JPH0627148B2 - 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,
It is impossible to completely prevent No. 11 (August 1974) and the like. Therefore, attempts have been made to use calcium stearate, various aromatic compounds and the like as voltage stabilizers. The additive bleeds out, and there is a problem in long-term performance retention (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 excellent ethylene copolymer crosslinked products such as dielectric breakdown characteristics, long-term performance retention, flexibility, and no metal catalyst residue. We succeeded in developing a crosslinked ethylene copolymer having excellent properties that satisfy the above requirements.

That is, the present invention relates to ethylene and general formula (I), (Wherein R ¹ represents H or —CH ₃ , and R ² represents a C _1-15 halogenated alkyl, respectively) and the halogenated alkyl ester of an ethylene type α, β unsaturated acid Alkyl ester group unit is 0.005-1
A cross-linked product obtained by heat-crosslinking or random-beam cross-linking a random copolymer containing 0 mol% in the presence of a chemical cross-linking agent, said cross-linking being determined by the measuring method specified in JIS C3005. It is intended to provide a crosslinked ethylene copolymer for electrical insulation, which has a gel fraction of 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 ¹ represents H or —CH ₃ , and R ² represents a C _{1 to 15} alkyl halide.) Halogenated alkyl ester of ethylene type α, β unsaturated acid (monomer) And a copolymer represented by the formula (I): 0.005 to 10 mol%, preferably 0.005 to 5 mol%
It contains about mol%.

Examples of the monomer represented by the general formula (I) include R
² is dibromomethyl, dichloromethyl, trifluoroethyl, difluoromethyl, trichloroethyl, tribromoethyl, triiodide, monofluoroethyl, monochloroethyl, monochloromethyl, monofluoromethyl, monobromomethyl, trifluoromethyl, trichloromethyl , Tribromomethyl, methyl triiodide, tetrafluoroethyl, tetrachloroethyl, tetrabromoethyl, pentafluoroethyl, pentachloroethyl,
Pentabromoethyl, pentafluoropentadecanyl,
Pentachlorotridecanyl, heptafluorodecanyl,
Examples thereof include groups such as heptadecyl fluorodecanyl, heptadecyl chlorodecanyl, hexafluorononyl, and heptadecyl chlorodecanyl.

As the halogen atom of R ² of the monomer represented by the general formula (I), F, Cl, Br and I are used.
Alternatively, Cl is preferable, and one having F is particularly preferable.

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

The ethylene copolymer used in the present invention may contain other monomers for modifying the resin in addition to ethylene and the monomer represented by the general formula (I), and the modifying monomer is 10 mol%. Can be included. As the modifying comonomer, a monomer known to be capable of ethylene copolymerization can be used.

For example, vinyl acetate, vinyl propylene oxide, and other vinyl esters, ethyl acrylate, methyl acrylate, butyl acrylate, and other acrylic acid esters, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and other methacrylic acid esters, acrylic acid, methacrylic acid, and other ethylene esters. They are 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 resin, other thermoplastic resins such as polyethylene and polypropylene ethylene-vinyl acetate copolymer, which are commonly used for resin materials of this type, are used. It can be used by blending with polymers, etc., petroleum resin, wax, stabilizer, antistatic agent, antiaging agent, voltage stabilizer, carbon black, UV absorber, synthetic rubber or natural rubber, lubricant, inorganic It is also possible to mix and use a filler and the like.

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 which is 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 activity is larger than that of ethylene, the monomer represented by the general formula (I) is usually polymerized in an ethylene state containing 0.001 to 4 mol%, preferably 0.001 to 2 mol% based on the total amount in the polymerization system. Let

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 0.5-30
About wt% 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 fatty acid 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 used as it is after being separated from the monomer by a separator according to a conventional method of high pressure radical polymerization.
Various post-treatment steps, such as those already used for products obtained by the high-pressure radical polymerization method, 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. This crosslinking can be carried out by adding 0.5 to 4 parts by weight, preferably 1 to 3 parts by weight of a normal chemical crosslinking agent to 100 parts by weight of the ethylene copolymer, or cobalt 60 or a linear accelerator. Electron beam cross-linking may be performed by irradiating with about 5 to 20 megarads, or the ethylene copolymer may be cross-linked with a vinyl monomer having an alkoxysilane such as vinyltrimethoxysilane in advance or afterwards. You can also let it. 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) hexane-3, benzoyl peroxide, etc. which are usually used as chemical cross-linking 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 alkyl ester group unit of 0.005
-10 mol%, preferably 0.005-5 mol%. The crosslinked product has a gel fraction of 40% or more determined by the measuring method specified in JIS C3005.
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 an agitated autoclave type continuous reactor with an internal volume of 1.5, ethylene was dissolved in ethyl acetate at a rate of 40 kg / hr and trifluoroethyl acrylate (abbreviated as TFEA) at a rate of 500 g / hr. 0.17 / hour, propylene / 560 / hour, tert-butyl peroxyisobutyrate as a catalyst, a solution of n-hexane dissolved at a rate of 2 g / hour was continuously supplied at a rate of 570 m / hour, and the polymerization pressure was 2400 kg / cm. ^2. Polymerization was carried out at a polymerization temperature of 220 ° C. to prepare an ethylene copolymer.

