Patent Description:
Cross-linked polyethylene insulating material has many advantages and is currently the most important insulating material for power cables. At present, there is a tendency for cross-linked polyethylene insulated power cables to replace the other cables at various voltage levels. However, the manufacturing process of the cross-linked polyethylene insulating material inevitably introduces impurities, whose amount and size significantly affect working life and operating stability of the cables made of the insulating material. Electrical treeing would easily occur due to the impurities when the cross-linked polyethylene insulating material is used under a strong alternating electric field, causing quickly and early breakdown of the insulating layers of the cables. In most situations, the breakdown of the insulating layers due to electrical tree makes the working life of the cables far less than expected.

In order to improve the working stability and lifetime of the cross-linked polyethylene insulated cables, the most commonly used method in the field is to modify the insulating material. The modification of the cross-linked polyethylene using a voltage stabilizer has a long history. Until now a variety of voltage stabilizers have emerged.

<CIT> discloses a cross-linked polyethylene insulating material for a high voltage direct current cable, whose preparation involves treating low-density polyethylene with dicumyl peroxide and <NUM>,<NUM>'-dihydroxybenzophenone.

Generally, the use of the voltage stabilizer can significantly improve the resistance to electrical treeing in the cross-linked polyethylene insulator, increasing the inception voltage of electrical tree and prolonging the time from the electrical treeing inception to the breakdown of the material.

However, the voltage stabilizers in prior art are usually small molecule additives containing benzene rings and having a certain polarity. Within the range of their effective addition amount, the voltage stabilizers in prior art would lead to increase in dielectric loss tangent and decrease in electrical resistivity of the insulating material. As an insulating material for alternating current (AC) cables, the value of the dielectric loss tangent at <NUM> has to be limited to a standard range, and the smaller the value is, the better the transmission capacity and performance of the AC cables are improved.

At present, relying on the existing technology, it is difficult to improve the resistance to electrical treeing by adding a voltage stabilizer without increasing the dielectric loss of the insulating material, which means that it is difficult to solve the contradiction between the electrical resistance performance and the dielectric loss performance. It is important and significant to design and synthesize a new voltage stabilizer, which, in its effective addition amount, can improve the resistance to electrical treeing, prolong the working life, and improve the insulation resistivity of the insulating material, and can further limit the value of the dielectric loss tangent of the insulating material to a standard range.

An object of the present invention is to overcome the deficiencies in prior art by using a maleic anhydride modified voltage stabilizer whose structural formula is represented by Formula <NUM>:
<CHM>
Also described nerein, but not part or the claimed invention, is.

a method for preparing the maleic anhydride modified voltage stabilizer, including following steps:.

wherein a molar ratio of <NUM>,<NUM>-dihydroxybenzophenone, maleic anhydride, tetrahydrofuran, and catalyst is <NUM>:(<NUM>-<NUM>):(<NUM>-<NUM>):(<NUM>-<NUM>).

Preferably, the catalyst in step (<NUM>) is concentrated sulfuric acid or p-toluenesulfonic acid.

Preferably, in step (<NUM>), stirring time is <NUM>-<NUM> hours(h), and stirring temperature is <NUM>-<NUM>.

The reaction scheme of the preparation method is as follows:
<CHM>.

The present invention provides the use of the maleic anhydride modified voltage stabilizer in a cross-linked polyethylene AC cable insulating material.

In particular, the present invention provides a cross-linked polyethylene AC cable insulating material as defined in the appended claims, which comprises the maleic anhydride modified voltage stabilizer of formula I.

The cross-linked polyethylene AC cable insulating material of the present invention comprises the following components by mass: 100phr of low-density polyethylene, <NUM>-<NUM>. 2phr of a maleic anhydride modified voltage stabilizer, <NUM>-<NUM>. 5phr of an antioxidant, and <NUM>-<NUM>. 2phr of an initiator. The low-density polyethylene has a melt index of <NUM>-<NUM>/<NUM> at <NUM> and <NUM> load and a density of <NUM>-<NUM>/cm<NUM>.

