AU679453B2 - Process for the preparation of olefin polymers - Google Patents

Description

OPI DATE 12/04/94 APPLN. ID 48157/93 |lii j III jII AOJP DATE 07/07/94 PCT NUMBER PCT/EP93/02419 AU9348157

INTL

(51) International Patent Classification 5 (11) International Publication Number: WO 94/06831 C08F2/44, i0/00 A l (43) International Publication Date: 31 March 1994(31.03.94) (21) International Application Number: PCT/EP93/02419 (74) Common Representative: CIBA-GEIGY AG; Patentabteilung, Klybeckstrasse 141, CH-4002 Basle (CH).

(22) International Filing Date: 8 September 1993 (08.09.93) (81) Designated States: AT, AU, BB, BG, BR, BY, CA, CH, Priority data: CZ, DE, DK, ES, FI, GB, HU, JP, KP, KR, KZ, LK, 2924/92-4 17 September 1992 (17.09.92) CH LU, LV, MG, MN, MW, NL, NO, NZ, PL, PT, RO, RU, SD, SE, SK, UA, US, UZ, VN, European patent (AT, BE, CH, DE, DK, ES, FR, GB, GR, IE, IT, LU, (71) Applicant (for all designated States except US): CIBA-GEI- MC, NL, PT, SE), OAPI patent (BF, BJ, CF, CG, CI, GY AG [CH/CH]; Klybeckstrasse 141, CH-4002 Basle CM, GA, GN, ML, MR, NE, SN, TD, TG).

(CH).

(72) Inventors; and Published Inventors/Applicants (for US only) ROTZINGER, Bruno With international search report.

[CH/CH]; Schulstrasse 22, CH-4127 Birsfelden (CH).

COLUMBERG, Alfred [CH/CH]; 10 bis, chemin Frank-Thomas, CH-1208 Geneve PAUQUET, Jean-Roch [BE/CH]; Auf der Schanz 33, CH-4303 Kaiseraugst (CH).

(54)Title: PROCESS FOR THE PREPARATION OF OLEFIN POLYMERS (57) 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.

L LL IL L L I WO 94/06831 PCT/EP93/02419 -1- Process for the preparation of olefin polymers The present invention relates to a process for the preparation of olefin polymers in which hydrotalcites, zeolites or metal oxides and optional stabilisers are added during the polymerisation. The invention also relates to the olefin polymers so obtained.

The low-pressure polymerisation of olefms with organometallic comple catalysts (e.g.

Ziegler-Natta catalysts) usually results in a finely powdered polymer which is extruded in an extruder before being shaped by processing. In this granulation, substances such as stabilisers, corrosion inhibitors, colour enhancers, antistatic agents or other processing auxiliaries. However, this granulation is not always desired or possible, inter alia, with polymers of high molecular weight.

Recently, it has proved possible by using solid supported catalysts to prepare spherical, granular-type polymers that no longer have to be granulated by extrusion, but can be processed direct. Suitable supports for these solid catalysts have been found to be in particular spherical magnesium halides of specific particle size as disclosed, inter alia, in DE-A-2 641 960. The anhydrous magnesium halide forms with TiCl 4 and electron donors insoluble complexes which are then activated with aluminium alkylene. The stereospecificity and activity are enhanced by using electron donors such as carboxylic acid esters or compounds containing Si-O-C bonds as disclosed, inter alia, in 977.

As the polymers so obtained no longer have to be granulated, it was then desired to add modifiers which are important for processing and long-term stability during polymerisation. The addition of many conventional modifiers stabilisers) interferes with the olefin polymerisation and causes discolouration of the polymers.

The machines used in further processing of the polymers, e.g. calanders, are subject to corrosion. The corrosive action of the polymer on metal surfaces is generally attributed to catalyst residues or degradation products of the catalyst system. Up to now it has been b II I L I r r _g L WVO 9)4/06831 PCT/EP93/02419 -2necessary to add a corrosion inhibiting compound in a separate processing step.

It is known (EP-A-192 987 or EP-A-0 350 444) that sterically hindered amine stabilisers of the polyalkylpiperidine type do not interfere with the polymerisation and do not substantially discolour the polymer and effect good thermal oxidative stability.

It has further been proposed (EP-A-254 348) to add organic phosphites or phosphonites as antioxidants.

It is also known to add sterically hindered amine stabilisers of the polyalkylpiperidine type in conjunction with organic phosphites or phosphonites during the polymerisation (EP-A-0 351 360).

Surprisingly, it has now been found that the addition of compounds of the series of the hydrotalcites, zeolites or metal oxides which do not release water under the reaction conditions, in conjunction with optional stabilisers, does not interfere with the polymerisation of olefins and substantially prevents corrosion otherwise occurring during polymerisation, and that excellent long-term stability is achieved by adding further stabilisers.

Accordingly, the invention relates to a process for the preparation of olefin polymers by polymerisation using transiticn metal catalysts, which comprises carrying out the polymerisation by adding at least one compound of the series of the hydrotalcites, zeolites or metal oxides that do not release water under the reaction conditions.

The polymerisation is preferably carried out with a solid supported transition metal catalyst which has been prepared by reacting an aluminium compound carrying at least one alkyl group with a compound of a metal of the IVth subgroup of the Periodic Table.

The olefins polymerisable by this process are ethylene and a-olefins such as propylene, but-1-ene, 4-methylpent-1-ene or 5-methylhex-l-ene, as well as mixtures of olefis, typically ethylene-propylene or propylene in admixture with minor amounts of higher a-olefins. The process for the polymerisation and copolymerisation of propylene is of particular interest The polymerisation catalysts are transition metal catalysts. They typically consist of a ~PIL~- IIII -q CIIIP-~DLIB~L~& WO 94/06831 PCT/EP93/02419 -3magnesium dihalide in active form and a titanium compound. Catalysts with the other metals of the IVth subgroup of the Periodic Table (Zr and Hf) are also suitable. By magnesium dihalide in active form is meant one in whose X-ray spectrum the line of strongest reflectivity is broader than the corresponding line in the spectrum of the inactive magnesium halide.

It is preferred to use magnesium dichloride or magnesium dibromide as magnesium dihalide. The titanium compounds preferably contain at least one titanium-halide bond. It is particularly preferred to use titanium tetrachloride.

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

After reaction of the magnesium halide component with the titanium compound and, where appropriate, the electron donor, excess titanium compound and excess electron donor ar conveniently washed off with an inert solvent, typically with hexane or heptane.

The catalyst so prepared is activated by reaction with an aluminium compound which carries at least one alkyl group and is used preferably as a solution in an alkane.

Exemplary of suitable aluminium alkyls are AI(C 2 H5) 3 or Al(C 4 H9) 3 It is possible to use an electron donor as co-activator, conveniently an organic silicon compound that contains at least one Si-O-C bond, as disclosed in EP-A-45 977. Typical examples of such silicon compounds are phenyl triethoxysilane, phenyl trimethoxysilane, diphenyl dimethoxysilane, methyl triethoxysilane, dimethyl diethoxysilane or ethyl trimethoxysilane.

