AT324009B

Piperidine derivatives

Abstract

This record has no abstract on file.

AT324009B, drawing sheet 1 — Sheet 1 of 13

Term

Term ended

Expired 30 November 1992, 33.8 years ago.

8 claims: 3 independent, 5 dependent

1
CLAIMS:(I) 5 or their salts, where η is 1, 2 or 3, R x an alkyl group having 1 to 12 carbon atoms or a substituted alkyl group of the formula -CH 2 -CH 2 -X 1 or -CH 2 ~ X 2 means, where Χ χ -OH, -OCH, -OCR, or -OC-NH-R, 3 II 3 II 4 oo 10 is, x 2 Phenyl, -CH = CH 2 , CN, -CH-CH 2 or -C-ORj O is, R 3 Alkyl having 1 to 20 C atoms, alkenyl having 2 to 4 C atoms, aryl having 6 or 7 C atoms or aralkyl having 7 or 8 C atoms, R 4 Alkyl having 1 to 12 C atoms, cyclohexyl or aryl having 6 or 7 C atoms, ^ denotes alkyl having 1 to 20 C atoms, alkenyl having 3 or 4 C atoms or cyclohexyl, 15 and Rj, if η = 1, represents a monovalent group, u. either a cyanoethyl group or a benzyl group or an acyl group CR. II 6 O where R G Hydrogen, benzyl, vinyl, propenyl, cyclohexyl, a group tert. CH I 4 H ch-ch 2 /, -OH or - z O-- 0H x ^ / ii tert. C 4 H 9 tert. C 4 H 9 20 Alkyl having 1 to 20 carbon atoms or aryl having 6 to 10 carbon atoms, or R 2 a carbamoyl group -C-NH-R, II 7 O is where R ? Alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 12 carbon atoms or aryl of 6 to 11 carbon atoms, or, if n = 2, R 2 represents a divalent group, u. either one of the groups - C-, -CC-, -CRC- or -C-NH-R - NH-CII II II II 8th II II 9 11 ooooo oo No. 324009 wherein Rg is an alkylene group having up to 18 carbon atoms, a phenylene group or the group - (CH 2 ) -S- (CH 2 ) and Rg is an alkylene group having up to 20 C atoms, a cycloalkylidene radical having 5 to 15 C atoms or an arylene group having 6 to 15 C atoms, or R 2 is a divalent group obtained by removing two hydroxyl groups from a phosphorus-containing acid, or when n = 3, Rj represents a trivalent group derived from phosphorous acid, phosphoric acid or boric acid, with the proviso that if OOOOOO or a trivalent group means the number of carbon atoms of R 1 designated alkyl group is limited to 5 to 12,
5
5, Process according to claims 1 to 4, characterized in that the polymeric material is a polyolefin or an olefin copolymer.
6
6th Process according to claims 1 to 4, characterized in that the polymeric material is one containing the recurring group -C-NH, preferably a polyamide or polyurethane.

Independent claims3

617 paragraphs in 17 sections, as filed

OE 324009 © Pamphlets considered to delineate the prior art:

DT-0S2040983, DT-OS2043748, DT-OS 1770689, ÖS-PS3640928

No. 324009

The invention relates to a method of stabilizing polymeric material against the damaging one

Influence of light and / or heat, using piperidine derivatives.

In the German patent application 1929 928 and the corresponding US Pat. No. 3,640,928 are - with reference to the suitability as stabilizers for plastics - compounds of the general formula

n, wherein R and R are the same or different and each represent an alkyl group or, together with the carbon atom to which they are bonded, a saturated alicyclic group or a group of the formula

CH.

'3 .CH,

n is an integer from 1 to 3, inclusive, and when η 'is 1, R j is an acyl group derived from an aliphatic, alicyclic or heterocyclic monocarboxylic acid, an N-substituted carbamoyl group other than an N- derived substituted carbamic acid, an N-substituted thiocarbamoyl group derived from an N-substituted thiocarbamic acid, a monovalent group, which was obtained by removing a hydroxyl group from an oxo acid, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group or a group of the formula

CH. CH3

kl '

ΓΗ /

wherein R ^ and Ri have the meaning given above.

If n '2 means R3 a diacyl group derived from an aliphatic, alicyclic, aromatic or heterocyclic dicarboxylic acid, a dicarbamoyl group derived from a dicarbamic acid, a bis-thiocarbamoyl group derived from bis-thiocarbamic acid, a carbonyl group, a divalent group which is represented by Removal of two hydroxyl groups from an oxo acid obtains, an alkylene group, an arylene group or a Arylend ialkylengruppe.

When n> 3, Rj represents a triacyl group derived from an aliphatic, alicyclic, aromatic or heterocyclic tricarboxylic acid, a tricarbamoyl group derived from tricarbamic acid, a tris-thiocarbamoyl group derived from tris-thiocarbamic acid, a trivalent group obtained by removing three hydroxyl groups from an oxo acid, an alkanetriyl group, arenetriyl group or an arenetriyl trialkylene group.

It has now been found that certain piperidine derivatives substituted at the 1 and 4 positions are effective stabilizers for polymers, particularly degradation due to light or heat.

The invention relates to a method for stabilizing polymeric material against the damaging effect of light and / or heat, using piperidine derivatives, characterized by the addition of a compound of formula

No.324009 or salts thereof, wherein η is 1, 2 or 3, R is an alkyl group having 1 to 12 C atoms or a substituted one

Alkyl group of the formula wherein X is X, X,

(I)

-CH2-CH2-X1 or -CH2~ X2

-OH, -OCH ,, -OCR, or -OC-NH-R.

3 II 3 II 4 oo

Phenyl, -CH = CH2, CN, -CH-CH2 or -C-ORg ^ O ^, Rj is alkyl having 1 to 20 C atoms, alkenyl having 2 to 4 C atoms, aryl having 6 to 7 C atoms or aralkyl having 7 or 8 C atoms, R4 Alkyl having 1 to 12 C atoms, cyclohexyl or aryl having 6 or 7 C atoms, Rg is alkyl having 1 to 20 C atoms, alkenyl having 3 or 4 C atoms or cyclohexyl, and R ^ if η = 1 is a monovalent group, u, zw. either a Cyanoäthylgruppe or a benzyl group or an acyl group -C-R "where R is hydrogen, benzyl, vinyl, propenyl, cyclohexyl, a group tert.CH ι y tert, C4H9

-CH-CH- / q \ _OH or _ / Q \ _OH tert. CH

y tert. C4HG

Alkyl having 1 to 20 carbon atoms or aryl having C to 10 carbon atoms, or R2 a carbamoyl group

-C-NH-R.

is where R? Alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 12 carbon atoms or aryl of 6 to 11 carbon atoms, or if n = 2, Rjj represents a divalent group, and the like; either one of the groups

Τ 'o

-CC-,

II 0 o

-CRC- or

II 8th II oo

-C-NH-R_-NH-C-,

II II in which RG an alkylene group having up to 18 carbon atoms, a phenylene group or the group

- (CH2)2-S- (CH2)2and Rj represents an alkylene group having up to 20 C atoms, a cycloalkylidene radical having 5 to 15 C atoms or an arylene group having 6 to 15 C atoms, or R2 means a divalent group that you get

No. 324009 when removing two hydroxyl groups from a phosphorus-containing acid, or when n = 3, R2 represents a trivalent group derived from phosphorous acid, phosphoric acid or boric acid, with the proviso that when R2

OO OO

OO or a trivalent group means the number of carbon atoms of R1 designated alkyl group is limited to 5 to 12.

If Rx or R4 is an alkyl group having 1 to 12 carbon atoms, this may be, for example, a methyl,

Ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or π-dodecyl group.

Rj, Rg, RG and R? in the meaning of alkyl having 1 to 20 C atoms, for example, the groups listed above may represent, but they may also represent an n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl group.

For optimum compatibility with polyolefin substrates, preferred compounds are those wherein the alkyl substituents Rx and / or R4 5 to 12 and the alkyl substituents R3, Rg, RG or R7 Contain 5 to 20 carbon atoms.

When Rg is an alkenyl group having 3 or 4 C atoms, it may be, for example, propenyl, allyl or methallyl. R3 in the meaning of alkenyl having 2 to 4 carbon atoms may mean the same radicals, in addition also vinyl.

Rg and R4 in the meaning of aryl having 6 or 7 carbon atoms may be phenyl or tolyl, RG and R? in the meaning of aryl having 6 to 10 or 6 to 11 carbon atoms, moreover, higher alkylated phenyl radicals such as. B. butylphenyl or dimethylphenyl or a naphthyl radical.

When Rg is an aralkyl group having 7 or 8 carbon atoms, it may be, for example, benzyl, .beta.-phenylethyl or .alpha.-phenylethyl.

R? in the meaning of cycloalkyl having 5 to 12 carbon atoms, for example, cyclopentyl, methylcyclopentyl, cyclohexyl, butylcyclohexyl, dimethylcyclohexyl or Decahydronaphthyl be.

