CN107418206B - High-dispersion graphene heat-conducting master batch and preparation method thereof - Google Patents
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Abstract
The invention provides a high-dispersion graphene heat-conducting master batch and a preparation method thereof. The graphene master batch effectively solves the problem that graphene is easy to agglomerate, can ensure the uniform dispersion of graphene, and better exerts the excellent heat-conducting property of the graphene.
Description
Technical Field
The invention relates to the field of graphene materials, in particular to a high-dispersion graphene heat-conducting master batch and a preparation method thereof.
Background
The mainstream heat conduction material in the market still mainly comprises aluminum and copper metal or alloy, but the heat conduction coefficient is lower, generally in the range of 300 plus 500W/m.K, and the current graphene and the product thereof have the characteristics of more excellent heat conduction performance and light weight compared with the heat conduction material mainly comprising the traditional aluminum and copper metal or alloy, have huge application prospects in the fields of heat dissipation of rubber tires, heat dissipation of electronic components such as L ED lamp covers and the like, and attract attention and do not break the application.
Graphene is a planar carbon nanomaterial consisting of a layer of carbon atoms, the thinnest two-dimensional material currently known, with a thickness of only 0.335nm, consisting of a hexagonal lattice. Graphene is the thinnest, hardest nanomaterial known to the world, and it is almost completely transparent, absorbing only 2.3% of light; the heat conductivity coefficient is as high as 5300W/m.K, higher than that of carbon nano tube and diamond, and its electron mobility is over 15000cm at normal temp2V.s, higher than carbon nanotube or silicon crystal, and a resistivity of only about 10-6Omega cm, lower than copper or silver, is the material with the smallest resistivity in the world. Because of its extremely low resistivity and high electron transfer rate, it is expected to be used for the development of a new generation of thinner and higher-conduction electronic devices or transistors. However, in practical applications, graphene has a plurality of problems and restriction factors, and the easy agglomeration of graphene is a main obstacle for the research and application of graphene.
Graphene cannot be stably present in a single layer due to strong van der waals interaction force, thermal conductivity of graphene is sharply reduced once the graphene is agglomerated and stacked, and graphene layers are difficult to open once the graphene is stacked, so that re-peeling is required. At present, the dispersibility of graphene is improved through a dispersant, but the conventional dispersant and dispersing means are difficult to achieve the dispersing effect because the graphene is different from common inorganic powder.
Chinese patent application No. 201410042709.8 discloses a graphene modified polypropylene master batch and a preparation method thereof, wherein polypropylene particles are subjected to static graphene dry powder spraying modification, then the modified polypropylene particles and additive components are uniformly mixed and then are fed into a double-screw extruder for melting and mixing, and finally the mixture is extruded through a die head for granulation. According to the invention, the graphene dispersibility is improved by directly performing electrostatic treatment on the graphene dry powder, but the graphene is used as a raw material, so that the raw material cost is increased, and the uniformity of the graphene covering polypropylene particles is reduced along with the consumption of electrostatic charge transfer, so that the later-stage graphene is unevenly distributed in the master batch, and the yield is low.
The invention discloses a resin/graphene conductive plastic master batch and a preparation method and application thereof, wherein the resin/graphene conductive plastic master batch is prepared by heating water, a resin/graphite conductive master batch, a physical foaming agent and an isolating agent in an autoclave and then quickly discharging the heated resin/graphite conductive master batch at low pressure, so that the resin/graphene conductive plastic foaming master batch prepared by an explosion stripping method is obtained. According to the method, graphite is used as a raw material, the problem that graphene is not easy to disperse is solved, and the graphite sheet is peeled off when the graphene permeates into the graphite sheet and expands under the condition of sudden pressure release by utilizing the dissolving capacity of the supercritical physical foaming agent. But the blasting strength is not easy to master, the quality of the obtained graphene is difficult to guarantee, and potential safety hazards exist in the operation process.
Therefore, in order to improve the dispersibility of graphene in the production, processing and use processes, a preparation scheme which can effectively solve the problem that graphene is easy to agglomerate and improve the uniform dispersibility of graphene in a master batch is needed, and the excellent heat-conducting property of graphene can be further better exerted.
