CS258701B1

CS258701B1 - Stabilizing composition for polypropylene

Info

Publication number: CS258701B1
Application number: CS832892A
Authority: CS
Inventors: Tadeas Rzyman; Zuzana Samuhelova; Marta Povazancova; Pavol Caucik; Julius Durmis; Milan Karvas; Jan Masek
Original assignee: Tadeas Rzyman; Zuzana Samuhelova; Marta Povazancova; Pavol Caucik; Julius Durmis; Milan Karvas; Jan Masek
Priority date: 1983-04-25
Filing date: 1983-04-25
Publication date: 1988-09-16
Also published as: CS289283A1

Abstract

Riešenie sa týká stabilizačně]' kompozície pre polypropylén na báze piperidinolu s antioxidantmi, ktorá obsahuje 0,01 až 0,3 % hmot. izokyanurátového antioxidantu všeobecného vzorca I, v ktorom R znamená 3,5- -di-terc.butyl-4-hydroxybenzyl 2,6-dimethyl- -3-hydroxy-4-terc.butylbenzyl alebo 6-13‘,5‘- -di-terc.butyl-4‘-hydroxyfenyl/-4-oxa-3- -oxo-hexyl a 0,05 až 1,0 % hmot. jedného alebo viacerých derivátov 4-substituovaného- -2,2,6,6-tetrametylpiperidínu všeobecného vzorca II, v ktorom X znamená vodík alebo metylskupinu a A je acylový zvyšok, v ktorom X znamená vodík alebo metylskupinu a A je acylový zvyšok odvodený od nasýtenej alebo nenasýtenej alifatickej karboxylovej kyseliny s dvojnou vážbou s 2 až 18 atómami uhlíka v 100 % hmot. stabilizovanej zmesi·The solution relates to a stabilizing composition for polypropylene based on piperidinol with antioxidants, which contains 0.01 to 0.3 wt. % of an isocyanurate antioxidant of the general formula I, in which R represents 3,5- -di-tert.butyl-4-hydroxybenzyl 2,6-dimethyl- -3-hydroxy-4-tert.butylbenzyl or 6-13',5'- -di-tert.butyl-4'-hydroxyphenyl/-4-oxa-3- -oxo-hexyl and 0.05 to 1.0 wt. % of an isocyanurate antioxidant of the general formula I, in which R represents 3,5- -di-tert.butyl-4-hydroxybenzyl 2,6-dimethyl- -3-hydroxy-4-tert.butylbenzyl or 6-13',5'- -di-tert.butyl-4'-hydroxyphenyl/-4-oxa-3- -oxo-hexyl one or more derivatives of 4-substituted-2,2,6,6-tetramethylpiperidine of the general formula II, in which X represents hydrogen or methyl and A is an acyl radical, in which X represents hydrogen or methyl and A is an acyl radical derived from a saturated or unsaturated aliphatic carboxylic acid with a double bond of 2 to 18 carbon atoms in 100% by weight of the stabilized mixture;

Description

238701

BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a stabilizer for polypropylene based on piperidinol esters with antioxidants.

Polypropylene is very sensitive to heat and light. Therefore, during the processing and during use, it is necessary to protect it so that it maintains good mechanical, physical and chemical properties for as long as possible. The procedures and methods for its protection are well known. For many decades, primary and secondary antioxidant compositions with UV absorbers of benzophenones have been used (U.S. Pat. No. 4,288,631, Brit.pat., 1,380,449) and benzotriazoles (U.S. Pat. No. 278,589; 4,278,500). several compounds from the group of spherically shielded amines as light stabilizers for polymers have been patented (Eur. Pat. Appl. 682; Europ. Pat. Appl. 17,617; Eur. Pat.Appl. 19,578; Eur., Pat Z2 997, U.S. Pat.

