Stabilization of synthetic polymers by means of certain piperidine derivatives

Methods for preparing a stabilized synthetic polymer composition.

The present invention relates to the stabilization of synthetic polymers against deterioration by light and heat, by the use of 1-substituted derivatives of piperidine.

The compound 2,2,6,6-tetramethylpiperidine which is not substituted in position .1 is described as a photostabilizer for polyolefins in the Japanese patent 46-31773 · On the other hand, various derivatives of piperidine substituted in position 1 general formula

<img file="LU69904A1_D0001.tif" />

where n is 1 or 2; and when n is equal to 1, Σ represents an alkyl, alkyl, propargyl, benzyl, ethoxycarbonylmethyl, 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxy-2-phenethyl 2-acyloxyethyl, 2-acyloxy-2-phenethyl, acetyl group or methoxycarbonyl, and when n = 2 ^ X represents a hexamethylene group; are known to have other applications, particularly in pharmacy, but they have never been described as polymer stabilizers, see for example, J. Pharmacol, 13, 501-20 (1958),

J. Med. Chem. 6, 381-4 (1963), J. Org. Chem. 27, 1695-1703 (1962), OA 62, 9098h, Beilstein, 20,129, British Patent Specifications Nos. 834290 and 1143371.

We have now discovered that certain piperidine derivatives are unexpectedly effective as stabilizers for synthetic polymers and in particular against thermal and heat degradation.

According to the invention, synthetic polymers are stabilized, against deterioration by light and heat, by the addition of at least one of the piperidine derivatives substituted in position 1 of formula ': ...... .. .....

<img file="LU69904A1_D0002.tif" />

in which R and R represent methyl groups, or R_ and Rb form together with the carbon atom to which they are linked a cyclohexyl group; R_q represents a methyl group and R ^ represents an alkyl group having from 1 to 5 carbon atoms, or R_q and R ^ together with the carbon atom to which they are attached form a cyclopentyl group, a cyclohexyl group, a group of formula;

<img file="LU69904A1_D0003.tif" />

1Ö or a group of formula 'î

<img file="LU69904A1_D0004.tif" />

n ss 1 or 2; and when n = 1, R represents an oxyl radical, a hydroxy group, an alkyl, substituted alkyl, alkenyl, alkynyl, aralkyl, substituted aralkyl, or acyl; or when n = 2, R 15 represents an alkylene group (the chain of which may be optionally interrupted by an oxygen atom), 2-butenylene, a group of formula -CHgCO-OR ^ -O-COCHg (in which R? represents an alkylene or xylylene group), or a group of formula -OHg-CHg-O-CO- (R⁸)_m-C0-0-CH₂CH₂ (where m = 0 or 1, and R⁸represents an alkylene group (the chain of which may be optionally interrupted by a sulfur atom), an alkenylene, phenylene or 1,4-cyclohexylene group).

A preferred subgroup of compounds of formula (I) is that in which η = '1, i.e. the compounds of formula

<img file="LU69904A1_D0005.tif" />

in which R. R,, R and R, have the meaning given 4 S »DC O.

above and R¹ represents an oxyl radical, a hydroxy, alkyl, substituted alkyl, alkenyl, alkynyl, aralooyl, substituted aralkoyl or acyl group.

In formula (la), when R^-'is an alkyl group, it may for example be a methyl, ethyl, propyl, butyl, pentyl or hexyl group. when R is a substituted alkyl group, it can be a haloalkyl group such as 2-chloroethyl, 2-bromoethyl or 2-chloropropyl; an epoxyalkyl group such as 2,3epoxypropyl; a hydroxyalkyl group such as 2-hydroxyethyl,

2-hydroxypropyl or 3-hydroxypropyl; an alkoxycarbonylalkyl group such as hexyloxycarbonylmethyl; an alkoxyalkyl group such as 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl or 3-methoxypropyl; or an acyloxyalkyl group such as 2-acetoxyethyl, "1

2-acetoxypropyl or 2-stearoyloxyethyl. When R is an alkenyl group, it may for example be alkyl or methallyl. When R is an alkynyl group it may for example be propeirgyle. When

AT

R is an aralooyl group, it can for example be benzyl or ή

cZ -methylbenzyl. When R is a substituted aralooyl group, it may for example be a hydroxyaralkyl group such as 2-hydroxy

-2-phenethyl. When R is an acyl group, it may for example be an aliphatic acyl group such as formyl or acetyl.

ώ ".

<img file="LU69904A1_D0006.tif" />

4‘

The preferred compounds of formula (la) are those in which R is an oxyl radical, a group a^notcoyl of 1 to 8 carbon atoms, haloalkyl of 1 to 5 carbon atoms, cyanoalkyl of 1 to 5 carbon atoms, epoxyalkyl of 3 or 4 carbon atoms, hydroxyalkyl of 2 to 5 carbon atoms acyloxyalkyl of 4 to 20 carbon atoms, aminoalkyl of 2 to 4 carbon atoms, alkoxycarbonylalkyl of 3 to 21 carbon atoms, alkoxyalkyl of 3 to 20 carbon atoms, alkenyl of 3 to 6 carbon atoms, alkynyl of 3 to 6 carbon atoms , aralcoyl from 7 to. 20 carbon atoms, hydroxyaralkyl of 8 to 12 carbon atoms or acyl of 2 to 18 carbon atoms.

R_&amp; and R ^ are preferably methyl groups. R_vs and R ^ are preferably methyl groups or together with the carbon atom to which they are linked, a cyclohexyl group or a group of formula:

<img file="LU69904A1_D0007.tif" />

and preferably methyl groups.

Another preferred subgroup of 'compounds of formula (I) is that of formula:' '

<img file="LU69904A1_D0008.tif" />

ή in which n - 1 or 2, and when n = 1, R represents an alkyl group of 1 to 18 carbon atoms; alkenyl of 3 to 10 carbon atoms; alkynyl of 3 or 4 carbon atoms; benzyl which can optionally be substituted by up to 3 substituents on the phenyl ring, the substituents being able to be the same or different?

rents and being selected from a chlorine atom, an alkyl group in C1-C6 alkoxy and a hydroxy group; phenethyl; 2,3 · epoxypropyl; a group of formula j-CHg-CO-OR * (in which R^AT represents an alkyl group of 1 to 1.8 carbon atoms, alkenyl the de 3 to 6 carbon atoms, phenyl, benzyl, cyclohexyl, or

2,3-époxypropyie); a group of formula -CHg-CHR ^ R ^ / in which r3 represents a hydrogen atom, a methyl or phenyl group); R ^ represents a hydroxy group or a group of formula -O-COR, in which R ^ represents an alkyl group of 1 to 17 carbon atoms, alkenyl of 2 to 4 carbon atoms, phenyl which may optionally be substituted by up to with 3 substituents (the substituents being able to be identical or different and chosen from a chlorine atom, a C1-C6 alkyl group, alkoxy in ^VS1„8* ^and kyûroxy), benzyl, 3,5-di-t-butyl-4-hydroxyphenétbyle, styryl or cyclohexyle /; or a group of formula -CO-R ^ (in which R ^ represents a hydrogen atom, a methyl group, alkenyl of 2 or 3 carbon atoms, alkoxy of 1 to 8 carbon atoms, benzyloxy or phenoxy); or when n = 2, R¹ represents an alkylene group of 1 to 6 carbon atoms (the chain of which may possibly be interrupted by an oxygen atom); 2-butenylene, a group of formula CH_oC0-0-R ^ -0-C0CH_o- (in which

R 'represents an alkylene group of 2 to 6 carbon atoms, or xylylene); a. formula group -0H_oCH_o-0-C0 (R⁸) -C0-0-CH_oCH_not8 2 2 / in which n = 0 or 1, and · R represents an alkylene group having from 1 to 10 carbon atoms (whose alkylene chain may optionally be 'interrupted by a sulfur atom), alkenylene from 2 to 4 atoms carbon, phenylene, or 1,4r-cyclohexylene7.

