CN109321994B - A kind of polyacrylonitrile-based carbon fiber dry and wet spinning dope and preparation method thereof - Google Patents
A kind of polyacrylonitrile-based carbon fiber dry and wet spinning dope and preparation method thereof Download PDFInfo
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- CN109321994B CN109321994B CN201811160027.1A CN201811160027A CN109321994B CN 109321994 B CN109321994 B CN 109321994B CN 201811160027 A CN201811160027 A CN 201811160027A CN 109321994 B CN109321994 B CN 109321994B
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- polyacrylonitrile
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 61
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 61
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000002166 wet spinning Methods 0.000 title claims abstract description 8
- 238000000578 dry spinning Methods 0.000 title claims abstract 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 95
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 66
- 238000001891 gel spinning Methods 0.000 claims abstract description 47
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000003756 stirring Methods 0.000 claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 20
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 16
- -1 azo compound Chemical class 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000003999 initiator Substances 0.000 claims abstract description 4
- 239000012429 reaction media Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 59
- 239000007788 liquid Substances 0.000 claims description 51
- 238000007334 copolymerization reaction Methods 0.000 claims description 45
- 229920000642 polymer Polymers 0.000 claims description 43
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 20
- 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 19
- 239000011550 stock solution Substances 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 13
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 12
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 12
- 238000001704 evaporation Methods 0.000 claims description 11
- 239000010409 thin film Substances 0.000 claims description 11
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 9
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 7
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 7
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 3
- MTLWTRLYHAQCAM-UHFFFAOYSA-N 2-[(1-cyano-2-methylpropyl)diazenyl]-3-methylbutanenitrile Chemical compound CC(C)C(C#N)N=NC(C#N)C(C)C MTLWTRLYHAQCAM-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims 5
- 238000005187 foaming Methods 0.000 claims 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 2
- NRSMWHGLCNBZSO-UHFFFAOYSA-N 2-ethylidenebutanedioic acid Chemical compound CC=C(C(O)=O)CC(O)=O NRSMWHGLCNBZSO-UHFFFAOYSA-N 0.000 claims 1
- OQTRPSFMBXCQIY-UHFFFAOYSA-N azane;2-methylidenebutanedioic acid Chemical compound N.OC(=O)CC(=C)C(O)=O OQTRPSFMBXCQIY-UHFFFAOYSA-N 0.000 claims 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 125000004494 ethyl ester group Chemical group 0.000 claims 1
- 239000012530 fluid Substances 0.000 claims 1
- KKOZDMQONVIQBM-UHFFFAOYSA-N methyl 2-methylpropanoate Chemical compound COC(=O)C(C)C.COC(=O)C(C)C KKOZDMQONVIQBM-UHFFFAOYSA-N 0.000 claims 1
- 230000003068 static effect Effects 0.000 claims 1
- 150000003462 sulfoxides Chemical class 0.000 claims 1
- 238000009987 spinning Methods 0.000 abstract description 26
- 229920001577 copolymer Polymers 0.000 abstract description 5
- 230000002349 favourable effect Effects 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 238000007872 degassing Methods 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 229910021529 ammonia Inorganic materials 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000005086 pumping Methods 0.000 description 9
- RTTAGBVNSDJDTE-UHFFFAOYSA-N 4-ethoxy-2-methylidene-4-oxobutanoic acid Chemical compound CCOC(=O)CC(=C)C(O)=O RTTAGBVNSDJDTE-UHFFFAOYSA-N 0.000 description 7
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 7
- IZFHMLDRUVYBGK-UHFFFAOYSA-N 2-methylene-3-methylsuccinic acid Chemical compound OC(=O)C(C)C(=C)C(O)=O IZFHMLDRUVYBGK-UHFFFAOYSA-N 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- FRKMZLXCWXPBOB-UHFFFAOYSA-N diazanium;2-methylidenebutanedioate Chemical compound [NH4+].[NH4+].[O-]C(=O)CC(=C)C([O-])=O FRKMZLXCWXPBOB-UHFFFAOYSA-N 0.000 description 5
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 description 1
- KBFJHOCTSIMQKL-UHFFFAOYSA-N 3-methoxycarbonylbut-3-enoic acid Chemical compound COC(=O)C(=C)CC(O)=O KBFJHOCTSIMQKL-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
- C08F220/46—Acrylonitrile with carboxylic acids, sulfonic acids or salts thereof
