DE2132303A1 - New triazine derivatives - Google Patents

Description

CLBA-GEIGY AG, CH-4002 Basel

3-7095 +

Dr. F. At the same time. · Or Π. Λρτη, τηη

Dr.R Kooriigcliarfjor - Dipl. F'hys. R. Ho! Zbi '; he

Dr. r. Z '! R -! -> t: in j: n.

P fl I a η! C n ν ο ι ί i <S MCncen 2. .'rr-ih'-iui τ.; .->. ' ,!. ¹ I.

New triazine derivatives

109882/1978

The present invention relates to new triazine derivatives, which contain two phenyl radicals bound via heteroatom bridges and a phosphono group, their production process, and their use as antioxidants.

The triazine derivatives according to the invention correspond the formula

N HCh-A-Z- / V-Z '-A · -OH

(i) H I

1 ^OR

OR ¹

in which A and A ^{1 are the} same or different and each represent an optionally substituted phenyl radical which is bonded ^{to Z or Z 1 in position 1}

and carries a hydroxyl group in position 4, Z and Z ^{1 are} identical or different and a bridge member represents -0-, -S- or -NQ-, with the meaning hydrogen, alkyl, alkoxy or -CN for Q, R and Pv ¹ are identical or different and each represent an optionally substituted alkyl, cycloalkyl or phenyl radical.

The substituents on the phenyl radicals are primarily alkyl or cycloalkyl, the term Alkyl is to be understood as meaning both branched and unbranched alkyl.

Triazine derivatives of the formula are in the foreground of interest

10 9882/1978

wherein R ₁ and R 'are the same or different and an alkyl group having 1 to 8 carbon atoms, R ₂ and R' are the same or different and are hydrogen or an alkyl group having 1 to 8 carbon atoms, R, an alkyl group having 1 to 18 carbon atoms or a Phenyl group and X and X ^{1 are} identical or different and represent a bridge member -O- or -NH-.

The substituents R_ and R 'are preferably in the m- or p-position to R, and Rj.

Particularly noteworthy are the symmetrically substituted triazines of the formula (2), i.e. those with two the same substituents on the triazine ring as the compounds of the formulas

(3)

109882/1978

2Ί 323

wherein R _{2 is} an alkyl group having 1 to 4 carbon atoms

and B. _c hydrogen or an alkyl group with 1 to 4 carbons .5

Represent atoms of matter and R, and X the meaning given

have / the Connections of > - x ~ o formula -OH ^R 4 JJ (4) HO- ^ 2 "Vx- < ^E 5 - \ j - I.
N = P '
\
OR ₃

wherein R .. ^ R ₁ ,, R ₁ - and X have the meaning given, the compounds of the formula

(5)

c-x-CS> -oh

wherein R ^ is a branched alkyl radical having 3 or 4 carbon atoms and R _{7 is} hydrogen , methyl

or a branched alkyl radical with 3 or 4 carbons x ■

represent material atoms. and R-. and X has the meaning given have and the compounds of the formula

109882/1978

C (CH ₃ ) NC (GE ₃ )

wherein X and R-. have the meaning given.

R-. preferably represents a straight chain in these formulas Alkyl group with 1 to 18, especially with 1 to 4 Carbon atoms.

The compounds of formula (I) are expedient made by making a compound of the formula

(7) HO-A-Z-C Ci-Z ¹ -A ¹ -OH

HI

NN -

Shark

where Hai means a halogen atom and A, A ', Z and Z' have the meaning given, with a compound of the formula

(8) P OR ¹

OR "

109882/197 «

reacted in which R and R ^{1 have} the meaning given and R "is the same or different from R or R ¹ and denotes an optionally substituted alkyl, cycloalkyl or phenyl radical.

■ To prepare the triazine derivatives of the formula (2), a compound of the formula -, -

(9)

Shark

where Hal is a halogen atom and R ,, R ', Rp, R', X and X ^{T have} the meaning given, with a phosphite of the formula ' ,

(10)

to, in which R. has the meaning given.

In the formulas (7) and (9), halogen is preferably chlorine.

The reaction can be carried out in a solvent or mixture of solvents which is inert towards the reactants be made. Possible solvents are, for example: dichlorobenzene, trichlorobenzene, perchlorethylene, Diethylene glycol dialkyl ethers, p-cymene.