Of the divalent hydrocarbon radicals, Rg can be an alkylene group of up to 18 carbon atoms and Rg an alkylene group of up to 20 carbon atoms. Examples of such groups are the ethylene, trimethylene, tetramethylene, hexamethylene, dodecamethylene or octadecamethylene group. Means RG a cycloalkylidene group having 5 to 15 carbon atoms, it may be, for example, 1,4-cyclohexylidene, hexahydro-p-xylylene, 1,4-decahydronaphthylene or 2, 5-dimethyl-1,4-cyclohexyliden act.

If Rg is an arylene group having 6 to 15 carbon atoms, this can be done, for example, by B. 1,4-phenylene, 1,3-phenylene,

1,5-naphthylene, 1,4-naphthylene, 4,4'-diphenylenemethane or 5-methyl-l, 2-phenylene.

Preference is given to compounds of the formula (I) or salts thereof in which η is 1, 2 or 3, Rx an alkyl group having 1 to 12 C atoms, a benzyl group, a hydroxyethyl group or a group

Alk-OC-CH and Alk is an alkyl group having 1 to 3 carbon atoms, Rg, if η = 1, means a monovalent group, u. zw, either a cyanoethyl group or a benzyl group or an acyl group

-CR, where RG Benzyl, cyclohexyl, a group

tert. C4 HG tert.CH 4 9

Alkyl having 1 to 20 carbon atoms or aryl having 6 to 10 carbon atoms, or R2 a carbamoyl group

No. 324009

c-nh-r7

O is where R? Alkyl having 1 to 18 carbon atoms or aryl having 6 to 10 carbon atoms, or, if n = 2, R2 represents a divalent group, u. between one of the groups

-CRC- or -C-NH-R-NH-Cit * ii-li y ii where Rg is an alkylene group having up to 8 C atoms or a phenylene group and RG an alkylene group having up to 6 C atoms or an arylene group having 6 to 10 C atoms, or, if n = 3, R2 represents a boric acid residue, with the proviso that if R2

-SR6 ·

CR-C4 4 or the boric acid residue means the number of carbon atoms of Rx designated alkyl group is limited to 5 to 12 be10.

Depending on whether it is R2 is an optionally substituted alkyl radical, an acyl radical or a carbamoyl radical, the substances which can be used according to the invention for stabilizing polymers are ethers, esters or urethanes of N-substituted 2,2,6,6-tetramethyl-4-hydroxypiperidines, of which the esters and the urethanes are meaningful in the foreground.

Amongst the esters to be emphasized are the compounds of the formula

1 > _ / II / \ 0 _ CH3 n or salts thereof, wherein η is 1 or 2, Rx represents an alkyl group having 5 to 12 C atoms, an allyl or benzyl group, and R10when η = 1, hydrogen, cyclohexyl, vinyl, propenyl, benzyl, alkyl having 1 to 20 carbon atoms or aryl having 6 to 10 carbon atoms, and when n = 2, an alkylene group mitlbisl8 C-atoms or a group

ch-ch-ch-ch-s2means.

Among the urethanes are the compounds of formula CH3 /CH3

R -N ^ \ _O-C-NH1 \ - / II o ch3 chs or their salts, where η is 1 or 2, Rx an alkyl group having 1 to 12 C atoms, an allyl or benzyl group, and Ruwhen η = 1, an alkyl group having 1 to 20 C atoms, a cycloalkyl group having 5 to 12 C atoms or an aryl group having 6 to 12 C atoms or, when n = 2, an alkylene group having up to 20 C atoms, a cycloalkylidene group having 5 to 15 carbon atoms or an arylene group having 6 to 15 carbon atoms.

The meaning that Rlo and Rlx as alkyl, aryl or cycloalkyl, the same for RG or R? quoted meaning. R ^ in the meaning of alkylene corresponds to that for R8th given meaning and the meaning of Ru as alkylene, cycloalkylidene or arylene corresponds to that for RG meaning indicated.

No. 324009

Examples of compounds which can be used according to the invention in which η is 1 are, for example:

4-benzyloxy-1,2,2,6,6-pentamethylpiperidine,

4- (2-cyanoethylcyclo) -l, 2,2,6,6-pentamethylpiperidine, ln -dodecyl-4-benzyloxy-2,2,6,6-tetramethylpiperidine, ln-octadecyl-4- (2'-cyanoethoxy ) 2,2,2,6-tetramethylpiperidine, 1-allyl-4-benzyloxy-2,2,6,6-tetramethylpiperidine, 1-benzyl-4-benzyloxy-2,2,6,6-tetramethylpiperidine, (2'-hydroxyethyl) -4-benzyloxy-2,2,6,6-tetramethylpiperidine, 1- (cyanomethyl) -4-benzyloxy-2,2,6,6-tetramethylpiperidine, 1- (cyanomethyl) -4- ( 2'-cyanoethoxy) -2,2,6,6-tetramethylpiperidine, l- (2 ', 3'-epoxypropyl) -4-benzyloxy-2,2,6,6-tetramethylpiperidine, 1- (2'-methoxyethyl) -4-benzyloxy-2,2,6,6-tetramethylpiperidine, 1- (2'-acetoxyethyl ) -4-benzyloxy-2,2,6,6-tetramethylpiperidine, 1- (2'-benzoyloxyethyl) -4- (2'-cyanoethoxy) -2,2,6,6-tetramethylpiperidine,

1- [21- (methylcarbamoyloxy) ethyl] -4-benzyloxy-2,2,6,6-tetramethylpiperidine, 1- [2 '- (phenylcarbamoyloxy) ethyl] -4- [2' - (cyanoethoxy)] - 2,2,6,6-tetramethylpiperidine,

1- [2 '- (ethoxycarbonyl) methyl] -4- (2'-cyanoethoxy) -2,2,6,6-tetramethylpiperidine, ln -octyl-2,2,6,6-tetramethylpiperidinyl-4-benzoate, ln -dodecyl-2,2,6,6-tetramethylpiperidinyl-4-n-octanoate, ln-dodecyl-2,2,6,6-tetramethylpiperidyln-4-p-chlorobenzoate, 1-allyl-2,2, 6,6-tetramethylpiperidinyl-4-n-octanoate, 1-allyl-2,2,6,6-tetramethylpiperidinyl-4-cyclohexanecarboxylate, 1-allyl-2,2,6,6-tetramethylpiperidinyl-4-benzoate, Benzyl 2,2,6,6-tetramethylpiperidinyl-4-n-octanoate, 1-Benzyl-2,2,6,6-tetramethylpiperidinyl-4- (2'-ethylhexanoate), 1-benzyl-2,2,6,6-tetramethylpiperidinyl-4-stearate, 1-benzyl-2,2,6 , 6-tetramethylpiperidinyl-4-benzoate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethylpiperidinyl-4-acetate, 1- (21-hydroxyethyl) -2,2,6,6-tetramethylpiperidinyl 4-laurate, 1- (2'-hydroxyethyl) -2,2,6,6-tetramethylpiperidinyl-4-stearate, 1- (2'-hydroxyethyl) -2,2,6,6-tetramethylpiperidinyl-4-benzoate , 1- (cyanomethyl) -2,2,6,6-tetramethylpiperidinyl-4-benzoate, 1- (2 ', 3'-epoxypropyl) -2,2,6,6-tetramethylpiperidinyl-4-acetate, 1- (2-acetoxyethyl) -2,2,6,6-tetramethylpiperidinyl-4-laurate,

1- [2 '- (methylcarbamoyloxy) ethyl] -2,2,6,6-tetramethylpiperidinyl-4-benzoate,

1- [2i- (phenylcarbamoylaxy) ethyl] -2,2,6,6-tetramethylpiperidinyl-4-isobutyrate, 1-ethoxycarbonylmethyl-2,2,6,6-tetramethylpiperidinyl-4-p-methoxybenzoate, 4-methylcarbamoyloxy -l, 2,2,6,6-pentamethylpiperidine,

4-Isopropylcarbamoyloxy-l, 2,2,6,6-pentamethylpiperidine,

4-tert. Butylcarbamoyloxy-1,2,2,6, 6-pentamethylpiperidine,

4-n-hexylcarbamoyl-1,2,2,6,6-pentamethylpiperidine,

4- (2'-ethylhexylcarbamoyloxy) -1,2,2,6,6-pentamethylpiperidine,

4-n-dodecylcarbamoyloxy-l, 2,2,6,6-pentamethylpiperidine,

4-n-octadecylcarbamoyloxy-1,2,2,6,6-pentamethylpiperidine,

4-Cyclohexylcarbamoyloxy-l, 2,2,6,6-pentamethylpiperidine, 4- (3'-methylcyclohexylcarbamoyloxy) -l, 2,2,6,6-pentamethylpiperidine, 4- (4'-tert-butylcyclohexylcarbamoyloxy) -l , 2,2,6,6-pentamethylpiperidine, 4-cyclohexylmethylcarbamoyloxy-l, 2,2,6,6-pentamethylpiperidine,

4-phenylcarbamoyloxy-l, 2,2,6, 6-pentamethylpiperidine,

4-m-tolylcarbamoyloxy-1,2,2,6,6-pentamethylpiperidine,

4-p-tolylcarbamoyloxy-1,2,2,6,6-pentamethylpiperidine,

4-a-naphthylcarbamoyloxy-l, 2,2,6,6-pentamethylpiperidine, 4-cyclohexylcarbamoyloxy-l-ethyl-2,2,6,6-tetramethylpiperidine, 4-methylcarbamoyloxy-ln-propyl-2,2,6, 6-tetramethylpiperidine,

4-methylcarbamoyloxy-l-sec. -butyl-2,2,6,6-tetramethylpiperidine, 4-n-octadecylcarbamoyloxy-in-butyl-2,2,6,6-tetramethylpiperidine, 4-methylcarbamoyloxy-ln-octyl-2,2,6,6-tetramethylpiperidine .

