CN116065250A - Polyacrylonitrile spinning solution and preparation method and application thereof - Google Patents
Polyacrylonitrile spinning solution and preparation method and application thereof Download PDFInfo
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- CN116065250A CN116065250A CN202111275918.3A CN202111275918A CN116065250A CN 116065250 A CN116065250 A CN 116065250A CN 202111275918 A CN202111275918 A CN 202111275918A CN 116065250 A CN116065250 A CN 116065250A
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- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 45
- 238000009987 spinning Methods 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 52
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 claims abstract description 41
- 239000000243 solution Substances 0.000 claims abstract description 39
- 229920006350 polyacrylonitrile resin Polymers 0.000 claims abstract description 32
- 239000007864 aqueous solution Substances 0.000 claims abstract description 28
- 239000002245 particle Substances 0.000 claims abstract description 23
- 235000011837 pasties Nutrition 0.000 claims abstract description 16
- 238000010008 shearing Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000006185 dispersion Substances 0.000 claims abstract description 12
- 238000009826 distribution Methods 0.000 claims abstract description 10
- 238000004062 sedimentation Methods 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 8
- 238000010009 beating Methods 0.000 claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 36
- 239000012295 chemical reaction liquid Substances 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 17
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 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 8
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000035484 reaction time Effects 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
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-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
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 239000002002 slurry Substances 0.000 abstract description 16
- 238000001125 extrusion Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 3
- 238000010924 continuous production Methods 0.000 abstract description 2
- 229920006253 high performance fiber Polymers 0.000 abstract description 2
- 239000004753 textile Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 9
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 239000011550 stock solution Substances 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- 239000004917 carbon fiber Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000004537 pulping Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000009778 extrusion testing Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- ASMZBOYDOWEBKG-UHFFFAOYSA-L Cl(=O)(=O)[O-].[Na+].[Na+].Cl(=O)(=O)[O-] Chemical compound Cl(=O)(=O)[O-].[Na+].[Na+].Cl(=O)(=O)[O-] ASMZBOYDOWEBKG-UHFFFAOYSA-L 0.000 description 1
- 235000015842 Hesperis Nutrition 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 235000012633 Iberis amara Nutrition 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000005303 weighing 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Artificial Filaments (AREA)
Abstract
The invention relates to the technical field of textile chemicals and high-performance fibers, in particular to a polyacrylonitrile spinning solution, a preparation method and application thereof. The preparation method of the polyacrylonitrile spinning solution comprises the following steps: (1) Mixing polyacrylonitrile resin with a first sodium thiocyanate aqueous solution with the temperature of 10-25 ℃, and carrying out dispersion beating at the temperature of 15-25 ℃ to form a pasty mixture; (2) Mixing the pasty mixture with a second sodium thiocyanate aqueous solution at 100-140 ℃, and shearing at a high speed at 80-90 ℃ to obtain a polyacrylonitrile spinning solution; the number average particle diameter of the polyacrylonitrile resin is 2-9 um, the particle diameter distribution index is 1.5-2.8, and the sedimentation value is 3.0-4.2. The preparation method disclosed by the invention has the advantages that the slurry viscosity is low, the fluidity is good in the preparation process of the polyacrylonitrile spinning solution, the slurry can be used for continuous production, the solid content of the prepared polyacrylonitrile spinning solution is high, the viscosity is small, and the extrusion uniformity and stability are good.
Description
Technical Field
The invention relates to the technical field of textile chemicals and high-performance fibers, in particular to a polyacrylonitrile spinning solution, a preparation method and application thereof.
Background
Carbon fiber is widely applied to different fields of aerospace, satellite rockets, automobile industry, wind power, sports and leisure articles and the like due to the characteristics of high specific strength, high specific modulus, good chemical stability, low thermal expansion coefficient and the like, and the global demand is increased year by year. Among the three organic fiber precursors, polyacrylonitrile is the one with the highest use ratio and the best product quality. The development and application of carbon fibers are playing an increasingly important role in improving national military competence and industrial product competitiveness. In the production process of carbon fibers, the properties of the precursor are a major factor restricting the properties of the carbon fibers.
