DE1569059A1 - Heat-resistant polymer compositions - Google Patents

Description

DIPL-ING. S. STAcCärfcK ■ * - "- ·.

ί-ψΓ. ibO'J

for the patent application of 1569059 Imperial Chemical Industries Limited, London, S * W.1.,

concerning:

Heat-resistant polymer compounds

The priority of filing in the UK on April 2, 1965

and May 6, 1964 is used The invention relates to the making of high Polymers, especially nylon, polypropylene and polyethylene, against degradation caused by, for example, heat.

According to the invention, polymer compositions are created whose Heat resistance through the addition of at least one stabilizing compound of the formula:

QH

or the formula:

has been increased, where R-, and R "hydrogen atoms or Represent alkyl groups and at least one of them represents an alkyl group, preferably a tertiary alkyl group, and where 3L and R ^ are hydrogen atoms or alkyl, aralkyl or represent acyl groups and are identical to or different from one another, or where R. is a group the formula;

OH

or the formula:

represents, the bridging group A being a divalent one Radical is preferably an alkylene radical.

, Stabil! SierungsvQFbinduag
At © ija © ^ / with swöi via the Ueoerlarttokungsgruppe -A-

Enclosure systems need the _{substitutions in these systems by R 2} , R, and R, put in front of them

each other gleioli au his 9 09848/1245

If R and R are alkyl groups, they contain usually up to 18 carbon atoms. As preferred terb.-alkyl groups can be, for example, tert.-butyl, tert.-amyl, Mention terb.-octyl, tert.-nonyl and terb.-dodecyl groups.

If R. or R represents alkyl groups, they contain at most 24 carbon atoms each. But if they represent aralky groups, they each contain a maximum of 30 Carbon atoms. Examples of suitable aralkyl groups include benzyl, hydroocybenzyl and alkylbenzyl radicals and also mention more substituted benzyl radicals. The acyl groups represented by R ^ or R ~ can expediently e.g. from monocarboxylic acids of the aliphatic or aromatic series. So you can e.g. Caproyl-, Valeroyl-, Jfyristoyl-, Lauroyl-, Sbearoyl-, Oleyl, 2,4, 4-trimethylb.exanonyl-, 2-ethylhexanoyl-, Be benzoyl, phthaloyl, and substituted aroyl groups. The acyl group used preferably contains 9 to 13 carbon atoms. The acyl groups can also derive from di- and tricarboxylic acids, i.e. they can be e.g. adipoyl, sebacoyl or succinoyl groups. The stabilizing compounds used according to the invention can be added to the polymer in any suitable manner. So they can be added to the polymer during its manufacture, or to the molten polymer, or to the Polymer can be applied to the surface after production. If the stabilizing agent is, for example, in the form of a solution or dispersion in a liquid medium is applied to the polymer, the treated polymer becomes preferably heated to cause migration of the stabilizer into the polymer.

In the case of a Bylon polymer, an addition of 0.01 Ms is required 2% by weight of the stabilizer based on weight of the polymer is enough to make the polymer completely heat-resistant in most cases, e.g. to the heating that Nylon yarns are experienced in the production of car tires reinforced with such yarns.

The following stabilizing compounds are particularly suitable: 2-Andno-4-tert.-butylphenol, 2-N-sec.-butylamino- -4-tert. -feutylphenol, 2-H-sec. -butylamino-4,6-oLitert ;. -butylphenol, 2-IsOPrOPyIaIBiHO - ^ - JG-Oi-tert.-butylphenol, Bis-6-H-

909848/1245

BATH ORIGINAL

- (tert 2 ^l -hydro3iy-4 ^f "~ butylplienyl.) -Äthjlendiaiiiin, 4-H-isopropylamino-2,6-di-tert ~ biitylphenol, H-stearoylanino-2,6-di-tert.-Butylphenol. 2-Stearoylainino-4-tert-butylphenol.

Compared to the usual amine antioxidants, they have Stabilizing compounds according to the invention have the advantage that they result in only a very slight coloration of Lead nylon polymers and do not affect the appearance of the polymers.

In this specification, the term "nylon" means synthetic polyamides having multiple amide bonds in the main polymer chain, such as the well-known polyhexamethylene adipamide and the well-known folycaprolactam.

Especially in the case of polyolefin polymers, the above mentioned Formulas defined phenols mixed with e.g. dilauryl thiodipropionate has been used to provide increased stability. to achieve izing effect.

The invention is illustrated below with the aid of exemplary embodiments explained in more detail purely by way of example, all quantities being based on weight.

Examples Λ until ?

General

There are 0.1 V ¹ I ¹ GiIe a 0.4% solution of the stabilizing agent in formic acid to S parts of a 10% solution of Foi; -iiexamethyienadipamid added in formic acid. A layer of this polyamide formed by brushing on a sheet of glass is then aged in an air-heated oven at 220 ° C. after the formic acid has evaporated in an oven at ^ 00 ° C.

The color of the pi? Obe is compared with that of a similar ITylon layer without ^: stabilizing agents after aging times of different lengths. After an aging time of one minute, the stabilized nylon layer is much less discolored than the Eontroll layer; - · *.: - ■ -'- '■ - "- / ^ - ■ ·' ■ '': <'- :: '. c

Βεφί .

