CN115947883B - High-quality polyacrylonitrile and controllable synthesis method and application thereof - Google Patents
High-quality polyacrylonitrile and controllable synthesis method and application thereof Download PDFInfo
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- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 72
- 238000001308 synthesis method Methods 0.000 title abstract description 14
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 26
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 19
- QSVOWVXHKOQYIP-UHFFFAOYSA-N 2-dodecylsulfanylcarbothioylsulfanyl-2-methylpropanenitrile Chemical compound CCCCCCCCCCCCSC(=S)SC(C)(C)C#N QSVOWVXHKOQYIP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229940123973 Oxygen scavenger Drugs 0.000 claims abstract description 8
- -1 4-cyano-4- [ (dodecyl sulfanyl) sulfanyl ] pentanoic acid Chemical compound 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- JGHKDVSIFPFNIJ-UHFFFAOYSA-N dodecylsulfanylmethanedithioic acid Chemical group CCCCCCCCCCCCSC(S)=S JGHKDVSIFPFNIJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 22
- 238000009987 spinning Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 230000002194 synthesizing effect Effects 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 12
- 108010015776 Glucose oxidase Proteins 0.000 claims description 8
- 239000004366 Glucose oxidase Substances 0.000 claims description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- 229940116332 glucose oxidase Drugs 0.000 claims description 8
- 235000019420 glucose oxidase Nutrition 0.000 claims description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 5
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 108010001816 pyranose oxidase Proteins 0.000 claims description 2
- 150000003384 small molecules Chemical class 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 31
- 238000009826 distribution Methods 0.000 abstract description 22
- 239000000178 monomer Substances 0.000 abstract description 20
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 18
- 239000004917 carbon fiber Substances 0.000 abstract description 18
- 239000002904 solvent Substances 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 34
- 229920000642 polymer Polymers 0.000 description 23
- 239000012467 final product Substances 0.000 description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 12
- 238000005227 gel permeation chromatography Methods 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 238000005286 illumination Methods 0.000 description 9
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 238000007865 diluting Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 8
- 230000001376 precipitating effect Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000003999 initiator Substances 0.000 description 5
- 230000000977 initiatory effect Effects 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000003321 amplification Effects 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
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- 238000011109 contamination Methods 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
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- 239000011550 stock solution Substances 0.000 description 1
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- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the technical field of polyacrylonitrile carbon fibers, in particular to high-quality polyacrylonitrile and a controllable synthesis method and application thereof. The controllable synthesis method of the polyacrylonitrile specifically comprises the steps of mixing an acrylonitrile monomer, a chain transfer agent and an oxygen scavenger in an organic solvent to obtain a mixed solution, and then carrying out polymerization reaction under a light source; wherein the chain transfer agent is one or more of 2-cyano-2-propyldodecyl trithiocarbonate, 2- (dodecyl trithiocarbonate group) -2-methylpropanoic acid and 4-cyano-4- [ (dodecyl sulfanyl) sulfanyl ] pentanoic acid; the molar ratio of the acrylonitrile monomer to the chain transfer agent is 200-10000: 1. the synthesis method has extremely high monomer conversion rate, and can obtain the acrylonitrile polymer with controllable molecular weight and narrower molecular weight distribution. Meanwhile, the polymerization system has good oxygen resistance and universality in different solvent systems.
Description
Technical Field
The invention relates to the technical field of polyacrylonitrile carbon fibers, in particular to high-quality polyacrylonitrile and a controllable synthesis method and application thereof.
Background
The carbon fiber is high-strength and high-modulus fiber with carbon content of more than 90%, and has a series of excellent performances such as high strength, high modulus, low density, high temperature resistance and the like, so that the carbon fiber is widely applied to the fields such as aerospace, national defense and military, energy, civil construction, sports and the like. The precursor for producing the carbon fiber mainly comprises three main types of polyacrylonitrile carbon fiber, pitch-based carbon fiber and viscose-based carbon fiber. The carbon fiber processed by polyacrylonitrile is the mainstream of carbon fiber production because of relatively simple process and optimal performance. In the process flow of preparing the polyacrylonitrile-based carbon fiber, the quality of the polyacrylonitrile precursor is a key factor for determining the preparation of the high-quality carbon fiber, and the production of the high-quality polyacrylonitrile precursor requires the production technology of the high-quality polyacrylonitrile spinning solution and the advanced spinning technology. Wherein, the synthesis of the high-quality polyacrylonitrile spinning solution is key.