Further transition metal catalysts typically consist of a chromium compound on a solid support, e.g. alumina or silica or mixtures thereof. Examples of such catalysts, also called Phillips catalysts, will be found in US-A-2 825 721.

The polymerisation with these catalysts can be carried out by known methods in liquid phase or in the gas phase. The liquid phase may conveniently be an aliphatic hydrocarbon or the liquid monomer itself.

The compounds of the series of the hydrotalcites, zeolites or metal oxides that do not release water under the reaction conditions are added to the polymerisation medium at the ~c -sl ea pa Irsa paP- ge WO 94/06831 PCT/EP93/02419 -4start, during, or towards the end of the polymerisation.

Compounds of the series of the hydrotalcites, zeolites or metal oxides are the naturally occurring minerals as well as synthetically prepared compounds.

Compounds of the series of the hydrotalcites may be illustrated by the general formula '(OH)2 In wherein

M

2 Mg, Ca, Sr, Ba, Zn, Cd, Pb, Sn and/or Ni, M~3 =Al, B orBi,

A

n is an anion of valency n, n is a number from 1 to 4, x is a number from 0 to m is a number from 0 to 2, and A OH, Br, C10 4

HCO

3

CH

3 COO, C 6

H

5 COO- 2

C

3 2

SO

4 2 OO-, (CHOHCOO) 2 2

(CHOH)

4

CH

2 0HCOO-. CH 4

(COO)

2 2

(CH

2

COO)

2 2

CH

3 CHOHCOO-, Si0 3 2 Si0 4 4 Fe(CN) 6 3 Fe(CN) 6 4 or HP0 4 2 Other hydrotalcites which may conveniently be used in the process described above are compounds of the general formula Ia Mx+Al2(OH)2x+6nz(An) 2 *mH20 (la) wherein M 2 is at least one metal of the series of Mg and Zn, Mg being preferred, A n is an anion of the series of C0 3 2 OH- and S 2 and n is the valency of the anions, m is a positive number, preferably from 0.5 to 5, and x and z are positive numbers, and x is preferably 2 to 6 and z is smaller than 2.

Preferred compounr of the series of the hydrotalcites are those of the general formula I M2+lx .M3-+x (OH)2 in I~L~s L WO 94/06831 WO 94/683 1PCT/EP93/0241 9 wherein M 2 is Mg or denotes a solid solution of Mg and Zn, An- is GO 3 2 x is a number from 0 to 0.5 and mn is a number from 0 to 2.

Particularly preferred hydrotalcites are those of formulae A1 2 0 3 .6Mg@ C0 2 121120) Mg 4 5 A1 2

(OH)

13 C0 3 .3,511 2 0, 2

O

3

'CO

2 *9H 2

O,

4MgO.Al 2 0 3 .C0 2 .6H 2 0, ZnO*3MgO*AI 2 Oy.CO 2 8-91120 od~r ZnO.3MgO.Al 2 Oy'CO 2 *5-611 2 0.

In the practice of this invention it is also possible to use zeolites of the general formula(X wherein n is the charge of dhe cation M, M is an element of the first or second main group of the Periodic Table, y :x is a number from 0.8 to 1.2, and w is a number from 0.5 to The preferred per se known zeolites which may be used in the above process have an average pore diameter of 3-5 A, including those of the NaA type that have an average effective pore diameter of 4 A, for which reason they are also called 4A zeolites.

Illustrative examples of suitable zeolites are the compounds: Na, 2 [(AlO 2 12 (SiO 2 2 121120 Ca 4 5 Na 3 [(AI0 2 12 (SiO 2 )l 2 ].3011 2 0 WO 94/06831 PCT/EP93/02419 -6-

K

9 Na 3 [(A10 2 12 (SiO 2 12 J.27H20 Metal oxides can also be used in the process of this invention. Oxides of divalent metals are preferred. Oxides of metals of the second main group or subgroup of the Periodic Table are especially preferred, and zinc or magnesium oxide is most preferred.

The novel compounds are dried to remove the unbound or only loosely bound water at 50-800 0 C, preferably 80-400 0 C, provided they are not already sufficiently dry and have been stored wivh exclusion of moisture. Drying can be carried out under vacuum or int gas. The surfaces of the substances can be treated with surface active reagants such as carboxylic acids or linear alcohols of 8 or more carbon atoms, conveniently stearic acid.

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

The process is preferably carried out using additional stabilisers.

A particularly preferred embodiment of the invention comprises carrying out the above process by the further addition of a compound that contains at least one 2,2,6,6-tetramethylpiperidine radical and that has a molecular weight above 500, or by the further addition of a phosphorus(HII) compound. The use of such a 2,2,6,6-tetramethylpiperidine compound with a phosphorus(EI) compound is particularly preferred.

The sterically hindered amines, preferably piperidines, are known in particular as light stabilisers, but they act here also as antioxidants, i.e. they impart thermal oxidative stability to the polymer. These compounds contain one or more than one group of formula I L- ~L L~1_11 p P -PC I WO 94/06831 WO 9406831PCT/EP93/02419 -7- They may be oligomeric or polymeric compounds.

Particularly important stabilisers are the following classes of tetramethylpiperidines: a) compounds of formula BI

H

3 C

CH

3 [R1. OH 0--R 2

OD,

wherein n is a number from 1 to 4, preferably I or 2, RI is hydrogen, oxyl C 1

-C

1 2 alkyl,

C

3 -C~alkenyl, C 3

-C

8 alkynyl, 0 7

-C

1 2 aralkyl, CI-C 8 alkanoyl, C 3

-C

5 alkenoyl, glycidyl or a group -CH 2 CH(OH)-Z, wherein Z is hydrogen, methyl or phenyl, the preferred meanInlg of RI b -ing Cl-C 4 alkyl, allyl, benzyl, acetyl or acryloyl, and R 2 if n is 1, is hydrogen,

C

1

-C,

8 aikyl which may be interrupted by one or more than one oxygen atom, cyanoethyl, benzyl, glycidyl, a monovalent radical of an aliphatic, cycloaliphatic, araliphatic, unsaturated or aromatic carboxylic acid, carbarnic acid or or phosphorus containing acid, or is a monovalent~ silyl radical, preferably a radical of an aliphatic carboxylic acid of 2 to 18 carbon atoms, of a cycloaliphatic carboxylic acid of 7 to 15 carbon atoms, of an cx,B-unsaturated carboxylic acid of 3 to 5 carbon atoms or of an aromatic carboxylic acid of 7 to 15 carbon atoms, and, if n is 2, is CI-C, 2 alkylene, C 4 -Cl 2 alkenylene, xylylene, a divalent radical of an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, dicarbamic acid or phosphorus containing acid, or is a divalent silyl radical, preferably a radical of an aliphatic dicarboxyHic acid of 2 to 36 carbon atoms, of a cycloaliphatic or aromatic dicarboxylic acid of 8 to 14 carbon atoms, or of an aliphatic, cycloalitphatic: or aromatic dicarbamnic acid of 8 to 14 carbon atoms, and, if n is 3, is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, of an aromatic tricarbainic acid or of a phosphor-us containing acid, or is a trivalent silyl radical, and, if n is 4, is a tetravalent radical of an aliphatic, cy loaliphatic or aromatic tetracarboxylic acid.