As the polyacrylonitrile spinning solution, there are usually used N, N-dimethylformamide, dimethyl sulfoxide, N-dimethylacetamide and sodium thiocyanate aqueous solutions. The aqueous solution of sodium thiocyanate is nontoxic compared with other solvents, and is an excellent solvent used in the polyacrylonitrile spinning process. However, polyacrylonitrile is dissolved in sodium thiocyanate aqueous solution, gel and other phenomena are easy to occur in the dissolution process, the solubility is low, the viscosity of the prepared polyacrylonitrile spinning solution is high, and the like, and the polyacrylonitrile spinning solution is an important factor for restricting the preparation of high-performance PAN precursor.
Disclosure of Invention
The invention aims to solve the problems of low solid content and high viscosity of a polyacrylonitrile spinning solution in the prior art, and provides a polyacrylonitrile spinning solution, a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a polyacrylonitrile spinning solution, comprising the steps of:
(1) Mixing polyacrylonitrile resin with a first sodium thiocyanate aqueous solution with the temperature of 10-25 ℃, and carrying out dispersion beating at the temperature of 15-25 ℃ to form a pasty mixture;
(2) Mixing the pasty mixture with a second sodium thiocyanate aqueous solution with the temperature of 100-140 ℃, and shearing at a high speed at the temperature of 80-90 ℃ to obtain a polyacrylonitrile spinning solution;
the number average particle diameter of the polyacrylonitrile resin is 2-9 um, the particle diameter distribution index is 1.5-2.8, and the sedimentation value is 3.0-4.2.
The second aspect of the invention provides a polyacrylonitrile spinning solution prepared by the preparation method.
The third aspect of the invention provides an application of the polyacrylonitrile spinning solution in preparation of polyacrylonitrile precursor.
According to the preparation method of the polyacrylonitrile spinning solution, the obtained pasty mixture is low in viscosity, good in fluidity and stable in property, and after the pasty mixture is mixed with the high-temperature high-concentration sodium thiocyanate solution, the sodium thiocyanate solution is easy to diffuse into the polyacrylonitrile particles; the polyacrylonitrile spinning solution has the advantages of low slurry viscosity, good fluidity, high solid content and low viscosity, and can be used for continuous production.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
According to a first aspect of the present invention, there is provided a method for preparing a polyacrylonitrile spinning solution, the method comprising the steps of:
(1) Mixing polyacrylonitrile resin with a first sodium thiocyanate aqueous solution with the temperature of 10-25 ℃, and carrying out dispersion beating at the temperature of 15-25 ℃ to form a pasty mixture;
(2) Mixing the pasty mixture with a second sodium thiocyanate aqueous solution at 100-140 ℃, and shearing at a high speed at 80-90 ℃ to obtain a polyacrylonitrile spinning solution;
the number average particle diameter of the polyacrylonitrile resin is 2-9 um, the particle diameter distribution index is 1.5-2.8, and the sedimentation value is 3.0-4.2.
According to a preferred embodiment of the invention, the first aqueous sodium thiocyanate solution has a mass concentration of 30 to 35 wt.%, preferably 31 to 34 wt.%.
According to a preferred embodiment of the present invention, the mass content of the polyacrylonitrile resin in the slurry mixture is 18 to 25wt%, preferably 19 to 23wt%.
According to a preferred embodiment of the present invention, the mass content of the polyacrylonitrile resin is 10 to 13wt%, preferably 11 to 12.5wt%, based on the total weight of the polyacrylonitrile spinning solution.
According to a preferred embodiment of the invention, the second aqueous sodium thiocyanate solution has a mass concentration of 56-65 wt.%.
According to a preferred embodiment of the invention, the mass ratio of the pasty mixture to the second aqueous solution of sodium thiocyanate is 30-35 wt%.
According to the present invention, there is no particular requirement for the polyacrylonitrile, and the polyacrylonitrile having the aforementioned properties in the art can be applied to the present invention, and for the present invention, there is provided a process for producing polyacrylonitrile having the aforementioned properties, which comprises:
mixing an acrylonitrile monomer, a first comonomer and a second comonomer in pure water, carrying out polymerization reaction under the polymerization reaction condition through a water-soluble initiator, obtaining a polymerization reaction liquid after the reaction is finished, and obtaining the polyacrylonitrile resin through removing monomers, washing with water, filtering and drying the polymerization reaction liquid.
In the present invention, the removal of the monomer means removal of the unreacted monomer under vacuum.