109882/1978

However, the reaction is preferably carried out in the melt, advantageously under an inert gas atmosphere, for example, worked under nitrogen

will. The reaction is between 40 and 220 ° C., preferably between 100 and 200 ° (^ carried out, the reaction time from a few minutes to a few hours, generally 1/2 to 5 hours. The reaction time depends primarily on the reaction temperature chosen. The reaction time, on the other hand, also depends depends on the extent to which the halide formed in the reaction, generally a chloride, is used to shift the balance in favor of the inventive Triazine derivatives is removed from the Reaktipnsgemxsch. For the purpose of removing the halide by distillation, one therefore leads the reaction with advantage (especially when higher molecular weight halides are formed) under reduced Pressure through. At the same time, any solvent present is distilled away, so that the inventive Compounds after the reaction has ended in more

«Or remain in a less pure state.

The monohalotriazines to be used as starting materials for the present process are inherent known ways, for example as in patent 3 255 19I. described.

109882/1978

The new compounds described are valuable antioxidants, i.e. they are suitable for stabilization of organic materials against oxidative decomposition, which means, above all, thermally accelerated oxadation. as Materials that can be protected include:

1. Polymers derived from mono- or doubly unsaturated hydrocarbons, such as polyethylene, which optionally can be crosslinked, polypropylene, polyisobutylene, polymethylene butene-1, Polymethylpentene-1, polybutene-1, polyisoprene, Polybutadiene, polystyrene, polyisobutylene. Copolymers of the underlying homopolymers mentioned Monomers, such as ethylene-propylene copolymers, propylene-butene-1 copolymers, Propylene-isobutylene copolymers, styrene-butadiene copolymers, and terpolymers of ethylene and propylene with a diene such as hexadiene, dicyclopentadiene or ethylidene norbonene; Mixtures of the above homopolymers, such as, for example, mixtures of polypropylene and polyethylene, polypropylene and poly-butene-1, polypropylene and polyisobutylene.

2. Halogen-containing vinyl polymers, such as polyvinyl chloride, polyvinylidene chloride, Polyvinyl fluoride, but also polychloroprene and chlorinated rubbers »

5. Polymers that differ from α, ß-unsaturated acids and their Derive derivatives such as polyacrylates and polymethacrylates, polyacrylamides and polyacrylonitrile, as well as their copolymers with others Vinyl compounds such as acrylonitrile / butadiene / styrene, acrylonitrile /

Styrene and acrylonitrile / styrene / acrylic ester copolymers.

109882/1978

4. Polymers that are different from unsaturated alcohols and amines or their aryl derivatives or acetals, such as polyvinyl alcohol, Polyvinyl acetate, stearate, benzoate, maleate, polyvinyl butyral, polyallyl phthalate, polyal / lylmelamine and their copolymers with other vinyl compounds such as ethylene / vinyl acetate copolymers.

5. Homo- and copolymers derived from epoxies, such as Polyethylene oxide or the polymers derived from bisglycidyl ethers derive. '

6. Polyacetals, such as polyoxymethylene and polyoxyethylene, as well those polyoxymethylenes which contain ethylene oxide as a comonomer.

7fc polyphenylene oxides.

8. Polyurethanes and polyureas.

9. Polycarbonates.

10. Polysulfones. (

11. Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or from aminocarboxylic acids or the corresponding lactams, such as polyamide 6, polyamide 6/6, polyamide 6 / IO, polyamide 11, polyamide 12.

12. polyesters derived from dicarboxylic acids and dialcohols and / or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene glycol terephthalate, poly-1,4-dimethylolcyclohexane terephthalate.

10 9882/1978

IJ. Crosslinked polymers, which are different from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde resins.

14. Alkyd resins, such as glycerol-phthalic acid resins and their mixtures with melamine-formaldehyde resins.

15. Unsaturated polyester resins that differ from copolyesters Derive saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, as well as their halogen-containing, visually combustible modifications.

16. Natural polymers, such as cellulose, gum, proteins, as well their polymer homologchemically modified derivatives, such as cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers, like methyl cellulose.

For a good antioxidant effect, 0.01 to 5 % _{, preferably 0.1 to 2% 3 of} the compounds according to the invention, based on the substrate to be protected, are generally sufficient. The antioxidants can be incorporated into the materials to be protected alone or together with other additives such as plasticizers, pigments, light stabilizers (UV absorbers), further antioxidants, optical brighteners, with or without the aid of solvents.