Disclosure of Invention
Aiming at the technical defect that graphene in graphene heat-conducting master batch is easy to agglomerate in the prior art, the invention provides the high-dispersion graphene heat-conducting master batch and the preparation method thereof.
In order to solve the problems, the invention adopts the following technical scheme:
a preparation method of a high-dispersion graphene heat-conducting master batch comprises the following specific operation steps:
(1) stripping graphite powder in liquid by adopting a mechanical stripping method, and adding a graphite powder stripping agent in the stripping process to obtain graphene dispersion liquid, wherein the mechanical stripping method comprises any one of screw extruder stripping, ball mill stripping, millstone mill stripping, sand mill stripping, vibration mill stripping and ultrasonic stripping, and the liquid is one or more of water, methanol, ethanol and acetone;
(2) preparing a silicon dioxide aerogel precursor solution by using a silicon source, adding the graphene dispersion solution obtained in the step (1) into the silicon dioxide aerogel precursor solution, uniformly stirring, standing the silicon dioxide aerogel precursor solution at the temperature of 30-80 ℃ for 0.1-24 hours, and adjusting the temperature to 60-70 ℃ to obtain a graphene composite silicon dioxide aerogel precursor solution;
(3) standing the graphene composite silica aerogel precursor solution for 0.5-10 hours, adding aluminum hydroxide colloid, adjusting the pH value to 5-7 to obtain graphene composite silica aerogel precipitate, putting the graphene composite silica aerogel into a drying oven, and drying at the temperature of 60-70 ℃ for 13-20 hours to obtain graphene composite silica aerogel;
(4) grinding and dispersing graphene composite silicon dioxide aerogel into carrier resin, adding a surfactant, uniformly stirring, and extruding and granulating to obtain the high-dispersion graphene heat-conducting master batch.
Preferably, the graphite powder raw material is at least one of crystalline flake graphite, expanded graphite, highly oriented graphite, thermal cracking graphite and graphite oxide.
Preferably, the graphite powder stripping agent is any one of HTAB, TDOC, SDS, PBA, SDBS, DOC, PSS and P-123.
Preferably, the silicon source is any one of ethyl orthosilicate, methyl orthosilicate, propyl silicate and water glass.
Preferably, the carrier resin is one or more of polyethylene resin, polypropylene resin, polystyrene resin, polyamide resin, polysulfone resin and polyether resin;
preferably, the surfactant is at least one of stearic acid, sodium dodecyl sulfate, tween-80, sodium dodecyl benzene sulfonate and an aluminate coupling agent.
Preferably, the silicon source is added into the alcohol solvent, the temperature of the alcohol solvent is set to be 30-60 ℃, the stirring speed is 100--5-5×10-5）。
Preferably, the stirring speed in the step (2) is 200-800 rpm.
A high-dispersion graphene heat-conducting master batch is characterized by being prepared by the method. Graphene is enclosed in silicon dioxide aerogel and then ground into fine particles, so that the problem that graphene is easy to agglomerate is effectively solved, the uniform dispersion of graphene can be guaranteed, and the excellent heat-conducting property of graphene can be better exerted.
In the existing scheme, in the preparation technology of dispersing the graphene modified master batch without a dispersing agent, the graphene has a plurality of problems and restriction factors, and the easy agglomeration of the graphene is a main obstacle for restricting the research and application of the graphene. Once agglomerated and stacked, graphene has a sharp decrease in thermal conductivity. Graphene cannot be stabilized in a monolayer form due to strong van der waals interaction, and needs to be re-exfoliated once a layer stack is difficult to open. At present, the dispersibility of graphene is improved through a dispersant, but the conventional dispersant and dispersing means are difficult to achieve the dispersing effect because the graphene is different from common inorganic powder. In view of the above, the invention provides a method for preparing a high-dispersion graphene heat-conducting master batch, which comprises the steps of adding a graphene slurry peeled off by grinding into a precursor solution of silica aerogel, then gelling, carrying out colloid sealing and drying with aluminum hydroxide, sealing graphene in silica aerogel micropores, then grinding and refining into fine particles, wherein a graphene microstructure is among the silica aerogel micropores, macroscopical particles are large particles attached to the silica aerogel, and then carrying out conventional dispersion and granulation by adding carrier resin to obtain the high-dispersion graphene heat-conducting master batch.
