CS269002B1

CS269002B1 - Stabilizing composition containing esters of piperidinole with antioxidants for polypropylene

Info

Publication number: CS269002B1
Application number: CS832894A
Authority: CS
Inventors: Marta Ing Povazancova; Pavol Ing Caucik; Zuzana Ing Samuhelova; Tadeas Ing Rzyman; Julius Ing Csc Durmis; Milan Ing Csc Karvas; Jan Ing Masek
Original assignee: Povazancova Marta; Caucik Pavol; Zuzana Ing Samuhelova; Tadeas Ing Rzyman; Durmis Julius; Karvas Milan; Masek Jan
Priority date: 1983-04-25
Filing date: 1983-04-25
Publication date: 1990-04-11
Also published as: CS289483A1

Abstract

Riešenie sa týká stabilizačnej koapozície pre polyaér, ktorá aé zlepšené vlastnosti a obsahuje 0,01 až 0,3 % haot. Jedného alebo viacerých derivátov fenolického antioxidantu všeobecného vzorca I alebo všeobecného vzorca II kde R Je aetyl, terč. butyl alebo fenyl, Z J· aetyl, atyl, terč. butyl, alkyl odvodený od polyaérov ao atrednýa polyaerizačnýa stupnoa 5 až 50 získaných polyaerizéciou alfa-alkánov a 2 až 4 atóasaii uhlíka alebo 3-oxa-4-oxo-dokozyl a 0,05 al 1,0 56 haot. Jedného alebo νίβω cerých derivátov 4-aubatituovaného-2,2, ° 6,6-tetraaetylpiperidínu všeobecného vzorca III v ktoroa X znaaená vodík alebo aetylakupinu a A Je acylový zvyšok odvodený od nasýtenej alebo nenaeýtenej alifatickej karboxylovej^kyseliny a dvojnou vazbou s 2 až 18 atoaaai uhlíka v 100 56 haot. stabilizovanej zaesiThe solution concerns stabilization coaposition for a polyaer which has been improved properties and contains 0.01 to 0.3 % haot. One or more derivatives phenolic general antioxidant of formula I or formula II wherein R is ethyl, target. butyl or phenyl, From J, aethyl, atyl, target. butyl, alkyl derived from polyaeros and an attractive polyaerization grades 5 to 50 obtained by polyaerization alpha-alkanes and 2-4 atoms carbon or 3-oxa-4-oxo-docosyl and 0.05 and 1.0 56 ha. One or νίβω black derivatives of 4-aubatited-2,2, 6,6-tetraaethylpiperidine of the formula III wherein X is hydrogen or an acetyl group and A is an acyl residue derived from saturated or unsaturated aliphatic carboxylic acid and a double bond with 2 to 18 atoaaai and carbon in 100 56 haot. stabilized zaesi

Description

EN 269 0.02 B1 1

The invention and the invention relates to a piperidinol ester conjugation composition with 3 snioxidants prepolypropylene.

Polypropylene is a polymeric material highly sensitive to aeration and heat. Thus, during the process, it must be stabilized against theraoxidation and during use against thermo and photooxidation, so as to maintain the long term mechanical, physical and chemical properties of the soil. From both technical practice and literature, many methods are known for its thermal and light stabilization methods. Very well-proven stabilizing systems with primary antioxidant compositions with benzophenone / Brit type UV absorbers. pat. 380,449) and benztriazoles / US Pat. 4,278,590]. Since 1967, a substantial number of compounds have been patented from the group of sterically hindered amines as light stabilizers for polymers. The 2,2,6,6-tetramethylpiperidinol derivatives are among the most effective / useful. 3 640 928, Eur. pat. Appl. 22,997, DE-OS 2,560,314]. In the aforementioned aa teaches that these compounds can be used alone or in combination with other stabilizers, fillers and pigments.

