DE1161012B - Stabilized molding compounds made from crystalline polyolefins - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Boarding school Class: C 08 f

GERMAN

PATENT OFFICE

EDITORIAL

German class: 39 b -22/06

Number:
File number:
Registration date:
Display day:

M 52841IV c / 39 b May 14, 1962 January 9, 1964

The invention relates to stabilized molding compositions based on poly-α-olefins, in particular Polypropylene made with stereospecific catalysts, which is a raw material for fibers, films and represent other objects.

It is known that products based on polyolefins when processed in the heat a Sustained decomposition, especially in the presence of atmospheric oxygen.

Finished products based on crystalline polyolefins are against the influence of light and against thermal treatment sensitive.

This degradation effect can be achieved by adding loading; be special protection material for polymers, particularly during the preparation of fibers or films, is comparable decreases.

In general, small for this ^purpose: amounts of amines, aminophenols, chelates of transition metals (Ni), organotin compounds, triazole compounds, zinc compounds, Dithiocarb- ao amate, phenols, phosphites, mercaptans, oximes, polyquinolines, sulfur derivatives, silicones or Thiophos- ■ phosphites used.

However, these substances have the disadvantages of staining or a low stabilizing activity, or these two disadvantages together. With stabilized threads made of polypropylene and z. B. 4% phenyl-ß-naphthylamine, which has been exposed to the summer sun for 30 days, the tensile strength _; to 20% of the initial value, and the elongation is reduced to 5% of the initial value. With sample threads made of polypropylene, but without the stabilizing amines, almost the same values are obtained under the same conditions. If, instead of the amines mentioned, an aminophenol, such as. B. The stearyl-p-aminophenol is used, and the filaments lasts 15 hours in a ventilated oven at 120 ⁰ C, the tensile strength at 65 ° / o and the elongation to 81% of the output values is reduced.

With phenols or phosphites polyolefin intrinsic viscosity is greatly reduced, while fragile threads obtained after treatment for 7 hours at 13O ⁰ C. In addition, stains are always found with all of the substances mentioned.

In contrast, the stabilizers used according to the invention bring about improved stability against UV rays and against thermal aging and, in addition, have no discoloration or stain-forming effect on the moldings produced therewith.

The invention now relates to stabilized molding compositions made from crystalline polyolefins, in particular stabilized ones Molding compounds made from crystalline polyolefins

Applicant:

Montecatini Societä Generale per l'lndustria Mineraria e Chimica, Milan (Italy)

Representative: ,

Dr.-Ing. A. v. Kreisler,, -;

Dr.-Ing. K. Schönwald, Dr.-Ing. Th. Meyer, Dipl.-Chem. Dr. rer. nat. J. F. Fues and Dipl.-Chem. Dr. H. G. Eggert, patent attorneys, Cologne 1, Deichmannhaus

Named as inventor: .. ■ .-. . ,

Giuseppe Leandri, Milan (Italy),

Claimed priority:

Italy of 16 May 1961 (No. 9119)

their polypropylene, and aminophenol derivatives containing 0.02 to 2 percent by weight as aminophenol derivative, based on the polyolefin, a compound of the general formula,

R —CONH- <

= X

OCO-R '

in which R and R 'are identical or different aryl or alkyl radicals.

A particularly effective stabilizer is 1,4-dibenzoyl-p-aminophenol

-CONH

-OCO

Other suitable stabilizers are:

1,4- (or 1,2- or 1,3-) diacetylaminophenol, 1,4- (or 1,2- or 1,3-) dipropionylaminophenol,

1,4- (or 1,2- or 1,3-) dibutyrylaminophenol, 1,2- (or 1,3-) dibenzoylaminophenol, 1,4- (or 1,2- or 1,3-) dinaphthoylamino

phenol,
1,4- (or 1,2- or 1,3-) acetylbenzoylamino-

phenol,
1,4- (or 1,2- or 1,3-) propionylbenzoylaminophenol.

These stabilizers can also be used together with other known stabilizers, in particular with

309 778/402

UV-absorbing substances and with common additives such as pigments, dyes, fillers and especially acid-binding products, such as inorganic salts of stearic acid, are used will.

