CN117431652B - Method for preparing polyacrylic fiber through dry spinning - Google Patents
Method for preparing polyacrylic fiber through dry spinning Download PDFInfo
- Publication number
- CN117431652B CN117431652B CN202311715232.0A CN202311715232A CN117431652B CN 117431652 B CN117431652 B CN 117431652B CN 202311715232 A CN202311715232 A CN 202311715232A CN 117431652 B CN117431652 B CN 117431652B
- Authority
- CN
- China
- Prior art keywords
- fiber
- polyacrylic
- polyacrylic acid
- preparing
- spinning
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 121
- 238000000034 method Methods 0.000 title claims abstract description 59
- 238000000578 dry spinning Methods 0.000 title claims abstract description 40
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 80
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 80
- 238000009987 spinning Methods 0.000 claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 59
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 58
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052742 iron Inorganic materials 0.000 claims abstract description 29
- 230000003197 catalytic effect Effects 0.000 claims abstract description 27
- 150000003839 salts Chemical class 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 17
- 238000009998 heat setting Methods 0.000 claims abstract description 16
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 28
- -1 iron ion Chemical class 0.000 claims description 28
- 238000004090 dissolution Methods 0.000 claims description 18
- 238000002386 leaching Methods 0.000 claims description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 15
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 14
- 229960002089 ferrous chloride Drugs 0.000 claims description 12
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical group Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 230000009471 action Effects 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical group [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 21
- 239000000243 solution Substances 0.000 description 37
- 239000011259 mixed solution Substances 0.000 description 26
- 239000004342 Benzoyl peroxide Substances 0.000 description 12
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 12
- 235000019400 benzoyl peroxide Nutrition 0.000 description 12
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 12
- 229960000907 methylthioninium chloride Drugs 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 150000002505 iron Chemical class 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000004042 decolorization Methods 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 238000001891 gel spinning Methods 0.000 description 3
- 238000002074 melt spinning Methods 0.000 description 3
- 238000002166 wet spinning Methods 0.000 description 3
- 229920006125 amorphous polymer Polymers 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000001291 vacuum drying 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
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/52—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated carboxylic acids or unsaturated esters
-
- 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
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
-
- 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
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/04—Dry spinning methods
-
- 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
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/12—Stretch-spinning methods
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Artificial Filaments (AREA)
Abstract
The invention relates to a method for preparing polyacrylic fiber by dry spinning, which comprises the following steps: extruding a polyacrylic acid spinning solution containing ferric salt and ethanol from a spinneret to form a spinning trickle, volatilizing a solvent in hot air, solidifying and forming, stretching and heat setting; the content of ferric salt in the polyacrylic acid spinning solution is 2.5-3.0wt% and the content of ethanol is 2.5-7.5wt%. The preparation method has the advantages of simple preparation process, short process period, low cost and the like, and the prepared fiber has higher stretching rate, higher mechanical property, high water resistance, better catalytic activity and iron ion fixing capability.
Description
Technical Field
The invention belongs to the technical field of textile materials, and relates to a method for preparing polyacrylic fibers by dry spinning.
Background
In recent years, with the rapid development of the spinning industry technology, fiber forming and processing technologies are mature gradually, and most of the fibers produced at present meet the basic use requirements of people, but in face of the increasing market demands, it is necessary to explore specific processes and conditions to simplify the fiber preparation process and improve the fiber performance.
Polyacrylic acid, an amorphous polymer, has the characteristics of a fiber-forming polymer, and can be used for preparing polyacrylic acid fibers. In the prior art, spinning is generally performed through technologies such as wet spinning, melt spinning and gel spinning, but when polyacrylic fibers are prepared through the wet spinning technology, parameters and process conditions which need to be met are various, the fiber preparation process is complex and the period is long, for example, patent CN113083372A discloses a heterogeneous oxidation reaction catalytic fiber preparation method, primary fibers coordinated by iron ions are mainly stretched in a solidification medium or an air medium, and the polyacrylic fibers are prepared through a heat setting technology, so that the obtained fibers are low in strength, complex in preparation process, long in period and high in cost; when the polyacrylic acid fiber is prepared by the melt spinning technology, the phenomena of difficult fiber forming and drawing and yarn breakage occur in the preparation process, and the prepared fiber has the problems of low drawing multiple, poor performance and the like; when the polyacrylic acid fiber is prepared by the gel spinning technology, the phenomena of slower solidification and formation of the fiber, easy breakage in stretching, bubble in gel, gel aggregation and difficult phase separation can occur in the preparation process, and the prepared fiber has the problems of low stretching multiple, poor fiber forming, poor performance and the like.