In the formula (ib), when n = 1: when R 1 is an alkyl group, it may for example be a methyl, ethyl, pro pyle, butyl, isobutyl, isopentyl, hexyl, octyl, dodecyl or actadecyl group; when it is an alkenyl group, it may for example be an allyl, crotyl, 2-hexenyl or 2-decenyl group; when it is an alkynyl group, it may for example be propargyl or 2-butynyl; and when it is a benzyl or substituted benzyl group it may for example be an o-, m- or p-chlorobenzyl, p-methylbenzyl, p-ethylbenzyl, p-isopropylbenzyl, p-methoxybenzyl, p-butoxybenzyl, p-octoxybenzyl group or 3,5-di-t-butyl-4hydroxybenzyle.

when R is an alkyl group, it may for example be a methyl, ethyl, butyl, isopentyl, octyl, dodecyl group,

<img file="LU69904A1_D0009.tif" />

<img file="LU69904A1_D0010.tif" />

• ·· y. ..¾. · ·&gt;

'or octadecyl; and when it is an alkenyl group, it may for example be an alkyl, crotyl or 2-hexenyl group. c when ïr is an alkyl group, it may for example be a methyl, ethyl, propyl, isopropyl, heptyl, 1-ethyl5 pentyl, undecyl, pentadecyl or heptadecyl group; when it is an alkenyl group, it may for example be a vinyl, 1propenyl, isopropenyl or 2-methyl-1-propenyl group; and when it is a substituted or unsubstituted phenyl group, it may for example be a phenyl, m- or p-chlorophenyl, 2,4-dichlorophenyl, o- or p-methylphenyl, p-isopropylphenyl, p-butylphenyl, p- group. ethoxyphenyl, p-butoxyphenyl, p-octoxyphenyl, 3,4,5-trimethoxyphenyl, o-hydroxyphenyl or 3 »5-di-t-butyl-4-hydroxyphenyl.

When R ^ is an alkenyl group, it may for example be a vinyl or 1-propenyl group; and when it is an alkoxy group, it may for example be a methoxy, ethoxy, isobutoxy or ootoxy group.

ή

In formula (Ib), when n = 2: when R is an alkylene group, it can for example be a methylene, ethylene, tetramethylene or hexamethymene group; and when it is an alkylene group whose chain is interrupted by an oxygen atom, it may for example be an oxidiethyl group, η

When R ′ is an alkylene group, it may for example be an ethylene, tetramethylene or hexamethylene group; and when it is a xylylene group, it may for example be an m25 or p-xylene group.

When R ° is an alkylene group, it can for example be a methylene, ethylene, tetramethylene, octamethylene or decamethylene group; when it is an alkylene group the chain of which is interrupted by a sulfur atom, it may for example be a thiodiethyl group; when it is an alkenylene group, it can for example be a vinylene group, 2-propene-1,2-ylene or 2-butenylene; and when it. is a phenylene group, it may for example be an m- or £ -phenylene group.

The following groups are the preferred groups for R in formula (Ib) when n = 11

Alkyl of 4 to 12 carbon atoms, in particular butyl, octyl and dodecyl; allyl; benzyl optionally substituted on the phenyl ring by an alkyl group in O ^ _ ^, methoxy or 3&gt; 5- &lt;3.it-butyl-4-hydroxy; and in particular unsubstituted benzyl; a p?

group of formula - CHg-CO-OR, in particular when R. is an alkyl group of 1 to 18 carbon atoms or allylej a group of formula -CHg-GHR ^ R ^, in particular when ïP is a hydrogen atom, a methyl or phenyl group (and preferably an atom of hydrogen), and when is a hydroxy group or a group of formula -O-COR ^ (in which R ^ is an alkyl group of 1 to 17 carbon atoms or 3,5-di-t-butyl-4-hydroxyphenethyl) ; an alkenyl group of 2 or 3 carbon atoms; a phenyl group which may be optionally substituted with a C 1-4 alkyl, C 1-6 alkoxy or hydroxy group, and in particular an unsubstituted phenyl group. ·, Ή

The following groups are the preferred groups for R in formula (Ib) when n = 2:

Alkylene of 2 to 6 carbon atoms, in particular ethynene or hexamethylene; a group of formula -CH_o-C0-0-R -O-CO-CH ", in which R 'is preferably an alkylene group having from 2 to 6 carbon atoms, in particular ethylene or hexamethylene; a group of formula -OHg-CHg-O-CO-R ^ -CO-O-OHg-CHg- "in which Βθ is preferably an alkylene group of 1 to 8 carbon atoms, in particular methylene, ethylene, tetramethylene or octamethy20 lene, or an m- or jg-phenylene group.

The following non-limiting list is a list of preferred compounds of formula (I). The reference numbers of the compounds will be used below to identify them in Examples 1 to 7.

1 ) '1,2,2,6,6-pentamethylpiperidine, ·

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

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

4) 1-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) 1-propargyl-2,2,6,6-tetramethylpiperidine,

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

10) 1-phenethyl1-2,2,6,6-tetramethylpiperidine,

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

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

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

14) 1 - (jg-methylhenzyl) -2,2,6,6-t and ramethylpiperidine,

15) 1- (3,5-di-t-butyl-4-hydroxybenzyl) -2,2,6,6-tetramethylpiperidine, ...

