DE2425984A1 - STABILIZATION OF SYNTHETIC POLYMERS - Google Patents

Description

Dr. F. Zumstein Sr. - Dr. E. Assmann Dr. R. Koenigsberger - Dlpl.-Phys. R. Holzbauer - Dr. F. Zumstein Jun.

PATENT LAWYERS

TELEPHONE: COLLECTIVE NO. 2253 41 _{8 MUNCH} EN2. TELEX 529979 BRÄUHAUSSTRASSE 4 TELEGRAMS: ZUMPAT

CHECK ACCOUNT: MUNICH 91139-809. BLZ 70O1O080

BANK ACCOUNT: BANKHAUS H. AUFHÄUSER KTO.-NR-397997. Bank code 700 3O6 OO

97 / N

Case FP-7411-2

SANKYO COMPANY LIMITED, Tokyo / Japan Stabilization of synthetic polymers

According to the invention, a synthetic polymer composition which is resistant to photo and thermal decomposition is stabilized, provided the dipiperidyl derivatives in a sufficient to prevent such decomposition Amount contains.

The invention relates to a synthetic polymer composition. In particular, it relates to a photo- and thermal decomposition stabilized synthetic polymer composition containing a dipiperidyl derivative in one contains sufficient amount to prevent such decomposition.

From "J.Org.Chem.", 27, 1695 (1962), some 4,4 »-dihydroxy- 4,4 · - dipiperidyl derivatives are known with regard to their usefulness for pharmaceuticals. However, their usefulness for stabilizing synthetic polymers has not been known until now It has now been found that dipiperidyl derivatives of the following formula I or an acid addition salt thereof have a remarkable stabilizing effect on synthetic polymers against photo- and thermal decomposition thereof.

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The following formula comes to the dipiperidyl derivatives

CH ₃ CH ₃ CH CH ₃

NR ^f

CH ₃ CH ₃

where R and R ¹ , which may be the same or different, each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an aliphatic or aromatic acyloxyalkyl group, a cyanoalkyl group, a haloalkyl group , an epoxyalkyl group, an alkoxycarbonylalkyl group, an aliphatic acyl group, an alkoxycarbonyl group or an aralkoxycarbonyl group.

Because of their excellent characteristic properties, synthetic polymers are widely used in various Shapes such as fibers, films, sheets, other shaped articles, latiees and foams are used. However own these polymeric materials have the disadvantage that they have poor stability to light and heat. There are various stabilizers as a means of preventing the deterioration or deterioration of these synthetic polymers known. However, there are still problems associated with these known stabilizers which have to be resolved.

A primary object of the invention is to provide a stabilizer for synthetic polymers which is a dipiperidyl derivative of Formula I above or an acid addition salt thereof. Another aim of the invention is to a synthetic polymer composition that is resistant to destruction is stabilized to create a synthetic polymer and incorporated therein at least one dipiperidyl— derivative of the formula I or an acid addition salt thereof in one to prevent destruction or deterioration contains sufficient quantity.

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In the above general formula I, R and R ^{1 may be mentioned} ! Hydrogen atom; Alkyl groups having 1 to 8, preferably 1 to 4 carbon atoms, such as methyl, ethyl, butyl, propyl and octyl groups; Alkenyl groups with 3 to 6 carbon atoms, such as, for example, allyl, crotyl and 2-hexenyl, preferably the allyl group; Alkynyl groups with 3 or 4 carbon atoms, preferably the 2-propynyl group; Aralkyl groups with 6 carbon atoms in the aryl part and 1 or 2 carbon atoms in the alkyl part, such as the benzyl and phenethyl groups; Hydroxyalkyl groups with 1 to 4 carbon atoms, preferably the 2-hydroxyethyl group; Alkoxyalkyl groups with 1 to 8, preferably 1 to 4 carbon atoms in the alkoxy part and 1 to 4, preferably 1 or 2 carbon atoms in the alkyl part, such as 2-ethoxyethyl, ethoxymethyl, 2-propoxyethyl and 3-methoxypropyl groups; aliphatic acyloxyalkyl groups whose acyl radical is either saturated and has 2 to 18 carbon atoms or is unsaturated and has 3 to 6 carbon atoms, and whose alkyl part has 1 to 4, preferably 2 carbon atoms, such as, for example, 2-acetoxyethyl, 2-stearoyloxyethyl, 2 -Acryloyloxyäthyl-, 2-Methacryloyloxyäthyl-, 2-Crotonoyloxyäthyl- and 2-Sorboyloxyäthylgruppen; ' aromatic acyloxyalkyl groups, the aromatic ring of which can be substituted with 1 to 3 substituents, selected from alkyl with 1 to 4 carbon atoms and hydroxy, and the alkyl part of which has 1 to 4, preferably 2 carbon atoms, preferably substituted or unsubstituted benzoyloxyalkyl groups, such as 2-Benzo- yloxyethyl, 2- (p-tert-butylbenzoyloxy) ethyl and 2-salicyloyloxyethyl groups; Cyanoalkyl groups with 2 or 3 carbon atoms, such as, for example, 2-cyanoethyl and cyanomethyl groups; Haloalkyl groups with 1 to -3 carbon atoms, such as, for example, 2-chloroethyl; Epoxyalkyl groups, preferably 2,3-epoxypropyl; Alkoxycarbonylalkyl groups with 1 to 18, preferably 1 to 8 carbon atoms in the alkoxy part and 1 or 2 carbon atoms in the alkyl part, such as ethoxycarbonylmethyl, butoxycarbonylmethyl, hexyloxycarbonylmethyl and octyloxycarbonylmethylj aliphatic acyl groups which can be saturated and have 2 to 8 carbon atoms or preferably 3 unsaturated or have 4 carbon atoms, such as

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-A-

Acetyl, propionyl, butyryl, acryloyl and methacryloyl; Alkoxycarbonyl groups having 2 to 9 carbon atoms such as methoxycarbonyl · ·, butoxycarbonyl and octyloxycarbonyl groups; and aralkoxycarbonyl groups, preferably benzyloxycarbony1 «

As the acid component of the acid addition salts, there can be mentioned, for example organic acids such as benzoic acid, p-tert-butylbenzoic acid, 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid, Maleic acid, oxalic acid, acetic acid, methylsulfonic acid and p-toluenesulfonic acid, and inorganic acids such as sulfur acidic acid, phosphoric acid and hydrochloric acid.

