DE2627688A1 - DISABLED PIPERIDINE CARBONIC ACIDS, METAL SALTS THEREOF AND THEREFORE STABILIZED POLYMERS - Google Patents

Description

CIBA-GEIGYAG, CH-400 ?. Basel

E ψ ⁷ '' * ^. "■" L ^Ιϊ *. '*' ^Λ '' l Κ Ί V * "

Case 3-9965 / GCS 730/10401/1 + 2
Germany

Hindered piperidine carboxylic acids, metal salts thereof and polymers stabilized therewith

The invention relates to the stabilization of organic material that is normally subject to decomposition. In particular The compound relates to the protection of synthetic polymers against harmful degradation, such as discoloration and embrittlement, due to irradiation of light, in particular by ultraviolet light,

It is known that irradiation, especially in the near ultraviolet range, has a deleterious influence on both on the appearance as well as on the properties of organic

609884/1136

see has polymers. E.g. colorless ones usually turn yellow or lightly colored polyesters in sunlight, as well as cellulose and cellulose acetates. Polystyrene will discolor and becomes fragile, accompanied by a loss of beneficial physical properties when exposed to light, while vinyl resins, such as polyvinyl chloride and polyvinyl acetate, stain and degrade. The rate of air oxidation of polyolefins, such as polyethylene and polypropylene, is accelerated considerably by ultraviolet light.

US Pat. No. 3,120,540 describes the reaction of substituted 4-piperidinols with acid anhydrides of the formula

O = C C = O

described, where η is 1-4, and bis (polymethyl) -4-piperidyl alkanoate can be obtained. In the example of this patent, the salt of 1,2,2,6,6-pentamethyl-4-piperidinol is used with the acid of the formula

^CH X / ^CH 3 0 0 CH - Ή y 0 - C _{- (CH 2} ) ₂ - C - OH

CH CH

as a possible intermediate in the synthesis of bis (hydrogen sulfate) -salt of bis- (1,2,2,6,6-pentamethyl-4-piperidyl) succinats specified. The compounds according to US Pat. No. 3,120,540 are said to have pronounced pharmacological effectiveness in the

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Have lower blood pressure. It has now been found that half esters of hindered piperidines against organic materials Stabilize the degradation effect of ultraviolet light.

The invention accordingly relates to a new class of UV stabilizers, namely compounds of the formula

O O

0-CHa -0-0 J-M (I),

where R-, are the same and are hydrogen or alkyl of 1-6 carbon atoms mean R2 is hydrogen, alkyl with 1-12 carbon atoms, Alkenyl with 3-4 carbon atoms, propargyl, benzyl, benzyl substituted with alkyl, aliphatic acyl with 1-4 carbon atoms, C ^ -C ^ -i is alkoxyalkyl or oxyl, Ro straight-chain alkenylene with 2-4 carbon atoms, 1,2-cycloalkylene or 1,2-cycloalkenylene with 4-6 carbon atoms, 2,3-bicycloalkylene or 2,3-bicycloalkenylene having 7-8 carbon atoms or 1,2-, 1,3-, or 1,4-phenylene, or straight-chain Is alkylene with 1-4 carbon atoms substituted by alkyl or alkenyl with 1-18 carbon atoms, which is straight-chain alkylene, substituted by alkyl, a total of more than 10 carbon atoms, m hydrogen or barium, nickel, manganese, calcium, copper, zinc, magnesium, sodium, potassium, Cobalt, tin, or dialkyl tin, ζ is 1-4, where the value of ζ is equal to the valence of m.

R2 can be hydrogen or alkyl with 1-12 carbon atoms in particular alkyl having 1-4 carbon atoms, hydrogen and methyl being particularly preferred, furthermore

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e.g. ß-methoxyethyl, alkenyl with 3-4 carbon atoms, in particular Allyl, propargyl, benzyl or alkyl substituted benzyl. Acyl Ro is especially alkanoyl with 1-4, preferably 2-4 carbon atoms, e.g. acetyl, or alkenoyl with 2-4 carbon atoms, e.g. acryloyl or crotonyl.

Examples of R ^ are hydrogen, methyl, ethyl, n-propyl, isopropyl, η-butyl, isobutyl, n-hexyl, n-octyl, n-dodecyl, Al 13 ⁷ I, a-methallyl, propargyl, benzyl, α- Methylbenzyl and α-p-dimethylbenzyl.

Examples of cyclic groups R- are 1,2-cyclobutylene, 1,2-cyclohexylene, 4-cyclohexen-1,2-ylene, BieyeIo [2,2,1] hept-2,3-ylene and bicyclo [2.2.2] oct-2,3-ylene, especially bicyclo- [2 , 2, l] hept-5-en-2, 3-ylene and 1,2-phenylene.

Examples of non-cyclic groups R are octadecylethylene, dodecylethylene, 2-dodecenylethylene, 2-octenylethylene, 2-butenylene, vinylene, methyl vinylene, octyl vinylene and octadec3 ^r l-vinylene.

Hydrogen and nickel are preferred among the M radicals.

A preferred group of compounds of the formula I are those in which R 1 is hydrogen or methyl, R _{0 is} hydrogen, methyl, allyl, benzyl, acetyl, acryloyl or crotonyl, Ro, m and ζ have the preferred meanings above.

The invention also relates to stabilized mixtures, which are stabilized against degradation by ultraviolet light, containing an S3 ⁷ synthetic organic polymer that is normally subject to decomposition by ultraviolet light.

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and is about 0.005 to 5 parts by weight of the polymer 7 _O a compound of formula I, in particular from 0.01 to 2 wt .-%.

The compounds of the formula I can be used in combination with other light stabilizers, such as 2- (2-hydroxyphenyl) benzotriazoles, 2-hydroxybenzophenones ^ nickel complexes and benzoates be used.

The stabilizers according to the invention are suitable for organic Material that is subject to thermal, oxidative or photodecomposition. Material that so stabilized are, for example, organic polymers including homopolymers, copolymers, and mixtures thereof, such as vinyl resins from the polymerization of vinyl halides or the copolymerization of vinyl halides with unsaturated polymerizable Compounds, e.g. vinyl esters, α, β-unsaturated acids, ot, ßunsaturated Esters, α, β-unsaturated ketones, α, β-unsaturated Aldehydes and unsaturated hydrocarbons such as butadiene and styrene; Poly-oct-olefin, like high and low dense polyethylene, crosslinked polyethylene, polypropylene, poly (4-methyl) -1-pentene and the like, including Copolymers of α-olefins; like ethylene-propylene copolymers, txnd the like; Polydienes such as polybutadiene, polyisoprene, and the like, including copolymers with other monomers, polyurethanes, such as made from polyols and organic polyisocyanates, and polyamides, such as polyhexamethylene adipamide and polycarbonates such as those made from bisphenol-A and phosgene; Polyacetals, such as polyethylene terephthalate polyacetal; Polystyrene, polyethylene oxide; Polyacrylates such as polyacrylonitrile; Polyphenylene oxides such as those made from 2,6-dimethylphenol and the like; and copolymers such as

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those of polystyrene include copolymers of butadiene and styrene and those made by copolymerization of Acrylonitrile, butadiene and / or styrene.

Other materials produced by the compounds of the invention can be stabilized are e.g. lubricating oils of the aliphatic ester type, e.g. ethylene diazelate, pentaerithrityl tetracaproate and the like, animal and vegetable oils, such as linseed oil, fat, talc, lard, peanut oil, Cod liver oil, castor oil, palm oil, corn oil, cottonseed oil and the like, hydrocarbons such as petrol mineral oil, fuel oil, Drying oil, cutting fluids, waxes, resins and the like, salts of fatty acids such as soaps and the like, and alkylene glycols, e.g. 2-methoxyethanol, 2 ~ (2-methoxyethoxy) -ethanol, Triethy! Glycol, octaethylene glycol, dibutylene glycol, Dipropylene glycol and the like.

