CN111621879B - Polybenzazole graphite fiber and preparation method thereof - Google Patents
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Abstract
The invention discloses a polybenzazole-based graphite fiber and a preparation method thereof, wherein the graphite fiber takes polybenzazole short fibers with the axial elastic modulus of more than 250GPa as raw fibers, inorganic polymer graphite fibers with the carbon content of more than 99 percent can be obtained by sequentially carrying out high-temperature carbonization and graphitization treatment under the inert gas atmosphere, and the axial heat conductivity coefficient of the fiber is more than or equal to 1000W/m.K measured by adopting a steady-state heat flow method at the temperature of 200-300K. The invention does not need to pre-oxidize the polybenzazole fiber protofilament, thereby not only simplifying the process flow, but also reducing the energy consumption and lowering the preparation cost, meanwhile, the heat conductivity coefficient of the provided polybenzazole-based graphite fiber can reach more than or equal to 1000W/m.K under the temperature of 200-300K, and the invention can provide a heat dissipation material with high heat conductivity meeting the requirement for the field of electronic components and fills the blank in the field.
Description
Technical Field
The invention belongs to the technical field of graphite fibers and preparation thereof, and particularly relates to polybenzazole-based graphite fibers which are excellent in heat conductivity and particularly suitable for heat dissipation materials of electronic and electric appliances, and a preparation method thereof.
Background
The carbon fiber is an inorganic polymer fiber with carbon content of more than 90 percent prepared by taking organic fiber as a precursor (protofilament) through pre-oxidation, low-temperature carbonization (300-850 ℃) and high-temperature carbonization (1000-1600 ℃). The graphite fiber is not specifically defined scientifically, and generally refers to a carbon fiber having a carbon content of 99% or more. The carbon fiber can be classified into polyacrylonitrile-based, viscose-based, pitch-based or phenolic-based carbon fiber according to the difference of the precursor. The carbon fiber is further treated at a high temperature of 2200 to 3000 ℃, and about 5 percent of non-carbon elements are removed, so that the carbon fiber can be converted into graphite fiber. However, the conversion of carbon fibers to graphite fibers is difficult. Easily graphitized fiber, graphite micro-crystal layer spacing d after high-temperature heat treatment (002) The stacking thickness Lc is reduced and increased to form a three-dimensional ordered structure, namely, the structure can be converted to an ideal graphite structure; non-graphitizable fibers, in a high temperature heat treatment process, d (002) Slow decrease, limited increase in stack thickness Lc, only generationTwo-dimensional turbostratic graphite structure. The polyacrylonitrile-based, viscose-based and phenolic-based carbon fibers belong to non-graphitizable carbon fibers, and the asphalt-based carbon fibers belong to graphitizable fibers. Carbon fibers and graphite fibers have high strength, high modulus and other properties, but graphite fibers have high carbon content and high tensile modulus compared to carbon fibers, and therefore graphite fibers are also called high modulus carbon fibers, and they are generally used for reinforcing various materials such as resins, rubbers, ceramics and metals, and are widely used in various industrial fields such as aerospace, building materials, sporting goods and heat dissipation materials for electronic and electrical appliances.
When the carbon fiber and the graphite fiber are used as heat dissipation materials of electronic and electric appliances, the carbon fiber and the graphite fiber are doped into matrix resin for use. In application, the heat conductivity coefficients of the polyacrylonitrile-based carbon fiber, the viscose-based carbon fiber and the phenolic-based carbon fiber are not high, generally 200-700W/m.K, the heat conductivity effect is not ideal, and only the asphalt-based graphite fiber obtained by further graphitizing the asphalt-based carbon fiber has better heat conductivity. Such as XN-100 pitch-based Graphite fibers manufactured by Nippon Graphite Fiber Corporation, have a thermal conductivity of 800 to 900W/m.K.