According to the invention, it is preferred that both R al & R ^{1 are} hydrogen, an alkyl group with 1 to 4 carbon atoms, the allyl group, the benzyl group, an alkoxyalkyl group with 1 to 4 carbon atoms in the alkoxy part and 1 to 2 carbon atoms in the alkyl part, aliphatic acyloxyethyl groups, their acyl part is either saturated and has 2 to 18 carbon atoms or is unsaturated and has 3 to 6 carbon atoms', a benzoyloxyethyl group, the benzene ring of which can be substituted with 1 to 3 substituents selected from alkyl with 1 to 4 carbon atoms and hydroxy, or an alkoxycarbonylmethyl group with 1 to 8 carbon atoms in the alkoxy part.

It is particularly preferred that both R and R ¹ denote hydrogen, an alkyl group having 1 to 4 carbon atoms, the allyl group, the benzyl group or an alkoxycarbonylmethyl group having 1 to 8 carbon atoms in the alkoxy part.

As typical examples of the dipiperidyl derivatives according to the invention of the general formula I the following compounds may be mentioned:

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1) 4,4'-dihydroxy-2,2,6,6,2 ', 2 ·, 6', 6'-octamethyl-4,4 · -dipiperidyl ,

2) 4,4'-dihydroxy-1,2,2,6,6,1 ·, 2 ', 2', 6 ', 6'-decamethyl-4,4'-dipiperidyl,

3) 4,4'-dihydroxy-2,2,6,6,2 ·, 2 ', 6 ·, 6'-octamethyl-ljl'-dioctyl-4,4 · -dipiperidyl,

4) 1,1 »-Diallyl-4,4 · -dihydroxy-2,2,6,6,2 ', ^2f , 6», 6 · -octamethyl-4,4' -dipiperidyl,

5) 4,4 »-dihydroxy-2,2,6,6,2 ', 2 ·, 6 ⁽ , 6 · -octamethy1-1,1'-di- (2-propynyl) -4,4'-dipiperidyl ,

6) l, l'-dibenzyl-4,4 ^f -dihydroxy-2,2,6,6,2 ', 2 ^t , 6 ^t , 6 ^f -octamethyl-4,4'-dipiperidyl,

) 4,4'-dihydroxy-1,1'-bis- (2 ~ hydroxyethyl) -2,2,6,6,2 ·, 2 ·, 6 ', 6 · octamethyl-4,4'-dipiperidyl,

8) 1,1'-bis (2-ethoxyethyl) -4,4'-dihydroxy-2,2,6,6,2 ', 2', 6 ', 6'-octamethyl-4,4'-dipiperidyl ,

9) 1,1 '-bis- (2-äcetoxyäthyl) ~ 4,4-dihydroxy-2,2,6,6,2 ^1, 2', 6 x, 6 x ■ octamethyl-4,4 · -dipiperidyl ,

10) 4,4'-dihydroxy-2,2,6,6,2, 2 ', 6', 6'-octamethyl-ljl'-bis- (2-stearoyloxyethyl) -4,4'-dipiperidyl,

11) 1,1'-bis-C 2-acryloyloxyethyl) -4,4 · -dihydroxy-2,2,6,6-.2 ·, 2 ', 6 ·, 6' -octatnethyl-4,4'-dipiperidyl,

12) 4,4'-dihydroxy-1,1 · bis (2-methacryloyloxyethyl) -2,2,6,6-2 ', 2', 6 ··, 6 »-octamethyl-4,4'-dipiperidyl,

13) 1,1'-bis (2-crotonoyloxyethyl) -4,4 · dihydroxy-2,2,6,6-2 ', 2', 6 ', 6'-octamethyl-4 _s 4'-dipiperidyl ,

14) 4,4'-dihydroxy-2,2,6,6,2 ', 2', 6 ', 6'-octamethy1-1,1'-bis- (2-sorboyloxyethyl) -4,4 · -dipiperidyl ,

15) 1,1 · -Bis- (2-benzoyloxyethy1) -4,4 ¹ -dihydroxy-2,2,6,6-2 ·, 2 ·, 6 ·, 6 · octamethyl-4,4'-dipiperidyl ,

16) 1,1'-bis- (2-p-tert-butylbenzoyloxyethyl) -4,4'-dihydroxy- 2,2,6,6,2 ', 2', 6 ', 6'-octamethyl-4,4'-dipiperidyl,

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17) 4,4 · -Β ^ γαΓοχγ-2,2,6,6,2 ·, 2 ·, 6 ·, 6'-octamethyl-1, l'-bis- (2-salicyloyloxyethyl) -4,4 ' -dipiperidyl,

18) 1,1 · -Bi s- (cyanomethyl) -4,4'-dihydroxy-2,2,6,6,2 ·, 2 ·, 6 ·, 6 · octamethyl-4,4 -Dipiperidyl,

19) l, l ^f -Bis- (2-chloroethyl) -4,4'-dihydroxy-2,2,6,6,2 ', 2', 6 ', 6'-octamethyl-4,4'-dipiperidyl ,

20) l, l'-bis (2,3-epoxypropyl) -4,4 ^r -dihydroxy-2,2,6, G, 2 ^t , 2 ', 6', 6 · - octamethyl-4,4 ' -dipiperidyl,