The current industrial method for synthesizing polyacrylonitrile mainly comprises two main types of a one-step method of homogeneous polymerization and a two-step method of aqueous suspension polymerization. Homogeneous polymerization means that monomers are polymerized in a specific solvent to directly obtain a uniform acrylonitrile polymer solution, the obtained polymer does not need to be purified and separated, and can be directly used for spinning after single removal and defoaming. The two-stage process is understood to mean that the polymerization is carried out in aqueous suspension, the polymer being dissolved in a suitable solvent and spun. The polymer obtained by the method generally has higher relative molecular mass, and can well meet the requirements of the high-end field, but the method has complicated steps and high cost, and the existence of a small amount of residues in the product can influence the final performance of the carbon fiber obtained in the subsequent carbonization treatment. To synthesize high-quality carbon fiber, the polyacrylonitrile spinning solution is required to meet the requirements of high molecular weight, narrow molecular weight distribution, no impurity residue such as metal ions and the like.
Compared with the traditional free radical polymerization, the controllable active free radical polymerization can well realize effective regulation and control of the molecular weight, molecular weight distribution, structure and the like of the polymer, and is expected to be used for preparing high-quality carbon fiber spinning stock solution. Among the numerous controlled living polymerization methods, reversible addition-fragmentation chain transfer (RAFT) polymerization has received a great deal of attention because of its wide range of applicable monomers, strong molecular design ability, high terminal chain activity, and the like. At present, in the prior art, when RAFT polymerization is used for synthesizing polyacrylonitrile, a thermal initiation mode is mostly adopted. For example, in the prior art CN 110078860A, a preparation method of acrylonitrile (PAN) polymer with low polydispersity index (PDI) is disclosed, which belongs to thermal initiation in RAFT polymerization, and an initiator is added when the polymer is used, and initiation free radical initiation reaction is generated by decomposing the initiator, but the controllability of the method is poor, and additional energy consumption is caused by heating and other conditions.
Based on the characteristics of light cleanliness, environmental protection, low energy consumption and the like, a light-operated RAFT method using light as external stimulus to regulate and control polymerization reaction has been rapidly developed in recent years. Currently, a light-operated RAFT polymerization system mainly comprises a monomer, a photocatalyst and a chain transfer agent, wherein the catalyst reacts with the chain transfer agent after illumination so as to initiate polymerization reaction. However, in this system, the catalyst residues can cause polymer contamination, which affects the properties of the final product. And the molecular weight distribution of the product obtained by the existing light-operated RAFT polymerization system is wider, the controllability is poor, and meanwhile, the system does not have oxygen resistance and is not beneficial to large-scale amplification.
In the prior art, zhang Jianxiong finds the application of TTP in photolytic RAFT polymerization of (methyl) acrylic ester regulated by 2-cyano-2-propyldodecyl trithiocarbonate (TTP), but the application of TTP in photolytic RAFT polymerization of the (methyl) acrylic ester is not high in the molecular weight and monomer conversion rate of the obtained polymer, and the controllability of the molecular weight and the molecular weight distribution of the polymer is poor.
And for polyacrylonitrile, the polarity of the monomer is strong, meanwhile, the polymer is insoluble in the monomer solution, so that higher requirements are put on a polymerization system, and meanwhile, the control of the molecular weight and the molecular weight distribution is more difficult.
Disclosure of Invention
The invention provides a high-quality polyacrylonitrile and a controllable synthesis method and application thereof, which are used for solving the defects that the molecular weight distribution of a product obtained by a light-operated RAFT polymerization system in the prior art is wider, the controllability is poor, and the system does not have oxygen resistance and is not beneficial to large-scale amplification, so that the controllable synthesis of the high-quality polyacrylonitrile is realized.