The compounds according to the invention are in particular as UV light stabilizers suitable, especially for protection of polyolefins, e.g. polyethylene, polypropylene, poly-1-butene, Poly-1-pentene, poly-3-methyl-1-butene, poly-4-methyl-1-pentene, various ethylene-propylene copolymers and the like.

In general, the stabilizers of the invention will be in about 0.01 to about 5 percent by weight of the stabilized mixture applied although this may vary according to the specific substrate and application. A preferred area is from about 0.05 to about 2%, especially 0.1 to about 1%.

For addition to the polymer substrate, the stabilizers can be used before the polymerization or after the polymerization,

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during the usual processing, e.g. by hot mixing, of the substrates during extrusion, pressing, injection molding or the like can be added to films, fibers, threads, hollow bodies and the like. The heat stabilizing properties these compounds can make the polymers beneficial against degradation during processing at high temperatures, as they are normally used. The stabilizers can also be used in a suitable solvent dissolved and sprayed onto the surface of films, fabrics, fibers and the like in order to stabilize them. If the polymer is made from a liquid monomer, as in the case of styrene, the stabilizer can be in the monomer be dispersed or dissolved prior to polymerization or curing.

The compounds according to the invention can also be used in combination used with other additives, such as antioxidants, sulfur-containing esters, such as stearyl-ß-thiodipropionate (DSTDP), Dilauryl-ß-thiodipropionate (DLTDP) in amounts from 0.01 to 2% by weight of the organic material, and the like, pour point depressants, Corrosion and rust inhibitors, dispersants, demulsifiers, anti-foaming agents, fillers, such as glass and other fibers, carbon black, accelerators and other chemicals used in rubber compounding, Plasticizers, color stabilizers, di- and tri-alkyl and -alkylphenyl-phosphites, as well as other phosphites, e.g. distearylpentaerythritol diphosphite, heat stabilizers, UV light stabilizers, Antiozonants, colors, pigments, metal chelators, dye sites, and the like. Often, combinations result with other additives, such as those of the type mentioned above, in particular with sulfur-containing esters, phosphates and / or UV light stabilizers, better results in certain

6 0 3884/1136

Applications than one from the properties of each component could expect.

The following formula shows co-stabilizers that are used in certain Cases very useful in combination with the stabilizers according to the invention are:

n ^H 2n

RO-CG _n H _2n
0

where R is alkyl of 6-24 carbon atoms and η is a whole Number from 1 to 6 is. Of these compounds, dilauryl β-thiodipropionate and distearyl β-thiodipropionate are particularly suitable. The above co-stabilizers are used in amounts of 0.01 to 2% by weight of the organic material, in particular from 0.1 to 1%.

Although the compounds according to the invention also up to To some extent act as thermal stabilizers, after all it is when processing polymers at high temperature advantageous to use an antioxidant in addition.

In most applications, it is desirable to incorporate sufficient thermal antioxidant into the resin to prevent the To protect plastic against thermal and oxidative decomposition. The amount of antioxidant corresponds to that of the sunscreen agent, namely from about 0.005 to 5%, in particular from 0.01 to 2% (weight). Representative for such antioxidants

609884/1136

dantien are phosphite esters such as triphenyl phosphite and dibutyl phosphite and alkylaryl phosphites such as dibutylphenyl phosphite and the like.

The best results have been obtained with a preferred class of antioxidants, the hindered phenols. These connections result in the best thermal stabilization with the least discoloration of the substrates. Among these phenolic Antioxidants are:

Di-n-octadecyl (3-tert-butyl-4-hydroxy-5-methylbenzyl) malonate 2,6-di-tert-butylphenol

2,2'-methylene-bis- (6-tert-butyl-4-methylphenol) 2,6-di-tert-buty-hydroquinone

Octadecyl ~ (3,5-di-tert-butyl-4-hydroxybenzylthio) acetate 1,3-Tris- (3-tert-butyl-6-methyl-4-hydroxyphenyl) -butane

1,4-bis (3,5-di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene

2,4 ~ bis (3,5-di-tert-butyl ~ 4-hydroxyphenoxy) -6- (n-octylthio) -1,3,5-triazine

2,4-bis- (4-hydroxy-3,5-di-tert-butylphenoxy) -6- (n-octylthioethylthio) -1,3,5-triazine

2,4-bis (n-octylthio) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine

2,4,6-tris- (4-hydroxy-3,5-di-tert-butylphenoxy) -1,3,5-triazine n-Octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate n-Octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate 2- (n-Octylthio) methyl 3,5-di-tert-butyl-4-hydroxybenzoate

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n-Octadecanoyl-di-2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy ] -äthylamiii

1,2-propylene di- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]

Pentaerythrityl tetra [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]

Di-octadecyl (3,5-di ~ tert-butyl-4-hydroxybenzyl) phosphonate

Di-octadecyl 1- (3,5-di-tert-butyl-4-hydroxyphenyl) ethane phosphonate.

The above phenolic hydrocarbon stabilizers are known and many of them are commercially available.

The above antioxidants are listed for illustration purposes only. Other antioxidants can work with equal success can be used. The above antioxidants and other related antioxidants are detailed in the following patents described:

Dutch patent 67/1119, Dutch patent 68/03498, and US patents 3,255,191; 3,330,859; 3,644,482; 3,281,505; 3,531,483; 3,285,855; 3,364,250; 3,368,997; 3,356,944 and 3,758,549.

The compounds according to the invention can thereby be prepared be that one piperidinol of the formula II

Cxi, -, CH .-. R-, R-.
'2 1/1

₀ -N> -OH II

2 ν

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wherein It, and R "have the above meaning, with an acid anhydride of formula III

III

in which R "has the above meaning. In the case of 1,3- and 1,4-Phenylene can be prepared by the compounds Reacting a piperidinol II with isophthalic acid or terephthalic acid by means of the usual esterification reactions.

An alternative process for the preparation of the compounds according to the invention is characterized in that one Piperidinol II with a diacid of the formula IV

R ₃ (COOH) ₂ IV,

wherein R- has the above meaning.

The acids and acid anhydrides which are reacted with the compounds of the formula II can be known per se Process are produced.

The metal salts according to the invention can be prepared by adding a hindered piperidinecarboxylic acid of the formula I. with a reactive derivative of a metal or metal complex, e.g. sodium hydroxide or the like. Alternatively

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and especially in the case of metal complexes or metals other than alkali metals, a double conversion is indicated. For example, a sodium salt of a compound according to the invention can be treated with nickel chloride. Similarly, other halides such as magnesium dichloride, barium chloride and the like can be used and the corresponding ones Obtained metal derivatives.

The compounds of formula II can be prepared in a similar manner are, as described in the German patent application DT-OS 2 352 658, in particular by reducing the corresponding ^ -Piperidone by catalytic hydrogenation, or e.g. with lithium aluminum hydride. The corresponding 4-ketone can be prepared by reacting an aliphatic ketone, e.g. a higher homologous phonacetone, with ammonia, e.g. 2,3,6-trimethyl ~ 2,6-diethyl-4-oxo-piperidine is made from Methyl ethyl ketone and ammonia obtained analogously to W. Traube in Chem. Ber. 41, (1908), 777. The corresponding 4-ketone can also by hydrolysis of an alkyl substituted tetrahydropyridine obtained in the presence of an acidic catalyst, analogously to US Pat. No. 3,513,170, or according to DT-OS 2,429,745; 2,429,746; 2,429,935; 2,429,936 and 2,429,937.

Compounds of the formula I with R2 being acyl can by Acylation of the corresponding N-H compounds with corresponding carboxylic acids, anhydrides, esters or halides in an can be produced in a known manner.

The following examples illustrate the invention without limiting it.

