JPS6016969B2 - Olefin polymer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to stabilized compositions of olefin polymers, particularly olefin polymer compositions that are resistant to deterioration due to contact with heavy metals.

Conventionally, olefin polymers such as polyethylene, polypropylene, and polybutene have been used in many fields because they have excellent physical and chemical properties.

At that time, as is well known, when olefin polymers are used alone, they deteriorate due to heat, light, or oxygen during processing or use, so various antioxidants have been developed and used to prevent this. ing. However, in cases where contact between olefin polymers and heavy metals such as copper, iron, and nickel cannot be avoided, for example, coating copper wire with olefin polymers, plating olefin polymers with heavy metals, or coating olefin polymers with pigments containing heavy metals. In cases such as coloring of coalescence, the mere use of the above-mentioned conventional antioxidants provides little resistance to deterioration due to contact between the olefin polymer and heavy metals.

Furthermore, when there is a risk of contact between the liquid amorphous olefin polymer and copper, for example when using the liquid amorphous olefin polymer 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 give olefin polymers resistance to deterioration caused by heavy metals, N,N'-dibenzoylhydrazine, N-penzoyl-N'-salicyloylhydrazine, N,N'-dibutyrylhydrazine, N ,N′
-distearoylhydrazine, N-salicyloyl-N'
-stearoylhydrazine, N,N'-bis(para-monomethylbenzoyl)hydrazine, N,N'-diacetyl lucidic acid dihydrazide, N,N'-distearoylgenohiraic acid dihydrazide, dihexanoylhydrazine, N,N
'-bis[8-(3.5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, N,N'-bissalicyloylhydrazine, oxalobis(benzylidene hydrazide), N-salicylidene-N'- Deterioration inhibitors such as salicyroylhydrazine have been developed, but
The deterioration prevention effect of these materials is still not satisfactory.

The inventors used parts by weight of olefin polymer 10 and the general formula [where R is a methyl group or a methoxycarbonyl group, and n is 0 or 1].

] 0.001-5
The present inventors found that a composition of approximately 100% by weight had excellent stability against deterioration of olefin polymers, particularly against deterioration due to contact with heavy metals, and completed the present invention. Examples of the olefin polymer in this invention include amorphous or crystalline homopolymers or copolymers of olefins such as ethylene, propylene, butene-1, isobutene, bentene-1, and 4-methylbentene-1, and these olefins and unsaturated carbon atoms. Alkyl esters of acids such as methyl acrylate, ethyl acrylate, methyl methacrylate,
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, for example, by the following reaction.

[However, R is a methyl group or a methoxycarbonyl group, and n is 0 or 1.

) The above reaction is carried out for 0 to 100 pm in the presence or absence of an organic solvent such as N-dimethylacetamide, carbon tetrachloride, chloroform, benzene, dichlorobenzene, methylene chloride, methyl acetate, or N-methyl-2-pyrrolidone. C,
Preferably, it proceeds easily at a temperature of 10 to 30°C. To extract the deterioration inhibitor of the present invention from the reaction product mixture after the reaction, for example, the reaction product mixture is poured into a large excess of water, the precipitated solid is evaporated, and the mixture is mixed with water or an alkaline compound. The solid obtained by washing with an aqueous solution is
For example, it may be recrystallized using a recrystallization solvent such as acetic acid or N-dimethylacetamide. Specific examples of suitable deterioration inhibitors in this invention include N,N'-bis(2,
4-hexadienoyl)hydrazine, N,N'-bis(
5-methoxycarbonyl-2,4-bentadienoyl)
Examples include hydrazine, N,N'-pis(2,4-hexagenoyl)fumaric acid dihydrazide, and N,N'-pis(5-methoxycarbonyl-2,4-pentagenoyl) fumaric acid dihydrazide.

In this invention, the amount of the deterioration inhibitor added to the olefin polymer is 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the olefin polymer. be.

