Stabilization of synthetic polymers by means of certain piperidine derivatives

© Start of patent period: 1975 06 15 Longest possible duration:

S Issued on: 1976 0 «12

Inventor:

© dependence:

© Pamphlets considered to delineate the prior art:

OE 328 745

Nr.328745

The invention relates to a process for stabilizing synthetic polymers against degradation under the influence of light and heat by means of substituted in the l-position piperidine derivatives.

The compound 2,2,6,6-tetramethylpiperidine, that is an unsubstituted in the l-position piperidine, has already been proposed as a polyolefin to light stabilizing Stabilisa5 gate with Japanese Patent Publication no. 46-31773, on the other hand have been different, in the l-position substituted piperidine derivatives of the general formula

<img file="AT328745B_D0001.tif" />

where n is 1 or 2 and, when n is 1, X is an alkyl, allyl, propargyl, benzyl, ethoxycarbonylmethyl, 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxy-2-phenylethyl , 2-acyloxyethyl, 2-acyloxy10 -2-phenylethyl, acetyl or Meihoxycarbonylgruppe and, if n is 2, X is a hexamethylene group, for other uses, in particular for use in pharmacy, proposed, however, they have not yet been proposed for use as stabilizers for polymers; see. for example, J.Pharmaeol, 13, [1958], pp. 501 to 520, J. Med. Chem., 6, [1963] pp. 381 to 384, J. Org. Chem. 27, [1962], Sl 695 to 1703, CA, 62.9098h, Beilstein, 20, p.129, British Patent No. 834,290 and No. 1,143,371.

It has now been found that certain 1-membered piperidine derivatives are unexpectedly effective stabilizers for synthetic polymers and capable of protecting such polymers from degradation under the influence of light and heat.

According to the invention, synthetic polymers are stabilized against the influence of light and heat by introducing into these polymers at least one piperidine derivative of the general formula ## STR5 ## which is substituted by 1-one

<img file="AT328745B_D0002.tif" />

is incorporated, wherein R_a and Rj&gt; represent methyl groups or R_a and R ^ together with the carbon atom bearing these groups form a cyclohexyl group, R_c a methyl group and Rj is an alkyl25 group having 1 to 5 carbon atoms or R_c and Rj together with the carbon atom bearing these groups, a cyclopentyl group, a cyclohexyl group, a group of the general formula

CH ³ .CH.

NH

CH "

CH.

or a group of the general formula

CH.

CH.

, CH "\ / ^X ·

CH,

No.328745, where n is 1 or 2 and if n is 1, R¹ a qxyl group, a hydroxy group, a

Alkyl group, a substituted alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, a substituted aralkyl group or an acyl group, or when n is 2, R¹ an alkylene group with optionally an oxygen atom interrupted chain, a 2-ButenyIengruppe, a group of the general formula - CH₂ CO - O - R - O - COCH ₂ with the meaning of an alkylene group or a xylylene group for R⁷, or a group of the general formula - CH ₂- CH₂ - O-CO-f R^8th C is OO-CH-CHj, meaning zero or 1 for m and the meaning of an alkylene group with chain optionally interrupted by a sulfur atom, an alkenylene group, a phenylene group or a 1,4-cyclohexylene group for R;

A group of compounds which can preferably be used according to the invention are those of the general formula (1) in which n is 1 and which of the general formula

<img file="AT328745B_D0003.tif" />

correspond, wherein R_a, R ^, R_c and Rj have the meaning given above and R¹ is a qxyl group, a hydroxy group, an alkyl group, a substituted alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, a substituted aralkyl group or an acyl group.

An alkyl group R appearing in formula Y) may be, for example, a methyl, ethyl, propyl, butyl, pentyl or hexyl group. A substituted alkyl group R¹ For example, a haloalkyl group such as the 2-chloroethyl, 2-bromoethyl or 2-chloropropyl group, an epoxyalkyl group such as the 2,3-epoxypropyl group, a hydroxyalkyl group such as the 2-hydroxyethyl, 2-hydroxypropyl or 3-hydroxypropyl group an alkoxycarbonylalkyl group such as the hexyloxycarbonylmethyl group, an alkoxyalkyl group such as the 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl or 3-methoxypropyl group or an acyloxyalkyl group such as the 2-acetaxylethyl, 2-acetoxypropyl or 2-stearoylaxylethyl group. An alkenyl group R¹ may be, for example, the allyl or methallyl group. An alkynyl group R¹ may be for example the propargyl group. An aralkyl group R¹ For example, it may be the benzyl or a-methylbenzyl group. A substituted aralkyl group R may be, for example, a hydroxyalkyl group such as the 2-hydroxy-2-phenylethyl group. An acyl group R¹ For example, it may be an aliphatic acyl group such as the formyl or acetyl group.

In particular, those compounds of general formula (Ia) are used in which R¹ a Qxyl group, an alkyl group having 1 to 8 C atoms, a haloalkyl group having 1 to 5 C atoms, a cyanoalkyl group having 1 to 5 C atoms, an epoxyalkyl group having 3 or 4 C atoms, a hydroxyalkyl group having 2 to 5 C atoms, an acyloxyalkyl group having 4 to 20 C atoms, an aminoalkyl group having 2 to 4 C atoms, an alkoxycarbonylalkyl group having 3 to 21 C atoms, an alkoxyalkyl group having 3 to 20 C atoms, an alkenyl group having 3 to 6 C-atoms, an alkynyl group having 3 to 6 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a hydroxyalkyl of 8 to 12 carbon atoms or an acyl group having 2 to 18 carbon atoms.

R_a and Re are preferably methyl groups. R_c and R &lt;j are preferably methyl groups or, together with the carbon atom bearing these groups, form a cyclohexyl group or a group of the general formula

CH,

CH "

NH

CH

CH

In particular, R_c and R ^ represents methyl groups.

Another group of compounds which can preferably be used according to the invention are those of the general formula (1) which have the general formula

- 4 No.328745

<img file="AT328745B_D0004.tif" />

where n is 1 or 2 and, if n is 1, R¹ an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 3 to 10 carbon atoms, an alkynyl group having 3 or 4 carbon atoms, one in the phenyl radical optionally up to three substituents of the same or different kind, u.zw. Chlorine, alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 8 carbon atoms and hydroxyl-bearing benzyl group, a

2.3- Epoxypropylgruppe, a phenethyl group, a group of the general formula -CH₂~ CO-OR²with the meaning of an alkyl group having 1 to 18 C atoms, an alkenyl group having 3 to 6 C atoms, a phenyl group, a benzyl group, a cyclohexyl group or a 2,3-epoxypropyl group for R², a group of the general formula - CH - CHR R with the meaning of hydrogen, a methylene group or a phenyl group for R and the meaning of a hydroxy group or a group of the general formula --O - COR⁵ (where R⁵ an alkyl group having 1 to 17 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an optionally up to three substituents of the same or different type, u.zw. Chlorine, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or a phenyl group bearing a hydroxy group, a benzyl group, a 3,5-di- (tert-butyl) -4-hydraxyphenethyl group, a styryl group or a cyclohexyl group) for R⁴ or a group of the general formula - CO - R with the

Meaning of hydrogen, a methyl group, an alkenyl group having 2 or 3 carbon atoms, a Alkoxyθ group having 1 to 8 carbon atoms, a benzyloxy group or a phenoxy group for R or, if n is 2, R is an alkylene group having 1 to 6 C atoms and optionally interrupted by an oxygen atom chain, a 2-butenylene group, a group of the general formula - CH ₂COOR⁷- O-COCH20 with the meaning of an alkylene group having 2 to 6 C atoms or a xylylene group for R⁷ or a group of the general formula - CH ₂ - CH ₂ - O - CO - (- CO - O - CH₂ - CH ₂ - having the meaning of zero or 1 for m and an alkylene group having 1 to 10 carbon atoms and optionally interrupted by a sulfur atom chain, an alkenylene group having 2 to 4 carbon atoms, a phenylene group or a

1.4-cyclohexylene group for R^8th is.