Substituents defined as CI-C, 2 alkyl may typically be methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethyihexyl, n-nony' n-decyl, n-undecyl or n-dodecyl dxtr.

WO 94/06831 WO 94/06831PCT/EP93/02419 -8-

R

2 as Cl-Cl 8 alkyl may be the groups listed above and may additionally be n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

RIas C 3

-C

8 alkenyl may typically be 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl, 4-tert-butyl-2-butenyl.

R1as C 3

C

8 ailkynyl is preferably propargyL.

R' as C 7

-C,

12 arakyl is preferably phenethyl and, most preferably, benzyl.

RIas C 1

-C

8 alkanoyl is typically formyl, propionyl, butyryl, octanoyl, but is preferably acetyl and, as C 3

-C

5 alkenoyl, is preferably acryloyl.

R

2 defined as a monovalent radical of a carboxylic acid is typically the radical of acetic acid, capronic acid, stearic acid, acrylic acid, niethacrylic acid, benzoic acid or 1-(3,5-ditert-butyl-4-hydroxyphenyl)propionic acid.

R

2 defined as a divalent radical of a dicarboxylic acid is Cypically the radical of malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, maleic acid, phthalic acid, dibutylmalonic acid, dibenzylmalonic acid, butyl-(3,5-di-tert-butyl-4-hydroxybenzyl)malonic; acid or bicycloheptendicarboxylic acid.

R

2 defined as a trivalent radical of a tricarboxylic acid is typically the radical of rximellitic acid or of nitrilotriacetic acid.

R

2 defined as a tetravalent radical of a tetracarboxylic acid is typically the tetravalent radical of butane- 1,2,3,4-tetracarbooxylic acid or of pyromellitic acid.

R

2 defined as a divalent radical of a dicarbaniic acid is typically the radical of hexamethylenedicarbamic: acid or of 2,4-toluylenedicarbarnic acid.

b) Compounds of formula (III) WO 94/06831 WO 9406831PCr/E P93/024 19 -9-

H

3 C

CH

3 R 3 1 4 R .N N--R(I)

H

3 C CH 3

I

wherein n is 1 or 2, RI is as defined under R 3 is hydrogen, C 1

-C,

2 alkyl,

C

2

-C

5 hydroxyaflkyl, C 5 -C-7cycloalkyl, C 7

-C

8 aralkyl, C 2 -Clgalkanoyl, C 3

-C

5 alkenoyl or benzoyl and, R 4 if n is 1, is hydrogen, C 1

-C

1 8 alkyl, C 3

-C

8 alkenyl, C 5

-C

7 cycloalkyl, Cj-C 4 alkyl which is substituted by a hydroxyl, cyano, alkoxycarbonyl or carbaxnido group,, glycidyl, a group of formula -CH 2 -CH(OH)-Z or of formula -CONH-Z, wherein Z is hydrogen, methyl or phenyl; or, if n is 2, R 4 is C 2 -Cl 2 alkylene, C 6

-C,

2 aryiene, xylylene, a

-CH

2

-CH(OH)-CH

2 group or a -CH 2 -CH(OH)-C1i 2 group, wherein D is

C

2 -Cl 0 allcylene, C 6

-C,

5 arylene, C 6

-C

12 cycloalkylene, or, with the proviso that R 3 is not alkanoyl, alkenoyl or benzoyl, R 4 is also a divalent radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbarnic acid or may also be the -Ca- group, or R 3 and

R

4 when taken together, if n is 1, may be the divalent radical of an aliphatic, cycloaliphatic or aromatic 1,2- or 1,3-dicarboxylic acid.

Substituents defined as Cl-Cl 2 alkyl or Cj-Cj 8 alkyl have the meanings already given under a).

Substituents defined as C 5

-C

7 cycloalkyl are preferably cyclohexyl.

R3as C 7

-C

8 aralkyl is preferably phenylethyl or, most preferably, benzyl. R 3 as

C

2

-C

5 hydroxyalkyl is preferably 2-hydroxyethyl or 2-hydroxypropyl.

R

3 as C 2 -Cl 8 alkanoyl is typically propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl, octadecanoyl, but is preferably acetyl and, as C 3

-C

5 alkenoyl, is preferably acryloyl.

R4as C 2

-C

8 alkenyl is typically allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl.

Ras CI-C 4 alkyl which is substituted by a hydroxyl, cyano, alkoxycarbonyl or carbamido group typically includes 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, methuxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or WO 94/06831 WO 9406831PCF/EP93/0241 9 2-(dimethylcarbamoyl)ethyl.

Substituents defined as C 2

-C,

2 alkylene may typically be ethylene, propylene, 2,2-dimethyipropylene, tetrainethylene, hexamethylene, octainethylene, decamethylene or dodecamethylene.

Substituents defined as C 6 -Cl 5 arylene may typically be mn- or p-phenylerne, 1,4-naphthylene or 4,4'-dilphenylene.

D as C 6

-C

12 cycloalkylene is preferably cyclohexylene.

Illustrative examples of polyalkylpiperidine compounds of this class are the following compounds: N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)-N,N'-dibutyladiparnide N,N'-bis (2,2,6,&tetramethylpiperidin-4-yl)-N,N'-dicyclohexyl-2hydroxypropylene- 1,3-diamine the compound of formula

N-CH

2 -CH(OH)-CH-- 0

N

OH

3

-C

N-CH

2 -CH(OH)-CHZ -0

C

4

H

9

OH

3

OH

3

OH

3 c) 'Compounds of formula (IV) WO 94/06831 WO 94/683 1PCT/EP93/02419

[H

3 C

CH

3 0 j INRb

(IV),

[H

3 CXCl-fe in wherein n is 1 or 2, R 1 is as defined under a) and R 5 if n is 1, is C 2

-C

8 alkylene or

C

2

-C

8 hydroxyalkylene or C 4

-C

22 acyloxyalkylene, and, if n is 2, is the (-CH 2 2

C(CH

2 2 group.

R 5 as C 2

-C

8 alkylene or C2 2 -Cshydroxyalkylene may be ethylene, 1-methylethylene, propylene, 2-ethyipropylene or 2-etliyl-2-hydroxymethylpropylene.

