CS200791B1 - Light-stable polymeric mixtures - Google Patents

Description

For light stabilization of polymers, the most commonly used are either? - (2-hydroxyphenyl) benzotriszole derivatives or? -Hydroxy-1-olkoxybenzophenones. The addition of these stabilizers to the polymers provides them with resistance to the harmful effects of sunlight and atmospheric scaling. The compounds hitherto used as light stabilizers have some disadvantages, of which the following can be mentioned. It is characterized by a relatively high volatility, which causes problems in the technological processing of polymers. In addition, the most commonly used light stabilizers hitherto used are washed out relatively quickly from the polymers with water, detergents or organic solvents.

We have found that polymer blends, degrading compounds of? -Hydroxy-4-alkoxybenzophenone of general formula (1) ...

H HO e

wherein R is normal or branched alkyl of 1-18 carbon atoms, cyclohexyl, methylcyclohexyl, and R ¹ is hydrogen, or branched or branched alkyl of 1 to 18 carbon atoms, not only has improved resistance to harmful ultraviolet radiation, but they are resistant to light degradation even after washing, even after thermal stress at higher temperatures, and at the same time during processing, there are no technological problems associated with the light stabilization of the light stabilizers.

As compounds of formula (1), for example, the following compounds can be used: 2-hydroxy-4-methoxy-5-tert-butylbenzophenone 2-hydroxy-4- (2-ethylhexyloxy) -5-tert-butylbenzophenone 2-hydroxy-4- n-octyloxy-5-tert-butylbenzophenone 2-hydroxy-4-n-dodecyloxy-5-tert-butylbenzophenone 2-hydroxy-4-n-butoxy-5-tert-butylbenzophenone 2-hydroxy-4-n-octyloxy-5 - / 1,1,3,3-tetramethylbutyl / benzophenone 2-hydroxy-4-n-butoxy-5- (1-phenylethyl) benzophenone 2-hydroxy-4- (2-ethylhexyloxy) -5-cyclohexylbenzophenone

The polymeric light-stable compositions are prepared by adding stabilizers of formula (I) after polymerization, such as e.g. by mixing the compound as well as other additives into the melt by one of the usual technical methods, or by applying the dissolved or dispersed compound to the polymers followed by evaporation of the solvent.

The compounds of formula (I) may also be added to the motif in the form of a concentrate having a concentration of 2.5 to 25% by weight. of these compounds. The concentration of the compounds of formula (I) in the resulting polymer mixture is 0.01 to 5% by weight. calculated on the stabilized material. Preferably, a concentration of 0.05 to 0% by weight, in particular 0.1 to 0.8% by weight, is used. calculated on the stabilized material to which the compounds of formula (1) are added.

As polymers, e.g. low or high density polyethylene, polypropylene, polyisobutylene, polystyrene, polyvinyl chloride, polymethyl methacrylate, polyacrylonitrile, polyurethanes, polycarbonates, polyamides, polysulfones, polyesters, and copolymers thereof. Other additives which can be used together with the stabilizers of the present invention are as follows:

a / Antioxidants such as:

2,6-di-tert-butyl-4-methylphenol 2-tert-butyl-4,6-dimethylphenol

2,6-dimethyl-4-alkylphenol having 1 to 50 carbon atoms

2.2 * -tiobie- / 6-tert-butyl-4-aatylfenol /

2,2'-methylene-bis- / 6-tert-butyl-4-methylphenol /

1,3,5-tri- (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4-bis- (3-tert-butyl-4-hydroxy-5-methylbenzyl) malonic acid dioctadecyl ester 6-trimethylbenzene esters of [4- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid with octadecanol, 2-ethylhexynol and pentaerythritol.

