JPS6016967B2 - polyolefin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to stabilized compositions of polyolefins, particularly polyolefin compositions that are resistant to degradation due to contact with heavy metals.

Conventional, polyethylene, polyp.

Polyolefins such as pyrene and polybutene have excellent physical and chemical properties and are used in many fields. At that 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. There is. However, in cases where contact between polyolefin and heavy metals such as copper, iron, or nickel cannot be avoided, such as when coating copper wire with polyolefin, plating polyolefin with heavy metals, or coloring polyolefin with pigments containing heavy metals, However, the mere use of the above-mentioned conventional antioxidants shows little resistance to deterioration due to contact between polyolefins and heavy metals.

Furthermore, when there is a risk of contact between the liquid amorphous polyolefin and copper, for example when using the liquid amorphous polyolefin as an insulating oil for cables,
There is a requirement for resistance to deterioration due to contact with copper, but this requirement cannot be met simply by using the conventional antioxidants.

Therefore, in order to give polyolefins resistance to deterioration caused by heavy metals, N,N'-dibenzoylhydrazine, N-benzoyl-N'-cytyloylhydrazine, N,N'-dibutyrylhydrazine, N,N'-
Distearoylhydrazine, N,N'-bis[8-(3
, 5-ditert-butyl-4-hydroxylphenyl)propionyl]hydrazine, N-N'-bissalycyloylhydrazine, oxalobis(benzylidenehydrazide)
, N-salicylidene-N'-salicyloylhydrazine, and other deterioration inhibitors have been developed, but the deterioration prevention effects of these agents are still not satisfactory.

The inventors used 100 parts by weight of polyolefin and the general formula: [where R is an alkyl group having 1 to 4 carbon atoms;
2 is a formula or a group represented by the formula.

It was discovered that a composition consisting of 0.001 to 5 parts by weight of the compound (deterioration inhibitor) represented by Completed the invention of a lever.

The polyolefin in this invention includes ethylene,
Propylene, butene-1, isobutene, pentene-1,
Polyolefin amorphous or crystalline homopolymers or copolymers such as 4-methylbentene-1, alkyl esters of these olefins and unsaturated carboxylic acids, such as methyl acrylate, ethyl acrylate, methyl methacrylate, methacrylate, etc. Examples include copolymers of ethyl acrylate or saturated carboxylic acids with vinyl esters 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.

or [However, R is an alkyl group having 1 to 4 carbon atoms.

] Synthesis can be performed in the same manner when the carboxyl group is substituted at the meta position of the benzene ring. [The reaction represented by formula 11 and {3} is carried out in the presence or absence of a lower alcohol such as methyl alcohol or ethyl alcohol.
0000, preferably at a temperature of 10 to 30°C. Further, for the reactions represented by formulas [2} and '4}, ordinary hydrolysis methods can be used. When hydrolysis is carried out in an aqueous alkali solution such as sodium hydroxide or potassium hydroxide, the hydrolysis proceeds easily at a molecular weight of 10 to 4,000. When hydrolysis is carried out in an aqueous alkali solution, it is necessary to neutralize or acidify the reaction solution by adding an acid after the reaction. In order to isolate the anti-deterioration agent of the present invention from the reaction product mixture after the reaction, for example, the precipitated solid may be collected in a furnace and recrystallized with water. Specific examples of suitable deterioration inhibitors in this invention include N-acetyl-N'-(paracarboxybenzoyl)hydrazine, N-propionyl-N'-(paracarboxybenzoyl)hydrazine,
N-butyryl N'-(paracarboxybenzoyl)
Examples thereof include hydrazine, N-valeIJ-N'-(para-ruboxybenzoyl)hydrazine, and N-acetyl-N'-(meth-ruboxybenzoyl)hydrazine.

In this invention, the amount of the anti-deterioration agent added to the polyolefin is 0.00 parts by weight of the polyolefin 10.
The amount ranges from 0.01 to 5 parts by weight, preferably from 0.01 to 3 parts by weight.

