CN112442892B - Method for catalytically hydrolyzing polyacrylonitrile material under acidic condition - Google Patents
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- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 45
- 239000000463 material Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 33
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 17
- 230000003301 hydrolyzing effect Effects 0.000 title claims abstract description 9
- 239000000835 fiber Substances 0.000 claims abstract description 61
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000003929 acidic solution Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- -1 hydrogen ions Chemical class 0.000 claims abstract description 9
- 230000007935 neutral effect Effects 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical group Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 5
- 230000007062 hydrolysis Effects 0.000 abstract description 4
- 229920001002 functional polymer Polymers 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000012467 final product Substances 0.000 description 24
- 238000010521 absorption reaction Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 239000004753 textile Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- 238000002479 acid--base titration Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000004566 IR spectroscopy Methods 0.000 description 5
- JIAARYAFYJHUJI-UHFFFAOYSA-L Zinc chloride Inorganic materials [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010945 base-catalyzed hydrolysis reactiony Methods 0.000 description 1
- 229910001451 bismuth ion Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
- D06M11/55—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
- D06M11/13—Ammonium halides or halides of elements of Groups 1 or 11 of the Periodic Table
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
- D06M11/155—Halides of elements of Groups 2 or 12 of the Periodic Table
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
- D06M11/55—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
- D06M11/56—Sulfates or thiosulfates other than of elements of Groups 3 or 13 of the Periodic Table
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
- D06M11/64—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with nitrogen oxides; with oxyacids of nitrogen or their salts
- D06M11/65—Salts of oxyacids of nitrogen
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- D—TEXTILES; PAPER
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
- D06M2101/28—Acrylonitrile; Methacrylonitrile
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Artificial Filaments (AREA)
Abstract
The invention relates to a method for catalyzing and hydrolyzing a polyacrylonitrile material under an acidic condition, belonging to the field of functional polymer materials. Adding a catalyst into the acidic solution to obtain a mixed solution, and heating to 60-130 ℃; and adding a PAN material into the mixed solution, reacting for 0.5-6 h, taking out the material after the reaction is finished, and washing to be neutral to obtain the PAN-COOH fiber. According to the method, the catalyst is added into the reaction solution, so that the concentration of hydrogen ions in the reaction solution is reduced, and the hydrolysis rate of the PAN material in a low-concentration acidic solution is increased.
Description
Technical Field
The invention relates to a method for catalytically hydrolyzing a Polyacrylonitrile (PAN) material under an acidic condition, in particular to a method for preparing a high-strength carboxylic acid type functional material by adding a catalyst into a reaction liquid to improve the hydrolysis rate of the PAN material in a low-concentration acid solution, and belongs to the field of functional polymer materials.
Background
The carboxyl group (-COOH) serves as a functional group, which can impart various effects to the material. In the field of air purification, the material containing carboxyl can effectively remove alkaline harmful gas in the air and purify the living environment. In the field of sewage treatment, a material containing carboxyl can adsorb heavy metal ions in water through ion exchange to treat industrial wastewater. In the field of new materials, materials containing carboxyl are used as substrates, functional compounds containing amino or other groups are grafted, and various functional materials can be prepared.
PAN contains nitrile group (-CN) which can be converted into carboxyl group (-COOH) or metal salt (-COOM) of carboxyl group under acid or alkaline condition, and is the main matrix for preparing carboxyl-containing material by chemical modification. There are two main methods of hydrolysis of PAN materials: acid-catalyzed hydrolysis and base-catalyzed hydrolysis. Wherein, the acid catalyzed hydrolysis usually takes a high-concentration inorganic acid solution as a reaction solution to hydrolyze the PAN fiber under the heating condition. A large amount of inorganic acid is used during the reaction, and high concentration of acid not only corrodes equipment but also makes post-treatment difficult. Hydrochloric acid is volatile, which makes it difficult to operate at boiling; high concentrations of sulfuric acid solutions may dissolve the PAN material, affecting the application of the hydrolysate.
Disclosure of Invention
In view of the above, the present invention provides a method for catalytically hydrolyzing Polyacrylonitrile (PAN) material under acidic conditions. According to the method, the catalyst is added into the reaction solution, so that the concentration of hydrogen ions in the reaction solution is reduced, and the hydrolysis rate of the PAN material in a low-concentration acidic solution is increased.
In order to achieve the purpose of the invention, the following technical scheme is provided.