The invention provides a synthetic method of polyacrylonitrile, which comprises the following steps: mixing an acrylonitrile monomer, a chain transfer agent, an oxygen scavenger and the like in a solvent to obtain a mixed solution, and then carrying out polymerization reaction under a light source; wherein the chain transfer agent is one or more of 2-cyano-2-propyldodecyl trithiocarbonate, 2- (dodecyl trithiocarbonate group) -2-methylpropanoic acid and 4-cyano-4- [ (dodecyl sulfanyl) sulfanyl ] pentanoic acid; the molar ratio of the acrylonitrile monomer to the chain transfer agent is 200-10000: 1.
in the prior art, the control of molecular weight in the synthesis of polyacrylonitrile is generally realized by adjusting reaction time, monomer concentration, initiator concentration and the like; the invention is discovered by accident after a great deal of researches, under the system, the polymerization reaction is initiated by using a light source as external stimulus, the molecular weight of the polymer can be controlled by only regulating and controlling the molar ratio of the acrylonitrile monomer to the chain transfer agent, and the controllability is greatly improved; compared with the prior art, the monomer conversion rate is obviously improved under the system, the molecular weight controllability of the prepared acrylonitrile polymer is effectively enhanced, and the molecular weight distribution can be ensured to be narrower.
Preferably, the molar ratio of acrylonitrile monomer to chain transfer agent is 500 to 6000:1.
preferably, the concentration of the acrylonitrile monomer is 5 to 40 weight percent based on the total mass of the mixed solution; more preferably, the concentration is 15 to 26wt%.
The present inventors have found that when the acrylonitrile concentration is within the above range, the molecular weight controllability of the resulting polyacrylonitrile is more strong, and the molecular weight distribution is narrower.
Preferably, the oxygen scavenger is one or more of glucose oxidase, pyranose oxidase, triethanolamine and trimethylamine.
More preferably, the oxygen scavenger is used in an amount of 0.05 to 2wt% based on the total mass of the mixed solution; more preferably 0.1 to 0.5wt%.
Preferably, the light source is ultraviolet or visible light.
More preferably, the wavelength of the light source is 420-460 nm.
Preferably, the polymerization time is from 0.5 to 48 hours, more preferably from 6 to 24 hours.
In the present invention, since the polymerization reaction is photoinitiated, there is no particular limitation on the reaction temperature. Preferably, the polymerization reaction temperature is 0 to 80 ℃, more preferably 20 to 45 ℃.
In the invention, the reaction system has universality in different solvent systems, and a person skilled in the art can select different organic solvents to use according to actual needs.
Preferably, the organic solvent comprises one or more of dimethyl sulfoxide, dimethylacetamide, ethylene carbonate and N, N-dimethylformamide.
Preferably, the synthesis method further comprises: after the polymerization reaction is finished, carrying out precipitation treatment on a reaction product; wherein the used precipitant is a mixture of water and small molecular alcohols.
After the polymerization reaction is finished, the used precipitant is a mixture of water and small molecular alcohols.
More preferably, the small molecule alcohol comprises methanol, ethanol or isopropanol.
Preferably, the volume ratio of the water to the alcohol is 10 to 0.1:1, more preferably 2 to 0.5:1.
in a specific implementation, after the reaction product is subjected to precipitation treatment, a person skilled in the art can perform conventional post-treatment operations such as subsequent filtration, drying and the like according to actual conditions.
The invention further provides polyacrylonitrile which is prepared by the synthesis method.
Preferably, the molecular weight of the polyacrylonitrile is 10,000-420,000 g/mol, and the molecular weight distribution is 1.1-1.5.
The invention also provides a preparation method of the polyacrylonitrile precursor, which comprises the following steps: preparing polyacrylonitrile precursor from a polyacrylonitrile spinning solution; when the polyacrylonitrile spinning solution is obtained through polymerization, the synthesis method of the polyacrylonitrile is used, and the mixed solution also comprises a comonomer.
Preferably, the comonomer is one or more of butyl acrylate, itaconic acid, acrylic acid, methyl methacrylate, methyl acrylate, vinyl acetate, methacrylic acid, n-butyl methacrylate, isobutyl methacrylate and acrylamide.