The maleic anhydride modified voltage stabilizer in the present application is used as a voltage stabilizer in the cross-linked polyethylene AC cable insulating material. The voltage stabilizer has graftable chemical activity and can be grafted onto the cross-linked polyethylene through free radical reaction caused by a cross-linking agent, preventing migration and precipitation of the voltage stabilizer, which can increase the inception voltage of the AC electrical treeing in the cross-linked polyethylene for a long term. As a traditional voltage stabilizer, <NUM>,<NUM>-dihydroxybenzophenone can increase the inception voltage of the electrical treeing to a certain degree. However, <NUM>,<NUM>-dihydroxybenzophenone as the voltage stabilizer can only be simply physically mixed with the cross-linked polyethylene. Moreover, <NUM>,<NUM>-dihydroxybenzophenone is easy to precipitate, so that its long-term effect is difficult to guarantee. In addition, <NUM>,<NUM>-dihydroxybenzophenone has a negative impact on both the insulation resistivity and the dielectric loss tangent of the cross-linked polyethylene AC cable insulating material, resulting in a decrease in resistivity and an increase in dielectric loss tangent. After long-term experimental exploration of various voltage stabilizers, the inventors found that grafting the voltage stabilizer to the polymer macromolecule via a chemical bond can significantly improve the migration resistance of the voltage stabilizer. In addition, the inventors also found that maleic anhydride has a chemical bond with a high polarity, which can introduce a deep charge trap into the polymer, thereby restricting migration and conduction of charge carriers under the electric field, and resulting in significant increase in the electrical resistivity of the cross-linked polyethylene AC cable insulating material.

As a preferred embodiment of the cross-linked polyethylene AC cable insulating material, the antioxidant is antioxidant <NUM>.

As a preferred embodiment of the cross-linked polyethylene AC cable insulating material, the initiator is dicumyl peroxide.

Further, the present invention provides a method for preparing the cross-linked polyethylene AC cable insulating material, including following steps:.

Compared with prior art, the present invention has following beneficial effects. The present invention provides the maleic anhydride modified voltage stabilizer, which is used as a voltage stabilizer in the cross-linked polyethylene AC cable insulating material. In the range of effective addition amount, the maleic anhydride modified voltage stabilizer can improve the resistance to electrical treeing, prolong the working life, and improve the insulation resistivity of the insulating material, and can further limit the value of the dielectric loss tangent of the cross-linked polyethylene AC cable insulating material to a standard range.

In order to better illustrate the objects, technical solutions and advantages of the present invention, the present invention will be further described below with reference to specific embodiments and drawings.

In a first aspect, the present example provides a maleic anhydride modified voltage stabilizer whose structural formula is represented by Formula <NUM>:
<CHM>.

In a second aspect, the present example provides a method for preparing the maleic anhydride modified voltage stabilizer, including the following steps of:.

wherein a molar ratio of <NUM>,<NUM>-dihydroxybenzophenone, maleic anhydride, tetrahydrofuran, and catalyst (concentrated sulfuric acid) is <NUM>:<NUM>:<NUM>:<NUM>.

<FIG> shows an infrared absorption spectrum of the maleic anhydride modified voltage stabilizer. It can be seen from <FIG> that the absorption peaks at <NUM>-<NUM> and <NUM>-<NUM>, respectively, correspond to asymmetric and symmetric stretching vibration absorption of C=O in maleic anhydride. Many similar characteristic peaks can be observed in the spectra of <NUM>,<NUM>-dihydroxybenzophenone and the maleic anhydride modified voltage stabilizer. Except the range of <NUM>-<NUM>-<NUM> corresponding to benzene ring skeleton vibration absorption bonds, the peaks at <NUM>-<NUM> and <NUM>-<NUM> in the spectrum of <NUM>,<NUM>-dihydroxybenzophenone and at <NUM>-<NUM> and <NUM>-<NUM> in the spectrum of the maleic anhydride modified voltage stabilizer are attributed to -OH and C=O which are connected with benzene ring. In addition, the spectrum of the maleic anhydride modified voltage stabilizer has a new peak (<NUM>-<NUM>) corresponding to the ester group C=O, indicating that maleic anhydride was successfully esterified with <NUM>,<NUM>-dihydroxybenzophenone.