A method for catalytically hydrolyzing polyacrylonitrile materials under acidic conditions, the method steps comprising:
adding a catalyst into the acidic solution to obtain a mixed solution, and heating to 60-130 ℃; and adding a PAN material into the mixed solution, reacting for 0.5-6 h, taking out the material after the reaction is finished, and washing to be neutral to obtain the PAN-COOH fiber.
The catalyst is bismuth nitrate oxidant or zinc chloride transition metal salt; preferably, the catalyst is bismuth nitrate, zinc chloride or nickel sulfate.
The acid solution is prepared from an acid substance; preferably, the acidic substance is an inorganic acid(ii) a More preferably, the acidic material is sulfuric acid (H) 2 SO 4 ) Hydrochloric acid (HCl) or nitric acid (HNO) 3 )。
Hydrogen ions (H) in the acidic solution + ) The concentration of (B) is 1mol/L to 6mol/L.
The solvent of the mixed solution is deionized water, ethanol, ethylene glycol, dimethylformamide or dimethyl sulfoxide; preferably, the solvent is deionized water.
The metal ions and H in the catalyst + The mass ratio of (a) to (b) is 1; preferably, the metal ions in the catalyst are reacted with H + The mass ratio of (1).
The ratio of the volume (mL) of the mixed solution to the mass (g) of the PAN material is (1-8978) zxft 8978; preferably, the ratio of the volume of the mixed solution to the mass of the PAN fiber is 50.
The reaction temperature is preferably 80 ℃ to 120 ℃.
The PAN material comprises textile fibers, engineering fibers, yarns, gauze, non-woven fabrics, spunlaced fabrics and needled fabrics.
The mass transfer enhancement is preferably effected by stirring during the hydrolysis reaction.
Advantageous effects
1. The invention provides a method for catalytically hydrolyzing PAN material under acidic conditions, which hydrolyzes PAN material under low-concentration acidic solution by adding a catalyst. Compared with the prior art, the PAN material with unit mass is hydrolyzed by using the acidic solution with the same hydrogen ion concentration, the PAN-COOH fiber generated by the method has high carboxyl content and more sufficient reaction; in addition, the PAN material with the same amount is hydrolyzed to generate PAN-COOH fibers with the same amount, the method has the advantages of less usage amount of acidic substances, lower usage amount of hydrogen ions in the reaction process, lower production cost and more environment-friendly process conditions.
2. According to the method, the PAN material is hydrolyzed by using the low-concentration acidic solution as the reaction solution, so that the corrosion to equipment and the dissolution to the PAN material are reduced, and the PAN-COOH fiber with higher strength is obtained.
Drawings
Fig. 1 is a graph of the infrared absorption spectrum of PAN textile fibers.
FIG. 2 is an infrared absorption spectrum of PAN-COOH fibers obtained in example 1.
Detailed Description
The invention is described in detail below with reference to the drawings and specific embodiments, but the invention is not limited thereto.
In the following examples:
(1) Fourier transform infrared spectroscopy (FTIR): compacting the fiber sample by adopting an intelligent component of a Nicolet 6700 Fourier transform infrared spectrometer under the test condition that the scanning wave number is 400-4000 cm -1 Resolution of 4cm -1 The number of scans 32.
(2) The method for measuring the carboxyl content is an acid-base titration method, and specifically comprises the following steps:
1g of product to be detected is accurately weighed: shaking and reacting in 100mL of 0.1mol/L standard sodium hydroxide solution for 30min, taking 20mL of supernatant, titrating by using 0.1mol/L standard hydrochloric acid solution, and calculating the content of carboxyl.
(3) Testing the fiber strength:
using a Uster Hvi 1000 fiber tester: manufactured by the swiss Uster company; the breaking strength of the fibers to be tested was measured according to the method specified in GB/T14337-1993 test methods for breaking Strength and elongation of synthetic staple fibers.
(4) The length of the PAN textile fibers was 38mm.
Comparative example 1
Heating 200ml of 3mol/L sulfuric acid solution to 100 ℃, wherein the solvent of the sulfuric acid solution is deionized water, adding 4g of PAN textile fiber, carrying out reflux reaction for 2 hours, stirring by a magnetic rotor, taking out the fiber after the reaction is finished, and washing the fiber to be neutral by the deionized water to obtain a final product.
The structure of the final product of this comparative example was determined by infrared spectroscopy at 2240cm -1 The relative intensity of the characteristic peaks on the left and right is weakened, which shows that the relative content of-CN groups in the product is reduced, and the final product obtained by the comparative example is 3400cm -1 The absorption peak of the left and right active hydrogen is strong and sharp, 1069.61cm -1 The C-O expansion vibration absorption peak becomes wide and strong and is 1739.23cm -1 Has a C = O expansion and contraction vibration absorption peakThe presence of-COOH groups in the final product was noted, and it was found that the final product obtained in this comparative example was PAN-COOH fibers.
