CS211116B1 - Stabilizing method of 4,9-di(l substituted by phenoxy(p-3,5,8,10 tetraoxa-4,9-diphospha-spiro)l5,5)p-hendecane polymers - Google Patents

Abstract

Brief Description of the Invention: 4,9-di [substituted phenoxy] -3, ξ, 8,10- -Tetraoxa-4,9-diphosphaspiro [5.5 J hendecans they protect very effective polymers especially thermal and thermo-oxidative polyolefins degradation during processing. provide also protection against long-term aging » even in atmospheric conditions.

Description

(54) Process for stabilizing polymers of 4,9-di [substituted phenoxyl-3,5,8,10-tetraoxa-4,9-diphospha-spiro [5,5 '] - hendecanes

Brief Explanation of the Invention: 4,9-di [substituted phenoxy] -3, ξ, 8,10-tetraoxa-4,9-diphosphaspiro [5.5] hendecanes protect very effective polymers, especially polyolefins, from thermal and thermooxidative degradation during processing. They also provide protection against long-term aging »even in atmospheric conditions.

21,116

21116

The invention relates to a process for stabilizing polymers of 4,9-di-substituted phenoxy-3,5,8,10-tetraoxa-4,9-diphosphaspiro with 5,5 * hendecanes.

Recently, various types of phosphorous-containing stabilizers, such as e.g. aromatic-aliphatic phosphites and mixed phosphites based on pentaerythritol. Said compounds interfere effectively in oxidation reactions and act as inhibitory. They contribute significantly to increasing the stability of polymers in the processing and use of polymeric products. In addition to inhibiting heat and oxygen reactions, they have the ability to form complexes with metals. They are characterized by a protective effect against aging caused by light, in particular in combination with UV stabilizers of different types, such as e.g. substituted hydroxybenzophenones, hydroxybenztriazoles, organic Ni complexes, sterically hindered amines and the like. Phosphites are used to maintain the original color of the polymers, which is of great importance both in the processing and in the use of the finished products.

The phosphorus-containing stabilizers used hitherto have to be combined with other antioxidants, especially phenolic, in thermally demanding applications, have lower resistance to hydrolysis, and they themselves decompose at relatively low temperatures.

We have found that by adding 0.01 to 2% by weight of the compound of formula I

3 * wherein R, R, R ^J are normal or branched alkyl groups having 1 to 18 carbon atoms, aralkyls having 7 to 9 carbon atoms, cycloalkyls having 6-7 carbon atoms, m, n, r are whole numbers from 0 and 3. With a polymeric material, we obtain very good heat-resistant polymers while maintaining excellent light stability, hydrolysis and color fastness. The compounds of the formula I themselves decompose only at high temperatures.

In stabilizing the polymeric materials against the effects of heat, light and oxygen, other stabilizing agents such as antioxidants, light stabilizers can be used simultaneously.

Example 1

Mixtures with various types of phosphorus-containing stabilizers were prepared for powdered polypropylene TatraFrene with a melt index at 230 ° C of 8 g / 10 min and an isotactic content of 96.2%. The mixtures were prepared by homogenization on a Brabender plastograph at 190 ° C, under a nitrogen atmosphere, homogenization time of 5 min. After homogenization, the samples were compressed into 0.5 mm films at 260 ° C, compression time 10 min and subjected to aging in a forced-air oven at 140 ° C. Samples of exposed mixtures were checked at regular time intervals and the change at which observable onset of degradation occurred was recorded. The lifetime, i.e. j. mean time of onset of degradation in 5 parallel exposed samples. The samples were placed on an aluminum plate in an oven.