Compared with the technologies of wet spinning, melt spinning, gel spinning and the like, the dry spinning has the advantages of simple process, low cost and high production speed. However, the prior art cannot prepare polyacrylic fibers by dry spinning because: polyacrylic acid is an amorphous polymer, and is not easy to solidify and form, has low curing speed and poor fiber forming performance in the dry spinning forming process, so that polyacrylic acid fiber cannot be formed effectively, and therefore, the preparation of polyacrylic acid fiber cannot be widely applied in the field of dry spinning.
Therefore, it is of great importance to explore a simple preparation process to produce a dry-stretched polyacrylic fiber material.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a method for preparing polyacrylic acid fiber by dry spinning, and the prepared fiber has the advantages of higher stretching rate, higher mechanical property, high water resistance, better catalytic activity and iron ion fixing capability.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for preparing polyacrylic acid fiber by dry spinning comprises the following steps: extruding polyacrylic acid spinning solution containing ferric salt (as cross-linking agent and active component of catalytic reaction) and ethanol from a spinning nozzle to form spinning trickle, volatilizing solvent in hot air, solidifying and forming, stretching and heat setting; the content of ferric salt in the polyacrylic acid spinning solution is 2.5-3.0wt%, the content of ethanol is 2.5-7.5wt%, and the ferric salt is ferrous salt and/or ferric salt.
The prior art can not prepare the polyacrylic acid fiber through dry spinning, the invention overcomes the defects of the prior art, and the polyacrylic acid fiber is successfully prepared through dry spinning because: (1) the polyacrylic acid spinning solution contains ferric salt, the ferric salt can coordinate polyacrylic acid before spinning forming, so as to promote solidification forming of fibers and provide assistance for completion of a post-stretching process, the content of the ferric salt in the polyacrylic acid spinning solution is controlled to be 2.5-3.0wt%, when the content of the ferric salt in the spinning solution is too high, the phenomenon of gel aggregation of the spinning solution in a short time can occur, so that spinning forming can not be performed, and when the content of the ferric salt in the spinning solution is too low, the phenomenon that spinning trickles after dry spinning can not be formed in time and finally can not be solidified into filaments can occur; (2) the polyacrylic acid spinning solution contains ethanol, the ethanol is used as a boiling point reducing agent of the spinning solvent, volatilization of the spinning solvent can be accelerated, forming of polyacrylic acid fibers is facilitated, polyacrylic acid is slightly dissolved in the ethanol, a small amount of ethanol is added into the spinning solution to reduce the evaporating temperature of the spinning solvent, and the fiber solidification forming rate is accelerated.
As a preferable technical scheme:
according to the method for preparing the polyacrylic acid fiber through dry spinning, the polyacrylic acid spinning solution is composed of 10-15wt% of polyacrylic acid, 9-18wt% of formamide, 2.5-7.5wt% of ethanol, 2.5-3.0wt% of ferric salt and the balance of water, wherein the formamide can be used as a fiber softener and modifier, and can form a plurality of hydrogen bond structures with carboxyl or hydroxyl on the polyacrylic acid, so that Van der Waals force among molecular chains is increased, and the flexibility and mobility of the molecular chains are increased, thereby being beneficial to forming the fiber with high stretching multiple.
The method for preparing the polyacrylic acid fiber by dry spinning comprises the steps that polyacrylic acid is an acrylic acid-maleic anhydride copolymer, and the polyacrylic acid is obtained by polymerizing acrylic acid and maleic anhydride with the mass ratio of 90:10-97.5:2.5 under the action of an initiator (benzoyl peroxide) (the method is a solution polymerization method); the monomers commonly used for preparing polyacrylic acid in the prior art mainly comprise acrylic acid and methacrylic acid, and experiments show that the fiber forming performance of an acrylic acid-maleic anhydride copolymer formed by polymerization is better than that of a methacrylic acid-maleic anhydride copolymer, so that the acrylic acid-maleic anhydride copolymer is selected as a polymer for preparing a polyacrylic acid spinning solution.