The invention has no special requirements on the conditions of water washing, filtering and drying of the polymerization reaction liquid, and the conditions of water washing, filtering and drying which are conventional in the field are suitable for the polymer reaction liquid of the invention; preferably, the polyacrylonitrile resin drying process is performed under nitrogen atmosphere at a temperature of 100-150 ℃, preferably under nitrogen atmosphere at a temperature of 110-130 ℃.
According to a preferred embodiment of the invention, the total content of acrylonitrile monomer, first comonomer and second comonomer is from 30 to 45wt%, preferably from 35 to 42wt%, based on the mass of the entire polymerization system.
According to a preferred embodiment of the invention, the first comonomer content is 1 to 5 wt.%, preferably 2 to 4 wt.%, based on the total mass of monomers.
According to a preferred embodiment of the invention, the second comonomer content is 0.5 to 2.0 wt.%, preferably 0.8 to 1.5 wt.%, based on the total mass of monomers.
According to a preferred embodiment of the present invention, the ratio of the mass of the water-soluble azo initiator to the total mass of the monomers is 0.2% to 0.7%:1, preferably 0.25% -0.65%: 1.
according to a preferred embodiment of the present invention, the polymerization conditions include: the reaction temperature is 60 to 80℃and preferably 65 to 75 ℃.
According to the present invention, the reaction time is reasonably adjusted according to the reaction temperature, preferably, the polymerization time is 60 to 100min, more preferably, 70 to 90min
According to a preferred embodiment of the present invention, the first comonomer is selected from at least one of methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate and vinyl acetate.
According to a preferred embodiment of the present invention, the second comonomer is selected from at least one of methacrylic acid, acrylic acid, itaconic acid, acrylamide and methacrylamide.
According to a preferred embodiment of the present invention, the polymerization liquid solid content is 25 to 42wt%, preferably 31 to 42wt%, more preferably 35 to 42wt% of the polymerization liquid solid content.
According to a preferred embodiment of the present invention, the polymerization reaction liquid has a viscosity of 300 to 500cp.
According to a second aspect of the invention, the invention provides a polyacrylonitrile spinning solution prepared by the preparation method.
According to a third aspect of the invention, the invention provides an application of the polyacrylonitrile spinning solution in preparing polyacrylonitrile precursor.
The present invention will be described in detail by examples.
Examples 1 to 10
The first comonomer and the second comonomer are methyl acrylate and itaconic acid respectively, and the feeding mass ratio of acrylonitrile to methyl acrylate to itaconic acid is 96:3:1. The total monomer addition amounts based on the weight of the entire polymerization system are shown in Table 1. The initiator is azo diisobutylamidine hydrochloride (AIBA), and the addition amount of the initiator is shown in table 1 based on the total weight of acrylonitrile, methyl acrylate and itaconic acid. Introducing all monomers, an initiator and pure water into a continuous stirring polymerization kettle, carrying out polymerization reaction under the polymerization condition, obtaining a polymerization reaction liquid after the reaction is finished, removing unreacted monomers in the polymerization reaction liquid under a vacuum state, and then carrying out vacuum filtration washing and drying treatment at 120 ℃ in a nitrogen atmosphere to obtain the polyacrylonitrile resin powder.
Comparative examples 1 to 4
The first comonomer and the second comonomer are methyl acrylate and itaconic acid respectively, and the feeding mass ratio of acrylonitrile, methyl acrylate and itaconic acid monomers is 96:3:1. The total monomer addition amounts based on the weight of the entire polymerization system are shown in Table 1. The initiator adopts sodium chlorate-sodium metabisulfite (oxidation-reduction system), and the adding amount of the initiator is shown in table 1 based on the total weight of acrylonitrile, methyl acrylate and itaconic acid. The polymerization reaction time and temperature are shown in Table 1, after the reaction is finished, the polymerization reaction liquid is obtained, unreacted monomers in the polymerization reaction liquid are removed in a vacuum state, and the obtained polymer is subjected to vacuum filtration washing and drying treatment at 120 ℃ in a nitrogen atmosphere, so that polyacrylonitrile resin powder with controllable particle size and uniform distribution is obtained.