If n is equal to 1 in formula (Tb), the following fades are conceivable, for example:

An alkyl group R¹ For example, methyl, ethyl, propyl, butyl, isobutyl, isopentyl,

Hexyl, octyl, dodecyl or octadecyl. An alkenyl group R¹ may be, for example, an allyl, crotyl, 2-hexenyl or 2-decenyl group. An alkynyl group R¹ may be, for example, a propargyl or 2-butynyl group. A substituted benzyl group R¹ For example, it is possible to use an o, m or p-chloro-benzyl, p-methylbenzyl, p-ethylbenzyl, p-isopropyl-benzyl, p-methoxybenzyl, p-butoxybenzyl, p-octylbenzyl or 3,5-dicarboxylic acid. (tert-butyl) -4-hydroxybenzyl group.

If R² is an alkyl group, it may be, for example, the methyl, ethyl, butyl, isopentyl, octyl, dodecyl or octadecyl. An alkenyl group R may be, for example, the allyl, crotyl or 2-hexenyl group.

An alkyl group R⁵ may be, for example, the methyl, ethyl, propyl, isopropyl, hepyl, 1-ethylpentyl, undecyl, pentadecyl or heptadecyl group. An alkenyl group R⁵ may be, for example, the vinyl, 1-propenyl, isopropenyl or 2-methyl-1-propenyl group. An optionally substituted phenyl group R⁵ For example, the phenyl group itself or the m- or p-chlorophenyl, 2,4-dichlorophenyl, o- or p-methylphenyl, p-isopropylphenyl, p-tert. Butylphenyl, p-ethaxyphenyl, p-butoxy-40-phenyl, p-octaxyphenyl, 3,4,5-trimethoxyphenyl, o-hydraxyphenyl or 3,5-di- (tert-butyl) -4-hydroxyphenyl.

EineAlkenylgruppeR⁶ may be, for example, the vinyl or 1-propenyl group. An alkoxy group R⁶ For example, it may be the methoxy, ethoxy, isobutaxy or octaxy group.

If in formula (Tb) n is equal to 2, the following cases are conceivable, for example:

An alkylene group R¹ may be, for example, the methylene, ethylene, tetramethylene or hexamethylene group. An alkylene group R having an oxygen atom in the chain¹ is, for example, the Qxydiäthylgruppe.

An alkylene group R⁷ For example, it may be the ethylene, tetramethylene or hexamethylene group.

A xylylene group R⁷ may be, for example, the m- or p-xylylene group.

An alkylene group R^8th may be, for example, the methylene, ethylene, tetramethylene, octamethylene or decamethylene group. An alkylene group having a sulfur atom in the chain is, for example, the thiodiethyl group. An alkenylene group R^8th is, for example, the vinylene, 2-propene-1, 2-ylene5

No. 328745 g

or 2-butenylene group. A phenylene group R is, for example, the m- or p-phenylene group.

If n is 1, in formula (Ib) the following groups R are¹ prefers:

An alkyl group having 4 to 12 C atoms, in particular the butyl, octyl or dodecyl group.

An allyl group.

A benzyl group which in the phenyl radical optionally has from 1 to 4 C-atoms alkyl,

Methoxy or 3,5-di- (tert-butyl) -4-hydroxy substituted, in particular the benzyl group itself.

A group of the general formula - CH CO - OR, in particular such a group with the Be4 2 interpretation of an alkyl group having 1 to 18 carbon atoms or an allyl group for R.

4

A group of the general formula -CH₂-CHR R, in particular such a group with the meaning of hydrogen, a methyl group or a phenyl group, especially with the meaning of hydrogen for R³ and with the meaning of a hydroxy group or a group of the general formula --O - COR⁵ for R⁴where R⁵ an alkyl group having 1 to 17 carbon atoms, a 3,5 - di- (tert-butyl) -4-hydroxyphenäthylgruppe, an alkenyl group having 2 or 3 carbon atoms or an optionally by alkyl having 1 to 4 carbon atoms, alkoxy with 1 to 8 carbon atoms or hydroxy-substituted phenyl group, in particular the phenyl group itself, is.

If n is equal to 2, the following groups R are in formula (Ib)¹ prefers:

An alkylene group having 2 to 6 C atoms, in particular the ethylene or hexamethylene group.

A group of the general formula - CH-CO-O-R⁷ - O - CO - CH -, in particular such

2 γ

Group with the meaning of an alkylene group having 2 to 6C atoms for R, especially with the meaning of the ethylene or hexamethylene group for R.

A group of the general formula - CH ₂ - CH ₂ - O - CO - R^8th - CO - O - CH ₂ - CH ₂ With the meaning of an alkylene group having 1 to 8 C atoms for R^8th, in particular with the meaning of the methylene, ethylene, tetramethylene, octamethylene or m or p-phenylene group for R^8th,

In the following, individual compounds of the general formula (I) which are preferably used according to the invention are listed by list without limitation. The serial numbers appearing in the list are used in Examples 1 to 7 to identify the compounds.