C

4

-C

22 acyloxyallky.lene may be 2-ethyl-2-acetoxymethylpropylene.

d) Compounds of formulae VA, YB and VC H lI R 6

(A

3 C OH 3 0 C -7

R

1 NN 1 Y

(VC)

WO 94/06831 WO 9406831PCT/EP93/02419 -12wherein n is 1 or 2, RI is as defined under R 6 is hydrogen, Cl-Cl 2 alkyl, allyl, benzyl, glycidyl or C 2 -C~alkoxyalkyl, and R 7 if n is 1, is hydrogen, CI-C 12 alkYI, 0 3 -Cqalkenyl,

C

7 -Cgaralkyl, C 5

-C

7 cycloalkyl, C 2

-C

4 hydroxyalkyl, C 2

-C

6 alkoxyalkyl, C6-Cloary1, glycidyl or a group of formula -(CH 2 )p-COO-Q or of formula -(CH 2 )p-O-CO-Q, wherein p is 1 or 2 and Q is Cj-C 4 allcyl or phenyl, or if n is 2, is C 2

-C,

2 alkylene, C 4 -Cl 2 alkenylene,

C

6 -Cl 2 arylene, a -CH 2

-CH(OH)-CH

2

-O-D-O-CH

2

-CH(OH)-CH

2 group, wherein D is

C

2 -Cl 0 alkylene, C 6

-C

15 arylene, C 6

-C

12 CYCloalkylene, or is a -CH 2

CH(OZ')CH

2

(OCH

2

-CH(OZ')CH

2 2 group, wherein Z' is hydrogen, C 1

-C,

8 alkyl, allyl, benzyl,

C

2 -Cl 2 alkanoyl or benzoyl, T, and T~2 are eacil independently of the other hydrogen or CCoalyl or C' 7 -Cqaralkyl which may be substituted by halogen or 0 1

-C

4 alkyl, or T, and TI2, together with the linking carbon atom, form a C 5

-C

12 cycloalkane zing.

Substituents; defined as C 1

-C

12 alkyl may typically be methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-buLyl, n-hexyl, n-octyl, 2-ethyihexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

Substituents defined as C 1 -Cl 8 alkyl may be the groups cited above and may additionally be n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

Substituents defined as 0 2

-C

6 alkoxyalkyl may typically be niethoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, tert-butoxyethyl, isopropoxyethyl or propoxypropyl.

R7as C 3

-C

5 alkenyl may be 1-propenyl, allyl, methallyl, 2-butenyl or 2-pentenyl.

R

7 T, and T 2 as C 7 -Cgaralkyl are preferably phenethyl or, most preferably, benzyl. A cycloalkane ring formed by T, and T 2 together with the linking carbon atom may be a cyclopentane, cyclohexane, cyclooctane or cyclododecane ring.

R7as C 2

-C

4 hydroxyalkyl may be 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

R

7 T, and '122 as C 6 -Cj 0 aryl are preferably phenyl, a- or 1-naphthyl, which may be substituted by halogen or Cl-C 4 alkyl.

R

7 as C 2 -Cl 2 alkylene may typically be ethylene, propylene, 2,2-dimethylpropylene,

I

WO 94/06831PC/93049 PCT/EP93/02419 13 tetramethylene, hexamethylene, octainethylene, decamethylene, cr dodecamnethylene.

R

7 as C 4

-C,

2 alkenylene is preferably 2-butenylene, 2-pentenylene or 3-hexenylene.

R7as C 6

-C

12 arylene is typically mn- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.

Z' as C 2 -Cl 2 alkanoyl may be propionyl, butyryl, octanoyl, dodecanoyl, but is preferably acetyl.

D as C 2

-C

10 a~kylen, C 6

-C,

5 arylene or C 6

-C,

2 cycloalkylene is as defined under b).

Illustrative examples of polyallcylpiperidines of this class are the following compounds: 2,2,4,4-tetrarnethyl-7-ora-3,20-dilaza-21-oxo-dispiro[5. 1.1 1.2]-heneicosane 8-acetyl-3-dodecyl-1,3,8-triaza-7,7,9,9-tetaanethylspiro[4,5]decane-2,4-dione or the compounds of the following formulae:

OH

3

,CH

3 OH 3 CH3 NH-C =0 0=0 I CHO)HI X N-OH 3 S- N H 2 OH0HO 2 -0OH 2

-H(H)H

2 N -0C

OH

3

OH

3 0H

OH

3

OH

3

OH

3

OH

3 NH-C=0 0O-NH 0H 3 -N N N-H 3 OH CH 3 0O 3

O

3

OH

3

OH

3 OH 3

OH

3 NH-O 0 =--NH HN OH/ NH OH CH 3 U 0 OH 3

OH

3 13 WO 94/06831 WO 9406831PCT/EP93/0241 9 14 e) Compounds of formula VI

R

N"'N

LR9 N

R

(VI)

wherein n is 1 or 2 and R 8 is a group of formula

CH

3

OH

3 xN-R1

CH

3

OH

3 wherein RI is as defined under E is or -NR11-, A is C 2

-C

6 alkylene or and x is 0 or 1, R 9 has the meaning of R 8 or is a group -NR11R' 2

-OR'

3

-NHCH

2 OR 1 3 or

-N(CH

2

OR'

3 2 RIO, if n 1, has the meaning of R 8 or R 9 and, if n 2, is a group wherein B is C 2

-C

6 alkylene which may be interrupted by R11 is C,-Cl 2 alkyl, cyclohexyl, benzyi or C,-C 4 hydroxyalkyl or a group of formula R' sCI-C, 2 alkyl, cyclohexyl, benzyl, C 1

-C

4 hydroxyalkyl, and R' 3 is hydrogen, Cl-Cl 2 alkyl or phenyl, or R1 1 and R 12 when taken together, are C 4

-C

5 alkylene or

C

4

-C

5 oxaalkylene, typically

-CH

2

CH

2 -CH2H2 0' or are agroap of formula

-CH

2

CH

2

-CH

2

CH

2 PCr/EP93/02419 WO 94/06831 or R 1 I and R 12 are also each a group of formula

CH

3

N

HN

CH

3 Substituents defined as Cl-C, 2 alkyl may typically be methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethyihexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl dar.

Substituents defined as Cl-C 4 hydroxyalky1 may typically be 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

A as C 2

-C

6 alkylene may be ethylene, propylene, 2,2-dimethylpropylene, tetramethylene or hexaniethylene.

R" and R 12 together as C 4

-C

5 alkylene or oxaalkylene may be tetramethylene, pentamethylene or 3-oxapentamethylefle.