More preferably, the comonomer is used in an amount of 0.5 to 20mol%, preferably 2 to 5mol%, based on the total amount of acrylonitrile monomer and comonomer.
The invention further provides the polyacrylonitrile precursor prepared by the preparation method.
In a specific implementation process, a person skilled in the art can prepare the polyacrylonitrile carbon fiber by conventional operations such as carbonization, calcination and the like on the polyacrylonitrile precursor according to actual conditions.
According to the invention, the polyacrylonitrile and the polyacrylonitrile precursor can be used for initiating the RAFT polymerization reaction by using the reaction system and the chain initiator and the acrylonitrile monomer with limited dosage and adopting an external light source as stimulus, so that the synthesis method of the high-quality carbon fiber spinning solution acrylonitrile polymer with environmental protection and strong controllability is realized.
Based on the technical scheme, the invention has the beneficial effects that:
the invention provides a high-quality polyacrylonitrile and a controllable synthesis method and application thereof, and the method and the application reconstruct a reaction system by using a light-control RAFT polymerization technology, so that the molecular weight of an acrylonitrile polymer has high controllability, the molecular weight distribution is narrow, and meanwhile, an initiator or a photocatalyst is not required to be additionally added, the product is pure, and a foundation is laid for synthesizing high-quality carbon fibers. Secondly, the system has extremely high monomer conversion rate (more than 95 percent), can simplify post-treatment process flows such as single removal and the like, and greatly saves cost, thereby meeting the requirement of industrial production. In addition, the system does not need heating or stirring, and light with low energy consumption is used as external stimulation to regulate and control the reaction, so that the energy consumption is greatly saved. Meanwhile, the system constructed by the invention has universality for different solvent systems, has no special requirement on reaction temperature, and does not need additional heating and the like.
Drawings
In order to more clearly illustrate the invention or the technical solutions of the prior art, the drawings that are needed for the embodiments will be briefly described below, it being obvious that the drawings in the following description are some embodiments of the invention and that other drawings can be obtained from these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a nuclear magnetic resonance spectrum of the monomer conversion rate measurement provided in example 1 of the present invention;
FIG. 2 is a GPC chart of the acrylonitrile polymer synthesized under conditions of varying monomer to chain transfer agent ratios as provided in example 2 of the present invention;
FIG. 3 is a GPC chart of the synthesized polymer provided in example 3 of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Unless otherwise indicated, the starting materials used in the examples were commercially available conventional starting materials, and the technical means used were conventional means well known to those skilled in the art.
In the embodiment of the invention, gel permeation chromatography is adopted to measure the molecular weight and molecular weight distribution of the acrylonitrile polymer; the monomer conversion under different conditions was determined using nuclear magnetism.
Example 1
The embodiment provides a controllable synthesis method of polyacrylonitrile, which specifically comprises the following steps:
the acrylonitrile monomer was filtered with alumina powder, 1.5mL of acrylonitrile monomer, 7.5. Mu.L of 2-cyano-2-propyldodecyl trithiocarbonate, 4.5mg of glucose oxidase and 3.0mL of dimethyl sulfoxide were measured, and charged into a 10mL quartz reaction tube at 4mW cm -2 Is reacted for 24 hours under the illumination intensity of the (C). Wherein the molar ratio of the acrylonitrile monomer to the chain transfer agent is 1070:1, and the concentration of the acrylonitrile monomer is 26wt%.
Diluting the obtained product by using dimethyl sulfoxide, precipitating a sample by using a mixed solution of methanol and water as a diluent, and drying and collecting a final product after suction filtration. The nuclear magnetism is adopted to measure the monomer conversion rate, as shown in figure 1, the obtained monomer conversion rate is 96%, which shows that the system has high monomer conversion rate and shows strong industrial application value. Meanwhile, the molecular weight of the obtained polymer is 59,500g/mol; the molecular weight distribution was 1.23.