1) 1,2,2,6,6-pentamethylpiperidine

2) 1-butyl-2,2,6,6-tetramethylpiperidine

3) 1-octyl-2,2,6,6-tetramethylpiperidine

4) l-dodecyl-2,2,6,6-tetramethylpiperidine

5) 1-octadecyl-2,2,6,6-tetramethylpiperidine

6) 1-allyl-2,2,6,6-tetramethylpiperidine

7) 1-Crotyl-2,2,6,6-tetramethylpiperidine

8) l-propargyl-2,2,6,6-tetramethylpiperidine

9) 1-Benzyl-2,2,6,6-tetramethylpiperidine

10) 1-phenethyl-2,2,6,6-tetramethylpiperidine

11) 1- (o-chlorobenzyl) -2,2,6,6-tetramethylpiperidine

12) 1- (m-chlorobenzyl) -2,2,6,6-tetramethylpiperidine

13) 1- (p-chlorobenzyl) -2,2,6,6-tetramethylpiperidine

14) 1- (p-methylbenzyl) -2,2,6,6-tetramethylpiperidine

15) 1- [3,5-di- (tert-butyl) -4-hydroxybenzyl] -2,2,6,6-tetramethylpiperidine

16) 1- (p -methoxybenzyl) -2,2,6,6-tetramethylpiperidine

17) 1- (2,3-epoxypropyl) -2,2,6,6-tetramethylpiperidine

18) 1-Methoxycarbonylmethyl-2,2,6,6-tetramethylpiperidine

19) 1-ethoxycarbonylmethyl-2,2,6,6-tetramethylpiperidine

20) 1-butoxycarbonylmethyl-2,2,6,6-tetramethylpiperidine

21) 1-Octaxycarbonylmethyl-2,2,6,6-tetramethylpiperidine

22) l-Dodecyloxycarbonylmethyl-2,2,6,6-tetramethylpiperidine

23) 1-Octadecyloxycarbonylmethyl-2,2,6,6-tetramethylpiperidine

24) l-Allyloxyearbonylmethyl-2,2,6,6-tetramethylpiperidine

25) 1-Benzyloxycarbonylmethyl-2,2,6,6-tetramethylpiperidine

26) l-Cyclohexyloxycarbonylmethyl-2,2,6,6-tetramethylpiperidine

27) 1- (2-hydroxyethyl) -2,2,6,6-tetramethylpiperidine

28) 1- (2-hydroxypropyl) -2,2,6,6-tetramethylpiperidine

29) 1- (2-hydroxy-2-phenylethyl) -2,2,6,6-tetramethylpiperidine

30) 1- (2-acetoxyethyl) -2,2,6,6-tetramethylpiperidine

31) 1- (2-acetoxypropyl) -2,2,6,6-tetramethylpiperidine

32) 1- (2-acetoxy-2-phenylethyl) -2,2,6,6-tetramethylpiperidine

33) 1- (2-propionyloxy-2-phenylethyl) -2,2,6,6-tetramethylpiperidine

Nr.328745

34) 1- (2-Butyrylaxypropyl) -2,2,6,6-tetramethylpiperidine

35) 1- (2-Lauroylaxyethyl) -2,2,6,6-tetramethylpiperidine

36) 1- (2-Lauroylaxypropyl) -2,2,6,6-tetramethylpiperidine

37) 1- (2-Lauroyloxy-2-phenylethyl) -2,2,6,6-tetramethylpiperidine

38) 1- (2-stearoyloxyethyl) -2,2,6,6-tetramethylpiperidine

39) 1- (2-stearoyloxy-2-phenylethyl) -2,2,6,6-tetramethylpiperidine

40) 1- (2-Aeryloyloxyethyl) -2,2,6,6-tetramethylpiperidine

41) 1- (2-crotonoyl-oxyethyl) -2,2,6,6-tetramethylpiperidine

42) 1- (2-crotonoyloxypropyl) -2,2,6,6-tetramethylpiperidine

43) 1- (2-methacryloyloxyethyl) -2,2,6,6-tetramethylpiperidine

44) 1- (2-benzoyloxyethyl) -2,2,6,6-tetramethylpiperidine

45) 1- (2-benzoyloxypropyl) -2,2,6,6-tetramethylpiperidine

46) 1- (2-benzoylaxy-2-phenylethyl) -2,2,6,6-tetramethylpiperidine

47) 1- [2- (m-chlorobenzoyloxy) ethyl] -2,2,6,6-tetramethylpiperidine

48) 1- [2- (p-chlorobenzoyloxy) -2-phenylethyl] -2,2,6,6-tetramethylpiperidine

49) 1-j2- (p-toluoyloxy) -propyl] -2,2,6,6-tetramethylpiperidine

50) 1- [2- (p-tert-butylbenzoyloxy) ethyl] -2,2,6,6-tetramethylpiperidine

51) 1- [2- (3,5-di-tert-butyl-4-hydroxybenzoyloxy) -propyl] j-2_J 2, 6, 6-tetramethylpiperidine

52) 1- [2- (p-Methoxybenzoyloxy) -2-phenylethyl] -2,2,6,6-tetramethylpiperidine

53) 1- (2- (3,4,5-trimethoxybenzoyloxy) ethyl] -2,2,6,6-tetramethylpiperidine

54) 1- [2- (p-butoxybenzoyloxy) ethyl] -2,2,6,6-tetramethylpiperidine

55) 1- [2- (p-octoxybenzoyloxy) -propyl-2,2,6,6-tetramethylpiperidine

56)

57)

58)

59)

60) 61) 62)

63)

64)

65)

66)

67)

68)

69)

70)

71)

72)

73)

74)

75)

1- (2-Salicyloyloxyethyl) -2,2,6,6-tetramethylpiperidine 1- (2-phenylacetoxyethyl) -2,2,6,6-tetramethylpiperidine 25 58) 1- {2- [3- (3,5-) Di-tert-butyl-4-hydroxyphenyl) -propionyloxy] ethyl} -2,2,6,6-tetramethylpiperidine

1- (2-cinnamoyloxy-2-phenylethyl) -2,2,6,6-tetramethylpiperidine 1- (2-cyclohexanecarbonylaxypropyl) -2,2,6,6-tetramethylpiperidine 1-kormyl-2,2,6,6 tetramethylpiperidine l-acetyl-2,2,6,6-tetramethylpiperidine 30 63) 1-Acryloyl-2,2,6,6-tetramethylpiperidine 1-crotonoyl-2,2,6,6-tetramethylpiperidine 1-methoxycarbonyl-2,2 , 6,6-tetramethylpiperidine, 1-octoxycarbonyl-2,2,6,6-tetramethylpiperidine, 1-benzyloxycarbonyl-2,2,6,6-tetramethylpiperidine

1,2-bis- (2,2,6,6-tetramethylpiperidino) -ethane, 4-bis (2,2,6,6-tetramethylpiperidino) -butane 1, 6-bis- (2,2,6, fr -tetramethylpiperidino) ~ hexane 2,2'-bis (2,2,6,6-tetramethylpiperidino) -ethyl ether

1,4-bis- (2,2,6,6-tetramethylpiperidino) -trans-2-butene

1,2-Bis (2,2,6,6-tetramethylpiperidinoacetoxy) ethane 1, 6-bis (2,2,6,6-tetramethylpiperidinoacetaxy) hexane

1,4-bis (2,2,6,6-tetramethylpiperidinoacetoxy) benzene

76) Bis- [2- (2,2,6,6-tetramethylpiperidino) ethyl] -j-oxalate

77) Bis [2- (2,2,6,6-tetramethylpiperidino) ethyl] malonate

78) Bis [2- (2,2,6,6-tetramethylpiperidino) ethyl] -suencinate

Bis- [2- (2,2,6,6-tetramethylpiperidino) ethyl] adipate bis [2- (2,2,6,6-tetramethylpiperidino) ethyl] sebacate bis [2- (2, 2, 6, 6-tetramethylpiperidino) ethyl] -l, 10-decanedicarboxylate Bis- [2- (2,2,6,6-tetramethylpiperidino) ethyl] thiodipropionate 50 83) Bis- [2- (2,2 , 6,6-tetramethylpiperidino) ethyl-maleate

Bis [2- (2,2,6,6-tetramethylpiperidino) ethyl] terephthalate

85) bis [2- (2,2,6,6-tetramethylplperidino) ethyl] isophthalate

86) Bis [2- (2,2,6,6-tetramethylpiperidino) ethyl] -1,4-cyclohexanedicarboxylate

Piperidine derivatives of the general formula (I) can be prepared by methods known per se, for example 55, according to the reactions (A) to (F) given below. The compounds of the general formulas (Π), (V), (II) obtainable according to these reactions Va), (Vm), (X), (Xa), (XU), (XIV) and (XVI) are all subgroups of compounds of general formula (I).