In recent years, in the field of electronic and electrical devices, along with the rapid development of integration technology and assembly technology, electronic components and logic circuits are continuously developed in the directions of high performance, lightness, thinness and smallness, so that the heat generation of electronic components is increased. The heat accumulation of the electronic components can not only reduce the processing capacity of the large-scale integrated circuit, but also cause the components to be easy to damage, and seriously affect the service life and the quality reliability of the product. Therefore, it is more important to effectively dissipate heat generated by the electronic components to the outside. In other words, the need for developing heat dissipation materials with higher thermal conductivity is pressing.
5/6/1993, published as JP1993-163619; patent publication No. JP1997-119024, entitled "No. 1236224242454, which is an improvement in the yield of cellulose, no. 5/6/1997", two japanese patents to mitsubishi chemical corporation disclose pitch-based graphite fibers having a high thermal conductivity, and the thermal conductivity in the fiber axial direction is said to be 1000W/m · K or more. However, the value is obtained by compounding graphite fibers and resin to prepare a composite material, measuring parameters such as heat transfer rate of the composite material by a laser scattering method (transient method), and substituting the parameters into a theoretical formula for calculation. Since the thermal conductivity of the fibers is not directly measured, it is influenced by various factors such as the kind and thermal conductivity of the resin, the degree and state of orientation of the fibers, and the thickness of the composite material, so that the thermal conductivity measured by this method is generally high. Because a steady-state thermal flow method is used which is currently developed for directly determining the thermal conductivity of fibers by applying a certain thermal flow to the sample [ this method is based on the Standard ASTM D5470 "Standard test method for thermal conductivity properties of thermal conductive electrical insulation materials", see cryoengineering Vol. 28, page 533 (1993) of Ten-Bo et al. The thermal conductivity of this pitch-based graphite fiber of Mitsubishi chemical corporation was measured, and the axial thermal conductivity was only 800W/mK but not 1000W/mK or more at a temperature of 300K (26.85 ℃ C.). In addition, the preparation methods disclosed in these two japanese patents use petroleum pitch or coal pitch as raw materials, and the pitch as raw material is refined, spun, pre-oxidized, carbonized to prepare carbon fiber, and then graphitized at high temperature to prepare graphite fiber, so the preparation methods have many process steps, complicated process and large energy consumption.
CN102978747 discloses a patent entitled "a graphite fiber and a method for preparing the same" which discloses a polyacrylonitrile-based graphite fiber, but does not give a specific thermal conductivity value of the fiber; in the method, two coating treatments are required at the carbonization stage of the polyacrylonitrile-based carbon fiber, the process is complicated, and the heat conductivity coefficient of the graphite fiber prepared by using the polyacrylonitrile-based carbon fiber which is difficult to graphitize cannot be estimated to be high. CN 104862828 discloses a name of 'a high thermal conductivity carbon fiber and a preparation method thereof', the patent is a high thermal conductivity polyacrylonitrile-based carbon fiber prepared by adding graphene concentrated solution, and the thermal conductivity coefficient of the carbon fiber is stated to be 200-1000W/m.K. Obviously, the prepared fiber has low heat conductivity coefficient, and the preparation process is more complicated. CN107119348 discloses a patent entitled "a graphite fiber and a method for preparing the same", which discloses a graphite fiber prepared by vapor deposition method. The method has the advantages of very harsh preparation conditions, low preparation efficiency, high cost and no industrial application prospect.
In summary, the prior art mainly has the following disadvantages: 1. the thermal conductivity coefficient of the graphite fiber is not high enough, and the thermal conductivity coefficient of the heat dissipation material in the field of electronic and electric appliances at present is difficult to reach the target value of 1000W/m.K; 2. the preparation of the graphite fiber is mostly polyacrylonitrile-based or asphalt-based, and the protofilament needs to be subjected to pre-oxidation, carbonization and graphitization in sequence, so that the preparation process is long and the cost is high.
Disclosure of Invention
The invention aims to provide a polybenzazole graphite fiber, which has axial heat conductivity coefficient not less than 1000W/m.K measured by a steady-state heat flow method at the temperature of 300K, excellent heat conductivity and is particularly suitable for heat dissipation materials of electronic and electrical appliances.