A number of Japanese patents from Sumitomo Chemical Co. are polyolefin compositions wherein a polyearray, a sterically shielded piperidine amine and a combination with phenolic antioxidants / Japan, is used as the light stabilizer. Kokai Tokkyo Koko8 '; 81 62,839; 81, 62,840.

The subject of Ger. off. New phenolic stabilizers from Ciba-Geigy AG, where the stabilizer molecule contains both sterically hindered phenol and sterically hindered piperidine. Such derivatives are characterized by increased processing and thermal stability. UVA absorber antioxidant compositions achieve greater stabilizing efficacy, usually by increasing the concentration of antioxidants and combining them with each other, in particular with secondary antioxidants. In the case of sterically shielded amines, due to the mechanism of their provision, the situation is much more complicated.

The 2,2,6,6-tetramethyl-4-piperidinol esters are excellent light stabilizers, but do not adequately protect polypropylene during processing, even during prolonged thermal stress. To this end, it is desirable to combine them with antioxidants so as to provide protection during processing, some resistance to the composition for a longer period of application of higher temperatures during application and, in particular, to achieve higher resistance to UV exposure. Important attention has been paid to the increased concentration of the antioxidant used. , as it influenced the system's lightfastness both negatively and negatively.

It has been found that the desired properties of the stabilizing composition of the piperidine esters with the antioxidants over the polypropylene of the invention. The essence of the invention is that the stabilizing composition of the piperidinol ester with the antioxidants for polypropylene comprises from 0.01 to 0.3% of the single or multiple phenolic antioxidant derivatives of the general formula I

R

HIM

FROM

R / 1 /

or Formula II

HIM

R / 11 / EN 269 002 B1

where R is methyl, target. butyl or phenyl, Z is methyl, ethyl, target. butyl, alkyl-derived polymers with a moderate polymerization degree of 5-50 obtained by polymerization of alpha-elenes and 2-4 carbon atoms, or 3-oxa-4-OXOdocoyl and 0.05 to 0% by weight of one or more derivatives of the 4-subunitized 2,2,6,6-tetramethylpiperidine of the general formula and III

In which X is hydrogen or methyl and A is an acyl radical removed from a saturated or unsaturated aliphatic; carboxylic acid and from 2 to 18 carbon atoms in 100% by weight. stabilized,) mixtures.

It has also been found to be preferred that the compound of Formula I is a compound of Formula Ia

(Ia), or a compound of formula Ib / Ib / wherein the moiety of the polymerized C2-4 alpha-alkene is a medium polymerization stage of 20 to 50 or a compound of formula Ic

CH 2 CO 2 COOC, 8h32 (Ic), CS 269 002 B, 3 by Formula II Compound of Formula IIa

(XI and / or compound of formula III) is a compound consisting of 37 to 70 wt. a compound of formula III wherein A is stearyl, from 29 to 52 wt. bile. in Formula III wherein A is palmitoyl, from 0.2 to 6% by weight. zldč. vSeob. of formula III wherein A is heptadecanoyl, from 0.1 to 5% by weight; zldč. vSeob. of formula III wherein A is myristoyla from 0.2 to 6 wt. zldč. vSeob. of formula III wherein A is oleoyl and X is hydrogen. The present invention has improved its stability and is characterized by increased resistance to thermal oxidation degradation and excellent stability. Parebne sdstéle. They can be used to make any product, including polypropylene fibers. It is possible to add other additives such as calcium stearate, antioxidants, OV and colorants, fillers, pigments and the like. It is possible to prepare by conventional methods used to prepare stabilized polypropylene.

The concentration of phenolic antioxidants ranges from 0.01 to 0.3%, depending on the type of antioxidants and the desired stability properties, most often from 0.03 to 0.2% by weight.

Said antioxidants are commercially available and patented (CS 185 959).

In addition to the technical advantage, the use of the mixture in question also has an economic effect if the optical concentration of the individual components of the mixture is used, while the system is sufficiently protected by process, heat and light. .....-

However, the following examples illustrate the invention. The preparation of the mixture as well as the characteristics of the polypropylene used will be mentioned before each example. Foil foils of 0.5 mm were prepared by pressing at 260 ° C for 10 minutes. and 19.6 bar.