Illustrative examples of polyalkylpiperidines of this class are the compounds of the following formulae:

N(C

4

H

9 2

OH

3

OH

3 N H C3

C

2

H

5 -N N N

N-C

2

H

OH

3

OH

3 0 2 C0H H 3

OH

3 WO 94/06831 WO 9406831PCI'/EP93/02419 -16-

R

N)""N

H

3

C

ti N K 3 C CH

OH

3 OH 3

CH

2 -CH- NH NH

OH

3

OH

3

OH

3

OH

3 Nk HN CH 2 -CHZ-NH- N -L NH-CH 2

-CH-

OH

3

CH

3

CH

3 CA N I HN N

NNHOH

2

CH

2 N CH 2

CH

2 NH N> N

NH

A N N ~N

OH

3

OH

3 N NC3

H

A49-

N-C

4

H

9 CAN "AW N C OH H

H

3

OH

3

OH

3 N OH 3

OHA

3

OH

3

OH

3

OH

3

OH

3 N OH 3

H

OH

3 N OH 3

OH

3 N OH 3

H.~J

WO 94/06831 WO 9406831PCT/EP93/02419 18-

R-NH-(CH

2 3 -N 3

-NH-R

CH

3

OH

3 R-NH-(CH2) 3 -N O 2 2 '0 2 3

-NH-R

OH

3 OH 3 N

I

r, N

N-OH

3 N N O H 3

OH

3

C

4 Hq-N

OH

3

OH

3

OH

3 N OH 3

OH

3

OH

3 O H 3 I I I7 R- (OH 2 3 N (OH 2 2 N (OH 2 3 N R WO 94/06831 WO 9406831PCT/EP93/02419 19- R CA COH 3

OH

3 N

I

N N-OH 3

OH

3

O

3

C

4

H

9

-N

OH

3

OH

3

OH

3 N OH 3

OH

3

OH

3

OH

3

CBH

17 -N NH N N 78)

C

8

H

1 .7 N N NH(CH 2 3

OH

3 OH 3

OH

3 N OH 3 Hj

OH

2

OH

2 0H

OH

3

OH

3

OH

3 O H 3 79)

IC

OH

3

OH

3 N" N

HO-CH

2

CH

2 -N N J N W1H 9

L;

4

H

9

OH

3

OH

3 WO 94/06831 WO 9406831PCT/EP93/02419 0H 2 -CH=0H 2

H

3 C N H 3 N 4 H 9 3

OH

H3C CH N kN CH 3

OH

3

H

2 0C=HC-H 2 C- N N N-N-CH 2

-CH=CH

2

H

3 C OH 3 CA H 3 f) OligomerIc or polymeric compounds whose structural roptatig unit contains one or more than one 2,2,6,6-tearaalkylpiperidine radical of formula preferably polyesters, polyethers, polyamides, polyainines, polyurethanes, polyureas, polyamninotriazines, poly(meth)acrylates, polysiloxanes, poly(meth)acrylamides and their copolymers which contain such radicals.

Illustrative examples of 2,2,6,6-polyalkylpiperidine light stabilisers of this class are the compounds of the following formulae, wherein m is a number from 2 to about 200.

OH

3

OH

3 0 0 81) -{-C-CH 2 -CH2- C-0-0H 2 -CH- N 0-3

OH

3 OH 3 82)

OH

3

OH

3 O H 3

OH,

3

-FCH

2

-CH

2 -N 0 O-(OH 2 0-0N-CHg-CH2-0-

O-(OH

2 4

OH

3

OH

3 OH 3

OH

3 -i WO 94/06831 WO 9406831PCT/EP93/024 19 -21-

OH

3

C

2 HSI O H 3 CA 0 N H-(0H 2 3 -N NH- C C -NH N-(CH)-NH- C C C--

OH

3

CCH

3

OH

3 2

H

5

H

3

C

2

H

OH

3

OH

3 I I NH- C- CH 2 0- H 3 ON H 3

OH

3 N (OH 2 6

N

OH

3 CF, 3

OH

3

OH

3

OH

3 GH 3 N 0H 2 -CH(OH)-CH2 S- I m

OH

3

OH

3 .0H 3 0CH 3 86)

F-

CAH 0 1 II 0 4

H

9 PCT/EP93/02419 WO 94/06831 22 NN (OH 2

N

N l CHa CH~n CH:;

CH

3

OH

3

OH

3 88) 89) o C 2

H

C;

2

H

0 -m

OH

3 r

OH

3

OH

3 0-

N-OCH

3

OH

3

OH

3 PCI'/EP93/02419 Wo 94/06831 -23

I~

C-H

2 o==c

C

6

H

13

-N

C H 3

CH

3

CH

3 (0

N~

IN (OH 2 6 N

OH

3

OCH

3

OH

3

N

3

CH

3 O1 H 3 N CH3 3

OH

93) 94)

OH

3

OH

3

CH

3

I

OH

3

XN

H

WO 94/06831 WO 40831PT/EP93/02419 -24-

(OH

2 3 95)0

OH

3 ON H 3

CH

3

OH

3

K

9 C4(R)N yNy N(R)0 4

H

9

N

N I 96) H 9 4 R)N N I O 2 2 N N (OH 2 3 N H 2-3

N(R)C

4

H

9

H

9

C

4 (R)N N N(R)C 4

H

9 wherein R= H 3 C

OH

3

NH

H

3 C

OH

3 and N Nor H

H

9

C

4 (R)N

NRC

Among these classes of light stabilisers, classes e) and f) are especially suitable, in

I

WO 94/06831 WO 9406831PCT/EP93I 02419 particular those teti-aalkylpiperidines which contain s-triazie groups. Other particulariy suitable compounds are compounds 74, 76, 84, 87, 92 und The amount of tetramethylpiperidine added will depend on the desired degree of stabilisation. Normally 0.0 1 to 5 by weight, preferably 0.05 to 1 7o by weight, based on the polymer, will be addecL It is preferred hat the molar ratio of tetrainethylpiperidine and aluminium alkyl should not be substanitially greater then 1.

The phosphorus(If) compounds added ar, optional additional stabilisers to the polymerisation may be phosphites, phosphnites or phosphinites. Th0ey may contain one or more thian one phosphoric ester group. it, is Dreferred to use a phosphrus(U[) compound of formula A, B, C or D

R,

2 A B OX x

R

7 0% RI P /1-R P R O R 8 0( C D wher'in 1., 1 and R 2 are each independently of the other Cl-C 12 allcyl, CS-Cgcycloallryl, phenyl, phenyl which is substituted by one to three CI-Cl 2 alkyl groups, or are a radical

-OR

3

R

3 is C 6 -C20alkYl, C 5

-C

8 cycloalkyl, phenyl or phenyl which is substituted by one to thre

C

1

-C,

2 alkyl groups, and

R

4 is unsubstituted phenylene or naphthylene or phenylene or naphthylene. which are substituted by C 1

-C,

2 alkyl, or is a radical-O-R 5 wher-.in

R

5 is unsubstituted phenylene or naphthylene or phenylene or nay "thylene which are substituted by Cl-C 12 alkyl, or is a radical -Phen-R 6 -Phen-, wherein Phen is phenylene,

R

6 is -SO 2

-CH

2 7, or -C(C11 3 2

R

7 and R 8 are each independently of the other phenyl or phftnyl which is substituted by one to three Cl-,C, 2 alkyl groups, and the two substituents R 7 mid R 8 may also be linked WO 94/06831 PCT/EP93/02419 -26by a C 1

-C

12 alkylene group, and

R

9 is F, Cl, Br or I, preferably F.