According to the method for preparing the polyacrylic acid fiber through dry spinning, the ferric salt is ferrous chloride or a mixture of ferrous chloride and ferric chloride in a molar ratio of 7:3-9:1, and compared with the fiber prepared by the method, the fiber prepared by the method has a more stable ionic crosslinking network and is more excellent in mechanical property, water resistance, catalytic activity and iron ion fixing capability.
The method for preparing the polyacrylic fiber by dry spinning is characterized in that the solvent is volatilized in hot air and solidified and formed at the temperature of 40-80 ℃ for 1-5 hours.
In a dry spinning process for preparing polyacrylic fibers as described above, stretching is carried out in air.
A dry spinning method for preparing polyacrylic fiber is described above, and the stretching multiple is 4-6.
The method for preparing the polyacrylic fiber by dry spinning is characterized in that the heat setting temperature is 60-140 ℃ and the time is 1.5-12h.
The method for preparing the polyacrylic fiber by dry spinning has the advantages that the tensile strength of the polyacrylic fiber is 0.41-0.99cN/dtex, the elongation at break is 83.08-132.13%, the shrinkage in water is 14.43-30.47%, the dissolution rate in water is 17.72-22.37%, the catalytic activity is 5-10min, and the average iron ion leaching concentration is 2.08-4.76mg/L.
The beneficial effects are that:
according to the invention, based on a dry spinning process and a stretching process, ethanol is introduced into a spinning solvent, ferric salt is introduced into the spinning solution, so that the forming of the polyacrylic acid fiber is facilitated, and the parameters and process conditions which need to be satisfied are fewer, so that the problems of complex preparation flow, longer period, high process cost and the like of the polyacrylic acid fiber in the prior art are solved, and finally, the prepared polyacrylic acid fiber has higher stretching multiple, good force performance, high water resistance, good catalytic activity and iron ion fixing capability.
Detailed Description
The invention is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
The following are test methods for each performance in the examples:
mechanical properties: the mechanical properties of the fiber samples were tested using a YG026 type electronic single fiber brute force instrument (Winzhou high test instruments Co., ltd.) at a stretching speed of 10mm/min, a temperature of 25 ℃, a relative humidity of 30%, and a fiber grip distance of 10mm; when the fiber sample is broken under the action of external force, the ratio of the elongation of the fiber sample after stretching to the length before stretching is the elongation at break in units; tensile strength is the maximum tensile force in cN/dtex that can be sustained in a tensile test before breaking the fiber sample.
Shrinkage in water: immersing a fiber sample with a certain length into 10mL of deionized water, measuring the length of the fiber after shrinkage after immersing for 10min at 25 ℃, and then calculating the shrinkage rate of the fiber in water, wherein the calculation formula is as follows:
； (1)
wherein S is the shrinkage in water (%), Z 0 For the fiber length (cm) before shrinkage, Z is the fiber length (cm) after shrinkage.
Dissolution rate in water: placing the fiber sample in a filter paper bag, soaking the fiber sample in deionized water at 85 ℃ for 4 hours, then taking the filter paper bag out of the deionized water, placing the filter paper bag in a vacuum drying oven at 60 ℃ for full drying, and then calculating the dissolution rate of the fiber sample, wherein the calculation formula is as follows:
； (2)
wherein G is the dissolution rate (%), m in water 0 For the dry fiber mass before dissolution (g), m 1 For the total mass (g), m of the fibers and the filter paper bag before dissolution 2 Is the total mass (g) of the dissolved fibers and the filter paper bag.
Catalytic activity: at 25℃10mL of MB (methylene blue) aqueous solution having a mass concentration of 20mg/L was added to a 50mL beaker, and 2. Mu.L of H was measured using a pipette 2 O 2 Adding the fiber into a beaker, weighing 0.06g of the fiber, placing the fiber into the MB aqueous solution, continuously oscillating the beaker, monitoring the absorbance value of a target solution at 664nm wavelength by using a TU-1810 type ultraviolet-visible spectrophotometer (Beijing general analysis instrument Co., ltd.), obtaining the Decolorization Rate (DR) of the MB aqueous solution by using a formula (3), evaluating the catalytic performance of the fiber, taking out a fiber sample from the beaker when the DR is higher than 90%, removing residual moisture on the surface of the fiber by using filter paper, and recording the time required for the DR to reach 90%, thus obtaining the catalytic activity; the fiber decolorized new MB aqueous solution was reused in the above steps to evaluate its reusability; the formula of the decoloring rate is as follows:
； (3)
wherein DR is a decoloring ratio (%), C 0 Concentration of initial MB in aqueous solution (mg/L), C 1 Concentration of MB in aqueous solution after treatment (mg/L), C 1 From the standard curve of concentration-absorbance.
