JPS6111257B2 - - Google Patents

Description

[Detailed description of the invention]

This invention provides a polyolefin stabilizing composition,
In particular, it relates to polyolefin compositions that are resistant to deterioration due to contact with heavy metals. Conventionally, polyolefins such as polyethylene, polypropylene, and polybutene have been used in many fields because they have excellent physical and chemical properties. At this time, as is well known, when polyolefin is used alone, it deteriorates due to heat, light, or oxygen during processing or use, so various antioxidants have been developed and used to prevent this. ing. However, if contact between polyolefins and heavy metals such as copper, iron, or nickel cannot be avoided,
For example, in cases such as coating copper wire with polyolefin, plating polyolefin with heavy metals, and coloring polyolefin with pigments containing heavy metals, it is difficult to prevent polyolefin from deteriorating due to contact with heavy metals. shows almost no resistance. Furthermore, when there is a risk of liquid amorphous polyolefin coming into contact with copper, for example when liquid amorphous polyolefin is used as an insulating oil for cables, resistance to deterioration due to contact with copper is required. However, this requirement cannot be met simply by using the conventional antioxidants. Therefore, in order to make polyolefins resistant to deterioration caused by heavy metals, N.
N'-dibenzoylhydrazine, N-benzoyl-N'-salicyloylhydrazine, N・N'-dibutyrylhydrazine, N・N'-distearoylhydrazine, N・N'-bis[β-(3.5 - Ji 3rd
Degradation inhibitors such as butyl-4-hydroxyphenyl)propionyl]hydrazine, N・N'-bissalicyloylhydrazine, oxalobis(benzylidenehydrazide), and N-salicylidene-N'-salicyloylhydrazine have been developed. Although,
The deterioration prevention effect of these materials is still not satisfactory. The inventors used 100 parts by weight of polyolefin and the general formula (However, R is an alkyl group having 1 to 4 carbon atoms.) A composition consisting of 0.001 to 5 parts by weight of the compound (deterioration inhibitor) represented by the above formula is effective against deterioration of polyolefins, especially deterioration due to contact with heavy metals. The present invention was completed based on the discovery that it has excellent stability against. The polyolefin in this invention includes ethylene, propylene, butene-1, isobutene,
Amorphous or crystalline homopolymers or copolymers of olefins such as pentene-1,4-methylpentene-1, and alkyl esters of these olefins and unsaturated carboxylic acids, such as methyl acrylate, ethyl acrylate, and methacrylate. methyl acid,
Examples include copolymers of ethyl methacrylate or vinyl esters of saturated carboxylic acids, such as vinyl acetate, mixtures of these various polymers, and liquid amorphous polymers such as propylene and butene. The deterioration inhibitor in this invention can be easily obtained from terephthalic acid monoalkyl monochloride and terephthalic acid dihydrazide, for example, by the following reaction. The above reaction consists of N-dimethylacetamide, N-
It proceeds at temperatures between 0 and 100°C in the presence of organic solvents such as methyl-2-pyrrolidone and tetrahydrofuran. To isolate the anti-deterioration agent of the present invention from the reaction product after the reaction, for example, the reaction product mixture is poured into a large excess of water, the precipitated solid is collected, and this collection is mixed with, for example, dimethylformamide and water. It may be recrystallized using a recrystallization solvent such as a mixed solvent of Specific examples of suitable deterioration inhibitors in this invention include N.N'-bis(para-methoxycarbonylbenzoyl)terephthalic acid dihydrazide, N.N'-bis(para-ethoxycarbonylbenzoyl)terephthalic acid dihydrazide, N・
N'-bis(para-n-propoxycarbonylbenzoyl)terephthalic acid dihydrazide, N.
N'-bis(para-isopropoxycarbonylbenzoyl)terephthalic acid dihydrazide, N.
N'-bis(para-n-butoxycarbonylbenzoyl)terephthalic acid dihydrazide, N・N'-
Examples include bis(para-tert-butoxycarbonylbenzoyl)terephthalic acid dihydrazide. In this invention, the amount of the anti-deterioration agent added to the polyolefin is 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the polyolefin.
The amount is within parts by weight. If the amount is less than 0.001 part by weight, the deterioration prevention effect is insufficient, and if the amount is more than 5 parts by weight, no improvement in the deterioration prevention effect is observed. The above anti-deterioration agent may be blended into the polyolefin by any method suitable for making a uniform composition.