Among the compounds of formula A it is preferred to use those compounds wherein R 1 and R 2 are a radical -OR 3 and R 3 is C 6 -C20alkyl, phenyl or phenyl which is substituted by one to three C 1

-C

1 2 alkyl groups.

Among the compounds of formula B it is preferred to use those compounds wherein R 2 is a radical -OR 3 -3 is phenyl or phenyl which is substituted by one to three C 1

-C

1 2 alkyl groups, and R 4 is a diphenylene radical.

Among the compounds of formula C it is preferred to use those compounds wherein R 1 is a radical -OR 3

R

3 is phenyl or phenyl which is substituted by one to three C 1

-C

12 alkyl groups.

It is preferred to use a phosphorus(III) compound which contains at least one P-O-Ar group, and Ar is a mono-, di- or trialkylphenyl radical.

Illustrative examples of eligible phosphorus(lII) compounds are: triphenyl phosphite, decyl diphenyl phosphite, phenyl didecyl phosphite, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerytritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-ditert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, bis(2,6-di-tert-butyl-4methylphenyl) pentaerythritol diphosphite.

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

Besides the phosphorus(II) compound, it is possible to add further co-stabilisers and modifiers that do not interfere with the polymerisation. It is preferred at add antioxidants of the sterically hindered phenol type to the polymerisation. These phenols are standard antioxidants for organic materials and are frequently used for stabilising polymers.

Illustrative examples of such phenolic antioxidants are: ~1 WO 94/06831 WO 9406831PCTr/EP93/02419 -27 1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-te.-t-butyl- 4,6-dimethyiphenol, 2,6-di-tert-butyl.4-ethylphenol, 2,&-di-tert-butyl-4-n--butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(ii-methylcyclohexyl)..4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-ticyclohexylphenol, 2,6-di-tert-butyl-4-methoxyxnethylphenol, 2,6-dinonyl-4-methylphenol, 2,4-dirnethyl-6- (1 '-methylundec-l '-yl)phenol, 2,4-dimethyl-6-(1 '-niethyiheptadec-l1'-yl)phenol, 2,4-dimethyl-6-(1'-methylttidec- l-yl)phenol and mixtures thereof.

2. Alkvlthiomethvlphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiornethyl-6-methylphenol, 2,4-dfioctylthiomethyl-6-ethylphenol and 2,6-didodecylthiomethyl-4-nonylphenol.

3. Hydrogioe n lvae hdouns fo-eaple 2,6-di-tert-buityl-4-methoxyphenol, 2,5-dil-tert-butylhydroqiincoi-,-. 2,5-di-tert-ainylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhyclroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate and di-tert-butyl-4hydroxyphenyl) 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-methylphenol), 4,4'-thiobis- (6-tert-butyl-2-methylphenol), 4,4'-thiobis(3,6-di-sec-amylphenol) and 4,4'-bis-(2,6-dimethyl-4-hydroxypheny!) disulfide.

Alkylidene bisphenols, for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6- (ac-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-butyiphenol), 2,2'-ethylidenebis(6-tert- butyl-4isobutylphenol), 2,2'-rnethylenehis[6-(cz-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-(ax,a-diniethylbenzy)- 4-nonyiphenol], 4,4'-methylencbis(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(3tert-butyl-5-methyl-2-hydroxybenzyl)- 4-methyiphenol, 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(3bis[2-(3' -tert-butyl-2' hydroxy- WO 94/06831 WO 9406831PCT/EP93/02419 -28- '-methylbenzyl)-6-tert-butyl-4-methylphenyl] terephthalate, 1,1 -bis (3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4hydroxyphenyl)propane, 2,2-bis(5-tertbutyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane and 1,1 ,5,5-tetra(5-tertbutyl-4-hydroxy-2-methylphenyl)pentae.

6. N- and S-Benzyl compounds, for example 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl 4-hydroxy-3,5-dimethylbenzyl-mercaptoacetate, butyl-4-hydroxybznzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide and isooctyl. butyl-4-hydroxybenzylmercaptoacetate.

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

8. Aromatic hydroxybenzyl compounds, for example 1,3,5-tris(3,5-di-tert-butyl-4hydroxybenzyl)-2,4,&tri-nethylbenzene, 1 ,4-bis (3,5-di-tert-butyl-4-hydroxybenzyl)- 2,3,5,6-tetramethylbenzene and 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-tiazine, 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-hyciroxyphenylethyl)- 1,3,5-triazine, 1 ,3,5-tris(3,5di-tert-butyl-4-hydroxyphenylpropionyl)hexahydro- 1,3,5-triazine and 1 ,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

Benzylphosphonates, for example dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl. 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl 4-hydroxybenzylphosphonate, dioctadecyl 5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate and the calcium salt of monoethyl. 3,5-di-tert-butyl-4-hydroxybern.zylphosphonate.

11. Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide and octyl.

N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

WO 94/06831 WO 9406831PCT/EP93/02419 29 12. Esters of f-(3,5-di-tert-butvl-4-hydroxynhenyl)propionic acid with mono- or poiylllydric 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)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethyihexanediol, timethyloipropane and 4-hydroxymethyl- 1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

13. Esters of 1-(5-tert-butyl-4-hydroxv-3-methyliphenyl)propionic acid with mono- 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, pentaeryth-itol, tris(hydroxyethyl) isocyanurate, N,N'-bis-(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trinethylolpropane and 4-hydroxymethyl- 1-phospha-2,6,7-trioxabicyclo- [2.2.23octane.

14. Esters of f-(35-dicyclohexyl-4hvdroxyphenvl~pronionic acid with mono- 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)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethyihexanediol, tinmethylolpropane and 4-hydroxymethyl- 1-phospha-2,6,7-trioxabicyclo-[2.2.2]-octane.

Esters of 3,5 .di-tert-butyl-4-hydroxyphenylacetic acid with mono- 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- (hydroxy ethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, nrimethylhexanediol, trimethy,'olpropane and 4-hydroxymethyl- 1-phospha-2,6,7-trioxabicyclo[2.2.2]octae.

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

Preferred antioxidants are those listed in 6, 8, 9, 12, 13, 14 and 16, especially 6, 8, 9 and WO 94/06831 PCIT/EP93/02419 12. Particularly suitable antioxidants are octadecyl B-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene.

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

The invention is illustrated in more detail by the following non-limitative Examples in which, and also in the description and claims, parts and percentages are by weight, unless otherwise stated.

Example 1: Preparation of the catalyst g of anhydrous magnesium chloride and 5 g of titanium tetrachloride-ethyl benzoate complex are milled in in a ball mill with stainless steel balls for 24 hours at room temperature 22 0 C) under argon. The solid catalyst component so obtained contains 2 titanium.