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Artificial Filaments (AREA)
Abstract
本发明具体涉及一种聚丙烯腈基碳纤维干湿法纺丝原液及其制备方法，以二甲基亚砜为反应介质，偶氮类化合物为引发剂，丙烯腈为第1单体，衣康酸或其衍生物为第2单体，丙烯酸或其衍生物为第3单体，经聚合、脱单调制粘度、脱泡制成，通过调节体系组分配比结合搅拌转速设置，制备特性粘度为1.6‑5dL/g高粘度聚合体系，在聚合阶段获得适合干湿法纺丝的高分子量共聚物，然后在脱单阶段利用外加溶剂调节体系的动力粘度至120‑600Pa·s，脱泡后得到适合干湿法纺丝的纺丝原液体系。本发明分步调控纺丝原液所需的技术指标，较易制备性能均一的纺丝原液，有利于干湿法稳定连续地纺制碳纤维原丝。The invention specifically relates to a dry-wet spinning dope for polyacrylonitrile-based carbon fibers and a preparation method thereof. The dimethyl sulfoxide is used as a reaction medium, an azo compound is used as an initiator, acrylonitrile is the first monomer, and itaconic is used as the first monomer. The acid or its derivative is the second monomer, and the acrylic acid or its derivative is the third monomer. It is prepared by polymerization, de-monomerization, viscosity modulation, and defoaming. By adjusting the composition ratio of the system and setting the stirring speed, the prepared intrinsic viscosity is 1.6-5dL/g high-viscosity polymerization system, obtain high-molecular-weight copolymer suitable for dry and wet spinning in the polymerization stage, and then use an external solvent to adjust the dynamic viscosity of the system to 120-600Pa s in the de-singulation stage, and obtain after degassing Dope system suitable for dry and wet spinning. The invention regulates the technical indexes required by the spinning dope in steps, can easily prepare the spinning dope with uniform performance, and is favorable for the stable and continuous spinning of carbon fiber raw filaments by dry and wet methods.
Description
Technical Field
The invention belongs to the technical field of carbon fiber preparation, and particularly relates to polyacrylonitrile-based carbon fiber dry-wet spinning solution and a preparation method thereof.
Background
The polyacrylonitrile-based carbon fiber has a series of excellent performances such as high specific strength, high specific modulus, high temperature resistance, corrosion resistance, fatigue resistance, electric conduction, heat transfer and the like, and is widely applied to the military and civil industries such as aerospace, national defense, nuclear energy, transportation, body goods, medical appliances and the like. The dry-wet spinning method has the characteristics of realizing high-speed spinning, improving the utilization efficiency of equipment and reducing the cost, and the carbon fiber spun by the dry-wet spinning method has few surface defects, is favorable for preparing high-performance carbon fiber and is an important direction for the development of the technical field of carbon fiber preparation. However, the dry-wet spinning has higher requirements on the viscosity of the spinning solution and the molecular weight index of the polymer, and the preparation of the stable spinning solution is the primary condition for industrially and continuously spinning the carbon fiber precursor by the dry-wet method. Patent 200710056083.6 proposes a method for preparing high molecular weight acrylonitrile copolymer spinning solution by using azobisisoheptonitrile as initiator, the molecular weight of the obtained copolymer is between 10 and 90 ten thousand, but when the molecular weight of the polymer of the system is larger, the viscosity of the system is too large, and the spinnability is poor. The patent 201310514386.3 provides a preparation method of polyacrylonitrile carbon fiber spinning solution with controllable viscosity, the method mainly obtains the spinning solution with the viscosity of 20-120 Pa.s by preparing low molecular weight products, the molecular weight and the viscosity of the spinning solution prepared by the method are low, the stable operation of dry-wet spinning is difficult to ensure, sodium allylsulfonate or sodium methallylsulfonate is adopted as a second monomer, and the existence of sodium element damages the stability of the spinning solution and the carbon fiber structure, and is not beneficial to the preparation of carbon fibers. Patent 201410584734.9 proposes to prepare ultra-high molecular weight spinning dope by using a batch feeding method, patent 200910234653.5 proposes to prepare high-viscosity spinning dope by using step-by-step polymerization, and patent 200510016572.X prepares high-performance polyacrylonitrile-based carbon fiber spinning dope by using acrylonitrile, itaconic acid and beta-itaconic acid amide as monomers to carry out copolymerization reaction. The preparation methods lack effective regulation and control means of the viscosity of the spinning solution when the molecular weight of the polymer is higher, and are not beneficial to continuously and stably spinning carbon fiber precursors.