- ö,

16) 1- (jg-methoxybenzyl) -2,2,6,6-t etramethylpiperidine, • 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-bu.toxycarbonylmethyl-2,2,6,6-tetramethylpiperidine,

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

22) 1-dodecyloxycarbonylmethyl-2, '2,6,6-tetramethylpiperidine,

23) 1-octaâeoycloxyoarbonylméth3 &lt;L-2,2,6,6-tetramethylpiperidine,

24) 1-allyloxycarbonylmethyl-2,2,6,6-tetramethylpiperidine,

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

26) 1-cyclohexyloxycarbonylmethyl-2,2,6,6-tetramethylpiperidine,

27) 1 - (2-hydroxyethyl) -2,2,6,6-t etramethylpip eridine,

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

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

- 15 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-tet ramé thylpipé ridinè,

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

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

35)^-1- (2-lau.royloxyethyl) -2,2,6,6-t etramethylpiperidine,

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

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

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

39) 1- (2-st aroyloxy-2-phenylethyl) -2,2,6,6-t etramethylpipe ridine, '25 40) 1- (2-acryloyloxyethyl) -2,2,6,6-tetramethylpiperidine,

41) 1- (2-crotonoyloxyethyl) -2,2,6,6-tetramethylpipe ridine,

42) 1- (2-crotonoyloxypro pyl) -2,2,6,6-t etramethylpiperidine,

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-benzoyloxy-2-phenylethyl) -2,2,6,6-tetramethylpiperidine,

47) 1 - / * 2- (m-chlorobenzoyloxy) ethyl7-2,2,6,6-t etramethylpiperidine,

48) 1- / 2- (jg-chlorobenzoyloxy) -2-phenylethyl / -2,2,6,6-tetramethylpiperidine,

49) 1- / 2 - (_ £ -toluoyloxy) propyVⁱ-2,2,6,6-tetramethylpiperidine,

50) 1- / 2- (£ -t-butylbenzoyloxy) ethyl / -2,2,6,6-tetramethylpiperidine,

51) 1- / 2- (3 "5" di ~ f-butyl-4-hydroxybenzoyloxy) propyl72,2,6,6tetramethylpiperidine,

52) 1- / 2- (j3-methoxybenzoyloxy) -2-phenylethyl7-2,2,6,6,6-tetramethylpiperidine,

ΛΛ

Λ. .-i '' Λ. ' •. ·: ··· '

Λ ·

;/&gt;?

.Χ · ν-. ·. . ·. · ··: ··· - ·. ·

<img file="LU69904A1_D0011.tif" />

'53) 1- / 2- (3,4,5-trimethoxybenzoyloxy) ethV ~ 2,2,6,6-tetramethylpiperidine, · ·

54) 1- / 2- (£ -butoxybenzoyloxy) ethyl / -2,2,6,6-tetramethylpiperidine,

55) 1- / 2- (jß-octoxybenzoyloxy) propyl / -2,2,6,6-tetramethylpiperidine,

56) 1- (2-sälicyloyloxyethyl) -2,2,6, ô-tétzaméthylpiperériine,

57) · 1- (2-phenylacetoxyethyl) -2,2,6,6-tetramethylpiperidine,

58) 1- 2- / 3- (3,5-di-t-butyl-4-hydroxuphenyl) propionyloxy / ethyl 2,2,6,6-t etramethylpiperidine,

59) 1- (2-cinnamoyloxy-2-phenylethyl) -2,2,6,6,6-tetramethylpipericLine,

60) 1- (2-oyclohexanecarbonylöxypropyl) -2,2,6,6-tetramethylpiperidine,

61) 1-formyl-2,2,6,6-tetramethylpiperidine

62) 1-acetyl-2,2,6,6-tetramethylpiperidine,

63) 1-acryloyl-2,2,6,6-tetramethylpiperidine ,,

64) 1-crôtonoyl-2,2,6,6-tetramethylpiperidine,

65) 1-methoxycarbonyl-2,2,6,6-tetramethylpiperidine,

66) 1-octoxycarbonyl-2,2,6,6-tetramethylpiperidine,

67) 1-benzyloxycarbonyl-2,2,6,6-tetramethylpiperidine,

68) 1,2-bis (2,2,6,6-tetramethylpiperidino) ethane,

69) 1,4-bis (2,2,6,6-tetramethylpipetidino) butane,

70) 1,6-bis (2,2,6,6-tetramethylpiperidino) hexane,

71) 2,2 '~ bis (2,2,6,6-tetramethylpiperidino) ethyl ether,

72) 1,4-bis (2,2,6,6-tetramethylpiperidino) -trans * 2-butene,

73) 1,2-bis (2,2,6,6-tetramethylpipé ri dino-ace toxy) ethane,

74) 1,6-bis (2,2,6,6-tetramethylpiperidino-acetoxy) hexane,

75) Jj, 4-his (2,2,6,6-tetramethylpiperidino-aoetoxy) benzene, ·

76) Bis / §! - (2,2,6,6-tetramethylpiperidino) ethyl /, oxalate,

77) Bis / 2- (2,2,6,6-tetramethylpiperidino) ethyl / malonate,

78) Bis / 2- (2,2,6,6-tetramethylpiperidion) ethyl / succinate,

79) bis / 2- (2,2,6,6-tetramethylpiperidion *) ethyl / adipate,

80) bis / 2- (2,2,6,6-tetramethylpiperidino) ethyl / Sebacate,

81) bis / 2- (2,2,6,6-tetramethylpiperidino) ethyl / 1,10-decane dicarboxylate,

82) bis / 2- (2,2,6,6-tetramethylpiperidino) ethyl / thiodipropionate ate3) bis / 2- (2,2,6,6-t etramethylpiperidino ') ethyl /, maleate

84) bis / 2- (2,2,6,6-tetramethylpiperidino) ethyl / terephthalate,

85) bis / 2- (2,2,6,6-tetramethylpiperidino) ethyl / 'isophthalate,

86) 1,4-Cyclohexane-bis / 2- (2,2,6,6-tetramethylpiperidino) ethyl dicarboxylaye / · · ·

The piperidine derivatives of formula (I) can be prepared by known methods, such as the following reactions (A) to (P). The products of these reactions having the formulas (II),. ··. * ·

<img file="LU69904A1_D0012.tif" />

, 'Ίλ ·. ·, AV. ·. . · &lt;

·&gt;.&lt;·

<img file="LU69904A1_D0013.tif" />

<img file="LU69904A1_D0014.tif" />

• · Γ^: ,, 10 · (V), (Va), (VIII), (x), (Xa), (XIl), (XIV) and (XVI) are subgroups of compounds of formula (I).

(A) - The compounds of formula (II) can be prepared by reacting a substituted piperidine of formula III with a héglonégure (IV), by the process described in English patent 834290 in which the piperidine (III) reacts with allyl bromide according to the reaction scheme.

<img file="LU69904A1_D0015.tif" />

in which R_&amp;, R ^, R_q and R ^ have the meanings mentioned above and n = 1 or 2 and

Q. · · When n = 1, R-⁷ represents an alkyl, alkenyl, alkynyl, substituted or unsubstituted benzyl, phenethyl, 2,3-epoxypropyl, cyanoalkyl, aminoalkyl, alkoxyalkyl group or the group -CH_o-C0-0R²in which R has the meaning already defined); or when n = 2, Εθ represents an alkylene group (optionally interrupted by an oxygen atom), 'or 2 -but enylene; Y represents a halogen atom.

(B) - The compounds of formula (V) and (Va) can be prepared by transesterification of a substituted piperidine of formula (VI) with an alcohol of formula (VII) or a diol of formula (VII)_at)

<img file="LU69904A1_D0016.tif" />

(VI)

<img file="LU69904A1_D0017.tif" />

(V) (VII) λ 't' ·? *

<img file="LU69904A1_D0018.tif" />

<img file="LU69904A1_D0019.tif" />

'(VI) (Vila) (Va)

7 in which R_at, R- ^, R ,, R ^, R and R * have the meanings already defined, and represents an alkyl group.

(0) - The compounds of formula (VIII) can be prepared by reacting a substituted piperidine (II) with an epoxide (IX), by the method described in English patent 1143371.