21) 1,1 · -Bis- (ethoxycarbonylmethyl) -4,4'-dihydroxy-2,2,6,6-2 ·, 2 ·, 6 ¹ , 6 · -octaraethy1-4,4 · «dipiperidyl,

22) 4,4 · -dihydroxy-2,2,6,6,2 ', 2 ·, 6', 6'-octamethyl-l, l'-bis (octyloxycarbonylmethyl) -4,4'-dipiperidyl,

23) l-acetyl-4,4'-dihydroxy-2,2 _? 6,6,2 ·, 2 ', 6', 6 · -octamethyl-4,4'-dipiperidyl,

24) l, l'-diacetyl-4,4'-dihydroxy-2,2,6,6,2 ·, 2 «, 6 ·, 6'-octamethyl-4,4'-dipiperidyl,

25) l, l'-diacryloyl-4,4'-dihydroxy-2,2,6,6,2 ·, 2 ', 6 ·, 6'-octamethyl-4,4'-dipiperidyl,

26) 1,1 -Bi s- (bu toxycarbonyl) -4,4 ■ -dihydroxy-2,2,6,6,2 ', 2', 6 ', O * - octamethyl-4,4'-dipiperidyl and

27) 1,1 · -Bis- (benzyloxycarbonyl) -4,4'-dihydroxy-2 _τ 2,6,6,2 *, 2 · -6 ', 6'-octamethyl-4,4'-dipiperidyl.

Among the dipiperidyl derivatives to be used according to the invention of Formula I above are those wherein each of R and R 'is hydrogen or the methyl group in the above mentioned literature, while the other compounds of the general formula I according to the invention are new Represent connections.

The dipiperidyl derivatives according to the invention of the above general Formula I can be synthesized by methods expressed by the following reaction formulas:

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-R (R *)

(R and R ¹ here have the above meaning and X represents a halogen atom.)

If compounds of the formula III with a halide (R-X) in the presence of an organic or inorganic base as an acid- binding agent are reacted, compounds of the formula IV are obtained in the case of an equimolar reaction. But when the halide is used in twice the molar amount per mole of the compound of the formula III, become compounds of formula VI obtained. Similarly, compounds of the formula VI can be obtained from compounds of the formula IV.

A compound of the formula VI in which both R and R ^{1 represent} the methyl group can also be obtained in high yields by reacting the compounds of the formula III with formic acid and formalin.

Furthermore, a compound of the formula VI in which both R and R ^{1 represent} a 2-hydroxyethyl group can be prepared by reacting the compounds of the formula III with ethylene oxide in the presence of an acid.

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It has also been found that the compounds of the formula III or VI can be prepared more advantageously from compounds of the formula II or V by the following method instead of the customary method described above. The desired compound of the formula III or VI can namely be obtained in a yield of over 80 % by reacting metallic sodium and an acid with a compound of the formula II or V, dissolved in a non-polar solvent, in the heat.

In carrying out the above improved process, a compound of Formula II or V is in a non-polar Solvents such as benzene, toluene and xylene, are dissolved, and metallic sodium and an acid are added to to cause the reaction. It is desirable that the metallic sodium be in an amount of 2 to 3 moles per mole of the compound of formula II or V is used.

When using the improved process, the presence of the acid is particularly important in increasing the yield of the desired product. In general, the synthesis of a Pxnakolverbxndung from a ketone proceeds in the absence of an acid only with low yield (see "Bull.Soc.Chim. France", 1946 , 256). The acid is preferably used in an amount of 1 to 1.2 moles per mole of the metallic sodium used.

As the acid, organic acids such as acetic acid, benzoic acid and p-toluenesulfonic acid, and inorganic acids such as Hydrochloric acid gas can be used.

The reaction temperature is not particularly critical, but it is desirable to keep the reaction at the boiling point of the used Perform solvent. Generally, heating to 50% for 30 minutes to 5 hours will stop the reaction up to 100 ° C.

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After the reaction has ended, the desired product is isolated by customary procedures. For example, the The reaction mixture is filtered, the filtrate is concentrated, the remaining crystals are collected and, if necessary, passed through Purified recrystallization.

According to the invention, the term "synthetic polymer" includes:

Including polyolefins

Olefin homopolymers, such as low and high density polyethylene, polypropylene, polystyrene, polybutadiene, Polyisoprene, other olefin homopolymers and copolymers of olefins with other ethylenically unsaturated ones Monomers, such as ethylene / propylene copolymers, ethylene / butene copolymers, ethylene / vinyl acetate copolymers, Styrene / butadiene copolymers, acrylonitrile / styrene / butadiene copolymers and copolymers of others Ethylene-forming unsaturated monomers with olefins j

Polyvinyl chlorides and polyvinylidene chlorides including homopolymers of vinyl chloride and vinylidene chloride, Vinyl chloride / vinylidene chloride copolymers and Copolymers of each vinyl chloride and vinylidene chloride with vinyl acetate or other ethylene-forming unsaturated monomers;

Polyacetals such as polyoxymethylene and polyoxyethylene; Polyesters such as polyethylene terephthalate; Polyester ether;

Polyamides such as 6-nylon, 6,6-nylon, 6, ΙΟ-nylon, and 10-nylon; Polyurethanes;
.Polycarbonates and
Epoxy resins.

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The dipiperidyl derivatives to be used as stabilizers according to the invention of the general formula I can be converted into a synthetic polymeric material according to various customary methods Prior art methods can be easily incorporated. The stabilizer can be the synthetic polymer in any an optional step of producing a molded article. For example, the stabilizer is in the form of a dry powder mixed with the synthetic polymer, or a suspension or emulsion of the stabilizer mixed with the synthetic polymer.