Average iron ion leaching concentration: the H was catalyzed with a certain amount of fibers following the procedure described in the test of catalytic activity 2 O 2 Decolorizing MB aqueous solution, separating the fiber from MB aqueous solution when the decolorization ratio reaches a desired value, and obtaining a fiber according to the literature Chen S Q, xu N K, ren M R, et al PEI/GO-coded poly (acrylic acid-co-hydroxyethyl methacrylate) fiber as a carrier to support iron ions and its catalytic performance for methylene blue decolorization [ J]The method described in 531-543, journal of Macromolecular Science Part A-Pure and Applied Chemistry, 2020, 57 (7) measures the concentration of iron ions in the MB aqueous solution after decolorization and calculates the average iron ion leaching concentration during recycling of the fiber decolorized MB aqueous solution, with the formula:
mg/L； （4）
wherein AE is the average iron ion leaching concentration, A i And n is the number of recycling times for the absorbance value of the mixed solution after the constant volume.
The following are the manufacturer and brand of the raw materials in each example:
acrylic acid: the manufacturer is Tianjin chemical reagent limited company, and the specification is chemical purity;
maleic anhydride: the manufacturer is Shanghai Ala Biochemical technology Co., ltd, and the specification is analytically pure;
benzoyl peroxide: the manufacturer is Shanghai Ala Biochemical technology Co., ltd, and the specification is analytically pure;
formamide: the manufacturer is Tianjin chemical reagent limited company, and the specification is analytical grade;
ethanol: the manufacturer is Tianjin Fengsha chemical reagent technology Co., ltd, and the specification is analytically pure;
water: tianjin blue ocean industry water manager.
Example 1
A method for preparing polyacrylic fiber by dry spinning comprises the following steps:
(1) Preparing raw materials;
polyacrylic acid: acrylic acid-maleic anhydride copolymer, the preparation process is: at normal temperature, a mixed solution I is composed of 0.15g of benzoyl peroxide, 17.5g of acrylic acid, 2.50g of maleic anhydride and 100g of deionized water, and a mixed solution II is composed of 0.1g of benzoyl peroxide and 30g of acrylic acid; adding the mixed solution I into a four-neck flask with a stirrer, a nitrogen guide pipe and a reflux condenser, stirring at a speed of 180r/min at 85 ℃ under nitrogen atmosphere for reaction, dropwise adding the mixed solution II into the mixed solution I (dropwise adding time is 30 min), continuously reacting for 2h, and separating, drying, crushing, washing and re-drying to obtain powdery polyacrylic acid;
formamide;
ethanol;
iron salt: ferrous chloride;
water;
(2) Preparing a polyacrylic acid spinning solution;
10wt% of polyacrylic acid, 9wt% of formamide, 5wt% of ethanol, 2.73wt% of ferric salt and the balance of water are mixed to obtain a polyacrylic acid spinning solution;
(3) The process flow comprises the following steps: extruding the polyacrylic acid spinning solution obtained in the step (2) from a spinneret to form a spinning trickle, volatilizing a solvent in hot air, solidifying and forming, stretching and heat setting; wherein the temperature for volatilizing the solvent in hot air and solidifying and forming is 60 ℃, the time is 2 hours, the stretching is 5 times of stretching in the air, the temperature for heat setting is 130 ℃, and the time is 5 hours.
The tensile strength of the polyacrylic fiber prepared by the method is 0.42cN/dtex, the elongation at break is 120.32%, the shrinkage in water is 30.47%, the dissolution rate in water is 21.56%, the catalytic activity is 10min, and the average iron ion leaching concentration is 4.59mg/L.
Comparative example 1
A process for preparing polyacrylic fibres by dry spinning, substantially as described in example 1, with the only differences: the content of iron salt in the polyacrylic acid spinning solution was 1.5wt%.