The scheme disclosed by the invention has the advantages of simple preparation process, wide raw material source, no pollution and low cost, and the prepared precursor solution has stable quality, is easy to store and transport and is easy to realize large-scale industrial production.
One typical application is: the high-dispersion graphene heat-conducting master batch disclosed by the invention is added into PPS polyphenylene sulfide by 5%, and the heat-conducting coefficient of the obtained heat-radiating material reaches 2.6W/m.k through high-dispersion stirring, banburying and double-screw extrusion molding. The heat dissipation performance is far higher than that of the method of adding metal aluminum powder and directly adding graphene powder.
The invention provides a high-dispersion graphene heat-conducting master batch and a preparation method thereof, and compared with the prior art, the high-dispersion graphene heat-conducting master batch has the outstanding characteristics and excellent effects that:
1. according to the high-dispersion graphene heat-conducting master batch and the preparation method, the graphene slurry is added with the precursor solution of the silicon dioxide aerogel, then gelation and colloid sealing drying are carried out, the graphene is sealed in the silicon dioxide aerogel and is grinded and refined into fine particles, the microstructure of the graphene is among micropores of the silicon dioxide aerogel, the macro structure is large particles attached to the silicon dioxide aerogel, the dispersion is easy, and the heat-conducting coefficient is high.
2. The scheme is prepared in a pure physical mode, the damage of chemical reaction to the graphene structure is avoided, the obtained product is high in quality, and the pollution to the environment is less.
3. The master batch is convenient to use, can be directly added and used as common master batches in the plastic field, and is widely applied to heat dissipation of high-load rubber tires, heat dissipation of rubber pads, heat dissipation of electronic component joints, heat dissipation of L ED and the like, so that the application of graphene serving as a high-efficiency heat dissipation material in the plastic field is promoted.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
(1) Taking 30 parts by weight of flake graphite powder, stripping the graphite powder in methanol by adopting a ball mill, setting the rotating speed of the ball mill to be 1000 revolutions per minute and the stripping time to be 3 hours, adding 2 parts of a graphite powder stripping agent HTAB in the stripping process, and stripping and crushing the graphite powder by the ball mill to obtain a graphene dispersion liquid;
(2) adding 10 parts by weight of tetraethoxysilane into methanol, setting the temperature of the methanol at 30 ℃ and the stirring speed at 100 rpm, then sequentially adding water and industrial waste acid, and adjusting the pH value to 3 to obtain the silicon dioxide aerogel precursor solution, wherein the molar ratio of tetraethoxysilane to methanol to water to industrial waste acid is 1:5:2:1 × 10-5Then, adding 40 parts by weight of the graphene dispersion liquid obtained in the step (1) into a silicon dioxide aerogel precursor liquid, uniformly stirring at a stirring speed of 200 rpm, standing the silicon dioxide aerogel precursor liquid at the temperature of 30 ℃ for 0.1 hour, and adjusting the temperature to 60 ℃ to obtain a graphene composite silicon dioxide aerogel precursor liquid;
(3) standing the graphene composite silica aerogel precursor solution for 0.5 hour, adding aluminum hydroxide colloid, adjusting the pH value to 5 to obtain graphene composite silica aerogel precipitate, putting the graphene composite silica aerogel into a drying oven, and drying at the temperature of 60 ℃ for 13 hours to obtain graphene composite silica aerogel;
(4) grinding the graphene composite silicon dioxide aerogel, dispersing the ground graphene composite silicon dioxide aerogel into 20 parts by weight of polyethylene resin, adding 0.3 part by weight of stearic acid, uniformly stirring, and granulating by using a double-screw extruder to obtain the high-dispersion graphene heat-conducting master batch.
The graphene heat-conducting master batch obtained in the embodiment is added into PPS polyphenylene sulfide in a proportion of 5%, and heat-conducting performance tests are carried out after mixing, and the main performance is shown in the following table 1, wherein the heat-radiating performance is far higher than that of the master batch added with metal aluminum powder and directly added with graphene powder, and L ED optical lenses, light-scattering elements, high-efficiency heat-radiating elements, light-reflecting and light-diffusing plates and the like are applied.