Another object of the present invention is to provide a method for preparing the above polybenzazole-based graphite fiber; the preparation method has the advantages of short flow, high yield, low cost and industrial application prospect.
The invention provides a polybenzazole-based graphite fiber, which is characterized in that the graphite fiber is an inorganic polymer graphite fiber with carbon content higher than 99 percent, which is obtained by taking a polybenzazole fiber with axial elastic modulus more than 250GPa as a raw fiber and carrying out high-temperature carbonization and graphitization treatment, and the axial heat conductivity coefficient of the fiber is more than or equal to 1000W/m.K measured by adopting a steady-state heat flow method at the temperature of 200-300K.
When polybenzazole graphite fiber with axial elastic modulus of 250-320 GPa is used as raw fiber, inorganic polymer graphite fiber with carbon content of 99.1-99.7% is obtained after high-temperature carbonization and graphitization treatment, the axial thermal conductivity of the fiber is 1000-1050W/m.K measured by adopting a steady-state heat flow method at the temperature of 200K, and the axial thermal conductivity of the fiber is 1035-1100W/m.K measured by adopting the steady-state heat flow method at the temperature of 300K.
The polybenzazole fiber protofilament in the polybenzazole-based graphite fiber is prepared from any one of a polybenzazole homopolymer or a random copolymer, an alternating copolymer or a block copolymer with the percentage content of a polybenzazole structural unit being more than or equal to 85 percent by a conventional liquid crystal spinning process. The polybenzazole homopolymer or the random copolymer, the alternating copolymer and the block copolymer with the percentage content of the polybenzazole structural unit being more than or equal to 85 percent can be prepared by the following prior art: wolf et al, U.S. Pat. No. 4,034,036' liquid crystal Crystalline Polymer compositions, processes and Products "; CN 101506412B "polybenzazole fiber and phenylenepyridobisimidazole fiber"; in new year, etc., CN 102936342B "a semi-continuous preparation method of poly (p-phenylene benzobisoxazole) polymer"; sikkema et al, US 8263221B2, "high inner viscosensitivity polymers and fibers therefrom"; buxing Wei et al, CN 105350108B, "a method for preparing a poly [2, 5-dihydroxy-1, 4-phenylenepyridobisimidazole ] fiber; jinningman et al, ZL 200410093359.4, "AB type poly-p-phenylene benzobisoxazole monomer and its synthesis and application".
It is to be noted that the structural units contained in the polybenzazole polymer used for producing the polybenzazole fiber filaments are preferably those capable of forming a lyotropic liquid crystal polymer. The structural units shown in a to d are preferable, the structural units shown in a or c are more preferable, the structural units shown in a are most preferable, and the structural units shown in a are most preferable, namely, the poly-p-phenylene benzobisoxazole polymer is most preferable.
The invention provides a preparation method of the polybenzazole-based graphite fiber, which is characterized in that the polybenzazole-based graphite fiber is obtained by treating polybenzazole fiber protofilaments with the axial elastic modulus of more than or equal to 250GPa according to the following process steps and conditions:
1) Placing the polybenzazole fiber protofilament in a heat treatment furnace, and carbonizing for 1-5min at 1200-1500 ℃ in an inert gas atmosphere to obtain pre-graphitized fiber;
2) Further raising the temperature in the heat treatment furnace to 2200-3000 ℃, and continuously carrying out high-temperature graphitization treatment on the pre-graphitized fiber for 1-10min to obtain the polybenzazole graphite fiber with the carbon content higher than 99%.
The polybenzazole fiber precursor used in the preparation method is prepared from polybenzazole homopolymer or any one of random copolymer, alternating copolymer or block copolymer with the percentage content of polybenzazole structural units being more than or equal to 85 percent through a conventional liquid crystal spinning process.