4-phenylcarbamoyloxy-l-allyl-2,2,6,6-tetramethylpiperidine,

4-phenylcarbamoyloxy-1-benzyl-2,2,6,6-tetramethylpiperidine,

4-methylcarbamoyloxy-1- (2'-hydroxyethyl) -2,2,6,6-tetramethylpiperidine,

No. 324009

7-methylcarbamoyloxy-1- (2 ', 3'-epoxypropyl) -2,2,6,6-tetramethylpiperidine,

4-carbamoyl-o- (2'-methoxyethyl) -2,2,6,6-tetramethylpiperidine,

4-dimethylcarbamoyloxy-1- (2'-acetoxyethyl) -2,2,6,6-tetramethylpiperidine,

4-n-Hexylcarbamoyloxy-l- [2 '- (methylcarbamoyloxy) ethyl] -2,2,6,6-tetramethylpiperidine;

Examples in which n 2 means:

(Ln-octyl-2,2,6,6-tetramethyl-4-piperidinyl) sebacate bis-,

(Ln-dodecyl-2,2,6,6-tetramethyl-4-piperidinyl) adipate bis-,

Bis (1-allyl-2,2,6,6-tetramethyl-4-piperidinyl) adipate,

Bis (1-allyl-2,2,6,6-tetramethyl-4-piperidinyl) thiopheny-2 ', 5'-dicarboxylate,

Hexane-l ', 6'-bis- (4-carbamoyloxy-l, 2,2,6,6-pentamethylpiperidine,

2 ', 4', 4'-trimethylhexane-1 ', 6'-bis- (4-carhamoyloxy-1,2,2,6,6-pentamethylpiperidine),

Cyclohexane-l, 3'-bis (4-carbamoyloxy-l, 2,2,6,6-pentamethylpiperidine),

Benzene-1 ', 4'-bis (4-carbamoylaxyl-1,2,2,6,6-pentamethylpiperidine),

Toluene-2 ', 4'-bis (4-carbamoyloxy-l, 2,2,6,6-pentamethylpiperidine),

Naphthalene-l ', 5> -bis (4-carbamoylaxy-l, 2,2,6,6-pentamethylpiperidine),

Diphenylmethane-4 ', 4 l'bis- (4-carbamoyloxy-l, 2,2,6, 6-pentamethylpiperidine),

Toluene-2 ', 4'-bis (4-carbamoyloxy-ln-propyl-2,2,6,6-tetramethylpiperidine),

Hexane-l ', 6'-bis (4-carbamoyloxy-in-butyl-2,2,6,6-tetramethylpiperidine),

Hexane-l6'-bis- (4-carbamoyloxy-ln-octyl-2,2,6,6-tetramethylpiperidine),

2 ', 4', 4'-trimethylhexane-l ', 6'-bis- (4-carbamoyloxy-ln-octadecyl-212,6,6-tetramethylpiperidine),

Cyclohexane-l ', 4'-bis- (4-carbamoyloxy-1-yllyl-2,2,6,6-tetramethylpiperidine),

2 ', 4', 4'-trimethylhexane-l ', 6'-bis- (4-carbamoyloxy-l-allyl-2,2,6,6-tetramethylpiperidine),

Toluene-2 ', 4'-bis (4-carbamoyloxy-1-benzyl-2,2,6,6-tetramethylpiperidine),

Toluene-2,4-bis [4-carbamoyloxy-l- (2'-hydroxyethyl) -2,2,6,6-tetramethylpiperidine],

Diphenylmethane-4 ', 4-bis- [4-carbamoyloxy-1- (2'-cyanoethyl) -2,2,6,6-tetramethylpiperidine,

Toluene 2, 4 "-bis [4-carbamoyloxy-1- (2-acetoxyethyl) -2,2,6,6-tetramethylpiperidine,

Hexane-1,6-bis [4-carbamoyloxy-1- (2'-methylcarbamoylethyl) -2,2,6,6-tetramethylpiperidine];

Examples in which n 3 means:

phosphite tris (l-hexyl-2,2,6,6-tetramethyl-4-piperidinyl)

Tris (1-octyl-2,2,6,6-tetramethyl-4-piperidinyl) phosphate,

borate tris (l-dodecyl-2,2,6,6-tetramethyl-4-piperidinyl)

Tris (1-allyl-2,2,6,6-tetramethyl-4-piperidinyl) -phosphate,

Tris (1-benzyl-2,2,6,6-tetramethyl-4-piperidinyl) borate,

Tris- [1- (2'-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinyl] phosphate,

The invention also relates to the use of salts of the compounds of the formula (I). For example, salts of inorganic acids, such as the phosphates, carbonates, sulfates and chlorides, and salts of organic acids, such as ζ. Acetates, stearates, maleates, citrates, tartrates, oxalates, benzoates.

Examples of such salts are:

4-benzyloxy-l, 2,2,6,6-pentamethylpiperidine hydrochloride,

Bis (1-hexyl-2,2,6,6-tetramethyl-4-piperidinyl) sebacate sulfate,

Octyl-2,2,6,6-tetramethylpiperidinyl-4-β- (3 ', 5'-di-tert, -butyl-4'-hydroxyphenyl) -propionate bicarbonate,

4-methylcarbamoyloxy-l, 2,2,6,6, camoylpiperidine acetate,

1, 6-bis- (4'-carbamoyloxy-l ', 2', 2 ', 6', 6> -pentamethylpiperidine) hexane stearate,

4-phenylcarbamoyl-l, 2,2,6,6-pentamethylpiperidine benzoate, 1-benzyl-2,2,6,6-tetramethylpiperidinyl-4-n-octanoate-35'-di-tert. butyl-4'-hydroxybenzoate,

4- (2'-Cyanoethoxy) -1,2,2,6,6-pentamethylpiperidine hydrogen maleate,

4-Stearylcarbamoyloxy-l, 2,2,6,6-pentamethylpiperidine citrate, 1- (2'-hydroxyethyl) -2,2,6,6-tetramethylpiperidinyl-4-n-octanoate tartrate.

The novel compounds which can be used according to the invention can be prepared by processes known per se. So can ζ. B. 2,2,6,6-tetramethyl-4-hydroxypiperidine first in the 1-position by a Rx Substituted previously substituted radical, and the N-substituted 4-hydroxypiperidinol thus obtained is then converted by a known method of etherification, esterification or by reaction with an isocyanate in the respective ether, ester or urethane.

Alternatively, one may substitute 2,2,6,6-tetramethyl-4-hydroxypiperidine first at the hydroxyl group and then carry out the substitution of the NH group. For the substitution of the NH group, which is sterically hindered in the present case, is suitable in particular, the reaction with ethylene oxide to form the N-, hydroxyethyl, which subsequently etherified, esterified or can be reacted with isocyanate. Furthermore, the NH group can be reacted, for example, with benzyl chloride, allyl chloride, epichlorohydrin or chloroacetic acid esters. The implementation of such substitution reactions is described in more detail in the examples.

Nr.324009

Above all, their stabilizing effect against UV irradiation should be emphasized, so that the process according to the invention is particularly suitable for the photoprotection of polyolefins ,

Not only compared to commercially available sunscreens, but also compared to the compounds of German Offenlegungsschrift 1929 928 mentioned above, the compounds of formula (I) by improved solubility in polymers, especially improved solubility in polyolefins, with effective equality or superiority. Another advantage of the compounds of formula (I) is that they do not cause discoloration of the substrates, but protect them from discoloration by exposure to light or heat.

Examples of polyolefins for which the process of the present invention is well-suited are high and low density polyethylene, polypropylene, and polystyrene, as well as polymers of butene-1, pentene-1, 3-methylbutene-1, pentene-1, and co- and Terpolymers of olefins, in particular of ethylene or propylene.

Other polymeric materials which are sensitive to photodegradation and whose properties are improved by the incorporation of compounds of the formula (I) are, for example, natural and synthetic rubbers, the latter containing, for example, homo-, co- and terpolymers of acrylonitrile, Butadiene and styrene.

Other substrates for which the process is useful include polyvinyl chloride, polyvinylidene chloride and vinyl chloride copolymers, polyvinyl acetate, and condensation polymers and addition polymers containing ether, ester (of monocarboxylic acids, sulfonic acids or carbonic acids), amide or urethane moieties. These polymers may be the basis of a surface coating medium, for example, in oil-based or oil-based or alkyd or polyamide resin based paints and varnishes.