If the amount is less than 0.001 parts by weight, the deterioration preventing agent is not sufficient, and even if the amount is more than 5 parts by weight, no improvement in the deterioration prevention effect is observed. The deterioration inhibitor may be blended into the polyolefin by any method suitable for making a uniform composition, such as by dissolving or dispersing the deterioration inhibitor in a low boiling point solvent, mixing it with the polyolefin, and then removing the solvent by volatilization. Alternatively, methods such as heating the polyolefin to a temperature higher than its melting point on a roll and mixing the above-mentioned deterioration inhibitor, or mixing the polyolefin and the above-mentioned polyolefin using various types of mixers can be applied. In addition, the anti-deterioration agent in this invention includes conventionally known stabilizers, dispersants, plasticizers, antistatic agents, fillers,
It can also be used in combination with pigments.

Known stabilizers include 2,6-di-tert-butyl-para-cresol, 2,6-di-tert-butylphenol, 4,4
'-Methylenepis (2,6-di-tert-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)
butylphenol), 6-(4-hydroxy-3,5-
di-tert-butylanilino)-2,4-bis(n-octylthio)-1,3,5. triaziso, 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'-methylenepis (4-ethyl-6-tert-butylphenol), 1,3,5-trimethyl-2,4,6 tris (3 , 5-di-tert-butyl-4-hydroxybenzyl)benzene, dialkyl-3, Examples include organic phosphorus compounds such as 3-thiodipropionic acid ester, trilauryl phosphite, trilauryl trithiophosphite, and 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 1 N-acetyl-N'-(paracarboxybenzoyl)
Synthesis of hydrazine/methoxycarbonylbenzoylhydrazine (melting point 198.0-199.0oo)5.
8℃ and 3.0℃ of acetic anhydride were added to 8℃ of methanol and heated at 79 to 80℃ for 1 hour.

The precipitated solid was collected in a furnace. The obtained solid was recrystallized with methanol and then dried under reduced pressure to give a melting point of 210.0 to 210.
．． 5.0 qo of white crystals of N-acetyl-N'-(para-methoxycarbonylbenzoyl)hydrazine were obtained. The elemental analysis values of this crystal were as follows.
Elemental analysis value (%) C, 56.16; Sun, 5-11; N, 11.92C, .
Day. Calculated value (%) C as 2N204, 55.93;
Sun, 5.12; N, 11.86 2.0 ml of N-acetyl-N'-(para-methoxycarbonylbenzoyl)hydrazine thus obtained was added to 12 ml of 7% by weight aqueous sodium hydroxide solution, I worshiped the lantern for 10 minutes at ~35oo.

The reaction product mixture was heated in a furnace, and concentrated hydrochloric acid was added to the resulting furnace liquid to make the liquid acidic. The produced solid was collected in a furnace and washed with water.
The obtained solid was recrystallized twice with water and then dried under reduced pressure at 120 oo for 6 hours to obtain N-acetyl-N'-(paracarboxybenzoyl)hydrazine, which is a white crystal with a melting point of 252.0 to 253.0°C. I got 8 evenings. The elemental analysis values of this crystal were as follows. Elemental analysis value (%) C, 54.05; day, 4.52; N, 11.92 C, o
H. Calculated value (%) C as oN204, 54.05;
Sun, 4.54; N, 12.61 Synthesis Experimental Example 2 Synthesis of N-valeryl-N'-(para-carboxybenzoyl)hydrazine/Gular methoxycarbonylbenzoylhydrazine 22.3 days and valeric anhydride 23.7 days In addition to methanol at 300 mA, the mixture was heated at 30 to 3,500 mA for 3 hours, and then left overnight.

The reaction product mixture was poured into 700 cups of water, and the produced solids were collected in a furnace and washed with water. The obtained water-containing solid was dried and then recrystallized with benzene to obtain 27.19 N-valeryl-N-(p-methoxycarbonylbenzoyl)hydrazine as white crystals with a melting point of 168.0 to 169.0°C. The elemental analysis values of this crystal were as follows. Elemental analysis value (%) C, 60.53; Sun, 6.36; N, 10.07 C, 4
Calculated value (%) C as day, 8N204, 60.43;
Sun, 6.47; N, 10.07 1.0 mL of the thus obtained N-bale IJ-N'-(para-methoxycarbonylbenzoyl)hydrazine was added to 6 volumes of a 5% by weight aqueous sodium hydroxide solution. In addition, I prayed for three hours between 30 and 35 pm.