<img file="LU69904A1_D0020.tif" />

in which R_&amp;, R ^, Ηθ, R ^ and R ^ have the meanings already defined.

(L) - The compounds of formulas (X) and Xa) can be prepared by reacting a substituted piperidine of formula (VIII) or (Villa) with a reactive derivative of an appropriate acid, for example an acid chloride of formula (XI) or (Xla) by the method described in English patent 1143371.

<img file="LU69904A1_D0021.tif" />

V.

<img file="LU69904A1_D0022.tif" />

(XI) (χ)

<img file="LU69904A1_D0023.tif" />

<img file="LU69904A1_D0024.tif" />

.'X ♦: &lt;&gt; ·

*.·?

-¾

<img file="LU69904A1_D0025.tif" />

&gt;?.·&gt;.

? Λ \ · '

Λ V ·?:&gt; ·

S ':. · ·'. ·, · /. / &amp; · · /

X: *

<td> ♦</td><td>. .. 'n _V-n / - • Ç 'k ζ N-CII CII₂-OIÎ</td><td>• + yco4R⁸-) - coy m</td>

<td></td><td> / ^Rd R , vs</td><td> •</td>

<td></td><td>(Villa)</td><td>(XIa)</td>

<img file="LU69904A1_D0026.tif" />

ηι λ * 5 8 in which R_at, R ^, R, R, R, R and Y have the meanings already defined.

(E) - The compounds of formula (XII) can be prepared by reacting a substituted piperidine of formula (III) with a reactive derivative of an appropriate acid, for example a chloride of formyl acid XIII by the method described in J. Med. Chem.

6, 381-4 (1963):

<img file="LU69904A1_D0027.tif" />

• h R^UCOY

R

<img file="LU69904A1_D0028.tif" />

\ not

N-CO-R (XII) (XIII) in which 'R, R-, R and R, have the meanings already de "i 4 Q" DO Q.

finished: R represents a methyl or alkenyl group; and Y represents a halogen atom.

The compounds of formula (XIV) can be prepared by an analogous process, except that chlorocar13 is used

<img file="LU69904A1_D0029.tif" />

·&gt;

<img file="LU69904A1_D0030.tif" />

bonate (XV) in place of the acid halide (XIII) R_

V_7^H + C1CO-OR / R /

<img file="LU69904A1_D0031.tif" />

(XIV) (ΪΠ) (XV) in which R, R,, R and R ,, have the meanings already dex p 3, DC CL finished; and R * represents an alkyl, benzyl or phenyl group. (B) - The compounds of formula (XVI) can be prepared by reacting a substituted piperidine of formula (III) on an ethyl orthoforraate in the presence of an acid catalyst:

<img file="LU69904A1_D0032.tif" />

R

R, · y — b &lt;N-CIIO

R ^Cl'c (XVI) in which R_&amp;, R ^, R_q and R ^ have the meanings already defined.

Reactions (A), - (L) and (E) which take place with the formation of a hydrogen halide are conveniently carried out with an acid binding agent. The usual organic or inorganic bases can be added to the reaction system as acid-binding agents, or alternatively an excess of curtain piping as starting material can serve the same purpose. The reactions can be carried out by heating the reagents in an inert solvent, or without solvent.

The transesterification reaction (B) is carried out by heating in the presence of a catalyst such as an alkoxide of an alkali metal, an amide or a hydroxide. The alcohol formed during the reaction is preferably removed from the reaction medium.

The compounds of formula (I) give synthetic polymeric materials an exceptionally high degree of stability against deterioration by light and heat. In addition, this improved stability is obtained without discoloration of the polymeric material and without adversely affecting the other light protection agents, stabilizers, plasticizers and pigments which can also be added to the polymer. Consequently, the invention provides a composition comprising a synthetic polymer and at least one compound of formula (I).

Synthetic polymers which can be stabilized by means of the compounds of formula (I include:

polymers of olefins, dienes and styrenes such as homopolymers of olefins, dienes and styrene. (e.g. high and low density polyethylenes, polypropylenes, polystyrenes, polybutadienes -and polyisoprenes), and copolymers of olefins, dienes and styrene with each other or with ethylenically unsaturated monomers (e.g. ethylene / propylene, ethylene / butene, ethylene / vinyl acetate, styrene / butadiene and acrylonitrile / butadiene / styrene copolymers);

polymers of vinyl chloride and vinylidene such as homopolymers of vinyl chloride and vinylidene, 'vinyl chloride / vinylidene chloride copolymers and copolymers of vinyl chloride or vinylidene chloride with vinyl acetate vinyl or other ethylenically unsaturated monomers;

polyacetals, for example polyoxymethylene and polyoxyethylene; polyesters, for example polyethylene terephthalate; polyamides, for example nylon-6, nylon 6-6, nylon 6nio and nylon 12; polyurethanes, for example polyurethanes of polyethers or polyesters; and epoxy resins, for example reaction pydducts of epichlorohydrins and polyphenols.

Synthetic polymers stabilized by the compounds of formula (I) can be used in the preparation of a wide variety of products, for example filaments, fibers, threads or yarns, films, sheets and other articles molded., - latexes, foams and paints.

<img file="LU69904A1_D0033.tif" />

The amount of stabilizer of formula (I) necessary for effective stabilization of synthetic polymers depends on various factors such as the type and properties of the polymer concerned, the use to be made of it, the intensity and the duration of exposure to light and heat, and the presence of other stabilizers. However, it is generally satisfactory to use from 0.01 $ to 5.0 preferably from 0.1 to 2 $ by weight of stabilizers) of formula (X), relative to the weight of synthetic polymer.

The stabilizers of formula (I) can be readily incorporated into the synthetic polymers by conventional techniques, at any convenient stage prior to the manufacture of articles molded therefrom. For example, the stabilizer and the polymer can be stored in a mixer in the dry state, or a solution or suspension of the stabilizer in a suitable solvent or dispersant (for example an inert organic solvent such as methanol, ethanol or acetone) can be added to the pulverized polymer and the whole intimately mixed. Alternatively the stabilizer can be added during the formation of the polymer, for example, the latex type step during the preparation of the polymer, to give a pre-stabilized polymeric material.