1. 2- (N ~ sec-butylamino) -4- tert. butylplienol

2. 4-amino-2,6-diter. -butylplienol

3 · 2-N-sec-butylamino-4,6-di-tert-butyl phenol -

4. 4-N-isopropylamino-2,6-di-tert-butylphenol

5. 4-H-stearoylami.no- -3-methyl-6-tert. butylplienol

6. Bis-N, N ^l - (2 ^l -hydroxy-

-5'-tert-butylphenyl) ethylenediamine

7. Control sample (oline stabilizer)

30 min white

dto.

dto.

ivory colored

White

dto.

Brown

Aging time 60 min 45 min ivory
coloured ivory
coloured dto. dto. dto. dto. brownish-
isabelle-
coloured dto. ivory-
see you isabell
en-colored dto. ivory
coloured dto. dark brown medium brown

Example 8

4-N-stearoylamino-2,6-di-tert-butylphenol or H -N-stearoylamino-methyl-e-tert-butylphenol is added to pulverulent polypropylene, whereupon the mixture is shaken for 5 minutes. The mixture, whose concentration is given of stabilizing agent in the following table, is then triturated 5 min *> ^e i ⁰ O 17O. There are then pressed sheets with a thickness from 0.45 to 0.55 a ™ from this mixture at 130 ⁰ C and anscliessend cooled under pressure. The plate samples are heated in an air heated at 150 Einzellenofen ⁰ O, up / enters embrittlement of the sample. In Table I below, the corresponding embrittlement times are given, which should be compared with the embrittlement time of 33 days for a commercially available antioxidant.

Table I.

Compound concentration in poly- embrittlement-

time (days)

Concentration in polypropylene (%)

4-N-stearoylamino-2,6-di-tert-butylphenol

4-N-stearoylamino- -3-methyl-6-tert-butylphenol

0.5

0.5

9 0 9 8 4 8/1 2 k 5

44

BAD ORtGlNAL

1569Ö59

In Table II are the results of similar experiments reproduced, in which an additional 0.25% dilaurylbhiodipropionate is added to the polypropylene. It's out of it it can be seen that this leads to an increased stabilizing effect for the first two compounds compared to the Results according to Table I.

Table II

Compound concentration in poly- embrittlement

propylene (%) time (days;

'4-N-stearoylamino-0.25 64

2,6-di-tert-bubylphenol

4-H-stearoylamino-0.25 70

3-methyl-6-tert

butylphenol

2-N-stearoylamino-0.25 ^ 42

4-tert-butylphenol

2-N-stearoylamino-0.25 36

4-tert-octylphenol
Example 9

A stainless steel autoclave was used with:

8,000 parts nylon 66 (hexamethylene diamine adipate) 3,000 parts water

48.5 molecular fractions of a 20% by weight / volume aqueous acetic acid solution

6.6 parts of 4-tert-Oc-byl-2-stearoylaminophenol

charged, whereupon the mixture is subjected to the following polymerization conditions:

Heating time temperature pressure

step .

1 2 hours room temp. -) 210 ^o 0 1 at -> 17.5 at

2 1 hour 21O ⁰ O- * 225 ° 0 17.5 at

3 1 hour 225 ° 0 ^ 265 ⁰ O 1 at-> 17.5 at

cd 4 35 min 265 ° 0 »285 ° C 1 at

<° UWöt

^ The polymer was extruded as a tape Ml quenched in water. Chips obtained from this tape were ^{melt-spun under steam at 290 0} O to form a 20-filament yarn. The yarn was drawn, increasing its original length 3.7 times, to give a final gauge of 70 denier. This yarn was then compared in its heat resistance with a gAD ORIGINAL control yarn without stabilizers, whereby one

noted the number of terminal amine groups on the polymer before and after heating. A loss of terminal amine groups during the heating means a thereby "damage caused while the retaining means a successful stabilization of terminal amine groups. The yarns were continuously passed through a heated chamber through, 'where they were subjected to Jose skilled heat treatment at 220 ⁰ C. The number of terminal amine groups of the yarn before and after the heat treatment was measured with the following results:

Endstandsip; e Amine groups per 10 ^ Before the heat treatment After the Varmebhdlp; .

Trial yarn 41.5 jr 29.0

(with 4-tert-octyl-2-stearoylaminophenol)

Control yarn 41.8 25.4

It can be seen from this that, under the specified conditions, the yarn with stabilizing agent has 12.5 terminal amine groups lost per 10 g. In contrast, the control yarn lost 16.4 terminal amine groups per 10 g.

ORIGINAL INSPECTED 909848/1245

Claims (1)

- 7 - Claim Heat-resistant polymer compositions made from a polymer and a Stabilizing compound, characterized in that the stabilizing compound is a compound of the formula: OH OH or the formula: R is selected, where R, and R ^ are hydrogen atoms or alkyl groups represent and at least one of them represents an alkyl, preferably a tertiary alkyl group, and wherein R. and Ep water s to ff atoms or alkyl, aralkyl or Represent acyl groups and are identical to or different from one another, or where R ^. a group of the formula: or the formula! R. represents, with the bridging group -A- a two-valued Radical, preferably an alkylene radical. Ot-IKG. H. FINCKE, DIML-IMC. H.! EAR DIPL-INQ-S-STASGEIT 0-9 848/1245