The carboxyl content of the PAN-COOH fiber prepared in the comparative example is 0.28mmol/g measured by an acid-base titration method; the fiber strength test shows that the breaking strength of the PAN-COOH fiber prepared by the comparative example is 3.21cN/dtex.
Comparative example 2
Heating 200ml of 1mol/L nitric acid solution to 100 ℃, wherein the solvent of the nitric acid solution is deionized water, adding 4g of PAN textile fiber, carrying out reflux reaction for 2h, stirring by a magnetic rotor, taking out the fiber after the reaction is finished, and washing the fiber to be neutral by the deionized water to obtain a final product.
The structure of the final product of this comparative example was determined by infrared spectroscopy at 2240cm -1 The relative intensity of the characteristic peaks on the left and right is weakened, which shows that the relative content of-CN groups in the product is reduced, and the final product obtained by the comparative example is 3400cm -1 The absorption peak of the left and right active hydrogen is strong and sharp, 1069.61cm -1 The C-O stretching vibration absorption peak becomes wide and strong, and is 1739.23cm -1 The stretching vibration absorption peak of C = O indicates that the final product has a — COOH group, and it is understood that the final product obtained in this comparative example is PAN-COOH fiber.
The carboxyl content of the PAN-COOH fiber prepared in the comparative example is 0.11mmol/g measured by an acid-base titration method; the fiber strength test shows that the breaking strength of the PAN-COOH fiber prepared by the comparative example is 4.45cN/dtex.
Example 1
Adding 8.00g of bismuth nitrate into 200ml of nitric acid solution with the concentration of 1mol/L, wherein the solvent of the nitric acid solution is deionized water, bismuth ions and H + Heating to 100 ℃, adding 4g of PAN textile fiber into the mixed aqueous solution, carrying out reflux reaction for 2 hours, stirring by a magnetic rotor, taking out the fiber after the reaction is finished, and washing the fiber to be neutral by deionized water to obtain a final product.
The structure of the final product of this example was examined by infrared spectroscopy, and the results are shown in FIG. 2; the characteristic peak of infrared absorption of-CN group (2243.09 cm) can be seen from the infrared absorption spectrum of PAN textile fiber in FIG. 1 -1 ),Strong and sharp, indicating a high content of-CN groups. In FIG. 2 the-CN group is at 2240cm -1 The relative intensity of the left and right characteristic peaks is obviously weakened compared with that of figure 1, which shows that the relative content of-CN groups is reduced, 3400cm -1 The absorption peak of the left and right active hydrogen is strong and sharp, 1069.61cm -1 The C-O stretching vibration absorption peak becomes wide and strong, and is 1739.23cm -1 The presence of a stretching vibration absorption peak of C = O indicates that a large number of — COOH groups are present in the final product, and it is understood that the final product obtained in this example is PAN-COOH fibers.
The carboxyl content of the PAN-COOH fiber prepared in the example was determined to be 0.36mmol/g by acid-base titration. The fiber strength test shows that the breaking strength of the PAN-COOH fiber prepared in the embodiment is 4.27cN/dtex.
Example 2
Adding 1.40g of zinc chloride into 200ml of hydrochloric acid solution with the concentration of 2mol/L, wherein the solvents of the hydrochloric acid solution are deionized water, zinc ions and H + Heating to 100 ℃, adding 4g of PAN textile fiber into the mixed solution, performing reflux reaction for 2 hours, stirring by a magnetic rotor, taking out the fiber after the reaction is finished, and washing the fiber to be neutral by deionized water to obtain a final product, wherein the mass ratio of the substances is 1.
The structure of the final product of this example was determined by infrared spectroscopy at 2240cm -1 The relative intensity of the characteristic peaks on the left and right is weakened, which indicates that the relative content of-CN groups in the product is reduced, and the final product obtained in the example is 3400cm -1 The absorption peak of the left and right active hydrogen is strong and sharp, 1069.61cm -1 The C-O stretching vibration absorption peak becomes wide and strong, and is 1739.23cm -1 The stretching vibration absorption peak of C = O indicates that a large number of — COOH groups are present in the final product, and it is understood that the final product obtained in this example is PAN-COOH fiber.
The carboxyl content of the PAN-COOH fiber prepared in the embodiment is measured to be 0.40mmol/g by an acid-base titration method. The fiber strength test shows that the breaking strength of the PAN-COOH fiber prepared in the embodiment is 4.22cN/dtex.