The good stabilizing effect of the new compounds can be seen, for example, under accelerated aging effects

109882/1978

at temperatures above 100 C. A subject to these conditions Polypropylene, which contains an antioxidant, only shows signs of discoloration or discoloration after a much longer period of time. embrittlement of the material compared to a stabilizer-free polypropylene.

In the description and the examples, unless otherwise stated, parts always mean parts by weight and Percentages are always percentages by weight. The melting points of the new compounds are not corrected.

109882/1978

example 1

11.1 parts of the compound of formula

Cl C

(11)

(CH J, C * *

are together with 8.3 parts of triethyl phosphite under nitrogen atmosphere heated to 140 to 145 C for 3 hours. The melt is then dissolved in -45 parts of chloroform Add 50 parts of hexane, concentrate to half the volume and cool to 0 C. The precipitated product is sucked off and washed with hexane. 11.3 parts of the compound are obtained the formula:. Stabilizer No. 1

Melting point 14 ° C

109882/1978

The compound of formula (11) used as the starting material and having a melting point of 23 7 to 219 ° C. is obtained in 86% yield by reacting 18.5 parts of cyanuric chloride with 44.5 parts of 2,6-di-tert-butyl- hydroquinone in 250 parts of acetone by allowing a solution of 8 parts of sodium hydroxide in 195 parts of water to be added dropwise at 35 to 40 ° C. in the course of 5 hours in such a way that the p _H -Yfert does not rise above. The resulting suspension is then cooled to 0 ° C., and the precipitated product is filtered off with suction, washed with water and dried.

In an analogous manner, when using the compounds of the formulas

CH (CH ₅ )

109882/1978

l4 -

(14)

C-NH

(15) Β

(16) B.

(17) H.

109-882 / 137

the connections of the formulas

109882/1978

(18) H.

C NH-

CH ₃ OH

"3

(19)

Stabilizer No. 2

P (CH-),

Melting point 244 to 246 ° C

OG ₂ H ₅

CH (CH-.)

Melting point 115

Stabilizer No. 3 2 2

OH
CH (CH,)

Stabilizer No. 4

I / ^OC 2 ^H 5

D = P

Stabilizer No. 5

C (CH-)

109882/1978

"■ Stabilizer No. 6

C (CH ₃ ) 3 J \

HO - - C3 ilH - C C -

C (CH ₅ )

■ Stabilizer No. 7

c (cii ₅ ) ₅

OH

OC ₂ H,

\ Λ2 ^

O = P

₃ ^
Η0- / Λ-

CH.

-NH-

ft

Qr-

O = P

Melting point 108 ° decomposition stabilizer Kr. 8

-NH:

CH ₃ VOH

Stabilizer No. 9

OH-0-0

O = P

Melting point up to 212 to 2Γ3 C

obtain.

1QS882 / 197?

Example 2

5.5 parts of the compound of formula (11) are added together with 9.1 parts of trioctadecyl phosphite under a nitrogen atmosphere melted at 50C. This is followed by Vacuum (0.5 Torr) heated to 180 ° C. and the octadecyl chloride formed was distilled off. After 30 minutes it is Reaction ended. 11 parts of a yellow, viscous oil are obtained, from which, after chromatography, on Silica gel and extraction with chloroform to give the compound of the formula

. Stabilizer no.

£ _> - OH (CH VC £

O = P

^0C 18 ^H 37

is isolated.

Melting point after recrystallization from acetone / water / water 40 ° to 4l ° C.

10S882 / 1978

formula

In an analogous way, the connection of the

Stabilizer No. 11

O = P

obtain. Melting point 95 to 96 ° C.

In an analogous manner, when using the compounds of the formulas (11), (12), (13) and the connections of the formulas'

C (CH ₅ )

Stabilizer No. 12

C (CH ^).

Stabilizer no

t ^OO 18 ^H 37

O = P

10988 2/1978

Stabilizer No.

PiCH ₅ ) ₃

C (CH ₃ )

O = P

Stabilizer No. 15

O = P

37

Stabilizer No. 16

Melting point 259 to 260 ° C

109882/1978

C (CH)

HO - /]) - C (CH ₃ J ₃

- 21 -

Stabilizer # 17 C (J.

Pel

Ber: C 70.40 H 9.88 N 4.48 Get: 70.48 10.06 4.55

0 =

Stabilizer no.

OH-

Light yellow pel

-0

.0 _ / ypH

\ C (CH,

/ ^C 8 ^H 17

C = P.