The reaction product mixture was filtered through a furnace, and concentrated hydrochloric acid was added to the resulting furnace liquid to make the liquid acidic. The produced solid was collected in a furnace and washed with water.
After recrystallizing the obtained solid twice with water, 130-135o
Dry under reduced pressure at o for 6 hours, melting point 247.0-248.0
0.8% of white crystals of N'-(paracarboxybenzoyl)hydrazine were obtained. The elemental analysis values of this crystal were as follows. Elemental analysis value (%) C, 58.95; Day, 6.05; N, 10.63C. 3
Calculated value (%) C, 59.09 as day, 6N204:
Sun, 6.05; N, 10.61 Synthesis Experimental Example Synthesis of 3N-acetyl-N-(metal-carboxybenzoyl)hydrazine Dimethyl isophthalate (manufactured by Wako Pure Chemical Industries, Ltd.) 82 minutes and 85% hydration 37 parts of hydrazine and 800 parts of methanol
and reacted under reflux for 6 hours.

After the reaction product mixture was allowed to stand, it was filtered. The obtained furnace liquid was concentrated using a rotary evaporator. The precipitated solid was collected in a furnace and washed with a methanol-water mixed solvent (1:1 volume ratio). After drying the obtained water-containing solid, 800M ethyl ether was added.
After washing with
~131,000 white crystals of metamethoxycarbonylbenzoylhydrazine 17.9% were obtained. The elemental analysis values of this crystal were as follows. Elemental analysis value (%
) C, 55.677; Sun, 5-15; N, 14.43 C
9th,.

Calculated value as N2〇3 (%) ○, 55.74; day, 5
．． 17;N, 14.65 Meta-
Add 3.9 parts of methoxycarbonylbenzoylhydrazine and 2.3 parts of acetic anhydride to 50' of methanol;
We watched the lights for 4 hours at 0-35o0.

The reaction product mixture was poured into 100 ml of water, and the resulting solid was drained and washed with water. The obtained water-containing solid was dried and then recrystallized with a benzene-methanol mixed solvent (15:1 volume ratio) to obtain N-acetyl-N'-(methoxycarbonylbenzoyl), which is a white crystal with a melting point of 149.5 to 150.500. 2.6 ml of hydrazine monohydrate was obtained. The elemental analysis values of this crystal were as follows. Elemental analysis value (%) C, 52.06; Sun, 5-43; N, 11-190,.
Calculated value (%) C, 51.97 as day, 4N205:
Day, 5.51:N, 11.02 1.2 hours of the thus obtained N-acetyl-N'-(methoxycarbonylbenzoyl)hydrazine monohydrate was added to a 7% by weight aqueous sodium hydroxide solution. In addition to 1 at 30-35q○
I worshiped the lights for 0 minutes.

The reaction product mixture was heated in a furnace, and concentrated hydrochloric acid was added to the resulting furnace liquid to make the liquid acidic. The produced solid was collected in a furnace and washed with water.
After recrystallizing the obtained solid twice with water, the temperature was 135-140o.
Dry under reduced pressure at o for 6 hours, melting point 228.5-229.0
0.90% of white crystals of N-acetyl-N'-(methacarboxybenzoyl)hydrazine were obtained. The elemental analysis values of this crystal were as follows. Elemental analysis value (
%) C, 53.95: Day, 4.558; N, 12.55C,
oH. Calculated value (%) C, 54.05 as state 204:
Day, 4.

50:N, 12.61 Next, examples and comparative examples will be shown.

In Examples and Comparative Examples, parts indicate parts by weight, and M.
1. indicates the melt flow index measured according to ASTM D1238. Further, the symbols in Examples and Comparative Examples mean the following deterioration inhibitors. A; N-acetyl-
N'-(para-ruboxybenzoyl)hydrazine B;
N-barre IJ le-N'-(para-ruboxybenzoyl)hydrazine C; N-acetyl-N'-(metal-ruboxybenzoyl)hydrazine a; N,N'-dibesoylhydrazine b; N-benzoyl N'-Salicyroylhydrazine c
;N,N'-dibutyrylhydrazine d;N,N'-distearoylhydrazine e;N,N'
-bis{8-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl}hydrazine f; N,N'-pissalicyloylhydrazine g; N-salicyloyl-N'-steroylhydrazine h: N, N
'-bis(p-methylbenzoyl)hydrazine i;N
, N'-bis(para-methoxybenzoyl)hydrazine j: N,N'-bis(para-acetoxybenzoyl)hydrazine k; oxalobis(benzylidene hydrazide) 1: N-salicylidene-N'-salicyloylhydrazine m; N-stearoyl N′-{8-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl}hydrazine n; 8-(3,5-di-tert-butyl-4-hydroxyphenyl)propionylhydrazine o ; N,N'-dicrotonoylhydrazine p; N-salicyloyl-N'-(para-monomethylbenzoyl)hydrazine q; N-salicyloyl,
RuN'-(para-methoxybenzoyl)hydrazine r
: N-salicyloyl-N'-(para-acetoxybenzoyl)hydrazine s; N-salicyloyl-N'-(para-carboxybenzoyl)-hydrazine t; N,N'-pis(para-carboxybenzoyl)hydrazine u; N,
N'-bis(orthocarboxybenzoyl)hydrazine Examples 1 to 3 Powdered additive-free isotactic polypropylene (M.
1.5) 10 foundation units, tetrakis [methylene 3-(3
,5-di-tert-butyl-4-hydroxyphenyl).