The tensile strength of the polyacrylic fiber prepared by the method is 0.36cN/dtex, the elongation at break is 103.24%, the shrinkage in water is 34.28%, the dissolution rate in water is 27.56%, the catalytic activity is 15min, and the average iron ion leaching concentration is 4.21 mg/L.
Comparative example 2
A process for preparing polyacrylic fibres by dry spinning, substantially as described in example 1, with the only differences: the content of iron salt in the polyacrylic acid spinning solution was 3.5wt%.
The tensile strength of the polyacrylic fiber prepared by the method is 0.40cN/dtex, the elongation at break is 147.41%, the shrinkage in water is 28.49%, the dissolution rate in water is 24.14%, the catalytic activity is 12min, and the average iron ion leaching concentration is 4.94mg/L.
Comparing comparative examples 1, 2 and example 1, it is known that the fiber matrix is too fluffy due to the higher content of ferric salt in the spinning solution in comparative example 2, the internal crosslinking structure is not compact, the fixing ability to iron ions is insufficient, the tensile strength and catalytic activity of the fiber are reduced, and the breaking elongation and average iron ion leaching concentration are increased; however, the spinning solution in comparative example 1 has a low iron salt content, and the fiber produced has an insufficient degree of iron ion crosslinking structure, which results in a decrease in tensile strength, elongation at break and catalytic activity of the fiber, and an increase in the average iron ion leaching concentration.
Example 2
A method for preparing polyacrylic fiber by dry spinning comprises the following steps:
(1) Preparation of raw materials
Polyacrylic acid: acrylic acid-maleic anhydride copolymer, the preparation process is: at normal temperature, a mixed solution I is composed of 0.15g of benzoyl peroxide, 17.5g of acrylic acid, 2.50g of maleic anhydride and 100g of deionized water, and a mixed solution II is composed of 0.1g of benzoyl peroxide and 30g of acrylic acid; adding the mixed solution I into a four-neck flask with a stirrer, a nitrogen guide pipe and a reflux condenser, stirring at a speed of 200r/min at 85 ℃ under nitrogen atmosphere for reaction, dropwise adding the mixed solution II into the mixed solution I (dropwise adding time is 30 min), continuously reacting for 2h, and separating, drying, crushing, washing and re-drying to obtain powdery polyacrylic acid;
formamide;
ethanol;
iron salt: a mixture of ferrous chloride and ferric chloride in a molar ratio of 7:3;
water;
(2) Preparing a polyacrylic acid spinning solution;
10wt% of polyacrylic acid, 9wt% of formamide, 5wt% of ethanol, 2.58wt% of ferric salt and the balance of water are mixed to obtain a polyacrylic acid spinning solution;
(3) The process flow comprises the following steps: extruding the polyacrylic acid spinning solution obtained in the step (2) from a spinneret to form a spinning trickle, volatilizing a solvent in hot air, solidifying and forming, stretching and heat setting; wherein the temperature for volatilizing the solvent in hot air and solidifying and forming is 60 ℃, the time is 2 hours, the stretching is 5 times of stretching in the air, the temperature for heat setting is 130 ℃, and the time is 5 hours.
The tensile strength of the polyacrylic fiber prepared by the method is 0.99cN/dtex, the elongation at break is 83.08%, the shrinkage in water is 14.43%, the dissolution rate in water is 17.72%, the catalytic activity is 5min, and the average iron ion leaching concentration is 2.08mg/L.
Comparative example 3
A process for preparing polyacrylic fibres by dry spinning, substantially as described in example 2, with the only differences: the content of ethanol in the polyacrylic acid spinning solution was 2.0wt%.
The tensile strength of the polyacrylic fiber prepared by the method is 0.87cN/dtex, the elongation at break is 140.27%, the shrinkage in water is 32.46%, the dissolution rate in water is 25.67%, the catalytic activity is 7min, and the average iron ion leaching concentration is 2.97mg/L.
Comparative example 4
A process for preparing polyacrylic fibres by dry spinning, substantially as described in example 2, with the only differences: the content of ethanol in the polyacrylic acid spinning solution was 8.0wt%.
