JPS6016970B2 - polyolefin formulation - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to stabilized formulations of polyolefins, particularly polyolefin formulations that are resistant to degradation 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. . However, in cases where contact between polyolefin and heavy metals such as copper, iron, and nickel cannot be avoided, such as when coating copper wire with polyolefin, plating polyolefin with heavy metals, and coloring polyolefin with pigments containing heavy metals,
Mere use of the conventional antioxidants provides little resistance to deterioration due to contact between polyolefins and heavy metals.

Furthermore, in cases where there is a risk of liquid amorphous polyolefin coming into contact with copper, such as 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 give polyolefins resistance to deterioration caused by heavy metals, N,N'-dibenzoylhydrazine, N-benzoino-N'-salicyloylhydrazine, N,N'-diphthyrylhydrazine, N , N'-distearoylhydrazine, N,N'-bis[81(3
, 5-di3butyl-4-hydroxyphenyl)propiol]hydrazine, N,N'-bissalicyloylhydrazine, oxalobis(benzylidenehydrazide), N
-Salicylidene-N'-Salicyloylhydrazine, N-
Salicyloyl N'-stearoylhydrazine, N,N
'-bis(para-methylbenzoyl)hydrazine, N,
Anti-deterioration agents such as N-diacetyl dihydrazide, N,N'-distearoyl white acid dihydrazide, and dihexanoylhydrazine have been developed, but the anti-deterioration effects of these agents are still not satisfactory. do not have.

The inventors discovered that 100 parts by weight of polyolefin and N,N
'-Diacetyl fumaric acid dihydrazide 0.001-5
It was found that a blend consisting of parts by weight of polyolefins has excellent stability against deterioration of polyolefins, especially deterioration due to contact with heavy metals, and the present invention was completed based on this finding.

The polyolefin in this invention includes ethylene,
propylene, butene-1, isoptene, pentene-1,
Amorphous or crystalline homopolymers or copolymers of olefins such as 4-methylbentene-1, and alkyl esters of these olefins and unsaturated carboxylic acids, such as methyl acrylate, ethyl acrylate, methyl methacrylate, and methacrylate. Examples include copolymers of vinyl esters of ethyl acid or saturated carboxylic acids, such as vinyl acetate, mixtures of these various polymers, and liquid amorphous polymers such as propylene and butene.

N,N'-diacetyl fumaric acid dihydrazide can be easily obtained, for example, by the following reaction.

The above reaction is carried out in the presence or absence of an organic solvent such as methanol, ethanol, N-dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone, or dioxane at 10 to 170°C, preferably 30 to 130 q○
The process proceeds at a temperature of

To separate N,N'-diacetyl fumaric acid dihydrazide from the reaction product mixture after the reaction, for example, the reaction product mixture is poured into a large excess of water, the solid matter is collected in a furnace, and the collection product is mixed with, for example, methanol, After washing with an organic solvent such as ethanol or acetone, it may be dried under reduced pressure. In this invention, the amount of N,N'-diacetyl fumaric acid dihydrazide added to the polyolefin is 0.001 to 5 parts by weight, preferably 0.0 parts by weight, based on 10 parts by weight of the polyolefin.
The amount is within the range of 1 to 3 parts by weight.

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 method for blending N,N'-diacetyl fumaric acid dihydrazide into the polyolefin may be any method suitable for producing a uniform composition.
For example, you can heat polyolefin to above its melting point on a hot roll and mix N,N'-diacetyl fumaric acid dihydrazide, or you can mix polyolefin and N,N'-diacetyl fumaric acid using various mixers. A method such as mixing with dihydrazide can be applied.

Further, N,Nr-diacetyl fumaric acid dihydrazide can 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 paracrusol, 2,6-di-tert-butylphenol, 4,4
-methylenebis(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) ), 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-ditert-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-
Phenolic compounds such as ethyl-6-tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, didodecyl-3,3-thiodidi Dialkyl-3,3-thiodipropionic acid esters such as propionic acid ester, dioctadecyl-3,3'-thiodipropionic acid ester, and organic compounds such as trilauryl phosphite, trilauryl trithiophosphite, tris(nonylphenyl) phosphite, etc. Examples include phosphorus compounds.

Next, an experimental example of the synthesis of N,N'-diacetyl fumaric acid dihydrazide will be shown.

Synthesis Experiment Example Synthesis of N,N'-diacetyl fumaric acid dihydrazide 5.0 ml of fumaric acid dihydrazide (decomposition temperature 220oC) was added to 200 ml of methanol. did.

To this solution, 7.0 g of acetic anhydride 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 matter was collected in an oven, washed with methanol, and dried under reduced pressure to obtain N,N'-diacetyl fumaric acid dihydrazide 6, which is a white crystal with a melting point of 350 qo.
．． I got 0 nights. The elemental analysis values of this crystal were as follows. Elemental analysis value (%) C, 42.07; day, 5.24: N, 24.60 C8 day, calculated value as 2N404 (%) C, 42.11: day, 5.26; N, 24.56 The crystals were indestructible or elutriated when heated in carbon tetrachloride, chloroform, benzene, dichlorobenzene, methylene chloride, methyl acetate, methanol, and ethanol.

