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    • 专利摘要:
    POLUSHER. COMPOSITIONS containing acrylonitrile-butadiene-styrene copolymer or impact polystyrene and a phenolic stabilizer, characterized in that. in order to improve its resistance to thermal oxidation, it contains a compound of the general formula ck as a phenolic stabilizer. t cn, cn, where R is methyl or tert.-butyl, in the following ratio of components, wt.%: Acrylo nitrile buta (L-dienstyrene copolymer or impact polystyrene -99.4-99.9; indicated phenolic stabilizer O, 1-0 , 6
    公开号:SU1153834A3
    申请号:SU823520356
    申请日:1982-12-02
    公开日:1985-04-30
    发明作者:Розенбергер Зигфрид
    申请人:Циба Гейги Аг (Фирма)；
    IPC主号:
    专利说明:

    tnl-2-methylphenol); 1,1-bis- (5-tert-butyl-4-hydroxy-2-methylphenyl) -butane; 2,6-di- (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol j 1,1, 3-tris- (5-tert-butyl-4-hydroxy 2-methylphenyl) -butane; 1, 1-bis- (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecylmercaptobutane, ethylene glycol bis-3,3-bis- (3-tert-butyl-4-hydroxyphenyl) - butyrate; di- (3-tert-butyl-4 hydroxy-5-methylphenyl) -dicyclopentadiene, di- 2- (3-tert-butyl-2-hydroxy-3-methylbenzyl) -6-tert-butyl-4-methylphenyl terephthalate . 1.5. Benzyl compounds: 1,3,5-tri (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, di- (3,5-di-ter-butyl-4 -oxybenzyl) -sulfide, 3,5-di-tert-butyl-4-hydroxybenzyl-mercaptoacetic ACID isooctyl ester bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -dithiol terephthalate 1, 3,5- tric- (3,5-di-tert-but-1-4-hydroxybenzyl) -isocyanuapj 1, 3,5-tris- (4-ter-butyl-8-hydroxy-2, 6-dimesh1benzyl) -isocyanurate; 3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid, dioctadecyl ester of calcium salt of 3,5-di-tert-but-4-hydroxybenzyl phosphoric acid monoethyl ester. 1.6. Adyl: minifenols: 4-hydroxylauric anilide, acid J 4-hydroxystearic acid anilide; 2,4-bis-octylmercapto-6- (3,5-di-TET-butyl-4-oxyaniline) -S-triazine. 1.7 Esters of p- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with pentaerythritol, tris-oxystil-isocyanurate, di-hydroxyethyl diamide diamide. 1.8. Esters of ft - (5-tert-butyl-4-hydroxy-3-methylphenyl) -propionic acid with mono- or polyhydric alcohols, for example with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol , triethylencicol, pentaerythritol, tcc-hydroxyethyl isocyanurate, diamide, dihydroxyethyl oxalic acid. 1.9.Amides of / t - (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid: 344 N, (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hexamethylenediaminium JN, N-di - (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -trimethylenediamine, N, K-di- (3,5-di-tert-butyl-4-hydroxyphenyl-propionyl) -hydrazine. 2. UV absorbers and light-shielding products. 2.1.2- (2 -Oxyphenyl) -benztriazoles, for example, 5-methyl-j 3, 5 di-tert-butyl-} 5 -tert-butyl, 5 (1,1,3,3-tetramethyl-butyl) -J 5-chloro-3, 5-di-tert-butyl- {5-chloro-3-tert-butyl-5-methyl-, 3-sec-butyl-5-carbo-butyl-, 4-octoxy-3 , 5-di-tert-amyl-benzonazol. 2.2.2-Oxybenzophenones, for example 4-hydroxy-, 4-methoxy-i 4-octoxy-4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-; 4,2, 4-trioxy, 2-hydroxy-4,4-dimethoxy-derivatives. 2.3. Esters of benzoic acids substituted under known conditions, for example, 4-tert-butyl-phenyl salicylate, phenyl salicylate, octyl phenyl salicylate, dibenzoyl resordine, bis (4-tert-butyl-benzoyl) -resorcinol, benzoyl-resorcinol, 2,4-di 3,5-di-tert-butyl-4-hydroxybenzoic acid tert-butylphenyl ester. 2.4. Acrylates, for example, oC-cyano-, / 3 -diphenylacrylic acid ethyl ester or isooctyl ester (- ipiaHO-fl j / -diphenylacrylic acid, c-carbomethoxy-3 methyl ester, (3-cyric acid, OC methyl ester -cyano /., UZ-methyl-P-methoxy-cinnamic acid or OO butyl ester -cyano- /./3-methyl-1-methoxy-cinnamic acid, / -carbomethoxy-h-methoxy-cinnamic acid methyl ester, N - ((-carbomethoxy-, / cyano-vinyl) -2-methyl-indoline. 