For example, the deterioration inhibitor is dissolved or dispersed in a low boiling point solvent, mixed with the polyolefin, and then the solvent is removed by volatilization, or the polyolefin is heated on a hot roll to a temperature higher than its melting point and then the deterioration inhibitor is mixed. Alternatively, a method of mixing polyolefin and the above deterioration inhibitor using various mixers etc. can be applied. Moreover, the anti-deterioration agent in this invention can also be used in combination with conventionally known stabilizers, dispersants, plasticizers, antistatic agents, fillers, pigments, and the like. Known stabilizers include 2,6-di-tert-butyl-para-cresol, 2,6-di-tert-butylphenol, 4,4'-methylenebis(2,6-di-tert-butyl),
butylphenol), 4,4'-methylenebis(3
-methyl-6-tert-butylphenol), 4.
4'-bis(2,6-di-tert-butylphenol),
4,4'-thiobis(2-methyl-6-tert-butylphenol), 4,4'-thiobis(2-methyl-
5-tert-butylphenol), 6-(4-hydroxy-3,5-di-tert-butylanilino)-2,4-
Bis(n-octylthio)-1,3,5-triazine, tetrakis[methylene 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, octadecyl-3-(3,5-di tert-butyl-4-hydroxyphenyl) propionate, 1,1,3-tris(2-methyl-4-
hydroxy-5-tert-butylphenyl)butane,
2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-butylidenebis(3
-methyl-6-tert-butylphenol), 2.
2'-methylenebis(4-ethyl-6-tert-butylphenol), 1,3,5-trimethyl-2.
Phenol compounds such as 4,6-tris(3,5-ditert-butyl-4-hydroxybenzyl)benzene, didodecyl-3,3'-thiodipropionic acid ester, dioctadecyl-3,3'-thiodidi Dialkyl-3,3'- such as propionate ester
Thiodipropionic acid ester, trilauryl phosphite, trilauryl trithiophorphiite,
Examples include organic phosphorus compounds such as tris(nonylphenyl)phosphite. Next, an experimental example of synthesis of the anti-deterioration agent according to the present invention will be shown. Synthesis Experiment Example Synthesis of N・N'-bis(para-methoxycarbonylbenzoyl) terephthalic acid dihydrazide 1 g of terephthalic acid dihydrazide is suspended in 50 ml of N-dimethylacetamide, and 2.1 g of monomethyl terephthalate is added to this suspension. After adding Ride with stirring at room temperature, the mixture was stirred at room temperature for 8 hours. The reaction product mixture was added to a large excess of water, the resulting solid was collected, and the resulting collection was dissolved in a mixed solvent of dimethylformamide and water (volume ratio 1:
After recrystallizing in step 1), dry under reduced pressure to determine the melting point.
2.0 g of N.N'-bis(para-methoxycarbonylbenzoyl)terephthalic acid dihydrazide was obtained as white crystals with a temperature of 280.0 to 281.5°C. The elemental analysis values of this crystal were as follows. Elemental analysis value (%) C, 60.18; H, 4.46; N, 10.62 Calculated value (%) as C ₂₆ H ₂₂ N ₄ O ₈ C, 60.23; H, 4.25; N, 10.81 Next, Examples and Comparisons Give an example. In Examples and Comparative Examples, parts are parts by weight, and MI is
Melt flow index measured according to ASTM D1258 is shown. Further, the symbols in the comparative examples mean the following known deterioration inhibitors. a; N-Salicylidene-N'-salicyloylhydrazine b; Oxalobis(benzylidene hydrazide) c; N.N'-bis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine d; N-benzoyl-N'-salicyloylhydrazine e; N.N'-bis(para-octoxybenzoyl)terephthalic acid dihydrazide f; N.N'-bissalicyloyl terephthalic acid dihydrazide Example 1 Powder Tetrakis [methylene 3-
(3,5-ditert-butyl-4-hydroxyphenyl)propionate) methane 0.2 part, 3,3'-distearyl thiodipropionate 0.5 part, 2,6-
1.0 part of di-tert-butyl-para-cresol and 0.2 part of N.N'-bis(para-methoxycarbonylbenzoyl)terephthalic acid dihydrazide were premixed in a mixer. This mixture was heated to 190°C.
The mixture was placed in a Brabender Plastograph with a rotational speed of 60 rpm and kneaded for 5 minutes. Next, a 0.5 mm thick film was produced from this mixture by pressing at 190° C. using a spacer. A 60-mesh copper mesh was sandwiched between the two films created in this way, a 0.8 mm thick spacer was used, and a 190 mesh
A copper mesh embedded film was prepared by pressing at ℃. A test piece was prepared by cutting out a rectangle of 50 mm x 30 mm. The above test piece was suspended in a gear oven in an air atmosphere at 150°C, and the number of days until it became brittle was measured, and it was 60 days. Comparative Examples 1 to 7 Examples 1 to 7 were carried out in the same manner as in Example 1, except that the deterioration inhibitor of this invention was not added at all, or the deterioration inhibitors listed in Table 1 were used instead of the deterioration inhibitor of this invention. The results obtained are shown in Table 1.