TABLE 1 raw material compositions and polymerization conditions for examples 1-10 and comparative examples 1-4
To examine the polymerization conditions of examples and comparative examples, the degree of reaction can be characterized by the solid content of the polymerization liquid by the following specific methods: taking a certain mass of polymerization reaction liquid, repeatedly carrying out suction filtration and washing to remove monomers, an initiator and other impurities, drying in a 60 ℃ oven until the weight is constant, weighing the powder weight, and obtaining the solid content as the weight ratio of the powder weight to the polymerization reaction liquid; the fluidity of the reaction liquid can be characterized by the viscosity of the reaction liquid, and the specific method is as follows: the reaction liquid slurry is stirred uniformly, a rotor S63 is selected by adopting a rotary rheometer (DV-II-P type), the rotating speed is 70RPM, and the viscosity data is read 30 seconds after the rotation is started. The specific test results are shown in Table 2.
TABLE 2 Properties of the polymerization reaction solution
To examine the molecular weight of the polymerization products of examples and comparative examples, the molecular weight and its distribution were measured by Gel Permeation Chromatography (GPC) by: PMMA is used as a standard sample, and 0.065mol/LNaNO 3 DMF is a flowing sample, the flow rate is 1.5ml/min, and the temperature is 40 ℃; to examine the size and distribution of polymer particles, the WQL particle size and distribution of polymer particles can be measured by a WQL particle analyzer, which comprises the following specific steps: preparing a polymer sample into 0.1-1.0% aqueous solution, carrying out ultrasonic treatment for 2min, and then measuring the particle size and distribution of the aqueous solution by using a particle meter, wherein the particle size and distribution comprises a number average particle size, a weight average particle size and a particle size distribution index; to examine the sedimentation behavior of polymer particles in water, the sedimentation value can be determined by: taking a polymer sample to be analyzed, drying, screening by using a sample separating screen with 85 meshes, taking 10g of the screened polymer, diluting with water, transferring into a 100ml cylinder with a stopper, diluting to 100ml, adding the stopper, shaking, standing for 24h, and reading the sedimentation volume. Sedimentation value = sedimentation volume/10 (ml/g). The test results are shown in Table 3.
TABLE 3 Polymer molecular weight, particle size and sedimentation value
Examples 11 to 20
Mixing the polyacrylonitrile resin powder obtained in examples 1-10 with NaSCN aqueous solution with the temperature of 20 ℃ and the concentration of 32.6wt%, controlling the content of the polyacrylonitrile resin in the mixture to 21wt%, and maintaining the temperature of the mixture material at 20 ℃ for dispersion and pulping to ensure that the polyacrylonitrile resin is uniformly dispersed in the NaSCN aqueous solution to form a pasty mixture; and then the mixture and a 58% NaSCN aqueous solution at 140 ℃ are fed into a high-speed shearing machine, the temperature of the mixture material is maintained at 80 ℃, and the mixture material is rapidly dissolved under the rapid dispersion and grinding effects of the high-speed shearing machine, so that the spinning crude stock solution is obtained. The resin content and NaSCN content are shown in Table 4, based on the weight of the whole crude liquid system.
Example 21
Mixing the polyacrylonitrile resin powder obtained in the example 8 with NaSCN aqueous solution with the temperature of 11 ℃ and the concentration of 35wt%, controlling the content of the polyacrylonitrile resin in the mixture to be 25wt%, and maintaining the temperature of the mixture material to be 11 ℃ for dispersion and pulping to ensure that the polyacrylonitrile resin is uniformly dispersed in the NaSCN aqueous solution to form a pasty mixture; and then the mixture and a 60% NaSCN aqueous solution at the temperature of 100 ℃ are fed into a high-speed shearing machine, the temperature of the mixture material is maintained at 90 ℃, and the mixture material is rapidly dissolved under the rapid dispersion and grinding effects of the high-speed shearing machine, so that the spinning crude stock solution is obtained. The resin content and NaSCN content are shown in Table 4, based on the weight of the whole crude liquid system.
Example 22
Mixing the polyacrylonitrile resin powder obtained in the example 8 with NaSCN aqueous solution with the temperature of 25 ℃ and the concentration of 30wt%, controlling the content of the polyacrylonitrile resin in the mixture to be 18wt%, and maintaining the temperature of the mixture material to be 25 ℃ for dispersion and pulping to ensure that the polyacrylonitrile resin is uniformly dispersed in the NaSCN aqueous solution to form a pasty mixture; and then the mixture and a 65% NaSCN aqueous solution at 120 ℃ are fed into a high-speed shearing machine, the temperature of the mixture material is maintained at 85 ℃, and the mixture material is rapidly dissolved under the rapid dispersion and grinding effects of the high-speed shearing machine, so that the spinning crude stock solution is obtained. The resin content and NaSCN content are shown in Table 4, based on the weight of the whole crude liquid system.