The amount of the compound of the formula (I) incorporated into the organic material to obtain maximum protection against decomposition by light varies according to the properties of the organic material to be treated and according to the intensity of the light-rubbing treatment and Duration of irradiation. However, for the fattening purposes, it is sufficient from the stabilizer of the formula (I) 0.01 to 5% by weight, more preferably 0.1 to 2% by weight. -%, based on the weight of the substrate to use.

To carry out the process, the novel stabilizers are incorporated into the polymeric material by known methods. For example, the stabilizer may be mixed with the polymer in an internal mixer.

Alternatively, the stabilizer can be added to the powdered polymer as a solution or slurry in a suitable solvent or dispersing agent, for example in an inert organic solvent such as methanol, ethanol or acetone, and the whole mixture can be mixed well in a mixer and the solvent can subsequently removed. As a further alternative, the compound may be added to the polymer during the preparation of the latter, for example in the latex stage of polymer manufacture, to obtain pre-stabilized polymeric material.

In addition to the addition according to the invention of the novel stabilizers of the formula (I), it is possible to add further known substances, as are customary in the case of polymer formulations, such as, for example, B. Phenol or amine type antioxidants, AV absorbers and light stabilizers, phosphite stabilizers, peroxide decomposers, polyamide stabilizers, basic co-stabilizers, polyvinyl chloride stabilizers, flocculants, plasticizers, lubricants, emulsifiers, antistatic agents, flame retardants, pigments, carbon black, asbestos, glass fibers, kaolin and talc.

Examples of suitable antioxidants are those of the sterically hindered phenols type, such as those of the following groups.

(1) Phenolic compounds of the general formula

Q- (CH2)W-A1 in which Q

R

CR (CoCr)2 , -C- (CH2)W-Q

COOR '

Nr.324009

R is hydrogen or lower-alkyl, R 'is lower-alkyl, R is an alkyl group having 6 to 24 carbon atoms, w is an integer of 0 to 4.

Examples of compounds as shown above are:

Di-n-octadecyl-a- (3,5-di-tert-butyl-4-hydroxybenzyl) -malonate,

Di-octadecyl-a- (3-tert-butyl-4-hydroxy-5-methylbenzy1) malonate,

Di-n-octadecyl-ot, a'-bis (3-tert-butyl-4-hydroxy-5-methylbenzyl) malonate.

(2) Phenolic compounds of the general formula

QR '

Examples of this are:

2.6- Di-tert. butyl-p-cresol,

2-methyl-4,6-di-tert-butylphenol, etc.,

2.6- dioctadecyl-p-cresol.

(3) Phenolic compounds of the formula

QC H -QW 2w

Examples of this type of connection are:

2.21-Methylenebis (6-tert-butyl-4-methylphenol),

2.21- methylene-bis- (6-tert-butyl-4-ethylphenol), 4,4'-butylidene-bis- (2,6-di-tert-butylphenol),

4,4 '- (2-butylidene) bis (2-tert-butyl-5-methylphenol),

2,2'-methylene-bis- [6- (2-tert-methylcyclohexyl) -4-methylphenol], 2,2'-methylenebis (3-tert-butyl-5-ethylphenol),

4,4-methylene-bis- (3,5-di-tert-butylphenol),

4,4'-methylenebis (3-tert-butyl-5-methylphenol),

2,2'-methylenebis (3-tert-butyl-5-methylphenol) u. similar.

(4) Phenolic compounds of the formula

ROQ

Illustrative examples of such compounds are:

2,5-di-tert. -butylhydrochinon,

2, 6-di-tert. -butylhydrochinon,

2, 5-di-tert. -butyl-4-hydroxyanisole, (5) phenolic compounds of the formula

QSQ

Illustrative examples of such compounds are:

4,4'-thiobis (2-tert-butyl-5-methylphenol),

4,4'-thiobis- (2-tert-butyl-6-methylphenol),

2,2'-thiobis- (6-tert-butyl-4-methylphenol),

4,4'-thiobis (2-methyl-5-tert-butylphenol).

(6) Phenolic compounds of the formula

O

II

Q- (CH2)2- S- (CH2)w-C- OR »

Illustrative examples of such compounds are:

acetate octadecyl (3,5-dimethyl-4-hydroxybenzylthio)

Dodecyl- (3,5-di-tert-butyl-4-hydroxybenzylthio) -propionate.

(7) Phenolic compounds of the formula

T / Q

CH- (CH ") -CH / w 2w \ T/ w where T is hydrogen or Q.

No. 324009

Illustrative examples of such compounds are:

1.1.3- tris- (3,5-dimethyl-4-hydroxyphenyl) -propane,

1.1.3- tris- (5-tert-butyl-4-hydroxy-2-methylphenyl) -butane,

1.1.5.5- Tetrakis- (3'-tert-butyl-4'-hydroxy-6 -mefliylphenyl) -n-pentane.

(8) Phenolic compounds of the formula

CH, CH B1qch-\O/-ch>b'/ - \ »ch3 ch2b3 where B1, B2 and B3 Hydrogen, methyl or Q, provided that when B1 and B3 Mean Q, then B2 Hydrogen or methyl, and when B2 Q means then B1 and B3 Mean hydrogen or methyl.

Illustrative examples of such compounds are:

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

1,3,5- tri (3,5-di-tert-butyl-4-hydroxybenzene) -2,4,6-trimethylbenzene, (9) phenolic compounds of the formula

SD

I

N - N ^^

(Q) -NH nz where Z is NHQ, -SD or -OQ, D is an alkyl group having 6 to 12 carbon atoms or (C H_) -S-R v w 2w 'means.

Illustrative examples of such compounds are:

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

6- (4-hydroxy-3-methyl-5-tert-butylanilino) -2,4-bis (n-octylthio) -1, 3,5-triazine,

6- (4-hydroxy-3,5-dimethylanilino) -2,4-bis (n-octylthio) -1, 3, 5-triazine,

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

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

2,4-Bis- (4-hydroxy-3,5-di-tert-butylanilino) -6- (n-octylthio) -l, 3, 5-triazine.

(10) Phenolic compounds of the formula

Zi q-o'Z'Z 'wherein Z1

-OQ, -SD or -S- (CH) -SD w 2w.

Illustrative examples of such compounds are:

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

2,4,6-tris- (4-hydroxy-3,5-di-tert-butylphenoxy) -l, 3, 5-triazine,

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

No. 324009

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

2,4-bis (4-hydroxy-3-methyl-5-tert-butylphenoxy-6- (n-octylthio) -l, 3,5-triazine,

2,4,6-tris- (4-hydroxy-3-methyl-5-tert-butylphenaxy) -l, 3, 5-triazine,

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

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

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

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

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

2,4-bis (4-hydroxy-3,5-di-tert-butylphenaxy) -6- (n-octylthioethylthioio) -l, 3,5-triazine,

2,4-Bis- (4-hydroxy-3,5-ditit. -Butylphenoxy) -6- (n-dodecyltinoethylthio) -1, 3,5-triazine.

(11) Phenolic compounds of the formula (Q-CzH2zCOO-CzH2z) -rm-(R)4-p 'wherein p is an integer from 2 to 4 and R|| T a tetravalent group such as an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aliphatic mono- or dithioether group having 1 to 30 carbon atoms, an aliphatic mono- and diether group having 1 to 30 carbon atoms, z represents an integer of 0 to 6.

Illustrative examples of such compounds are:

Subclass I:

n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate, n-octadecyl-2- (3,5-di-tert-butyl-4-hydroxyphenyl) -acetate, n-octadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, n-hexyl-3,5-di-tert. -butyl-4-hydroxyphenylbenzoate, n-dodecyl-3,5-di-tert. -bulyl-4-hydroxyphenyl benzoate,

Neododecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate,

Dodecyl-β- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate,

Ethyl a- (4-hydroxy-3,5-di-tert-butylphenyl) -isobutyrate,

Octadecyl-α- (4-hydroxy-3,5-di-tert-butylphenyl) -isobutyrate,

Octadecyl-a- (4-hydroxy-3,5-di-tert-butylphenyl) -propionate.