Disclosure of Invention
The invention aims to solve the problem that the viscosity is not easy to regulate and control when the molecular weight of the polymer of the existing spinning solution is higher, and provides a polyacrylonitrile-based carbon fiber dry-wet spinning solution and a preparation method thereof.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a polyacrylonitrile-based carbon fiber dry-wet spinning stock solution is prepared by using dimethyl sulfoxide as a reaction medium, an azo compound as an initiator, acrylonitrile as a 1 st monomer, itaconic acid or a derivative thereof as a 2 nd monomer, and acrylic acid or a derivative thereof as a 3 rd monomer through copolymerization, and then performing defoaming to prepare the polyacrylonitrile-based carbon fiber dry-wet spinning stock solution.
Further, the raw materials of the components are added in parts by weight: 200 parts of dimethyl sulfoxide, 0.05-0.5 part of azo compound, 30-80 parts of acrylonitrile, 0.1-2 parts of itaconic acid or derivatives thereof and 0.01-2 parts of acrylic acid or derivatives thereof. Under the proportion, a high-viscosity polyacrylonitrile copolymer polymerization liquid system with the intrinsic viscosity of 1.6-5dL/g can be effectively obtained, and the solid content of the system is high, thereby being beneficial to improving the productivity.
Still further, the azo compound is one of azobisisobutyronitrile, azobisisovaleronitrile or dimethyl azobisisobutyrate. The above compounds have appropriate decomposition initiation speed under polymerization conditions, and the reaction is easy to control.
Furthermore, the derivative of itaconic acid is one or a mixture of several of ammonium itaconate, methyl itaconate and ethyl itaconate in any ratio.
Furthermore, the acrylic acid derivative is one or a mixture of several of methyl acrylate, ethyl acrylate, methyl methacrylate or ethyl methacrylate in any ratio.
A preparation method of polyacrylonitrile-based carbon fiber dry-wet spinning solution comprises the following steps:
1) a polymerization stage: under the protection of inert gas, adding dimethyl sulfoxide, azo compounds, acrylonitrile, itaconic acid or derivatives thereof and acrylic acid or derivatives thereof into a reactor with stirring for copolymerization reaction, and adding ammonia to adjust the pH value of a polymerization solution to 8-9 when the intrinsic viscosity of a copolymerization product is 1.6-5 dL/g;
2) a demonomerization stage: removing unreacted monomers from the polymerization liquid after the pH value is adjusted for 1-8h by using a rotary thin film evaporation method until the mass concentration of the residual acrylonitrile is less than 0.1%, and adjusting the dynamic viscosity of the polymerization liquid to 120-600 Pa.s by using dimethyl sulfoxide;
3) and (3) a defoaming stage: and (3) vacuumizing the defoaming unit equipment to 0.01-30kPa, introducing the polymerization liquid with the adjusted viscosity into the defoaming unit equipment, and continuously or statically defoaming completely to obtain the polyacrylonitrile-based carbon fiber dry-wet spinning solution.
Further, the polymerization stage comprises the following raw materials in parts by weight: 200 parts of dimethyl sulfoxide, 0.05-0.5 part of azo compound, 30-80 parts of acrylonitrile, 0.1-2 parts of itaconic acid or derivatives thereof and 0.1-2 parts of acrylic acid or derivatives thereof. Under the condition of the proportion, a high-viscosity polymerization liquid system with the intrinsic viscosity of the copolymerization product of 1.6-5dL/g can be effectively obtained, and the solid content of the system is high, thereby being beneficial to improving the productivity.
Further, the reaction temperature of the copolymerization reaction is 45-75 ℃, and the stirring speed is 20-150 r/min. The polymerization temperature is over 75 ℃, the polymerization reaction speed is high, and the implosion or low molecular weight of a polymerization product is easy to cause; the stirring speed is more than 150r/min, the shearing force is large, a high molecular weight polymerization product is not easy to obtain, the stirring speed is less than 20r/min, and the polymerization reaction heat is not easy to remove in time.
Furthermore, the temperature in the demonomerization kettle in the demonomerization stage is 60-80 ℃, and the temperature of the added dimethyl sulfoxide is the same as the temperature in the demonomerization kettle. The temperature is over 80 ℃, the polymer is unstable, the temperature is lower than 60 ℃, the demonomerization speed is too slow, and the demonomerization efficiency is low.
