CN104151531A - Intermediate phase asphalt raw material for producing carbon fibers and preparation method thereof - Google Patents
Intermediate phase asphalt raw material for producing carbon fibers and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to an intermediate phase asphalt raw material for producing carbon fibers and a preparation method thereof, wherein the intermediate phase asphalt raw material intermediate phase content determined through the polarizing microscope method is 100%, S1/S2 in the infrared absorption spectrogram of the intermediate phase asphalt is more than 1.7, S1 is the area of the absorption peak at the wavelength of 2800-2990 cm<-1>, S2 is the area of the absorption peak at the wavelength of 2990-3150 cm<-1>, S3/S4 in the <13>C nuclear magnetic resonance spectrogram of the intermediate phase asphalt is less than 19, S3 is the area of the absorption peak with the chemical shift of 23.8-58.0 ppm, and S4 is the area of the absorption peak with the chemical shift of 8.0-23.8 ppm. According to the present invention, methylnaphthalene and other naphthalene compounds are adopted as raw materials, hydrogen fluoride-boron trifluoride is adopted as a catalyst, and the polymerization conditions are controlled to prepare the intermediate phase asphalt. Compared with the intermediate phase asphalt in the prior art, the intermediate phase asphalt of the present invention has characteristics of excellent spinnability, excellent pre-oxidation property and simple preparation process control, and can be adopted as the industrial production raw material of the high strength and high modulus asphalt-base carbon fibers.
Description
Technical field
The present invention relates to carbon element industrial circle, be specifically related to a kind of mesophase pitch raw material and preparation method who is applicable to the preoxidation excellent performance of preparing high-performance carbon fibre.
Background technology
High-performance carbon fibre light weight also has high strength and high elastic coefficient, bring into play huge effect in fields such as national defense industry, aerospace, hard-core technology, pillar industry, daily lifes as high value material, the demand of high-performance carbon fibre is to be greater than 10% speed phenomenal growth year by year.
According to used raw material classification, carbon fiber can be divided into polyacrylonitrile-radical (PAN) carbon fiber, asphalt base carbon fiber and viscose base carbon fibre etc.Carbon fiber product is mainly first two at present, and wherein PAN base carbon fibre output accounts for 70%, and asphalt base carbon fiber accounts for 30%.Because the distinguishing features such as asphalt base carbon fiber raw material sources are extensive, production cost is low, price is about PAN base carbon fibre 1/3～1/4, carbon yield is high, good rigidly, heat conductivility excellence receive the very big concern of industry.
Asphalt base carbon fiber refers to that the mixture that is rich in condensed-nuclei aromatics compound and heterogeneous ring compound taking pitch etc. is as raw material, a based carbon fiber of preparing by spinning, preoxidation, carbonizing treatment.Be divided into again universal asphalt base carbon fiber and high-performance asphalt base carbon fiber according to the difference of its performance, the former is prepared by isotropic pitch, claims again isotropic pitch carbon fiber, and the latter is prepared by mesophase pitch, therefore be called again mesophase asphalt carbon fiber.Mesophase pitch be by coal-tar pitch, petroleum pitch etc. for raw material make through thermal polycondensation reaction or taking condensed-nuclei aromatics compound if the derivative of naphthalene, anthracene etc. and these compounds is as raw material, form through catalyzing and condensing, average molecular mass is at 400 to several thousand nematic liquid crystal, its optically-active anisotropy is due to due to the ordered arrangement structure of flat condensed-nuclei aromatics molecule.When this mesophase pitch is during at melt-spinning, melt during by nozzle slit owing to being subject to stress, flat aromatic hydrocarbon molecule is arranged by the axial orientation of fiber, keep this oriented structure not to be destroyed in follow-up preoxidation and carbonization engineering, finally can obtain the high-performance asphalt base carbon fiber that orientation is good.
Industrial mesophase pitch spinning, is all generally after pitch is heated to melt-flow state, becomes hundreds of～thousands of monofilament through the spinning jet ejection that contains hundreds of～thousands of holes; Every several thousand monofilament are collected into immediately fibrous bundle and carry out rolling.Then at next step preoxidation stage and carbonation stage, be all the processing of directly merging into a branch of form and carry out serialization with the form of such fibrous bundle or a few bundle.In pre-oxidation treatment process, in fibrous bundle, closely between connected monofilament, be very easy to melting, adhesion phenomenon occur, not only cause the seriously phenomenon such as fracture of wire even of tow fluffing, what impact was produced carries out smoothly, also can be because surface imperfection is serious, cause the carbon fiber strength of final preparation low.