The infrared absorption spectrum of this crystal was as shown in the figure. Next, Examples and Comparative Examples will be shown. In Examples and Comparative Examples, parts indicate parts by weight, and M. 1. is ASTM D1
Figure 2 shows the melt flow index measured according to 238. Further, the symbols in the comparative examples mean the following deterioration inhibitors. a; N,N'-dibenzoylhydrazine b; N-benzoyl-N'-salicyloylhydrazine c; N,N'-
Dibutyrylhydrazine d; N,N'-distearoylhydrazine e; N,N'
-bis{B-(3,5-di-tert-butyl-4-hydroxyphenyl)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'-Salicyroylhydrazinek;N
, N'-diacetyl source royal acid dihydrazide 1; N,N
-Distearoyl Toraoh Shiraic Acid Dihydrazide M; Dihexanoylhydrazine Example 1 Powdered additive-free isotactic polypropylene (M.
1.5) 10$ Taiko, Tetrakis [Methyroso 3-(3,
5-di-tert-butyl-4-hydroxyphenyl)propionate] 0.2 part of methane, 0.5 part of distearyl 3,3'-thiodipropionate, 2,6-di-tert-butyl-paracresol 1. N obtained in the foundation and synthesis experiment examples,
0.2 part of N'-diacetyl fumaric acid dihydrazide was premixed with a mixer.

This mixture was heated at a temperature of 190 quarts and a rotation speed of 6 quarts. p. m.
The mixture was poured into a Brabender Plastograph and kneaded 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 silk embedded film was prepared by sandwiching a mesh copper net and pressing at 190° C. using spacers having a thickness of 0.8 ribs. A test piece was prepared by cutting this into a rectangle of 5 x 30 pieces. The above test piece was hung in a gas chamber with an air atmosphere of 150 oo, and the number of days until it formed into arms was measured. The result was 73 days. Comparative Examples 1 to 14 Examples except that N,N'-diacetyl fumaric acid dihydrazide was not added at all or a deterioration inhibitor listed in Table 2 was used instead of N,N-diacetyl fumaric acid dihydrazide. Table 1 shows the results obtained in the same manner as in Example 1.

Table 1 Example 2 Ten parts of a beret made of additive-free high-density polyethylene (M.1.0.30) were heated at 190q0 and at a rotational speed of 6. p. m. After 2 minutes, 0.15 parts of tetrakis[methylene 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane and N obtained in the synthesis experiment example were added. 0.2 part of N'-diacetyl fumaric acid dihydrazide was charged and mixed for an additional 6 minutes.

Next, from this mixture, using a subacer, 190 qo
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 substrate with a thickness of 0.8 ribs was used.
A copper silk embedded film was prepared by pressing at 190:00. This was cut into a rectangle of 1 length x 5 sides 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. '(20q0, atmospheric pressure) The deterioration prevention effect was determined by the method of determining the time (minutes) (induction period).

The result was 170 powders. Comparative Examples 15-28 Except that N,N'-diacetyl fumaric acid dihydrazide was not added at all, or instead of N,N'-diacetyl fumaric acid dihydrazide, the deterioration inhibitor listed in Table 2 was used. Table 2 shows the results obtained using the same machine as in Example 2.

Table 2 Example 3 Low density polyethylene (M.
1.0.25), and the induction period was determined in the same manner as in Example 2, except that the falconry temperature (temperature of Brabender blast graph) was set to 140 oo.

The result was 155 minutes. Comparative Examples 29-42 Except that N,N'-diacetyl fumaric acid dihydrazide was not added at all, or instead of N,N'-diacetyl fumaric acid dihydrazide, the deterioration inhibitor listed in Table 3 was used. Table 3 shows the results obtained in the same manner as in Example 3.

Table 3

[Brief explanation of the drawing]

The figure is an infrared absorption spectrum diagram of N,N'-diacetyl fumaric acid dihydrazide.

Claims (1)

[Scope of Claims] 1. A polyolefin blend comprising 100 parts by weight of polyolefin and 0.001 to 5 parts by weight of N,N'-diacetyl fumaric acid dihydrazide. 2. A formulation according to claim 1, wherein the polyolefin is an ethylene homopolymer, an isotactic polypropylene, an ethylene-propylene copolymer or an ethylene-vinyl acetate copolymer. 3 N,N'-diacetyl fumaric acid dihydrazide is 0
．． 2. A formulation according to claim 1, wherein the amount is 0.01 to 3 parts by weight. 4 Conventionally known stabilizers, dispersants, plasticizers, antistatic agents,
A formulation according to claim 1, further comprising fillers or pigments.