The amount of the dipiperidyl derivative of the formula I to be added to the synthetic polymer according to the invention can be varied within a wide range, depending on the type and properties of the synthetic polymeric material and the particular intended use of the resulting stabilized composition. Generally, it is added in an amount of 0.01 to 5% by weight based on the amount of the synthetic polymer, but the range suitable for practical use depends on the kind of the synthetic polymer. For example, in the case of a polyolefin, the stabilizer is used in an amount of 0.01 to 2.0% by weight, preferably 0.02 to 1.0% by weight, and in the case of a polyvinyl chloride or polyvinylidene chloride in an amount of 0.02% by weight to 1.0% by weight, preferably 0.02 to 0.5% by weight, incorporated. In the case of polyurethane or polyamide of the stabilizer in an amount of O ₈ Ol to 5, O% by weight, preferably 0.02 to 2, O% by weight, is incorporated.

The stabilizer according to the invention can be used alone or in combination with known antioxidants, UV light absorbers, metal-deactivating agents, fillers, organic Pigments and other additives can be used. Especially when the stabilizer according to the invention is used in conjunction with a? UV absorber for a polymer containing organic pigment is used, the reduction of the light stabilizing effect of the UV absorber, due to the organic

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Pigment, so that this gives particularly favorable results can be obtained.

Examples of antioxidants, UV light absorbers, and others Additives that are used together with the stabilizer according to the invention are described below:

Antioxidants

2,6-dialkylphenols, such as, for example, 2,6-di-tert-butyl-4-methylphenol, 2-tert. Butyl-4,6-diethylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol and 2,6-dioctadecyl-4-methylphenol.

Derivatives of alkylated hydroquinones, such as 2,5-di-tert-butyl-hydroquinone, _{2,5-di-tert-amyl-t} hydrochinou 2,6-di-tert-butyl-hydroquinone, 2,5- Di-tert.-TDutyl-4-hydroxyanisole, J ^^ Di-tert.-butyl - ^ - hydroxy-anisole vnä Tris- (3,5-di-tert-butyl-4-hydroxyphylenyl) phosphite, 3,5- Di-tert-butyl-4-hydroxyphenyl stearate, di- (3,5-di-tert-butyl-A-hydroxyphenyl adipate.

Hydroxylated thiodophenyl ethers, v; ie "for example 2,2 * -Q3iio-M s- (6-tert-butyl-4-methylphenol), 2,2'-thiobi s- (4-oetylpb.eiiol) 4,4 ' -a? hiobis- (6-tert .- 'butyl-3-methylplienol), di-sec.-amylphenol) and
phenol), 4.4 ¹

Alkylidene bisphenols , such as, for example, 2.2 ^l methylene bis (6-tert-butyl-4-methylphenol), 2,2'-ethylene-bis (6-tert-butyl-4-ethylphenol) ), 4, * '-Methylene _{-bis- (6-tert-butyl-2-methylphenol), 4 i} 4'-methylene-bis- (2,6-di-tert-butylphenol) , 2,6-di- (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 2,2 * -MethylenebiG-C4-methyl-6- (a-methylcyclohexyl) -phenol], Ί methyl-2-hydroxyphenyl) butane, 1, i-bis - ^ - tert. 2-methyl-phenyl) -butane, 2,2-bis- (5-tert-butyl-4-hydroxy-2-methyl

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phenyl) butane, 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 1,1,3 ~ tris- (5-tert-butyl-4-hydroxy-2-methylphynyl) -butane, 2,2-bis- (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-ndodecylmercapto-butane, 1,1,5,5-tetra (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane imd ethylene glycol bis «[3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate.

0-, N- and S-benzyl compounds , such as, for example, 3 _i 5 _i 3 ^l >> 5 ^l i-tetra-tert-butyl- ^, ^ ¹ -dihydroxydibenzyl ether, 4-hydroxy-3 »5-dimethylbenzyl-mercaptoacetic acid octadecyl ester , Τγχ- (3ϊ5-di-tert-butyl-4-hydroxybenzyl) amine and bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithiol terephthalate.

Hydroxybenzylated halonic esters , such as, for example, 2,2-bis- (3 _? 5-di-tert-butyl-2-hydroxybenzyl) -malonic acid dioctadecyle ster, 2- (3-tert-butyl - ^ - hydroxy-5 -me thylbenzyl) malonic acid di oc tade cylester, 2,2-bis (3, 5-di-tert-butyl-4-hydroxybenzyl) -malonsäuredidodecylmercaptoäthylester and 2,2-bis ~ (3i5-di-tert. -butyl-4-hydroxybenzyl) dialonic acid di- (4-tert-octylphenyl) ester.

Hydroxybenzyl aromatics, such as, for example, 1,3,5-0? Ri- (3,5-di-tert-butyl-4-hydroxybenzyl) -3,4,6-tri-methylbenzene, 1,4-di- (3, 5-di-tert-butyl-4-hydroxybenzyl) -2.3> 5,6-tetramethylbenzene and 2,4,6-tri- (3,5-di-tert-butyl-4-hydroxybenzyl) phenol .

s-triazine compounds , such as 2,4-bis-octylmercapto ~ 6- (3,5-di-tert-butyl-4-hydroxyanilino) -s-triazine, 2-octylmercapto-4,6-bis- ( 3,5-di-tert-butyl-4-hydroxyanilino) -s-triazine, 2-octylmercapto-4,6-bis- (3,5-di-tert-butyl-4-hydroxyphenoxy) -triazine, 2 _t 4,6-tris- (3,5-di-tert-butyl-4-hydroxyphenoxy) -stria zine, 2,4,6-tris- (3,5-di-tert-butyl-4- hydroxyphenylethyl) -s-triazine and 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate.

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Amides of 3,5-di-tert-butyl-4 "hydroxyphenyl-propionic acid, as in spie1swei se 1,3» 5-tri- (3 »5-di-tert-butyl-4- hydroxyphenylpropionyl) -hexahydro-s-triazine and N,! P -Di- (3,5-di-tert-butyl-4- hydroxyphenyl-propionyl) -hexamethylenediamine.