The stabilized synthetic polymer compositions according to the invention may optionally contain various conventional additives such as the following.

antioxidants

- simple 2,6-diaIcoylphenols such as, for example,

2.6- di ~ t-butyl ~ methylphenol, 2-t-butyl-4,6-dimethylphenol,

2.6- t-butyl-4-methoxymethylphenol and 2,6-dioctadecyl-4methylphenol;

- derivatives of alkylated hydroquinones such as 2,5-di30 t-butylhydroquinone, 2,5-di-t-amylhydriquinone, 2,6-o-tbutylhydroquinone, 2,5-di-t-butyl- 4-hydroxyanisole, 3,5-dit-butyl-4-hydroxyanisole, tris phosphite (3,5-di-t-butyl4-hydrodyphenyl), 3,5-di-t-butyl-4 stearate ~ hydroxyphenyl and di- (3,5-di-t-butyl-4-hydroxyphenyl) adipate /

- hydroxylated thiodiphenyl ethers such as 2,2'thio-bis (6-t-butyl4methylphenol), 1e 2,2'-thiobis (4 ~ octylphenol), 4,4'-thiobis (6-t-butyl- 3-methylphenol), 4,4'-thiobis (3,6-di-s-amyl-4,4 '-bis (2,6 ~ dimethyl-4-hydroxyphenyl);

-alkidene-blsphenols such as 2,2'-methylene-bis

<img file="LU69904A1_D0034.tif" />

'(6-t-butyl-4-methylphenol), 2,2'-methylene-bis (6-t-hutyl-p ethylphenol), 4&gt; 4'-methylene-his (6-t-butyl ~ 2 -methylphenol, '4,4'-methylene -bis (2,6-di-t-butylphenol), 2,6-âi- (3-t-butyl5-methyl-2-hydroxybenzyl) -4-methylphenol, 2,2'-methylene-bis / 4-methyl-6 - (^ - methylxyxlohexyl-phenol / 1,1-bis (3,5-dimethyl2-hydroxyphenyl) butane, 1,1-bis (5-t -butyl-4-hydroxy-2-methylphenyl) butane, 2,2-rbis (5-t-butyl-4-hydroxy-2-methylphenyl) butane, 2,2-bis (3,5-di-t-butyl-4-hydroxyphenyl); propane, the

1,1,3-tris (5-t-butyl-4-hydroxy-2-methylphenyl) butane, 2,2-bis (5-t-butyl-4-hydroxy-2-methylphenyl) -4-n- dodecylmercaptobutane, 1,1,5,5-tetra (5-t-butyl-4-hyâroxy-2-methylphenyl) pentane and bis / 3,3-bis (3'-butyl-4¹-hydroxyphenyl) butyrate / ethylene glycol;

- fl^es 0-, N- and S-benzyl compounds such as, for example, 3,5,3 'ether, 5' -tetra-t-butyl-4,4'-dihydroxybenzyl ether, octadecyl ester of acid 4-hydroxy-3,5-dimethylbenzyl-mercaptoacetic acid, tri (3,5-di-t-butyl-4-hydroxybenzyl) amine and bis (4-t-butyl-3-hydroxy-2,6-) dithiolterephthalate dimethylbenzyl);

- hydroxybenzylated malonic esters such as, for example, the dioctadecyl ester of 2,2-bis-3,5-di-t-butyl-2-hydroxybenzyl) malonic acid, the dioctadecyl ester of 2- ( '3 ~ t-butyl-4-hydroxy-5 ~ methylbenzyl) maloniqns, 1' di-dodecylmercaptoethyl ester of 2,2-bis (3,5-di-t-butyl-1-hydroxyben25 zyl) malonic acid and the di (4-t-octylphenyl) ester of 2,2bis (3,5-di-t-but, yl-4-hydroxybenzyl) malonic acid;

- &amp;^es hydroxybenzyl aromatic compounds such as, for example, 1,3,5-tri (3,5-di-t-butyl-4-hydroxybenzyl) -2,4,6 trimethyl benzene, 1,4 ~ di (3,5 -di-t-butyl-4-hydroxybenzyl) -2,330 5,6-tetramethylbenzene and 2,4,6-tri- (3,5-di-t-butyl-4-hydroxy ~ benzyl) phenol;

- s-triazine compounds such as, for example,

2,4-bis-octylmercapto-6 (3,5-di-t-butyl-4-hydroxyanilino) ~ s- triazine, 2-octylmercapto-4,6-bis (3,5-di-t-butyl- 4-hydroxyanilino)

-s-triazine, 2-octylmercapto-4,6-bis (3,5-di-t-butyl-4-hydroxyphenoxy) -s-triazine, 2,4,6-tris (3,5-di- t-butyl-4-hydroxyphenoxy) -s-triazine, 2,4&gt; 6-tris (3,5 ~ di-t-butyl-4-hydroxyphenylethyl) -s-triazine and isocyanurate of 1; 3,5 ~ tris (3,5-di-t-butylhydroxybenzyle);

- äeg amides of 3,5-to-t-but, yl-4-hydroxyphenyl- acid. propionics such as 1,3,5-tris (3,5-ài-t-butyl4-hydroxyphenyl-propionyl) hexahydro-s-triazine and N, N'-bis (3 »5-di-t -butyl ~ 4-hydroxyphenylpropionyl) -hexamethylenediamine;

· -Esters of 3,5-di-t-butyl-4-hyclroxyphen.ylpropionlque and mono or polyaloools such as, for example, those obtained, naked with methanol, ethanol, 'octadecanol , 1 d-6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, diethylene glycol, thiodiethylene glycol, neopentyl glycol, pentaerythritol, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolethane, trimethylopropane, tris-hydroxyethyl osocyanurate and 4-hydroxymethyl-1phospha-2,6,7-trioxabicyclo / 2,2,2 / -octane; ,

- 5-t-butyl-4-hydroxy-3-methylphenylpro15 pionlque acid esters and mono or. polyalcohols such as, for example, those obtained with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propane diol , diethylene glycol, thiodiethylene glycol, neopentyl glycol, pentaerythritol,. 3-thiaundecanol, 3-thiapentadeca 20 nol, trimethyl hexanediol, trimethylolethane, trimethylolpropane, trishydroxyethyl isocyanurate and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo / 2,2,2 / octane ;

- esters of 3,5-di-t-but, yl-4-hydroxyphenylacetic acid and of mono or polyalcohols, such, for example, those obtained 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, isocyanurate trishydroxy ethyl and 4-hydroxymethyl-1phospha-2,6,7-trioxabicyclo / 2_B 2.2 / -octane;

- Acylamininphenols such as, for example, the amide of N- (3,5-di-t-butyl-4 ~ hydroxyphenyl) stearic acid and N, N '$ is (3,5-di-t -butyl-4-hydroxyphén_therel) thiobisatamide;

- benzyl phosphonates such as, for example, the dimethyl ester of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid, the diethyl ester of 3,5-di-t-butyl acid 4-hydroxyben ~ zylphosphonic, the dioctadecylic ester of 3,5-di-tbutyl-4-hydroxybenzylphosphonlque and the dioctadecylic ester of 5-t-butyl-4-hydroxy-3-methylbenzyl-phosphonic acid;

•1

<img file="LU69904A1_D0035.tif" />

S

Oi

<img file="LU69904A1_D0036.tif" />

- amino aryl derivatives such as, for example, phenyl-1-naph.tylamine, phenyl-2-naphthylamine, N, N'-diphenylp-phenylenediamine, N, N'-dï-2-naphtyl-p- phenylenediamine, the

N, N'-di-s-butyl-p-phenylene-diamine, 6-ethoxy-2,2,4-trimethyl5 1,2- ^ dihydroquinoline, 6-dodecyl-2,2,4-trimethyl-1 , 2-dihydroquinoline, mono- and α-octyliminodibenzyl as well as 2,2,4-trimethyl-1,2-dihydroquinoline;

- UV absorbers and light protection agents:

- 2- (2'-hydroxyphenyl) benzotriazoles such as, for example, 5'-methyl, 3 ', 5'-di-t-butyl, 5'-t-butyl, 5' derivatives - (1,1 ,