i 116 2

Used stabilizer conc. 0.3% Drying life C in hours) ^R fM (%) First 4 Second Trisnonylphenyl 29 ¹ - Third tris (1-fenyletylfenyl) phosphite 40 - 4th tris (2,4-ditert-butylphenyl) phosphite 46 74.0 5th distearylpentaerytritol diphosphite 18 - 6th 4,4-11,1'-phenylene-di (0,0,0,0-tetra (2,4ditercbutylfenyl) diphosphonate 32 74.1 7th 4,9-Di [2-tert-butyl-4- (1,1) dimethylbenzylphenoxy] -3,5,8,1O-tetraoxa-4,9-diphosphaspiro [5,5] hendecane 283 75.5 8th 4,9-Di [2,6-dimethylphenyloxy] -3,11,8,10-tetraoxa-4,9-diphosphaspiro [5,5] hendecan 126 9th 4,9-Dit2-tert-butyl-4-methylphenyloxy] -3,5> 8,10-tetraoxa-4,9-diphosphaspiro [5,5 J hendecan] 271 10th 4,9-Di [2,6-dicyclohexylphenyloxy] -3,5,8,10-tetraoxa-4,9-diphosphaspirol5,5] hendecane - 112 11th 4,9-Di2,6-diisopropylphenyloxy] -3,5, S, 10-tetraoxa-4,9-diphosphaspirof5,5J hendecane 315 12th 4,9-Di [2,4-di-tert-butylphenyloxy] -3,5,8,10-tetraoxa-4,9-diphosphaspiro [5.5] hendecane 265 13th 4,9-Di [2- (1,1'-dimethylbenzyl) -4-methylphenoxy] 3,5,8,10-tetraoxa-4,9-diphosphaspiro [5,5] hexanecane 250

1) Rpjj (%) - Reflection coefficient indicating the% of reflected light, measured on a Carl Zeis Jena Leukometer at a 459 mm wavelength blue filter.

Example 2

Polypropylene powder blends (type as in Example 1) with phosphorus-containing stabilizers were subjected to repeated extrusion stress through a laboratory screw of dimensions D-26, L-20D at temperatures; 1-band 200 ° C, 2-band 260 ° C and extrusion head 250 ° C. The polymer was extruded in the form of a string and, after cooling with water, was chopped into granules. After individual transitions, the melt index was determined according to ČSN 640861 (temperature 230 ° C).

Stabilizer used Melting index after transitions

conc. 0.3% 0 3 5 10 First ___ 12 42 79 185 Second tris (1-fenyletylfenyl) phosphite 9 13 19 43 Third tris (2,4-ditere.butylfenyl) phosphite 10 11 13 24 4th 4,4 * (1,1 * -diphenylene) 0,0,0,0-tetra-12,4-di-tert. butylphenyl) diphosphate t 9 10 12 20 5th 4,9-Di [2-tert-butyl-4- (1,1-dimethylbenzyl) phenoxy] -3,5,8,10-tetraoxa-4,9-diphosphaspiro (5,5 ') hendecane 7 9 11 20

Example 3

From the polypropylene powder described in Example 1, mixtures with phosphorus-containing stabilizers were prepared and subjected to stress in a Brabender plastograph mixing chamber; stressed at 190 ° C in an air atmosphere. The time taken to reduce the relative viscosity to half was observed. The stabilizer concentration was 0.2%.

Used stabilizer conc. 0.2%

Relative viscosity time to 50 # (min)

First - 10 Second Trisnonylphenyl 17 Third tris (1-phenylethylphenyl) phosphite, 23 4th three s (2,4-di-tert-butylphenyl) phosphite 29 5th 4,4 '- (1,1'-diphenylene) 0, 0,0,0-tetra (2,4-ditert-butylphenyl) diphosphonite 58 6th 4,9-Di [2-tert-butyl-4- (1,1-dimethylbenzyl) phenoxy] -3,5,8,1O-tetraoxa-4,9-diphosphaspiro [5,5] handecane 66 7th 4,9-Di [2-tert-butyl-4-methylphenyloxy] -, 3,5,8,1O-tetraoxa-4,9-diphosphaspiro [5.5. ] Hendecanol 63 8th 4,9-Di [2,6-diisopropylphenyloxy} 3,5,8,10-tetraoxa-4,9-diphosphaspiro [5,5] hendecane 58 9th 0,1 2,6-di-tert-butyl-4-methylphenol + 0,1 4,4 (1,1-biphenylene) 0,0,0,0-tetra- (2,4-di-tert-butylphenyl) diphosphonic acid 102 , 0th 0.1 2,6-di-tert-butyl-4-methylphenol + + 0,1 4,9-Di [2-tert-butyl-4- (1,1-dimethylbenzyl-phenyloxy) -3,5,8 * 10-tetraoxa-4,9-diphosphaspiro [5,5] -hendecane 153.9