For fear of the bad phenomenon that melting, adhesion occur between monofilament in preoxidation process, each processing condition that people attempt to adopt adjusting to optimize preoxidation process solve, and comprise preoxidation temperature rise rate, temperature, time, atmosphere gas velocity, the tow speed of travel etc.Even but these conditions are all set in optimum value, the phenomenon of monofilament adhesion also cannot all be eliminated.Someone adopts the kind that changes atmosphere gas, for example replace air or oxygen with the strong ozone of oxidation capacity, sulfurous gas or nitrogen peroxide etc., but because these gaseous corrosions are strong, must carry out anti-corrosive treatment to preoxidation equipment on the one hand, also must set up on the other hand special treatment facility and process these oxide compounds after using, thereby cause the raising of production cost.Somebody proposes the technology that uses release agent such as silica flour, finish etc. to carry out pre-treatment and then carry out preoxidation tow, and due to before follow-up carbonizing treatment, these release agents must be removed, so increased complicacy and the production cost of production process.Also someone has proposed to use transfer roller, guide roller etc. to carry out to the fibrous bundle sticking together the method that solution is knitted, but this method cannot be eliminated the defect that fiber surface has formed, so must cause the carbon fiber strength of final production low.
Summary of the invention
Object of the present invention is exactly to provide a kind of mesophase pitch raw material and preparation method that carbon fiber is used that produce in order to overcome the defect that above-mentioned prior art exists.
Object of the present invention can be achieved through the following technical solutions: a kind ofly produce the mesophase pitch raw material that carbon fiber is used, it is characterized in that, the middle phase content of the described mesophase pitch raw material of measuring with polarized light microscopic method is 100%; S1/S2 > 1.7 on the infrared absorpting light spectra of described mesophase pitch, wherein S1 is 2800～2990cm
-1absorption peak area, S2 is 2990～3150cm
-1absorption peak area; Described mesophase pitch
13s3/S4 < 19 on C nmr spectrum, wherein S3 is that chemical shift is the absorption peak area of 23.8～58.0ppm, S4 is that chemical shift is the absorption peak area of 8.0～23.8ppm.Meet the mesophase pitch raw material of these indexs, have excellent preoxidation performance, preoxidation preparation process is simple and easy to control, and production cost is low, the few intensity of prepared carbon fiber surface defect is high, is suitable as the suitability for industrialized production raw material of high strength and modulus asphalt base carbon fiber.
The middle phase content of described mesophase pitch raw material is 100%.If middle phase content is low, on the one hand, when molten state, isotropy component and anisotropy component will be separated, and hinder normally carrying out of spinning.On the other hand, the asphalt stock that middle phase content is low, cannot obtain high-performance mesocarbon fiber the most at last.So middle phase content is 100%.
Described mesophase pitch, S1/S2 > 1.7 on its infrared absorpting light spectra, wherein S1 is 2800～2990cm
-1absorption peak area, S2 is 2990～3150cm
-1absorption peak area.Infrared absorption spectrum 2800～2990cm
-1the stretching vibration absorption peak of fatty C-H, 2990～3150cm
-1it is the stretching vibration absorption peak of fragrant C-H.With 2800～2990cm
-1absorption peak area and 2990～3150cm
-1the ratio S1/S2 of absorption peak area S2, represents the number of fatty carbon and aromatic carbon relative content in molecular structure.This value is larger, illustrates that in mesophase pitch molecule, fatty carbon content is higher, and the preoxidation performance of spinning pitch prill fiber is out better.S1/S2 > 1.7, illustrates that fatty carbon and the ratio of aromatic carbon content are greater than 1.7.If S1/S2≤1.7, in molecular structure, aromatic carbon structure relative content is too high, and the oxidation susceptibility of pitch fibers is poor, and oxidation rate is slow, easily occurs monofilament adhesion phenomenon in preoxidation process, is unfavorable for serialization production.
Described mesophase pitch,
13on C nmr spectrum, S3/S4 < 19, wherein S3 is that chemical shift is the absorption peak area of 23.8～58.0ppm, the absorption peak area that S4 is 8.0～23.8ppm.