(A) Compounds of formula (H) can be prepared by reaction of a substituted piperidine (EU) with a

Halide (IV) are prepared according to the method specified in British Patent No. 834,290, im

78)

79)

80) 81) 82)

83)

84)

Nr.328745

Framework of the same piperidine (ΙΠ) is reacted with allyl bromide:

<img file="AT328745B_D0005.tif" />

In the above reaction sehema have R_a, R ^, R_c and Rj has the meaning already given, where n is 1 or 2 and, in the case n, 1 R⁹ an alkyl group, an alkenyl group, an alkynyl group, a substituted or unsubstituted benzyl group, a phenethyl group, a 2,3-epoxypropyl group, a

Cyanoalkyl group, an aminoalkyl group, an alkoxyalkyl group or a group of the general formula ί 2 9 - CH₂ CO - OR with the already given meaning for R or for the case n is 2 R is an alkylene group with optionally interrupted by an oxygen atom chain or a 2-butenylene group and Y further represents a halogen atom.

(B) Compounds of the formulas (V) and (Va) can be obtained by transesterification of a substituted piperidine of the general formula (VI) with an alcohol of the general formula (VH) or a diol of the general formula (VIIa) according to the reaction equations or

<img file="AT328745B_D0006.tif" />

+ ROH (VH)

R

<img file="AT328745B_D0007.tif" />

<img file="AT328745B_D0008.tif" />

io

HO-R-OH (VHa)

<img file="AT328745B_D0009.tif" />

be made in which

R, R ^, R_c, Rj, R² and R⁷ have the already given meaning and B? ° represents an alkyl group.

(C) Compounds of the general formula (VBI) can be prepared according to the method described in British Patent 20 No. 1, 143,371 by reacting a substituted piperidine (IH) with a

Epoxide (K) according to the reaction scheme

Nr.328745

R ^xa R, (_)

NH + CH-CH-R / o

R

<img file="AT328745B_D0010.tif" />

c dH) (VHI), in which R_a, R ^, R_c, R ^ and R³ have the meaning already given.

(D) Compounds of formulas (X) and (Sa) may be prepared by the method described in British Patent No. 143,371 by reacting a substituted piperidine of formula (VHI) or (VHIa) with a reactive derivative of a suitable acid , for example, an acid halide of the formula (XI) or (XIa), according to the reaction scheme (K)

<img file="AT328745B_D0011.tif" />

<img file="AT328745B_D0012.tif" />

(vm) (xi) (X) or the reaction scheme

<img file="AT328745B_D0013.tif" />

c

YCO • COY

<img file="AT328745B_D0014.tif" />

(R^8th), wherein R_a, R ^, R_Q, Rj, R³, R⁵and R^8th, Y and m are as defined above, (E) compounds of the formula (ΧΠ) can be prepared according to the method described in J. Med. Chem., 6, [1963], pp. 381 to 384, by reacting a substituted piperidine (US Pat. EU) with a reactive derivative of a suitable acid, for example an acid halide of the formula (ΧΠΙ), corresponding to

scheme

Nr.328745

R

V^bG

NH + RCOY

R ^Rdc dH) (ΧΠΙ)

<img file="AT328745B_D0015.tif" />

be made in which

R_a, Ry. R_c and R 1 have the meaning already given above,

R¹¹ is a methyl group or an alkenyl group and 5 Y represents a halogen atom.

Compounds of the formula (XIV) can be prepared by a similar method but using instead of the acid halide (ΧΠΙ) a chlorocarbonate (XV) and according to the reaction scheme a R.

a R, / 12 (NH + C1CO-OR^U / \ ₁₂\ N-CO-OR

R dc (HI) (XV) (XIV) is worked, in which R_a&gt; R ^, R_c and R 1 are as defined above and R is an alkyl group, a benzyl group or a phenyl group.

(F) Compounds of formula (XVI) can be prepared by reacting a substituted piperidine (III) with o-formic acid ethyl ester in the presence of an acidic catalyst according to the reaction scheme

<img file="AT328745B_D0016.tif" />

'NH

R, (IH) + ch &lt;oc₂H₅)₃

<img file="AT328745B_D0017.tif" />

be prepared, in which R_a, R ^, R_c and R, j have the meaning already given.

The reactions (A.), (D) and (E) proceeding with elimination of hydrogen halide are expediently carried out in the presence of an acid-binding agent, as which customary organic or inorganic bases can be added to the reaction mixture or else an excess of pyridine used as starting material can be used.

The reaction can be carried out by heating the reactants in an inert solvent, but it is also possible to work in the absence of a solvent.

The transesterification (B) is carried out in the presence of a catalyst, for example an alkali metal alkoxide, -amide or -hydroxyds, under heating, wherein the liberated during the reaction of alcohol is preferably removed from the reaction mixture.

Compounds of the general formula (I) give exceptionally high synthetic polymers

Resistance to degradation under light and heat. In addition, this increased stability is achieved without discoloration of the polymer and without adverse effect on the polymers possibly added further light stabilizers, stabilizers, plasticizers or pigments. Accordingly, the invention provides a synthetic polymer and at least one compound of the general For10

No.328745 mel (I) containing mixture created.

Synthetic polymers stabilizable by compounds of general formula (I) are, inter alia

Olefin, diene and styrene polymers, such as homopolymers of olefins, dienes and styrene, for example polyethylenes of low and high density, polypropylene, polystyrene, polybutadiene or polyisoprene, copolymers of olefins, dienes and styrene with one another or with other ethylenically unsaturated monomers, for example ethylene Propylene copolymers, ethylene-butene copolymers, ethylene-vinyl acetate copolymers, styrene-butadiene copolymers or acrylonitrile-butadiene-styrene copolymers,

Vinyl chloride and vinylidene chloride copolymers, such as homopolymers of vinyl chloride and vinylidene 10 chloride, vinyl chloride-vinylidene chloride copolymers, and copolymers of vinyl chloride or vinylidene halide with vinyl acetate or other ethylenically unsaturated monomers,

Polyacetals, such as polyoxymethylene and polyoxyethylene,

Polyester, such as polyethylene terephthalate,

Polyamides such as nylon-6, nylon-6, 6- nylon-6,10 and nylon 12,

Polyurethanes such as polyether polyurethanes and polyester polyurethanes and

Epoxy resins, such as reaction products of epichlorohydrin with polyphenols.