The stabilizers are also suitable for stabilizing mixtures of the crystalline polyolefins with organic or inorganic color pigments.

The stabilized molding compositions according to the invention can be shaped into fibers, films or finished goods will.

The spinning of the molding compositions according to the invention is preferably carried out in such a way that they are pressed through spinnerets in which the ratio of length to diameter is greater than one. After spinning, the yarns are drawn in a ratio between 1: 2 and 1:10 and at temperatures between 80 and 150 ^° C. in drawing devices which are heated with hot air, steam or a liquid or by means of a heating plate.

The stabilizing compounds are generally added to the polyolefin in solid form with stirring mixed in.

However, the stabilizers can also be added by other procedures, such as Mixing the polyolefin with a solution of the stabilizing agent in a suitable solvent and subsequent evaporation of the solvent or by adding the stabilizing agent to the Polyolefin at the end of the polymerization. It is also possible to have the stabilizing effect by applying to achieve the stabilizing compound on the finished product, e.g. B. by immersing the latter into a solution or dispersion of the stabilizing agent and subsequent evaporation of the solvent.

ίο The specified stabilizers show a good one Compatible with the polyolefins when molten and do not cause staining.

The stabilized molding compositions according to the invention are particularly suitable for the production of Mono- and plurifils, staple fibers, dyeable yarns, bulky yarns, films and ribbons.

The invention is illustrated in the following examples.
The polymer used in these examples was prepared from an alkyl aluminum compound and a crystalline transition metal halide with the aid of stereospecific catalysts.

Examples 1 to 4

The data of these examples are given in the table.

example 1 Example 2 Example 3 Example 4

Composition of the mixture:

a) polypropylene [η]

Ash content (%)

Residue after heptane extraction (%)

b) stabilizer

Stabilizer (%)

Processing the mixture

Color of the mixture melted in a test tube at 250 ° C / 10 minutes

Spinning Conditions:

Screw ^{temperature (0} C) ...

Head temperature ( ⁰ C)

Spinneret ^{temperature (0} C)

Spinneret type

Maximum pressure (kg / cm ² )

Winding speed
(m / min.)

Stretching conditions:

Temperature (° C)

medium

Stretch ratio

Serimetric properties of the
stretched yarn:

Tensile strength (g / den)

Strain (%)

1.48 0.12

93.9

1,4-dibenzoyl-p-aminophenol

0.2 Henschel mixer

clear

230 230 240

60 / 0.5 χ 10 mm 40

190

120

Steam 1: 5

5.45 25

1.48
0.12

93.9

1,4-dibenzoyl-p-aminophenol

0.5
Henschel mixer

clear

230
180
240

60 / 0.8 χ 12 mm
35

170

120

steam
1: 5

5.4
19th

1.48
0.12

93.9

1,4-dibenzoyl-p-aminophenol

1
Henschel mixer

clear

230
230
240

60 / 0.8 χ 16 mm
40

170

120

steam
1: 5

5.25
21

1.48
0.12

93.9

Henschel mixer

clear

230
250
250

40 / 0.8 χ 16 mm
50

290

120

steam
1: 5

5.75
29.8

5 Thermal degradation: example 1 Example 2 6th Example 4 Decrease in intrinsic viscosity Example 3 by pre-pressing (° / ₀ ) Stability at accelerated ther 74.5 75 73.5 mixer aging: 79 Residual tensile strength after 15 hours storage in one Drying cabinet with ventilation run at 120 ⁰ C (%) Stability in sunlight: 61 73 brittle Residual tensile strength according to 80 200 hours exposure with Summer sunlight (° / o) 51 62 39 80

Claims (1)

Claim: Containing stabilized molding compositions made from crystalline polyolefins and aminophenol derivatives as an aminophenol derivative 0.02 to 2 percent by weight, based on the polyolefin, of a compound the general formula R-CONH OCO-R ' in which R and R 'are identical or different aryl or alkyl radicals. 309 778/402 12.63 © Bundesdruckerei Berlin