DE2018716A1 - - Google Patents

Description

, MASUh {§ € HWUIZ)

fHPgS! ilS @ || e! JfS ^

welefee

ORIGINAL INSPECTED

tive influences.

The new compounds correspond to the formula

IH

where Y _{1 is} a branched alkyl radical with a maximum of 4 carbon atoms, 23, a hydrogen atom or a branched alkyl radical with a maximum of% carbon atoms and η is an integer from I to 16 *

They are also of a certain practical interest Compounds of the formula

(2)

η a whole number of 1 lais Connections with besonjefs e the Iprinel.

Bigensehaften are

ill

BATH

wherein Ζ 'denotes a methyl or tert-butyl radical and ρ is an integer from 3 to 8.

Of particular practical interest are connections that of the formula

NH-CO- (CH ₂ ) -CO-HH

(H ₃ C) ₃ CC (CH ₃ J ₃

correspond, -wherein ρ stands for an integer of 3 ^Dis 8 Compounds-of the formula (1) can be prepared ^ by a compound of the formula ..'..--

L

wherein Yy and Z have the meaning given., with a compound of the formula

wherein A is a hydroxyl, halogen or RO group / Ή lower alkyl radical and η is an integer from 1 to 16

- in a - against the reactants _/ - 'inert solvent or in the melt, optionally N ^ using a water elimination catalyst or when using an acid halide using an acid acceptor, at temperatures of 20 to 25Ο ⁰ C implemented. Appropriate

BATH ORIGINAL

molar equivalent amounts are used, i.e. about 2 mol of amine (formula 5) per 1 mol of acid (derivative) according to formula (6). -

Compounds of the formula (2) are obtained by using the compound of the formula

(CH ₃ ) ₃ O

with a dicarboxylic acid halide of the formula

Shark - OC - (CHg) ^ CO - Shark

where Hai is a halogen atom and η is an integer from 1 to 16 means in a solvent inert to the reactants or in the melt, optionally in the presence an acid acceptor, at temperatures of 20 to 250 ° C.

Compounds of the formula (3) are obtained by adding a compound of the formula

009846/1992

. ■■■ "■ - 5 - *

wherein Z ¹ ^ is a methyl or tert-butyl radical, with a dicarboxylic acid halide of the formula

(10) Hal — OC— (CH ₂ ) —GO — Hal, ^ -

where Hai is a halogen atom and ρ is an integer from 3 to mean, reacts with one another in a very corresponding manner as indicated above. ■

Compounds of the formula (4) are obtained in a corresponding manner by reacting a compound of Formula (7) with a compound of the formula (10).

The novel compounds described are valuable antioxidants, ie they are suitable for stabilizing organic materials against oxidative ΐ decomposition, such as by light-induced oxidation or thermally accelerated oxidation. Materials that can be protected include:

Homo- and copolymers made from ethylenically unsaturated compounds such as vinyl chloride, vinylidene chloride, styrene, Butadiene, isoprene, ethylene, propylene, acrylic and methacrylic acid derivatives, e.g., acrylic acid alkyl esters, acrylic acid amides, and acrylonitrile; Polyamides, e.g. made of g-capro- ' lactam or from adipic acid and a diamine polyester such as terephthalic acid glycol polyester; natural and syn-

009846/1992

thetic rubbers! Lubricating oils! Benzinej vegetable and animal oils and fat waxes, j cellulose and cellulose compounds such as cellulose esters.

Particularly noteworthy is the excellent antioxidant effect of the compounds defined above Polymer plastics, especially poly-α-olefins like polypropylene.

For a good Antioxydanswirkung ranging from 0.01 to 5% of the novel compounds, based on the substrate to be protected _£ generally in-out. The Antloxydantien to materials to be protected, alone or together with other additives such as plasticizers, pigments, light stabilizers (UV absorbers), secondary antioxidants factors _s optical brighteners, Hitzestabilisa- "in which may be incorporated with or without the aid of solvents.

The good stabilizing effect of the new compounds shows up e.g. under accelerated aging conditions at temperatures above 100 ° C »One of these conditions exposed polypropylene containing an antioxidant shows signs of wear only after a much longer period of time a discoloration or »brittleness of the material, compared to a stabilizer-free polypropylene

Ie in the following examples mean ^ if If otherwise stated, the parts are parts by weight and di-e

009846/1892

Percentages by weight. The melting points of the new Connections are not corrected.

009 8 46/1992

example 1

11.05 parts of 2,6-di-tert-butyl-4-aminophenol (made from 11.75 parts of 2,6-di-tert-butyl-4-nitrosophenol by reduction with sodium hydrosulfite in an alkaline solution) are dissolved in 150 parts of methylene chloride. Then 4 parts of pyridine are added as an acid acceptor. 4.6 parts of adipic acid chloride, dissolved in 100 parts of methylene chloride, are added dropwise to the dark red solution and the reaction mixture obtained is stirred for one hour at reflux temperature (40 ° C.).