Polymerisation of propylene The polymerisation is carried out in a 3 litre stirred and thermostatically controlled stainless steel autoclave which is evacuated before the start of the polymerisation for minutes at 110 0 C (13 Pa) and is afterwards flushed for 30 minutes with propylene gas at 110 0 C. The autoclave is cooled to 20 0 C and 300 mg of S-1, 300 mg of H-1 and 300 mg of P-1 are added to the autoclave as solid or as 5-10 solution in hexane. Then 25 mg of the solid catalyst component are activated for 10 minutes with half of a solution of 4 mmol of trietiyl aluminium and 1.6 mmol of triethoxyphenylsilane in 25 ml of hexane and suspended in the autoclave under argon. The autoclave is flushed with the second half of the hexane solution. The autoclave is closed and charged with hydrogen (6 kPa) and 600 g of liquid propylene. With stirring, the contents of the autoclave are heated to 70 0 C and kept at this temperature for 4 hours. Excess propylene is then discharged and the resultant polymer is treated with 10 ml of isopropanol at 70 0 C to deactivate the catalyst and then dried under vaccum for 1 hour at 70 0

C.

The following tests are carried out on the polymer: For the corrosion test, the polymer is compression moulded on a hot press for 30 minutes at 280 0 C between carefully cleaned iron plates. The iron plates are then stored for -r a u WO 94/06831 PCr/EP93/02419 -31- 24 hours at 100 humidity at room temperature 220C). Corrosion is assessed visually.

The colour of the polymer is characterised by the Yellowness Index (YI) according to ASTM D 1925-70.

The polymer corrodes the iron plates only insignificantly. It has a YI of 2.3.

Comparative Example 2: The procedure of Example 1 is repeated, but without using 300 mg of S-1, to give a polymer which, with the same catalyst yield, severely corrodes the iron plates and has a YI of Examples 3 and 4: The procedure of Example 1 is repeated, replacing S-1 with 300 mg of S-2/300 mg of to give a polymer that corrodes the iron plates insignificantly/slightly and has a YI of 2.3/ 2.2.

Example Polypropylene powder, prepared as in Example 3, is processed in a Brabender plastograph for 10 minutes at 2300C. The melt is taken from the kneader and compressed to a c. 5 mm board. In the corrosion test, the iron plates exhibit no crrtosion after the melt processing.

Comparative Example 6: The polymer prepared according to comparative Example 2 is processed as described in Example 5. The iron plates are severely corroded after the melt processing.

Examples 7 and 8: The stability to oxidative degradation is measured by the time taken until marked embrittlement of the polymer occurs in oven ageing at elevated temperature. This test is carried out with boards which are obtained by compression moulding polypropylene powder obtained as described in Example 1 by adding 300 mg of S-1, 300 mg of H-1 and 300 mg of P-1 and 300 mg of S-5, 300 mg of H-1 and 300 mg of P-1 at 230°C. The time taken until embrittlement is 11 days for both polymers at an oven temperature of 1350C.

Comparative Example 9: A polymer prepared and tested in accordance with the particulars of Examples 7 and 8, but L II WO 94/06831 PCT/EP93/02419 -32without the addition of S-1 and S-5, also becomes brittle after 11 days. This finding means that the addition of S-1 and S-5 does not affect the stability of the polymer to oxidative degradation.

Comparative Example A polymer prepared and tested in accordance with the particulars of Examples 7 and 8, but without the addition of S-1 and S-5 as well as H-1 and P-l, becomes brittle after 1 day.

Examples 11-14: Polymerisation is carried out as described in Example 1, but using 44 mg of solid catalyst component, 6.4 mmol of triethyl aluminium and 2.4 mmol of triethoxyphenylsilane. The following compounds are used instead of compounds S-1 and H-1: Example Additive Corrosion YI 11 H-1 S-3 slight 2.3 12 H-1 S-4 slight 13 H-2 S-3 slight 14 H-3 S-3 slight 2.8 The following addiives are used in the Examples: S-1: [Mg45Al 2

(OH)

13 CO3-3,5H 2 0] (this compound is sold by by Kyowa Chemicals, Japan, under the tradename DHT-4A). The compound is vacuum dried over phosphorus pentoxide at 95 0 C for 24 hours.

S-2: [Mg 4 ,Al 2

(OH)

13 CO3-3,5H 2 0] calcined (this compound is sold by by Kyowa Chemicals, Japan, under the tradename DHT-4C).

S-3: zink oxide (dried) S-4: molecular sieve 4A (dried) magnesium oxide (dried) 1- g -9 1 II C ~PC qLI WO 94/06831 WO 94/06831PCr/EP93/02419 33

(H

2 6 -NR NNR- (OH 2 6 -NRNjH H-1 N H nwhere tert. C 8

H

17 M> 2500

CH

3 OH 3 R is N H

OH

3

CH

3 H-2: R-NH-(CH 2 3 -N O 2 2

N-(H)

3 j-NH-R O H 3

OH

3 N

I

N /N-OH 3 N N C49N

OH

3

OH

3

OH

3 N OH 3

O;H

3 WO 94/06831PC/9/049 PCr/EP93/02419 -34- C H 3 H1-3: 0 Mri>1500

CH

3 ON C H 3

OH

3

O

3

C(CH

3 3 P-1

C(CHA)

Claims (12)

1. A process for the preparation of an olefin polymer by polymerisation with a transition metal catalyst, which comprises carrying out the polymerisation by adding a) 0.005% to 5% of at least one compound of the series of the hydrotalcites, zeolites or metal oxides that does not release water under the reaction conditions and either b) 0.01 to 5% by weight of a 2,2,6,6, -tetramethylpiperidine having a molecular weight above 500 or c) 0.01 to 1% by weight of a phosphorus (III) compound or mixtures of components b) and c).

2. A process according to claim 1, which comprises preparing an olefin polymer by using a solid supported catalyst which has been prepared by reacting an aluminium compound carrying at least one alkyl group with a compound of a metal of the IVth 15 subgroup of the Periodic Table. S3. A process according to claim 1, wherein the catalyst is a chromium compound which is on a support. So 20 4. A process according to claim 1, wherein the compound of the series of the hydrotalcites, zeolites, metal oxides or a similarly synthetically prepared compound that does not release water under the reaction conditions is used after drying at 50-800 0 C, preferably from 80-400 0 C.