2.5. Nickel compounds, for example nickel complexes of 2,2-thio-bis-4- (1,1,3,3-tetramethylbutyl) -phenolT like 1: 1- or 1: 2 complex, under known conditions with additional ligands, such as i-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters of 4-oksi3, 5-di-tert -butnlbeneilfosfornoy isloty as methyl esters or etylovogo; nickel complexes keto Xim, as 2-hydroxy-4-methyl-phenyl-undecyl-ketone-xnme, nickel complex 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, under known conditions with additional ligands. 2.6. Spatially obstructed amines, for example bis- (2,2,6,6-tetramethyl-piperidyl) -sebacate bis- (1,2,2,6,6-pentamethylpiperidyl) -sebacate; bis-1,2,2,6,6-pentamethyl-piperidyl ester of H-butyl-3,5-di-tert-butyl-4-hydroxybenzyl-malonic acid; the condensation product of 1-hydroxyethyl-4-hydroxypiperidine with succinic acid, the condensation product of N, N- (2,2,6,6-tetramethylpiperid-1) hexamethylenediamine with 4-tert-octyl amino-2,6-dichloro-1,3 , 5-symn-triazine; tris- (2,2,6,6-tetramethylpiperyl dil) -nitriltriacetate. 2.7 oxalic acid diamides, for example 4,4-di-octyloxyoxanilide 2,2-dioctyloxy-5,5-di-trag-butyl-oxoanilide; 2,2-di-dodecyl-5,5-di-treg-butyl-oxanilide, 2-ethoxy-2-ethyl-oxanilide N, N-bis- (3-dimethylaminopropyl) -oxalamide 2 is Si-5-third -butyl-2-ethyl-oxanilide and its mixture with 2-ethoxy-2-ethyl-5,4-di-tert-butyl-oxanylide {a mixture of ortho- and G7ara-methoxy-, as well as O and P-ethoxy-disubstituted oxanyl3. Metallic deactivators, for example N, N-diphenyl oxalic acid diamide / N-calicyl-N-salicy loylhydrazine; N, N -bis-salicyloyl hydrazine, K, s-bis- (3, 5-di-Treg-butyl-4-hydroxyphenylpropionyl) -hydrazine; 3-salicyloyl-amino-1,2,4-triazole; dihydrazide-bis-benzylidene-oxalic acid. 4. Phosphites and Phosphates 2,4-di-tert-butylphenyl) -pentaerythritol-diphosphite, tristearyl-sorbitol-triphosphite, tetraxis-) 2,4-di-butylphenyl) -4,4-biphenylene-diphosphonite. 5. Destructive peroxides compounds, for example, esters of β-thio-di-propionic acid; lauryl stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercapto-benzimidazole, zinc dibutyldithiocarbamate, dioktadetsilsulfid pentaerythritol getraksie - (/ E -dodetsnlmerkapto) propionate. 6. Polyamide stabilizers, for example, copper salts in combination with iodine and / or phosphorus compounds and salts of divalent manganese, 7. Main stabilizers, for example, melamine, polyvinylpyrrolidone. dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali and alkaline earth metals of higher fatty acids for example calcium stearate, zinc stearate, magnesium stearate, sodium ricinoleate, potassium palmitate, antimony pyrocatecholate or tin pyrocatecholate. 8. Crystallization agents, for example 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid. 9. Fillers and enhancers, for example calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and metal hydroxides, carbon black, graphite. to. Other additives, such as softeners, plasticizers, emulsifiers, pigments, optical brighteners, flame retardants, antistatic agents, porophores. Try about 3,5-di- (3, 5-di-tert-butane-1-4-hydroxybenzyl) -2,4-dimethyl-6-ter-butylphenol. .21.5 g 2, 4-dsh-. tyl-6-tert-butylphenol is dissolved in 60 ml of methanol and shifted from 11 g of 80% sulfuric acid. Then, about 60 g of 4-methoxymethyl-2,6-di-tert-butylphenol are added over 6 hours with stirring under nitrogen atmosphere at (under reflux). The reaction mixture was incubated for 6 hours at 70 ° C. After cooling, the reaction product crystallized out as colorless crystals. It is sucked off on a coup and, by infusion with hexanoM, suction, infusion with water containing NaOH and subsequent suction is purified. T. pl. 140 C (from methanol). Example 2. The procedure of Example 1 is followed. However, instead of 2,4-dimethyl-6-ret-butylphenol, 2,4,6-trimethylphenol is used in an adequate amount of V. 3.5-di- (3 5 -di-tert-butyl) is obtained. 4-hydroxy-benzyl) -2 .4,6-trimethylphenol. T. pl. 204 C.. Example 3. 