Comparative examples 5 to 7
Polyacrylonitrile spinning dope was prepared by the method of examples 11 to 20 using the polyacrylonitrile resin powder obtained in comparative examples 1 to 3. The resin content and NaSCN content are shown in Table 4, based on the weight of the whole crude liquid system. The resin content and NaSCN content are shown in Table 4, based on the weight of the whole crude liquid system.
Comparative example 8
Unlike in example 18, the polyacrylonitrile resin powder prepared in example 8 was mixed with an aqueous NaSCN solution having a temperature of 10℃and a concentration of 50% by weight, the content of the polyacrylonitrile resin in the mixture was controlled to 12% by weight, and dispersion beating was carried out while maintaining the temperature of the mixture at 10℃to uniformly disperse the polyacrylonitrile resin in the aqueous NaSCN solution to form a slurry-like mixture; and heating the mixture to 90 ℃ and sending the mixture into a high-speed shearing machine, and rapidly dissolving the mixture under the rapid dispersing and grinding actions of the high-speed shearing machine to obtain the spinning crude stock solution. The resin content and NaSCN content are shown in Table 4, based on the weight of the whole crude liquid system.
Comparative example 9
Unlike example 18, the polyacrylonitrile resin powder prepared in example 8 was fed into a high-speed shearing machine together with a 50% aqueous solution of NaSCN at 140 ℃ according to the feed ratio of table 4, and the mixture was maintained at 80 ℃ and rapidly dissolved under the rapid dispersion and grinding action of the high-speed shearing machine, to obtain a spinning dope. The resin content and NaSCN content are shown in Table 4, based on the weight of the whole crude liquid system.
TABLE 4 Polyacrylonitrile dope formulation conditions
To examine the slurry mixture conditions of examples 11 to 22 and comparative examples 5 to 9, the viscosity of the slurry mixture was measured by using a DV-II-P type rotary rheometer by: firstly, uniformly stirring the slurry mixture, selecting an S63 rotor with the rotating speed of 70RPM, and reading viscosity data 30 seconds after starting rotation; the viscosity of the slurry mixture was measured again and the stability was compared after allowing to stand at a constant temperature of 25℃for 24 hr; the fluidity of the slurry mixture was measured by measuring about 50mL of the slurry with a 100mL beaker, pouring the slurry at an angle of 60 DEG after stirring the slurry mixture uniformly, observing the residual condition of the slurry on the wall of the beaker, allowing the mixture to flow down completely without wall hanging, depositing the mixture with a certain thickness after flowing out to form a slight wall hanging, and increasing the deposition thickness with flowing-out time to form a wall sticking state, wherein the specific results are shown in Table 5.
TABLE 5 viscosity, flowability and stability of slurry mixtures
To examine the properties of the spinning dope of examples 11 to 22 and comparative examples 5 to 9, the dope viscosity was measured by using a DV-II-P type rotary rheometer by: firstly, placing a spinning stock solution sample in a constant-temperature water bath at 54 ℃ for heat preservation for 3 hours, selecting an S63 rotor with the rotating speed of 2.0RPM, and starting a rotation reading to stably read viscosity; the spinning dope stock solution uniformity and spinnability can be measured by a constant temperature extrusion test, and the specific method is as follows: the self-made spinning dope extrusion test device is used for testing the extrusion average length, the extrusion quality within 1 minute and the number of broken ends of a dope with a certain volume (600 mL) under a certain pressure (0.3 MPa) and a certain temperature (45 ℃), the dope passes through a filter with 400 meshes of filter materials and then passes through an extrusion outlet with a pore diameter of 3mm, and then the self-weight flows down, and the test result is shown in Table 6.
TABLE 6 dope viscosity, uniformity and stability
As can be seen from the results of Table 5, according to the present invention, the polyacrylonitrile resin was mixed with the first aqueous sodium thiocyanate solution at a temperature of 10 to 25℃and was then dispersed and beaten at a temperature of 15 to 25℃to obtain a slurry-like mixture having good fluidity and stable properties.