The polybenzazole fiber precursor used in the above preparation method is a short fiber, and the length thereof is preferably 3 to 10mm. When the length of the staple fiber is less than 3mm, the polybenzazole precursor fiber bundle becomes loose, and the generated static electricity makes the polybenzazole precursor fiber bundle easy to fluff, so that the volume of the staple fiber is too large, and the treatment efficiency is reduced. On the other hand, when the length of the short fibers exceeds 10mm, the bulk density of the short fibers is significantly reduced, making it difficult to control the length distribution of the fired graphite fibers. Therefore, in order to ensure good firing efficiency and effectively control the length of the graphite fiber produced, the length of the short fiber is preferably in the range of 3 to 10mm.
The inert gas used in the above production method is any of nitrogen, argon or carbon dioxide gas, and nitrogen is preferred.
Compared with the prior art, the invention has the following beneficial technical effects:
1. the polybenzazole graphite fiber provided by the invention has the thermal conductivity coefficient of 200-300K, and the axial thermal conductivity coefficient can reach more than or equal to 1000W/m.K when the axial thermal conductivity coefficient is measured by adopting a steady-state heat flow method, so that the polybenzazole graphite fiber not only can provide a heat dissipation material with high thermal conductivity meeting the requirement for the field of electronic components, but also fills the blank in the field.
2. The method for preparing the polybenzazole-based graphite fiber adopts the polybenzazole fiber protofilament with the axial elastic modulus of more than 250GPa as a raw material, and the polybenzazole fiber protofilament is not required to be pre-oxidized, so that the process flow is simplified, the energy consumption is reduced, and the preparation cost is reduced.
3. The method for preparing the polybenzazole-based graphite fiber adopts the polybenzazole fiber short fiber protofilament, and the specific length is controlled to be 3-10mm, so that the carbonization and graphitization treatment efficiency can be improved, and the length of the prepared graphite fiber can be effectively controlled.
Detailed Description
The following examples are given to further illustrate the present invention, and it should be noted that the following examples should not be construed as limiting the scope of the present invention, and the skilled practitioner can make some insubstantial modifications and adaptations of the present invention based on the present disclosure.
In addition, it is to be noted that the thermal conductivity given in the following examples and comparative examples was obtained by performing the test using the steady-state heat flow method.
Example 1
The poly-p-phenylene benzobisoxazole fiber (PBO fiber, model CG-HM) with the structural unit of (a) is processed into 3mm short cut fiber protofilament with the elastic modulus of 250GPa, and is placed in a heat treatment furnace, and the PBO fiber is carbonized in nitrogen atmosphere. When the temperature is increased, the mass loss is found to be 32 percent in the heating process of 630-790 ℃; the mass was further reduced by about 8% when the temperature was increased to about 1500 ℃ for 1 min. The polybenzazole fiber protofilament is converted into pre-graphitized fiber after the mass loss; and then, further raising the temperature in the heat treatment furnace to 2200 ℃ and firing for 10min to obtain the poly-p-phenylene benzobisoxazole graphite fiber. The yield of the graphite fiber was calculated, and (%) = (weight after firing/weight before firing) × 100% =57.5%. The carbon content of the graphite fiber was 99.5%.
The thermal conductivity coefficient of the obtained graphite fiber measured at 200K is 1000W/m.K; the thermal conductivity measured at 300K was 1030W/m.K.
Example 2
The poly-p-phenylene benzobisoxazole fiber (PBO fiber, model CG-HM) with the structural unit of (a) is processed into chopped fiber strands with the length of 6mm, the elastic modulus of the poly-p-phenylene benzobisoxazole fiber is 300GPa, and the poly-p-phenylene benzobisoxazole fiber is placed in a heat treatment furnace and carbonized in the nitrogen atmosphere. When the temperature is increased, the mass loss is found to reach 30 percent in the heating process of 630-790 ℃; the mass was further reduced to about 9% when the temperature was increased to about 1400 ℃ for 3 min. The polybenzazole fiber protofilament is converted into pre-graphitized fiber after the mass loss; and then, the temperature in the heat treatment furnace is further increased to 2800 ℃ and the mixture is fired for 5min to obtain the poly (p-phenylene benzobisoxazole) graphite fiber. The yield of the graphite fiber is 58.0 percent, and the carbon content is 99.7 percent.