Subclass II:

2- (n-octylthio) -ethyl-3,5-di-tert. butyl-4-hydroxybenzoate,

2- (n -octylthio) -ethyl-3,5-di-tert, -butyl-4-hydroxyphenylacetate,

2- (n-octadecylthio) ethyl 3,5-di-tert-butyl-4-hydroxyphenylacetate,

2- (n-octadecylthio) -ethyl-3,5-di-tert-butyl-4-hydroxybenzoate,

2- (2-hydroxyethylthio) -ethyl-3,5-di-tert. butyl-4-hydroxybenzoate,

2,2'-thiodiethanolbis (3,5-di-tert-butyl-4-hydroxyphenyl) acetate,

Diethyl glycol bis (3,5-di-tert-butyl-4-hydroxyphenyl) propionate,

2- (n-octadecylthio) -äthyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate,

2,2'-thiodiethanol-bis-3- (3,5-di-tert-bufyl-4-hydroxyphenyl) -propionate,

Stearamido-N, N-bis- [ethylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], n-butylimino-N, N-bis- [ethylene-3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate],

2- (2-Stearoyloxyääiylttiio) -ättiyl-3,5-di-tert. butyl-4-hydroxybenzoate,

2- (2-hydroxy-di-ethylthio) ethyl-7- (3-methyl-5-tert-butyl-4-hydroxyphenyl) -heptanoate,

2- (2-stearoyloxyethylthio) -ethyl 7- (3-methyl-5-tert-butyl-4-hydroxyphenyl) -heptanoate. Subclass III:

1,2-propylene glycol bis (3,5-di-tert-butyl-4-hydroxyphenyl) propionate,

Ethylene glycol-bis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate],

Neopenlylglycol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate],

Ethenylene glycol bis (3,5-di-tert-butyl-4-hydroxyphenylacetate),

Glycerol-in-octadecanoate-2,3-bis- (3,5-di-tert-butyl-4-hydroxyphenylacetate),

Pentaethylthritol toi-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate],

1,1,1-trimethylolethane tris-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate,

Sorbitol hexa- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate],

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

2-hydroxy-ethyl-7- (3-methyl-5-tert-butyl-4-hydroxyphenyl) -heptanoate,

2-stearoyloxyethyl 7- (3-methyl-5-tert-butyl-4-hydroxy-phenyl) -heptanoate,

1,6-n-hexanediol bis [(3 ', 5'-di-tert-butyl-4-hydroxyphenyl) propionate].

No.324009 (12) Phenolic compounds of the formula

OR, where x is an integer of 1 or 2.

Illustrative hints of such compounds are:

Di-n-octadecyl-3,5-di-tert. butyl 4-hydroxybenzylphosphonate, di-n-octadecyl-3-tert-butyl-4-hydroxy-5-methylbenzylphosphonate, di-n-octadecyl-1- (3,5-di-tert-butyl-4-) hydroxyphenyl) ethane phosphonate, di-n-tetradecyl-3,5-di-tert. butyl 4-hydroxybenzylphosphonate, di-n-hexadecyl-3,5-di-tert. butyl 4-hydroxybenzylphosphonate, di-n-docosyl-3,5-di-tert. butyl 4-hydroxybenzylphosphate, di-n-octadecyl-3,5-di-tert. -butyl-4-hydroxybenzylphosphonate, (13) Phenolic compounds of the formula (CH) WQ I f

N.N

QW (H2Cf f X (CH2WQ where W and Q have the definitions given above.

Illustrative examples of such compounds are:

Tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate.

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

While any of the aforementioned antioxidants may be used together with the ultraviolet light stabilizers of the present invention, the antioxidants of the above-mentioned groups 1, 8, 9, 10, 11, 12 and 13 are preferable.

The most preferred hindered phenols are those of Groups 1, 9, 11, 12 and 13.

Further examples of antioxidants are those of the aminoaryl series, for example aniline and naphthylamine derivatives as well as their heterocyclic derivatives such as:

Phenyl-1-naphthylamine,

Phenyl-2-naphthylamine,

N, Ν'-diphenyl-p-phenyldiamine,

N, N> - sec. - butyl-p-phenylenediamine,

6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline,

6-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline,

Mono- and di-octyliminodibenzyl and polymerized 2,2,4-trimethyl-1,2-dihydroquinoline.

Ultraviolet absorbents and light stabilizers include (a) 2- (2i-hydroxyphenyl) benzotriazoles, for example 5'-methyl; 3 ', 5'-di-tert-butyl; 5'-tert-butyl; 5-chloro-3 ', 3'-di-tert, butyl; 5-chloro-3'-tert-butyl-5'-methyl-; 3'-sec-butyl-5'-tert-butyl; 3 '- (a-Metiiylbenzyl) -5'-methyl; 3 '- (a-methylbenzyl) -5'-methyl-5 "chlorine; 4'-octoxy; 3 ', 5'-di-tert-amyl; 3'-methyl-5'-carbomethoxyäthyl-; 5-Chloro-3 ', 5'-di-tert, -amyl derivatives.

(b) 2,4-bis (2'-hydroxypbenyl) -6-alkyl-S-triazines, for example the 6-ethenyl or 6-undecyl derivatives "(c) 2-hydroxybenzophenones, for example the

4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4,2 ', 4'-trihydroxy or 2' -hydroxy-4 ', 4'-dimethoxy derivatives ,

(d) 1,3-bis (2'-hydroxybenzoyl) benzenes, for example

1,3-bis (21-hydroxy-4'-hexyloxybenzoyl) benzene,

1,3-bis (2-t-hydroxy-4'-octoxybenzoyl) benzene,

1,3-bis- (2> -hydroxy-4'-dodecyloxybenzoyl) benzene.

No.324009 (e) aryl esters of optionally substituted benzoic acids, such as

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

(f) acrylates, for example a-cyano-0,0 -diphenylacrylic acid ethyl or -isooctylester.a-carbomethoxycinnamic acid methyl or butyl ester and N- (0-carbomethoxyvinyl) -2-methylindoline.

(g) Ni compounds such as the nickel complexes of 2,2-thio-bis (4-tert-octylphenol), for example the: 1- and 1: 2 complexes, which may optionally contain other ligands, such as n-butylamine Triethanolamine or N-cyclohexyl diethanolamine; Nickel complexes of bis (4-tert-octylphenyl) sulfone such as the 2: 1 complex, which may optionally contain other ligands such as 2-ethyl-caproic acid; Nickeldibutyldithiocarbamate; Nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters such as the methyl, ethyl or butyl esters; the nickel complex of 2-hydroxy-4-methylphenyl undecyl ketone oxime; and nickel 3,5-di-tert. butyl-4-hydroxybenzoate; and (h) oxalic diamides, for example, 4,4'-dioctyloxyoxanilide,

2,2'-dioctyloxy-5,5'-di-tert-butyl-oxanilide,

2,2'-di-dodecyloxy-5,5'-di-tert-butyl-oxanilide,

2-ethoxy-5-tert. butyl-2'-ethyl-oxanilide,

2-ethoxy-2'-ethyl-oxanilide.

Mixtures of oxanilides disubstituted in the o- and p-position by metiioxy or ethoxy groups and the compound of the formula

CH3 /CH3 (CH,) - NHCOCONH (CH2)3N ch3xch

Phosphite stabilizers include triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, trinonyl phenyl phosphite, trilauryl phosphite, trioctadecyl phosphite, 3,9-diisodecyloxy-2,4,8, 10-tetraoxa-3,9-diphosphaspiro [5,5] undecane and tri- (4 -hydroxy-3,5-di-tert-butylphenyl) phosphite.

Peroxide-decomposing compounds for polyolefins include esters of O-thiodipropionic acids, for example the lauryl, stearyl, myristyl or tridecyl esters, salts of mercaptobenzimidazoles such as the zinc salt and diphenylthiourea.

Suitable polyamide stabilizers include copper salts in combination with iodides and / or other phosphorus compounds and salts of divalent manganese.

Basic co-stabilizers are, for example, polyvinyl pyrrolidone, melamine, benzoguanamine, triallyl cyanurate, di-cyandiamide, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal and alkaline earth salts of higher saturated or unsaturated fatty acids, such as calcium stearate.

Polyvinyl chloride stabilizers include organic tin compounds, organic lead compounds and Ba / Cd salts of fatty acids.

Examples of flocculating or nucleating agents are 4-tert-butylbenzoic acid, adipic acid and diphenylacetic acid,

These additives are used in an amount of 0.01 to 5% by weight, based on the weight of the untreated polymer material.

The following examples illustrate the invention without, however, limiting it. The parts and percentages are by weight unless otherwise specified.

Examples 1 to 5: A mixture of 11.86 parts of 1-allyl-2,2,6,6-tetramethylpiperidin-4-ol, 7.7 parts of cyclohexanecarboxylic acid and 1, 0 part of tetra-n-butyl titanate in 100 parts Xylene was heated under reflux for 60 hours. Removal of the xylene by distillation under reduced pressure gave an oily solid which was heated at reflux conditions with 0.5 part of sodium carbonate and 0.5 part of carbon powder in 25 parts of water for 1 h. Removal of the water by distillation under reduced pressure gave a black one Residue repeatedly extracted with ether. The acidified ether extracts were dried and the ether was removed by distillation under reduced pressure to give a yellow oil which was distilled under reduced pressure to give 5.0 parts (1-allyl-2,2,6,6 Tetramethyl-4-piperidinyl) cyclohexanecarboxylate as a colorless oil with a boiling point of 130 ° C at 0, 0.05 mm Hg.

Analysis (for CigH33NO2)

Calculated: C 74.22 H 10.82 N 4.56%

Found: C 74.86 H10.65 N4.26%.

Table I gives a list of esters 2 to 5 made using the method described above.

Nr.324009

Nr.324009

Examples 6 to 12: A mixture of 28.3 parts of 2,2,6,6-tetramethyl-4-piperidinyl-n-octanoate and 8.55 parts of benzyl bromide was stirred and heated for 72 h at 1105 ° C, ether was added the cooled reaction mixture was added and the formed during the reaction of 2,2,6,6-tetramethyl-4-piperidinyl-n-octanoate hydrobromide was filtered off. The ether solvent was distilled by distillation at reduced pressure to give 16.40 parts of 1-benzyl-2,2,6,6-tetramethyl-4-piperidinyl-n-octanoate having a boiling point of 180 ° C at 0, 1 mm Hg received.