As can be seen from the results of Table 6, the slurry mixtures prepared in examples 11 to 22 were mixed with a second aqueous solution of sodium thiocyanate at 100 to 140℃and sheared at a high speed at 80 to 90℃so that the concentrated solution of sodium thiocyanate easily diffused into the particles, and the obtained polyacrylonitrile spinning solution was uniformly dissolved, and had few gel particles, low viscosity and good extrusion uniformity, and was suitable for preparing high-quality polyacrylonitrile filaments.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. The preparation method of the polyacrylonitrile spinning solution is characterized by comprising the following steps of:
(1) Mixing polyacrylonitrile resin with a first sodium thiocyanate aqueous solution with the temperature of 10-25 ℃, and carrying out dispersion beating at the temperature of 15-25 ℃ to form a pasty mixture;
(2) Mixing the pasty mixture with a second sodium thiocyanate aqueous solution at 100-140 ℃, and shearing at a high speed at 80-90 ℃ to obtain a polyacrylonitrile spinning solution;
the number average particle diameter of the polyacrylonitrile resin is 2-9 um, the particle diameter distribution index is 1.5-2.8, and the sedimentation value is 3.0-4.2.
2. The preparation method according to claim 1, wherein,
the mass concentration of the first sodium thiocyanate aqueous solution is 30-35 wt%; and/or
The mass content of the polyacrylonitrile resin in the pasty mixture is 18-25 wt%.
3. The production method according to any one of claims 1 or 2, wherein the mass content of the polyacrylonitrile resin is 10 to 13wt%, based on the total weight of the polyacrylonitrile spinning solution; and/or
The mass concentration of the second sodium thiocyanate aqueous solution is 56-65wt%; and/or
The mass ratio of the pasty mixture to the second sodium thiocyanate aqueous solution is 30-35 wt%.
4. The production method according to any one of claims 1 to 3, wherein the production method of polyacrylonitrile comprises:
mixing an acrylonitrile monomer, a first comonomer and a second comonomer in pure water, carrying out polymerization reaction under the polymerization reaction condition through a water-soluble initiator, obtaining a polymerization reaction liquid after the reaction is finished, and obtaining the polyacrylonitrile resin through removing monomers, washing with water, filtering and drying the polymerization reaction liquid.
5. The process according to any one of claim 1 to 4, wherein,
based on the mass of the whole polymerization system, the total content of the acrylonitrile monomer, the first comonomer and the second comonomer is 30 to 45 weight percent, preferably 35 to 42 weight percent; and/or
The content of the first comonomer is 1-5wt%, preferably 2-4 wt%, based on the total mass of the monomers; and/or
The second comonomer content is 0.5 to 2.0wt%, preferably 0.8 to 1.5wt%, based on the total mass of the monomers; and/or
The mass ratio of the water-soluble azo initiator to the total mass of the monomers is 0.2% -0.7%: 1, preferably 0.25% -0.65%: 1.
6. the preparation method according to claim 5, wherein,
the polymerization conditions include: the reaction temperature is 60-80 ℃, preferably 65-75 ℃; and/or
The reaction time is 60-100min, preferably 70-90min.
7. The preparation method according to claim 5 or 6, wherein,
the first comonomer is at least one selected from methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate and vinyl acetate; and/or
The second comonomer is selected from at least one of methacrylic acid, acrylic acid, itaconic acid, acrylamide and methacrylamide.
8. The process according to any one of claim 5 to 7, wherein,
the solid content of the polymerization reaction liquid is 25-42wt%; and/or
The viscosity of the polymerization reaction liquid is 300-500cp.
9. A polyacrylonitrile spinning solution prepared by the preparation method of any one of claims 1 to 8.
10. Use of the polyacrylonitrile spinning solution according to claim 9 for the preparation of polyacrylonitrile filaments.
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| CN102400239A (en) * | 2010-09-17 | 2012-04-04 | 中国石油化工股份有限公司 | Method for manufacturing polyacrylonitrile base carbon fiber precursor |
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| CN109721677A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of preparation method of polyacrylonitrile spinning solution for carbon fiber |
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| CN112679654A (en) * | 2019-10-17 | 2021-04-20 | 中国石油化工股份有限公司 | Preparation method of polyacrylonitrile resin with controllable particle size and uniform distribution |
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| CN102400239A (en) * | 2010-09-17 | 2012-04-04 | 中国石油化工股份有限公司 | Method for manufacturing polyacrylonitrile base carbon fiber precursor |
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