Esters of 3,5-di-tert-butyl-4-hydrox; H3henyl-propionic acid with mono- or polyhydric alcohols, such as methanol, ethanol, octadecanol, 1,6-Hexati-diol, 1,9-ethylene glycol ITonandiol _t , 1,2-propanediol, diethylene glycol, thiodiethylene glycol, neopentylglycol, pentaerythritol, 3-thia-undecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolethane ,. Trimethylolpropane, tris-hydroxyethyl isocyanurate and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2,2] octane

Esters of 5-tert-butyl- ^ -hydrpxy- 3-methylphenylpropionic acid with monohydric or polyhydric alcohols, such as, for example, methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-konanediol, ethylene glycol, 1 , 2-propanediol, diethylene glycol, thiodiethylene glycol, keopentylglycol, pentaerythritol, 3-thia-undecanol, 3-thia-pentadecanol, i-trimethylhexanediol, trimethylolethane, trimethylolpropane, trishydroxyethyl-isocyamyclo-2,6,7-hydroxymethyl-1-phosphymethyl-1, 6-phosphate - [2 _f 2.2] octane.

Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with monohydric or polyhydric alcohols, such as, for example, methanol, ethanol, octadecanol, T, 6-hexanediol, 1,9-iTonanediol, ethylene glycol, 1,2-propanediol , Diethylene glycol, OFhiodiethylene _{glycol t} neopentyl glycol, pentaerythritol, 3-thia-undecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolethane, trimethylolpropane, tris-hydroxyethyl-iso-cyanurate and 4-hydroxymethyl-2,6,7-tri-oxaioxabethyl-1-phosphaioxabethyl-1 - [2.2.2] octane.

Acylaminophenols such as K- (3,5-di-tert-butyl-4-hydroxyphenyl) -stearic acid amide and IT, H'-di- (3,5-di-tert-butyl-4-hydroxyphenyl ) -thio-bis-acetamide.

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Benzyl phosphonates, such as, for example, 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonic acid dimethyl ester, 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonic acid diethyl ester, 3,5-di-ated. butyl-4-hydroxybenzyl-phosphonic acid dioctadeeyl ester and ^ tert-butyl- ^ hydroxy - ^ - methylbenzyl-pliosplionic acid diocta-

decyl ester. '

Aminoaryl derivatives, like playing SWEi se phenyl-1-napnthylamin, -.! Haenyl-2-naphthylamine, N _s N ^f -diplienyl-p-piienyleiidlaiiiin, H ", N '-di; 2-naphthyl-p-plienylenediaBiin, UTiN'-di-sec-butyl-p-phenylenediamine, 6 -lthoxy-2,2,4-trimethyl-1, ^ - dihydroquinoline, 6 ~ dodecyl-2,2,4-trimethyl-1,2-dihydroquinolirL _i mono- and di-octylimonodi- \ benzyl and polymerized 2,2, 4-TrI-methyl-1,2-dihydroquinoline.

UV light absorbers and light stabilizers

2- (2'-hydroxyphenyl) -benztriazoles , such as the 5'-methyl-, 3 ', 5'-di-tert-butyl-, 5'-tert-butyl-, 5' - (1,1 , 3,3-tetramethylbutyl) -, 5-chloro-3 ', 5'-di ~ tert-butyl-, 5-chloro-3'-tert-butyl-

5'-methyl-, 3'-sec-butyl-S'-tert-butyl-, 3 '- (α-methylbenzyl) -5'-methyl-, 3' - (α-methylbenzyl) -5 '-methyl-5-chloro-, 4'-hydroxy-, 4'-methoxy-, 4'-octoxy-, 3 ⁽ , 5'-di-tert-amyl-, 3 ^r -methyl-5'-carboniethoxyethyl - and 5-chloro-3 ', 5'-di-tert-amyl derivatives.

2,4-bis (2'-hydroxyphenyl) -6-alkyl-s-triazines , such as, for example, the 6-ethyl, 6-undecyl and 6-heptadecyl derivatives.

2 — Hydroxybenzoph enones, such as, for example, the 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ·, 4 · trihydroxy- and 2'-hydroxy-4,4'-dimethoxy derivatives.

1,3-bis- (2'-hydroxy-benzoyl) -benzenes , such as 1,3-bis- (2'-hydroxy-4 '-hexyloxy-enzoyl) -benzene, 1,3-bis- (2' -hydroxy-4 'octoxy-benzoyl) -benzene and 1,3-bis- (2 ^f -hydroxy-4'-dodecyloxybenzoyD-benzene.

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Esters of optionally substituted benzoic acids , such as

Phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis- (4-tert-butylbenzoyl) -resorcinol, Benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid, 2,4-di-tert-butylphenyl ester, octadecyl ester or ~ 2-methyl-4,6-di-tert-butylphenyl ester.

Acrylates , such as ethyl α-cyano-β-diphenylacrylate or isooctyl ester, methyl α-carbomethoxy-cinnamate, ethyl α-cyano-β-methyl-p-methoxy-cinnamate and N-(β-carbomethoxyvinYl) -2-methylindoline.

Nickel compounds, such as, for example, nickel complexes of 2,2'-thio-bis (^ -tert.-octylphenol), such as the 1: 1 and 1: 2 complex, optionally with other ligands such as n-butylamine, triethanolamine or N. -Cyclohexyl-diethanolamine; Nickel complexes of bis- {4-tert-octylphenyD-sulfone, such as the 2:! Complex, optionally with other ligands, such as 2-ethylcaproic acid, nickel-dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert. -butylbenzylphosphonic acid monoalkyl esters, such as the methyl, ethyl or butyl ester, the nickel complex of 2-hydroxy-4-ynethylphenylundyl ketone oxime and nickel 3,5-di-tert-butyl-4-hydroxybenzoate.