Further, the dynamic viscosity of the polymerization solution in the demonomerization stage is the viscosity of the polymerization solution at 40 ℃ measured by the falling ball method.
Aiming at the defects of the prior art, firstly, a high molecular weight and high viscosity polymerization system is prepared by adjusting the component proportion of the system and combining the setting of stirring speed and taking the intrinsic viscosity of a copolymerization product as an index, a high molecular weight copolymer suitable for dry-wet spinning is obtained in the polymerization stage, then the dynamic viscosity of the system is adjusted by using an external solvent in the demonomerization stage, and a spinning solution system suitable for dry-wet spinning is obtained after defoaming.
Compared with the prior art, the invention has the following beneficial effects:
the molecular weight of the copolymer is regulated and controlled in the polymerization stage, the viscosity of a system is regulated and controlled in the demonomerization stage, the technical indexes required by the spinning stock solution are regulated and controlled step by step, the spinning stock solution with uniform performance is easy to prepare, and the dry-wet method is favorable for stably and continuously spinning the carbon fiber precursor.
By adopting the scheme of the invention, the prepared spinning solution has the intrinsic viscosity of 1.6-5dL/g, the dynamic viscosity of 120-600 Pa.s and the mass concentration of residual acrylonitrile of less than 0.1 percent, thereby obtaining better technical effect.
Detailed Description
The present invention is further described with reference to the following examples, which are provided for illustration only and are not intended to limit the scope of the present invention.
Example 1
The polyacrylonitrile-based carbon fiber dry-wet spinning solution in the embodiment is prepared from the following raw materials: 200kg of dimethyl sulfoxide, 0.05kg of azobisisobutyronitrile, 40kg of acrylonitrile, 0.15kg of itaconic acid and 0.01kg of acrylic acid.
The preparation method of the polyacrylonitrile-based carbon fiber dry-wet spinning solution comprises the following steps:
1) a polymerization stage: under the protection of nitrogen, 200kg of dimethyl sulfoxide, 0.05kg of azodiisobutyronitrile, 30kg of acrylonitrile, 0.1kg of itaconic acid and 0.01kg of acrylic acid are added into a reactor with stirring to carry out copolymerization reaction, the polymerization reaction temperature is 75 ℃, the stirring rate is 150r/min, the intrinsic viscosity of a copolymerization product is measured by using a Ubbelohde viscometer, and when the intrinsic viscosity of the copolymerization product is 1.6dL/g, ammonia is added to adjust the pH value of a polymerization solution to 8;
2) a demonomerization stage: pumping the polymer liquid with the adjusted pH value into a demonomerization kettle by a pump, wherein the temperature in the demonomerization kettle is 80 ℃, removing unreacted monomers for 1 hour by a rotary thin film evaporation method, the mass concentration of residual acrylonitrile is 0.1%, and adjusting the dynamic viscosity of the polymer liquid to 120 Pa.s by using dimethyl sulfoxide, wherein the adding temperature of the dimethyl sulfoxide is 80 ℃, and the dynamic viscosity of the polymer liquid is the viscosity of the polymer liquid at 40 ℃ measured by a falling ball method;
3) and (3) a defoaming stage: and (4) vacuumizing the defoaming unit equipment to 5kPa, introducing the polymerization liquid with the adjusted viscosity into the defoaming unit equipment, further vacuumizing to 0.01kPa, and standing and defoaming completely to obtain the polyacrylonitrile-based carbon fiber dry-wet spinning stock solution.
The resulting copolymerization product of the dope had an intrinsic viscosity of 1.6dL/g and a dynamic viscosity of 120 pas.
Example 2
The polyacrylonitrile-based carbon fiber dry-wet spinning solution in the embodiment is prepared from the following raw materials: 200kg of dimethyl sulfoxide, 0.5kg of azodiisovaleronitrile, 65kg of acrylonitrile, 2kg of itaconic acid and 2kg of methyl acrylate.