13c-NMR can detect the structure composition of carbon skeleton in organic compound, chemical shift the absorption peak of 8.0～23.8ppm corresponding be the straight chained alkyl carbon atom in aliphatics mechanism, and the absorption peak of 23.8～58.0ppm corresponding be the cycloalkanes carbon atom in aliphatic structure.With the ratio S3/S4 of the absorption peak area S3 of 8.0～23.8ppm and the absorption peak area S4 of 23.8～58.0ppm, represent the ratio of cycloalkanes carbon atom and straight chained alkyl carbon content in the aliphatic structure of pitch prill molecule.This value is less, represents that cycloalkanes carbon content is relatively few, and straight chained alkyl carbon content is many, and the fiber preoxidation performance that such mesophase pitch spins is just better.S3/S4 < 19, illustrates that cycloalkanes carbon atom and the content ratio of straight chained alkyl carbon atom are less than 19.If S3/S4 >=19, cycloalkanes carbon structure content is relatively many, and the oxidation susceptibility of pitch fibers is poor, and oxidation rate is slow, easily occurs monofilament adhesion phenomenon in preoxidation process, is unfavorable for serialization production.
A kind of preparation method who produces the mesophase pitch raw material that carbon fiber uses, it is characterized in that, the method is: taking naphthalene series compound as raw material, under catalyzer, carrying out polyreaction taking hydrogen fluoride and boron trifluoride, wherein hydrofluoric consumption is 5～15 times of feed molar number, and the consumption of boron trifluoride is 0.2～1.0 times of feed molar number;
Polymeric reaction temperature is 250～300 DEG C, and when temperature is during higher than 300 DEG C, reaction is violent, causes the excessive polymerization of methylnaphthalene, and the pitch softening point obtaining is high.In the time that temperature is less than 250 DEG C, the pitch that in the middle of cannot obtaining, phase content is 100%.
Polymerization reaction time changes along with raw material type, temperature of reaction and catalyst levels difference, and common 30～300 minutes, preferably 60～240 minutes.In the time that the reaction times is greater than 300 minutes, will cause excessive polymerization, the pitch softening point obtaining is higher.In the time that the reaction times is less than 30 minutes, react insufficient, the pitch that in the middle of cannot obtaining, phase content is 100%.
After polyreaction finishes, remove catalyzer HF-BF
3, products therefrom is 350 DEG C～450 DEG C in temperature, continues to be blown into nitrogen 2.0 minutes～20 hours, isolates low-boiling products, obtains mesophase pitch.
Described naphthalene series compound is the derivative of condensed-nuclei aromatics compound and condensed-nuclei aromatics compound, or the condenses that contains condensed-nuclei aromatics compound segment; Described condensed-nuclei aromatics compound is naphthalene, anthracene, phenanthrene or acenaphthene.
Described naphthalene series compound is methylnaphthalene or dimethylnaphthalene.
Described polyreaction is carried out in the acid corrosion-resistant reactor with whipping appts, and stirring operation runs through whole polymerization process and whole low-boiling products sepn process.
In described polymerization process, in reactor, filling with inert gas is protected conventionally.
In order to solve the melting adhesion problems of pitch fibers in the pre-oxidation treatment stage, the inventor studies and finds that simple effective method is to start with from middle phase pitch prill raw material, develop a kind of mesophase pitch raw material, the fiber itself that raw material spins thus just has excellent preoxidation performance, be that oxidizing reaction speed is fast, at lower temperature, oxidizing reaction just can occur.Such fiber is entering after pre-oxidation reactor, and in temperature-rise period, the oxidizing reaction of every monofilament just occurs, and monofilament just there will not be melting adhesion phenomenon so.Is the asphalt stock preoxidation performance with what kind of molecular characterization good? the inventor conscientiously studies by the molecular structure to mesophase pitch, in conjunction with a large amount of experimental verifications, find the molecular structure property index of the mesophase pitch raw material that meets above-mentioned requirements and prepared the method for this asphalt stock.Research finds, one, fatty carbon structure, than aromatic carbon structure, oxidizing reaction more easily occurs, and therefore in asphaltene molecule structure, the more preoxidation production processes that are just more conducive to of fatty carbon structure content.Two, fatty carbon structure is divided into again cycloalkanes carbon structure and straight chained alkyl carbon structure, and cycloalkanes carbon structure generation oxidizing reaction is wherein after dehydrogenation, has just become aromatic carbon structure, and its oxidation capacity will decline.Therefore, in fatty carbon structure, the content of cycloalkanes carbon is fewer, and the content of straight chained alkyl carbon structure is more, is just more conducive to the Quick Oxidation of pitch fibers.Above-mentioned fatty carbon structure and aromatic carbon structural content relative how many, can characterize by the ratio of character pair peak area on infrared absorption spectra, and this value is the bigger the better.In above-mentioned fatty carbon structure, cycloalkanes carbon structure and straight chained alkyl carbon structure content is relative how many, can pass through
13the recently reflection of characteristic of correspondence peak area on C nmr spectrum, this value is the smaller the better.Research is found, when meeting S1/S2 simultaneously, the molecular characterization of asphalt stock is greater than 1.7 and S3/S4 while being less than 19 this two conditions, the oxidation of prepared pitch fibers monofilament is very good, speed of response is fast, temperature rise period in pre-oxidation treatment has just completed pre-oxidation, has effectively avoided melting adhesion phenomenon.There is the mesophase pitch of this feature, mainly, by being prepared taking naphthalene series compound as raw material, need to control polymeric reaction condition.Although also can prepare in theory taking coal tar, heavy petroleum asphalt as the synthetic route of raw material the mesophase pitch meeting the demands, but its reaction process process will be very complicated, mesophase pitch prepared by common disclosed synthetic method is difficult to meet above characteristic index.Based on above lot of experiments result, complete the content of patent of the present invention.