example

The films of the polymer characterized in Example 1 and prepared as well were made into test specimens which were exposed in the Xenotte 450. The conditions were: black panel temperature 45 ° C, rel. humidity 65 #, cycle: dry running 171 min, showering 9 min, running with rotation. The increase in carbonyl groups was determined at regular time intervals. Differences from baseline were recorded as Ext. The mixtures contained 0.1 # 2,6-di-tert-butyl-4-methylphenol, 0.3% 2-hydroxy-4-octyloxybenzophenone and 0.15% calcium stearate as a basic stabilization system. An overview of the evaluated phosphorus-containing stabilizers is characterized by the time it takes to reach Ext. 0.3.

Used stabilizer conc. 0.2 #

Time in Xenoteste (h)

First Second tris (1-phenylethylphenyl) phosphite tri with (2,4-di-tert-butylphenyl) phospho 1 2 820 400 Third 4,4 '- (1,1'-diphenylene) 0,0,0,0-tetra- (2,4-di-tert-butylphenyl) diphosphonate 1 980 4th 4,9-Di [2-tert-butyl-4- (1,1'-dimethylbenzyl) -phenoxy] -3,5,8,1O-tetraoxa-4,9-diphosphaspiro [5,5-hendecane] 3 200 5th 4,9-Di [2-tert-butyl-4-methylphenyloxy] -3,5,8,10-tetraoxa-4,9-diphosphaspiro-L5,5J hendecane 3 250 6th 4,9-Di [2,4-di-tert-butylphenyloxy] -3,5,8,1O-tetraoxa-4,9-diphosphaspiro [5,5-hendecane] 2 840

Example 5

A mixture of high density polyethylene and antloxidants was prepared by homogenization in a Brabender plastograph at t. 200 ° C, stirring time 10 min. Foils of 0.5 mm thickness were pressed from the homogenized mixtures, which were subjected to oxygen treatment at 1B0 ° C and the time to the start of oxidation was determined. In both mixtures there was 0.15% tetrakismethylene-3- (3 ', 5'-dibutyl-4-hydroxyphenylpropionet).

IP-180 antioxidants used (weight%) (min)

1. 0,15 4,4 * - (1,1'-Diphenylene) 0,0,0,0-tetra- (2,4-di-tert-butylphenyl) diphosphonite 670

2. 0,15 4,9-Di [2-tert-butyl-4- (1,1-dimethylbenzylphenoxyl-3,5,8,10-tetraoxa-4,9-diphosphaspiro- [5,5] hexane 760)

Example 6

The thermal stability and volatility of the substances was measured on the ma3 derivatograph. production (Μ0Μ-Budapest) under conditions: atmosphere - static air, heating rate 5 ° C per minute.

Claims (3)

OBJECT OF THE INVENTION Process for stabilizing polymers to which other stabilizing agents such as antioxidants, light stabilizers against heat, light and oxygen can also be added simultaneously, characterized in that 0.01 to 2% by weight of a compound of the formula I are added to the polymer material V (R ³ ) _r (I) wherein b ', and R 6 are normally or branched alkyl having 1 to 18 carbon atoms, aralkyl From 7 to 9 carbon atoms, cycloalkyl of 6 to 7 carbon atoms and m, n and r are integers from 0 to 3. 2. A process according to claim 1, wherein the compound of formula (I) is 4,9-di [2-tert-butyl-4- (1,1) -dimethylbenzylphenoxy] -3,5,8,10- tetroxa-4,9-difosfaspiro- [5,5] Hendecanol. 3. The method according to claim 1, wherein the polymer is polypropylene, polyethylene, polystyrene or polyvinyl chloride.