For work-up, the reaction solution, from which pyridine hydrochloride has separated out, is placed on ice poured and the solvent was then distilled off with steam. The crude yield of the from steam distillation resulting product of the formula

(11) HO— <t> —NH-C0- {CH _o ·} -: - COH fs 24

is 13 * 2 parts.

00 9846/1992

After two recrystallization from methyl ethyl ketone-cyelohexane the analysis data are:

Melting point: a8o.5 to 28l ° C.

Microanalysis: Calculated: C 75 * 87 H 9 ^ 8 N 5.07,

Found: C 73.64 H 9/31 N 4.94.

The following are produced in an analogous manner:

009846/1992

link

Antioxidants

Melting point in C.

Analysis: calculated
found

12th

-33H-CO-CH ₂ -CO-J

254-255

C 72.90 H 9.08 Ή 5.49 C 72.78 H 9.08 N 5.59

(CH ₃ J ₅ C

H0 - ^^ inMJ0- ^ H ₂ ^^ 0 - lIH - ^^ - OH

C (CH,)

314-515

C 73.24 H 9.22 N 5.34 C 73.01 H 9.19 H 5.16

(OH -), C

251-253

C 73.56 H 9.35 JT 5.20 C 73.61. H 9.36 N 5.23

15th

199-200

C 70.78 H 9.57 N 9.17 C 70.75 H 9.87 N 8.88

fr O ■ Η ■ Ρ

8th"

There

to σ »

in σ »

co

σ »

in H

US

CM

in

in

CM

VO H

TTDl

VO

to
H in
O 3 'S W. W. 75.42 75.56

OO

or »

f ω

Rl ".

to

BAB / 1992

C- 00 3 .3 W. w in
CM C-
CM vo
C- VO *
C-

O

C-

to to

to to

W ■ ■ ■ W

O WHERE

CO H.

ORIGINAL INSPECTED

Connect Antioxidants ^(0Η 3> 3 \ / ⁰ < ⁰ V3 Enamel -190 Analysis: 73.24 calculated 9.22 N 5.34 application no. HO — κ ^ - NH-CO-fOH ,,) "-GO-NH - ^^ - OH Point found / 2 8 ^ - ^ C. 72.96 H 9.06 N 5.34 19th CH_ 189 C. H 72.54 8.93 N 5.64 O (H-C) C η I rtrr λ CD -210 C. .72.39 H. 9.01 N 5.79 CO ho— <3- NH-CO-KiH ₀ ) _o -G0-NH- <] 3-OH
C. O 00 σ H CD
^. 20th 209 (O co / ^H 3 73.87 9.48 Ν < > 5, Ο7 to . CH CH -191 H O ^ HoV ^ H σ 74.06 H 9.38 N 4.84 21st CH CH
\ 190 σ H j. CH- CH- 3 3

.- ■■ 13 -

Example 2

A mixture of 100 parts of unstabilized polypropylene (Profax 6501, Hercules Powder) and 0.2 parts of a compound according to the table below is processed on the calender bei.170 ⁰ C into a sheet and subsequently at 230 ° C and a pressure of 40 kg / cm pressed into a plate 1 mm thick. The plates obtained in this way are subjected to accelerated oxygen aging at 140 ° C. (air, normal pressure). The time which elapses until occurrence of the first to ^1-of Äuge noticeable cracks, is a measure of the antioxidative effect of the compound added. ·

Table I.

clogged compound Time to Rissbil
in hours
at 140 ^° C without addition
A. Commercially available antioxidants: 5
25 ·
28
100
260. 2,6-di-tert-butyl-4-diethylphenol
Methylene bis (3-methyl-4-hydroxy-5-tert.-
butylbenzene)
Thio-bis- (2-methyl-4 ~ hydroxy-5-tert.-
butylbenzene)
2,4- (5 ^l , 5'-Bi-tert-butyl-4-hydroxy-
phenylamino-6-octylmercapto-1,3 »5-triazir

0 0 9 84 6/19 9 2

Table II

Connections according to the invention:

Connect
application no. clogged compound Time to crack
education in
Hours at 140 ^ 13th (CH,), CC (CHj,
\. y
(CH,), GC (GHj-
JJ . Yy 500 14th
* (CH,), GC (CH,),
HO ^ Vv-mG H GO-NH- ^ r ^ OH
5 5 5 5 850 15th 3 3/3 3
HO- ^ yinMJ ^ CH ^ O-NH - ^ - OH
^ OTT \ Π Π ( ΠΤΤ ^
i0n "J_O u \ vj11—} ~
YY YY 1060 16 HO - ^^ M ^ GC> 40H-4öCQ-NH - ^^ - OH 1070

0Q984B / 1992

Example 3

A mixture of 100 parts of isoprene rubber, 5 parts of zinc oxide, 10 parts of titanium dioxide, 75 parts of barium sulfate, 1 part of stearic acid, 1.5 parts of 2-mercaptobenzothiazole, 2 parts of sulfur, 1 part of antioxidant according to the table below is on a two-roll mill at 7Ό ° C. for J> 0 minutes and then pressed by vulcanization for 20 minutes in a press at 140.degree. C. to give sheets 1 mm thick. From this, dumbbell-shaped, 8 cm long and 1 cm wide test specimens are punched out, which are then aged in an oven at 100 ° C. for 50 hours. By measuring the breaking load and elongation at break before and after aging, one can see the decrease in mechanical strength or the antioxidant effect of the incorporated connections.