Compared with prior art, this mesophase pitch preoxidation excellent performance, the oxidizing reaction speed of pitch monofilament is fast, effectively avoid the problem of melting adhesion in pre-oxidation treatment engineering, can ensure carrying out smoothly of production operation, also make pre-oxidation process process simple and easy to control, production cost is low, the few intensity of prepared carbon fiber surface defect is high, is suitable as the suitability for industrialized production raw material of high strength and modulus asphalt base carbon fiber.
Embodiment
Further describe the present invention by specific implementation method below, but range of application of the present invention is not limited only to the following example.
Embodiment 1
Methylnaphthalene, hydrogen fluoride and boron trifluoride compound are added to reactor with the molar ratio of 1: 5: 0.5,, after 120 minutes, give off catalyzer hydrogen fluoride and three boronation fluorine and reclaim use 280 DEG C of reactions.Then reactor is warming up to 350 DEG C, continues to pass into nitrogen 8 hours to remove low-boiling products, cooling obtains mesophase pitch.Measuring the middle phase content that this mesophase pitch uses is 100%, and on infrared absorpting light spectra, S1/S2 is 2.11,
13on C nmr spectrum, S3/S4 is 3.76.
By this centre phase pitch prill after 320 DEG C are carried out melt-spinning, pitch fibers tow is carried out in air atmosphere to pre-oxidation treatment, temperature condition is for keeping 20min with 5 DEG C/min from room temperature to 100 DEG C, 0.5 DEG C/min from 100 DEG C to 300 DEG C, 300 DEG C, preoxidation excellent property, the monofilament of pitch fibers are smooth without melting adhesion phenomenon, treating processes.By pre-oxygen silk in nitrogen atmosphere, carry out carbonizing treatment with 10 DEG C/min under room temperature is warmed up to 2500 DEG C, keeps the condition of 10min, obtain asphalt base carbon fiber, detect observe tow smooth in appearance have no fluffiness, also without adhesion vestige, tensile strength is 3.75GPa, and tensile modulus is 752GPa.
Embodiment 2
Methylnaphthalene, hydrogen fluoride and boron trifluoride compound are added to reactor with the molar ratio of 1: 10: 0.5,, after 120 minutes, give off catalyzer hydrogen fluoride and three boronation fluorine and reclaim use 280 DEG C of reactions.Then reactor is warming up to 350 DEG C, continues to pass into nitrogen 8 hours to remove low-boiling products, cooling obtains mesophase pitch.Measuring the middle phase content that this mesophase pitch uses is 100%, and on infrared absorpting light spectra, S1/S2 is 2.17,
13on C nmr spectrum, S3/S4 is 1.22.
By this centre phase pitch prill after 320 DEG C are carried out melt-spinning, pitch fibers tow is carried out in air atmosphere to pre-oxidation treatment, temperature condition is for keeping 20min with 5 DEG C/min from room temperature to 100 DEG C, 0.5 DEG C/min from 100 DEG C to 300 DEG C, 300 DEG C, preoxidation excellent property, the monofilament of pitch fibers are smooth without melting adhesion phenomenon, treating processes.By pre-oxygen silk in nitrogen atmosphere, carry out carbonizing treatment with 10 DEG C/min under room temperature is warmed up to 2500 DEG C, keeps the condition of 10min, obtain asphalt base carbon fiber, detect observe tow smooth in appearance have no fluffiness, also without adhesion vestige, tensile strength is 3.70GPa, and tensile modulus is 738GPa.