Oxalic acid diamides, such as 4,4'-dioctyloxyoxanilide, 2,2 ^f -dioctyloxy-5,5'-di-tert-butyloxanilide, 2,2'-didodecyloxy-5,5 ·· - di-tert-butyloxanilide, 2-Ethoxy-5-tert-butyl-2 ^f -äthyloxanilid, 2-Äthoxy-2 · -äthyloxanilid, N, N · -Bis- (3-dimethylaminopropyl) -oxalamide, mixtures of o- and p-methoxy and o- and p-ethoxy-disubstituted oxanilides and mixtures of-2-ethoxy-5-tert-butyl-2'-ethyl-oxanilide with 2-ethyl-2'-ethyl-5,4 • -di-tert-butyloxanilide.

Metal & esaktivatoren as "beispielsv / else oxanilide, isophthalic '■ acid aihydrazid ,, sebacic acid-TDIs-phenylhydrazide, bis-ljenzyliden oxalyl dihyärazid, !!, H'-diaceto l-adipic acid-dihydraaid,' N yli '- Bis-sal-icyloyl-oxalic acid dihjrarazid, N ₁ K ¹ -is-salicyloyl- \ hydrazine and K, N ^l -Bis- (3,5-di-tert .- 'butyl - ^ - liydroxyphenylpro-; pionyl) - hydrazine.

409882/1040

Phosphites , such as triphenyl phosphite, di-phenyl-alkyl phosphite, phenyl-dialkylphosphite, trinonylphenylphosphite, trilauryl phosphite, trioctadecylphosphite, 3j9-di-isodecyloxy-2 _J 4,8 ₎ 10-tetraoxa-3 _J 9-diphöspha- spiro- [5.53-u2idecane and tri- (4-hydroxy-3,5-di-tert-butylphenyl) phosphite.

Peroxide-decomposing compounds , such as, for example, esters of β-thio-dipropionic acid, for example lauryl, stearyl-, myystyl or tridecyl esters, salts of 2-mercaptobenzimidazole, for example the zinc salt and diphenylthiourea.

Polyamide stabilizers, such as copper salts in combination with iodides and / or phosphorus compounds and salts of divalent manganese.

Basic costabilizers , such as polyvinylpyrrolidone, melamine, benzoguanamine, triallyl cyanurate, dicyandiamide, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes and alkali metal salts and alkaline earth metal salts of higher saturated or unsaturated fatty acids, e.g. calcium stearate, sodium stearate, K-palmitate and Zn-stearate.

PYC stabilizers , such as organic tin compounds, organic lead compounds and Ba / Cd salts of fatty acids.

Nucleating agents such as 4- tert -butylbenzoic acid, adipic acid and diphenylacetic acid.

Other additives such as plasticizers, lubricants, e.g. glycerol monostearate, emulsifiers, antistatic agents, fire retardants, pigments, carbon black, asbestos, glass fibers, kaolin and talc. ·

The following examples illustrate the invention.

409882/1040

In Examples 1 to 6 below, compositions comprising a synthetic polymer and incorporated therein contain a dipiperidyl derivative of the formula I according to the invention, and the stabilizing one achieved with the aid of the dipiperidyl derivative Effect illustrated. Examples 7 and 8 describe methods of making dipiperidyl derivatives of formula I illustrated.

example 1

0.25 parts by weight of a stabilizer according to the invention were mixed with 100 parts by weight of a polypropylene ("Noblen JHH-G", Trade name of Mitsui Toatsu Chemicals Inc.j recrystallized twice from chlorobenzene) melt-mixed, and the mixture was formed into a sheet with a thickness of 0.5 mm under pressure. The sheets so produced were in one Fadeometer exposed to ultraviolet light rays at 45 ° C, and the time required for the sheet to become brittle was determined.

The results are given in Table I.

Example 2

0.25 parts by weight of a stabilizer according to the invention with 100 parts by weight of a high density polyethylene ("Hi-zex", trade name of Mitsui Toatsu Chemicals Inc.j recrystallized twice from toluene) melt blended and the mixture became a sheet of starch under pressure shaped by 0.5 mm. The sheets thus prepared were subjected to ultraviolet light irradiation at 45 ° C in a fadeometer and the time required for the "sheet to become brittle was determined."

The results are given in Table I.

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- 18 Table I.

Stabilizer compound no,

Polypropylene

High density polyethylene

1 2 4 6 8 21

900 hours 2060 hours 840 1900 1120 2380 940 2080 700 1340 780 1820

no stabilizer

60

400

Example 3

In 100 parts by weight of a polystyrene (. "Styron", trade name of the Asahi Dow Limited; recrystallized from benzene / methanol) 0.25 part by weight of a stabilizer according to the invention was introduced, and the mixture was made into a under pressure at 180 ° C Compression molded plate with a thickness of 1.5 mm. This plate was made in a xenon fadeometer (1.5 kW; model FX-I by Toyo Rika) irradiated for 3000 hours. The change in the yellowness index of the test sample treated in this way was under Use of a Japanese color difference colorimeter Industrial Standard-K 7103 intended. The change in yellowness - Index was calculated according to the following equation:

/ 1 YI = YI - YIo

YI: change in yellowness index, YI: post-exposure yellowness index; and YIo: the initial yellowness index of the test sample mean..

The results are given in Table II.

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- 19 -
Table II stabilizer
Connection no. Example 4 YIo 2 ' 1
2
4th
6th 1.8
1.9
2.0
1.8 no stabilizer 1.8 Δ ^ΥΙ 8.0
8.6
8.2
7.8 35.2

0.25 part by weight of a stabilizer according to the invention was 100 parts by weight of a 6-nylon resin ("CM 1Ο11", trade name from Toray Industries Inc.) and the mixture melt blended. The melted mixture was molded under pressure into a film with a thickness of about 0.1 mm by means of a molding press.