Calcd: C 68.33 H 9 ₂ 7 N 5-P9 Found: 68.06 9.31 5.27

\ s '

HO-

Stabilizer no.

O = P

/ ^0CH 3

OCH.

Q—

C (CH) / ³ ^ VOH

Melting point 207 -

2P8 ° C

can be obtained.

109882/1978

The following, previously known stabilizers were also tested as comparative compounds in the application examples:

2,6-di-tert-butyl-4-methylphenol

Methylene bis (3-methyl ~ 4-hydroxy-5-tert.buty! Benzene)

Thio-bis- (2-methy1-4-hydroxy-5-tert-butylbenzene)

2,4 ~ (3,5-di-tert-buty 1-4-hydroxyphenylamino) -6-octylmercapto-1,3 * 5-triazine

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

2.- (2'-Hydroxy-S'-methy! Phenyl) -benztriazole

Stabilizer No. 20 Stabilizer Mr. 21 Stabilizer No. 22

Stabilizer No. 23 Stabilizer No. 24 Stabilizer No. 25

109882/1978

Example 3

A mixture of LOO parts of unstabilized polypropylene (Profax 6501, Hercules Powder) and 0.2 parts of a compound according to the table below A is processed on the calender at 170 ° C into a sheet and then at 230 ⁰ C and a pressure of 40 kg / cm pressed into a plate of 1 mm thickness. The plates obtained in this way are subjected to accelerated oxygen aging at 140 ° C. (air, normal pressure). The time it takes for the first visible cracks to appear is a measure of the antioxidant effect of the added compound.

Table A.

Blocked connection
(Stabilizer no.) Time to crack in
Hours at 140 ° C without addition 5 k. Commercially available antioxidants
dantien 25th
28
100
260 20th
21
22nd
2> 780
1030
19 7 8 ⁷¹ °
1220 B. According to the invention
links 1
11
¹⁷ 10 9882 /
18th

Example 4

100 parts of polypropylene (melt index J>, 2.) are kneaded in a Brabender plastograph for 10 minutes at 200 ° C. with the stabilizers listed in Tables B and C below. This ensures a homogeneous distribution of the stabilizers. The mass obtained in this way is then pressed in a plate press at a plate temperature of 250 ° C. to give plates 1 mm thick. With the aid of a microtome, chips (shavings) with a thickness of 25 μ are cut from the plates obtained in this way. These chips are clamped between stainless steel grids and the sample carriers obtained in this way are suspended in a convection oven and aged at 135 ° C or ΐ4γ ° 0. The end point is taken as the time after which degraded polypropylene falls out in powdered form when you knock lightly on the grilles (check 1 - 2 χ daily).
For results see Tables B and C.

109882/1978

Table · B

Blocked connection Time to Decomposition in hours (Stabilizer no.) at 135 ° C at 147 ⁰ C Without addition 20th 10 A. Commercially available antioxidants
dantien 0.2 % 20
0.2 % 21
0.2 % 22 20th
50
120 . 10
20th
35 B. According to the invention
ties 0.2 % 1
0.2 % 3
0.2 % JLO
0.2 % JLL
0.2 % 17 165
165
230
310
38O 65
65
95
120
I6O

109882/1978

- 2 B

Table C.

Blocked connection
(Stabilizer no.) 1 % '20 + 0.3 % DLTDP *) Time to. to the Decomposition in hours 0, 1 % + 0.3 · ^ " at 135 ° at ΐ4γ ° 0, 1% + 0.3 % " 40 15th 0, 1 % _1 + 0.3 % DLTDP 60 20th 0, 1 % 3 + -0.3-Si ^M 140 48 "0, 1 % IO + 0.3 % " 165 65 0, 1 % Ii + 0.3 % " 240 95 0, 1 % IZ + 0.3 % " 360 130 0, 380 160 38O 160

*) Dilauryl thiodipropionate

109882/1978

Example 5 Stabilization of low pressure polyethylene

38 g of low pressure polyethylene are used along with 0.1 # one in the below Table D additives are kneaded in a Brabender plastograph, this being determined by the kneading resistance generated torque is continuously registered. The degradation of the polymer results in a rapid decline of the torque after a characteristic induction period for the additive:

Table D.