Example 3
2.20g of nickel sulphate were added to 200ml of a 1mol/L sulphuric acid solution, the sulphur being presentThe solvent of the acid solution is deionized water, zinc ions and H + Heating to 100 ℃, adding 4g of PAN textile fiber into the mixed solution, performing reflux reaction for 2 hours, stirring by a magnetic rotor, taking out the fiber after the reaction is finished, and washing the fiber to be neutral by deionized water to obtain a final product, wherein the mass ratio of the substances is 1.
The structure of the final product of this example was determined by infrared spectroscopy at 2240cm -1 The relative intensity of the characteristic peaks on the left and right is weakened, which indicates that the relative content of-CN groups in the product is reduced, and the final product obtained in the example is 3400cm -1 The absorption peak of the left and right active hydrogen is strong and sharp, 1069.61cm -1 The C-O stretching vibration absorption peak becomes wide and strong, and is 1739.23cm -1 The stretching vibration absorption peak of C = O indicates that a large number of — COOH groups are present in the final product, and it is understood that the final product obtained in this example is PAN-COOH fiber.
The carboxyl content of the PAN-COOH fiber prepared in the example was determined to be 0.39mmol/g by acid-base titration. The fiber strength test shows that the breaking strength of the PAN-COOH fiber prepared by the embodiment is 4.23cN/dtex.
The carboxyl content and the breaking strength of the PAN-COOH fibres obtained in the respective proportions and examples were compared, the results being shown in table 1 (below):
TABLE 1 comparison of the carboxyl content of PAN-COOH fibers
As can be seen from Table 1, the PAN-COOH fibers obtained in examples 1 to 3 have not only a significantly higher amount of carboxyl groups than comparative example 1 and a significantly higher fiber strength than comparative example 1, but also H using an acid solution + The concentration is also lower; as can be seen from the data of comparative example 2 and example 1, PAN-COOH fibers obtained by the method of the present invention were obtained by hydrolyzing PAN material per unit mass with an acidic solution having the same hydrogen ion concentrationThe carboxyl content is high, and the reaction is more sufficient; in conclusion, compared with the prior art, the PAN-COOH fiber prepared by the method disclosed by the invention contains a large amount of carboxyl and has good strength.
The present invention includes, but is not limited to, the above embodiments, and any equivalent substitutions or partial modifications made under the principle of the spirit of the present invention should be considered as being within the scope of the present invention.
Claims (6)
1. A method for catalyzing and hydrolyzing polyacrylonitrile materials under acidic conditions is characterized in that: the method comprises the following steps:
adding a catalyst into an acidic solution to obtain a mixed solution, and heating to 60-130 ℃; adding a PAN material into the mixed solution, reacting for 0.5 to 6 hours, taking out the material after the reaction is finished, and washing to be neutral to obtain PAN-COOH fibers;
the catalyst is bismuth nitrate;
the acid solution is prepared from acid substances;
the concentration of hydrogen ions in the acidic solution is 1-6 mol/L;
the solvent of the mixed solution is deionized water;
the mass ratio of the metal ions to the hydrogen ions in the catalyst is 1:100 to 1:10;
the ratio of the volume of the mixed solution to the mass of the PAN material is 100 mL: 1 g-5 mL: 1g;
the acidic substance is sulfuric acid, hydrochloric acid or nitric acid.
2. The method of claim 1, wherein the polyacrylonitrile material is catalytically hydrolyzed under an acidic condition: the mass ratio of the metal ions to the hydrogen ions in the catalyst is 1: 50-1: 10.
3. The method of claim 1, wherein the polyacrylonitrile material is catalytically hydrolyzed under an acidic condition: the ratio of the volume of the mixed solution to the mass of the PAN fiber is 50 mL: 1 g-8 mL: 1g.
4. The method of claim 1, wherein the polyacrylonitrile material is catalytically hydrolyzed under an acidic condition: the reaction temperature is 80-120 ℃.
5. The method of claim 1, wherein the polyacrylonitrile material is catalytically hydrolyzed under an acidic condition: the method increases agitation during the reaction.
6. The method of claim 1, wherein the polyacrylonitrile material is catalytically hydrolyzed under an acidic condition:
the mass ratio of metal ions to hydrogen ions in the catalyst is 1: 50-1: 10;
the ratio of the volume of the mixed solution to the mass of the PAN fiber is 50 mL: 1 g-8 mL: 1g;
the reaction temperature is 80-120 ℃;
the method increases agitation during the reaction.
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