Example 2
(1) Taking 32 parts by weight of expanded graphite powder, stripping the graphite powder in methanol by adopting a ball mill, setting the rotating speed of the ball mill to be 1500 revolutions per minute and the stripping time to be 3.5 hours, adding 2.5 parts of a graphite powder stripping agent TDOC in the stripping process, stripping and crushing the graphite powder by the ball mill to obtain a graphene dispersion liquid;
(2) adding 15 parts by weight of methyl orthosilicate into ethanol, setting the temperature of the ethanol to be 30-60 ℃, and under the condition that the stirring speed is 100-500 rpm, sequentially adding water and industrial waste acid, and adjusting the pH value to be 3.5 to obtain silicon dioxide aerogel precursor solution, wherein the molar ratio of the methyl orthosilicate to the ethanol to the water to the industrial waste acid is 1:10:4:2 × 10-5Then adding 42 parts by weight of the graphene dispersion liquid obtained in the step (1) into a silicon dioxide aerogel precursor liquid, uniformly stirring at a stirring speed of 300 revolutions per minute, standing the silicon dioxide aerogel precursor liquid at the temperature of 40 ℃ for 1.5 hours, and adjusting the temperature to 60 ℃ to obtain a graphene composite silicon dioxide aerogel precursor liquid;
(3) standing the graphene composite silica aerogel precursor solution for 1 hour, adding aluminum hydroxide colloid, adjusting the pH value to 7 to obtain graphene composite silica aerogel precipitate, putting the graphene composite silica aerogel into a drying box, and drying at the temperature of 65 ℃ for 15 hours to obtain graphene composite silica aerogel;
(4) grinding and dispersing the graphene composite silicon dioxide aerogel into 25 parts by weight of polypropylene resin, adding 0.5 part by weight of lauryl sodium sulfate, uniformly stirring, and granulating by using a screw extruder to obtain the high-dispersion graphene heat-conducting master batch.
The graphene heat-conducting master batch obtained in the embodiment is added into PPS polyphenylene sulfide in a proportion of 5%, and heat-conducting performance tests are carried out after mixing, wherein the main performance is shown in the following table 1, and the heat-radiating performance is far higher than that of the master batch obtained by adding metal aluminum powder and directly adding graphene powder.
Example 3
(1) Taking 34 parts by weight of high-orientation graphite powder, stripping the graphite powder in ethanol by adopting a ball mill, setting the rotating speed of the ball mill to be 1800 rpm, and the stripping time to be 4.0 hours, adding 3 parts of a graphite powder stripping agent SDS in the stripping process, and stripping and crushing the graphite powder by the ball mill to obtain a graphene dispersion liquid;
(2) adding 15 parts by weight of propyl silicate into propanol, setting the temperature of the propanol to be 39 ℃ and the stirring speed to be 250 rpm, then sequentially adding water and industrial waste acid, and adjusting the pH value to be 3.5 to obtain the silicon dioxide aerogel precursor solution, wherein the molar ratio of the propyl silicate to the propanol to the water to the industrial waste acid is 1:10:6:2.5 × 10-5Then adding 30 parts by weight of the graphene dispersion liquid obtained in the step (1) into a silicon dioxide aerogel precursor liquid, uniformly stirring at a stirring speed of 400 rpm, standing the silicon dioxide aerogel precursor liquid at the temperature of 50 ℃ for 5 hours, and adjusting the temperature to 65 ℃ to obtain a graphene composite silicon dioxide aerogel precursor liquid;
(3) standing the graphene composite silica aerogel precursor solution for 7.5 hours, adding aluminum hydroxide colloid, adjusting the pH value to 6 to obtain graphene composite silica aerogel precipitate, putting the graphene composite silica aerogel into a drying oven, and drying at the temperature of 65 ℃ for 16 hours to obtain graphene composite silica aerogel;
(4) dispersing graphene composite silica aerogel into 25 parts by weight of polystyrene resin, adding 0.5 part by weight of sodium dodecyl benzene sulfonate, uniformly stirring, and granulating by a screw extruder to obtain the high-dispersion graphene heat-conducting master batch with the size of 3.5 mm.
The graphene heat-conducting master batch obtained in the embodiment is added into PPS polyphenylene sulfide in a proportion of 5%, and heat-conducting performance tests are carried out after mixing, wherein the main performance is shown in the following table 1, and the heat-radiating performance is far higher than that of the master batch obtained by adding metal aluminum powder and directly adding graphene powder.