Stabilizer no. Induction period in minutes without addition
1
2
10 20th
50
40
65

109882/1978

Example '6

Stabilization of polyamide 6

100 parts of polyamide 6 granules are mixed with 0.5 parts of trisnonylphenyl phosphite and 0.5 part of any one of the following The additives listed in Table E are mixed, processed in a laboratory gelimate and then pressed out at 260 ° C. to give 1 mm test plates The plates are accelerated in a forced air oven at 140 C. Aging μηΐβΓΥ / ΟΓίΘη. The stabilizing effect of the Additives are judged on the brittleness of the films.

Table E.

Stabilizer no. Brittle after
hours without addition 18th 1 25th 2 54 34 11 27

109882/1978

- 29 Example J

100 g of unstabilized polyamide 12 granules ("Vestamid L 1901 "of Chem. Werke Hüls" is thorough with 1.0 gram mixed one of the stabilizers listed in Table P below, processed in a laboratory Gelimat and in a plate press at 260 C to give 1 mm test plates.

ο The oven aging stability at I50 C after 2, 5 * 10 and 20 days, by determining the viscosity 0.5 percent m-cresol solutions, tested. Simultaneously an unstabilized comparison sample, which was otherwise processed in the same way, is also tested. The relative viscosities (Viscosity of the solution divided by the viscosity of the pure solvent at the same temperature) according to the specified Oven aging times are given in Table P.

■ Table · Ρ

Stabilizer no. Relative viscosity in m-Oresol after oven aging at 150 ⁰ C After 2 days After j? Days After JLO days After _20 days without addition After JD days 1.60 1.48 1.45 1.40 20th
21
22nd i, 8i 1.65
1.64
1.61 1.49
1.51 '
1.50 1.42
1.42
1.41 1.40
1.42
1.40 mm
C.
egg ^! 2
5
9
10
11
19th 1.85
1.84
1.84 1.85
• 1.84
1.87
1.90
1.89
1.86 1.79
1.75
1.85
. , 1.84
1.82
1.86 1.65
1.59
1.62
1.76
1.70
1.68 1.54 O
1.49
1.54
1.60
1.56
1.55
_ ro - N
%
a 1.85
1.85
1.85
1.86
1.84
1.84

Example 8 Stabilization of synthetic rubber EFDM

Commercial EPDM rubber from Dutch Staatsmjinen is freed from the stabilizer by dissolving it in hot toluene and precipitating it with methanol. Samples of 40 g each of the dried, stabilizer-free material are kneaded together with 0.2% of one of the additives listed in Table G below in a Brabender plastograph, the torque caused by the kneading resistance being recorded continuously. (Table: torque in grams read off directly on the balance). At the same time, after 7 * 15 and 25 minutes, a sample is examined for the gel content (components insoluble in hexane). The gel contents increase with advancing aging, ie crosslinking of the polymer.

Table G.

Stabilizer no. Torque in grams according to:
7 min. 15 min. 25 min. 3300
3450
3400
3400 2600
3400
3300
3400 20th
0
0
0
1978 35
7th
10
8th without addition
10
11
17th 3900
3800
3700
3700 Gel content in percent according to:
7 Wed.n. 15 min. 25 min. 3
0
0
0
109882 / without addition
10
11
17th

-Example-1-9

Stabilization of polyurethane

In each case 0.25 parts of the additives in Table H are used in 100 parts of a 25 percent polyurethane solution (ESTANE 5707 from the company "Goodrich") solved cold.

About 400 μ thick films are drawn from these solutions on a glass plate with a film grinder, which after about 10 minutes of circulating air drying at 140 ° C. dry out to form films with a final thickness of 100 μ. The stabilizers are therefore present in the films in a concentration of 10 % . Samples of these films are exposed until the onset of visually perceptible yellowing in a xenotest device on a white card background.

Table H.

Stabilizer no. 10Ϊ Exposure time 882/1978 for distinct 600 Yellowing in Hours. without addition 150 5ΟΟ-6ΟΟ 25th 25Ο-3ΟΟ 2 300 5ΟΟ-6ΟΟ 2 + 25 9 300 6OO 9 + 25 11 300 11 + 25 19th 350 19 + 25

Elastomer fibers of a linear polyurethane (Enkaswing S5A the PA. AKU, Holland) are made from 20 liters of dimethylacetamide solution spun and the Paser precipitated in a toluene bath. The following are added to the precipitation bath:

1.5 % of the stabilizer 10

1,5 # 2- (2 ^f hydroxy-3 ^I , 5'-di-tert-butylphenyl) -

5-chloro-benzotriazole 1.5 % dilauryl thiodipropionate 2 % ethylenediamine 2 % silicone oil

A fiber is used as a comparison sample, which in the same way, but without the addition of the antioxidant according to the invention is produced for the precipitation bath.

