} - C-j ^ -3 CH ₃ CH ₃

86)

about

II '-cc ₄ hrs

4 ^π 9 • c CxH

4Π9 o

c-328

95)

96)

H ₉ C ₄ (R) N

H ₉ C ₄ (N) N _n N (R) C ₄ H ₉

Y Y

ΝγΝ _ NH (CH ₂ ) ₃ .NI

- N - (CH ₂ ) ₂ N (CH ₂ ) ₃

N (R) C ₄ H ₉

R

NH x

2-3

H ₉ C ₄ (R) N ^/ N N ' ^z ^ n (R) C ₄ H ₉ where R = h ₃ C ^ ^CH 3

Oh \

R 1 = ^N N or H

H ₉ C ₄ (R) NNN (R) C ₄ H ₉

Among the abovementioned light stabilizer groups, groups e) and f) are particularly suitable, and among them, in particular those tetraalkylpiperidines which contain s-triazine groups. Other particularly suitable compounds are compounds 74, 76, 84, 87, 92 and 95.

The amount of tetramethylpiperidine added will depend on the desired degree of stabilization. Normally, 0.01 to 0.1 is added

5.5% by weight, preferably 0.05 to 1% by weight of tetramethylpiperidine, based on the weight of the polymer. It is preferred that the molar ratio of tetramethylpiperidine to alkyl aluminum is not significantly greater than 1.

The trivalent phosphorus compounds added as optional additional stabilizers to the polymerization mixture may be phosphites, phosphonites or phosphinites. These compounds may contain one or more than one phosphoric acid ester group. It is preferred to use a trivalent phosphorus compound of the following formulas A to D.

In which

^The R ^{* * * * x} and R @ ² independently of one another are C -C -alkyl, _C -C _e -cycloalkyl, phenyl, phenyl which is substituted by one to three C? -C? - alkyl, or -OR ³ ,

R ³ is a C _e -C _2o alkyl group, a C _s -C _s -cycloalkyl, phenyl or phenyl which is substituted by one to three C? -C? -Alkyl groups

R ⁴ represents an unsubstituted phenyl or naphthylene group or a phenylene or naphthylene group which is substituted by a C 1 -C 4 -alkyl group, or an -O-R group ^with -O- in which

^R is an unsubstituted phenylene or naphthylene or phenylene or naphthylene which is substituted by C _x -C _i2 -alkyl, or phenyl group, R ^e -Fen- wherein

Fen is a phenylene group and

R ⁶ represents -O-, -S-, -SO ₂ -, -CH ₂ - or -C (CH ₃ )

R ⁷ and R ^a each independently of one another is phenyl or phenyl which is substituted by one to three C? -C? -Alkyl groups, wherein both substituents R ⁷ and R ^s can also be linked C-C _{i2 x} - alkylene and

R ⁹ is F, Cl, Br or I, preferably F.

Of the compounds of formula A, preference is given to compounds in which R ¹ and R ² are -OR ³ and R ³ is C ₆ -C ₂₀ -alkyl, phenyl or phenyl which is substituted by one or three C 1 -C ³ -alkyl groups. C 1-6 -alkyl groups.

Among the compounds of formula B it is preferred to use compounds in which R ² is -OR ^3, R ³ is phenyl or phenyl which is substituted by one to three C _i -C _i2 alkyl groups and ^R4 is a diphenylene.

Among the compounds of formula C it is preferred to use compounds in which R ¹ is a group -OR ^3, R ³ is phenyl or phenyl which is substituted by one to three C _x -C _x2 alkyl groups.

Preferably, a trivalent phosphorus compound is used which contains at least one P-O-Ar group and Ar is a mono-, dialkyl or trialkylphenyl group.

Illustrative examples of suitable trivalent phosphorus compounds are:

triphenylphosphite, decyldiphenylphosphite, phenyldidecyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol diphenyl dipentaerythritol diphosphite) tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite.

The amount of the trivalent phosphorus compound will depend on the amount of the piperidine compound added. Normally 0.01 to 1% by weight, preferably 0.05 to 0.5% by weight, of a trivalent phosphorus compound is added, based on the weight of the polymer.

In addition to the trivalent phosphorus compound, other co-stabilizers and modifiers can be added that do not interfere with the polymerization process. It is preferred to add antioxidants of the spherically hindered phenol type to the polymerization mixture. These phenols are standard antioxidants for organic substances and are often used to stabilize polymers. Illustrative examples of such phenolic antioxidants are:

1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert. butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (n-methylcyclohexyl) -4,6-dimethylphenol, 2, 6-dioctadecyl-4-methylphenol,

2,4.6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol,

2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6- (1'-methyl-1'-undecyl) phenol, 2,4-dimethyl-6- (1'-methyl-1'heptadecyl) phenol, 2, 4-Dimethyl-6- (1'-methyl-1'-tridecyl) phenol and mixtures thereof.

2. Alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol.

3. Hydroquinones and alkylated hydroquinones, for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol; 2,6-di-tert. butylhydroquinone, 2,5-di-tert. butyl-4-hydroxyanisole,

3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

4. Hydroxylated thiodiphenyl ethers, for example 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tert-butyl-3) methyl-phenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-thiobis (3,6-di-sec-amylphenol), 4,4'-bis (2,6 dimethyl-4-hydroxyphenyl) disulfide.

5. Alkylidenebisphenols, for example 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'-methylenebis [4- methyl-6- (<-methylcyclohexyl) phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (6-nonyl-4-methylphenol), 2,2'- methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2 2'-methylenebis- [6- (o-methylbenzyl) -4-nonylphenol], 2,2'-methylenebis [6- (o (, o (-dimethylbenzyl) -4-nonylphenol)], 4,4'- methylenebis (2,6-di-tert-butylphenol), 4,4'-methylenebis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol), 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis- (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecylmercaptobutane, ethylene glycol bis- [3,3-bis (3'-tert-butyl-4 ') -hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, bis [2- (3'-tert-butyl-2)] 1-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5-di tert-butyl-4-hydroxyphenyl) propane, 2,2-bis- (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane, 1,1,5,5-tetra (5 tert-butyl 4-hydroxy-2-mety1fenyl) pentane.

6. O-, N- and S-benzyl compounds, for example 3,5,3'5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tris ( 3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2,6-dimethyl-35-benzyl) dithioterephthalate, bis (3,5-di-tert-butyl-4) iso-octyl-3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate.

7. Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis- (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) malonate, didodecylmercaptoethyl-2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, bis [4- (1,1,3,3-tetramethylbutyl) phenyl] -2,2-bis ( 3,5-di-tert-butyl-4-hydroxybenzyl) malonate.

Aromatic hydroxybenzyl compounds, for example 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5- di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol.

9. Triazine compounds, for example 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1 , 3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine, 1,3,5-tris (3,5- di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3,5- di-tert-butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexahydro-1,3,5- triazine, 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

10. Benzylphosphonates, for example dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4 hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, calcium salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester.

11. Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate.

12. Esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with monovalent or polyhydric alcohols, for example with methanol, ethanol, octadecanol, 1,6-hexanediol,

1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'bis (hydroxyethyl) thioethanol hydrochloride, 3-propanediol, 3-propanol; trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

13. N- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid esters with monovalent or polyhydric alcohols, for example with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol , 1,2-propanediol, neopentylglycol, thiodiethylene glycol, diethylene glycol, trieths, ethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, trimethylol, 3-thiapentadol, 3-thiapentadol hydroxymethyl-l-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

14. Esters of β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with monovalent or polyhydric alcohols, for example with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1, 2-propanediol, neopentylglycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, phosphoromethyl, 4-thiapentadecanol, 3-thiapentadecanol 6,7-trioxabicyclo [2.2.2] octane.

15. Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with monovalent or polyhydric alcohols, for example with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol , neopentylglycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylpropanethiol, trimethylopexyl hexanol , 7-trioxabicyclo [2.2.2] octane.

16. β- (3,5-Di-tert-butyl-4-hydroxyphenyl) propionic acid amides, for example N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, N, N 1'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine.

Preferred antioxidants are those listed in paragraphs 6, 8, 9, 12, 13, 14 and 16, especially those mentioned in paragraphs 6, 8, 9 and 12. Particularly suitable antioxidants are octadecyl-beta- (3,5-di (tert-butyl-4-hydroxyphenyl) propionate and 1,3,5-tris-di-tert-butyl-4-hydroxybenzyl) 2,4,6-trimethylbenzene.

The amount of antioxidant added will depend on the amount of phosphorus trivalent compound added. Normally 0.005 to 0.5% by weight, preferably 0.01 to 0.2% by weight, of said antioxidant is added, based on the weight of the polymer.

In the following, the invention will be explained in more detail by means of specific examples thereof, the examples being illustrative only and in no way limiting the scope of the invention, which is clearly defined by the wording of the claims. All parts and percentages given in these examples are the same as in the specification and claims by weight unless otherwise specified.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

Preparation of Catalyst g of anhydrous magnesium chloride and 5 g of titanium tetrachloride / ethylbenzoate complex were milled for 24 hours at ambient temperature (about 22 ° C) and under argon in a ball mill with stainless steel balls. The solid catalyst component thus obtained contains 2% titanium.