<FIG> shows a proton nuclear magnetic resonance spectrum of the maleic anhydride modified voltage stabilizer. It can be known from <FIG> that the peaks between <NUM> ppm and <NUM> ppm are attributed to the chemical shifts of the acid anhydride protons (-CH=CH-). The aromatic protons of the benzene rings resonate around <NUM>, <NUM>, <NUM>, <NUM>, <NUM> and <NUM> ppm, and the peaks around <NUM> and <NUM> ppm belong to O-H. The integrated intensity ratio of the peaks is <NUM>:<NUM>:<NUM>:<NUM>:<NUM>:<NUM>:<NUM>:<NUM>:<NUM>:<NUM>:<NUM>:<NUM>:<NUM>:<NUM>, which is completely consistent with the theoretical value predicted according to structure calculation, confirming that the maleic anhydride modified voltage stabilizer has been successfully synthesized.

wherein a molar ratio of <NUM>,<NUM>-dihydroxybenzophenone, maleic anhydride, tetrahydrofuran, and catalyst (p-toluenesulfonic acid) is <NUM>:<NUM>:<NUM>:<NUM>.

The present example provides a cross-linked polyethylene AC cable insulating material, including the following components by mass: 100phr of low-density polyethylene, <NUM>. 2phr of a voltage stabilizer, <NUM>. 2phr of antioxidant <NUM>, and <NUM>. 5phr of dicumyl peroxide. The low-density polyethylene has a melt index of <NUM>/<NUM> at <NUM> and <NUM> load and a density of <NUM>/cm<NUM>. The voltage stabilizer is the maleic anhydride modified voltage stabilizer in Example <NUM>.

The present example also provides a method for preparing the cross-linked polyethylene AC cable insulating material, including the following steps of:.

The present example provides a cross-linked polyethylene AC cable insulating material, including the following components by mass: 100phr of low-density polyethylene, <NUM>. 2phr of a voltage stabilizer, <NUM>. 5phr of antioxidant <NUM>, and <NUM>. 2phr of dicumyl peroxide. The low-density polyethylene has a melt index of <NUM>/<NUM> at <NUM> and <NUM> load and a density of <NUM>/cm<NUM>. The voltage stabilizer is the maleic anhydride modified voltage stabilizer in Example <NUM>.

The present example provides a cross-linked polyethylene AC cable insulating material, including the following components by mass: 100phr of low-density polyethylene, <NUM>. 2phr of a voltage stabilizer, <NUM>. 4phr of antioxidant <NUM>, and 2phr of dicumyl peroxide. The low-density polyethylene has a melt index of <NUM>/<NUM> at <NUM> and <NUM> load and a density of <NUM>/cm<NUM>. The voltage stabilizer is the maleic anhydride modified voltage stabilizer in Example <NUM>.

The present comparative example provides a cross-linked polyethylene AC cable insulating material, including the following components by mass: <NUM> phr of low-density polyethylene, 2phr of a voltage stabilizer, <NUM>. 4phr of antioxidant <NUM>, and 2phr of dicumyl peroxide. The low-density polyethylene has a melt index of <NUM>/<NUM> at <NUM> and <NUM> load and a density of <NUM>/cm<NUM>. The voltage stabilizer is the maleic anhydride modified voltage stabilizer in Example <NUM>.

The present comparative example also provides a method for preparing the cross-linked polyethylene AC cable insulating material, including the following steps of:.

<FIG> shows infrared absorption spectra of the cross-linked polyethylene AC cable insulating materials of Example <NUM> and Comparative Example <NUM>, which is used to illustrate the cross-linking reaction between the maleic anhydride modified voltage stabilizer and the polyethylene. As can be seen from <FIG>, there are absorption peaks at <NUM>-<NUM> and <NUM>-<NUM> in the infrared spectrum of the cross-linked polyethylene AC cable insulating material of Comparative Example <NUM>, which are produced by unsaturated vinyl of the maleic anhydride modified voltage stabilizer. In the infrared spectrum of the cross-linked polyethylene AC cable insulating material of Example <NUM>, the absorption peaks at <NUM>-<NUM> and <NUM>-<NUM> have disappeared, indicating that during the cross-linking process, the free radicals in the unsaturated vinyl of the maleic anhydride modified voltage stabilizer are bonded to the macromolecular chain of the cross-linked polyethylene via addition reaction. Therefore, the maleic anhydride modified voltage stabilizer used as the voltage stabilizer of the cross-linked polyethylene AC cable insulating material is not easy to migrate or precipitate, and the voltage stabilization effect of the maleic anhydride modified voltage stabilizer can be maintained for a long time.

