JPH0627142B2 - Crosslinked ethylene copolymer for electrical insulation - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a crosslinked ethylene copolymer for electrical insulation.

The crosslinked product of the present invention has excellent impulse fracture resistance and A
In addition to the C breakdown characteristic, it is particularly excellent in water tree characteristics, and is industrially useful as a material for electric power cables that can prevent electrical deterioration (water tree deterioration) during actual use.

Prior art Crosslinked polyethylene based on low density polyethylene has excellent electrical properties and heat resistance, so CV
It is widely used as a cable insulating material, but dielectric breakdown occurs under ultra-high voltage, and higher performance materials are required.

For this reason, many studies have been conducted to improve the dielectric breakdown characteristics under ultrahigh voltage.

For example, the presence of impurities such as holes, water, and metal causes the concentration of electric charges, which lowers the dielectric breakdown characteristics. Therefore, as a material for ultrahigh-voltage cables, impurity removal technology is being investigated, and 100 μ or more. Clean polyethylene that does not contain contaminants and dry cross-linking technology that does not create voids have been developed. 275 by making full use of these technologies
Even KV cables have come into practical use.

However, insulation deterioration such as water tree deterioration after long-term use under high voltage (for example, Technical Report of the Institute of Electrical Engineers of Japan, Part I,
No. 11 (August 1974)) and the like cannot be completely prevented. Therefore, attempts have been made to use calcium stearate, various aromatic compounds, etc. as voltage stabilizers, but methods using these additives Has a problem in long-term performance retention due to additive bleed-out (for example, Japanese Patent Publication No. 48-24809, West German Patent No. 124).
8773 specification, French patent 1446401 specification etc.).

SUMMARY OF THE INVENTION In view of these circumstances, the present inventors have focused on the development of an excellent ethylene copolymer crosslinked product such as dielectric breakdown properties, long-term performance retention, flexibility, and no metal catalyst residue, We have succeeded in developing an ethylene copolymer cross-linked product with various characteristics.

That is, the present invention relates to ethylene and general formula (I), (In the formula, R is H or —CH ₃ , X is a halogen atom,
Y is a C _4-18 alkyl group, n is 0 or 1 and m is 1 to
4 is an integer of 1 to 4, and 1 is an integer of 1 to 4, respectively), and the ester group unit is 0.001 with a halogenated alkylated phenyl ester of an ethylene type α, β unsaturated acid represented by
A cross-linked product obtained by heat-crosslinking or random-beam cross-linking a random copolymer containing 5 to 10 mol% in the presence of a chemical cross-linking agent, which was determined by the measuring method specified in JIS C3005. It is intended to provide a crosslinked ethylene copolymer for electrical insulation, wherein the gel fraction of the crosslinked product is 40% or more.

EFFECTS OF THE INVENTION The crosslinked ethylene copolymer for electrical insulation of the present invention is excellent in withstand voltage characteristics, long-term insulation deterioration prevention characteristics (water tree deterioration prevention characteristics), flexibility, molding processing characteristics, etc. It exhibits extremely excellent performance as an insulating material for power cables.

DETAILED DESCRIPTION OF THE INVENTION The ethylene copolymer used in the present invention is a novel ethylene copolymer which has not been described in the literature.
(I), (In the formula, R is H or —CH ₃ , X is a halogen atom,
Y is a C _4-18 alkyl group, n is 0 or 1 and m is 1 to
4 is an integer of 1, and 1 is an integer of 1 to 4, respectively), and is a copolymer of a monomer represented by the general formula (I) in an amount of 0.005 to 10 mol%. , Preferably about 0.005 to 5 mol%.

Examples of the monomer represented by the general formula (I) include dibromononylphenyl methacrylate, dichlorononylphenyl methacrylate, dibromooctylphenyl methacrylate, dichlorooctylphenyl methacrylate, dibromostearylphenyl methacrylate, dichlorostearylphenyl methacrylate. Methacrylate, dibromononyl phenyl acrylate, dichlorononyl phenyl acrylate, dibromooctyl phenyl acrylate, dichlorooctyl phenyl acrylate, dibromostearyl phenyl acrylate, tribromononyl methacrylate, tribromononyl acrylate, tribromostearyl methacrylate, tribromostearyl Acrylate, bromodinonylphenyl methacrylate, bromodioctylphenyl Methacrylate, bromo dioctyl phenylalanine acrylate, difluoro nonylphenyl methacrylate, nourishment of nonylphenyl methacrylate, dibromo nonyl benzyl methacrylate, dichloro nonyl benzyl methacrylate.