Example 4
(1) Taking 35 parts by weight of expanded graphite powder, stripping the graphite powder in methanol by adopting a ball mill, setting the rotating speed of the ball mill to be 1500 revolutions per minute and the stripping time to be 3.5 hours, adding 2.5 parts of a graphite powder stripping agent TDOC in the stripping process, stripping and crushing the graphite powder by the ball mill to obtain a graphene dispersion liquid;
(2) adding 18 parts by weight of water glass into butanol, setting the temperature of an alcohol solvent butanol to be 60 ℃, and under the condition that the stirring speed is 500 rpm, sequentially adding water and industrial waste acid, and adjusting the pH value to be 3.6 to obtain the silicon dioxide aerogel precursor solution, wherein the molar ratio of the water glass to the butanol to the water to the industrial waste acid is 1: 40: 10:4 × 10-5Then adding 50 parts by weight of the graphene dispersion liquid obtained in the step (1) into a silicon dioxide aerogel precursor liquid, uniformly stirring at a stirring speed of 600 revolutions per minute, standing the silicon dioxide aerogel precursor liquid at a temperature of 75 ℃ for 16 hours, and adjusting the temperature to 70 ℃ to obtain a graphene composite silicon dioxide aerogel precursor liquid;
(3) standing the graphene composite silica aerogel precursor solution for 8 hours, adding aluminum hydroxide colloid, adjusting the pH value to 5 to obtain graphene composite silica aerogel precipitate, putting the graphene composite silica aerogel into a drying oven, and drying at the temperature of 70 ℃ for 19 hours to obtain graphene composite silica aerogel;
(4) dispersing graphene composite silica aerogel into 28 parts by weight of polysulfone resin, adding 0.5 part of aluminate coupling agent, uniformly stirring, and granulating by a screw extruder to obtain the 5mm high-dispersion graphene heat-conducting master batch.
The graphene heat-conducting master batch obtained in the embodiment is added into PPS polyphenylene sulfide in a proportion of 5%, and heat-conducting performance tests are carried out after mixing, wherein the main performance is shown in the following table 1, and the heat-radiating performance is far higher than that of the master batch obtained by adding metal aluminum powder and directly adding graphene powder.
Example 5
(1) Taking 35 parts by weight of expanded graphite powder, stripping the graphite powder in methanol by adopting a ball mill, setting the rotating speed of the ball mill to be 1500 revolutions per minute and the stripping time to be 3.5 hours, adding 2.5 parts of a graphite powder stripping agent PSS in the stripping process, stripping and crushing the graphite powder by the ball mill to obtain a graphene dispersion liquid;
(2) adding 20 parts by weight of propyl silicate into butanol, setting the temperature of an alcohol solvent butanol to be 60 ℃, and under the condition that the stirring speed is 500 r/min, sequentially adding water and industrial waste acid, and adjusting the pH value to be 4 to obtain a silicon dioxide aerogel precursor solution, wherein the molar ratio of the rice hull ash, the butanol, the water and the industrial waste acid is 1: 40: 10: 5 × 10-5Then adding 50 parts by weight of the graphene dispersion liquid obtained in the step (1) into a silicon dioxide aerogel precursor liquid, uniformly stirring at a stirring speed of 800 rpm, standing the silicon dioxide aerogel precursor liquid at a temperature of 80 ℃ for 24 hours, and adjusting the temperature to 70 ℃ to obtain a graphene composite silicon dioxide aerogel precursor liquid;
(3) standing the graphene composite silica aerogel precursor solution for 10 hours, adding aluminum hydroxide colloid, adjusting the pH value to 5 to obtain graphene composite silica aerogel precipitate, putting the graphene composite silica aerogel into a drying oven, and drying at the temperature of 70 ℃ for 20 hours to obtain the graphene composite silica aerogel;
(4) dispersing graphene composite silica aerogel into 20-30 parts by weight of polyether resin, adding 0.5 part of aluminate coupling agent, uniformly stirring, and granulating by a screw extruder to obtain the high-dispersion graphene heat-conducting master batch.
The graphene heat-conducting master batch obtained in the embodiment is added into PPS polyphenylene sulfide in a proportion of 5%, and heat-conducting performance tests are carried out after mixing, wherein the main performance is shown in the following table 1, and the heat-radiating performance is far higher than that of the master batch obtained by adding metal aluminum powder and directly adding graphene powder.