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example 1

2, 6-diet hyl-2, 3, 6-tr imet: hy l -pi per id in -4- ο 1

In a 2 liter 3-necked flask with a pounder, cooler and thermometer as well as nitrogen inlet tube, 197.3 g (1.0 mol) of 2,6-diethyl-2, 3, 6-trimethyl-piperidin-4-one are added, as well 500 ml 2 η sodium hydroxide and 500 ml absolute ethanol. Add to the stirred reaction mixture, which is kept under nitrogen 18.92 g (0.5 mol) of sodium borohydride are added in portions over the course of 1 ^ / 2 hours. The reaction mixture is then stirred overnight at room temperature. The reaction mixture is decanted into a 4 liter separatory funnel and 2 liters of water are added. The aqueous layer is separated and the organic layer with 500 ml Diluted ether. The ether solution is washed twice with 1 liter of water. The first aqueous layer is washed twice with 50 ml of ether extracted. The combined ether extracts are washed with 500 ml of water. The ethereal layers are united over 4 A molecular sieve dried and evaporated under reduced pressure. 187.4 g of the desired 2,6-diethyl-2 are obtained , 3,6-trimethyl-piperidin-4-ols that can be further purified by vacuum distillation, bp. 111-115 ° / 6 mm.

Example 2

O-Mono "(2 ', 6'-diethyl- 2', 3'-6'-trimethylpiperidyl -4 ') - 2-n octyl succinate

In a 1 liter 3-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet, 63.69 g (0.3 mol) of 2-n-octylsuccinic anhydride, 300 ml of VM&P naphthate (a aliphatic hydrocarbon solvent from SDP. 120-

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140 °, to and 59.79 g (0.3 mol) of 2,6-diethyl-2,3,6-trimethylpiperidin-4-ol. The reaction mixture is refluxed for 3 hours, then cooled to room temperature, a gel forming in the reaction vessel. The reaction mixture is placed in a stop piston and evaporated under reduced pressure at 100 ⁰ C to constant weight to yield 126.8 g after cooling the desired half-ester as a dark brown glass is obtained, characterized by the following analysis:

Elemental analysis:

Calculated for C _{o /} H, _c N0, FW 411.61

24 45 4

Calculated C 70.03 H 11.02 N 3.40 Found C 69.93 H 10.90 N 3.67.

Example 3

N i (II) -bis- fO-mono- (2 ', 6'-diethyl -2', 3'-6'-trimethyl-piperidyl-4 ') -2-n -octyl-succina't ]

In a 300 ml 3-neck flask with stirrer, nitrogen inlet, air cooler and drip funnel are added 20.58 g (0.05 mol) of 0-mono-2 ^1, 6'-diethyl-2 ·, 3 ", 6'-trimethyl -piperidyl-4 ¹ ) -2-n-octylsuccinate, 100 ml of water and 25 ml of 2 η sodium hydroxide solution (0.05 mol). The reaction mixture is stirred until the solution is complete (11/2 hours). Then a solution of 5.94 g (0.05 mol) of nickel chloride with 6 water of crystallization in 25 ml of water are added dropwise to the stirred solution over a period of 10 minutes. A pale green precipitate forms immediately. The reaction mixture is stirred for a further hour. Then 150 ml of ether are added with vigorous stirring.

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The mixture is transferred to a dropping funnel and the aqueous layer is separated off. The organic layer is added with 200 ml Washed with water and dried over 4 A molecular sieves. the Ether solution is filtered and evaporated to dryness. 19.8 g of the desired nickel salt are obtained as a green glass.

Example 4

Zn (II) -bis- [0 -m ono- (2 ', 6'- diethyl-2', 3 ', 6 ' -trimethyl- piperidyl- 4 ¹ ) -2-n-octyl-succinate]

In a 300 ml 3-neck flask equipped with a stirrer, nitrogen inlet, Air cooler and dropping funnel are added 20.58 g (0.05 mol) of 0-mono-2 ', 6'-diethyl-2', 3 ', 6' "trimethyl-piperidyl-4 ') -2-n-octyl succinate, 100 ml of water and 25 ml of 2 η sodium hydroxide solution (0.05 mol). The reaction mixture is stirred until complete dissolution has occurred (1 - ^ / 2 hours). Then 12.17 ml of a 2.055 η solution of zinc chloride in water was added dropwise to the stirred solution over the course of 10 minutes. It educates A heavy gummy precipitate immediately appears. The reaction mixture is stirred vigorously for 1 ^ / 2 hours. Then the aqueous layer decanted from the gummy precipitate. The precipitate is dissolved in 500 ml of chloroform. The chloroform solution is washed with 2 × 250 ml of water and dried over 4 Å molecular sieves. The chloroform solution will evaporated to dryness and gives 19.2 g of the desired zinc salt as a greasy brown glass.

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Example 5

According to Example 3, by adding NiCl ^ -δΗ, -, Ο through replaces an equivalent amount of the following metal chlorides:

a) MgCl ₂ -OH ₂ O

b) CoCl ₂ -6H ₂ O

c) CaCl ₂

the following metal salts are obtained:

a) Mg (II) -bis- [0-mono- (2 ', 6'-diethyl-2', 3 ', 6'-trimethylpiperi · dyl-4 ') - Z-n-octyl succinate],

a tan, rubbery solid product.

b) Co (II) -bis- [0-mono- (2 ^f , 6'-diethyl-2 ', 3', 6'-trimethylpiperidyl-4 ¹ ) -2-n-octyl-succinate],

a purple glass.

c) Ca (II) -bis- [0-mono- (2 ', 6'-diethyl-2', 3 ', 6'-trimethylpiperidyl-4 ¹ ) -2-n-octyl-succinate],

a tan, greasy glass.

Example 6

0-mono- (2 ', 6'-diethyl-2', 3 ', 6'-trimethyl-pi peridyl-4') -2-noctadecen-2 "-yl-succinate

According to Example 2 and in which the 2-n-octyl-succinic acid anhydride by an equivalent amount of 2-n-0ct: adecen-2-yl succinic anhydride replaced, one obtains the above half-ester. 609 3 8 4/1136

Example 7

Following the procedure of Example 2 and in which the 2-n-octyl succinic anhydride by an equivalent amount of the following anhydrides:

a) Cyclohexane-1,2-dicarboxylic acid anhydride

b) Bicyclo- [2.2.1] -hept-5 - en · - !, 2-dicarboxylic anhydride,

the following half-esters are obtained:

a) 0-mono- (2 ', 6'-diethyl-2', 3 ', 6'-trimethylpiperidyl-4 ¹ ) -cyclohexane-1,2-dicarboxylate

b) 0-Mono ~ (2 ', 6'-diethyl-2', 3 *, 6'-trimethylpiperidyl-4 ') -bicyclo- [2.2.1] -hept-5-ene-2,3-dicarboxylate.

Example 8

According to the method of Example 3 and in which the O-mono- (2 ', 6'-diethyl-2', 3'-6'-trimethylpiperidyl-4 ') -2-n-octyl succinate and replace the nickel chloride with 6 water of crystallization with an equivalent amount of the following compounds:

a) 0-mono- (2 ', 6'-diethyl-2 ¹ , 3', 6'-trimethyl-piperidyl-4 ') -2-n-octadecen-2 "-yl-succinate + CoCl ₂ ^ H ₂ O,

b) 0-mono- (2 ', 6'-diethyl-2', 3 ', 6'-trimethyl-piperidyl-4 ¹ ) -cyclohexane-1,2-dicarboxylate + MgCl ₂ ' 6H ₂ O

c) 0-mono- (2 ', 6'-diethyl-2 ¹ , 3', 6'-trimethyl-piperidyl-4 ¹ ) -bicyclo- [2.2. l] hept-5-ene-1,2-dicarboxylate + Ni

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the following metal salts are obtained:

a) Co (II) bis [O-mono (2 ', 6'-diethyl-2', 3 ', 6'-trimethylpiperidyl ^4-1) -2-n-octadecene-2 "~ yl ~ succinate ]

b) Mg (II) -bis- [0-mono- (2 ', 6'-diethyl-2', 3 ', 6'-trimethylpiperidyl-4 ¹ ) -cyclohexane-l ^ -dicarboxylate]

c) Ni (II) -bis- [O-mono- (2 ', 6'-diethyl-2', 3 ', 6'-trimethylpiperidyl-4 ^r ) -bicyclo- [2.2.1] -hept-5- ene-2,3-dicarboxylate.