The present example provides a cross-linked polyethylene AC cable insulating material, including the following components by mass: 100phr of low-density polyethylene, <NUM>. 8phr of a voltage stabilizer, <NUM>. 4phr of antioxidant <NUM>, and 2phr of dicumyl peroxide. The low-density polyethylene has a melt index of <NUM>/<NUM> at <NUM> and <NUM> load and a density of <NUM>/cm<NUM>. The voltage stabilizer is the maleic anhydride modified voltage stabilizer in Example <NUM>.

The present example provides a cross-linked polyethylene AC cable insulating material, including the following components by mass: 100phr of low-density polyethylene, <NUM>. 4phr of a voltage stabilizer, <NUM>. 4phr of antioxidant <NUM>, and 2phr of dicumyl peroxide. The low-density polyethylene has a melt index of <NUM>/<NUM> at <NUM> and <NUM> load and a density of <NUM>/cm<NUM>. The voltage stabilizer is the maleic anhydride modified voltage stabilizer in Example <NUM>.

The present example provides a cross-linked polyethylene AC cable insulating material, including the following components by mass: 100phr of low-density polyethylene, <NUM>. 4phr of antioxidant <NUM>, and 2phr of dicumyl peroxide. The low-density polyethylene has a melt index of <NUM>/<NUM> at <NUM> and <NUM> load and a density of <NUM>/cm<NUM>.

The present example provides a cross-linked polyethylene AC cable insulating material, including the following components by mass: 100phr of low-density polyethylene, <NUM>. 8phr of <NUM>,<NUM>-dihydroxybenzophenone, <NUM>. 4phr of antioxidant <NUM>, and 2phr of dicumyl peroxide. The low-density polyethylene has a melt index of <NUM>/<NUM> at <NUM> and <NUM> load and a density of <NUM>/cm<NUM>.

The inception voltages of electrical treeing of the cross-linked polyethylene AC cable insulating materials of Example <NUM> and Comparative Example <NUM> were tested, and the test results are shown in <FIG>.

Test method: The cross-linked polyethylene AC cable insulating materials of Example <NUM> and Comparative Example <NUM> were cut into <NUM>*<NUM>*<NUM> samples. Each sample was placed in a vacuum oven at <NUM> for degassing, accelerating precipitation and volatilization of the small molecular components from the sample. After degassing for <NUM>, the same tungsten needle electrode was inserted into the sample to form a need-plate electrode structure, by using which the inception voltage of electrical treeing of each sample was measured at a 500V/s boosted alternating voltage with a mains frequency. <NUM> samples were tested for each material, and the Weibull distribution statistical analysis was performed on the test results.

<FIG> shows the Weibull distribution plots of the inception voltages of electrical treeing of the cross-linked polyethylene AC cable insulating materials of Example <NUM> and Comparative Example <NUM>. As can be seen from <FIG>, the cross-linked polyethylene AC cable insulating material of Example <NUM> has a significantly higher electrical treeing inception voltage at the same cumulative failure probability, and has a significantly lower electrical treeing inducing probability under the same voltage. The characteristic electrical treeing inception voltage (scale: <NUM>. 256kV) is about <NUM>% higher than that of the unmodified comparative material (<NUM>. It is thus proved that the maleic anhydride modified voltage stabilizer of the present invention can significantly improve the resistance to electrical treeing. Even through a long-term degassing at a high temperature, the excellent performance of the maleic anhydride modified voltage stabilizer would not be affected. The increase in the electrical treeing inception voltage guarantees the long-term working stability and longer working life of the cross-linked polyethylene AC cable insulating material.

The values of dielectric loss tangent of the cross-linked polyethylene AC cable insulating materials of Examples <NUM>-<NUM> and Comparative Examples <NUM>-<NUM> were tested, and the test results are shown in <FIG> and <FIG>.

Test method: The cross-linked polyethylene AC cable insulating materials of Example <NUM>-<NUM> and Comparative Examples <NUM>-<NUM> were cut into <NUM>*<NUM>*<NUM> samples, and the values of dielectric loss tangent of the samples at different frequencies were measured.