Embodiment 3
Methylnaphthalene, hydrogen fluoride and boron trifluoride compound are added to reactor with the molar ratio of 1: 15: 0.5,, after 120 minutes, give off catalyzer hydrogen fluoride and three boronation fluorine and reclaim use 280 DEG C of reactions.Then reactor is warming up to 350 DEG C, continues to pass into nitrogen 8 hours to remove low-boiling products, cooling obtains mesophase pitch.Measuring the middle phase content that this mesophase pitch uses is 100%, and on infrared absorpting light spectra, S1/S2 is 2.29,
13on C nmr spectrum, S3/S4 is 1.04.
By this centre phase pitch prill after 320 DEG C are carried out melt-spinning, pitch fibers tow is carried out in air atmosphere to pre-oxidation treatment, temperature condition is for keeping 20min with 5 DEG C/min from room temperature to 100 DEG C, 0.5 DEG C/min from 100 DEG C to 300 DEG C, 300 DEG C, preoxidation excellent property, the monofilament of pitch fibers are smooth without melting adhesion phenomenon, treating processes.By pre-oxygen silk in nitrogen atmosphere, carry out carbonizing treatment with 10 DEG C/min under room temperature is warmed up to 2500 DEG C, keeps the condition of 10min, obtain asphalt base carbon fiber, detect observe tow smooth in appearance have no fluffiness, also without adhesion vestige, tensile strength is 3.72GPa, and tensile modulus is 720GPa.
Embodiment 4
Methylnaphthalene, hydrogen fluoride and boron trifluoride compound are added to reactor with the molar ratio of 1: 10: 0.2,, after 120 minutes, give off catalyzer hydrogen fluoride and three boronation fluorine and reclaim use 280 DEG C of reactions.Then reactor is warming up to 350 DEG C, continues to pass into nitrogen 8 hours to remove low-boiling products, cooling obtains mesophase pitch.Measuring the middle phase content that this mesophase pitch uses is 100%, and on infrared absorpting light spectra, S1/S2 is 2.12,
13on C nmr spectrum, S3/S4 is 3.55.
By this centre phase pitch prill after 320 DEG C are carried out melt-spinning, pitch fibers tow is carried out in air atmosphere to pre-oxidation treatment, temperature condition is for keeping 20min with 5 DEG C/min from room temperature to 100 DEG C, 0.5 DEG C/min from 100 DEG C to 300 DEG C, 300 DEG C, preoxidation excellent property, the monofilament of pitch fibers are smooth without melting adhesion phenomenon, treating processes.By pre-oxygen silk in nitrogen atmosphere, carry out carbonizing treatment with 10 DEG C/min under room temperature is warmed up to 2500 DEG C, keeps the condition of 10min, obtain asphalt base carbon fiber, detect observe tow smooth in appearance have no fluffiness, also without adhesion vestige, tensile strength is 3.68GPa, and tensile modulus is 740GPa.
Embodiment 5
Methylnaphthalene, hydrogen fluoride and boron trifluoride compound are added to reactor with the molar ratio of 1: 10: 1,, after 120 minutes, give off catalyzer hydrogen fluoride and three boronation fluorine and reclaim use 280 DEG C of reactions.Then reactor is warming up to 350 DEG C, continues to pass into nitrogen 8 hours to remove low-boiling products, cooling obtains mesophase pitch.Measuring the middle phase content that this mesophase pitch uses is 100%, and on infrared absorpting light spectra, S1/S2 is 2.16,
13on C nmr spectrum, S3/S4 is 1.17.
By this centre phase pitch prill after 320 DEG C are carried out melt-spinning, pitch fibers tow is carried out in air atmosphere to pre-oxidation treatment, temperature condition is for keeping 20min with 5 DEG C/min from room temperature to 100 DEG C, 0.5 DEG C/min from 100 DEG C to 300 DEG C, 300 DEG C, preoxidation excellent property, the monofilament of pitch fibers are smooth without melting adhesion phenomenon, treating processes.By pre-oxygen silk in nitrogen atmosphere, carry out carbonizing treatment with 10 DEG C/min under room temperature is warmed up to 2500 DEG C, keeps the condition of 10min, obtain asphalt base carbon fiber, detect observe tow smooth in appearance have no fluffiness, also without adhesion vestige, tensile strength is 3.70GPa, and tensile modulus is 728GPa.
Comparative example 1 (hydrogen fluoride content)
Methylnaphthalene, hydrogen fluoride and boron trifluoride compound are added to reactor with the molar ratio of 1: 0.5: 0.5,, after 120 minutes, give off catalyzer hydrogen fluoride and three boronation fluorine and reclaim use 280 DEG C of reactions.Then reactor is warming up to 350 DEG C, continues to pass into nitrogen 8 hours to remove low-boiling products, cooling obtains mesophase pitch.Measuring the middle phase content that this mesophase pitch uses is 100%, and on infrared absorpting light spectra, S1/S2 is 1.56,
13on C nmr spectrum, S3/S4 is 2.03.