Among the monomers represented by the general formula (I), the halogen atom is C
1 or Br is preferable, and Br is particularly preferable.

The polymer structure of the ethylene copolymer is preferably a random copolymer.

The ethylene copolymer used in the present invention can be modified by adding another monomer for modifying the resin in addition to ethylene and the monomer represented by the general formula (I). The modifying monomer is up to 10 mol%. Can be included. As the modifying comonomer, a monomer known to be copolymerizable with ethylene can be used.

For example, vinyl esters such as vinyl acetate and vinyl propionate, acrylic esters such as ethyl acrylate methyl acrylate and butyl acrylate, methacrylic acid esters such as methyl methacrylate, ethyl methacrylate and butyl methacrylate, ethylene such as acrylic acid and methacrylic acid. α, β unsaturated acids.

The above-mentioned novel ethylene copolymer used in the present invention has a number average molecular weight of 1,000 or more. When the molecular weight is less than 1000, long-term performance is deteriorated. The molecular weight is preferably 3000 or more.

Since the ethylene copolymer used in the present invention falls within the category of thermoplastic resins, other thermoplastic resins such as polyethylene, polypropylene and ethylene-vinyl acetate are commonly used for resin materials of this type. It can be used by blending with copolymers, petroleum resin, wax, stabilizer, antistatic agent, antiaging agent,
A voltage stabilizer, a carbon black, an ultraviolet absorber, a synthetic rubber or a natural rubber, a lubricant, an inorganic filler and the like can be blended and used.

The ethylene copolymer used in the present invention is produced by subjecting a predetermined monomer to copolymerization conditions,
It can be produced by a known high-pressure polyethylene production apparatus by radical polymerization.

This polymerization is preferably carried out continuously. As the polymerization apparatus, a continuous stirring tank reactor or a continuous tube reactor generally used in the high pressure radical polymerization method of ethylene can be used.

In the ethylene copolymer used in the present invention, ethylene and the monomer represented by the general formula (I) are supplied to the above-mentioned polymerization apparatus and radical-polymerized in the presence of the above-mentioned catalyst. In this case, the proportion of ethylene and the monomer represented by the general formula (I) is appropriately selected so as to obtain an ethylene copolymer having a desired composition, but the polymerization of the monomer represented by the general formula (I) Since the ability is higher than that of ethylene, the amount of the monomer represented by the general formula (I) is usually 0.0015 based on the total amount in the polymerization system.
Polymerization is carried out in the form of ethylene containing 3 to 3 mol%, preferably 0.0015 to 2 mol%.

It employed the polymerization pressure is a pressure exceeding 500 kg / cm ^2, preferably in the range of 1000~4000kg / cm ^2. The polymerization temperature is at least 120 ° C, but preferably in the range of 150 to 300 ° C.

The polymer formed in one or more reactors can be separated from the unreacted monomer and processed as in conventional high pressure polyethylene manufacture. The unreacted monomer mixture is mixed with an additional amount of the same monomer,
Repressurize and circulate in reactor. The additional amount of monomer added as described above is of a composition that restores the composition of the mixture to the original composition of the polymerization system, and generally this additional amount of monomer was separated from the polymerization vessel. It has a composition almost corresponding to that of the polymer.

In the above-mentioned method, the reactor is preferably a tank reactor in order to obtain an ethylene copolymer having a uniform composition.

The catalyst is usually dissolved in a solvent having a small chain transfer effect and directly injected into the reactor by a high pressure pump. Concentration is 0.5-3
About 0% by weight is desirable.

Suitable solvents include, for example, hexane, heptane, white spirit, hydrocarbon oils, cyclohexane, toluene, higher branched saturated fatty acid hydrocarbons, and mixtures of these liquids.

Further, in injecting the monomer represented by the general formula (I), it is dissolved alone or in a solvent having a small chain transfer effect,
Inject directly into the reactor with a high-pressure pump. Examples of the solvent include aromatic compounds such as ethyl benzoate, toluene and methyl benzoate, and aliphatic esters such as ethyl acetate.

In the high-pressure radical polymerization, a chain transfer agent is generally used for adjusting the molecular weight except for a special case.

In the above method, as the chain transfer agent, all chain transfer agents used in ordinary high pressure radical polymerization can be used.

These gaseous substances are injected into the suction side of the compressor, and liquid substances are injected into the reaction system by a pump.