2,2,6,6-tetramethylpiperidinolupatria derivatives are most effective (U.S. Pat. No. 3,640,928; 4,265,805: DE-OS 2,560,314; U.S. Pat. No. 8,117,034; Eur. Pat. Appl. 27,620). It is stated in the aforementioned patents that these compounds may be used separately or in combination with other stabilizers, fillers and pigments. Japanese Patent of Japan. Kokai Tokkyo Koho 81 62 834 is a light stabilization of polyolefins wherein a piperidine-based polymeric spherically-shaded amine, combined with an isocyanurate antioxidant, is used as the light stabilizer. The isocyanurate antioxidant itself is also the subject of Japanese Patent No. 10,066,568.

The secondary and tertiary amines of piperidine in combination with isocyanurate antioxidants are also the subject of Belgian patent 886 428.

Interesting piperidine derivatives and stabilizers for synthetic polymers include Eur. pat. Appl. 31 304.

Synthetic polymer compositions containing triazine derivatives used as light stabilizers are the subject of Eur. Pat.Appl. 22 080.

The proven light stabilizers of absorbent absorbers, the efficiency of which can be increased by combining them with antioxidants, the more we use the higher the concentration.

The 2,2,6,6-tetramethyl-4-piperidinol esters are excellent light stabilizers, and still do not protect the polypropylene during processing, or during long-term thermal treatment. To this end, it is desirable to combine them with antioxidants so as to provide good polymer protection during processing, improved resistance to prolonged heat build-up, excellent mechanical properties (strength and ductility), and more susceptibility to potency UV-radiation.

It has now been found that the aforementioned drawbacks are largely eliminated by the stabilizing com- ponent for ether-piperidinol-based polypropylene with the antioxidants of the invention.

The present invention is based on the fact that the stabilizing composition comprises from 0.01 to 0.3. an isocyanurate anti-oxidant of formula I

R - Li-R 10 (I) wherein R is 3,5-di-tert-butyl-4-hydroxybenzyl

2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl

or 6- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) -4-oxa-3-oxohexyl 258701 (ww) -h ^ ch ^ vohm ,

Cl ·.

and 0.05 to 1.0 wt. one or more 4-substituted-2,2,6,6-e-trametyl-4-piperidine derivatives of formula (II)

wherein X is hydrogen or methyl and A is an acyl radical derived from a saturated or unsaturated carboxylic aliphatic acid having from 2 to 18 carbon atoms in 100% by weight. of the stabilized mixture.

It has also been found to be advantageous if the mixture is formed by a compound of formula (I) wherein R is 3,5-di-tert-butyl-4-hydroxybenzyl and a mixture of compounds of formula (II) containing 37 to 70% by weight. % of the derivative in which A is stearoyl, 29 to 52% by weight. % of a derivative in which A is palmitoyl, 0.2 to 6% by weight; a derivative in which A is heptadecanoyl, 0.1 to 5% by weight; a derivative in which A is pyristoyl and 0.2 to 6% by weight in which A is oleoyl. The present compositions have good process stability, are characterized by improved resistance to thermo-oxidative degradation, provide excellent mechanical properties of the polypropylene and have excellent light stability. The colors are still. They can be used to prepare any polypropylene fiber product. We recommend combining them with other additives such as antioxidants, Ca stearate, UV absorbers, fillers, pigments and the like.

The compositions may be prepared by conventional methods used in the preparation of stabilized polypropylene.

The isocyanurate derivative concentration is used in the range of 0.01 to 0.3% by weight, most often 0.030 to 0.15% by weight.

The concentration of the piperidine derivatives is in the range of 0.05 to 1.0% by weight, preferably 0.1-0.5% by weight.

The use of the present composition provides technical advantages such as improved mechanical properties, improved processing resistance, increased thermal and light stability of propylene. By using optimal concentrations of the individual components of the mixture, it is possible to achieve an economic effect.

The following examples illustrate the invention. The preparation of the mixture and the type of polypropylene are mentioned before the examples. 0.5 mm thick films were prepared by compression molding at 260 ° C, at a pressure of 19.6 MPa for 10 minutes.