Evaluated by: - Processing stability - Multiple and stressed through CAKIL / D laboratory extruder 25 mm, L = 20 D / at 200/275/265 ° C, 35 rpm. by measuring the flow index / g / 10 min./ after the individual passes, - thermal stability in the air-dried sushi type Sffi-39 / Chirana /, temperature 140 ° C, monitoring the time to the beginning of degradation of the parallel samples patches / h /, - luminous stability in Xenoteste 450 / NSR, Hanau original / by monitoring irradiation time in hour to carbonyl increment by 0.3, under conditions: black panel temperature 45 ° C, relative humidity 60%, showering 9 min, dry run 5 'min ., framing of frames, - the stability of the aqueous mixtures was evaluated in natural weathering aging in Hurbanov / South Slovakia / and also after washing in linites / Original, Hanau, NSR / in distilled water containing 4 g / l detergent / TIX /, under conditions 50 ° C, 24h (1/90 ° C, 50h). Example 1

Additives were mixed into non-stabilized HPF 3 IT polypropylene powder "0 = 9.7 g / 10 min., Isotacticity 96.6% on laboratory extruder / number of passages 4 EN 269 002 B1 = 1 - 10". The results sd in the following table.

Stabilization% System Process. ITa, .Zg / 10 min./ 1. 10. Thermal stability / h /,. 10. Light stability / h / 1. 10 - 21.8 300 4 2 350 300 0.1% AO-I 10.2 50.9 22 18 1 100 700 0.25% HALS-1 22.9 300 22 14 8400 8400 0.1% AO-1 + 0.25% HALS-1 10.0 53.5 46 22 9200 9200 0.1% AO-I + 0.25% HALS-7 11.7 42.8 2000 330 5200 5000 0.1% AO-1 + 0.25% UVA-1 10.0 37.4 40 20 2450 2100 63.4 56 wt. 29.1 wt. 4.3 wt. %, 9 wt. %, 3 wt. AO-1: 2,6-di-tert-butyl-4-ethylphenolHALS-1: 4-palmitoyloxy-2,2,6,6-tetramethylpiperidine 4-palmitoyloxy-2,2,6,6-tetramethylpiperidine-containing 4-stearoyloxy-2,2,6,6-tetramethylpiperidine stabilizer % wt. % 4-heptadecanoyl-oxy-2,2,6,6-tetramethylpiperidine-4-stoyloxy-2,2,6,6-tetramethylpiperidine 1.3 wt. 4-oleoyloxy-2,2,6,6-tetramethylpiperidine HALS-7: Poles [2-N, N * -di / 2,2,6,6-tetramethyl-4-piperidinyl] hexanediaine-4- / 1-amino 1, 1,3,3 - tetramethyl-butane /] -, 3,5-triazine UVA-1: 2-hydroxy-4-octyloxybenzophenone Example 2

The mixtures were mixed into unstabilized powdered PP type HPF s = 9.0 g / 10 min. with an isotacticity of 96.9% on a Brabender plastograph at 90 ° C, 5 min. if?. The results sd in the following table.

Stabilization System Light Stability / h /

Gf V ·· .. AA—— A 4 »- J .. φ% flood flood h hl 0, 1% AO-1 800 650 500 0, 2% HALS-1 5700 5500 - 0, 1 56 A0-1 + 0.2% HALS-1 7100 6900 - 0, 1 56 A0-, + 0.2 56 HALS-2 2800 2300, 400 0, 1 56 A0-, + 0.2 = 6 HALS-7 4600 4.50 - 0, 1% AO-1 + 0.25 56 HALS-1 8500 8200 7600 0, 1 «AO-1 + 0.25« HALS 7 6900 5600 4000 0, 1 56 AO-1 + 0.25 «UVA-, 1900, 600, 200 HALS-2: 4-ethanoyloxy-2,2,6,6-tetramethylpiperidine Example 3