The obtained film was subjected to an accelerated aging test under the following conditions, and then to Subjected to elongation test to determine elongation retention amount and tensile strength retention amount.

Aging conditions: '

1) Exposure to ultraviolet light in a fadeometer at 45 ° C for 200 hours.

2) Aging by heating in a compressed air oven at 160 ° C for 2 hours.

The results are given in Table III.

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Table III

Fadeometer stabilizer

Sator extent of the extent of the tension-connection- elongation strength No. retention,% retention,%

Air oven

Extent of the extent of elongation tensile strength. retention, % retention,%

2
6th

70 75

63 69

69 73

no stabilizer

53

18th

55

Example 5

0.5 part by weight of a stabilizer of the present invention became 100 parts by weight of a polycaprolactone type polyurethane ("Elastollan E-508O", trade name of Nippon Elastollan Industries Ltd.) was added and the mixture was heated, melted and then into a sheet about 0.5mm shaped.

The thus prepared sheets were subjected to ultraviolet light irradiation in a fadeometer at 45 ° C, and the times to be brittle were measured, and then an elongation test was carried out to determine the extent of retention of elongation and tensile strength. The results are given in Table IV.

. Table IV

Stabilizer compound no,

Extent of elongation retention, %

Extent of tensile strength retention, %

87 80 83

89 77 85

no stabilizer

Ί?

53

409882 / 104Q

Example 6

In 100 parts by weight of a polyester resin ("Ester-G13", trade name from Mitsui Toatsu Chemicals, Inc.) 1 part by weight of benzoyl peroxide and 0.2 part by weight of one of the present invention Stabilizer was incorporated and the mixture was stirred thoroughly. The mixture was heated to 60 ° C. for 30 minutes preheated and hardened by heating at 100 ° C. for 1 hour to obtain a plate with a thickness of 3 mm. This plate was placed in a weathering apparatus for 60 hours (Sunshine Weather-Meter), and the change in yellowness index was observed in the same manner as in Example 3 determined. The results are given in Table V. '

Tabel V / \ YI +8.4
+8.1
+ 8.7 stabilizer
Connection no. YIo +13.3 1
4th
6th 2.6
2.4
2.2 no Sta
bilizer 1.9 Example 7

31 g of triacetonamine were dissolved in 300 ml of toluene, and to the 18 g of acetic acid were added to the solution. The mixture was heated to 90-105 ° C. with stirring.

To the above solution, 7 g of metallic sodium was gradually added in the form of small pieces. After the metallic Sodium had completely dissolved, the reaction mixture was cooled and the crystals precipitated were separated by filtration. The filtrate was concentrated, and the residual crystals were recrystallized from benzene, whereby 27.4 g of the desired 4,4'-dihydroxy-2,2,6,6,2 ', 2', 6 ·, 6'-octamethyl-4,4'- dipiperidylS in the form of whiter

409882/1040.

Crystals of mp = 177 to 178 ° C were obtained. The yield was 87.7 %.

Analysis: ^c -i8 ^H 36 ^N 2 ^O 2

Calculated: C 69.18 H 11.61 N 8.77% Found: 69.05 11.53 8.73 %

IR spectrum (in Nujol):

y GH 3500 cm " ¹ and 3370 cm"¹; VNH 3280 cm " ¹ and 3240 cm" ¹ .

Example 8

3.1 g of 4,4 ^I -dihydroxy-2,2,6,6,2 ', 2 ^t , 6', 6'-octamethyl-4,4 ^f -dipiperidyl, obtained according to Example 7, 3.6 g of allyl bromide , 4.5 g of calcium hydrogen carbonate and 0.5 g of p-toluenesulfonic acid were added to 30 ml of dimethylformamide, and the mixture was heated to 120 ° to 130 ° C. for 5 hours with stirring.

The obtained reaction mixture was concentrated and the residue was dissolved in benzene, washed with 5% aqueous sodium hydrogen carbonate solution and then with water, dried over anhydrous potassium carbonate and concentrated. The remaining crystals were recrystallized from benzene to give the desired 1,1 'diallyl-4,4'-dihydroxy - ^, 2,6,6,2 ·, 2' ^l -6, 6'-octamethyl-4,4 '-dipiperidyl were obtained in the form of white crystals with a melting point of 127 to 128 ° C.

Analysis: C ₃₄ H ₄₄ N ₃ O ₂

Calculated: C 73.42 H 11.30 N 7.14 % Found: 73.33 11.24 7.21 %

IR spectrum (in Nujol):

yf OH 3520 cm " ¹ , VC = C 1640 cm" ¹ .

The following compounds can be obtained by essentially the same method as described in Example 8:

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4,4 · - Dihydroxy-1,2,2,6,6,1 ·, 2 ·, 2 ·, 6 ', 6'-

decamethyl-4,4'-dipiperidyl m.p. 148-149 ° C

1,1'-dibenzyl-4,4 »-dihydroxy-2,2,6,6-

2, 2, 6 ^f , 6 ^f -octamethyl-4,4'-dipiperidyl F = 216-217 ° C

4,4'-dihydroxy-1,1'-bis- (2-hydroxyethyl-2,2,6,6,2 ', 2 ·, 6', 6 • -octamethyl-4,4 • -dipiperidyl F = 286-288 ° C

1,1'-bis (2-ethoxyethyl) -4,4 · dihydroxy-2,2,6,6,2 ', 2', 6 *, 6'-octamethyl-4,4'-dipiperidyl F = 167-169 ° C