By this centre phase pitch prill after 320 DEG C are carried out melt-spinning, pitch fibers tow is carried out in air atmosphere to pre-oxidation treatment, temperature condition is for keeping 20min with 5 DEG C/min from room temperature to 100 DEG C, 0.5 DEG C/min from 100 DEG C to 300 DEG C, 300 DEG C, in fibrous bundle, between monofilament, there is even fracture of wire of melting adhesion, treating processes is not smooth, and oxidation susceptibility is poor.This is because aromatic carbon structural content in asphalt stock molecule is high, so oxidation rate causes slowly.By pre-oxygen silk in nitrogen atmosphere, carry out carbonizing treatment with 10 DEG C/min under room temperature is warmed up to 2500 DEG C, keeps the condition of 10min, obtain asphalt base carbon fiber, detect and observe that the fluffing of tow appearance is serious, have adhesion between monofilament, tensile strength is 3.50GPa, and tensile modulus is 580GPa.
Comparative example 2 (boron trifluoride content)
Methylnaphthalene, hydrogen fluoride and boron trifluoride compound are added to reactor with the molar ratio of 1: 10: 0.1,, after 120 minutes, give off catalyzer hydrogen fluoride and three boronation fluorine and reclaim use 280 DEG C of reactions.Then reactor is warming up to 350 DEG C, continues to pass into nitrogen 8 hours to remove low-boiling products, cooling obtains mesophase pitch.Measuring the middle phase content that this mesophase pitch uses is 100%, and on infrared absorpting light spectra, S1/S2 is 2.02,
13on C nmr spectrum, S3/S4 is 27.57.
By this centre phase pitch prill after 320 DEG C are carried out melt-spinning, pitch fibers tow is carried out in air atmosphere to pre-oxidation treatment, temperature condition is for keeping 20min with 5 DEG C/min from room temperature to 100 DEG C, 0.5 DEG C/min from 100 DEG C to 300 DEG C, 300 DEG C, in fibrous bundle, between monofilament, there is even fracture of wire of melting adhesion, treating processes is not smooth, poor this of oxidation susceptibility be because cycloalkanes carbon structure content in asphalt stock is high, so oxidation rate causes slowly.By pre-oxygen silk in nitrogen atmosphere, carry out carbonizing treatment with 10 DEG C/min under room temperature is warmed up to 2500 DEG C, keeps the condition of 10min, obtain asphalt base carbon fiber, detect and observe that the fluffing of tow appearance is serious, have adhesion between monofilament, tensile strength is 3.40GPa, and tensile modulus is 530GPa.
Embodiment 6 (temperature)
Methylnaphthalene, hydrogen fluoride and boron trifluoride compound are added to reactor with the molar ratio of 1: 10: 0.5,, after 120 minutes, give off catalyzer hydrogen fluoride and three boronation fluorine and reclaim use 250 DEG C of reactions.Then reactor is warming up to 350 DEG C, continues to pass into nitrogen 8 hours to remove low-boiling products, cooling obtains mesophase pitch.Measuring the middle phase content that this mesophase pitch uses is 100%, and on infrared absorpting light spectra, S1/S2 is 2.25,
13on C nmr spectrum, S3/S4 is 1.13.
By this centre phase pitch prill after 320 DEG C are carried out melt-spinning, pitch fibers tow is carried out in air atmosphere to pre-oxidation treatment, temperature condition is for keeping 20min with 5 DEG C/min from room temperature to 100 DEG C, 0.5 DEG C/min from 100 DEG C to 300 DEG C, 300 DEG C, preoxidation excellent property, the monofilament of pitch fibers are smooth without melting adhesion phenomenon, treating processes.By pre-oxygen silk in nitrogen atmosphere, carry out carbonizing treatment with 10 DEG C/min under room temperature is warmed up to 2500 DEG C, keeps the condition of 10min, obtain asphalt base carbon fiber, detect observe tow smooth in appearance have no fluffiness, also without adhesion vestige, tensile strength is 3.66GPa, and tensile modulus is 742GPa.
Embodiment 7 (temperature)
Methylnaphthalene, hydrogen fluoride and boron trifluoride compound are added to reactor with the molar ratio of 1: 10: 0.5,, after 120 minutes, give off catalyzer hydrogen fluoride and three boronation fluorine and reclaim use 300 DEG C of reactions.Then reactor is warming up to 350 DEG C, continues to pass into nitrogen 8 hours to remove low-boiling products, cooling obtains mesophase pitch.Measuring the middle phase content that this mesophase pitch uses is 100%, and on infrared absorpting light spectra, S1/S2 is 2.06,
13on C nmr spectrum, S3/S4 is 5.67.