Analysis (for CMHS9NO2)

Calculated: C 77.16 HlO.52 N 3.75%

Found: C 77.46 H10.50 N3.86%.

Table II lists a list of esters made using the method of Example 6.

No, 324009

Table II

<td rowspan="6">analysis</td><td rowspan="3">Found (%)</td><td>2</td><td>4.04</td><td>3.84</td><td>4, 32 l</td><td>4.45</td><td>t Tf *</td><td>4, 39</td>

<td rowspan="3">Calculated (%)</td><td>2</td><td>4.24</td><td>3, 71</td><td>4, 33</td><td>4.65</td><td>4.99</td><td>4.33</td>

<td colspan="3">Molecular formula</td><td>O* 2 3 2 CM ü *</td><td>O12 w Λ CM υ</td><td>CH NO 20 37 2</td><td>cf 2 t ~ · CM 2 0 0</td><td>cf 2nS 2 S υ</td><td>O n 2 s u</td>

<td colspan="3">example No.</td><td>c ~</td><td>00</td><td>05</td><td>0 pH</td><td>rh</td><td>03 r *</td>

No. 324009

Example 13: A mixture of 2.83 parts of 2,2,6,6-tetramethyl-4-piperidinyl-n-octanoate and 1.50 parts by volume of liquid ethylene oxide was placed in a 50 ml autoclave previously heated to -50 ° C was given. A pressure of 100 at nitrogen was applied and the autoclave was heated with stirring to 200 ° C for 3 h. Fractional distillation of the cooled reaction mixture gave 2.30 parts of 1- (2'-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinyl-n-octanoate with a boiling point of 186-187 ° C at 0.25 mm Hg, and the following elementary analysis.

Analysis (for C ^ H ^ NO,)

Calculated: C 69, 68 Hll.39 N4.28%

Found: C 69.93 H 11, 09 N 4.37%.

Example 14: A mixture of 3.27 parts of the product of Example 13, 0.60 parts of acetic acid and 0.1 part of tetra-n-butyl titanate in 40 parts of xylene was heated at reflux for 24 hours. The xylene solvent was removed by distillation under reduced pressure and the residue was fractionally distilled to give 1- (2-acetoxyethyl) -2,2,6,6-tetramethyl-4-piperidinyl-n-octanoate with a bp. from 190 to 192 ° C at 1 mm Hg,

Analysis (for C21hg9NO4)

Calculated: C 68.25 H 10.64 N 3.79%

Found: C 68.17 H 10.65 N3.36%.

Example 15: A mixture of 3.27 parts of the product of Example 13.0, 62 parts of methyl isocyanate and 0.1 part of 1,4-diazabicyclo [2.2.2] octane in 30 parts of dry benzene was refluxed for 24 hours h heated. The benzene solvent was removed by distillation under reduced pressure and the residue was crystallized from aqueous ethyl alcohol to give 1- (2'-methylcarbamoyloxyethyl) -2,2,6,6-tetramethyl-4-piperidinyl-n-octanoate a mp. from 61 to 63 ° C.

Analysis (for C21H40N2O4)

Calculated: C 65.59 H 10.48 N 7.28%

Found: C 65, 72 H 10.37 N 7.11%.

Example 16: 2.65 parts of acrylonitrile were added dropwise with stirring to a solution of 8.55 parts

1,2,2,6,6-Pentamethylpiperidin-4-ol and 0.30 parts of 40% potassium hydroxide solution in 80 parts of benzene added. The mixture was stirred at room temperature for 16 h, after which the solution was washed with water, dried and the benzene solvent was removed by distillation under reduced pressure. Fractional distillation of the residue under reduced pressure gave 1.70 parts of 4- (2'-cyanoethhaxy) -1,2,2,6,6-pentamethylpiperidine having a bp of from 105 to 106 ° C. and 0.1 mm Hg ,

Analysis (for C13H24N2O)

Calculated: C 69.60 H10.78 N 12.49%

Found: C 69.27 H 10.69 N 12.40%

In Table 17: A mixture of 4-benzyloxy-2,2,6,6-tetramethylpiperidine and 1.67 parts of ethyl a-bromoacetate in 30 parts of ethyl alcohol was heated at reflux for 115 hours. The ethyl alcohol solvent was removed by distillation under reduced pressure and the residue was fractionally distilled to give 4-benzyloxy-1-ethoxycarbonylmethyl-2,2,6,6-tetramethylpiperidine, b.p. 145-246 ° C at 0 ° C. 2 mm Hg received.

Analysis (for C ^ H ^ NOg)

H 9,37 N4,20%

H8.90 N3, 94%.

A mixture of 16.4 parts of 1,2,2,6,6-pentamethylpiperidin-4-ol, 6.27 parts of diisocyanate and 0.5 part of 1,4-diazabicyclo [2,2,2] octane was added in 150 parts heated dry benzene for 24 h at reflux. Removal of the benzene solvent by distillation under reduced pressure gave an oily solid which was poured onto 200 parts of water and stored for 24 hours. The solid that formed was collected by filtration, dried and crystallized from n-hexane to give 14.2 parts of 4-methylcarbamoyloxy-1,2,6,6-pentamethylpiperidine having a mp of 96 to 97 ° C received.

Analysis (for C12H24N2O2)

Calculated: C63.12 H 10.59 N12.27%

Found: C 63.28 H 10, 70 N 12, 09%.

Table III lists a list of urethanes made using the process described herein.

Calculated: C 72, 04

Found: C 71, 62

Examples 18 to 30:

No. 324009

Table III

<td rowspan="6">analysis</td><td rowspan="3">Found (%)</td><td>2</td><td>9.16</td><td>5.96</td><td>CO σΓ</td><td>9.53 (</td><td>9.02</td><td>8.87</td>

<td rowspan="3">Calculated (%)</td><td>x</td><td>9.39</td><td>00 '9</td><td>9.45</td><td>9.65</td><td>9.20</td><td>00 CO oo</td>

<td colspan="3">Molecular formula</td><td>C17H34N2 °2</td><td>OJ O 04 z 00 af R u</td><td>ο " 04 2 04 af t * -l u</td><td>cf N z tO 04 3k tH u</td><td>N O z 8th e 00 «- (ü</td><td>υ cf 04 z 8th 3k w υ</td>

<td colspan="3">example No.</td><td>05 rh</td><td>O 03</td><td>ί-1 C3</td><td>C3 03</td><td>CO C3</td><td>03</td>

Nr.324009

Table III (continued)

<td rowspan="6">analysis</td><td rowspan="3">Found (%)</td><td>2</td><td>8:41</td><td>CO O t-1</td><td>10. 83</td><td>TÜ 03 ©</td><td>9.86</td>

<td colspan="3">Molecular formula</td><td>CM O 4M 2 8th CM O</td><td>O* 2 ^ ar 00 CM u</td><td>ö * 2 ^ C0 2 OS CM u</td><td>ό * * ΈΜ U9 υ "</td><td>ό * 2 ^ 2 * CM " υ</td>

<td colspan="3">example No.</td><td>in 03</td><td>CO 03</td><td>t> 03</td><td>00 03</td><td>05 03</td>

Nr.324009

<td rowspan="6">analysis</td><td rowspan="3">Found (%)</td><td>Z</td><td>9.04</td>

<td rowspan="3">Calculated (%)</td><td>Z</td><td>8.69</td>

<td colspan="3">Molecular formula</td><td>O" z * a e O" rt u</td>

<td colspan="3">example No.</td><td>O co</td>

No. 324009

Examples 41 to 42; Sunscreen of polypropylene film.

Parts of polypropylene were homogenized with 0.076 part of n-octadecyl-β- (4'-hydroxy-3 ', 5> -tert-butyIphenyl) -propionate in a kneader at 200 ° C for 3 min. Then, 0.19 part of the product of Example 1 was added and homogenized for a further 7 min.

This mixture was molded under pressure at 260 ° C into films having a thickness of 0.1 mm, and the resulting films were quenched in cold water.

Samples measuring 44 X 100 mm were cut out of the 0.1 mm polypropylene films and subjected to light irradiation in an exposure apparatus. This device includes a round bench with 28 alternating sunlight and black light bulbs.

The sunlight lamps were 0.6 m long 20 W fluorescence tubes, characterized by a radiation maximum at 3100 Å. The black light lamps were 0.6-ra long 20 W ultraviolet tubes, characterized by a radiation maximum at 3500 Å. The samples were rotated concentrically around the lamp bank so that the radiation was uniformly distributed over the part to be examined.

The irradiated samples were periodically tested and parts of them were examined for percent elongation at break. The time taken for the sample to reach 50% of the original elongation at break was noted.

Similar experiments were conducted with polypropylene samples that did not contain stabilizers or known

Stabilizers or stabilizers, which are the subject of German Patent Application 1929 928, contained. The results obtained are shown in the following Table IV.