Example 2
The embodiment provides a controllable synthesis method of polyacrylonitrile, which specifically comprises the following steps:
the acrylonitrile monomer was filtered with alumina powder, 1.5mL of the acrylonitrile monomer, 3.0mL of dimethyl sulfoxide were measured, 2. Mu.L, 4. Mu.L, 8. Mu.L, 16. Mu.L of 2-cyano-2-propyldodecyl trithiocarbonate and 4mg of glucose oxidase were measured, respectively, and sequentially added to a 10mL quartz reaction tube, and the reaction tube was placed in a photoreactor at 4mW cm -2 Is reacted for 24 hours under the illumination intensity of the (C). Diluting the obtained product by using dimethyl sulfoxide, precipitating a sample by using a mixed solution of methanol and water as a diluent, and drying and collecting a final product after suction filtration. GPC was used to determine the molecular weight of the final product.
The molecular weight and molecular weight distribution of the resulting polymer at different monomer to chain transfer agent ratios are shown in Table 1, and GPC curves of the resulting acrylonitrile polymer at corresponding molar ratios are shown in FIG. 2. As can be seen from Table 1 and FIG. 2, the method has extremely high monomer conversion, and the obtained polymer has a narrow molecular weight distribution and meets the preset molecular weight; when the reaction time is fixed, the larger the molar ratio of the acrylonitrile monomer to the chain transfer agent is, the larger the molecular weight of the polymer is, which indicates that the method has strong designability, and the molecular weight of the polyacrylonitrile can be designed by regulating the molar ratio of the acrylonitrile monomer to the chain transfer agent.
TABLE 1 molecular weight and distribution of polymers obtained from different molar ratios of acrylonitrile monomer M to chain transfer agent
Example 3
The embodiment provides a preparation method of a polyacrylonitrile spinning solution, which specifically comprises the following steps:
the acrylonitrile monomer and methyl methacrylate monomer were filtered with alumina powder, 1.5mL of acrylonitrile monomer, 0.1mL of methyl methacrylate, 4.5. Mu.L of 2-cyano-2-propyldodecyl trithiocarbonate, 6mg of glucose oxidase and 3mL of dimethyl sulfoxide were measured, and the reaction tube was put into a photoreactor after sealing with a rubber stopper at 4mW cm -2 Is reacted for 24 hours under the illumination intensity of the (C). Wherein the molar ratio of the acrylonitrile monomer to the chain transfer agent is 2000:1, and the concentration of the acrylonitrile monomer is 25wt%. Diluting the obtained product by using dimethyl sulfoxide, precipitating a sample by using a mixed solution of methanol and water as a diluent, and drying and collecting a final product after suction filtration. GPC was used to determine the molecular weight of the final product. As shown in FIG. 3, the molecular weight of the resulting polymer was 121,930g/mol and the molecular weight distribution was 1.26.
Example 4
The embodiment provides a preparation method of a polyacrylonitrile spinning solution, which specifically comprises the following steps:
the acrylonitrile monomer and butyl acrylate were filtered with alumina powder, 1.35mL of acrylonitrile monomer, 0.05mL of butyl acrylate, 14.8mg of 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid, 6. Mu.L of triethanolamine and 3.0mL of dimethyl sulfoxide were weighed into a 10mL quartz reaction tube, and the reaction tube was placed into a photoreactor at 4mW cm -2 Is reacted for 24 hours under the illumination intensity of the (C). Wherein the molar ratio of the acrylonitrile monomer to the chain transfer agent is 500:1, and propyleneThe concentration of nitrile monomer was 24.6wt%. Diluting the obtained product by using dimethyl sulfoxide, using a mixed solution of methanol and water as a precipitant to precipitate a sample, and drying and collecting a final product after suction filtration. The molecular weight of the final product was determined by GPC, and the molecular weight of the polymer obtained was 27,000g/mol and the molecular weight distribution was 1.31.