The tensile strength of the polyacrylic fiber prepared by the method is 0.76cN/dtex, the elongation at break is 76.24%, the shrinkage in water is 21.49%, the dissolution rate in water is 22.84%, the catalytic activity is 10min, and the average iron ion leaching concentration is 3.42mg/L.
Comparing comparative examples 3, 4 and example 2, it is apparent that the tensile strength, elongation at break and catalytic activity of the fiber are reduced due to the excessively high content of ethanol in the polyacrylic acid spinning solution in comparative example 4, and the shrinkage in water, dissolution in water and average iron ion leaching concentration are increased; this is because polyacrylic acid is not easily dissolved in ethanol, the preparation period of the polyacrylic acid spinning solution is prolonged, and the matrix of the prepared fiber has structural defects such as air holes and the like left when the spinning solvent is rapidly evaporated; however, the content of ethanol in the polyacrylic acid spinning solution in comparative example 3 is too low, which results in a higher evaporation temperature of the spinning solvent of the fiber matrix, and is not easy to completely evaporate in a short time, so that the spinning solvent still remains in the fiber matrix, which is unfavorable for the fiber forming and drawing processes, and thus the performance of the obtained fiber is also reduced.
Example 3
A method for preparing polyacrylic fiber by dry spinning comprises the following steps:
(1) Preparation of raw materials
Polyacrylic acid: acrylic acid-maleic anhydride copolymer, the preparation process is: at normal temperature, a mixed solution I is composed of 0.15g of benzoyl peroxide, 25g of acrylic acid, 5g of maleic anhydride and 100g of deionized water, and a mixed solution II is composed of 0.1g of benzoyl peroxide and 20g of acrylic acid; adding the mixed solution I into a four-neck flask with a stirrer, a nitrogen guide pipe and a reflux condenser, stirring at the speed of 190r/min at the temperature of 85 ℃ under the nitrogen atmosphere for reaction, simultaneously adding the mixed solution II into the mixed solution I dropwise (the dropwise adding time is 30 min), continuously reacting for 2 hours, and separating, drying, crushing, washing and re-drying to obtain powdery polyacrylic acid;
formamide;
ethanol;
iron salt: a mixture of ferrous chloride and ferric chloride in a molar ratio of 8:2;
water;
(2) Preparing a polyacrylic acid spinning solution;
mixing 15wt% of polyacrylic acid, 9wt% of formamide, 5wt% of ethanol, 2.58wt% of ferric salt and the balance of water to obtain a polyacrylic acid spinning solution;
(3) The process flow comprises the following steps: extruding the polyacrylic acid spinning solution obtained in the step (2) from a spinneret to form a spinning trickle, volatilizing a solvent in hot air, solidifying and forming, stretching and heat setting; wherein the temperature for volatilizing the solvent in hot air and solidifying and forming is 60 ℃, the time is 2 hours, the stretching is 4 times of stretching in the air, the temperature for heat setting is 60 ℃, and the time is 12 hours.
The tensile strength of the polyacrylic fiber prepared by the method is 0.69cN/dtex, the elongation at break is 101.23%, the shrinkage in water is 17.38%, the dissolution rate in water is 20.16%, the catalytic activity is 8min, and the average iron ion leaching concentration is 3.49mg/L.
Example 4
A method for preparing polyacrylic fiber by dry spinning comprises the following steps:
(1) Preparation of raw materials
Polyacrylic acid: acrylic acid-maleic anhydride copolymer, the preparation process is: at normal temperature, a mixed solution I is composed of 0.15g of benzoyl peroxide, 18.75g of acrylic acid, 1.25g of maleic anhydride and 100g of deionized water, and a mixed solution II is composed of 0.1g of benzoyl peroxide and 30g of acrylic acid; adding the mixed solution I into a four-neck flask with a stirrer, a nitrogen guide pipe and a reflux condenser, stirring at 185r/min at 85 ℃ under nitrogen atmosphere for reaction, dropwise adding the mixed solution II into the mixed solution I (dropwise adding time is 30 min), continuously reacting for 2h, and separating, drying, crushing, washing and re-drying to obtain powdery polyacrylic acid;
formamide;
ethanol;
iron salt: a mixture of ferrous chloride and ferric chloride in a molar ratio of 9:1;
water;
(2) Preparing a polyacrylic acid spinning solution;
10wt% of polyacrylic acid, 18wt% of formamide, 2.5wt% of ethanol, 2.58wt% of ferric salt and the balance of water are mixed to obtain a polyacrylic acid spinning solution;
(3) The process flow comprises the following steps: extruding the polyacrylic acid spinning solution obtained in the step (2) from a spinneret to form a spinning trickle, volatilizing a solvent in hot air, solidifying and forming, stretching and heat setting; wherein the temperature for volatilizing the solvent in hot air and solidifying and forming is 80 ℃, the time is 1h, the stretching is 6 times of stretching in the air, the temperature for heat setting is 140 ℃, and the time is 1.5h.