The following were evaluated: - processing stability on plastographbrabender (NSR) by stressing polypropylene at 190 ° C in air to a drop in viscous viscosity to half value (min), thermal stability in STE-39 (Chirana) dryer at 140 degrees Celsius by observing the time to the beginning of the degradation of the five parallel samples (hrs), - the light stability in the Xenoteste 450 (Ori-Ilanau, NSR) by observing the time of radiation at hour to increment of carbonyl by 0.3 under the following conditions: temperature of black panel 45 ° C, rqlative vjh- 258701 bone 60%, showering 9 min, dry 51 min, rotating frames. When evaluating the filaments, the temperature of 35 ° C in the Xenoteste 150 (Original Hanau) to a decrease in fiber strength to half the value (50p.) In natural weather aging in I-Iurbanove (Southern Slovakia —————————————————————–—————————————————————————————————————————————————————_2007_01.html and in Poprad (Northern Slovakia - a percentage decrease in fiber strength over a certain period) Example 1 Additives were mixed into non-stabilized polypropylene powder (hereinafter PP) of HPP type with IT23o = 8.5 g / 10 min, isotactic, -da 96, 5% on a Brabender plastograph at 1800 h of sunlight, followed by 190 ° C for 10 min, N2. Stabilization System Processing Heat Stab. Light Stab. 450 slab. (min.) 2 Dry 140 ° C Xenotest pQv. stressed (h) (h) (h) unstabilized PP 7 8 300 150 0.15% HALS — 1 16 50 2 800 3 400 0.15% AO — 1 + 0.15 61 800 3 800 4 200 HALS — 1 HALS Hindered Amine Light Stabilisers is used to designate sterically shaded amines. HALS-1: a mixed stabilizer containing 63.4 wt. 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 29.1 wt. 4-palmitoyloxy-2,2,6,6-tetramethylpiperidine, 4.3 wt. 4-heptadecanoyloxy-2,2,6,6-tetramethylpiperidine, 1.9 wt. 4-myristoyloxy-2,2,6,6-tetramethylpiperidine 1.3 wt. 4-oleoyloxy-2,2,6,6-tetramethylpiperidine. AO-1: 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate Example 2

To non-stabilized PP HPFtype powder with IT230 = 9 g / 10 min. 96.9% isotactic is on a Brabender plastograph at 190 ° C, N 2.10 min. mix the following mixtures: B.

Stabilization system Thermal stability Light stability ° / by weight (h) Xenotest 450 (h) 0.1% AO — 1,800 1500 0.1% AO — 2 + 0.2% HALS — 1,100 5,800 0.1% AO —3 + 0.2% HALS — 1 1,500 7,000 0.1% AO — 1 + 0.2% HALS — 2,860 5,000 0.1% AO — 1 + 0.3% HALS — 1,980 5,700 0.1% AO — 1 + 0.3% HALS — 4 1700 5 700 0.1% AO — 1 + 0.3% HALS — 3,940 5,700 0.1% AO — 1 + 0.3% UVA— 1 1000 2 600 HALS-2: 4-etanoyloxy-2,2,6,6-tetramethylpiperidine HALS-3: 4-octanoyloxy-1,2,2,6,6-pentamethylpiperidine HALS — 4: Poly 2-N, N'-di- (2,2,6,6-tetramethyl-4-piperidinyl) hexanediamine-4- (1-amino-1,1,3,3-tetaramethyl-butane) 1,3,5-triazine UVA-1: 2-hydroxy-4-octyloxybenzophenone AO-2: 1,3,5-tris- (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) - isocyanurate AO-3: 1,3,5-tris- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) -4-oxa-3-oxo-hexyl isocyanurate Example 3 Isotactic Polypropylene Powder TATREN HPF (IT = 9.5 g / 10 min.) prepared compositions by granulation at a temperature 230 ° C and used to prepare polypropylene fibers on a spinning extruder with a screw diameter of 32 mm, using a spinneret 33z03 at a speed of nn-winding of 450 m / min. The spinning temperatures range from 312-315 ° C. The wound fiber 10 10 was deformed at 135 ° C to the degree de- The fineness of the deformed fibers of the formation 4.5. 5.0 dtex. 25B701

0.1% AO — 1 + 0.2% HALS — 1 0.1% AO — 1 + 0.3% HALS — 1 0.1% AO — 1 + 0.3% HALS — 4 0.1% AO-4 + 0.55% AO-5 + + 0.3% UVA-1AO-4: 2,6-di-tert-butyl-4-methylphenolAO-5: distearylthiodopropionate Examples of wound fibers prepared as in

The decrease in strength after 1,890 h in the Xenoteste (%) 33 33 32 half-strength of 990 h of Example 3 was prepared by curled filament deformation to a degree of deformation of ----0.0 with molding on a KK-2 machine on number of curves 3 - 7 cm. The rounded fiber was fixed in a flow of dry air at 130 ° C.