Example 5
The embodiment provides a preparation method of a polyacrylonitrile spinning solution, which specifically comprises the following steps:
the acrylonitrile monomer was filtered with alumina powder, 1.5mL of the acrylonitrile monomer was measured, 100mg of itaconic acid, 12. Mu.L of triethanolamine, 4.2mg of 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid and 3.0mL of dimethyl sulfoxide were charged into a 10mL quartz reaction tube, and the reaction tube was placed into a photoreactor at 5mW cm -2 Is reacted for 24 hours under the illumination intensity of the (C). Wherein the molar ratio of the acrylonitrile monomer to the chain transfer agent is 2000:1, and the concentration of the acrylonitrile monomer is 26wt%. Diluting the obtained product by using dimethyl sulfoxide, using a mixed solution of methanol and water as a precipitant to precipitate a sample, and drying and collecting a final product after suction filtration. The molecular weight of the final product was determined by GPC, the purity molecular weight of the obtained polymer being 110,000g/mol and the molecular weight distribution being 1.16.
Example 6
The embodiment provides a preparation method of a polyacrylonitrile spinning solution, which specifically comprises the following steps:
the acrylonitrile monomer, methyl acrylate monomer were filtered with alumina powder, 1.4mL of acrylonitrile monomer, 20. Mu.L of methyl acrylate were measured, 60mg of itaconic acid, 10mg of glucose oxidase, 4.2mg of 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid and 3.0mL of dimethyl sulfoxide were weighed into a 10mL quartz reaction tube, and the reaction tube was placed into a photoreactor at 4mW cm -2 Is reacted for 24 hours under the illumination intensity of the (C). Wherein the molar ratio of the acrylonitrile monomer to the chain transfer agent is 1830:1, and the concentration of the acrylonitrile monomer is 25%. Diluting the obtained product by using dimethyl sulfoxide, using a mixed solution of methanol and water as a precipitant to precipitate a sample, and drying and collecting a final product after suction filtration. Molecular weight of the final product was determined by GPC, molecular weight of the resulting polymer was 100,500g/mol, molecularThe amount distribution was 1.21.
Example 7
The embodiment provides a preparation method of a polyacrylonitrile spinning solution, which specifically comprises the following steps:
the acrylonitrile monomer was filtered with alumina powder, 1.35mL of the acrylonitrile monomer, 50mg of itaconic acid, 10mg of glucose oxidase, 2. Mu.L of 2-cyano-2-propyldodecyl trithiocarbonate, and 3.0mL of dimethyl sulfoxide were measured, and the reaction tube was placed in a photoreactor at 4mW cm -2 Is reacted for 24 hours under the illumination intensity of the (C). Wherein the molar ratio of the acrylonitrile monomer to the chain transfer agent is 3600:1, and the concentration of the acrylonitrile monomer is 24.6wt%. Diluting the obtained product with dimethyl sulfoxide, precipitating a sample by using a mixed solution of ethanol and water as a precipitating agent, and drying and collecting a final product after suction filtration. The molecular weight of the final product was determined by GPC, and the molecular weight of the obtained polymer was 195,800g/mol and the molecular weight distribution was 1.32.
Example 8
The embodiment provides a preparation method of a polyacrylonitrile spinning solution, which specifically comprises the following steps:
the acrylonitrile monomer and methyl methacrylate monomer were filtered with alumina powder, 1.35mL of acrylonitrile monomer, 0.05mL of methyl methacrylate, 8mg of 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid, 10mg of glucose oxidase and 3.0mL of dimethyl sulfoxide were weighed into a 10mL quartz reaction tube, and the reaction tube was placed into a photoreactor at 2mW cm -2 Is reacted for 24 hours under the illumination intensity of the (C). Wherein the molar ratio of the acrylonitrile monomer to the chain transfer agent is 930:1, and the concentration of the acrylonitrile monomer is 24.6wt%. Diluting the obtained product with dimethyl sulfoxide, precipitating a sample by using a mixed solution of ethanol and water as a precipitating agent, and drying and collecting a final product after suction filtration. GPC was used to determine the molecular weight of the final product, molecular weight of the resulting polymer being 56,300g/mol and molecular weight distribution being 1.24.