In an unstabilized powdered PP of HPP type with θ = 9.7 g / 10 min, the isotacticity of 96.6% on a laboratory extractor is multiple (krát) 5 times / extruded as follows:

Stabilization system A by weight 0.05 AO-L +0.15 AO-2 ++ 0.15 AO-5 + 0.3 UVA-10.1 AO-1 + 0.15 AO-2 ++ 0.15 AO- 5 + 0.25 HALS-1

Processing Company. 23θ / β / χον ________ 12.1 74.3 10.8 68.3

Thermal stability / h / 2700 1800 2300 1800

Light Stability / h / 2400 2100 5900 5200 EN 269 002 B1 5 AO-2: 4-pentadecakia / propenyl / -2,6-dimethylphenol AO-5: distearoylthiodipropionate Example 4

Mixtures of salting into powdered PP type HPF with IT2 ^ 0 = 9 g / 10 ', isotacticity 96.6% on Brabender plastograph at t - 190 ° C, 5 min.

Heat Stab. Lighting atab. % mass ___ _ __ / h / / h / 0.2 HALS-1 22 5000 0.1 AO-1 + 0.15 AO-2 + 0.15 AO-5 + 0.2 HALS-1 2300 4400 0 , 1 AO-1 + 0.15 AO-2 ♦ 0.3 HALS-1 + 0.15 AO-5 _ 2100 6800 0.1 AO-1 + 0.15 AO-2 + 0.15 AO-5 0.3 VVA-1 2000 2300 Example 5

To a non-stabilized HPF type polypropylene powder with IT? Q = 9 g / min min. With isotacticity 96.9% on Brabender plastic at 190 ° C, 5 min.

Stabilization System Mass Temp. staff. Λ pov. Light Stab. / h / Ljj PPS. kj / cm '0, 1 AO-3 700 700 150 0, 1 AO-3 + 0.3 HALS-1 700 9800 8000 6000 1200 0, 1 A0-3 +0.3 HALS-3 735 9600 6800 3400 1400 0 , 1 AO-3 + 0.3 HALS-4 720 9-100 8800 8000 1600 0, 1 AO-3 + 0.3 HALS-5 800 9300 8500 7700 1750 0, 1 AO-3 + 0.3 HALS-6 710 9500 7800 5700 1100 0, 1 AO-3 + 0,3 UVA-, 700 2000 1850 1600 700 AO-3: 3 »5-di-tert-butyl-4-hydroxyphenyl-octadecylpropionate HALS-3: 4-octamoyloxy- 1,2,2,6,6-pentamethylpiperidine HALS-4: a stabilizer containing 57.5 wt. Of 4-stearoyloxy-1,2,2,6,6-pentamethylpiperidine 36.4% hnot. 4-palmitoyloxy-1,2,2,6,6-pentamethylpiperidine 3.2% haot. 4-heptadecanoyloxy-1,2,2,6,6-pentamethylpiperidine 1.8 wt. myristoyloxy-1,2,2,6,6-pentamethylpiperidine 1.2 wt. 4-oleoyloxy-1,2,2,6,6-pentamethylpiperidine HALS-5: 4-stearoyloxy-1,2,2,6,6-pentamethylpiperidine HALS-6: mixed stabilizer containing 43.2 wt. 4-stearoyloxy-2,2,6,6-tetramethylpiperidine 51.9 wt. 4-palmitoyloxy-2,2,6,6-tetramethylpiperidine 2.3 wt. 4-heptadecanoyloxy-2,2,6,6-tetramethylpiperidine 1.6 wt. 4-myristoyloxy-2,2,6,6-tetramethylpiperidine 1.0 wt. 4-oleoyloxy-2,2,6,6-tetramethylpiperidine Example 6