2, 2,6,6, .2 ·, 2 ·, 6 ·, 6 · ^ octamethyl-4,4'-dipiperidyl F = 2O6-2O7.5 ° C

1,1 · -Bis- (2-acetoxyethyl) -4,4 · -dihydroxy-2,2,6,6,2 ^l , 2 ^l , 6 ^l , 6'-octamethyl-4,4'-dipipf

1,1 '-Bis- (2 - * - crotonoyloxyethyl) -4,4' -dihydroxy-2,2,6,6,2 ·, 2 ·, 6 ·, 6 · octamethyl-4,4 · dipiperidyl F = 146.5-148 ⁶ C

4,4 * -dihydroxy-1,1'-bis- (2,3-epoxypropy1) -2,2,6,6,2 ', 2', 6 *, 6 * -octamethyl ~ 4,4'-dipiperidyl F = 16 7-169 ° C

1-acetyl-4,4'-dihydroxy-2,2,6,6,2 ', 2 ·, 6', 6 · -

octamethyl-4,4'-dipiperidyl M = 139-14O ° C

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Claims (8)

Claims 1.) Synthetic stabilized against photo- and heat decomposition Polymer composition, in which in sufficient amount to prevent decomposition, a compound of the formula ^CH 3 / ^CH 3 CH3CH3 or an acid addition salt thereof is incorporated, in which R and R ¹ , which may be the same or different, are each hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an aliphatic or aromatic acyloxyalkyl group, a cyanoalkyl group, mean a haloalkyl group, an epoxyalkyl group, an alkoxycarbonylalkyl group, an aliphatic acyl group, an alkoxycarbonyl group or an aralkoxycarbonyl group. 2.) Synthetic polymer composition according to claim 1, characterized in that R and R ', which can be the same or different, each denote hydrogen, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 3 to 6 carbon atoms _f an alkynyl group having 3 or 4 carbon atoms, an aralkyl group with 6 carbon atoms in the aryl part and 1 or 2 carbon atoms in the alkyl part, a hydroxyalkyl group with 1 to 4 carbon atoms, an alkoxyalkyl group with 1 to 8 carbon atoms in the alkoxy part and 1 to 4 carbon atoms in the alkyl part, an aliphatic acyloxyalkyl group, the acyl part of which is either is saturated and has 2 to 18 carbon atoms or is unsaturated and has 3 to 6 carbon atoms and its alkyl part has 1 to 4 carbon atoms 4Ö9882 / 10A0 has an aromatic acyloxyalkyl group, its more aromatic Ring with 1 to 3 substituents selected from alkyl with 1 to 4 carbon atoms and hydroxy, substituted and the alkyl part of which contains 1 to 4 carbon atoms, a cyanoalkyl group with 2 or 3 carbon atoms, a haloalkyl group with 1 to 3 carbon atoms, a 2,3-epoxypropyl group, an alkoxycarbonylalkyl group with 1 to 18 carbon atoms in the alkoxy part and 1 or 2 Carbon atoms in the alkyl part, an aliphatic acyl group, which can be saturated and contain 2 to 8 carbon atoms or can be unsaturated and 3 or 4 carbon contains atoms, an alkoxycarbonyl group having 2 to 9 carbon atoms or a benzyloxycarbonyl group. 3.) Synthetic polymer composition according to claim 1, characterized in that both R and R ^{1 are} hydrogen, an alkyl group with 1 to 4 carbon atoms, the allyl group, the benzyl group, an alkoxyalkyl group with 1 to 4 carbon atoms in the alkoxy part and 1 or 2 Carbon atoms in the alkyl part, an aliphatic acyloxyethyl group, the acyl part of which is either saturated and contains 2 to 18 carbon atoms or is unsaturated and contains 3 to 6 carbon atoms in the acyl part, a benzoyloxyethyl group whose benzene nucleus has 1 to 3 substituents, selected from Alkyl with 1 to 4 carbon atoms, and hydroxy can be substituted, or an alkoxycarbonylmethyl group with 1 to 8 carbon atoms in the alkoxy part * 4.) Synthetic polymer composition according to claim 1, characterized characterized in that both R and R 'are hydrogen, an "alkyl group with 1 to 4 carbon atoms, the allyl group, denotes the benzylhr group or an alkoxycarbonylmethyl group having 1 to 8 carbon atoms in the alkoxy part. 5.) Synthetic polymer composition according to claim 1, characterized characterized in that the compound of formula (I) or an acid addition sala thereof in an amount of 4098Ö2 / 1Q4O 0.01 to 5.0% by weight, based on the amount of the synthetic polymer, is incorporated. 6.) Synthetic PolyraerzusaTtiraensetzung according to claim 1, characterized characterized in that the polymer is a polyolefin. 7.) Synthetic polymer composition according to claim 1, characterized characterized in that the polymer is selected from the group consisting of a polyvinyl chloride, a Polyvinylidene chloride, a polyacetal, a polyester, a polyester ether, a polyamide, a polyurethane, a polycarbonate and an epoxy resin. 8.) Synthetic polymer composition according to claim 1, characterized in that the compound of formula (I) is selected from the group consisting of 4,4 »-dihydroxy-2,2,6,6,2 ^r , 2 ', 6', 6'-octamethyl-4,4'-dipiperidyl, 4,4'-dihydroxy-1,2,2,6,6,1 ', 2', 2 ', 6 ·, 6'-decamethyl-4,4'- dipiperidyl, l, l ^l -diallyl-4,4'-dihydroxy-2,2,6,6,2 ^t , 2 ^l , 6 ', 6'-octa- · methyl-4,4'dipiperidyl, 1,1'-dibenzyl-4,4'-dihydroxy-2,2,6,6,2 ', 2', 6 ·, 6'-octamethyl-4,4'-dipiperidyl and 1,1'-bis (ethoxycarbonylmethyl) -4,4'-dihydroxy-2,2,6,6- 2 ', 2 ·, 6 ·, 6'-octamethyl-4,4'-dipiperidyl. 409882/1040