The ethylene copolymer produced in the reactor and used in the present invention may be separated from the monomer in a separator and used as it is according to a conventional method of high-pressure radical polymerization method. Various post-treatment steps, such as those used in the product obtained according to, may be carried out.

The ethylene copolymer thus obtained is used alone or with a thermoplastic resin such as polyethylene and ethylene-vinyl acetate copolymer, particularly a composition with an ethylene-based thermoplastic resin is crosslinked to form a crosslinked product. The cross-linking is carried out by adding an ordinary chemical cross-linking agent in an amount of 0.5 to 4 per 100 parts by weight of the ethylene copolymer.
1 part by weight, preferably 1 to 3 parts by weight may be blended, and may be irradiated with about 5 to 20 megarads of cobalt 60 or a linear accelerator for electron beam crosslinking, or an ethylene copolymer. It is also possible to crosslink a copolymer of a vinyl monomer having an alkoxysilane such as vinyltrimethoxysilane in advance or afterwards. When used for an electric cable, it is preferable to use the chemical crosslinking method among the above.

As the chemical cross-linking agent, for example, the following free radical generators can be used. Specifically, dicumyl peroxide, t-butyl cumyl peroxide, 2,5-
Dicumyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexene-3, benzoyl peroxide, etc. which are usually used as chemical crosslinking agents Is.

The crosslinked product of the present invention obtained as described above contains a copolymer of ethylene and a monomer represented by the general formula (I), and the crosslinked product has a halogenated alkylated phenyl ester group unit. 0.005-10 mol%, preferably 0.005-
5 mol% is included. The crosslinked product is JI
The gel fraction obtained by the measuring method specified by S C3005 is 40% or more. If the gel fraction is smaller than this value, the heat deformation rate obtained by the above-mentioned measurement method becomes large, which is a practical problem.

Experimental Example Reference Example 1 Using a stirring type autoclave type continuous reactor having an internal volume of 1.5, ethylene was added at 30 kg / hr, and dibromononylphenyl methacrylate (abbreviated as DBNPMA) was added at 100%.
What was dissolved in toluene at a ratio of g / 900 ml /
At this time, propylene is 400 / hour, and n-at a rate of 1 g of tert-butyl peroxyisobutyrate as a catalyst /
A solution dissolved in hexane was continuously supplied at a rate of 800 ml / hour, and polymerization was carried out at a polymerization pressure of 2600 kg / cm ² and a polymerization temperature of 220 ° C. to produce an ethylene copolymer.

The obtained ethylene copolymer has an MFR of 2.7 g / 10.
Min, number average molecular weight 20,100, DBNP in polymer
The MA content was 0.07 mol%.

Reference Example 2 Using the same reactor as in Reference Example 1, 100 g of DBNPMA
What was dissolved in toluene at a ratio of / was 9.7 /
At this time, without using propylene, a solution obtained by dissolving the same catalyst as used in Reference Example 1 in n-hexane at a rate of 5 g / 850 was prepared.
Polymerization was carried out in the same manner as in Reference Example 1 except that the polymerization temperature was ml / hour and the polymerization temperature was 218 ° C. to produce an ethylene copolymer.

The obtained ethylene copolymer has an MFR of 4.0 g / 10.
Min, number average molecular weight 18,900, DBNP in polymer
The MA content was 0.75 mol%.

Examples 1 and 2, Comparative Example 1 Ethylene copolymers produced in Reference Examples 1 and 2 and commercially available high-pressure polyethylene "Yukaron ZF30R" (Mitsubishi Yuka Co., Ltd., MFR = 1.0 g / 10 min) were used. The polymer was used as a sample polymer to evaluate the characteristics of these polymer cross-linked products.

The measuring method used for this characteristic evaluation is as follows.

(1) Molecular weight: By gel permeation chromatography.

(2) Comonomer content: By infrared spectroscopy.

(3) MFR: JIS K6760 (4) Density: JIS K6760 (5) Gel fraction: JIS C3005 (6) Electrical tree characteristics: Each 5 mm thick sheet was cut into 20 mm x 20 mm under the conditions described below. . A needle having a diameter of 1 mm and a tip radius of curvature of 5 μ was inserted into the cut piece by 15 mm. On the other hand, a silver paste was applied to the surface opposite to the side where the needle was inserted to prepare a test piece (see FIG. 1).

An alternating voltage was applied to this test piece at a boosting rate of 500 V / sec, and the generation start voltage of the electrical tree was measured.