If the amount is less than 0.001 parts 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 deterioration inhibitor can be blended into the olefin polymer by any method that can be used to make a uniform composition, such as by dissolving or dispersing the above deterioration inhibitor in a low boiling point solvent, mixing it with the olefin polymer, and then adding the solvent to the olefin polymer. Either volatilize and remove the olefin polymer, heat the olefin polymer above its melting point on a hot roll, and mix the above deterioration inhibitor, or mix the olefin polymer and the above deterioration inhibitor using various mixers. This method 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-paracresol, 2,6-di-tert-butylphenol, 4,4
-Methylenebis(2,6-di-tert-butylphenol) 4
, 4'-methylenepis(3-methyl-6-tert-butylphenol), 4,4'-bis(2,6-di-tert-butylphenol), 4,4-thiobis(2-methyl-6-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. 3-butylphenol)
, 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris( 3,5-di-tert-butyl-4
-hydroxybenzyl)benzene and other phenolic compounds, didodecyl-3,3'-thiodipropionate ester, dioctadecyl-3,3'-thiodipropionate ester and other dialkyl-3,3-thiodipropionate esters, trilaurylphosph Examples include organic phosphorus compounds such as trilauryltrithiophosphite, tris(nonylphenyl)phosphite, and the like.

Next, an experimental example of synthesis of the anti-deterioration agent according to the present invention will be shown.

Synthesis Experiment Example 1 Synthesis of N,N'-bis(2,4-hexadienoyl)hydrazine
The resulting solution was added to dimethylacetamide and heated while maintaining the liquid temperature at 25-30°C.

To this solution, 90% hydrazine hydrate was gradually added dropwise.
After completing the dripping, the lamp was lit for 3 hours at 30 to 35 oo. Pour the reaction product mixture into the water, collect the solid produced in a furnace,
Washed with water. The obtained solid was recrystallized twice with acetic acid and then dried under reduced pressure to obtain N, which is a pale yellow crystal with a decomposition temperature of 295°C.
N'-pis(2,4-hexadienoyl)hydrazine 3
．． I got 4 nights. The elemental analysis values of this crystal were as follows. Elemental analysis value (%) C, 65.61; Sun, 7.04; N, 12.58 C, 2
Calculated value (%) C as 6N202, 65.45;
Sun, 7.27; N, 12.73 In addition, the infrared absorption spectrum diagram of this crystal [KBr tablet, measuring device: Diffraction grating infrared spectrophotometer 22 matrix {■ Hitachi, Ltd.}] is the first
It was as shown in the diagram.

Synthesis Experiment Example 2 Synthesis of N,N'-bis(5-methoxycarbonyl-2,4-pentagenoyl)hydrazine A solution obtained by adding 0.4 hours of 80% hydrated hydrazine to 50' of N-methyl-2-pyrrolidone. The liquid temperature was kept at 15-2000℃ and the temperature was kept at 15-2000℃.

To this solution, a solution prepared by dissolving 2.3 g of muconic acid monomethyl chloride in 30 g of N-methyl-2-pyrrolidone was gradually added dropwise. After the dripping was completed, the lamp was lit for 1 hour at 30 to 3,500. The reaction product mixture was poured into the water, and the solid produced was collected in a furnace, washed with water, recrystallized with methanol, and dried under reduced pressure to obtain a product with a melting point of 101.0 to 101.500.
N,N'-bis(5-methoxycarbonyl-2,4-bentadienoyl)hydrazine, pale green crystals of 1.5
I got a 9. The elemental analysis values of this crystal were as follows. Elemental analysis value (%) C, 54.63; day, 5.19; N, 9.27 day, calculated value as 6N206 (%) C, 54.55: day, 5.19; N, 9 .09 The infrared absorption spectrum of this crystal was as shown in Figure 2.

Synthesis Experiment Example 3 Synthesis of N,N'-bis(2,4-hexadienoyl)fumaric acid dihydrazide Sorpic acid chloride 8.0 ml,
Fumaric acid dihydrazide 4.4 yen and ethyl acetate 15
Pour 0' into a flask equipped with a reflux device, and add 3' under reflux.
Time reacted.

After cooling the reaction product mixture, the produced solid was collected in a furnace, washed with ethanol and dimethylformamide, and dried under reduced pressure to produce N,N'-bis(2,4-hexane), which is a light brown crystal with a decomposition temperature of 30,000 or higher. 6.8 g of genyl fumaric acid dihydrazide was obtained. The elemental analysis values of this crystal were as follows. Elemental analysis value (%) C, 57.85; Sun, 5.94; N, 17.01 C, 6
Calculated value as 404 (%) C, 57.83: Day, 6.02; N, 16.87 This crystal contains carbon tetrachloride, chloroform, benzene, dichlorobenzene, methylene chloride, methyl acetate, methanol It did not fall off or was hardly soluble in ethanol when heated.