By this centre phase pitch prill after 320 DEG C are carried out melt-spinning, pitch fibers tow is carried out in air atmosphere to pre-oxidation treatment, temperature condition is for keeping 20min with 5 DEG C/min from room temperature to 100 DEG C, 0.5 DEG C/min from 100 DEG C to 300 DEG C, 300 DEG C, preoxidation excellent property, the monofilament of pitch fibers are smooth without melting adhesion phenomenon, treating processes.By pre-oxygen silk in nitrogen atmosphere, carry out carbonizing treatment with 10 DEG C/min under room temperature is warmed up to 2500 DEG C, keeps the condition of 10min, obtain asphalt base carbon fiber, detect observe tow smooth in appearance have no fluffiness, also without adhesion vestige, tensile strength is 3.72GPa, and tensile modulus is 720GPa.
Comparative example 3 (temperature)
Methylnaphthalene, hydrogen fluoride and boron trifluoride compound are added to reactor with the molar ratio of 1: 10: 0.5,, after 120 minutes, give off catalyzer hydrogen fluoride and three boronation fluorine and reclaim use 350 DEG C of reactions.Then reactor is warming up to 350 DEG C, continues to pass into nitrogen 8 hours to remove low-boiling products, cooling obtains mesophase pitch.Measuring the middle phase content that this mesophase pitch uses is 100%, and on infrared absorpting light spectra, S1/S2 is 1.83,
13on C nmr spectrum, S3/S4 is 24.0.
This centre phase pitch prill is carried out to melt-spinning at 320 DEG C, cannot carry out.Spinning after being warming up to 350 DEG C, strand less stable, has observed pitch decomposition gas and has produced.Pitch fibers tow is carried out in air atmosphere to pre-oxidation treatment, temperature condition is for keeping 20min with 5 DEG C/min from room temperature to 100 DEG C, 0.5 DEG C/min from 100 DEG C to 300 DEG C, 300 DEG C, in fibrous bundle, between monofilament, there is even fracture of wire of melting adhesion, treating processes is not smooth, and oxidation susceptibility is poor.This is because the content of cycloalkanes carbon structure in asphalt stock is high, so oxidation rate causes slowly.By pre-oxygen silk in nitrogen atmosphere, carry out carbonizing treatment with 10 DEG C/min under room temperature is warmed up to 2500 DEG C, keeps the condition of 10min, obtain asphalt base carbon fiber, detect and observe that the fluffing of tow appearance is serious, have adhesion between monofilament, tensile strength is 3.03GPa, and tensile modulus is 510GPa.
Comparative example 4 (temperature)
Methylnaphthalene, hydrogen fluoride and boron trifluoride compound are added to reactor with the molar ratio of 1: 10: 0.5,, after 120 minutes, give off catalyzer hydrogen fluoride and three boronation fluorine and reclaim use 200 DEG C of reactions.Then reactor is warming up to 350 DEG C, continues to pass into nitrogen 8 hours to remove low-boiling products, cooling obtains mesophase pitch.Measuring the middle phase content that this mesophase pitch uses is 25%.In the middle of such bitumen product, phase content is low, and when molten state, isotropy component and anisotropy component will be separated, normally spinning.Although adopt the polycondensation that again heats up improve in the middle of the method for phase content, with technology comparison provided by the invention, complicated operation, cost are high, industrial infeasible.
Comparative example 5 (raw material)
The distillate 3000g of 400～540 DEG C of heavy petroleum asphalts is mixed with 150g polymethylmethacrylate, add in autoclave, pass into nitrogen purging, flow is 3L/min, starts and stirs, and be at 270 DEG C, to react after 5 hours in temperature of reaction, reaction pressure is increased to 3MPa, be warming up to 350 DEG C and continue reaction 6 hours, relief pressure, slow cooling obtains mesophase pitch.Measuring the middle phase content that this mesophase pitch uses is 100%, and softening temperature is 270 DEG C.On infrared absorpting light spectra, S1/S2 is 0.83,
13on C nmr spectrum, S3/S4 is 4.89.