The thermal conductivity coefficient of the obtained graphite fiber measured at 200K is 1050W/m.K; the thermal conductivity was 1100W/m.K measured at 300K.
Example 3
The poly-p-phenylene benzobisoxazole fiber (PBO fiber, model CG-HM) with the structural unit of (a) is processed into a chopped fiber protofilament with the length of 10mm, the elastic modulus of the poly-p-phenylene benzobisoxazole fiber is 270GPa, and the poly-p-phenylene benzobisoxazole fiber is placed in a heat treatment furnace and carbonized in the nitrogen atmosphere. When the temperature is increased, the mass loss is found to be 28 percent in the heating process of 630-790 ℃; the mass was further reduced to about 7% when the temperature was increased to about 1200 ℃ for 5min of treatment. The polybenzazole fiber protofilament is converted into pre-graphitized fiber after the mass loss; and then, further raising the temperature in the heat treatment furnace to 3000 ℃ and firing for 1min to obtain the poly-p-phenylene benzobisoxazole-based graphite fiber. The yield of the graphite fiber is 56.3%, and the carbon content is 99.4%.
The thermal conductivity coefficient of the obtained graphite fiber measured at 200K is 1020W/m.K; the thermal conductivity measured at 300K was 1045W/m.K.
Example 4
Poly [2, 5-dihydroxy-1, 4-phenylenepyridobisimidazole ] fiber (hereinafter referred to as PIPD fiber, produced by Middy Cheng chemical industries, ltd., having an elastic modulus of 320GPa and processed into a chopped fiber strand of 3mm in length) having a structural unit (c) is placed in a heat treatment furnace, and the PIPD fiber is carbonized in a nitrogen atmosphere, at the time of temperature rise, it is found that the mass loss reaches 25% in the heating process of 630 ℃ to 790 ℃, and when the temperature rises to about 1300 ℃ for 5min, the mass is further reduced to about 9%, and the polybenzazole fiber strand is converted into a pre-graphitized fiber after the mass loss, and then the temperature in the heat treatment furnace is further raised to 2500 ℃ for 4min to obtain poly [2, 5-dihydroxy-1, 4-phenylenepyridobisimidazole ] based graphite fiber, the yield of the graphite fiber is 55.8%, and the carbon content is 99.2%.
The thermal conductivity coefficient of the obtained graphite fiber measured at 200K is 1010W/m.K; the thermal conductivity measured at 300K was 1035W/mK.
Example 5
Copolymerizing two polymers with structural units of (a) and (c), wherein the percentage content of (a) is 85%, obtaining a random copolymer, preparing fibers (PBO-co-PIPD fibers for short, produced by Zhonglan Chen photochemical company limited) through spinning, wherein the fibers have the elastic modulus of 250GPa and are processed into chopped fiber strands with the length of 3mm, placing the chopped fiber strands in a heat treatment furnace, and carbonizing the PBO fibers in a nitrogen atmosphere. When the temperature is increased, the mass loss is found to be 26 percent in the heating process of 630-790 ℃; the mass was further reduced to about 10% when the temperature was increased to about 1500 ℃ for 5min of treatment. The polybenzazole fiber protofilament is converted into pre-graphitized fiber after the mass loss; and then, the temperature in the heat treatment furnace is further increased to 3000 ℃ and the mixture is fired for 5min, so that the poly PBO-co-PIPD-based graphite fiber is obtained. The yield of the graphite fiber was 55.5%, and the carbon content was 99.1%.
The thermal conductivity of the obtained graphite fiber measured at 200K is 1015W/m.K; the thermal conductivity was 1040W/mK measured at 300K.
Comparative example
This comparative example is pitch-based Graphite Fiber from Nippon Graphite Fiber Corporation, under the designation XN-100.