Polymerization of propylene

The polymerization is carried out in a 3 liter stirred and thermostatically controlled stainless steel autoclave, which is evacuated for 30 minutes at 110 ° C (13 Pa) for 30 minutes before being polymerized and then purged with propylene gas at 110 ° C for 30 minutes. The autoclave is then cooled to 20 ° C and 300 mg of S-1, 300 mg of H-1 and 300 mg of P-1 in solid form or as a 5-10% solution in hexane are introduced into the autoclave. 25 mg of the solid catalyst component are activated for 10 minutes with half a solution of 4 mmol of triethylaluminum and 1.6 mmol of triethoxyphenylsilane in 25 ml of hexane and the catalyst is suspended in an autoclave under an argon atmosphere. The second half of the hexane solution is added to the autoclave. The autoclave is sealed and pressurized with hydrogen (6 kPa), then 600 g of liquid polypropylene are introduced. The contents of the autoclave are then heated to 70 ° C with stirring and maintained at this temperature for 4 hours. Excess propylene is separated and the resulting polymer is treated with 10 ml of isopropanol at 70 ° C to deactivate the catalyst and then dried under vacuum at 70 ° C for one hour.

The following tests were performed with the polymer obtained:

In the corrosion test, the polymer was compressed in a press for 30 minutes between two carefully cleaned steel plates at 280 ° C. These steel plates were then kept for 24 hours in an environment with ambient temperature and 100% humidity (ambient temperature equals about 22 ° C). The corrosion of the boards is evaluated visually.

The color of the polymer is characterized by a Yl-Yellowness Index according to ASTM D 1925-70.

The polymer corrodes steel plates only insignificant. YI equals 2.3.

Comparative Example 2

The procedure of Example 1 is repeated except that 300 mg of product s-1 is not used. A polymer is obtained which, at the same catalytic yield, significantly corrodes the steel plates and a Y1 of 2.5.

Examples 3 and 4

The procedure of Example 1 is repeated except that the product S-1 is replaced by 300 mg of the product.

S-2, respectively. 300 mg of product S-5 to give a polymer which is insignificant or not. weakly corrodes steel plates and Y1 is equal

2.3 resp. 2.2.

Example 5

The polypropylene powder, prepared according to Example 3, was processed for 10 minutes at 230 ° C in a Brabender plastograph. The melt removed from the mixer is pressed into a 5 mm plate. In the corrosion test, the steel plates show no corrosion after melt processing.

Comparative Example 6

The polymer prepared according to Comparative Example 2 is treated as described in Example 5. After the melt treatment, the steel plates are significantly corroded.

Examples 7 and 8

Stability to oxidative degradation is measured as the time required to achieve an apparent embrittlement of the polymer as it ages in the furnace at elevated temperature. This test is carried out with plates obtained by compression molding of the polypropylene powder obtained by the procedure described in Example 1 by adding 300 mg of S-1, 300 mg of H1 and 300 mg of P1 and 300 mg of S-5, 300 mg of H1 and 300 mg of product P1 at 230 ° C. The time required to achieve 40 embrittlement is 11 days for both polymers at an oven temperature of 135 ° C.

Comparative example 9

The polymer prepared and tested under the conditions of Examples 7 and 8, except that it did not contain the addition of S-1 and S-5, also crept after 11 days. This finding means that S-1 and S-5 do not affect the stability of the polymer against oxidative degradation.

Comparative Example 10

The polymer prepared and tested under the conditions of Examples 7 and 8, except that it did not contain the addition of S-1 and S-5, as well as H-1 and P-1, would become brittle after only one day.

Examples 11 to 14

The polymerization was carried out under the conditions of Example 1 except that 44 mg of the solid catalyst component, 6.4 mmol of triethylaluminum and 2.4 mmol of triethoxyphenylsilane were used. The following compounds are used in place of S-1 and H-1:

Example Additive Corrosion YI

11 H-L + S-3 mild 2.3 12 H-L + S-4 mild 2.5 13 H-2 + S-3 mild 2.5 14 H-3 + S-3 mild 2.8

The following ingredients are used in the examples:

Sl: (Mg _{4 with} Al ₂ (OH) _{X 3} CO _{3 and} 3.5H ₂ O) (this compound is commercially available from Kyowa Chemicals, Japan, under the tradename DHT-4A). The compound is dried in vacuo over phosphorus pentoxide at 95 ° C for 24 hours,

S-2: / Mg ^ _of A1 ₂ (OH) ₁₃ C 0 0 _{2 3} .3,5H / in the calcined form (this compound is sold by by Kyowa Chemicals, Japan, under the trade designation DHT-4C);

S-3: Zinc oxide (dried)

S-4: molecular sieve 4A (dried),

S-5: magnesium oxide (dried),

HNR - (CH ₂ ) ₆ -NRN.