b / Phosphites such as:

tri / L-fenyletylfenyl / phosphite

3.9- di '(2' et, ylhexyloxy) -2,4,8 ₎ 10 'tetraoxo-3,9-diphosphsspiro [5,5] -undecane triphenylphosphite trilauryltrithiophosphite triy-2-etylhexyl] -fcsfit d-2. Substituted benzenoic acid esters such as: phenylsalicylate 4-tert-octylphenylsalicylate benzoylresorcin dibenzoylresorcin c) Synergistic sulfur additives such as:

esters of thiodipropionic acid with 2-ethylhexanol, lauryl alcohol, stearyl alcohol d / UV-stabilizers such as:

D-1. 2- / 2-h-hydroxyphenyl / benzotriazole derivatives such as:

2- / 2-hydroxy-5-methylphenyl / benzotriazole

2- / 2-hydroxy-3,5-ditert-butylphenyl / benzotriazole

2- / 2-hydroxy-3> 5-butylphenyl / 5-chlorobenzotriazole

2- / 2-hydroxy-3-tert-butyl-5-methylphenyl / 2-chlorobenzotriazole

D-3 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-butylphenyl ester. Nickel compounds such as d-4. Aminic stabilizers such as:

nickel stearate

Nickel 2-ethylhexenoate nickel phosphate acid diester salts with 2-ethylhexanol, n-octanol, n-dodecanol, n-octadecanol, phenol, 4-tert-butylphenol, 4-tert-octylphenol, 4-1-phenylethyl / phenol,

Nickel 2,2-thiobis-4- / 1,1,3,3-tetramethylbutyl / phenolate as a 1: 1 or 1: 2 complex or with a longer ligand than n-butylamine, triethanolamine, nickel dibutyldithiocarbamate

2,2,6,6-tetramethylpiperazin.

4-stearoyloxy-2,2,6,6-tetramethylpiperidine bis- (2,2,6, β-tetramethylpiperidyl) adipate bis- [1,2,2,6-pentamethylpiperidyl] adipate bis- (2,2,6), 6-tetramethylpiperidyl / methacrylate nickel salt of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoethyl ester, nickel-nickel acetylacetonate nickel complex 1: 2 4-tert-butylphenylsalicylate nickel-3,5-di-tert-butyl -4-hydroxybenzoic acid, d-5.Qiemelic acid amides such as:

2-ethoxy-5-tert-butyl-2 ' -ethyloxanilide and a mixture thereof with 2-ethoxy-2 ' -ethyl, 5,4-diether, butyloxanilide and PVC stabilizers such as;

barium cadmium and zinc stearates, organooinidites, sulfur and sulfur-free compounds f / Other ingredients, such as:

humectants, lubricants, fillers, dryers, pigments, optical brighteners, antistatic agents and flame retardants.

Compounds of formula (I) may be prepared according to the process described in the invention.

certificates d. 183 262.

The light-stable polymer blends of the present invention have higher atmospheric stability, lower volatility, and are more resistant to scrubbing by detergent and organic solvents than the 2-hydroxybenzophenone derivatives used hitherto. The following examples illustrate the invention in more detail:

Example 1

A mixture of isotactic polypropylene with stabilizers was prepared in a mixing chamber of a BRABENDER plastograph at 190 ° C under a nitrogen atmosphere. Unstabilized powdered isotactic polypropylene with an isotactic index of 6.81 and a strength index of 4.29 g / 10 min. An overview of used stabilizers is given in the table of measured values. Foils of 0.5 mm thickness (compression temperature 260 ° C, time 10 min) were pressed from the unmixed mixtures, which were used to prepare the test samples for evaluation in Xenotest 450. During the xenotest exposure, samples were subjected to intervals of 48 and 48, respectively. 72 hours of bending and the exposure time to breakage / embrittlement / specimens was determined - durability in xenotest.