The preparation method of the polyacrylonitrile-based carbon fiber dry-wet spinning solution comprises the following steps:
1) a polymerization stage: under the protection of nitrogen, 200kg of dimethyl sulfoxide, 0.5kg of azodiisovaleronitrile, 65kg of acrylonitrile, 2kg of itaconic acid and 2kg of methyl acrylate are added into a reactor with stirring to carry out copolymerization reaction, the polymerization reaction temperature is 45 ℃, the stirring rate is 20r/min, the intrinsic viscosity of a copolymerization product is measured by using an Ubbelohde viscometer, and when the intrinsic viscosity of the copolymerization product is 5dL/g, ammonia is added to adjust the pH value of a polymerization solution to 8.5;
2) a demonomerization stage: pumping the polymer liquid with the adjusted pH value into a demonomerization kettle by a pump, wherein the temperature in the demonomerization kettle is 70 ℃, removing unreacted monomers for 8 hours by a rotary thin film evaporation method, the mass concentration of residual acrylonitrile is 0.095%, and then adjusting the dynamic viscosity of the polymer liquid to 600 Pa.s by using dimethyl sulfoxide, wherein the adding temperature of the dimethyl sulfoxide is 70 ℃, and the dynamic viscosity of the polymer liquid is the viscosity of the polymer liquid at 40 ℃ measured by a falling ball method;
3) and (3) a defoaming stage: and (4) vacuumizing the defoaming unit equipment to 30kPa, introducing the polymerization liquid with the adjusted viscosity into the defoaming unit equipment, and continuously defoaming completely to obtain the polyacrylonitrile-based carbon fiber dry-wet spinning solution.
The resulting copolymerization product of the spinning dope had an intrinsic viscosity of 5dL/g and a dynamic viscosity of 600 pas.
Example 3
The polyacrylonitrile-based carbon fiber dry-wet spinning solution in the embodiment is prepared from the following raw materials: 200kg of dimethyl sulfoxide, 0.12kg of dimethyl azodiisobutyrate, 60kg of acrylonitrile, 0.6kg of itaconic acid, 0.2kg of methyl acrylate and 0.8kg of methyl methacrylate.
The preparation method of the polyacrylonitrile-based carbon fiber dry-wet spinning solution comprises the following steps:
1) a polymerization stage: under the protection of nitrogen, 200kg of dimethyl sulfoxide, 0.12kg of dimethyl azodiisobutyrate, 60kg of acrylonitrile, 0.6kg of itaconic acid, 0.2kg of methyl acrylate and 0.8kg of methyl methacrylate are added into a reactor with stirring to carry out copolymerization reaction, the polymerization reaction temperature is 58 ℃, the stirring rate is 80r/min, the intrinsic viscosity of a copolymerization product is measured by using an Ubbelohde viscometer, and when the intrinsic viscosity of the copolymerization product is 4.0dL/g, ammonia is added to adjust the pH value of a polymerization solution to 9;
2) a demonomerization stage: pumping the polymer liquid with the adjusted pH value into a demonomerization kettle by a pump, wherein the temperature in the demonomerization kettle is 75 ℃, removing unreacted monomers for 8 hours by a rotary thin film evaporation method, the mass concentration of residual acrylonitrile is 0.096%, and then adjusting the dynamic viscosity of the polymer liquid to 420 Pa.s by using dimethyl sulfoxide, wherein the adding temperature of the dimethyl sulfoxide is 75 ℃, and the dynamic viscosity of the polymer liquid is the viscosity of the polymer liquid at 40 ℃ measured by a falling ball method;
3) and (3) a defoaming stage: and (3) vacuumizing the defoaming unit equipment to 30kPa, introducing the polymerization liquid with the adjusted viscosity into the defoaming unit equipment, vacuumizing to 5kPa, and standing and defoaming completely to obtain the polyacrylonitrile-based carbon fiber dry-wet spinning solution.
The resulting copolymerization product of the dope had an intrinsic viscosity of 4.0dL/g and a dynamic viscosity of 420 pas.
Example 4
The polyacrylonitrile-based carbon fiber dry-wet spinning solution in the embodiment is prepared from the following raw materials: 200kg of dimethyl sulfoxide, 0.14kg of azodiisovaleronitrile, 40kg of acrylonitrile, 0.9kg of ammonium itaconate and 0.9kg of acrylic acid.