Example 9

T est with artificial lighting

The destruction of most polymers by ultraviolet light is so slow at normal temperature that even in Absence of stabilizers testing the effectiveness of stabilizers generally either at a higher temperature or must be done in an accelerating art exposure machine to get results in useful time. The test performed on polymers under artificial light is as follows:

a) Sample preparation

5 mm film - unstabilized polypropylene powder (Hercules Profax 6501) is carefully mixed with 0.5% by weight of 0-mono- (2 ', 6'-diethyl-2 ¹ , 3', 6'-trimethyl-piperidyl ~ 4) - 2-n-octyl succinate and 0.2% by weight dioctadecyl-3,5-di-t-butyl-4-hydroxy-benzylphosphonate mixed. The mixed material is then placed on a 3 roll mill and mixed for 5 minutes at 182 ° C. The material obtained is then ^{pressure-pressed at 220 °} C. into 5 mm thick films under a pressure of 175 psi and water-cooled in the press.

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b) test method

This test is carried out in an FS / BL unit, enjoyable American Cyanamid, which consists of 40 tubes of alternating fluorescent sun lamps and black lights, 20 each. The 5 mm film sample is mounted on 3 "χ 2" IR card holders with 1/4 "χ 1" windows and on a rotating drum Mounted 2 inches from the FS / BL unit lamps. The time in hours is recorded until 0.5 carbonyl absorption units are achieved, according to the infrared spectrophotometer. The formation of the carbonyl functional groups in the polymer is proportional to the decomposition by the ultraviolet light.

Polypropylene stabilized with the above hindered piperidines is much more stable than unstabilized polypropylene. The polypropylene is also stabilized if the following stabilizers are the 0-mono- (2 ', 6'-diethyl-2' , 3 ', 6'-trimethyl-piperidyl-4') -2-n ~ octyl-succinate in the above • Replace procedure:

a) Ni (II) -bis- [0-mono- (2 ·, 6'-diethyl ~ 2 ', 3', 6'-trimethylpiperidyl-4 ¹ ) -2-n-octyl-succinate]

b) Zn (II) -bis- [0-mono- (2 ', 6'-diethyl-2', 3 ', 6 "-trimethylpiperidyl-4') -2-n-octyl-succinate]

c) Mg (II) -bis- [0-mono- (2 ', 6'-diethyl-2 ¹ , 3', 6'-trimethylpiperidyl-4 ¹ ) -2-n-octyl-succinate]

d) Co (II) -bis- [0-mono- (2 ', 6'-diethyl-2', 3 ', 6'-trimethylpiperidyl-4 ¹ ) -2-n-octyl-succinate]

e) Ca (II) -bis- [0-mono- (2 ', 6'-diethyl-2', 3 ', 6'-trimethylpiperidyl-4') -2-n-octyl-succinate]

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f) 0-mono- (2 ', 6' - diethyl-2 ', 3', 6'-trimethyl-piperidyl-4 ') -cyclohexane-l ^ -dicarboxylate

g) Ni (II) -bis- [0-mono- (2 ^!, 6 ^f -diethyl-1 ¹ , 2 ', 3', 6'-tetramethylpiperidyl-4 ¹ ) -2-n-octyl-succinate]

h) Ni (II) -bis- [0 ~ mono- (2 ', 6'-diethyl-2', 3 ', 6'-trimethylpiperidyl-4 ¹ ) -bicyclo- · [2 .2 .1] -hept -5-en-2,3-dicarboxylate]

i) Co (II) -bis- [0-mono- (2 ⁽ , 6 '-diethyl-2', 3 ', 6' -tritnethylpiperidyl-4 ') -2-n-octadecen-2 ^M -yl-succinate ]

j) Ni (II) -bis- [0-mono- (2 ·, 6'-di-n-butyl-2 ', 6'-dimethyl-3'-n-propyl-piperidyl-4') -2-n- octadecene-2 "-yl succinate].

Other hindered phenolic antioxidants can be used in place of di-octadecyl- (3,5-di-t-butyl-4-hydroxy-benz} '"l) phosphonate can be used in the above mixture, e.g. Di-n-octadecyl-a- (3-t-butyl-4-hydroxy ~ 4-methylbenzyl) -malonate, 2,4-bis ~ (noctylthio) -6- (3,4 "di-t-butyl-4" hydroxyaniline) -1,3,5-triazine, Octadecyl 3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate, Pentaerythritol tetrakis [3- (3,5-di "t-butyl-4-hydrox} ^ phenyl)] · propionate, tris (3,5-di-t ~ butyl-4-hydroxybenzyl) isocyanurate, 2,6-di-tert-butyl-4-methylphenol, N, N, N-tris- (3,5-di-tert. butyl-4-hydroxybenzyl) isocyanurate and 2,4,6-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-trimethylbenzyl.

The above compositions are also stabilized when the following UV absorbers are in the formulation in amounts of 0.01 to 2% are included:

a) 2- (2'-Hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole

b) 2-Hydroxy-4-methoxy-5-sulfobenzophenone trihydrate

c) 2-hydroxy-4-n-octoxybenzophenone

6 0 9 3 8 A / 1 1 3 6

d) [2,2 * thiobis (4-t-octylphenolate)] - n-butylamine-nickel-II

e) p-octylphenyl salicylate

f) 2,2'-Dihydroxy-4 ~ 4'-dimethoxybenzophenone

g) 2- (2'-Hydroxy-5'-methy! phenyl) -benzotriazole.

Example 10

High-density polystyrene resin containing elastomer (butadiene-styrene) is stabilized against the loss of elasticity due to UV radiation by adding 0.2% by weight of 0-mono- (2 ', 6'-diethyl-2', 3 ', 6'-trimethyl-piperidyl-4 ¹ ) -2-n-octyl succinate can be incorporated.

The unstabilized resin is dissolved in chloroform and the stabilizer is then added. The mixture is then poured onto a glass plate and the solvent evaporated to obtain a uniform film which, after drying, is removed and cut. It is then pressed for 7 minutes at a temperature of 163 ° at a pressure of 2000 psi to give films of uniform thickness (25 mm). The film is then cut into strips approximately 4 x 0.5 inches. A portion of these strips are tested for extensibility in an Instron Tensile Testing Apparatus (Instron Engineering Corporation, Quincy, Massachusetts). The remaining strips are placed in a VS / BL chamber according to Example 6 (B), but the samples are placed on a white cardboard and the time is measured until 507 _{o of} the extensibility is reached. The stabilized polystyrene resin retains its ductility longer than the unstabilized resin.

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Example 11

Uustabilized linear polyethylene is dissolved in methylene chloride with 0.5% by weight of the substrate of the nickel complex of 0-mono- (2 ', 6' -diethyl-2 ', 3', 6 '-trimethyl-piperidyl-4 ¹ ) - 2-noctyl succinate mixed and then dried in vacuo. The resin is then compounded in a 1 inch 24 / I = LZD extruder, melt temperature 232 ° C and pressed for 7 minutes at a temperature of 163 ° C and a pressure of 2000 psi into films of uniform thickness of 100 mils. The webs are then cut into 2x2 inch pieces. These samples are placed in an FS / BL exposure unit and periodic color measurements are made in a Hunter Color Difference Meter Model D25. Polyethylene stabilized with the above compound is much more stabilized than unstabilized polyethylene or polyethylene stabilized only with an antioxidant.