Synthetic polymers stabilized with compounds of the general formula (I) can be used to prepare a wide variety of products, for example threads, fibers, yarns, films, films or other shaped articles, latices, foams and paints.

The amount of a stabilizer of general formula (I) required for sufficiently stabilizing a synthetic polymer depends on various factors, for example, the nature and properties and ultimate use of the polymer to be stabilized, the expected duration and intensity of heat and light exposure, and any additional ones present Stabilizers is usually between 0.01 to 5.0% by weight, preferably 0.1 to 2% by weight, based on the synthetic Polyme25 re.

Stabilizers of the general formula (I) can be incorporated into synthetic polymers to be stabilized without difficulty in a conventional manner during any stage of preparation for the production of molded articles. For example, the stabilizer may be mixed with the synthetic polymer in the form of a dry powder, or may be added to the powdery polymer in the form of a suspension in a suitable solvent or dispersing agent such as an inert organic solvent such as methanol, ethanol or acetone, and then intimately mixed become. Another possibility is to add stabilizer already during the preparation of the polymer, for example during the latex stage occurring in the preparation of the polymer, in order to obtain a prestabilized polymer.

The mixtures of a synthetic polymer and a stabilizer of the general formula (I) may optionally contain various conventional additives, for example the following.

antioxidants

Simple 2, 6-dialkylphenols, such as

2, 6-di-tert. butyl-4-methylphenol 40 2-tert. Butyl-4,6-dimethylphenol

2, 6-di-tert. butyl-4-methoxymethylphenol and

2,6-dioctadecyl-4-methylphenol.

Derivatives of alkylated hydroquinones such as

2,5-di-tert. butylhydroquinone 45 2,5-di-tert. amylhydroquinone

2, 6-di-tert. butylhydroquinone

2.5- di-tert. butyl-4-hydroxyanisole

3.5- Di-tert. butyl-4-hydroxyanisole

Tris (3,5-di-tert-butyl-4-hydroxyphenyl) phosphite 50 3,5-di-tert. butyl-4-hydroxyphenyl stearate

Di (3,5-di-tert-butyl-4-hydraxyphenyl) adipate.

Hydroxylated thiodiphenyl ethers such as

2,2'-thio-bis- (6-tert-butyl-4-methylphenol)

2,2'-thio-bis- (4-oetylphenol)

4,4'-thio-bis- (6-tert-butyl-3-methylphenol)

4,4'-thio-bis (3, 6-di-s-amylphenol)

4,4'-thio-bis (6-tert-butyl-2-methylphenol) and

4,4'-bis (2, 6-dimethyl-4-hydraxyphenyl) disulfide.

Nr.328745

Alkylidenebisphenols, such as

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

2,2'-methylene-bis (6-tert-butyl-4-ethylphenol)

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

4,4'-methylene-bis (2,6-di-tert-butylphenol)

2,2-Di- (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol 2,2 '-Methylene-bis- [4-methyl-6- (o-methylcyclohexyl) -phenol]

1, 1-bis- (3,5-dimethyl-2-hydroxyphenyl) -butane

1, 1-Bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -butane 10 2,2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -butane

2,2-bis- (3,5-di-tert-butyl-4-hydroxyphenyl) -propane

1,1,3-Tris-5- (tert-butyl-4-hydroxy-2-methylphenyl) butane

2,2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane

1.1.5.5- Tetra- (5-tert-butyl-4-hydroxy-2-methylphenyl) -pentane and 15-ethylene glycol bis [3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) - butyrate].

Ο-, N- and S-benzyl compounds, such as

3,5,3 ', 5' -Tetra- (tert-butyl) -4,4'-dihydraxydibenzyl ether 4-Hydroxy-3,5-dimethylbenzylmercaptoacetic acid octadecyl ester tri- (3,5-di-tert-butyl-4-hydroxybenzyl) -amine and

Bis (4 "tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate.

Hydroxybenzylated malonic acid esters, such as

2,2-Bis (3,5-di-tert-butyl-2-hydroxybenzyl) -malonic acid dioctadecyl ester 2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) -malonic acid dioctadecyl ester

2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) -malonic acid dodecylmercaptoethyl ester and

2,2-Bis (3,5-di-tert-butyl-4-hydroxybenzyl) -malonic acid di (4-tert-octylphenyl) ester.

Hydroxybenzylaromaten, such as

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

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-triazines, such as

2,4-Bis-octylmercapto-6- (3,5-di-tert-butyl-4-hydroxyanilino) -s-triazine 2-Oetylmercapto-4,6-bis- (3,5-di-tert-butyl-4- hydroxyanilino) -s-triazine 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenaxy) -s-triazine 2,4,6-tris- (3,5-di-tert-butyl) tert-butyl-4-hydroxyphenoxy) -s-triazine

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.

Amides of 3,5-di-tert. butyl-4-hydraxyphenylpropionic acid, such as

1.3.5- Tris- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexahydro-s-triazine and N, Ν'-bis- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine.

Esters of 3,5-di-tert. Butyl-4-hydroxyphenylpropionic acid with monohydric or polyhydric alcohols such as esters of this acid with methanol, ethanol, octadecanol, 1, 6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, diethylene glycol, thiodiethylene glycol, neopentyl glycol, pentaerythritol , 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolethane, trimethylolpropane, tris-hydroxyethyl isocyanurate and 4-hydraxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2,2,2] oetane.

Ester of the 5-tert. butyl-4-hydroxy-3-methylphenylpropionic acid with monohydric or polyhydric alcohols, for example esters of this acid with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, diethylene glycol, thiodiethylene glycol, Neopentyl glycol, pentaerythritol, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolethane, trimethylolpropane, tris-hydroxyethyl isocyanurate and 4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2,2,2] octane.

Esters of 3,5-di-tert. Butyl-4-hydroxyphenylacetic acid with monohydric or polyhydric alcohols such as an ester of this acid with methanol, ethanol, octadecanol, 1, 6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, diethylene glycol, thi odiäthylenglykol, neopentyl glycol, Pentaerythritol, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol ,. Trimethylolethane, trimethylolpropane, trishydraxyethyl isocyanurate and 4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2,2,2] octane.

Acylaminophenols such as

N- (3,5-di-tert-butyl-4-hydroxyphenyl) -steramide and N, Ν'-bis- (3,5-di-tert-butyl-4-hydroxyphenyl) -thiobisacetamide.

Benzylphosphonates such as

3.5- Dirtert.butyl-4-hydrocyclobenzylphosphonic acid dimethyl ester

Nr.328745

3.5- DMert. butyl-4-hydrcKybenzylphosphonsäiirediättLylester

3.5- Di-tert. butyl-4-hydroxybenzylphosphonic acid dioctadecyl ester and 5-tert. butyl-4-hydraxy-3-methylbenzylphosphonsäuredioetadecylester.