To a non-stabilized HPF type polypropylene powder with an ITs isotacticity of 96.9% on a Brabender plaque at 190mSal of the mixture: 230 = 9 g / min, ° C, 5 min. under nitrogen at 6 CS 269 002 B1

Thermal StabA /

Stabilization System? _S352S22®S5 ^ ___

Luminous atab. A / 0.1 AO-4 1800 800 0.2 HALS-1 24 5400 OJ AO-4 + 0.2 HALS-1 1300 6200 OJ AO-4 + 0.3 HALS-1 1500 8300 0.1 AO-4 + 0.3 UVA-1 1950 2700 AO-4: pentaerythrityll-tetrakia-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate Example 7

Polymer: non-stabilized PP powder type HP? and ^2 ^ θ = 9.7 g / 10 ain. isotacticity 96,6%. Preparation: laboratory extruder CAM1L, temperatures 200/275/265 ° Speed: 35 rpm, number of passages 1 - 10

Stabilization system by weight

Process Thermal II * / h / 10 '/ stab. AND/

Light Stab. A / 0.25 Ϊ HALS-1 0.1 AO-4 + 0.25 HALS-1 23 300 12 61 24, 8 1700 1200 8400 8450 8800 8800 Example 8

Polypropylene skins have been prepared on a spinning machine with a prieaeroa screw of 32mm using a 33mm / 0.05mm nozzle with 33g / ain dosing. and a draw-off speed of 800o / min. The fibers were embossed on silk in a ratio of 1: 4.5 to one fineness of about 4.5 dtex. Polymer: powdered, non-stabilized PP type ΞΡΡ with ITjjq ~ θ S / '° AID ·

Stabilization System Xenotest% Weakness Decrease in% ________________________________________________________________ E2_2_900_hod ..__ 0, '1 AO-1 + 0,2 HALS-1 Halftime I23O h 0,' 1 AO-1 + 0,3 HALS-1 30 0, '1 AO -1 + 0.3 HALS-2 33 0.1 1 AO-1 + 0.55 AO-5 + 0.3 UVA-1 half-life 990 h field - time in A / when the flood strength of the fiber drops to 50 ¥

Claims

1. A stabilizer composition of piperidinol era with antioxidants for polypropylene comprising between 0.01 and 0.3% by weight of one or more derivatives of a phenolic antioxidant of formula I or formula II

(1) (11), wherein R is methyl, target. butyl or phenyl, Z is methyl, ethyl, target. butyl, alkyl-derived polymers with a moderate polymerization degree of 5 to. 50 obtained by the polymerization of alpha-alkenes having 2 to 4 carbon atoms or 3-oxa-4-oxodocosyl and 0.05 to 1.0 wt. one or more 4-substituted -2,2,6,6-tetramethylpiperidine derivatives of formula III

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

2. A stabilizing composition according to claim 1, wherein the compound of formula I comprises a compound of formula Ia

/ Ia / CS 269 002 Bl

3. A stabilizing composition according to claim 1, wherein the compound of formula I comprises a compound of formula Ib

(Ib), wherein the polymerized alpha-alkene moiety Cj-80 is the middle polymerization reaction 20 to 50.

4. The stabilizing composition according to claim 1, wherein Formula I comprises a compound of Formula Ic as a compound

CH 2 -CH 2 -COO-C | (Ic).

5. A stabilizing composition according to claim 1, wherein Compound II comprises Compound IIa.

/ IIa /.

6. The stabilizing co-composition according to claim 1, wherein the compound of formula (III) comprises a mixture of derivatives of 37 to 70% by weight. in which A is stearoyl, from 29 to 52% by weight; % of the derivative in which A is polynithoyl, from 0.2 to 6% by weight; % of the derivative in which A is heptadecanoyl, from 0.1 to 5% by weight; % of a derivative in which AJe is myristoyl and from 0.2 to 6% by weight; a derivative in which A is oleoyl and X is as defined in point 1 above.