This centre phase pitch prill is carried out to melt-spinning at 320 DEG C, cannot carry out.Spinning after being warming up to 330 DEG C, strand less stable, has observed pitch decomposition gas and has produced.Pitch fibers tow is carried out in air atmosphere to pre-oxidation treatment, temperature condition is for keeping 20min with 5 DEG C/min from room temperature to 100 DEG C, 0.5 DEG C/min from 100 DEG C to 300 DEG C, 300 DEG C, in fibrous bundle, between monofilament, there is even fracture of wire of melting adhesion, treating processes is not smooth, and oxidation susceptibility is poor.This is because aromatic carbon structural content in asphalt stock is high, so oxidation rate causes slowly.By pre-oxygen silk in nitrogen atmosphere, carry out carbonizing treatment with 10 DEG C/min under room temperature is warmed up to 2500 DEG C, keeps the condition of 10min, obtain asphalt base carbon fiber, detect and observe that the fluffing of tow appearance is serious, have adhesion between monofilament, tensile strength is 3.26GPa, and tensile modulus is 520GPa.
The explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.Be noted that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, make professional and technical personnel in the field can realize or use the present invention.To be apparent for those skilled in the art to the multiple modification of these embodiment, General Principle as defined herein can, in the situation that not departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (6)
1. produce the mesophase pitch raw material that carbon fiber is used, it is characterized in that, the middle phase content of the described mesophase pitch raw material of measuring with polarized light microscopic method is 100%; S1/S2 > 1.7 on the infrared absorpting light spectra of described mesophase pitch, wherein S1 is 2800～2990cm
-1absorption peak area, S2 is 2990～3150cm
-1absorption peak area; Described mesophase pitch
13s3/S4 < 19 on C nmr spectrum, wherein S3 is that chemical shift is the absorption peak area of 23.8～58.0ppm, S4 is that chemical shift is the absorption peak area of 8.0～23.8ppm.
2. the preparation method of the mesophase pitch raw material that a production carbon fiber as claimed in claim 1 is used, it is characterized in that, the method is: taking naphthalene series compound as raw material, under catalyzer, carrying out polyreaction taking hydrogen fluoride and boron trifluoride, wherein hydrofluoric consumption is 5～15 times of feed molar number, and the consumption of boron trifluoride is 0.2～1.0 times of feed molar number; Polymeric reaction temperature is 250～300 DEG C, and the reaction times is 30～300 minutes, after polyreaction finishes, removes catalyzer HF-BF
3, be warming up to 350 DEG C, continue to be blown into nitrogen 8 hours, isolate low-boiling products, obtain mesophase pitch.
3. a kind of preparation method who produces the mesophase pitch raw material that carbon fiber uses according to claim 2, it is characterized in that, described naphthalene series compound is the derivative of condensed-nuclei aromatics compound and condensed-nuclei aromatics compound, or the condenses that contains condensed-nuclei aromatics compound segment; Described condensed-nuclei aromatics compound is naphthalene, anthracene, phenanthrene or acenaphthene.
4. the preparation method who produces the mesophase pitch raw material that carbon fiber uses according to a kind of described in claim 2 or 3, is characterized in that, described naphthalene series compound is methylnaphthalene or dimethylnaphthalene.
5. a kind of preparation method who produces the mesophase pitch raw material that carbon fiber uses according to claim 2, it is characterized in that, described polyreaction is carried out in the acid corrosion-resistant reactor with whipping appts, and stirring operation runs through whole polymerization process and whole low-boiling products sepn process.
6. a kind of preparation method who produces the mesophase pitch raw material that carbon fiber uses according to claim 2, is characterized in that, in described polymerization process, in reactor, filling with inert gas is protected conventionally.
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| CN105177766A (en) * | 2015-09-28 | 2015-12-23 | 东华大学 | Preparation method of mesophase pitch continuous filaments |
| CN106497591A (en) * | 2016-10-21 | 2017-03-15 | 湖南大学 | A kind of preparation method for catalyzing and synthesizing mesophase pitch |
| CN107417244A (en) * | 2017-08-22 | 2017-12-01 | 安徽艾米伦特建材科技有限公司 | Insulation material and preparation method thereof |
| CN109763209A (en) * | 2019-01-31 | 2019-05-17 | 山东瑞城宇航碳材料有限公司 | A method of manufacture high thermal conductivity asphalt base carbon fiber |
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| CN107417244A (en) * | 2017-08-22 | 2017-12-01 | 安徽艾米伦特建材科技有限公司 | Insulation material and preparation method thereof |
| CN109763209A (en) * | 2019-01-31 | 2019-05-17 | 山东瑞城宇航碳材料有限公司 | A method of manufacture high thermal conductivity asphalt base carbon fiber |
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Application publication date: 20141119 |