In a specific implementation process, a person skilled in the art can prepare the polyacrylonitrile spinning solution provided in examples 3 to 8 into a polyacrylonitrile precursor according to need by using a conventional method in the art, and the description is omitted here.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (15)
1. A synthetic method of polyacrylonitrile is characterized in that an acrylonitrile monomer, a chain transfer agent and an oxygen scavenger are mixed in an organic solvent to obtain a mixed solution, and then polymerization reaction is carried out under a light source;
wherein the chain transfer agent is one or more of 2-cyano-2-propyldodecyl trithiocarbonate, 2- (dodecyl trithiocarbonate group) -2-methylpropanoic acid and 4-cyano-4- [ (dodecyl sulfanyl) sulfanyl ] pentanoic acid;
the oxygen scavenger is one or more of glucose oxidase, pyranose oxidase, triethanolamine and trimethylamine;
the molar ratio of the acrylonitrile monomer to the chain transfer agent is 200-10000: 1.
2. the method for synthesizing polyacrylonitrile according to claim 1, wherein the molar ratio of the acrylonitrile monomer to the chain transfer agent is 500-6000: 1.
3. the method for synthesizing polyacrylonitrile according to claim 1 or 2, wherein the concentration of the acrylonitrile monomer is 5 to 40wt% based on the total mass of the mixed solution.
4. The method for synthesizing polyacrylonitrile according to claim 3, wherein the concentration of the acrylonitrile monomer is 15 to 26wt% based on the total mass of the mixed solution.
5. The method for synthesizing polyacrylonitrile according to claim 1 or 2, wherein the amount of the oxygen scavenger is 0.05-2 wt% based on the total mass of the mixed solution.
6. The method for synthesizing polyacrylonitrile according to claim 5, wherein the amount of the oxygen scavenger is 0.1 to 0.5wt% based on the total mass of the mixed solution.
7. The method for synthesizing polyacrylonitrile according to claim 1 or 2, wherein the light source is ultraviolet or visible light.
8. The method for synthesizing polyacrylonitrile according to claim 7, wherein the wavelength of the light source is 420-460 nm.
9. The method for synthesizing polyacrylonitrile according to claim 1 or 2, characterized in that the method for synthesizing further comprises: after the polymerization reaction is finished, carrying out precipitation treatment on a reaction product; wherein the used precipitant is a mixture of water and small molecular alcohols.
10. The method of claim 9, wherein the small molecule alcohol comprises methanol, ethanol or isopropanol.
11. The method for synthesizing polyacrylonitrile according to claim 9, wherein the volume ratio of water to alcohol is 10-0.1: 1.
12. the method for synthesizing polyacrylonitrile according to claim 11, wherein the volume ratio of water to alcohol is 2-0.5: 1.
13. a method for preparing polyacrylonitrile precursor, which is characterized by comprising the following steps: preparing polyacrylonitrile precursor from a polyacrylonitrile spinning solution;
the method for synthesizing polyacrylonitrile according to any one of claims 1 to 12 is used when polymerizing the polyacrylonitrile spinning solution, and the mixed solution further comprises a comonomer.
14. The method of claim 13, wherein the comonomer is one or more of butyl acrylate, itaconic acid, acrylic acid, methyl methacrylate, methyl acrylate, vinyl acetate, methacrylic acid, n-butyl methacrylate, isobutyl methacrylate, and acrylamide;
the amount of the comonomer is 0.5 to 20mol% based on the total amount of the acrylonitrile monomer and the comonomer.
15. The method for producing a polyacrylonitrile precursor according to claim 14, wherein the amount of the comonomer is 2 to 5mol% based on the total amount of the acrylonitrile monomer and the comonomer.
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| JP2014221868A (en) * | 2013-05-13 | 2014-11-27 | 国立大学法人名古屋大学 | Method for producing block copolymer and photonic material using the same |
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| US3020265A (en) * | 1957-11-04 | 1962-02-06 | Du Pont | Acrylonitrile polymerization process |
| JP2014221868A (en) * | 2013-05-13 | 2014-11-27 | 国立大学法人名古屋大学 | Method for producing block copolymer and photonic material using the same |
| KR20200025826A (en) * | 2018-08-31 | 2020-03-10 | 주식회사 엘지화학 | Manufacturing method of polyacrylonitrile |
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