(7) Water tree characteristics: Sheets each having a thickness of 5 mm were cut into 25 mm x 25 mm pieces under the conditions described below. An injection needle having a diameter of 1 mm was inserted into the cut piece in an amount of 20 mm, and then it was pulled out by 15 mm while injecting distilled water. An aluminum foil having a width of 10 mm was attached to the side surface opposite to the side where the injection needle was inserted to obtain a test piece. (See Figure 2).

After applying an alternating voltage of 60 Hz and 10 KV to this test piece for 50 hours, the growth average length of the water tree was observed with an optical microscope.

(8) Impulse high-voltage fracture characteristics: Impulse high-voltage fracture characteristics were measured using each press-molded sample having a thickness of 50 μm described later.

For the measurement, a negative standard impulse voltage was used, application was started from a voltage of about 50% of the expected breakdown level, the voltage was boosted by step-up 2 KV / 3 times, and the voltage at which breakdown was reached was measured.

(9) Nonflammability: The oxygen index was measured according to JIS K7201.

The production of the crosslinked polymer and preparation of a sample for property evaluation were carried out by setting the temperature of the Brabender mixer at 110 ° C., 100 parts by weight of each sample polymer, 2 parts by weight of dicumyl peroxide as a crosslinking agent, and “ Santonox R "
Add 0.3 parts by weight and knead each for 5 minutes, and heat the kneaded sample to 50 ° C with a hot plate press kept at 130 ° C.
After preforming to a thickness of μm and a thickness of 5 mm, these were also pressed with a hot plate press at 180 ° C. and 100 kg / cm ² gauge pressure for 20 minutes.
It was heated and pressed for a minute to form a crosslinked body.

Using the crosslinked product, the above-mentioned test piece was prepared and the properties of the crosslinked product were evaluated. The results are shown in Table 1.

Examples 3-5, Comparative Examples 2-3 The ethylene copolymers obtained in Reference Examples 1-2 and "Yukaron Z"
"F30R" was used as a sample polymer, and a 6 KV grade, 1 × 250 mm ² crosslinked polyethylene insulated cable (insulation thickness 3.5 mm) was prepared at the compounding ratio shown in Table 2. An extrusion type semiconductive layer compound was used for the inner and outer semiconductive layers.

Immediately after manufacturing, an impulse breakdown test was performed on the obtained cable. Breakdown voltage is 200KV / 3 times after application, 1
It was determined by stepping up 0 KV / 3 times. Further, the obtained cable was flooded under the conditions of 6 KV and 1 KHz. After inundation and application of electricity, slice the insulator to a thickness of 0.5 mm and boil it.
The number of occurrences of boutite trie in the insulator was measured with an optical microscope at 400 times. Further, for the sample after the immersion in electricity, the AC breakdown value (AC breakdown value) was obtained under the conditions of 40 KV / 30 minutes application and 5 KV / 30 minutes step-up.

From the results shown in Tables 1 and 2, the cross-linked product of the present invention has excellent impulse breakdown resistance and AC breakdown resistance, as well as water tree characteristics and bow tie tree characteristics that are important as insulating materials for high voltage power cables. Is particularly excellent and is apparently useful for electrical insulation.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows a second test piece used for measuring electrical tree characteristics.
The figure is a schematic view of a test piece used for measuring water tree characteristics.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical indication C08F 220: 22) (72) Inventor Takeo Shimada 1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Petrochemical Co., Ltd. Company Resin Research Laboratory (72) Inventor Shinichi Irie 6th Yawata Kaigan Dori, Ichihara City, Chiba Furukawa Electric Co., Ltd. Chiba Electric Wire Works (72) Inventor Hitoshi Kimura 6th Hachiman Kaigan Dori, Ichihara City, Chiba Furukawa Electric Co., Ltd. Company Chiba Electric Wire Works (72) Inventor Masaki Matsuki 6th Hachiman Kaigan Dori, Ichihara City, Chiba Furukawa Electric Co., Ltd. Chiba Electric Wire Works

Claims (1)

[Claims] 1. Ethylene and general formula (I), (In the formula, R is H or —CH ₃ , X is a halogen atom,
Y is a C _4-18 alkyl group, n is 0 or 1 and m is 1 to
4 is an integer of 1 to 4, and 1 is an integer of 1 to 4, respectively), and the ester group unit is 0.005 to
A cross-linked product obtained by heat-crosslinking or random-beam cross-linking a random copolymer containing 10 mol% in the presence of a chemical cross-linking agent, said cross-linking being determined by the measurement method specified in JIS C3005. A crosslinked ethylene copolymer for electrical insulation, which has a gel fraction of 40% or more.