Example 12

A quantity of an SBR emulsion containing 100 g of gum (500 ml of 20% SBR from Texas US, Synpol 1500) stored under nitrogen is placed in a beaker and stirred vigorously. The pH of the emulsion is adjusted to 10.5 with 0.5 η sodium hydroxide solution.

50 ml of a 25% saline solution are added to the emulsion. A 6% saline solution, adjusted to a pH of 1.5 with hydrochloric acid, is poured into thin straw under strong Stirring added. When the pH reaches 6.5 the gum begins to coagulate and the addition is slowed down to to ensure uniform movement. The addition of the

609884/1136

acidic 6% saline solution is terminated when pH 3.5 is reached. The coagulated rubber coating of pK 3.5 is kept for 1/2 hour.

The coagulated gum is filtered off through a cloth and washed with distilled water. After 3 successive washing with fresh distilled water, the coagulated rubber is dried, firstly at 25 mm Hg and finally to constant weight under high vacuum (about 1 mm) at 40-45 ⁰ C.

The dried rubber (25 g) is ^{heated under nitrogen at 125 °} C. in a Brabender mixer. While mixing, 0.25 g (0.5%) Co (II) -bis- [0-mono- (2 ', 6'-diethyl-2', 3 ', 6'-trimethylpiperidyl-4 ¹ ) -2 -n-octyl succinate added. It is mixed for a further 5 minutes and then cooled and pressure-pressed at 125 ° to give platelets of 5 "χ 0.025".

The pellets are exposed in a xenon arc weatherometer. Color measurements (L-b) are taken after 45, 125 and 290 hours. The samples associated with the above compound are stabilized are much more light-stable than the unstabilized samples.

Example 13

To 50 g of polyacetal resin containing 0.1% of an acid binder, dicyandiamide, 0.2% by weight of Ca- (II) -bis- [0-mono ~ (2 ', 6'-diethyl-2 ¹ , 3' , 6'-trimethylpiperidyl ^4-1) -2-n-octyl succinate and mixed for 7 minutes at 200 ⁰ C in a Brabenderplasti recorder. The resulting formulation then becomes 40 mil films

6 0 9 8 8 4/1136

pressed at 215 ^° C. and 350 psi for 90 seconds, then quickly cooled in a cold press at 350 psi. The stabilized films are then pressed into 1.5 inch 2.5 inch 125 mil plaques for 2 minutes at contact pressure and 3 minutes at 300 psi at 215 ° C. Then it is tested according to Example 10 in order to determine the light stability of the samples. The stabilized samples are much more stable than the unstabilized ones.

Example 14

Unstabilized chips of carefully dried polyethylene terephthalate are dry with 1.0% Zn (II) -bis- [0-mono- (2 ', 6'-diethyl-2', 3 ', 6'-trimethylpiperidyl-4 ¹ ) - 2-n-octyl succinate mixed. 60/10 denier multifilament is spun at a melt temperature of 290 ⁰ C. The oriented fiber is wound onto white cards and exposed in a xenon arc fadeometer. Measurements are made periodically with a Hunter Color Difference Meter Model D25. The stabilized samples are much more light-stable than the unstabilized samples.

Example 15

a) A mixture of acrylonitrile-butadiene-styrene terpolymer and 1% by weight of 0-mono- (2 ', 6'-diethyl-2 ¹ , 3', 6'-trimethylpipcridyl-4 ¹ ) -2-n-octadecenyl- succinate withstands embrittlement on exposure to UV light longer than one without a stabilizer.

0 9 3 0 4/1136

b) A mixture of polyurethane made from toluene di ~ isocyanate and alkylene polyols, and 1% by weight Ni (II) -bis- [0-mono-2 ¹ , 6'-diethyl-2 ', 3', 6'-trimethylpiperidyl-4 ¹ ) -cyclohexane-1,2-dlcarboxylate is more stable to sunlight, fluorescent sun lamps, black lances and fluorescent lamps as coated polyurethane.

c) A mixture of polycarbonate made from bisphenol-A and phosgene and 1% by weight Ni (II) -bis- [0-mono- (2 ', 6'-diethyl-2 ', 3', 6 '-trimethylpiperidyl-4') -2-n-octadecen-2 "-yl succinate resists staining due to exposure to UV light longer than one without a stabilizer.

d) A mixture of polymethyl methacrylate and 0.25 wt. 70 0-mono- (2 ', 6'-diethyl-2 ¹ , 3', 6'-trimethylpiperidyl-4 ¹ ) -2-noctadecen-2 "-yl -succinat withstands discoloration due to UV exposure longer than one without a stabilizer.

Example 16

a) A stabilized polyamide (nylon 6,6) is produced by adding 0.1% Ni (II) -bis- [0-mono- (2 ^f , 6'-diethyl-2 ', 3', 6'- trimethylpiperidyl-4 ') phthalate is incorporated. The light stability of the stabilized mixture is better than that of unstabilized polyamide.

b) A stabilized polyphenylene oxide polymer (manufactured by polymerization of 2,6-dimethylphenol) is produced, in which 0.5% by weight Ni (II) -bis- [0-mono- (2 ', 6'-diethyl-2', 3 ', 6'-trimethylpiperidyl-4') - cyclohex-4- en-1,2-dicarboxylate incorporated. The stabilized mixture resists embrittlement

609834/113 6

longer than one without a stabilizer due to UV radiation.

c) Stabilized, crystalline polystyrene is produced by adding 0.1% by weight of Ni (II) -bis- [0-mono- (2 ', 6'-di-n-butyl-2', 6'- dimethyl-3'-n-propyl-piperidyl-4 ') -2-n-octadecen-2 "-yl succinate incorporated. The stabilized mixture withstands embrittlement due to UV radiation longer than such without stabilizer.

Antioxidants can also be incorporated into any of the above mixtures, e.g., di-n-octadecyl-α, α'-bis- (3-butyl-4-hydroxy-5 methylbenzyl) malonate, 2,4-B is - (4-hydroxy-3,5-di-t-butylphenoxy) -6- (n-octy1throethylthio) -1,3, 5-triazine, 2,4-bis- (3,5-di-t-butyl-hydroxyphenoxy) ~ 6 ~ (n-octylthio-1,3,5-triazine, Di-n-octadecyl-3- (3 ', 5'-di-t-butyl-4-hydroxyphenyl) propionate.

The invention also relates to compounds of the formula I ₅ in which M is a radical m ¹ (R), in which R is water, an alcohol, a glycol, a diol, a triol, a tetraol, a pentol, a hexytol or ammonia, an amine or is an amine alcohol. M ¹ is a metal as indicated for M above. In the case of M ¹ , ζ denotes the primary valence and η the coordination number of the metal.

The compounds in which M ^{denotes a radical M 1} (R) can be prepared by mixing equimolar amounts of the compounds containing M and the coligand R in a suitable solvent, heating under reflux and then evaporating to dryness. In particular, when M is nickel or R is n-butylamine, the compounds can be suspended in isopropanol, that n-butylamine are added and the

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Reflux mixture until solution is achieved. Then it is evaporated to dryness.

Example 17

O -mono- (2,2,6,6-tetramethylperidin -4-ol) -cyclohexane-1,2-dlcarboxylate

A. Into a 5 ml, 3-necked flask equipped with a stirrer, thermometer, stick inlet and Dean-Stark trap with a condenser are given 15.73 g (0.1 mol) of 2,2,6,6-tetramethylpiperidin-4-ol and 300 ml of xylene. The reaction mixture is briefly refluxed to remove water from the solvent. Then on 100 ° cooled and 15.42 g (0.1 mol) of cyclohexane-1,2-dicarboxylic anhydride are added in parts. The reaction mixture is then heated under reflux and stirring for 5 hours, then cooled to room temperature and suction filtered. The solids obtained are washed twice with hot isopropanol and dried. 29.25 g of the desired product are obtained as a white powder, mp 231-235 °.