. pionate] 0.2 parts of methane, 3,3'-thiodip.
0.5 parts of distearyl pionate, 2,6-di-tert-butyl-para-cresol 1. The base portion and 0.5 part of the deterioration inhibitor listed in Table 1 were premixed in a mixer. This mixture was heated at a temperature of 190°C and a rotation speed of 6 m. p. The mixture was poured into a Brabender Plastograph (M) and kneaded for 5 minutes. Next, a film having a thickness of 0.5 mm was made from this mixture by pressing at 190 oooo using a substrater. A 60-mesh copper net was sandwiched between the two films created in this way, and a 190-mesh substrate was used with a thickness of 0.8 mm.
A steel silk embedded film was made by pressing with qo. A test piece was prepared by cutting this into a rectangle of 5 sides x 3 sides. The above test piece was hung in a gas oven with an air atmosphere of 15 pi○, and the number of days until it formed arms was measured.

The results are shown in Table 1. Table 1 Comparative Examples 1 to 22 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 using the same aircraft.

Table 2 Examples 4 to 6 Additive-free high-density polyethylene (M.1.0.30) pellets with 10 anchorages at 190oo and rotational speed of 6mm. p. m. After 2 minutes, add 0.15 parts of tetrakis [methylene 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane and the deterioration inhibitor listed in Table 3. 0.2 part was added and kneaded for an additional 6 minutes.

Next, from this mixture, using Subasa, 190q○
A film having a thickness of 0.5 ribs was prepared by pressing with the following steps. A 60-mesh copper silk was sandwiched between the two sheets of furme created in this way, and a 0.8-thick willow substrate was used.
A copper silk embedded film was prepared by pressing at 9000 ml.
This was cut into a rectangle measuring 1 x 5 willows to prepare a test piece. Next, by the oxygen absorption method, that is, when the test piece was heated to 170 qo in an oxygen atmosphere, the relationship between the amount of oxygen absorbed and time was measured, and the amount of oxygen absorbed 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 reaches (2000, atmospheric pressure).

The results are shown in Table 3. Table 3 Comparative Examples 23 to 44 Example 4 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 7 to 9 Low density polyethylene (M
．． 1.0.25) and the kneading temperature (temperature of the Prabender plastograph) was set to 14000.
The induction period was determined in the same manner as in 6.

The results are shown in Table 5. Table 5 Comparative Examples 45 to 66 Example 7 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

Claims (1)

[Claims] 1 100 parts by weight of polyolefin, general formula; ▲ mathematical formula,
A polyolefin composition comprising 0.001 to 5 parts by weight of a deterioration inhibitor, which is a compound represented by ▼. [However, R^1 is an alkyl group having 1 to 4 carbon atoms, and R_
2 is a group represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 2. The composition according to claim 1, wherein the anti-deterioration agent is N-acetyl-N'-(para-carboxybenzoyl)hydrazine. 3. The composition according to claim 1, wherein the polyolefin is an ethylene homopolymer, an isotactic polypropylene, an ethylene-propylene copolymer, or an ethylene-vinyl acetate copolymer. 4. The composition according to claim 1, wherein the deterioration inhibitor is contained in an amount of 0.01 to 3 parts by weight. 5 Conventionally known stabilizers, dispersants, plasticizers, antistatic agents,
The composition according to claim 1, further comprising a filler or a pigment.