Aminoaryl derivatives such as e.g. Phenyl-1-naphthylamine, phenyl-2-naphthylamine, N, N'-diphenyl-p-phenylenediamine, N, N'-di-2-naphthyl-p-phenylenediamine, Ν, Ν'-di-s- butyl-p-phenylenediamine, 6-atebaxy-2,2,4-trimethyl-1,2-dihydroquinoline, 6-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline, mono- and dioctyliminodibenzyl and polymerized 2, 2,4-trimethyl-1,2-dihydroquinoline.

UV absorber and light stabilizer

2- (2'-hydroxyphenyl) benzotriazoles such as 5'-methyl, 3 ', 5'-di-tert-butyl, 5-tert-butyl, 10 5' - (1, 1,3,3 Tetramethylbutyl), 5-chloro-3 ', 5'-di-tert-butyl, 5-Cblor-3'-tert. butyl-5'-methyl, 3'-s-butyl-5'-tert. butyl, 3 '- (ce -methyl) benzyl) -5'-metbyl-, 3' - (a-methylbenzyl) -5'-methyl-5-ehloro, 4 '-hydroxy-, 4'-methoxy- '4'-Octoxy, 3', 5'-di-tert-amyl, 3'-methyl-5'-carbomethoxyethyl and 5-chloro-3 ', 5'-di-tert. amylderivate.

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

2-Hydroxybenzophenones such as 4-hydraxy, 4-methaxy, 4-octaxy, 4-decyloxy, 4-dodecylaxy, 4-benzylaxy, 4- (2 ', 4'-trihydroxy) - and 2' hydroxy-4'-dimetboxyderivate.

1,3-bis- (2'-hydroxybenzoyl) -benzenes such as

1,3-bis- (2'-hydraxy-4'-hexylaxybenzoyl) -benzene 20 1,3-bis (2'-hydroxy-4'-octaxybenzoyl) -benzene and

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

Esters of substituted benzoic acids, such as, for example, pbenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert-butylbenzoyl) -resorcinol, benzoylresorcinol and 2,4-di-tert. butylphenyl ester, octadecyl ester or 2-methyl-4,6-di-tert-butylphenyl ester of 3,5-di-tert-butyl-4-hydroxybenzoic acid.

Acrylates such as a-cyano-ß, ß -dipbenylacrylsäureäthylester or -isooctylester, ic-Carbomethoxyzimtsäuremetbylester, α-cyano-.beta.-methypp-methoxycinnamic acid methyl ester or butyl ester and N- (ß-Carbometboxyvinyl) -2-methylindoline.

Nickel compounds such as 2,2'-thio-bis (4-tert-octylphenol) complexes with nickel (for example, the 30 1: 1 'and 1: 2 complexes), optionally with other ligands such as n-butylamine, triethanolamine or N-cyclohexyl diethanolamine, complexes of nickel with bis (4-tert. octylphenyl) sulfone (for example the 2: 1 complexes), optionally together with other ligands such as 2-acebylcaproic acid, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters such as the methyl, ethyl or butyl ester , Nickel complexes of 2-hydroxy-4-methylphenyl undecyl ketaxime and nickel (3,5-di-tert-butyl-4-hydroxy) benzoate.

Qxalsäurediamide such as dioctyloxyaxanilide, 2,2 '-Dioctylcκy-5,5'-dl · tert.butylαxanilid, 2,2'-didodecyloxy-5,5'-di-tert. butyloxanilide, 2-acebaxy-5-tert. butyl-2'-ethylaxanilide, 2-ethyl-2'-ethylaxanilide, N, N'-bis (3-dimethylaminopropyl) -oxalamide, mixtures of o- and p-methoxy- and o- and p-ethoxydisubstituted-qxanilides and mixtures of 2-ethoxy-5-tert. butyl · 2'-ethylaxanilide with 2-ethoxy-2'-ethyl ·

-5,4'-di-tert. tertbutyloxanilide.

Metal deactivators such as qxanilide, isophthalic dibydrazide, sebacic acid (bis-phenylhydrazide), bisbenzylidenoxalic dihydrazide, N, N'-diacetyladipic dihydrazide, N, N'-bis-salicyloyloxalicarboxylic dibydrazide, Ν, Ν'-bis-salieyloylhydrazine and Ν, N'-bis ( 3,5-di-tert-butyl-4-by-tricycbenyl-propionyl) -hydrazine.

Phosphites such as triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, trinonylphenyl 45 phosphite, trilauryl phosphite, trioctadecyl phosphite, 3,9-diisodecylaxy-2,4,8,10-tetraaxa-3,9-diphosphaspirofo, 5] undecane and tris (4-hydroxy-3 , 5-di-tert-butylphenyl) phosphite.

Peracid deactivators such as esters of β-thiodipropionic acid (eg the lauryl, stearyl, myristyl and tridecyl esters), salts of 2-mercaptobenzimidazole (eg the zinc salt) and diphenylthiobeamic.

Polyamide stabilizers such as copper salts in combination with iodides and / or Phosphorverbindun50 gene and salts of divalent manganese.

Basic costabilizers, for example polyvinylpyrrolidone, melamine, benzoguanamine, triallyleneurourate, dicyandiamide, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes and alkali metal salts and alkaline earth metal salts of higher saturated or unsaturated fatty acids (for example calcium stearate, magnesium laurate, sodium bicinoleate, carbonyl). palmitate, zinc stearate).

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

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

Other additives such as plasticizers, lubricants (for example, glycerol monostearate), emulsifiers, antistatic agents, flame retardants, pigments, carbon black, asbestos, glass fibers, kaolin and talc.

Nr.328745

Stabilizers of the general formula (I) together with the above-mentioned antioxidants are particularly suitable for stabilizing olefin polymers.

The invention is explained in more detail below by Examples 1 to 7, in which the stabilizers corresponding to formula (I) are labeled with the numbers appearing in the list above. Preparations 1 to 6 following the examples serve to illustrate the preparation of stabilizers of the general formula ¢). Parts by weight and percentages are by weight in the absence of other information. The stabilizers A and B used in the examples for comparison purposes are commercially available products and represent chemically following compounds:

A: 2- (2-Hydoxy-3,5-di-tert-butylphenyl) -6-chlorobenzo-l, 2,3-triazole 10 B: 2- (2-Hydraxy-5-methylphenyl) - (benzo-l, 2 , 3-triazole).

Example 1: From 1000 parts by weight of powdery polypropylene having a melt index of 20 (230 ° C., 2160 g), 2 parts by weight of octadecyl β- (3,5-di-tert-butyl-4-hydraxyphenyl) propionate and 2 , 5bzw. 5 parts by weight of the inventively used and specified in Table I stabilizers mixtures were prepared, which were then homogenized in a kneader to Brabender at 200 ° C and then pressed in 15 a toggle press to 2 to 3 mm thick plates. From the plates thus produced, 0.3 mm thick films were then produced using suitable molds at 260 ° C in a platen press, which were then further processed into 0.1 mm thick films. For comparison purposes, a film was also further prepared without using a stabilizer.