3,3-tetramethylbutyl) ·. 5-chloro-3 ', 5'-di-t-butyl, 5-chloro-3 * -tbutyl-5'-methyl, 3'-s-butyl-5'-t-butyl, 3Ά -methylbenzyl / -5 'methyl, 3'-Æ -methylbenzyl / -5' -methyl-5-chloro, 4'-hydroxy- 4'15 methoxy, 4'-octoxy, 3 ', 5'-di-t-amyl, 3'- methyl-5'-carbomethoxyethyl and 5-chloro-3 ', 5'-di-t-amyl;

- 2,4-bis (2'-h.ydroxyphenyl) 6-alco, yl-s-triazines such as, for example, 6-ethyl, 6-undecyl and 6-heptad'écyl derivatives;

- 2-hydroxybenzophenones such as, for example, 4-hydroxy-, 4-methoxy, 4-oxtoxy, 4-decyloxy, 4-dodecyloxy, 4-benzylo- £ y, 4,2'-4'-trihydroxy derivatives and 2'-hydroxy-4,4'-dimethoxy;

- 1,3-bis (2'-hydroxybenzoyl) benzenes such as, for example, that 1,3-bis (2'-hydroxy ~ 4'-hexyloxybenzoyl) benzene; 1,3-bis25 (2 '~ hydroxy-4'-octoxybenzoyl) benzene and 1,3-bis (2'-hydroxy4'-dodecyloxybenzoyl) -benzene;

- at-^es esters of optionally substituted benzoic acids such as, for example, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-t-butylbenzoyl) resorcinol, benzoylresorcinol and ester 2,4-di- t-butylphenyl, octadecyl ester or 2-methyl ~ 4,6-di-t-butylphenyl ester of 3,5-âi-t-butyl-t4-hydroxybenzoic acid;

- acrylates such as, for example, the ethyl ester or the iso-octyl ester of -cyano acid / / # -diphenylacry35 lic, the methyl ester of the -carbomethoxycinnamic acode, the methyl ester or l butyl ester of bC-cyano -. # methyl-p-methoxycinnamic acid and N- (/ # - carbomethoxyvinyl) -2methylindoline;

- nickel compounds such as, for example, nickel complexes with 2,2'-thiobis (4-t-octylphenol) such as corn19 plexes 1: 1 and 1: 2, optionally with other ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine; nickel complexes with bis (4-t-octylphenyl) sulfone such as the 2: 1 complex, optionally with other ligands such as 2-ethylcaproic acid; nickel dibutyldithiocarbamate; nickel salts, monoalocyclic esters of 4-hydroxy-3,5-di-t-butylbenzylphosphonic acid such as methyl, ethyl or butyl ester; the nickel complex with 1s 2-hydro'xy-4-methyl phenyl undecyl ketonoxime; as well as 3.5, .i? 0 di-t-butyl-4-hy.droxybenzoate nickel;

- oxalic acid diamides such as, for example, 4,4 * -di ~ octyloxyoxanilide, 2,2'-dicctyloxy-5,5'-di-t-butyloxanilide, 2,2'-di- dodecyloxy-5,5'-di-t-butyloxanilide, 2ethoxy-5-t-butyl-2'-ethyloxanilide, 2-ethoxy-2'-ethyloxanili15 de, N, N'-bis (3-dimethylaminopropyl) oxalamide, mixtures of p-methoxy and disubstituted o- and p-ethoxy oxanilides as well as mixtures of 2-ethoxy-5-t-butyl-2'-ethoxyani '¹ ide and 2ethoxy-2'-ethyl-5,4'-di-t-butyloxanilide;

- metal deactivators such as, for example,

Oxanilide, dihydrazide of isophthalic acid, bisphenylhydrazide of sebaoic acid, dihydrazide of bist benzylidene oxalic acid, dihydrazide of N, N'-diacetyladipic acid, dihydrazide of Ν acid , Ν'-bis-salicycloxalique, N, N'-bissalicyloylhydrazine and N, N'-bis (3 »5-di ~ t-butyl-4 ~ hydroxyphenylpropionyl) hydrazine;

.25 - phosphites such as triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, trinonyl phenyl phosphite, trilauryl phosphite, trioctadecyl phosphite? 3,9-di-isodecyloxy-2,4,8,10-tetraf oxa-3,9-diphosphapiro / 5,5 / undecane and the phosphite of tris (430 hydroxy-3,5-di-t-butylphenyl) ;

"~ Deactivators of peroxides such as, for example, esters of B-thiodipropionic acid (for example lauryl, stearyl esters, '. Myristylic and tridecyl), 2-mercaptobenzimidazole salts (in particular zinc salt) and phenylthiourea di35;

- polyamide stabilizers such as, for example, copper salts in combination with iodides and / or phosphorus compounds and divalent manganese salts;

<img file="LU69904A1_D0037.tif" />

-::¾..

·%·:

fe 'λ &lt;ύ;

basic co-stabilizers such as, for example, polyvinym pyrrolidone, melamine, benzoguanamine, triallyl cyanurate, dicyandiamide, urea derivatives, hydrazine derivatives, amines, polyamides , polyurethanes, as well as alkali and alkaline earth metal salts of saturated or unsaturated higher fatty acids (e.g. Ca stearate, Mg laurate, Na ricinoleate, K palmitate and Zn stearate );

stabilizers for PVO such as, for example, organic tin compounds, organic lead compounds and • Ba / Cd salts of fatty acids;

- nucleating agents such as, for example, 4-t ~ butylbenzoic acid, adipic acid and diphenylaceric acid;

- other additives such as, for example, plasticizers, lubricants (such as glycerine monostearate), emulsifiers, carbon black, asbestos, fiberglass, kaolin and talc.

The use of stabilizers of formula (I) with the antioxidants mentioned above is particularly effective for the stabilization of olefin polymers.

The invention is illustrated by the following examples 1 to 7, in which the stabilizers of formula (I) are identified by the reference numbers given in the list mentioned above. Preparations 1 to 6 which follow the examples illustrate the preparation of the stabilizers of formula (I). All parts and percentages are by weight unless otherwise indicated. The stabilizers used for comparison in the examples are identified by the trademarks Tinuvin 327 and Tinuvin P from Ciba.G-reigy AG. and have the following chemical identity:

Trinuvin 327: 2-2-hydroxy-3,5-âi-t-butylphenyl) -6-chlorobenzo1,2,3-triazole,

Trinuvin P: 2 - (- 2-hydroxy-5-methylphenyl) benzo-1,2,3-triazole. Example 1

Mixtures of 1000 parts of polypropylene powder • 35 with a melt index of 20 (230 ° C, 2160 g), 2 parts of octadecyl ester of acid - (3,5-di ~ t-butyl) are made. -4-hydroxyphenyl) propionic acid and in turn 2.5 or 5 parts of each of the stabilizers of the invention indicated in Table 1. The mixtures are homogenized in a Bralender kneader at 200 ° C, then pre-pressed into sheets 2 to 3 mm thick in a knee press

<img file="LU69904A1_D0038.tif" />

' &gt;. ·

1st. The sheets are pressed in a plate press at 260 ° 0 using the appropriate dies first in 0.3 mm thick films and then in 0.1 ram thick films. A control film is also prepared which does not contain a stabilizer.