The infrared absorption spectrum of this crystal was as shown in FIG. Synthesis Experiment Example 4 Synthesis of N,N'-bis(5-methoxycarbonyl-2,4-bentagenoyl)fumaric acid dihydrazide A solution obtained by adding 3.0 ml of fumaric acid dihydrazide to 50' of dimethylacetamide was prepared. Set the liquid temperature to 20~23oo
I kept it there and worshiped it.

To this solution, a solution prepared by dissolving 7.5 volumes of muconic acid monomethyl chloride in 30 volumes of N-dimethylacetamide was gradually added dropwise. After the dropping was completed, the lamp was lit for 2 hours at 20 to 25 oo. The reaction product mixture was poured into water, and the solid produced was collected in a furnace, washed with water, further washed with ethanol, and dried under reduced pressure to give N,N'-bis(5-methoxy), which is a pale yellow crystal with a decomposition temperature of 271°C. 6.5 hours of carbonyl-2,4-bentagenoyl)fumaric acid dihydrazide was obtained. The elemental analysis values of this crystal were as follows. Elemental analysis value (%) C, 51.38; Sun, 4.85; N, 13.25 C, 8
Calculated value (%) as Day 2bu 408 C, 51.43; Day, 4.76:N, 13.33 This crystal contains N-dimethylacetamide, carbon tetrachloride, chloroform, benzene, dichlorobenzene, methylene chloride. , methyl acetate, N-methyl-2-pyrrolidone, methanol, and ethanol when heated.

The infrared absorption spectrum of this crystal was as shown in FIG. Next, examples and comparative examples will be shown. In Examples and Comparative Examples, parts indicate parts by weight, and M. 1. is ASTM
Melt flow index measured according to D1238 is shown. Further, the symbols in Examples and Comparative Examples mean the following deterioration inhibitors. A; N,N'-bis(2,4-hexadienoyl)hydrazine B; N,N'-bis(5-methoxycarbonyl-2,4-pentadienoyl)hydrazine C; N,N'-bis(2,4 −Hexadienoyl)
Fumaric acid dihydrazide D; N,N'-bis(5-methoxycarbonyl-2,4-pentagenoyl) fumaric acid dihydrazide a; N,N'-dibenzoylhydrazine b; N-benzoyl-N'-salicyloylhydrazine c
;N,N'-dibutyrylhydrazine d;N,N'-distearoylhydrazine e;N,N'
-bis{3-(3,5-di-tert-butyl-4-hydroxylphenyl)propionyl}hydrazine f; N,N'-bissalicyloylhydrazine g; N-salicyloyl-N'-stearoylhydrazine h; N,N
'-bis(p-methylbenzoyl)hydrazine i; oxalobis(benzylidene hydrazide) j; N-salicylidene-N'-salicyloylhydrazine k: N, N'
N,N'-distaroyl diacetyl dihydrazide 1; dihexanoylhydrazine Examples 1 to 4 Powdered additive-free isotactic polypropylene (M.
1.5) 10, tetrakis [methylene 3-(3,
5-di-tert-butyl-4-hydroxyphenyl)propionate] methane 0. In a mixer, mixer, 0.5 part of disterialyl 3,3'-thiodipropionate, 1.0 part of 2,6-di-tert-butyl-para-cresol, and 0.2 part of the deterioration inhibitor listed in Table 1 were added. Premixed.

This mixture was heated at a temperature of 190 degrees and a rotation speed of 6 degrees. p. m.
Brabender Plastograph was loaded and mixed for 5 minutes. Next, from this mixture, using Subaser, 19
000 to create a film with a thickness of 0.5. Between the two films made in this way, 60
A copper mesh embedded film was prepared by sandwiching a mesh copper net and pressing at 190 oo using a spacer with a thickness of 0.8. A test piece was prepared by cutting this into a rectangle measuring 5 sides x 3 sides. The test pieces were hung in a gas oven with an air atmosphere of 150 qo, and the number of days until they formed arms was measured.