The results are summarized in Table III. The values given are average values from 10 samples each. (Measurements in each case according to DIN-DVM 3504 using the so-called »Instron Tensile Tester). ·. In Table III mean

ρ
L = breaking load in kp / mra,

D. a elongation at break in %

00 9846/199 2

ORIGINAL INSPECTED

TABSLLB III

Antioxidant
the formula mechaniache
strength Oven aging 100 ° C
in hours 50 Decrease in without addition L.
D. 0 0.18
589 86
43 (16) L.
D '. · 1.28
1020 0.22
694 79
26th (19) L.
0 1.05
963 -0.49
853 59
17th 2,6-di-tert.
butyl-4-
methylphenol L.
D. 1.12
1033 0.14
638 84
33 0.88
952

0098A6 / 1992

Copy

- IT

example

100 parts of polyethylene granulate are mixed dry with 0/2 parts of antioxidant each according to the table below and then added on a two-roller mill. 140 ° C for 3 minutes processed into a homogeneous skin. This is then pressed in a press at 150 ° C. for 5 minutes to form a film 1 mm thick. For tear tests, dumbbell-shaped, 8 2 m long and 3 cm wide test specimens are punched out, which are then ^{aged in an oven at 85 ° C.} for 100 hours. By measuring the breaking load and elongation at break before and after aging, one can see the decrease in mechanical strength or the antioxidant effect of the incorporated connections.

The results are summarized in Table IV. The values given are in each case around average values from 10 samples each (measurements in accordance with DIN-DVM 350 * 1 using the so-called T Instron Tensile Testers).

In Table 17:

L β breaking load in kp / mm.

D ■■ elongation at break in %

009846/1992

■ #

copy

TABLE IV

Antioxidant
the formula mechanical
strength Oven temperature 100 ° C
in hours 50 Decrease in without addition L.
D. O 1.25
352 9
. 15th (16) L.
D. 1.37
414 1.25
376 VJi CO (19) L.
D. 1.36
394- 1.33
403 1 2,6-di-tert.
butyl-4-
methyl! phenol L.
D. 1.30
408 1.18
369 16
15th 1.44
439

0038 A6 / 1992 Dopy

Claims (1)

Claims Carboxamides, which have the formula / New HO- ^ I ^ -NH-CO-fcC where Y ₁ denotes a branched alkyl radical with at most 4 carbon atoms, Z denotes a hydrogen atom, or a branched alkyl radical with at most k carbon atoms and η denotes an integer from 1 to 16. 2. New carboxamides according to claim 1, which of the formula - (CB ₃ ) where η is an integer from 1 to 16 en
indicates. Me.u «carboxamides, which dor formula 009848/1992 copy £ NH-CCKCH ₀ ) -CO-NH / 2 P No. ¹ No. ¹ in which Z ¹ denotes a methyl or tert-butyl radical and ρ denotes an integer from 3 to 8. 4. New carboxamides according to claim 3, which of the formula Oe ^ NH-C0-fCH ₂ ) (H ₃ C) ₃ C )H correspond, where ρ is an integer from 3 to 8. 98Λ6 / 1992 5 · Use of carboxamides, as in -, ■ any one of claims 1 to 4 defined as antioxidants for polymer plastics. · 6. Use according to claim 5 of carboxamides, as defined in claim 4, as antioxidants for poly-α-olefins, in particular polypropylene. 7 procedures for the protection of organic materials, which are subject to damage or destruction due to oxidative influence, characterized in that compounds as defined in any one of claims 1 to 4, incorporated into the material to be protected with even distribution. 8. The method according to claim 7 *, characterized in that that polymer plastics at least one :, the compounds as defined in one of claims 1 to 4, in an amount of about 0.01 to 5 percent by weight incorporated in a homogeneous distribution. 9. The method according to claim 8, characterized in that compounds as defined in claim 4 are incorporated ^{into poly-α-oil efin plastics 4, in particular polypropylene.} 0098U / 19I2 Annex to the entry rom 16.6.1970 in the matter of the Patentaneeliang Deposit t CIBA AktianMicUfMifeaft U. Sign ι 21 687-BH / fef - οΗββ 6749 / B - 22 - ' 10. The method according to claim 7, "characterized in that that one of the compounds defined in one of claims 1 to 4 in combination with secondary Antioxidants, heat stabilizers and / or UV absorbers are used. 009846/1902