B. Essentially following the above procedure replacing the cyclohexane-1,2-dicarboxylic anhydride with an equivalent a lot of

a) Cyclohex-4-en-1,2-dicarboxylic acid anhydride

b) Bicyclo- [2.2.1] -hept-5-en-2,3-dicarboxylic acid anhydride

c) phthalic anhydride

thus one obtains the corresponding following compounds

609884/1 1 36

a) O-mono- (2,2,6,6 ~ tetramethylpiperidin-4-ol) -cyclohex-4-en-1,2-dicarboxylate, F. 245-247 °

b) 0-mono- (2,2,6,6-tetramethylpiperidin-4-ol) bicyclo- [2.2.1] hept ~ 5 ~ ene-2,3-dicarboxylate, mp 225-229 °

c) O-mono- (2,2,6,6-tetramethylpiperidin-4-ol) phthalate, 310-325 °.

C. If one follows in v. ^T e union sent to the above method A, and replaces the reactants with the appropriate amounts of the following reagents:

a) l-n-dodecyl-2,2,6,6-tetramethyl-piperidin-4-ol and cyclohex-4-en-1,2-dicarboxylic anhydride

b) l-Benzyl-2,2,6, 6-tetramethyl-piperidin-4-ol and Bicyclof 2 .2 .1] hept-5-en-2, 3 - dicarboxylic anhydride

thus one obtains the corresponding following compounds

a) O-mono- (l-n-dodecyl-2,2,6,6-tetramethyl-piperidin-4-ol) -cyclohex-4-en-1,2-dicarboxylate

b) O-mono- (1-benzyl-2,2,6,6-tetramethylpiperidin-4-ol) -bicyclo- [2.2.1] -hept ~ 5-en-2,3-dicarboxylate.

Example 18

O -mono- (2.2 _} 6,6- tetramethylplperidin-4-ol) maleate

A. Into a 300 tnl neck flask equipped with a stirrer, stirrer and Dean-Stark Trap, nitrogen inlet, drying tube and thermometer are added 31.82 g (0.20 mol) of 2,2,6,6-tetramethylpiperidin-4-ol and 200 ml of xylene. The reaction mixture is briefly to

609884/1 1 36

Heated to reflux, then ^{cooled to 80 °} C. and 19.83 (0.20 mol) maleic anhydride are added. The reaction mixture is heated under reflux for 2½ hours, then cooled to room temperature. The precipitate is filtered off with suction and treated with 400 ml of hot isopropanol. The solids obtained are dried under vacuum and give the desired material as a tan solid, mp 251-253 ° C.

B. Essentially following Procedure A above, replacing the maleic anhydride with an equivalent amount 2-dodecen-l-yl succinic anhydride is obtained accordingly the 0-mono ~ (2,2,6,6-tetramethylpiperidin-4-ol) -2-dodecen-lyl-succinate, 171-174 ° C.

C. Essentially following the procedure under A, replacing the reactants with appropriate amounts of the following reagents

a) 1,2,2,6,6-Pentamethyl-piperidin-4-ol and dodecylsuccinic anhydride

b) l-propargyl-2,2,6,6-tetramethylpiperidin-4-ol and citraconic anhydride

thus one obtains the corresponding following compounds

a) O-mono- (1,2,2,6,6-pentamethyl-piperidin-4-ol) -dodecyl succinate

b) O-mono- (1-propargyl-2,2,6,6-tetramethyl-piperidin-4-ol) -methyl maleate.

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Example 19

JJi- (lO-M. ^S "fO-mono- (2, 2,6, 6-tetrame.thylpir> eridin-4-ol) -cyclo h exa n -1,2 -dicarboxyJ aL ~ J_

A. In a 500 ml single-necked flask, add 12.46 g (0.04 mol) of 0-mono- (2,2,6,6-tetramethylpiperidin-4-ol) cyclohexane-1,2-dicarboxylate and 40 ml of methanol . 40 ml of 1.0 η methanol (see potassium hydroxide solution) are added to the suspension. The reaction mixture is swayed until solution has occurred. The reaction mixture is then concentrated to dryness under reduced pressure and further dried in vacuo at 80 ° / 0.1 ma / hour. 100 ml of anhydrous methanol are then added to the potassium salt thus formed. While stirring, a solution of 4.75 g (0.02 mol) of nickel dichloride with 6 water of crystallization in 50 ml of methanol is added over the course of 10 minutes. The reaction mixture is then suction filtered, and the filtrate is concentrated to half its volume under reduced pressure. 75 ml of ethanol are added to the methanolic solution, the mixture is suction filtered and the filtrate is reduced to half its volume. This process is repeated once more with ethanol and twice more with isopropanol. After the last addition of isopropanol, the reaction mixture is suction filtered and the filtrate is concentrated under reduced pressure. The residue is further in vacuo at 80 ⁰ C for (0.1 rnm) dried for 1 hour. The desired nickel salt is obtained as a green powder after it has been ground.

B. According to method A above and in which the O-mono- (2,2,6,6-tetramethylpiperidin-4-ol) -cyclohexane-1,2-dicarboxylate by an equivalent amount of

a) O-mono- (2,2,6,6-tetramethylpiperidin-4-ol-cyclohex-4-ene-1,2-dicarboxylate

609884/1 1 36

b) 0-mono- (2,2,6,6-tetramethylpiperidin-4-ol) bicyclo- [2.2.1] hept-5-en-2,3-dicarboxylate

replaced, one obtains the corresponding following substances

a) Ni (II) -bis- [0-mono- (2,2,6,6-tetramethylpiperidin-4-ol) -cyclohex-4-en-1,2-dicarbox3 ^r lat], green powder

b) Ni (II) -bis- [0-mono- (2,2,6,6-tetramethylpiperidin-4-ol) -bicyclo- [2.2.1] -hept-5-en-2,3-dicarboxylate] , yellow-green powder.

Example 20

A. Essentially following the procedure of Example 19A and uses the following metal complexes in place of nickel chloride

a) Copper III chloride

b) Manganese chloride

c) cobalt (II) chloride

d) zinc chloride

e) calcium chloride

f) magnesium chloride

so you get accordingly:

a) Cu (II) -bis- [0-mono- (2,2 _> 6,6-tetramethylpiperidin-4-ol) -cyclohexane-1,2-dicarboxylate]

b) Manganese (II) -bis- [0-mono- (2,2,6,6-tetramethylpiperidin-4-ol) cyclohexane-1,2-dicarboxylate]

609 P. 8 4/1136

c) Co (II) bis [0-mono- (2,2,6,6-tetramethylpiperidin-4-ol) cyclohexane-1,2-dicarboxylate]

d) zinc bis [0-mono- (2,2,6,6-tetramethylpiperidin-4-ol) -cyclohexane-1 , 2-dicarboxylate]

e) CaICiUm (II) -bis- [O-raono- (2,2,6,6-tetramethylpiperidin-4-ol) -cyclohexane-1,2-dicarboxylate].