An overview of the measured results is given in Table d. 1

Table d. 1

Number Composition of the stabilizer mixture Lifespan mixtures in weight. s in xenoteste / h / 1 Without stabilizer 160 2 0.2% Tri-Z1-phenylethylphenyl (phosphite) β-1 / 644 0,3% -dilauryltiodipropionate (S-1) 3 0.2% P-1 0.3% S-1 1437 0.3% 2-hydroxy-4- (2-ethylhexyloxy) -5-tert- » butylbenzophenone / UV-1 / 4 0.1% 2,6-di-tert-butyl-4-methylphenol / AO-1 612 0.4% S-1

Continuation of Table 2. 1

5 0.1% AO-1 0.4% S-1 1475 0.3 % UV-1 δ 0.1 P 4 % - (3,5,5-di-tert-butyl-4-hydroxy-phenyl-propionic acid octydecyl ester) (A0-2) % S-1 664 7 0.1 % AO-2 0.4 0.3 «S-1 % 2-hydroxy-4-dodecyloxy-5-tert-butylbenzophenone (11 / -2) 1480 8 0.2 % F-1 0.3 0.25 0.25 % S-1 % UV-1 % Nickel stearate 1850 i 9 0.1 0.4 % AO-2 % distearyl thiodipropionate 0.25 0.25 % UV-1 % Ni-complex of 4-tert-butylphenyl salicylate 1879 10 0.2 % F-1 0.3 0.25 0.25 % 3-1 % UV-1 % 2,4-di-tert-butylphenyl ester 3,5-di-tertbutyl-4-hydroxybenzoate 3750 11 0.1 % AO-2 0.25 0.25 % UV-1 % Adipic acid di- (1,2,2,6,6-pentamethylpiperidyl) ester 5085

Example 2

The isotectic polypropylene blends prepared as described in Example 1 were also exposed to natural atmospheric conditions. Table 2 summarizes the results.

Table 2. 2

Number mixtures Composition of stabilizer mixture /% w / % pSwater strength after exposure 33.2 kLy 57.6 kLy 180 kLy 1 ^B ez stabilizer 18 0 0 2 0.2% F-1 0.3% S-1 93 26 0 3 0.2% F-1 0.3% S-1 0.5% UV-1 100 100 79

Example 3

A mixture of stabilizers and unstabilized high pressure polyethylene (R) with a melt index of 2 g / 10 min was prepared. The mixture was prepared on a twin cylinder at 120 ° C (stirring time 10 minutes). Films of a thickness of 0.15 mm were prepared from the homogenized mixture by compression in an electric extrusion press at 160 ° C (pressing time 10 minutes). Test specimens were prepared from films and evaluated in Xenotest 4-50 using an IR spectrophotometer for CO group increment. An overview of the used stabilizers and measured values is given in Table S. 3 ·

Mixture number Composition of stabilizing mixture /% w / Time to reach ext = 0.3 / h / 1 volatile 910 2 0.1% AO-1 0.1% F-1 0.3% UV-1 2 100 3 0.1% AO-1 0.1% 4 _t 9-Di- (2-ethylhexyl) difoafitpentaeritritol 0.3% UV-1 3 260

Example 4.

Slurry PVC blends with stabilizers after homogenization in a mortar were gelatinized on a Buzuluk 200 x 400 double roller at 150 ° C for 10 minutes. Plates of 0.5 mm thickness were pressed from the calendered mixtures at 160 ° C (pressing time 10 minutes). Test plates were prepared from the a and plates to evaluate the change in mechanical properties in the Xenotte 450. An overview of the evaluated light stabilizers and measured values is given in Table δ. 4th

Basic recipe: polymer 100 d., Diisoctyl phthalate 50 d., Di- (mono-2-ethylhexylmaleine) dibutyltin 2 d-, wax E 0.5 parts.

Table δ.