100 p. unstabilized ABS powder mixed with stabilizer. The resulting mixture is mixed on rollers for 5 minutes at and then the sheets are stretched. Raw sheets are pressed on a hydraulic laboratory press for 6 minutes. Up to 1 mm thick plates, from which test samples are stamped in dimensions of 50 x 20 mm. The test of the activity of stabilizers added to the sample is carried out by aging the samples by heating in an air-circulation oven at. The criteria for the oxidation that occurs with aging is the infrared absorption spectrum of the surface, which is obtained through reflection spectroscopy. In particular, the increase in extinction of carbonyl (1720 cm) as a function of time is monitored and compared with the remaining constant absorption band (1455). In this case, as a measure of destruction, the optical density at 1720 cm О С О) opt. density at 1455 cm (CHj,). As an arbitrary end point, the time is chosen, after which V reaches 0.1 (T oi). The stabilization activity test (0.25 wt.%) In the ABS copolymer without synergist is given in Table. 1 test of the activity of the stabilizer (0.25 wt.%) In the ABS copolymer with the synergist dilaurylthiodiropionate (DLTDP 0.25 wt.%) - in the table. 2. Example 4. High impact polystyrene with 8 wt.% Polybutadiene and 0.035 wt.% 2,6-di-tert-butyl-p-cresol as the main stabilizer, 0.05 wt.% Zinc stearate as a softener, as well as 0., 1% by weight of one of the proposed antioxidants, is extruded twice at and the resulting granulate is pressed at 185 ° C for 3 minutes into gshastins for testing with a thickness of 2 mm. Test samples are aged in an air circulating oven. The yellowness index is determined according to ASTMD 1925 with (measurement of the test samples after 0.250, 500; 750 and 1000 hours) and at 160 ° C (measurement of the test samples through 0; 60; 90; 120 and 180 hours). The results are presented in table. 3. Impact viscosity (SZ), kgf-s / cm) is determined after aging at 160 ° C (measurement of test samples after 30; 60, 120; 150; 180; 240- 300, 360; 420; 480 min): SZ sample without stabilizer after 30 min 10.4 kgf-s / cm; The sample in Example 1 is not destroyed after 30 - 360 minutes, after 420 minutes the SZ sample is 7.9 kgf s / cm. Example 5. DP comparison tests of the known compound A and compound B (according to example 2) are carried out; the thermo-oxidative stability of the ABS copolymer is determined by means of DTA. 1000 hours of unstabilized ABS powder (22% polybutadiene) are carefully transferred from 1 or 6 parts of stabilizer A dissolved in 100 parts of cyclohexane. The solvent is removed, in vacuum at 40 ° C, the resulting powdered ABS is homogenized in a ball mill at room temperature for 12 hours. The determination of oxidation resistance is carried out by differential thermal analysis (DTA). About 5 mg of the stabilized powdered ABS copolymer, after weighing, are placed in an Aluminum container and subjected to testing in a TA 2000 instrument according to Mettler under the following conditions: 180 ° C, oxygen transmission 50 ml / min. The onset of oxidation is expressed in an increase in the temperature of the sample, which is recorded by a recorder. As a scale of resistance to oxidation, take time (min) to reach the maximum exothermic reaction:
    The results show the superiority of the compound according to the stabilizing effect. Thus, the proposed composition
    Table3
    权利要求:
    Claims (1)
    [1]
    POLYMERIC COMPOSITION containing acrylonitrile butadiene styrene copolymer or high impact polystyrene and phenolic stabilizer, which is due to the fact that. in order to increase its resistance to thermal oxidation, it contains as a phenolic stabilizer a compound of the general formula where R is methyl or tert.-butyl, in the following ratio, May.%:
    Acrylo nitrile butadiene styrene copolymer or high impact polystyrene - 99.4-99.9
    The specified phenolic stabilizer 0.1-0.6
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    法律状态:
    优先权:
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