Both fiber samples are exposed to 105 C in. For 15 hours artificially aged in a drying cabinet, being observed It is found that the unstabilized fiber will noticeably yellow, while the stabilized fiber will not show any discoloration shows.

109882 / 197S

■ Example — 'M:

Stabilization of polyacetal

100 parts of unstabilized homo-polyacetal (polyformaldehyde, Origin: Societa Italiana Resine) are made with 1.5 parts of calcium stearate and 0.2 parts of one of the in the mixed additives mentioned in Table I below, processed on a two-roll mill for 15 minutes and the rolled sheet deducted. Each 10 mg of the stabilized samples will be Heated to 220 C on the bowl of a sensitive thermobalance. The weight loss of the samples (in percent) is continuously registered.

Table I.

Stabilizer Kr. Weight loss ■ 10 min. in % after ■ 5 "min. · ■ 22nd 15 minutes. without addition 12th 9 51 i 12th 15th 10 5 10 17th 11 12th 15th 17th 7th 19th

109882/197 8

-Example 12

Stabilization of polymethyl methacrylate

.100 parts of poly (ethyl methacrylate) ("Resarit 400") are with 1.5 parts of an additive listed in Table K below intensely mixed. The mixture obtained is extruded in a laboratory extruder and then granulated. That The granulate obtained is then regranulated 25 times, After the 5th, 15th and 25th extrusion, a sample of the granulate is pressed into a 1 mm thick plate, which after its Color is judged.

Table K

Additive no. Color of the plastic according to 15 extrusions 25 extrusions 5 extrusions deep yellow Brown without addition yellow colorless slightly yellow 1 colorless colorless slightly yellow 17th colorless colorless slightly yellow 18th colorless colorless light yellow: 19th colorless

109882/197 8

Claims (1)

in which A and A ^{1 are} identical or different and denote an optionally substituted phenylene radical Position 1 is bound to E "or Z ¹ ■ · - ■ - :. - '-> - ·· - and in position k carries a hydroxyl group, Z and Z ^{1 are} identical or different and a bridge member represents -0-, -S- or -KQ-, meaning hydrogen, alkyl, alkoxy or -CN for Q, R and R ' are identical or different and denote an optionally substituted alkyl, cycloalkyl or benzene radical. ': £ ?. New triazine derivatives according to claim I ₁ those of the formula correspond, 109882/1978 where R ^ and R | are identical or different and an alkyl group with 1 to 8 carbon atoms, R ₂ and R 'are identical or different and are hydrogen or an alkyl group with 1 to 8 carbon atoms, R .. an alkyl group with 1 to 18 carbon atoms or a phenyl group and X and X ^{1 are} identical or different and represent a bridge member -0- or -NH-. '· "" - 3. New triazine derivatives according to patent claim \ those of the formula. ' . ■ - correspond, wherein R 1 is an alkyl group having 1 to 18 carbon atoms ³ ■ ■ · '· i or a phenyl group, Rj. an alkyl group with 1 to 4 Carbon atoms and R ^ hydrogen or an alkyl group represent with 1 to 4 carbon atoms and X is a bridge member -0- or -NH- means. . 4 · New triazine derivatives according to claim 1, which the formula correspond VJorin R, an alkyl group having 1 to 18 carbon atoms or a phenyl group, Rj, an alkyl group having 1 to 4 carbon atoms, and R ^ - represents and V / on Hydrogen or an alkyl group having 1 to h carbon atoms X is a bridge member -0- or - NH- means. 5 · New triazine derivatives according to claim 1, the of the formula - - * - ' N R ₆ correspond, where FL is an alkyl group with 1 to 18 carbon atoms or a phenyl group, Rg is a branched alkyl group with 3 or h carbon atoms and R "is hydrogen, methyl or a branched alkyl group with 3 or 4 carbon atoms and X is a bridge member -O- or -NH- . 6. · - New triazine derivatives according to claim 1, the of the formula "- - ·. C (OT,), A -, C (CH ₅ ) ₃ -OH
C (CH ^) ₅ . '■ correspond, in which R-, an alleyl group having 1 to 18 carbon atoms or a phenyl group and X is a bridge member -0- or
-NH- mean. 7. Use of the in any one of claims 1 to 6
defined compounds as antioxidants for organic
Materials. "■ 109882/1978