The obtained ethylene copolymer has MFR = 2.6 g / 10
Minutes, the number average molecular weight was 20,300, and the content of TFEA in the polymer was 0.29 mol%.

Reference Example 2 Using the same reactor as in Reference Example 1, TFEA was added at 500 g /
Polymerized in the same manner as in Reference Example 1 except that 2.52 / hour, propylene was 230 / hour, the same catalyst as used in Reference Example 1 was 460 m / hour, and the polymerization temperature was 210 ° C. Then, an ethylene copolymer was produced.

The obtained ethylene copolymer has MFR = 3.0 g / 10
Min, number average molecular weight 19,800, NVI content in the polymer
It was 3.1 mol%.

Reference Example 3 The same reactor as in Reference Example 1 was used, but instead of TFEA, 17 fluorolauryl acrylate was dissolved in ethyl acetate at a rate of 200 g / 100 m / hour, and the polymerization temperature was changed to 223 ° C. Polymerization was carried out in the same manner as in Reference Example 1.

The obtained ethylene copolymer has MFR = 2.0 g / 10
Minutes, the number average molecular weight was 20,600, and the content of 17 fluorolauryl acrylate in the polymer was 0.05 mol%.

Examples 1 to 3 and Comparative Example 1 Samples of ethylene copolymers produced in Reference Examples 1 to 3 and commercially available high-pressure polyethylene "Yukaron ZF30R" [Mitsubishi Yuka Co., Ltd., MFR = 1.0 g / 10 min] The polymer was used as a polymer to evaluate the characteristics of these polymer cross-linked products.

For the production of crosslinked polymer and preparation of samples for property evaluation, the temperature of the Brabender mixer was set to 110 ° C., 100 parts by weight of each sample polymer, 2 parts by weight of dicumyl peroxide as a crosslinking agent, and “ Santonox R ”0.
After adding 3 parts by weight and kneading each for 5 minutes, the kneaded sample was preformed to a thickness of 50 μm and a thickness of 5 mm by a hot plate press kept at 130 ° C., and then these were also hot plate pressed at 180 ° C. and 100 kg. A cross-linked body was obtained by heating and pressurizing at a pressure of / cm ² gauge for 20 minutes.

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: As described above, each molded into a 5 mm thick sheet, 2
It was cut out to 0 mm x 20 mm. 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: 2 sheets each formed into a 5 mm thick sheet as described above.
It was cut into 5 mm x 25 mm. An injection needle with a diameter of 1 mm was inserted into the cut piece in an amount of 20 mm, and then 15 mm was pulled out while injecting distilled water, and an aluminum foil in 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 breakdown characteristics: Impulse high-voltage breakdown characteristics were measured using the respective 50 μm thick sheets molded as described above.

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 increased by step-up 2 KV / 3 times, and the voltage at which breakdown was reached was measured.

(9) Nonflammability: The number of oxygen fats was measured according to JIS K7201.

Table 1 shows the evaluation results of the properties of the crosslinked ethylene copolymer.

Examples 4-7, Comparative Examples 2-3 Ethylene copolymers obtained in Reference Examples 1-3 and "Yukaron Z"
"F30R" was used as each sample polymer, and a 6 KV grade, 1 x 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, then 10
KV / 3 step-ups required. Further, the obtained cable was flooded under the conditions of 6 KV and 1 KHz. After the flooding, the insulator was sliced to a thickness of 0.5 mm, boiled, and then the number of votitley in the insulator was measured with an optical microscope at 400 times. In addition, for samples after flooding and charging, 40
After applying KV / 30 minutes, the AC breakdown value (AC breakdown value) was determined under the condition of 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 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 location C08F 220: 22) (72) Inventor Shinichi Irie 6th Hachiman Kaigan Dori, Ichihara, Chiba Furukawa Electric Co., Ltd. Company Chiba Electric Wire Works (72) Inventor Hitoshi Kimura 6th Hachiman Kaigan Dori, Ichihara City, Chiba Furukawa Electric Co., Ltd. Chiba Electric Wire Works

Claims (1)

[Claims] 1. Ethylene and general formula (I), (Wherein R ¹ represents H or —CH ₃ , and R ² represents a C _1-15 halogenated alkyl, respectively) and the halogenated alkyl ester of an ethylene type α, β unsaturated acid Alkyl ester group unit is 0.005-1
A cross-linked product obtained by heat-crosslinking or random-beam cross-linking a random copolymer containing 0 mol% in the presence of a chemical cross-linking agent, said cross-linking being determined by the measuring method specified in JIS C3005. A crosslinked ethylene copolymer for electrical insulation, which has a gel fraction of 40% or more.