<FIG> shows the values of dielectric loss tangent of the cross-linked polyethylene AC cable insulating materials of Examples <NUM> to <NUM> and Comparative Example <NUM>. <FIG> shows the values of dielectric loss tangent of the cross-linked polyethylene AC cable insulating material of Comparative Example <NUM>. It can be seen from <FIG> and <FIG> that the value of dielectric loss tangent of the cross-linked polyethylene AC cable insulating material of Comparative Example <NUM> at <NUM> is <NUM>; the value of dielectric loss tangent of the cross-linked polyethylene AC cable insulating material of Comparative Example <NUM> at <NUM> is <NUM>; the values of dielectric loss tangent of the cross-linked polyethylene AC cable insulating materials of Example <NUM>, Example <NUM>, and Example <NUM> at <NUM> are respectively <NUM>, <NUM>, and <NUM>. The above test results show that the addition of <NUM>. 8phr of the traditional voltage stabilizer <NUM>,<NUM>-dihydroxybenzophenone significantly increases the value of dielectric loss tangent of the cross-linked polyethylene AC cable insulating material from <NUM> to <NUM>, exceeding a basic requirement of less than <NUM> stipulated by a national standard. By using the maleic anhydride modified voltage stabilizer synthesized by the present invention as the voltage stabilizer in the effective addition range (<NUM>-<NUM>. 2phr) to increase the inception voltage of the electrical treeing in the cross-linked polyethylene AC cable insulating materials, the values of dielectric loss tangent of the prepared cross-linked polyethylene AC cable insulating materials are all less than the requirement of ≤<NUM> stipulated by the national standard with sufficient margin. Thus, the new voltage stabilizer synthesized by the present invention and the graft-modified cross-linked polyethylene insulating material prepared therefrom have relatively low dielectric loss.

The maleic anhydride modified voltage stabilizer of the present invention has a high polarity carbonyl group in its structure. After the cross-linking reaction between the maleic anhydride modified voltage stabilizer and the polyethylene material, a deep, evenly distributed charge trap is formed. Under the action of the charge trap, the resistivity of the cross-linked polyethylene AC cable insulating material increases, and the leakage current decreases. The dielectric loss of the cross-linked polyethylene AC cable insulating material under an alternating voltage is caused by current leakage on the one hand and by relaxation polarization on the other hand. Although the structure of the maleic anhydride modified voltage stabilizer has the high polarity carbonyl group, which may increase relaxation polarization, the molecular structure of the maleic anhydride modified voltage stabilizer of the present invention has a relatively small contribution to the relaxation polarization behavior at <NUM> but a more obvious inhibitory effect on current leakage, thus decreasing the dielectric loss tangent value of the material at <NUM>, which still meets the requirement of less than <NUM> at <NUM> stipulated by the standard.

The electrical conductivities of the cross-linked polyethylene AC cable insulating materials of Examples <NUM>-<NUM> and Comparative Example <NUM> were tested, and the test results are shown in <FIG>.

Test method: The cross-linked polyethylene AC cable insulating materials of Example <NUM>-<NUM> and Comparative Example <NUM> were cut into <NUM>*<NUM>*<NUM> samples, and the electrical conductivities of the samples at different strengths of electric field were measured.

<FIG> shows the electrical conductivities of the cross-linked polyethylene AC cable insulating materials of Examples <NUM>-<NUM> and Comparative Example <NUM> at different strengths of electric field. It can be seen from <FIG> that the electrical conductivities of the cross-linked polyethylene AC cable insulating material of Examples <NUM>-<NUM> are significantly lower than that of the cross-linked polyethylene AC cable insulating material of Comparative Example <NUM>; that is, the cross-linked polyethylene AC cable insulating material of the present invention has a higher electrical resistivity, which also reveals that the dielectric loss of the cross-linked polyethylene AC cable insulating material is decreased by the high polarity carbonyl group in the structure of the maleic anhydride modified voltage stabilizer via the mechanism of reducing the leakage current.

Claim 1:
A cross-linked polyethylene AC cable insulating material, comprising following components by mass:
100phr of low-density polyethylene,
<NUM>-<NUM>.2phr of a maleic anhydride modified voltage stabilizer,
<NUM>-<NUM>.5phr of an antioxidant, and
<NUM>-<NUM>.2phr of an initiator;
wherein the low-density polyethylene has a melt index of <NUM>-<NUM>/<NUM> at <NUM> and
<NUM> load and a density of <NUM>-<NUM>/cm<NUM>;
the maleic anhydride modified voltage stabilizer has a structural formula represented by Formula <NUM>:
<CHM>