Table IV

<td>example</td><td>stabilizer</td><td>Quotient of the times up 50% elongation at break with and without stabilizer additive</td>

<td>comparison</td><td>none</td><td>1.0</td>

<td>comparison</td><td>2- (2'-hydroxy-3, 5'-di-1-butyl-phenyl) -5-chlorobenzotriazole (commercial product)</td><td>3.2</td>

<td>comparison</td><td>4-phenylcarbamoyloxy-2,2,6,6-tetramethylpiperidine (Stabilizer No. 22 of German Patent Application 1929 928)</td><td>1.8</td>

<td>comparison</td><td>1,6-bis- [4'-carbamoyloxy-2 ', 2', 6 ', 6'-tetramethylpiperidine] hexane (stabilizer no. 44 of German Offenlegungsschrift 1929 928)</td><td>2.4</td>

<td>comparison</td><td>2,2,6,6-tetiamethylpiperidinyl) -4-benzoate (stabilizer no. 7 of German Offenlegungsschrift 1929 928)</td><td>2.6</td>

<td>31</td><td>(1-Allyl-2,2,6,6-tetramethyl-4-piperidinyl) -cyclohexanecarboxylate (stabilizer of the present process prepared according to Example 1)</td><td>5.1</td>

<td>32</td><td>4- (2-Cyanoethoxy) -1,2,6,6,6-pentamethylpiperidine (prepared according to Example 16)</td><td>6.0</td>

<td>33</td><td>Bis- (1-benzyl-2,2,6,6-tetramethyl-4-piperidinyl) sebacate (prepared according to Example 7)</td><td>5.0</td>

<td>34</td><td>1-ethoxycarbonylmethyl-2,2,6,6-tetramethylpiperidinyl-4- (p-methoxybenzoate) (prepared according to Example 8)</td><td>5.1</td>

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Table IV (continued)

<td>example</td><td>stabilizer</td><td>Quotient of the times up 50% elongation at break with and without stabilizer additive</td>

<td>35</td><td>1-Benzyl-2,2,6,6-tetramethylpiperidinyl-4- (2-ethylhexanoate) (prepared according to Example 2)</td><td>5.2</td>

<td>36</td><td>1- (n-Dodecyl) -2,2,6,6-tetramethylpiperidinyl-4-octanoate (prepared according to Example 4)</td><td>5.2</td>

<td>37</td><td>1- (2-hydroxyethyl) -2,2,6,6-tetramethylpiperidinyl-4-octanoate (prepared according to Example 13)</td><td>5.8</td>

<td>38</td><td>2,4-Bis- (4'-carbamoyloxy-1 ', 2', 2 ', 6', 6'-pentamethylpiperidine) -toluene (prepared according to Example 27)</td><td>5.2</td>

<td>39</td><td>4-p-tolylcarbamoyloxy-l, 2,2, 6,6-penta- methylpiperidine (prepared according to Example 23)</td><td>5.2</td>

<td>40</td><td>4-phenylcarbamoyloxy-l, 2,2,6, 6-penta- methylpiperidine (prepared according to Example 22)</td><td>5.6</td>

<td>41</td><td>4-methylcarbamoyloxy-l, 2,2, 6, 6-penta- methylpiperidine (Example 18)</td><td>5.8</td>

<td>42</td><td>1,6-bis- [4'-carbamoyloxy-l22 ', 6', 6'-pentamethylpiperidine] -hexane (prepared according to Example 26)</td><td>9.2</td>

Examples 43 to 45: Compatibility in Low Pressure Polyethylene,

The experiments described in Examples 31 to 42 were repeated, except that 0.25% by weight of the stabilizer to be tested was used, and instead of polypropylene, the substrate used was a low-density polyethylene. The pressing was carried out at 180 ° C and the compacts were deformed in mm thick plates at 15O ° C under pressure.

The slides were stored at 20 ° C and periodically visually inspected for the first sign of exudation.

The results obtained are summarized in Table V, where results of comparisons are also reported.

Table V

<td>example</td><td>Added light stabilizer</td><td>Time to Sweat out (days)</td>

<td>-</td><td>2,2,6,6-Tetramethylpiperidinyl-4-stearate (Stabilizer No. 2 of German Offenlegungsschrift 1929928)</td><td>15</td>

<td></td><td>sebacate bis (2,2,6,6-tetramethyl-4-piperidinyl) (Stabilizer according to German Laid-Open Publication 1929 928)</td><td>20</td>

Nr.324009

Table V (continued)

<td>example</td><td>Added light stabilizer</td><td>Time to exude (days)</td>

<td></td><td>4-Stearylcarbamoyloxy-2,2,6,6-tetramethylpiperidine (Stabilizer according to German Laid-Open Patent 1929928)</td><td>13</td>

<td>43</td><td>l-benzyl-2,2,6,6-tetramethyl-4-stearate (prepared according to Example 3)</td><td>> 50</td>

<td>44</td><td>Bis (l-benzyl-2,2,6,6-tetramethyl-4-piperidone dinyl) sebacate (prepared according to Example 7)</td><td>> 50</td>

<td>45</td><td>4-stearylcarbamoyloxy-1,2,6,6-pentamethylpiperidine (prepared according to Example 20)</td><td>> 50</td>

Examples 46 to 48: Compatibility in high pressure polyethylene.

The experiments described in Examples 43 to 45 were repeated, except that the deformation was carried out under pressure at 200 ° C and that high density polyethylene was used as the substrate.

The results obtained are listed in Table VI, which also contains a comparative experiment.

Table VI

<td>example</td><td>light stabilizer</td><td>Time to ooze (Days)</td>

<td>-</td><td>2,2,6,6-Tetramethylpiperidinyl-4-stearate (Stabilizer Nr, 2 of the German Laid-Open Publication 1929 928)</td><td>40</td>

<td>46</td><td>1-Benzyl-2,2,6,6-tetramethylpentamethylpiperidinyl-4-stearate (prepared according to Example 3)</td><td>> 75</td>

<td>47</td><td>4-stearylcarbamoyloxy-l, 2,2, 6, 6-penta- raethylpiperidin (prepared according to Example 20)</td><td>> 75</td>

<td>48</td><td>1- (n-dodecyl) -2,2,6,6-tetramethylpiperidinyl-4-octanoate (prepared according to Example 4)</td><td>> 75</td>

Examples 49 to 53: light protection of polystyrene.

100 Portions of crystalline polystyrene pellets were dry blended with 0.25 parts of 1-benzyl-2,2,6,6-tetramethylpiperidinyl-4-stearate and the dry mixture was then homogenized by extrusion. From the stabilized granules thus obtained, plates having a thickness of 2 mm were produced by injection molding. These plates were irradiated for 3000 hours in a Xenotest 150 exposure unit and then the yellow color of the plates was determined colorimetrically and the yellowness factor was calculated according to the following equation:

Yellowing factor

ΔΤ - ΔΤ (420) (680)

T (560)

X 100

Nr.324009

Therein, the ΔΤ values mean the loss of transmission of the sample bd wavelengths of 420 and 680 mm after the exposure, and T means the transmission value of a non-irradiated sample at a wavelength of 560 mm.

The results thus obtained as well as the results of comparative experiments and other compositions according to the invention are indicated in the following Table VII.

Table VII

<td>example</td><td>light stabilizer</td><td>Yellowing factor after 3000 h</td>

<td>49</td><td>1-benzyl-2,2,6,6-tetramethylpiperidinyl-4- (2-ethylhexanoate) (prepared according to Example 2)</td><td>9.8</td>

<td>50</td><td>l-dodecyl-2,2,6,6-tetramethyl-4- (n-octanoate) (prepared according to Example 4)</td><td>8.5</td>

<td>51</td><td>4- (2'-Cyanoethoxy) -1,2,2,6,6-pentamethylpiperidine (prepared according to Example 16)</td><td>8.0</td>

<td>52</td><td>4-Stearylcarbamoyloxy-1,2,2,6,6-pentamethylpiperidine (prepared according to Example 20)</td><td>7.5</td>

<td>53</td><td>Bis (1-benzyl-2,2,6,6-tetramethyl-4-piperidinyl) sebacate (prepared according to Example 7)</td><td>7.0</td>

Examples 54 to 56: Sunscreen of polyurethane films.

Parts by weight of a polyester-based film-forming polyurethane were dissolved in 75 parts by weight of a 1: 1 (volume) mixture of dimethylformamide and acetone, to which was added 1% by weight of 4- (2-cyanoethoxy) 10-1,2,2 , 6, 6-pentamethylpiperidine,

The clear and homogeneous solution was spread on a glass plate to a film having a thickness of 400 to 500 μ and then dried as follows:

at 50 ° C for 4 min, at 140 ° C for 6 min.

The final thickness of the film was 80 to 100 μ.

The dried film samples were removed from the glass plate, coated on a white paperboard and irradiated in a Xenotest 450 exposure unit. Half of the irradiated samples were covered to facilitate the subsequent visual assessment of the yellowing caused by the irradiation. The samples were controlled and evaluated visually at 100 hour intervals.

The results obtained are listed in the following Table VIII, where results are also listed with other stabilizers according to the invention.