[Table] Example 2 100 parts of additive-free high-density polyethylene pellets (MI 0.30) were charged into a Brabender plastograph at 190°C and a rotation speed of 60 rpm, and after 2 minutes, tetrakis[methylene 3-(3・5- di-tert-butyl-4
-Hydroxyphenyl)propionate]methane
0.15 parts and N・N′-bis(para-methoxycarbonylbenzoyl)terephthalic acid dihydrazide
0.2 part was added and kneaded for an additional 6 minutes. Next, a film with a thickness of 0.5 mm was produced from this mixture by pressing at 190° C. using a spacer. A 60-mesh copper mesh was sandwiched between the two films thus produced, and a 0.8 mm thick spacer was used to press the film at 190°C to produce a copper mesh-embedded film. This was cut into a rectangle of 10 mm x 5 mm to prepare a test piece. Next, by the oxygen absorption method, when the above test piece was heated to 170°C in an oxygen atmosphere, the relationship between the amount of absorbed oxygen and time was measured, and the amount of oxygen absorbed per 1 g of the test piece was determined. The deterioration prevention effect was determined by determining the time (minutes) (induction period) until the temperature reached 5 ml (20°C, atmospheric pressure). The induction period was 1420 minutes. Comparative Examples 8 to 13 Example 2 except that the deterioration inhibitors listed in Table 2 were used instead of the deterioration inhibitors in this invention.
Table 2 shows the results obtained in the same manner as above.

[Table] Example 3 The induction period was set in the same manner as in Example 2, except that low-density polyethylene (MI0.25) was used instead of high-density polyethylene, and the kneading temperature (Brabender plastograph temperature) was 140°C. I asked for it. The lag period is
It was 1340 minutes. Comparative Examples 14 to 19 Example 3 except that the deterioration inhibitors listed in Table 3 were used instead of the deterioration inhibitors in this invention.
Table 3 shows the results obtained in the same manner as above.

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Claims (1)

[Claims] 1. 100 parts by weight of polyolefin and general formula, Anti-deterioration agent which is a compound represented by 0.001-5
A polyolefin composition consisting of parts by weight. (However, R is an alkyl group having 1 to 4 carbon atoms.)