5. A process according to claim 1, which comprises the use of a synthetically prepared hydrocalcite or zeolite. -L -bJ~ba .WPfOCS MA FSiriCT5M41I(J<AI), IW;3 9~7 36

6. A process according to claimn 1, wherein the hydrotalcite conforms to the general formulae 3 2 n mI- 2 0(I wherein M2 Mg, Ca, Sr, Ba, Zn, Cd, Pb, Sn and/or Ni, M 3 1 -Al, BorBi, An is an anion of valency n, n is a number from I to 4, x is a number from 0 to is a number from 0 to 2, and Br-, C10 4 HCO 3 CH 3 COC11C0 C0 2 SO 2 OOOCHCO- 02 0 00-, (CHOHCOO) 2 -,(CHOH) 4 CH 2 OHCOO-. C 2 '-1 4 (COO) 2 2 (CTI 2 COO) 2 2 *CPI 3 CHOHCOO-, Si0 3 2 SiO 4 Fe(CN) 6 3 Fe(CN) 6 4 or 02- or M2A2O),i6(') -mH 2 O (1a) wherein M 2 is at least one metal of the se!ries of Mg and Zn, Mg being preferred, An, is an anion of the series of C0 3 2 00 HadS;and n is the valency of the anions, m is a positive number, preferably from 0.5 to 5, and x and z are positive numbers, and x is preferably 2 to 6 and z is smaller than 2.

7. A process according to claim 1, wherein the zeolite conforms to the general formula M,, 1 j(AlO 2 'O2)y] WvH 2 0 WX wherein n is the charge of the cation M, M is an element of the first or second main group of the Periodic Table, y :x is a number from 0.8 to 1.2, and ebjRA,. w is a number from 0.5 to i'.W O('SM IAPSPECI'4l1400.KICAN 1(97 -37-

8. A process according to claim 1, which comprises the use of an oxide of a divalent metal.

9. A process according to claim 1, which comprises the use of an oxide of a metal of the second main group r'nd subgroup of the Periodic Table. A process according to claim 1, which comprises the use of an oxide of zinc or magnesium.

11. A process according to claim 1, wherein a 2,2,6,6,-tetrarethylpiperidine having a molecular weight above 500 that contains in its molecule at least one s-triazine group is used. *1 12. A process according to claim 1, wherein a compound of formula 9 H N R (CH 2 6 NR- NR- (CH 2 6 NR- H H CH N N N n ,where R is NH ten. C 8 H 1 7 CH CH 3 Mn >2500 R R R-NH-(CH 2 3 -N (CH 2 2 N-(CH 2 3 -NH-R R H 3 or N N O N CH 3 CH 3 CH 3 CH 3 CH 3 N CH 3 -r 38 OH 3 (CH 2 o M1 1 >1500 CH 3 CH H 3 OH 3 CH 3 is used,

13. A process accordi-'g to claim 1, which comprises the use of a phosp~horus(JII) compound that contains at least one P-O-Ar group, where Ar is a mono-, di- or trialkyiphenyl radical. A process according to claim 1, which comprises the use of tris(2,4-di-tert- butylphenyl)phosphite or tetrakis(2,4-di-tert-bU Ltylphenyl)-4, 4'- byphienylenedisphosphionite. A process according to claim 1, wherein an antioxidant of the sterically hindered phenol type is used as additional stabiliser. 20 16. A process according to claim 1, which comprises the use of octadecyl. tert-butyl-4-hiydroxyphlenyl)propionate anid 1,3 ,5-tris(31, 5-.di-tert-butyl-4-hiydroxybenizyl)- @0 2,4, 6-trimethylbenzene as additional stabiliser.

17. A stabilised polyolefin prepared according to the process of claim 1.

18. Stabilised polypropylene prepared according to the process of claim 1. INENA11ONAL SEARCH REPORT [nte W Application No IPCT/EP 93/02419 t A.CLASIICAIO OF SUBJECT MAVI'ER IPC 5 C08F2/44 According to nteritonal Pate-t Clas~sification (IPC) or to both nations.1 classification and [PC Minimumn doctumentation seached (clasification system followed ;7,y classification symbols) IPC 5 C08F Douentation searched other than trinimumn documnentation to the extent that such documents are included in the fields seirched Electronic data base consulted during the international search (name of data t;se and, whete practical, search terms tis;,'d) C. DOCUMENTS CONSIDERED TO BE RELEVANT Cacoy citatson of document, with indication, where appropriate, of the relevant passages Relevant to claim No. X WO,A,92 13899 (AWAPATENT) 20 August 1992 1-3,5 see claims 1-10 see the Od~e document X EP,A,0 266 074 (BP CHEMICALS) 4 May 1988 1 see claims 1,2. see examples A EPA,0 500 073 (MITSUBISHI) 26 August 1992 1 see claii-zs 1,6. Further documents ca'e listed in th2, continuation of box C. lj Ptent family members are listed in An= !,esalc~4one ofdt dotimnisT' liter documcnt published after the international iling date A do'~mnt efiingthegenral5t~tifthe~ ~ch s ~or priority dale and not in conflict with the appicaton but **dcnsidefin t he b lsae of the~la rer a rtw chis ciud to understand the principle or theory underlying the consderd t beof aru*ulr rlevnceinvention earlier dovurnent butpbi~4o rate h nentoa document of particular relevance-, the claimed invention iling dati. pbieo rate h nentoa annot be conxidered novel or cannot be comadered to -L document which my tl'.row doubts on priority daiisvft) or involve an inventive step when the documilnt is taken alone w' -ch is cited to estabaish the publication date of another 'Y document of particular relevance; the claimed invention citation or other special reason (as specifie%; cannot be xzudered to involve an inventive step when the V document referring to an oral disclosure, use, eachbition or document ia combined with one or more other such docti- ither means imnns, such combination being obvious to a person slilled 'P doo-inoent published prior to the international tiling date but in the arn. lat 'r 1=n the priority ila~e claimed W document member of the salme patent family 1 Date rfthe actual completion of the international search Date of irrsslng of the initamalsonal search report 3 December 1993 17. 12, 93 Name nd mailing address of the ISA Authorized officer European Patenit Office, P.B. 5818& Patenulskan 2 NL 2280 HV WRlswtik Tel. 31-70) 340.22M.,Tx. 31 651.epo nl, eR ek R Fax: 31-70),340-3016DeR ck R Fom PCTIISA/210 (lecand sheet) (Ju-'ly 1552) INTERNATIoNAL SEARCH REPORT I iter rAi ApplicAtion No- Infoanto documntentiy ane PCT/EP 93/02419 'In search report -A-9213899 Publication dateI Patentl family member(s) Publication date

20-08-92 AU-A- 1241992 07-09-92 EP-A- 0570458 24-11-93 EP-A-0266074 04-05-88 FR-A- 2604710 08-04-88 FR-A- 2604711 08-04-88 DE-A- 3772149 19-09-91 EP-A- 0455930 13-11-91 WO-A- 8802379 07-04-88 JP-T- 1501067 13-04-89 US-A- 4970279 13-11-90 US-A- 5063110 05-11-91 US-A- 5225458 06-07-93 EP-A-0500073 26-08-92 JP-A- 4264140 18-09-92 JP-A- 5112725 07-05-93 JP-A- 5124161 21-05-93 US-A- 5262233 16-11-93 F~jrm PCT/ISA/210 t(pittamty annex) (July 1992)