The films thus prepared were then heat treated at 150 ° C for 1 h and immediately quenched in water at 15 ° C. In the course of the heat treatment, care was taken that the temperature did not drop below 150 ° C. The films obtained had a homogeneous, fine-spherulitic structure. From the films punched test specimens had an elongation at break of approximately 900%.

The polypropylene films thus produced were attached to a sample holder and tested in a tester (Xeno-150) as described in Japanese Industrial Standard L0843, and at regular intervals individual portions of the film were removed from the tester followed by five of the tester taken sections were punched out and their residual strain was determined. The exposure time after which the breaking elongation of the film had dropped to 50% of the value of the elongation before irradiation was used as a measure of the effectiveness of the stabilizers.

The results obtained are shown in Table I.

Table I

<td colspan="2">stabilizer</td><td rowspan="2">Time required for a drop in elongation at break to 50% of the initial value in hours</td>

<td>connection No.</td><td>added amount in parts by weight</td>

<td>3</td><td>2.5</td><td>4700</td>

<td>4</td><td>2.5</td><td>5140</td>

<td>8th</td><td>2.5</td><td>2200</td>

<td>21</td><td>2.5</td><td>4920</td>

<td>27</td><td>5</td><td>8900</td>

<td>29</td><td>5</td><td>4350</td>

<td>38</td><td>5</td><td>10500</td>

<td>39</td><td>5</td><td>6250</td>

<td>70 none</td><td>2.5</td><td>&gt; 6000 800</td>

Example 2: From 100 parts by weight of polypropylene (used after two recrystallizations from monochlorobenzene) and 0.25 parts by weight of stabilizers to be used according to the invention and indicated in Table Π and, for comparison purposes, the stabilizer A mixtures were prepared, which are melted down and were processed under heating and under pressure to 0.5 mm thick webs. Furthermore, for comparison purposes, a web was also prepared without using a stabilizer.

The thus produced webs were at 45 ° C in the standard Fade-Meter Type FA-1 Toyo Rika

Instruments Ine, Japan, (a modified version of the Atlas Fade-O-Meter type FDA-R, which complies with paragraph 3.8 of the Japanese Industrial Standard 1044-L) irradiated with ultraviolet radiation. The time required to embrittle the sheets is given in Table Π.

Example 3 From 100 parts by weight of high-density polyethylene (used after two-minute conversion from toluene) and in each case 0.25 parts by weight of a stabilizer to be used according to the invention, the number given in Table II and, for comparison purposes, the stabilizer A mixtures were prepared, which then in the heat and under pressure to 0.5 mm. strong webs were processed. To

For purposes of comparison, a web was also prepared without using a stabilizer.

The time required for embrittlement (embrittlement time) was determined by the method given in Example 2. The results obtained are shown in Table Π.

Table II

<td rowspan="2">Stabilizer no.</td><td colspan="2">Embrittlement time in hours</td>

<td>polypropylene</td><td>Polyethylene of high density</td>

<td>1</td><td>560</td><td>-</td>

<td>4</td><td>520</td><td>1400</td>

<td>6</td><td>640</td><td>1540</td>

<td>9</td><td>540</td><td>-</td>

<td>14</td><td>520</td><td>1340</td>

<td>21</td><td>500</td><td>-</td>

<td>27</td><td>900</td><td>-</td>

<td>29</td><td>480</td><td>-</td>

<td>38</td><td>1060</td><td>1860</td>

<td>62</td><td>340</td><td>-</td>

<td>70</td><td>860</td><td>1600</td>

<td>81</td><td>1100</td><td>1900</td>

<td>84</td><td>820</td><td>-</td>

<td>A</td><td>340</td><td>700</td>

<td>none</td><td>60</td><td>400</td>

EXAMPLE 4 From 100 parts by weight of polystyrene (used after two recrystallizations from a mixture of benzene and methanol) and 0.25 parts by weight of the stabilizer to be used in accordance with the invention, mixtures were prepared which were then added under pressure 180 ° C to 1 mm thick pelts were processed. For comparative purposes, a pell was also prepared without using a stabilizer.

The trowel thus prepared was irradiated with ultraviolet rays at 45 ° C for 500 hours in the fade meter described in Example 2, whereupon the color change on test pieces 15 made from the skins was determined using a color differential colorimeter according to Japanese Industrial Standard K-7103 and the change in the respective yellowness index with the equation

ΔΥΙ = YI - YI o

where ΔΥΙ is the change in the yellowness index, YI is the yellowness index after the specimen is irradiated, and ΥΙθ is the original yellowness index of the specimen.

The results obtained are shown in Table HI.

Table III

<td>stabilizer No.</td><td>YI 0</td><td>ΔΥΙ</td>

<td>9</td><td>4.4</td><td>+ 5.1</td>

<td>as</td><td>4.7</td><td>5.9</td>

<td>70</td><td>4.6</td><td>+ 6.1</td>

<td>84</td><td>4.5</td><td>+ 5,3</td>

<td>none</td><td>4.4</td><td>+ 17.1</td>

EXAMPLE 5 From 100 parts by weight of acrylonitrile-butadiene-styrene copolymers and in each case 0.5 parts by weight of the stabilizers which can be used according to the invention indicated in Table IV or of the comparative example 15

No. 3,28745 for stabilizer B used, mixtures were prepared which were kneaded at 160 ° C. for 6 minutes on kneading drums and then processed into about 0.5 mm thick skins. For comparison, a fur was further prepared without using a stabilizer.

The skins thus prepared were exposed in the Sunshine Weatherometer, which complies with the Japanese Industrial 5 Standard Z-0230 for Accelerated Weathering Test of Rustproofing Qils, paragraph 2, for 50 hours. The decrease in elongation in percent of the original elongation and the drop in the tensile strength in percent of the original tensile strength were then measured. The results obtained are shown in Table IV.

Table IV

<td>stabilizer No.</td><td>Elongation in% of original stretch (%)</td><td>Tensile strength in% of the original tensile strength</td>

<td>6</td><td>73</td><td>81</td>

<td>38</td><td>76</td><td>80</td>

<td>70</td><td>75</td><td>83</td>

<td>84</td><td>71</td><td>78</td>

<td>B</td><td>61</td><td>71</td>

<td>none</td><td>54</td><td>71</td>

Example 6 From 100 parts by weight of polyamide 6 and in each case 0.25 parts by weight of the stabilizers which can be used according to the invention and for comparison purposes, of the stabilizer B, mixtures were prepared which after melting in a compression molding machine under pressure to about 0.1 mm thick films were deformed. For comparison, a film was further prepared without using a stabilizer.

The films thus prepared were aged under the conditions given below, whereupon the elongation in percent of the original elongation and the tensile strength in percent of the original tensile strength were determined. The results obtained are shown in Table V.

Aging conditions:

1. Irradiation with ultraviolet radiation for 200 h at 45 C in Example 2 described

Fade-Meter.