The results are shown in Table 1. Table 1 Comparative Examples 1 to 14 Same as Example 1 except that the deterioration inhibitor of this invention was not added at all or the deterioration inhibitor listed in Table 2 was used instead of the deterioration inhibitor of this invention. Table 2 shows the results obtained in the same manner.

Table 2 Examples 5 to 8 Additive-free high-density polyethylene (M1.0.30) pellets with a diameter of 10 mm were set at 19,000 rpm and a rotational speed of 6 ratios. p. m. After 2 minutes, 0.15 part of tetrakis[methylene 3-(3.5-di-tert-butyl-4-hydroxyphenyl)propionate]methane and 0.1 part of the deterioration inhibitor listed in Table 3 were added to the Brabender Plastograph. Two parts were charged and kneaded for an additional 6 minutes.

Next, from this mixture, using Subaser, 19000
A film with a thickness of 0.5 skin was created by pressing with A 60-mesh copper silk was sandwiched between the two films created in this way, and a 0.8-thickness subesa was used.
A copper mesh embedded film was produced by pressing at 190°C.
A test piece was prepared by cutting this into a rectangular shape of 1 proboscis x 5 fences. Next, by the oxygen absorption method, that is, when the above test piece was heated to 17,000 °C in an oxygen atmosphere, the relationship between the amount of absorbed oxygen and time was measured, and the amount of absorbed oxygen per night of the test piece was 5%. The deterioration prevention effect was determined by the method of determining the time (minutes) (induction period) until the temperature reached (20 oo, atmospheric pressure).

The results are shown in Table 3. Table 3 Comparative Examples 15-28 Same as Example 5 except that the deterioration inhibitor of this invention was not added at all or the deterioration inhibitor listed in Table 4 was used instead of the deterioration inhibitor of this invention. Table 4 shows the results obtained in the same manner.

Table 4 Examples 9 to 12 Low density polyethylene (M1
．． 0.25) and the kneading temperature (temperature of the Prabender plastograph) was 140qC.
The induction period was determined in the same manner.

The results are shown in Table 5. Table 5 Comparative Examples 29-42 Example 9 except that the deterioration inhibitor of this invention was not added at all or the deterioration inhibitor listed in Table 6 was used instead of the deterioration inhibitor of this invention. Table 6 shows the results obtained in the same manner.

Table 6

[Brief explanation of the drawing]

Figure 1 shows N,N'-bis(2,4-hexagenoyl)
hydrazine, Figure 2 shows N,N'-bis(5-methoxycarbonyl-2,4-pentadienoyl)hydrazine, and Figure 3 shows N,N'-bis(2,4-hexagenoyl)fumaric acid dihydrazide. FIG. 4 is an infrared absorption spectrum diagram of N,N'-bis(5-methoxycarbonyl-2,4-pentadienoyl)fumaric acid dihydrazide. Figure/Saddle Z Figure Figure 3 Foil Figure 4

Claims (1)

[Claims] 1 100 parts by weight of an olefin polymer, general formula ▲ mathematical formula,
There are chemical formulas, tables, etc. An olefin polymer composition comprising 0.001 to 5 parts by weight of a deterioration inhibitor, which is a compound represented by ▼. [However, R is a methyl group or a methoxycarbonyl group, and n is 0 or 1. ]2 Anti-deterioration agent is N, N'
-bis(2,4-hexadienoyl)hydrazine. 3. The composition according to claim 1, wherein the anti-deterioration agent is N,N'-bis(5-methoxycarbonyl-2,4-pentadienoyl)hydrazine. 4. The composition according to claim 1, wherein the anti-deterioration agent is N,N'-bis(2,4-hexadienoyl)fumaric acid dihydrazide. 5. The composition according to claim 1, wherein the anti-deterioration agent is N,N'-bis(5-methoxycarbonyl-2,4-pentadienoyl)fumaric acid dihydrazide. 6. The composition according to claim 1, wherein the olefin polymer is an ethylene homopolymer, an isotactic polypropylene, an ethylene-propylene copolymer or an ethylene-vinyl acetate copolymer. 7. The composition according to claim 1, wherein the deterioration inhibitor is contained in an amount of 0.01 to 3 parts by weight. 8 Conventionally known stabilizers, dispersants, plasticizers, antistatic agents,
The composition according to claim 1, further comprising a filler or a pigment.