The preparation method of the polyacrylonitrile-based carbon fiber dry-wet spinning solution comprises the following steps:
1) a polymerization stage: under the protection of nitrogen, 200kg of dimethyl sulfoxide, 0.14kg of azodiisovaleronitrile, 40kg of acrylonitrile, 0.9kg of ammonium itaconate and 0.9kg of acrylic acid are added into a reactor with stirring for copolymerization, the polymerization temperature is 62 ℃, the stirring rate is 80r/min, the intrinsic viscosity of a copolymerization product is measured by using a Ubbelohde viscometer, and when the intrinsic viscosity of the copolymerization product is 3.8dL/g, ammonia is added to adjust the pH value of a polymerization solution to 8.7;
2) a demonomerization stage: pumping the polymer liquid with the adjusted pH value into a demonomerization kettle by a pump, wherein the temperature in the demonomerization kettle is 80 ℃, removing unreacted monomers for 5 hours by a rotary thin film evaporation method, the mass concentration of residual acrylonitrile is 0.092%, and then adjusting the dynamic viscosity of the polymer liquid to 280 Pa.S by using dimethyl sulfoxide, wherein the adding temperature of the dimethyl sulfoxide is 80 ℃, and the dynamic viscosity of the polymer liquid is the viscosity of the polymer liquid at 40 ℃ measured by a falling ball method;
3) and (3) a defoaming stage: and (3) vacuumizing the defoaming unit equipment to 18kPa, introducing the polymerization liquid with the adjusted viscosity into the defoaming unit equipment, vacuumizing to 3kPa, and standing and defoaming completely to obtain the polyacrylonitrile-based carbon fiber dry-wet spinning solution.
The resulting copolymerization product of the dope had an intrinsic viscosity of 3.8dL/g and a dynamic viscosity of 280 pas.
Example 5
The polyacrylonitrile-based carbon fiber dry-wet spinning solution in the embodiment is prepared from the following raw materials: 200kg of dimethyl sulfoxide, 0.09kg of dimethyl azodiisobutyrate, 40kg of acrylonitrile, 1.2kg of methyl itaconate and 0.9kg of ethyl acrylate.
The preparation method of the polyacrylonitrile-based carbon fiber dry-wet spinning solution comprises the following steps:
1) a polymerization stage: under the protection of nitrogen, 200kg of dimethyl sulfoxide, 0.09kg of dimethyl azodiisobutyrate, 40kg of acrylonitrile, 1.2kg of itaconic acid methyl ester and 0.9kg of ethyl acrylate are added into a reactor with stirring to carry out copolymerization reaction, the polymerization reaction temperature is 60 ℃, the stirring rate is 85r/min, the intrinsic viscosity of a copolymerization product is measured by using a Ubbelohde viscometer, and when the intrinsic viscosity of the copolymerization product is 3dL/g, ammonia is added to adjust the pH value of a polymerization solution to 8.3;
2) a demonomerization stage: pumping the polymer liquid with the adjusted pH value into a demonomerization kettle by a pump, wherein the temperature in the demonomerization kettle is 70 ℃, removing unreacted monomers for 4.5 hours by a rotary thin film evaporation method, the mass concentration of residual acrylonitrile is 0.081%, and then adjusting the dynamic viscosity of the polymer liquid to 328 Pa.S by using dimethyl sulfoxide, wherein the adding temperature of the dimethyl sulfoxide is 70 ℃, and the dynamic viscosity of the polymer liquid is the viscosity of the polymer liquid at 40 ℃ measured by a falling ball method;
3) and (3) a defoaming stage: and (3) vacuumizing the defoaming unit equipment to 18kPa, introducing the polymerization liquid with the adjusted viscosity into the defoaming unit equipment, vacuumizing to 3kPa, and standing and defoaming completely to obtain the polyacrylonitrile-based carbon fiber dry-wet spinning solution.
The copolymerization product of the spinning dope obtained had an intrinsic viscosity of 3dL/g and a dynamic viscosity of 328 pas.
Example 6
The polyacrylonitrile-based carbon fiber dry-wet spinning solution in the embodiment is prepared from the following raw materials: 200kg of dimethyl sulfoxide, 0.2kg of azobisisobutyronitrile, 50kg of acrylonitrile, 1.5kg of itaconic acid ethyl ester, 0.1kg of methyl methacrylate and 0.8kg of ethyl methacrylate.