Table VIII

<td>example</td><td>light stabilizer</td><td>Time to beginning of yellowing (B)</td>

<td>54</td><td>4- (2'-Cyanoethoxy) -1,2,2,6,6-pentamethylpiperidine (prepared according to Example 16)</td><td>200</td>

No. 324009

Table VIII (continued)

<td>example</td><td>light stabilizer</td><td>Time to beginning of yellowing (H)</td>

<td>55</td><td>l-dodecyl-2,2,6,6-tetramethylpiperidinyl-4-octanoate (prepared according to Example 4)</td><td>400</td>

<td>56</td><td>4-phenylcarbamoyloxy-ln-propyl-2,2,6,6-tetramethylpiperidine (prepared by hydrogenation of the corresponding 1-allyl compound)</td><td>400</td>

Examples 57 and 58: polypropylene fibers.

1000 Parts by weight of non-stabilized polypropylene powder were mixed well with 1 part by weight of n-octadecyl-β- (4'-hydroxy-3 ', 5'-di-tert-butylphenyl) -propionate and 2 parts by weight of an inventive Stabilizer dry mixed. The dry mixture was extruded at a cylinder temperature of 180 to 220 ° G and the resulting strand was granulated. The stabilized formulation thus obtained was melt-spun and drawn under the following conditions:

<td>Ex-brother t emperature</td><td>230/265/275 ° C</td>

<td>Melting temperature at the jet</td><td>270 ° C</td>

<td>spin speed</td><td>400 m / min</td>

<td>draw ratio</td><td>1: 5</td>

<td>Titre of the multifilaments</td><td>130/37 Denier</td>

<td>tensile strenght</td><td>6 g / den</td>

The multifilament thus obtained was mounted on a sample holder of a Xenotest 150 apparatus (Quarzlampen GmbH) using a white cardboard as a back side. At intervals of 200 h exposure time, five fiber samples each were examined for their residual tensile strength. The results obtained are plotted against the duration of the exposure and the exposure time (T), in which a 50% loss of the original tensile strength is obtained, is derived from the diagram. This value is taken as a refusal time ".

Table IX

<td>example</td><td>light stabilizer</td><td>refusal time T</td><td>quotient T stabilizer T comparison</td>

<td>-</td><td>2- (21-Hydroxy-3-t, 5-di-tert-methylphenyl) -5-chlorobenzotriazole</td><td>530</td><td>1.2</td>

<td>57</td><td>l-dodecyl-2,2,6,6-tetramethyl-4-piperidinyl- (35'-di-tert-butyl-4'-hydroxybenzoate)</td><td>1800</td><td>4.2</td>

<td>58</td><td>Bis- (1-allyl-2,2,6,6-tetramethyl-4-piperidyl) -sebaca t</td><td>2300</td><td>5.3</td>

Examples 59 to 63: polypropylene film,

The experiments described in Examples 31 to 42 were repeated except that the cooled polypropylene samples were subjected to light irradiation in a Xenotest 450 irradiation unit, in place of the described exposure apparatus.

Nr.324009

The results obtained are summarized in the following Table X, where results of each one

Comparative experiment without light stabilizer and with a commercially available light stabilizer are listed.

Table X

<td>example</td><td>light stabilizer</td><td>Time to failure (h)</td>

<td>-</td><td>none (comparison)</td><td>800</td>

<td>-</td><td>2- (2> -hydroxy-3 ', 5'-di-tert-butylphenol) -5-chlorobenzotriazole</td><td>1630</td>

<td>59</td><td>Bis- (1-Benzyl-2,2,6,6-tetramethyl-4-piperidinyl) - sebacate (Example 7)</td><td>8000</td>

<td>60</td><td>l-hydroxyethyl-2,2,6,6-tetramethylpiperidinyl -4-octanoate (Example 13)</td><td>5500</td>

<td>61</td><td>4-phenylcarbamoyloxy-l, 2,2,6, 6-pentamethyl- piperidine (Example 22)</td><td>7000</td>

<td>62</td><td>4-methylcarbamoyloxy-l, 2,2,6,6-pentamethyl- piperidine (Example 18)</td><td>6000</td>

<td>63</td><td>l-allyl-2,2,6,6-pentamethylpiperidinyl-4-cyclo- hexancarboxylat (Example 1)</td><td>5000</td>

Examples 64 to 6 7: polyamide fibers.

100 Parts by weight of polyamide 6 pellets containing 1.8 parts by weight of TiO2 were dry mixed with 0.5 part of 4-benzyloxy-l, 2,2, 6, 6-pentamethylpiperidine. The obtained mixture was melt-spun directly into monofilaments and a denier of 20%. The monofilaments were mounted on a white board and subjected to light irradiation in a Xenotest 450 irradiation unit.

After 500, 1000, 1500 and 2000 hours of exposure time, five fiber samples of each formulation were subjected to the

Time intervals were examined for their tensile strength. The arithmetic mean percent residual tensile strength was plotted as a function of exposure time. The scavenging time T to 50% of the original tensile strength was extrapolated from these plots.

Table XI

<td>example No.</td><td>light stabilizer</td><td>T</td>

<td>-</td><td>none (comparison)</td><td>475</td>

<td>64</td><td>4-Benzyloxy-1,2,2,6,6-pentamethylpiperidine</td><td>1420</td>

<td>65</td><td>1-Benzyl-2,2,6,6-tetramethylpiperidinyl-4-octanoate</td><td>1250</td>

<td>66</td><td>1-phenylcarbamoyloxy-l, 2,2,6, 6-pentamethylpiperidine (prepared according to Example 22)</td><td>1450</td>

<td>67</td><td>1,6-bis (4'-carbamoyloxy-1 ', 2', 21,6 ', 6' - pen- tamethylpiperidinyl) hexane (prepared according to Example 27)</td><td>1500</td>

No, 324009

1. Process for stabilizing polymeric material against the harmful influence of light and / or heat, using piperidine derivatives, characterized by the addition of a

Compound of the formula

Contents17

46 members in 25 offices

This recordMember, by publication datePriority claim15 more offices are in the list below

Priority claims3

Priority claims
Document	Office	Kind	Date
5548771	United Kingdom	A	1971-11-30
2845872	United Kingdom	A	1972-06-17
3547372	United Kingdom	A	1972-07-28

Members46

Family members, oldest first
Document	Office	Kind
IL40888A0	Israel	A0	1973-01-30
BE792043A	Belgium	A	1973-05-29
NL7216278A	Netherlands (Kingdom of the)	A	1973-06-04
DE2258752A1	Germany	A1	1973-06-07
ZA728468B	South Africa	B	1973-08-29
JPS4865180A	Japan	A	1973-09-08
BR7208426D0	Brazil	D0	1973-09-13
FR2182789A1	France	A1	1973-12-14
FR2183293A1	France	A1	1973-12-14
FR2183294A1	France	A1	1973-12-14
IT971346B	Italy	B	1974-04-30
AU4940972A	Australia	A	1974-05-30
DD106190A5	German Democratic Republic (until 1990)	A5	1974-06-05
GB1399239A	United Kingdom	A	1975-06-25
AT324009BThis record	Austria	B	1975-08-11
HU167244B	Hungary	B	1975-09-27
FR2182789B1	France	B1	1976-01-30
ES409079A1	Spain	A1	1976-04-16
CA997767A	Canada	A	1976-09-28
IL40888A	Israel	A	1976-10-31
ES437735A1	Spain	A1	1977-01-16
PL90214B1	Poland	B1	1977-01-31
CH585714A5	Switzerland	A5	1977-03-15
CH585715A5	Switzerland	A5	1977-03-15
CH586252A5	Switzerland	A5	1977-03-31
US4021432A	United States of America	A	1977-05-03
FR2183293B1	France	B1	1977-07-29
HU170685B	Hungary	B	1977-08-28
US4046737A	United States of America	A	1977-09-06
US4049647A	United States of America	A	1977-09-20
HK47877A	Hong Kong, China	A	1977-09-23
RO62513A	Romania	A	1977-12-15
SU584795A3	Soviet Union (until 1991)	A3	1977-12-15
FR2183294B1	France	B1	1978-05-26
MY7800025A	Malaysia	A	1978-12-31
CS190377B2	Czechoslovakia (until 1993)	B2	1979-05-31
RO64573A	Romania	A	1979-08-15
SU721008A3	Soviet Union (until 1991)	A3	1980-03-05
RO71050A	Romania	A	1981-09-24
USRE31342E	United States of America	E	1983-08-09
USRE31343E	United States of America	E	1983-08-09
NL174942B	Netherlands (Kingdom of the)	B	1984-04-02
JPS5920709B2	Japan	B2	1984-05-15
NL174942C	Netherlands (Kingdom of the)	C	1984-09-03
SE454277B	Sweden	B	1988-04-18
DE2258752C2	Germany	C2	1989-10-26

Piperidine derivatives

Abstract

Term

'3 .CH,

(I)

-CC-,

OO OO

R

COOR '

QR '

ROQ

QSQ

O

II

T / Q

SD

I

N.N

T (560)

X 100

Priority claims3

Members46

Events

Numbers

Titles2

Classification