Stabilization system% by weight Naturally flame retardant. old.

Poprad (free) Poprad (sheet) drop ° / o pév. strength after 1 780 smooth round. decrease% pdv. money after 1 780 smooth

Xenotest 150Pokles% pov. strength after 990 hpol time strength smooth obl. 0.1% AO — 1 + 0.2% HALS — 1 30 29 24 37 24 700 0.1% Ol + 0.2% HALS-4 25 28 25 29 30 640 0.1% AO — 4 + 0, 55% AO-5 + + 0.3% UCA-1 Half-life 1400 750 980 670 930 840 Strength Example 5 under the conditions given in Examples 4 and 4.

The staple dyed in the mass was ready

Stabilization System Light Stability Half-Life Xenotest 450% Strength 1% Gron. gelb. GR (τ / 2 — h)

1% Sandorin Rot BR 0.1 AO — 1 + 0.3 HALS — 1,450,460 0.1 AO — 1 + 0.3 HALS — 4,670,630 0.1 AO — 4 + 0.55 AO — 5+ + EXAMPLE 6 Powdered isotactic polypropylene having an IT value of 10.3 g / 10 min, powder compositions were prepared which were granulated at 230 ° C. Pigment pigments were added to the granules in the form of a concentrate so that the pigment concentration was 1%. The color compositions were spun on a spinneret with a screw diameter of 32 mm at a temperature of 305 ° C through a spinneret nozzle 33/03, at a winding speed of 450 m / min. From the wound fiber, deformed at 130 ° C prepared smooth densities of 5.0 dtex.

0.1% AO — 1 + 0.3% HALS — 10.1% AO — 1 + 0.3% HALS — 40.1% AO — 4 + 0.55 / o AO — 5 + + 0.3% UVA-1 Half Strength All of the above compositions in Examples 1-6 contained 0.15% Ca stearate.

Strength decrease (%) after 1000 h 1 ° / o Sandorin rot B1 in Xenoteste 450

1% Gromophthal gelb GR 25 32 14 8 half-strength 530 h 410 h

Claims

SUBJECT

We claim:

A stabilizer composition for polypropylene based on piperidinol esters with antioxidants, characterized in that it contains 0.01 to 0.3 wt. isocyanurate antioxidant of formula I

R

O. bl r.O

R

In which

R is 3,5-di-tert-butyl-4-hydroxybenzyl, 2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl or 6- (3 ', 5'-di-tert-butyl-4'- hydroxyphenyl] -4-oxa-3-oxo-hexyl and 0.05 to 1.0% by weight of one or more 4-substituted-2,2,6,6-tetramethylpiperidine derivatives of formula (II):

X is hydrogen or methyl; and A is an acyl radical derived from a saturated or unsaturated aliphatic carboxylic acid having from 2 to 18 carbon atoms in 100 wt. stabilized mixtures.

2. A stabilizing composition according to claim 1, wherein the isocyanurate antioxidant of formula I comprises:

1,3,5-tris- (3 ', 5'-di-tert-butyl-4'-hydroxybenzyl) isocyanurate and as a 4-substituted-2,2,6,6-tetramethylpiperidine of the formula II contains a mixture of derivatives consisting of from 37 to 70% by weight of a derivative in which A is stearoyl, from 29 to 52% by weight of a derivative in which A is palmitoyl, from 0.2 to 6% by weight of a derivative in which A is heptadecanoyl, from 0, 1 to 5% by weight of a derivative in which A is myristoyl and from 0.2 to 5% by weight of a derivative in which A is oleoyl and X is as defined in point 1.