The preparation method of the polyacrylonitrile-based carbon fiber dry-wet spinning solution comprises the following steps:
1) a polymerization stage: under the protection of nitrogen, 200kg of dimethyl sulfoxide, 0.2kg of azodiisobutyronitrile, 50kg of acrylonitrile, 1.5kg of itaconic acid ethyl ester, 0.1kg of methyl methacrylate and 0.8kg of ethyl methacrylate are added into a reactor with stirring to carry out copolymerization reaction, the polymerization reaction temperature is 65 ℃, the stirring rate is 100r/min, the intrinsic viscosity of a copolymerization product is measured by using an Ubbelohde viscometer, and when the intrinsic viscosity of the copolymerization product is 2.8dL/g, ammonia is added to adjust the pH value of a polymerization solution to 8.8;
2) a demonomerization stage: pumping the polymer liquid with the adjusted pH value into a demonomerization kettle by a pump, wherein the temperature in the demonomerization kettle is 65 ℃, removing unreacted monomers for 6 hours by a rotary thin film evaporation method, the mass concentration of residual acrylonitrile is 0.075%, and then adjusting the dynamic viscosity of the polymer liquid to 220 Pa.s by using dimethyl sulfoxide, wherein the adding temperature of the dimethyl sulfoxide is 65 ℃, and the dynamic viscosity of the polymer liquid is the viscosity of the polymer liquid at 40 ℃ measured by a falling ball method;
3) and (3) a defoaming stage: and (3) vacuumizing the defoaming unit equipment to 18kPa, introducing the polymerization liquid with the adjusted viscosity into the defoaming unit equipment, vacuumizing to 3kPa, and standing and defoaming completely to obtain the polyacrylonitrile-based carbon fiber dry-wet spinning solution.
The resulting copolymerization product of the dope had an intrinsic viscosity of 2.8dL/g and a dynamic viscosity of 220 pas.
Example 7
The polyacrylonitrile-based carbon fiber dry-wet spinning solution in the embodiment is prepared from the following raw materials: 200kg of dimethyl sulfoxide, 0.1kg of azodiisobutyronitrile, 80kg of acrylonitrile, 0.2kg of ammonium itaconate, 0.1kg of methyl itaconate and 0.5kg of acrylic acid.
The preparation method of the polyacrylonitrile-based carbon fiber dry-wet spinning solution comprises the following steps:
1) a polymerization stage: under the protection of nitrogen, 200kg of dimethyl sulfoxide, 0.1kg of azodiisobutyronitrile, 80kg of acrylonitrile, 0.2kg of ammonium itaconate, 0.1kg of methyl itaconate and 0.5kg of acrylic acid are added into a reactor with stirring to carry out copolymerization reaction, the polymerization reaction temperature is 65 ℃, the stirring rate is 150r/min, the intrinsic viscosity of a copolymerization product is measured by using a Ubbelohde viscometer, and when the intrinsic viscosity of the copolymerization product is 4.5dL/g, ammonia is added to adjust the pH value of a polymerization solution to 8.5;
2) a demonomerization stage: pumping the polymer liquid with the adjusted pH value into a demonomerization kettle by a pump, wherein the temperature in the demonomerization kettle is 60 ℃, removing unreacted monomers for 8 hours by a rotary thin film evaporation method, the mass concentration of residual acrylonitrile is 0.094%, and then adjusting the dynamic viscosity of the polymer liquid to 400 Pa.S by using dimethyl sulfoxide, wherein the adding temperature of the dimethyl sulfoxide is 80 ℃, and the dynamic viscosity of the polymer liquid is the viscosity of the polymer liquid at 40 ℃ measured by a falling ball method;
3) and (3) a defoaming stage: and (4) vacuumizing the defoaming unit equipment to 2kPa, introducing the polymerization liquid with the adjusted viscosity into the defoaming unit equipment, and continuously defoaming completely to obtain the polyacrylonitrile-based carbon fiber dry-wet spinning solution.
The resulting copolymerization product of the dope had an intrinsic viscosity of 4.5dL/g and a dynamic viscosity of 400 pas.
Example 8
The polyacrylonitrile-based carbon fiber dry-wet spinning solution in the embodiment is prepared from the following raw materials: 200kg of dimethyl sulfoxide, 0.05kg of azodiisovaleronitrile, 35kg of acrylonitrile, 1.2kg of itaconic acid, 0.8kg of itaconic acid ethyl ester and 0.01kg of ethyl methacrylate.