Second Old at 160 ° C for 2 h in Geo's Industrial Testing Methods for Vulcanized Rubber Paragraph 6.5 of Japanese Industrial Standard K-6301.

Table V

<td rowspan="2">stabilizer No.</td><td colspan="2">Fade-Meter Drop to% of original value</td><td colspan="2">Aging tester according to Geer Waste on% of the original sprüngli before value</td>

<td>strain</td><td>tensile strenght</td><td>strain</td><td>tensile strenght</td>

<td>9</td><td>68</td><td>75</td><td>60</td><td>67</td>

<td>81</td><td>76</td><td>78</td><td>62</td><td>88</td>

<td>B</td><td>52</td><td>65</td><td>34</td><td>59</td>

<td>none</td><td>23</td><td>51</td><td>27</td><td>55</td>

Example 7: From 100 parts by weight of a polyurethane resin of the polyeaprolactone type and in each case 25 0.5 parts by weight of the stabilizers which can be used according to the invention indicated in Table VI, mixtures were prepared which, after melting, were processed into about 0.5 mm thick skins. For comparison, a fur containing no stabilizer was further prepared.

The skins thus prepared were irradiated with Ultra Violet radiation for 15 hours at 45 ° C. in the fade meter described in Example 2, whereupon the elongation in percent of the original elongation and the tensile strength in percent of the original tensile strength were determined.

The results obtained are shown in Table VI.

Nr.328745

Table VI

<td>stabilizer No.</td><td>Elongation in% of original stretch (%)</td><td>Tensile strength in% of the original tensile strength</td>

<td>1</td><td>81</td><td>78</td>

<td>9</td><td>83</td><td>80</td>

<td>none</td><td>78</td><td>52</td>

Preparation 1: 1-Ocyl-2,2,6-frittetramethylpiperidine

On. A mixture of 56.4 parts by weight of 2,2,6,6-tetramethylpiperidine and 38.6 parts by weight of 1-bromooctane was heated to 125 to 130 ° C. for 120 hours. After cooling the reaction mixture, 2,2,6,6-tetramethylpiperidine hydrobromide formed during the reaction was filtered off. The filtrate was fractionally distilled to give the desired compound of bp = 168 ° C / 17 Torr.

Preparation 2: 1- (n-dodecyl) -2,2,6-freth tetramethylpiperidine

When the equivalent amount of 1-bromododecane was used instead of 1-bromooctane in the procedure of Preparation 1, the desired compound was obtained at Kp = 115 ° C / 0.004 Torr.

Preparation 3: 1-ethoxycarbonylmethyl-2,2,6,6-tetramethylpiperidine

When the equivalent amount of ethyl chloroacetate was used instead of the 1-bromooctane in the work according to Preparation 1, the desired compound was obtained with Kp. = 129 to 130 ° C / 13 Torr.

Preparation 4: 1-Octoxycarbonylmethyl-2,2,6,6-tetramethylpiperidine

A mixture of 45.4 parts by weight of 1-ethoxycarbonylmethyl-2,2,6,6-tetramethylpiperidine, 36.5 parts by weight of octan-1-ol and 0.5 parts by weight of lithium amide was heated to 110 to 115 ° for 48 hours C was heated, wherein the liberated during the reaction of alcohol was distilled off. Upon fractional distillation of the reaction mixture, 1-oct-octylcarbonylmethyl-2,2,6,6-tetramethylpiperidine with bp = 120 ° C / 0.005 Torr was obtained.

Preparation 5: 1- (2-Stearoylaxyethyl) -2,2,6,6-tetramethylpiperidine g (0.092 mol) of 1- (2-hydroxyethyl) -2,2,6,6-tetramethylpiperidine was dissolved in 30 g of chloroform whereupon The solution was saturated under cooling with dry hydrogen chloride and then treated with a solution of 27.9 g (0.092 mol) of stearoyl chloride in 30 g of chloroform. The reaction mixture was then heated at reflux temperature for 12 hours and then freed from chloroform under reduced pressure, whereupon the syrupy residue was taken up in excess sodium hydroxide solution and the resulting mixture was extracted with benzene. From the resulting extract, the benzene was evaporated in vacuo, whereupon the residue obtained was chromatographed on a column filled with silica gel. There were thus obtained 50% yield 25 g of the desired compound with mp = 30 ° C. The structure of the compound was confirmed by its magnetic nuclear resonance spectrum.

Preparation 6: 1- (2-Stearoylaxy-2-phenylethyl) -2,2,6,6-tetramethylpiperidine

When working according to Preparation 5 instead of the l- (2-hydroxyethyl) -2,2, 6, 6-tetramethylpiperidins l- (2-hydroxy-2-phenylethyl) -2,2, 6, θ-tetramethylpiperidine was used was chromatographed on a column filled with silica gel to give a liquid product which, by virtue of its elemental analysis and magnetic resonance spectrum, was substantially pure 1- (2-stearoyloxy-2-phenylethyl) -2,2,6,6-tetramethylpiperidine.

Analysis:

Calculated for C "H NO: 79, 63% C 11,65% H 2,65% N o5 61 2

Found: 79.36% C 11.91% H 2, 68% N.

Preparation 7: Bis- [2- (2,2,6,6-tetramethylpiperidino) -äthyU-succinate

A solution of 18.4 g (0.1 mole) of 1- (2-hydroxyethyl) -2,2,6,6-tetramethylpiperidine in 30 g of chloroform was saturated with dry hydrogen chloride under cooling and then with a solution of 7.5 g (0.049 mol) of succinyl chloride in 30 g of chloroform, followed by refluxing the reaction mixture for 15 hours and then washing successively with 10% sodium carbonate solution, then with water, and finally drying over anhydrous sodium sulfate. Evaporation of the volatile components from the resulting mixture left a residue which on recrystallization from ethanol gave 80 g of the desired compound, 18 g of the desired compound in pure form and mp = 77-78 ° C.

Preparation 8: 1-formyl-2,2,6,6-tetramethylpiperidine

A mixture of 5.0 g of 2,2,6,6-tetramethylpiperidine (p-toiolsulfonate), 70 g of ethyl orthoformate and 15 ml of dimethylformamide was refluxed for 3 hours and after completion of the reaction η

No. 328745 under reduced pressure by distilling ethyl ethyl styroformate and dimethylformamide, after which the resulting residue was filtered to remove crystalline substance and the crystalline substance was washed with ether. Filtrate and washings were combined, and the resulting mixture was washed first with aqueous sodium bicarbonate solution and then with water. The resulting organic layer was dried over anhydrous magnesium sulfate and devolatilized by evaporation to give 5.4 g of a residue which was chromatographed on a silica gel column eluting the column using a 10: 10 mixture of benzene and ethyl acetate ; 1 and the subsequent cleaning of the compound isolated from the eluate by sublimation, the desired compound in pure

Form and with mp = 71.5 to 72.5 ° C supplied.

Analysis:

Calculated for CH NO: 70.96% C 11.32% H 8.28% N Found: 71.14% C 11.36% H 8.26% N