The axial thermal conductivity coefficient of the graphite fiber of the comparative example at the temperature of 200K-300K is measured by adopting a steady-state heat flow method
The concentration of the water solution is less than 1000W/m.K. />
Claims (7)
1. A polybenzazole-based graphite fiber is characterized in that the graphite fiber is an inorganic polymer graphite fiber with carbon content higher than 99% obtained by taking a polybenzazole fiber with axial elastic modulus of more than 250GPa as a raw fiber and carrying out high-temperature carbonization and graphitization treatment, the fiber is measured to have axial heat conductivity coefficient of more than or equal to 1000W/m.K by adopting a steady-state heat flow method at the temperature of 200-300K, and the specific process steps and conditions are as follows:
1) Placing the polybenzazole fiber precursor in a heat treatment furnace, and carbonizing at 1200-1500 ℃ for 1-5min under the inert gas atmosphere to obtain pre-graphitized fiber;
2) Further raising the temperature in the heat treatment furnace to 2200-3000 ℃, continuously carrying out high-temperature graphitization treatment on the pre-graphitized fiber for 1-10min,
the polybenzazole fiber precursor is short fiber with length of 3-10 mm.
2. The polybenzazole-based graphite fiber according to claim 1, wherein the graphite fiber is an inorganic polymer graphite fiber having a carbon content of 99.1 to 99.7% obtained by using a polybenzazole fiber having an axial elastic modulus of 250 to 320GPa as a raw fiber, and subjecting the raw fiber to high-temperature carbonization and graphitization treatment, wherein the fiber has an axial thermal conductivity of 1000 to 1050W/m.K as measured by a steady-state heat flow method at a temperature of 200K, and has an axial thermal conductivity of 1035 to 1100W/m.K as measured by a steady-state heat flow method at a temperature of 300K.
3. The polybenzazole-based graphite fiber according to claim 1 or 2, wherein the polybenzazole fiber precursor used for preparing the graphite fiber is prepared from polybenzazole homopolymer or any one of random copolymer, alternating copolymer or block copolymer with the percentage content of polybenzazole structural units being not less than 85 percent through conventional liquid crystal spinning process.
4. The polybenzazole graphite fiber according to claim 3, wherein the polybenzazole polymer is a polymer of structural unit capable of forming lyotropic liquid crystal, specifically a polymer of structural unit represented by the following a-d:
a
b
C
d
5. the polybenzazole-based graphite fiber according to claim 1 or 2, characterized in that the inert gas used in the preparation of the graphite fiber is any of nitrogen, argon or carbon dioxide gas.
6. Polybenzazole-based graphite fiber according to claim 3, characterized in that the inert gas used in the preparation of the graphite fiber is any of nitrogen, argon or carbon dioxide gas.
7. Polybenzazole-based graphite fiber according to claim 4, characterized in that the inert gas used in the preparation of the graphite fiber is any of nitrogen, argon or carbon dioxide gas.
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| JP2010144299A (en) * | 2008-12-19 | 2010-07-01 | Polymatech Co Ltd | Graphitized fiber, and method for producing the same |
| CN107988660A (en) * | 2017-11-14 | 2018-05-04 | 哈尔滨工业大学深圳研究生院 | A kind of thermal chemical vapor deposition prepares the method and its application of three-dimensional grapheme fiber |
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| JP2010144299A (en) * | 2008-12-19 | 2010-07-01 | Polymatech Co Ltd | Graphitized fiber, and method for producing the same |
| CN107988660A (en) * | 2017-11-14 | 2018-05-04 | 哈尔滨工业大学深圳研究生院 | A kind of thermal chemical vapor deposition prepares the method and its application of three-dimensional grapheme fiber |
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| Kinetics of Carbonization and Graphitization of PBO Fiber;JAMES A. NEWELL;《Journal of Applied Polymer Science》;19961231;第60卷;第825-832页 * |
| 仝兴存.碳纤维.《电子封装热管理先进材料》.国防工业出版社,2016, * |
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