B. Essentially following the procedure of Example 19 Λ and replacing the reactants with appropriate amounts of the following Reagents

a) O-mono- (2, 2,6, 6-tetramethylpiperidi n-4-ol) -bicyclo- [2.2.1] -hept-5-en-2,3-dicarboxylate and manganese chloride

b) O - mono- (2,2,6,6-tetramethylpiperidin-4-ol) maleate and zinc chloride

c) O-mono- (2,2,6,6-tetramethylpiperidin-A-ol) -2-dodecen-1-yl succinate and magnesium chloride

so we get accordingly:

a) Manganese (II) bis [0-mono- (2, 2,6,6-tetrameth3 / lpiperidin-4-ol) bicyclo- [2.2.1] -hept-5-ene-2,3-dicarboxylate ]

b) zinc bis [0-mono- (2,2,6,6-tetramethylpiperidin-4-ol) maleate]

c) Magnesium (II) bis [0-mono- (2,2,6,6-tetramethylpiperidin-4-ol) -2-dodecen-1-yl-succinate]

609384/1136

Example 21

Ii ¹ Li Σ.Ώ. ~ ±> i s- [Om on o- (2, 2,6, 6 --te t ramp thy! Pipe ri din-4-ol) phthalate]

A. In a 500 ml 3-necked flask with stirrer, thermometer and
15.27 g (0.05 mol) of 0-mono- (2,2,6,6-tetramethylpiperidin-4-ol) phthalate and 20 ml of anhydrous are added to the dropping funnel
Methanol. 50 ml of 1 η are added to the stirred suspension
methanolic potassium hydroxide solution and 70 ml of methanol. The reaction mixture is stirred and briefly heated to 45 ° in order to dissolve the solution
to facilitate. The reaction mixture is then cooled to room temperature and a solution of 5.94 g (0.025 mol)
NiCl ^ * 6 £ L0 in 20 ml of methanol was added within 5 minutes. 10 ml of methanol are used to wash the dropping funnel
used. The reaction mixture is stirred for 10 minutes and 170 ml of isopropanol are added. After a further 45 minutes, the reaction mixture is filtered off with suction and the filtrate is evaporated to dryness under reduced pressure. The residue
is further dried under vacuum at 65 ° / 0.1 mm for 1 hour. The desired nickel salt is obtained as a green, glass-like powder.

B. Essentially following procedure A and replacing the nickel chloride with the following metal complexes

a) Manganese chloride

b) magnesium chloride

c) zinc chloride

so we get accordingly:

a) Manganese (II) bis [0-mono- (2,2,6,6-tetramethylpiperidin-4-ol) phthalate

609884/1 136

b) Magnesium (II) bis [0-mono ~ (2,2,6,6-tetramethylpiperidin-4-ol) phthalate ]

c) Zinc bis [O-mono- (2,2,6,6-tetramethylpiperidin-4-ol) phthalate].

Example 22

Bariu m-bis "[O-reono · - (2, 2 _f 6, 6- tetraffiethylpipaidin-4-ol ·) -cyclohexane-1,2-dica l · ' boxy l · at j

15.57 e are placed in a 1 liter single-necked flask with a magnetic stirrer (0.05 mol) 0-mono- (2,2,6,6-tetramethylpiperidin-4-ol) -carboxy lat and 200 ml of methanol. 25 ml of 1 η barium hydroxide solution in methanol are added to the stirred suspension. The reaction mixture is stirred for 15 minutes at room temperature. The slurry changes its appearance to a milky solution. the The reaction mixture is evaporated to dryness under reduced pressure and the barium salt as a colorless resin after drying obtained under vacuum at 65 ° / 0.1 mm.

609884/1 1 36

Example 23

Exposure test with artificial light, see example 9 Light stabilization data in polypropylene

Additive *

Time (hours) to 0.5 carbonyl absorption units

0 ~ mono- (2,2,6,6-tetramethylpiperidin-4-ol) -cyclohexane-1,2-dicarboxylate

0-mono- (2,2,6,6-tetramethylpiperidin-4-ol) -cyclohex-4-en-1,2-dicarboxylate

0-mono- (2,2,6,6-tetramethylpiper idin-4-ol) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylate

O-mono- (2,2,6,6-tetramethylpiperidin-4-ol) phthalate

Ni (II) -bis-O-raono- (2,2,6,6-tetraraethyl-piperidin-4-ol) -eyelohexane-1,2-dicarboxylate]

Ni (II) -bis- [0-mono- (2,2,6,6-tetramethyl-piperidin-4-ol) -cyclohex-4-en-1,2-dicarboxylate]

Ni (II) -bis- [0-tnono- (2,2,6,6-tetramethyl-piperidin-4-ol) -ma lea t]

Ni (II) -bis- [0-tnono- (2,2,6,6-tetramethyl-piperidin-4-ol) -phthalate]

Base resin alone

1310 570

1240 220

> 3010

2060

990

1210 200

609884/1

Table II

Light stabilization data in polypropylene

Additive time (hours) up to 0.5 carbonyl absorption properties

O-mono- (2,2,6,6-tetramethylpiperidin-4-oi) -2-dodecen-1yl-succinate 1970

O-mono- (2,2,6,6-tetramethyl-

piperidin-4-ol) maleate 2510

Ni (II) -bis- [0-mono- (2,2,6,6-tetramethyl-piperidin-4-ol) -2-dodecen-1-yl succinate] . 3420

Ni (II) -bis-fO-mono- (2,2,6,6-tetramethyl-piperidin-4-ol) -bicyclo- [2.2.1] -hept-5-ene ~ 2,3-dicarboxylate]> 1520

Base resin alone

* The formulation contains 0.5% additive and the base resin contains 0.2% antioxidant, dioctadecyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate.

Other hindered phenolic antioxidants can be used in place of di-octadecyl (3,5-di-t-butyl-4-hydroxybenzyl) phosphonate in the above mixture, e.g. such as di-n-octadecyl-a- (3-t- butyl 4-hydroxy-4-methylbenzyl) malonate, 2,4-bis- (n-octylthio) -6- (3,4-di-t-butyl-4-hydroxyaniline) -1,3,5-triazine , Octadecyl 3- (3 ', 5 ^l -di-t-butyl-4 ^l -hydroxyplienyl) propionate, pentaerythritol tetrakis- [3- (3,5-di-t-but3'l-4-hydroxy phenyl )] propionate, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 2,6-di-tert-butyl-4-methylphenol, N, N, N-tris- (3.5- di-tert-butyl-4-hydroxybenzyl) isocyanurate and 2,4,6-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-trimethylbenzyl.

609884/1

The following UV absorbers are incorporated into the mixture at concentrations of 0.01 to 2% :

a) 2- (2 '-IIydroxy-3', 5 '-di-t-bu.tylphei.iyl) -5-chlorobenzotriazole

b) 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate

c) 2 ~ hydroxy-4 ~ n-octoxybenzophenone

d) [2,2'-thiobis- (4 ~ t-octylphenolate)] -n-butylamine-nickel-II

e) p-octylphenyl salicylate

f) 2,2'-dihydroxy ~ 4,4'-dietethoxybenzophenone

g) 2- (2 '-hydroxy-5' -methylphenyl) -benzotria zol.

Example 24

In the test according to Example 10, the O-mono- (2,2,6,6-tetramethylpiperidin-4-ol) can be used with the same success as described there ~ cyclohexane-1,2-dicarboxylate ends.

Example 25

In the test according to Example 11, O-mono- (2,2,6,6-tetramethylpiperidin-4-ol) maleate can be used with the same success as described there use.

Example 26

In the test according to Example 12, 0-mono- (2,2,6,6-tetramethylpiperidin-4-ol) -cyclohex-4-en-1,2-dicarboxylate can be used with the same success as described there use.

609884/113 6

Example 27

In the test according to example 13 one can achieve the same success V7ie there described the Ni (II) -bis- [0-mono- (2, 2, 6, 6-tetramethylpiperidin-4-ol) Use -2-dodecen-l ~ yl - succinate.

Example 28

In the test according to Example 14, 0-mono-2- (2,2,6,6-tetramethylpiperidin-4-ol) -2-dodecenl-yl-succinate can be used with the same success use.

Example 29

In the test according to Example 15a), the Ni (II) -bis [0-mono- (2,2,6,6-tetramethylpiperidin-4-ol) maleate] can be obtained with the same success as described there. use,

b) In the test according to Example 15b), 0-mono- (2,2,6,6-tetramethylpiperidin-4-ol) cyclohexane-1,2-dicarboxylate can be used with the same success as described there use.

c) In the test according to Example 15c), the 0 ~ mono- (2,2,6,6-tetramethylpiperidin-4-ol) -bicyclo- [2.2.1] -hept-5- ene-2,3-dicarboxylate use.

d) In the test according to Example 15d), the Ni (II) -bis- [0-raono- (2,2,6,6-tetramethylpiperidin-4-ol) -cyclohexane-1,2- can be used with the same success as described there dicarboxylate] use.