The preparation method of the polyacrylonitrile-based carbon fiber dry-wet spinning solution comprises the following steps:
1) a polymerization stage: under the protection of nitrogen, 200kg of dimethyl sulfoxide, 0.05kg of azodiisovaleronitrile, 35kg of acrylonitrile, 1.2kg of itaconic acid, 0.8kg of itaconic acid ethyl ester and 0.01kg of ethyl methacrylate are added into a reactor with stirring for copolymerization, the polymerization temperature is 58 ℃, the stirring rate is 120r/min, the intrinsic viscosity of a copolymerization product is measured by using a Ubbelohde viscometer, and when the intrinsic viscosity of the copolymerization product is 3.5dL/g, ammonia is added to adjust the pH value of a polymerization solution to 8.9;
2) a demonomerization stage: pumping the polymer liquid with the adjusted pH value into a demonomerization kettle by a pump, wherein the temperature in the demonomerization kettle is 80 ℃, removing unreacted monomers for 6 hours by a rotary thin film evaporation method, the mass concentration of residual acrylonitrile is 0.088%, and then adjusting the dynamic viscosity of the polymer liquid to 260 Pa.S by using dimethyl sulfoxide, wherein the adding temperature of the dimethyl sulfoxide is 80 ℃, and the dynamic viscosity of the polymer liquid is the viscosity of the polymer liquid at 40 ℃ measured by a falling ball method;
3) and (3) a defoaming stage: and (3) vacuumizing the defoaming unit equipment to 10kPa, introducing the polymerization liquid with the adjusted viscosity into the defoaming unit equipment, vacuumizing to 1kPa, and standing and defoaming completely to obtain the polyacrylonitrile-based carbon fiber dry-wet spinning solution.
The resulting copolymerization product of the dope had an intrinsic viscosity of 3.5dL/g and a dynamic viscosity of 260 pas.
Example 9
The polyacrylonitrile-based carbon fiber dry-wet spinning solution in the embodiment is prepared from the following raw materials: 200kg of dimethyl sulfoxide, 0.4kg of dimethyl azodiisobutyrate, 30kg of acrylonitrile, 1kg of methyl itaconate, 0.5kg of ethyl itaconate, 0.01kg of ethyl acrylate and 0.01kg of methyl methacrylate.
The preparation method of the polyacrylonitrile-based carbon fiber dry-wet spinning solution comprises the following steps:
1) a polymerization stage: under the protection of nitrogen, 200kg of dimethyl sulfoxide, 0.4kg of dimethyl azodiisobutyrate, 30kg of acrylonitrile, 1kg of methyl itaconate, 0.5kg of ethyl itaconate, 0.01kg of ethyl acrylate and 0.01kg of methyl methacrylate are added into a reactor with stirring for copolymerization, the polymerization temperature is 60 ℃, the stirring rate is 120r/min, the intrinsic viscosity of a copolymerization product is measured by using an Ubbelohde viscometer, and when the intrinsic viscosity of the copolymerization product is 2.4dL/g, ammonia is added to adjust the pH value of a polymerization solution to 8.2;
2) a demonomerization stage: pumping the polymer liquid with the adjusted pH value into a demonomerization kettle by a pump, wherein the temperature in the demonomerization kettle is 70 ℃, removing unreacted monomers for 6 hours by a rotary thin film evaporation method, the mass concentration of residual acrylonitrile is 0.081%, and then adjusting the dynamic viscosity of the polymer liquid to 160 Pa.S by using dimethyl sulfoxide, wherein the adding temperature of the dimethyl sulfoxide is 70 ℃, and the dynamic viscosity of the polymer liquid is the viscosity of the polymer liquid at 40 ℃ measured by a falling ball method;
3) and (3) a defoaming stage: and (3) vacuumizing the defoaming unit equipment to 10kPa, introducing the polymerization liquid with the adjusted viscosity into the defoaming unit equipment, vacuumizing to 1kPa, and standing and defoaming completely to obtain the polyacrylonitrile-based carbon fiber dry-wet spinning solution.
The resulting copolymerization product of the dope had an intrinsic viscosity of 2.4dL/g and a dynamic viscosity of 160 pas.
The spinning solution prepared in the examples 1 to 9 is subjected to dry-jet wet spinning, solidification forming, washing, hot drawing, oiling, dry densification, steam drafting and relaxation setting to prepare polyacrylonitrile precursor, the diameter of the precursor is controlled to be 8 to 9 mu m, and the orientation degree is more than or equal to 94 percent. The polyacrylonitrile protofilament is subjected to six-stage pre-oxidation at 210-220-230-240-250-260 ℃, six-stage low-temperature carbonization at 350-400-500-600-700-800 ℃ and three-stage high-temperature carbonization at 1000-1200-1400 ℃ to obtain the high-strength polyacrylonitrile carbon fiber, and the test results of the polyacrylonitrile protofilament and the carbon fiber are shown in table 1.
TABLE 1 Polyacrylonitrile precursor Properties and carbon fiber tensile Strength
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
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