Number mixtures UV-abeorbér Change after exposure 4,117 hrs. Z * Z strength tensibility 1 - 43.0 0 2 0.5 <3. 2-hydroxy-4-me- toxybenzofenón 66.5 28.6 3 0,5 d. UV-1 87.6 57.2

Example 5

The suspension PVC with the stabilizers was mixed in a PRA30MIX mixer and the gelatin was electrically heated to a double cylinder at 170 ° C for 5 min. Foils of 0.05 mm thickness were removed from the blends and exposed to Xenotest 450

200,791 and evaluated for the evolution of chemical changes - by increasing the carbonyl groups (spectrophotometrically). An overview of the measured results is given in Table δ. 5 · Basic stabilization system: suspension PVC 100 d., Wax E 1 d., Di- (mono-2-ethylhexylmaleinan) -dibutyltin 2 d.

Tables 5, 5

Number mixtures UV-absorber After exposure 3,179 h. C = 0 1 2 0,5 d. UV-1 ° | ²⁸⁵ 0,086

Example 6

The volatility of the stabilizers themselves was determined as the mass loss from the cylindrical cup at 280 ° C for 20 minutes. The surface of the stabilizer in the crucible was 7.065 cm ² , the cup height was 40 mm. The cup was immersed in a 10 mm bath in a tempered Wood metal bath. The stabilizer weight was 1.5 g. The volatility results are given in Table δ. 6th

Table S. 6

UV absorber p Volatility g / dm 2-h.vdroxy-4-methoxybenzophenone 2/2-hydeoxy-5-methylphenyl / benzo- shaking 2-hydroxy-4-octyloxybenzophenone UV-1 14.0 12.9 5.3 4.5

Example 7

The isotactic polypropylene blends prepared in Example 1 were subjected to thermal stress in an air-drying oven at 60 and 80 ° C and the time (1/2) during which the UV-absorber concentration in the polymer dropped to half its original value. You? LEDs are summarized in table δ. 7 ·

TabuTka δ

UV absorber / ₂ / h / 60 ° C 80 ° C 2-hydroxy-4-methoxybenzophenone 22 4 2-hydroxy-4-oktyloxybenzo- phenone 4190 740 2- / 2-hydroxy-3,5 - <) iterc.- butylphenyl / 5-chlorbezo- triazole 2920 203 UV-1 52300 1130

Example 8

Isotactic polypropylene blends prepared as described in Example 1 were subjected to stress in 90 ° C warm water containing 5% detergent (Cl) in a washable monitor - LINITEST (Original Hanau, Germany). The wash results are summarized in Tables 5. 8.

Claims (2)

CLAIMS 1. Light-permanent polymer mixtures, characterized in that they contain from 0.01 to 5.0% by weight of a compound of the formula I q I? (1) wherein R is normal or branched alkyl of 1-18 carbon atoms, cyclohexyl, methylcyclohexyl and R 6 is hydrogen or normal or branched alkyl of 1-18 carbon atoms, respectively 0.01 to 3.0% by weight of an antioxidant selected ^from of the following groups: substituted phenol, substituted triaryl phosphite, esters of thiodipropionic acid with 8 aliphatic alcohols, optionally 0.01 to 2.5% by weight of a co-stabilizer selected from the following groups: substituted 2- (2-hydroxyphenyl) -benzotriazole, substituted phenyl benzoesters acids, nickel salts and organic ligand complexes, substituted 2,2,5,6-tetramethylpiperidines, substituted oxalic diamides, substituted 2,2,6,6-tetramethylpiperazines, the remainder to 100% being an organic polymer selected from the group consisting of high density polyethylene, polypropylene, polyisobutylene, polystyrene, polyvinyl chloride, polymethyl methacrylate, polyacrylonitrile, polyurethane ny, polykarbonéty, polyamides, polysulfones, polyesters, and their copolymers. 2. Svetlostéle polymer compositions according to claim 1, vyznažujúce in that as zlúženinu of formula I comprises a compound wherein R is t-butyl, 1,1,3,3-tetramethylbutyl, cyclohexyl, and R ¹ is methyl, ethyl, , n-butyl, n-ethyl, 2-ethylhexyl, n-dodecyl, n-octadecyl and the organic polymer is polypropylene, polyethylene, polyvinylchloride and polystyrene.