609884/1136

Example 30

a) In the test according to example 16a) you can do the same Success as described there with Ni (II) -bis- [0-mono- (2,2,6,6-tetramethylpiperidin-4-ol) -bicyclo- [2.2.1] -hept-5-en-2,3 -dicarboxylate] use.

b) The same can be used in the test according to Example 16b) Success as described there Ni (II) -bis- [0-mono- (2.2,6 «6-tetra ~ methylpiperidin-4-ol) -cyclohexan-l ^ -dicarboxylate].

c) In the test according to Example 16c), the Ni (II) -bis- [0 ~ mono- (2 , 2 , 6 ₅ 6-tetramethylpiperidin-4-ol) -cyclohex-4 can be used with the same success as described there -en-l, 2-dicarboxylate].

The other antioxidants given in Example 16 can also be used use with equal success.

6 0 3 8 8 4/1136

Claims (29)

Claims where R-, are the same and are hydrogen or alkyl with 1-6 carbon atoms, R «hydrogen, alkyl with 1-12 carbon atoms, alkenyl with 3-4 carbon atoms, propargyl, benzyl, benzyl substituted with alkyl, aliphatic acyl with 1-4 Carbon atoms, C-o '^ ll. Is alkoxyalkyl or oxyl, Ro straight-chain alkenylene with 2-4 carbon atoms, 1,2-cycloalkylene or 1,2-cycloalkenylene with 4-6 carbon atoms, 2,3-bicycloalkylene or 2,3-bicycloalkenylene with 7-8 carbon atoms or 1, 2-, 1,3-, or 1,4-phenylene, or straight-chain alkylene with 1-4 carbon atoms, substituted by alkyl or alkenyl with 1-18 carbon atoms, the straight-chain alkylene substituted by alkyl having a total of more than 10 carbon atoms has, m is hydrogen or barium, nickel, manganese, calcium, copper, zinc, magnesium, sodium, potassium, cobalt, tin, or dialkyltin, ζ is 1-4, the value of ζ being equal to the valence of m. 2. Compounds according to claim 1, wherein R is hydrogen or methyl, R2 is hydrogen, methyl, allyl, benzyl, acetyl, Is acryloyl or crotonyl, R-, m and ζ have the above meanings. 3. Compounds according to claim 1, wherein M is hydrogen or nickel. 609884/1136 4. Compound according to claim 1, 0-mono- (2 ', 6'-diethyl-2', 3 ', 6'-trimethylpiperididyl-4') -2-n-octyl succinate. 5. Compounds according to claim 1, Ni (II) -bis- [O-mono- (2 ', 6'-diethyl-2', 3 ', 6'-trimethylpiperidyl-4') -2-n-octyl succinate]. 6. Compounds according to claim 1, Co (II) -bis- [0 - mono ~ (2 ', 6' -diethyl-2 ', 3', 6 '-trimethylpiperidyl-4') -2-n-octyl-succinate]. 7. Compounds according to claim 1, Ca (II) -bis- [O-mono- (2 ', 6'-diethyl-2', 3 ', 6'-trimethylpiperidyl-4') -2-n-octyl succinate]. 8. Compounds according to claim 1, Mg (II) -bis- [0-mono- (2 ', 6'-diethyl-2', 3 ', 6'-trimethylpiperidyl-4') -2-n-octyl succinate]. 9. Compounds according to claim 1, Zn (II) -bis- [O-mono- (2 ', 6'-diethyl-2', 3 ', 6'-trimethylpiperidyl 4 ') - 2-n-octyl succinate]. 10. Compounds according to claim 1, Ni (II) -bis- [0-mono- (2 ', 6'-diethyl-2', 3 ', 6'-trimethylpiperidyl · 4 ¹ ) -2-n-octadecen-2 "-yl succinate]. 11. Compounds according to claim 1, O-mono- (2 ', 6'-diethyl-2 ¹ , 3', 6'-trimethylpiperidyl-4 ¹ ) -2-noctadecen-2 ^M -yl succinate. 609884/1 1 36 12. Compounds according to claim 1, O-mono- (2 ¹ , 6'-diethyl-2 ', 3', 6'-triraethylpiperidyl-4 ¹ ) -cyclohexane-1,2-dicarboxylate. 13. Compounds according to claim 1, Ni (II) -bis- [O-mono- (2 ', 6'-diethyl-2', 3 ', 6'-trimethylpiperidyl-4') -cyclohexane-l ^ -dicarboxylate. 14. Compounds according to claim 1, 0-mono- (2,2,6,6-tetramethylpiperidin-4-ol) -cyclohexane-1,2-dicarboxylate. 15. Compounds according to claim 1, 0-mono- (2, 2,6,6-tetratethylpiperidin-4-ol) bicyclo [2 .2.1] -hept-5-ene-2,3-dicarboxylate. 16. Compounds according to claim 1, Ni (II) -bis- [O-mono- (2,2,6,6-tetramethylpiperidin-4-ol) -cyclohexane-1,2-dicarboxylate]. 17. Compounds according to claim 1, Ni (II) -bis- [O-mono- (2,2,6,6-tetramethylpiperidin-4-ol) -cyclohex-4-en-1,2-dicarboxylate]. 18. Compounds according to claim 1, 0-mono- (2,2,6,6-tetramethylpiperidin-4-ol) -2-dodecen-1-yl succinate. 19. Compounds according to claim 1, 0-mono- (2,2,6,6-tetramethylpiperidin-4-ol) maleate. 609884/1 136 20. Compounds according to claim 1, Ni (II) -bis- [0-mono- (2,2,6,6-tetramethylpiperidin-4-ol) -2-docecen-1-yl-succinate. 21. Compounds according to claim 1, O-mono- (2,2,6,6-tetramethylpiperidin-4-ol) -cyclohex-4-en-1,2-dicarboxylate. 22. Compounds according to claim 1, 0-mono- (2,2,6,6-tetramethylpiperidin-4-ol) phthalate. 23. Compounds according to claim 1, Ni (II) -bis- [O-mono- (2,2,6,6-tetramethylpiperidin-4-ol) -bicyclo [2.2.1] -hept-5-ene-2,3-dicarboxylate]. 24. Compounds according to claim 1, Ni (II) bis [0-mono- (2,2,6,6-tetramethylpiperidin-4-ol) phthalate. 25. Compounds according to claim 1, Ni (II) bis [0-mono- (2,2,6,6-tetramethylpiperidin-4-ol) maleate]. 26. Containing stabilized, synthetic, organic polymer which is normally subject to UV destruction a) 0.005% -5% of a compound according to claim 1, b) 0-57o of a phenolic antioxidant, c) 0-5% of a thio-co-stabilizer, and d) 0-5% of a UV absorber. 27. The polymer of claim 26, wherein the polymer is a polyolefin. 609884/1 136 28. The polymer of claim 27, wherein the polyolefin is polypropylene. 29. Process for the preparation of compounds according to claim 1, characterized in that a piperidinol is used of formula II II, wherein R, and R ^ have the above meaning with an acid anhydride of formula III III, wherein R- has the above meaning, or a piperidinol II with isophthalic acid or terephthalic acid, or a piperidinol II with a diacid of the formula IV R ₃ - (COOH) ₂ IV, wherein R ~ has the above meaning, and, if desired, a hindered piperidinecarboxylic acid of the formula I with a reactive derivative of a metal or metal complex, or a double reaction of a metal salt with a
other metal compound, such as a metal salt. 609884/1 1 36