Table 1:
| performance index | Coefficient of thermal conductivity (W/m. k) |
| PPS polyphenylene sulfide | 0.33 |
| PPS with 5% aluminum powder added | 0.86 |
| 5% of graphene powder PPS is added | 1.02 |
| PPS with 5% addition of graphene masterbatch of example 1 | 2.61 |
| PPS with 5% addition of graphene masterbatch of example 2 | 2.17. |
| PPS with 5% addition of graphene masterbatch of example 3 | 2.22 |
| PPS with 5% addition of graphene masterbatch of example 4 | 2.63 |
| PPS with 5% addition of graphene masterbatch of example 5 | 2.35 |
Claims (8)
1. A preparation method of a high-dispersion graphene heat-conducting master batch comprises the following specific operation steps:
(1) stripping graphite powder in liquid by adopting a mechanical stripping method, and adding a graphite powder stripping agent in the stripping process to obtain graphene dispersion liquid, wherein the mechanical stripping method comprises any one of screw extruder stripping, ball mill stripping, millstone mill stripping, sand mill stripping, vibration mill stripping and ultrasonic stripping, and the liquid is one or more of water, methanol, ethanol and acetone;
(2) preparing a silicon dioxide aerogel precursor solution by using a silicon source, adding the graphene dispersion solution obtained in the step (1) into the silicon dioxide aerogel precursor solution, uniformly stirring, standing the silicon dioxide aerogel precursor solution at the temperature of 30-80 ℃ for 0.1-24 hours, and adjusting the temperature to 60-70 ℃ to obtain a graphene composite silicon dioxide aerogel precursor solution;
(3) standing the graphene composite silica aerogel precursor solution for 0.5-10 hours, adding aluminum hydroxide colloid, adjusting the pH value to 5-7 to obtain graphene composite silica aerogel precipitate, putting the graphene composite silica aerogel into a drying oven, and drying at the temperature of 60-70 ℃ for 13-20 hours to obtain graphene composite silica aerogel;
(4) grinding and dispersing graphene composite silicon dioxide aerogel into carrier resin, adding a surfactant, uniformly stirring, and extruding and granulating to obtain the high-dispersion graphene heat-conducting master batch.
2. The preparation method of the high dispersion graphene thermal conductive master batch according to claim 1, characterized in that: the graphite powder raw material is at least one of crystalline flake graphite, expanded graphite, high-orientation graphite, thermal cracking graphite and graphite oxide.
3. The preparation method of the high dispersion graphene thermal conductive master batch according to claim 1, characterized in that: the graphite powder stripping agent is any one of HTAB, TDOC, SDS, SDBS, PSS and P-123.
4. The preparation method of the high dispersion graphene thermal conductive master batch according to claim 1, characterized in that: the silicon source is any one of ethyl orthosilicate, methyl orthosilicate, propyl silicate and water glass.
5. The preparation method of the high dispersion graphene thermal conductive master batch according to claim 1, characterized in that: the carrier resin is one or more of polyethylene resin, polypropylene resin, polystyrene resin, polyamide resin, polysulfone resin and polyether resin;
6. the preparation method of the high dispersion graphene thermal conductive master batch according to claim 1, characterized in that: the surfactant is at least one of stearic acid, sodium dodecyl sulfate, tween-80, sodium dodecyl benzene sulfonate and aluminate coupling agent.
7. The preparation method of the highly dispersed graphene heat-conducting master batch as claimed in claim 1, wherein the silica aerogel precursor solution is prepared by adding a silicon source into an alcohol solvent, setting the temperature of the alcohol solvent to be 30-60 ℃, and under the condition of stirring at a speed of 100 rpm, sequentially adding water and industrial waste acid, and adjusting the pH value to be 3-4, wherein the silica aerogel precursor solution is obtained, and the ratio of the silicon source to the alcohol solvent to the water to the industrial waste acid is (1) (5-40) to (2-10) in terms of molar ratio (1 × 10) (1-10)-5-5×10-5）。
8. A high-dispersion graphene heat-conducting master batch, which is characterized in that the graphene heat-conducting master batch is prepared by the method of any one of claims 1 to 7.
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