The films are annealed for one hour at 150 ° C to prevent them from cooling to a lower temperature and immediately afterwards are soaked in water at 15 ° C. The resulting films have a homogeneous structure in the form of fine spherules. The test samples are taken by punching the films and have an elongation at break of approximately 900.

The polypropylene films thus formed are mounted on a sample holder and exposed in a tester

Χθηο-150. A: · at regular intervals; pieces of film are preveled in the apparatus, 5 test samples are punched there and their residual elongation is measured. The exposure time after which the elongation at break of the film decreased by $ 50 from its value before irradiation is determined and taken as a measure of the effectiveness of the stabilizers.

The results are given in Table 1.

TABLE 1

<td colspan="2"></td><td>Stabilizing</td><td colspan="2">Exposure time for a</td>

<td> 25</td><td>Compound</td><td>R ° Quantity added (parts)</td><td colspan="2">$ 50 growth in the initial value of the elongation at break (hours)</td>

<td> -</td><td> 3</td><td> 2,5</td><td></td><td> 4700</td>

<td></td><td> 4</td><td> 2,5</td><td></td><td> 5140</td>

<td></td><td> 8</td><td> 2,5</td><td></td><td> 2200</td>

<td> 30</td><td> 21</td><td> 2,5</td><td></td><td> 4920</td>

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

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

<td></td><td> 38</td><td> 5 ·</td><td></td><td> 1.0500</td>

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

<td> 35</td><td> 70</td><td> 2,5</td><td></td><td> &gt; 6000</td>

<td></td><td>nothingness</td><td></td><td></td><td> 800</td>

<td></td><td>Example</td><td> 2</td><td></td><td></td>

<td></td><td></td><td>We make mixtures of</td><td>100 games</td><td>propylene (Noblen</td>

JHH-G, marketed by Mitsui Toatsu Chemicals Inc., Japan, used after 2 recrystallizations from monochlorobenzene) and in turn 0.25 part of each of the stabilizers according to the invention

<img file="LU69904A1_D0039.tif" />

'• Λ &amp;

..i :: -:

. .¾. ·&gt; ΛΛ 'tion indicated in Table 2 and as a control of Tinuvin 327. The mixtures obtained are mixed, melted and molded by application of heat and pressure in sheets of 0.5 mm thick. A control sheet without stabilizer is also prepared.

The sheets thus prepared are exposed to ultraviolet light at 45 ° 0 in the Standard Fade-Meter Type FA-1 device manufactured and sold by Toyo Rika instruments Inc., Japan (a modification of the Atlas Fade-O-Meter Type FDA -R which meets the requirements of paragraph 3 ^ 8 of Japanese Industrial Standard 1044-L).

The time required to make each sheet brittle is given in • Table 2.

Example 3

Mixtures of 100 parts of high density polyethylene (HiôZex, marketed by Mitsui Toatsu Chemicals Inc. Ja15 pon, used after two recrystallizations from toluene) are made. 0.25 part of each of the stabilizers of the invention indicated in Table 2 and as a control for Tinuvin 327. The mixtures obtained are molded by application of heat and pressure in sheets of 0.5 mm thick. A control sheet without stabilizer is also prepared.

The embrittlement time of each sheet is measured by the same method as in Example 2 and the results are given in Table 2.

TABLE 2

Weakening time (hours

<td>Stabilizer No.</td><td>polypropylene</td><td>high density polyethylene</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>i860</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>

<img file="LU69904A1_D0040.tif" />

<img file="LU69904A1_D0041.tif" />

<img file="LU69904A1_D0042.tif" />

Λ · Λ.; . λ 'ΐ;

?&gt; Χ

TABLE (cont'd) • Tinuvun- 327 340 700 none '' · ⁶⁰ . ⁴⁰⁰

Example 4

Mixtures of 100 parts of polystyrene (Styron sold by Ashi-Lov / Limited, used after recrystallization from a benzene-methanol mixture) are made, and in turn 0.25 part of each of the stabilizers · 'according to the invention indicated in table 3 · The mixtures obtained are molded by application of heat and pressure into sheets 1 mm thick. A control sheet without stabilizer is also prepared.

The sheets thus prepared are exposed to ultra-violet light for 500 hours at 45 ° 0 in the Pade-Meter apparatus described in Example 2. The color difference before and after exposure to ultra-violet light is measured on test pieces of the leaves, by the method described in Japanese Industrial Standard K-7103, using a color difference colorimeter, and the variations in the yellowing index are calculated by the equation:

A Yl = Yl - yi₀ in which A Yl is the variation of the index.

Yl is the yellowness index after exposure and Yl is the initial yellowness index of the test piece.

The results are given in Table 3 ·

TABLE 3

Stabilizer No. ΥΙθ Yl

<td> 9</td><td> 4,4</td><td> + 5,1</td>

<td> 38</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>nothingness</td><td> 4,4</td><td> + 17,1</td>

Example 5

Mixtures of 100 parts of Kane-Ace B-12 acrylonitrile / butadiene / styrene resin are made, sold by Kanegafuchi 35 Chemical Industries Ldt. Japan) and in turn 0.5 part of each of the stabilizers of the invention indicated in Table 4 or of Tinuvin P as a control. The mixtures obtained are kneaded for 6 minutes in a roller kneader at 16O ° C, and then molded into sheets approximately 0.5 mm thick. A tei I "" sheet. - ΛΛ '&lt;- jnoin containing no stabilizer is also prepared.

The sheets thus prepared are exposed for 50 hours in the Sunshine Weather-ometer device prescribed in Japanese Industrial Standard Z-0230, entitled Accelerated '^ leathering Test of Rustproofings Oils, paragraph 2. The retention of the elongation is then measured. breaking, and tensile strength.

The results are given in the table

4.

<td></td><td>TABLE 4</td>

<td>Stabilizer No.</td><td>Retention of elongation</td>

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

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

<td> 70</td><td> 75 ,</td>

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

<td>Tinuvin-P</td><td> 61</td>

<td>nothingness</td><td> 54</td>

<td>Example 6</td><td></td>

We make mixtures of 100 parts sold by Toray Industries Inc.,

Retention of tensile strength

W of Nylon-6 (CM 1011, Japan) and in turn 0.25 part of each of the stabilizers of the invention indicated in Table 5 "or of Tinuvin-P. The mixtures obtained are melted and molded under pressure into films approximately 0.1 mm thick in a pressure molding machine. A control film not containing stabilizer is also prepared.

The films thus prepared are aged under the conditions described below, and the retention of the elongation at break and of the tensile strength is then measured. The results are given in Table 5.

Aging conditions

- Exposure to ultra-violet light for 200 hours at 45 ° C in the Fade-meter device described in Example 2.

- Aging for 2 hours at 16O ° C in the Geer's aging test device prescribed in Japanese Industrial Standard K-6301 entitled Physical Testing Methods for Vulcanized Rubber, paragraph 6.5.