H-L

Γν ^Ν

NH i

tert. CGH ^ y

NR- (CH ₂ ) s -NR 4 H n. while

M _n > 2500

R R

R-NH- _{(CH2) 3} -N - _{(CH2) 2} N (CH _{2) 3} -NH-R

ch ₃

I-Si-OH-3:

(CH ₂ ) ₃

^> 1500

Claims (21)

Process for the preparation of polyolefins by polymerization using a transition metal catalyst, characterized in that the polymerization is carried out by adding at least one compound from the group comprising hydrotalcites, zeolites and metal oxides which do not release water under the reaction conditions. Process according to claim 1, characterized in that the polyolefin is prepared. using a supported solid catalyst prepared by reacting an aluminum compound carrying at least one alkyl group is a metal compound IV. subgroup of the Periodic System of Elements. 3. The process of claim 1 wherein the catalyst is a supported chromium compound. Process according to claim 1, characterized in that the compound from the group comprising hydrotalcites, zeolites, metal oxides and also synthetically prepared compounds which do not release water under the reaction conditions is used after drying at a temperature of 50 to 800 ^e C, preferably at 80 to 400 ° C. Process according to claim 1, characterized in that a synthetically prepared hydrotalcite or zeolite is used. A process according to claim 1, characterized in that the hydrotalcite corresponds to the general formula I -mH ₂ O / n (I) in which M ² - represents Mg, Ca, Sr, Ba, Zn, Cd, Pb, Sn and / or Ni, M ³ * represents Al, B or Bi, A ⁿ means an anion with a power of n, n means number from 1 to 4. fc x means number from 0 to 0.5. m means number from 0 to 2 a And it means OH ', Cl', Br, I ', CIO4-, HCO3-, CH ₃ COO-, C ₆ H ₅ COO', CO ₃ ² ', SO ₄ ² ', 00 ' 00-, (CHOHCOO) ₂ ² -, (CHOH) 4 CH 2 OHCOO-. C2H4 (COO) 2 ² -, (CH ² COO) ₂ ² -, CH ³ CHOHCOO-, SiO ^{3 2} ', SiO ^{4 4} -, Fe (CN) 6 ³ -, Fe (CN) 6 ⁴ -, HPO ₄ ² ', or the general formula la M ²⁺ Al 2 (OH) 2x4k 5nz (A ⁿ -) 2 -mH ₂ 0 (la) ZV at least one of Mg and Zn, Mg, an anion of CO ₃ ^2- ', OH' and S ^2- and the valence of these anions, a positive number, preferably from 0.5 to 5 axes, are positive numbers, x is preferably 2 to 6 and z is less than 2. Process according to claim 1, characterized in that the zeolite corresponds to the general formula X in which M ² * is preferably A ^- means cooí ² I coo _ - n means m means (X) in which the cationic charge M is an element of the first or second main group of the Periodic System of Elements, y: x is a number of 0.8 to 1.2 and a number of 0.5 to 10. Process according to Claim 1, characterized in that a bivalent metal oxide is used. Method according to claim 1, characterized in that a metal oxide of the second main group or subgroup of the Periodic System of Elements is used. Process according to claim 1, characterized in that zinc oxide or magnesium oxide is used. Process according to claim 1, characterized in that 2,2,6,6-tetramethylpiperidine with a molecular weight of more than 500 or a trivalent phosphorus compound is added as an additional stabilizer during the polymerization. Process according to claim 1, characterized in that 2,2,6,6-tetramethylpiperidine with a molecular weight of more than 500 is added as an additional stabilizer. Process according to Claim 1, characterized in that 2,2,6,6-tetramethylpiperidine with a molecular weight of more than 500 and containing at least one s-triazine group in its molecule is used as an additional stabilizer. Process according to claim 1, characterized in that a compound of the formula is used as an additional stabilizer HNR - (CH ₂ ) ₆ —NRN v v ^Ν γ ^Ν NH t tSrt. CGH-J7 M _n > 2500 NR (CH ₂₎ s NR-1 H R R I I R-NH- _{(CH2) 3} -N - _{(CH2) 2} N (CH _{2) 3} -NH-R · clay Process according to Claim 1, characterized in that a trivalent phosphorus compound is used as an additional stabilizer. 16. The process according to claim 1, wherein the additional stabilizer is a trivalent phosphorus compound containing at least one P-O-Ar group in which Ar is a mono-, di- or trialkylphenyl group. Process according to claim 1, characterized in that tris (2,4-di-tert-butylphenyl) phosphite or tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite is used as an additional stabilizer. Process according to claim 1, characterized in that an antioxidant of the sterically hindered phenol type is used as an additional stabilizer. Process according to claim 1, characterized in that octadecyl beta (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and 1,3,5-tris (3,5-di-tert) are used as additional stabilizers. butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene. The stabilized polyolefin prepared by the process of claim First Stabilized polypropylene prepared by the process of claim 1.