. TABLE 5

Fade-Meter. Old Gess' test apparatus

<td></td><td>Stabilizing</td><td>Retention</td><td>Retention</td><td>Retention</td><td>Retention</td>

<td></td><td rowspan="2">NOT."</td><td>wing-</td><td>resistance</td><td>of the long-</td><td>some resistance</td>

<td></td><td rowspan="2">gement (^)</td><td>tance to the</td><td rowspan="2">ment ($)</td><td>tance to the</td>

<td></td><td></td><td>traction(/)</td><td>traotion (/)</td>

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

<td>VS</td><td> 81</td><td> 76</td><td> 78</td><td> 62</td><td> 68</td>

<td></td><td>Tinuvin-P</td><td> . 52</td><td> 65</td><td> 34</td><td> 59</td>

<td> , 10</td><td>. nothingness</td><td> 23</td><td> ’ 51</td><td> 27</td><td> 55</td>

<td></td><td>Example 7</td><td></td><td></td><td> •</td><td></td>

<td></td><td>We do</td><td>mixtures</td><td>'' of 100 games</td><td colspan="2">polyurethane resin</td>

<td></td><td colspan="2">polyoaprolactone type</td><td colspan="2">(E-5080, marketed by</td><td>Japanese</td>

<td></td><td>Elastran Oo.</td><td>Ltd? Japan)</td><td>and in turn</td><td>0.5 part of</td><td>each of the</td>

<td> - 15</td><td>stabilizers</td><td colspan="2">of the invention indicated in</td><td>table 6. The</td><td>mixtures</td>

obtained are melted and molded into sheets approximately 0.5 mm thick. A control sheet without stabilizer is also prepared.

The sheets thus prepared are exposed to ultra violet light for 15 hours at 45 ° 0 in the Fade-meter described in Example 2 and their retention of elongation at break and of tensile strength is then measured.

The results are given in Table 6.

TABLE 6

<td> 25</td><td>Stabilizer No.</td><td>Retention of elongation</td><td>Retension of the</td>

<td> •</td><td></td><td> (%)</td><td>tensile strength ($)</td>

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

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

<td> 30</td><td>nothingness</td><td> 78</td><td> 52</td>

Preparation 1

1-oot.yl-2,2,6,6-tetramethylpiperidine

A mixture of 56.4 parts of 2,2,6,6-tetramethylpiperidine and 38.6 parts of 1-bromooctane is heated to 125-130 ° 0 for 120 hours. After cooling, the reaction mixture is filtered to remove the 2,2,6,6-tetramethylpiperidine hydrobromide formed during the reaction. A fractional distillation of the filtrate provides the desired product, having a boiling point of 168 ° 0/17 t.s.

Preparation 2.

1-n-dodecyl-2,2,6,6-tetramethylpiperidine

The process of preparation 1 is repeated, replacing the

1-bromo-octane with an equivalent amount of 1-bromo-4dodecane.

The desired product is obtained having a boiling point of 115 ° C / 0.04 Torr.

Preparation 3

1-éthoxyoarbonylméthyl-2,2,6,6-tetramethylpiperidine

The process of Example 1 is repeated, replacing the ΙΙΟ bromo-octane with an equivalent amount of ethyl chloroacetate.

The desired product is obtained having a boiling point of 129-130 ° 0/13 æorrs.

Preparation 4

1-octoxycarbonylméthyl-2,2,6,6-tétrameth.ylpipéridine

A mixture of 45 »4 parts of 1-ethoxycarbonylmethyl-2,2,6,6tetramethylpiperidine, 36.5 parts of 1-octanol and 0.5 part of lithium amide is heated at 110-115 ° C for 48 hours, l ethyl alcohol formed during the reaction being removed by distillation. Fractional distillation of the reaction mixture provides 1-octoxycarbonylmethyl-2,2,6,6-tetramethylpiperidine having a boiling point of 120 ° 0 / 0.005 Torr.

Preparation 5

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

A solution of 26 g (0.092 mole) of 1- (2-hydroxyethyl) -2.2,

6,6-tetramethylpiperidine in 30 g of chloroform is saturated with dry hydrogen chloride, without cooling. A solution of

27.9 g (0.092 mole) of stearoyl chloride in 30 g of chloroform is added to the previous one and the reaction mixture is heated at reflux for 12 hours. The chloroform is removed from the reaction medium under reduced pressure and the residual liquor is treated with an excess of a 10% solution of sodium carbonate, and is extracted with benzene. The benzene is evaporated under vacuum from the extract and the residue is chromatographed on a column of silica gel, to give 25 g of the desired product having a melting point of 30 ° 0 (Yield 50 /) · The identity of the product has been confirmed by its nuclear magnetic resonance spectrum.

Preparation 6 l - ^ - stearoyloxy ^ -phenylethyl ^ -P, 2,6,6-tetramcth, yipperidine

Repeat the preparation process 5, replacing the

<img file="LU69904A1_D0043.tif" />

1- (2-hydroxyethyl) -2,2,6,6-tetramethylpiperidine by 1- (2hydroxy-2-phenylethyl) -2,2,6,6-tetramethylpiperidine. The silica gel chromatographic column gives a liquid product which appears to be, by elementary analysis and spectrography .RïÆN of 1- (2-stearoloxy-2-phenyl.thyl) -2,2,6,6-tëtramethylpiperidine.

Elementary analysis:

Calculated for C ^ Hg-jNOg: C 79.63 H 11.65 N 2.65 ¢.

Found: C 79.36 H 11.91 N 2.68%.

Preparation 7

Bis-2- (2,2,6,6-tetraniethylpipBridine) ethyl succinate

A solution of 18.4 g (0.1 mole) of 1- (2-hydroxyethyl) -2,2,6,6tetramethylpiperidine in 30 g of chloroform is saturated under cooling with hydrochloric acid. A solution of 7.5 g (0.049 mole) of succinoyl chloride in 30 g of chloroform is added to the previous one and the reaction mixture is heated under reflux for 15 hours. The mixture is then washed with three portions of a 10 $ solution of sodium carbonate, then with water and dried over anhydrous sodium sulfate. The volatile constituents are evaporated, leaving a residue which is recrystallized from ethanol to give 18 g of the desired pure product having a melting point of 77-78 ° O (Yield 80 0).

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

A mixture of 5.0 g of 2,2,6,6-tetramethylpiperidine p-toluenesulfonate, 70 g of ethyl orthoformate and 15 ml of dimethylformamide is heated for 3 hours at reflux. After completion of the reaction, the excess ethyl orthoformate and dimethylformamide are distilled under reduced pressure. The residue is filtered to remove the crystalline mass which is washed with ether. The filtrate and the washing waters are combined and washed with a solution of sodium hydrogen carbonate and with water. The organic phase is dried over anhydrous magnesium sulphate, the volatile constituents are evaporated, leaving 5.4 g of residue. The residue is chromatographed on a column of silica gel, eluted with a benzene / ethyl acetate mixture at 10/1 and then purified by sullimation to give the desired pure product having a fu point. sion of 51.5 - 52.5 ° C.

Elementary analysis': Calculated for Ο ^ θΗ ^ θΚΟ: 0 79.86 /; H 11.32%;

N 8.28 fi. Found: C 71.14 fi; H 11.36 fi; N 8.26 fi_at