The tensile strength of the polyacrylic fiber prepared by the method is 0.74cN/dtex, the elongation at break is 93.27%, the shrinkage in water is 16.43%, the dissolution rate in water is 19.63%, the catalytic activity is 7min, and the average iron ion leaching concentration is 2.74mg/L.
Example 5
A method for preparing polyacrylic fiber by dry spinning comprises the following steps:
(1) Preparation of raw materials
Polyacrylic acid: acrylic acid-maleic anhydride copolymer, the preparation process is: at normal temperature, a mixed solution I is composed of 0.15g of benzoyl peroxide, 17.5g of acrylic acid, 2.50g of maleic anhydride and 100g of deionized water, and a mixed solution II is composed of 0.1g of benzoyl peroxide and 30g of acrylic acid; adding the mixed solution I into a four-neck flask with a stirrer, a nitrogen guide pipe and a reflux condenser, stirring at a speed of 195r/min at 85 ℃ under nitrogen atmosphere for reaction, dropwise adding the mixed solution II into the mixed solution I (dropwise adding time is 30 min), continuously reacting for 2h, and separating, drying, crushing, washing and re-drying to obtain powdery polyacrylic acid;
formamide;
ethanol;
iron salt: a mixture of ferrous chloride and ferric chloride in a molar ratio of 7:3;
water;
(2) Preparing a polyacrylic acid spinning solution;
10wt% of polyacrylic acid, 9wt% of formamide, 7.5wt% of ethanol, 3.00wt% of ferric salt and the balance of water are mixed to obtain a polyacrylic acid spinning solution;
(3) The process flow comprises the following steps: extruding the polyacrylic acid spinning solution obtained in the step (2) from a spinneret to form a spinning trickle, volatilizing a solvent in hot air, solidifying and forming, stretching and heat setting; wherein the temperature for volatilizing the solvent in hot air and solidifying and forming is 40 ℃, the time is 5 hours, the stretching is 5 times of stretching in the air, the temperature for heat setting is 130 ℃, and the time is 5 hours.
The tensile strength of the polyacrylic fiber prepared by the method is 0.82cN/dtex, the elongation at break is 87.32%, the shrinkage in water is 15.97%, the dissolution rate in water is 18.37%, the catalytic activity is 6min, and the average iron ion leaching concentration is 2.37mg/L.
Example 6
A process for preparing polyacrylic fibers by dry spinning, substantially the same as in example 5, except that: the ferric salt prepared in step (1) is ferrous chloride.
The tensile strength of the polyacrylic fiber prepared by the method is 0.41cN/dtex, the elongation at break is 132.13%, the shrinkage in water is 29.16%, the dissolution rate in water is 22.37%, the catalytic activity is 10min, and the average iron ion leaching concentration is 4.76mg/L.
Comparing example 5 with example 6, it can be seen that the fiber prepared by using the mixed valence iron salt as the cross-linking agent in example 5 has a more stable ionic cross-linking network, and also has good mechanical property, water resistance, catalytic activity and iron ion fixing capability; in example 6, the mixture of ferrous chloride and ferric chloride is replaced by ferrous chloride as the cross-linking agent, and compared with the fiber prepared in example 5, the fiber matrix of the fiber has a loose ionic cross-linking network, the defects of an aggregation state structure are increased, the internal cross-linking structure is not compact, and the mechanical property, the water resistance, the catalytic activity, the iron ion fixing capability and other properties of the fiber are reduced.
The present invention is not limited to the above embodiments, and the present invention can be implemented with good effects.
Claims (8)
1. A method for preparing polyacrylic fiber by dry spinning is characterized in that the process flow comprises the following steps: extruding a polyacrylic acid spinning solution containing ferric salt and ethanol from a spinneret to form a spinning trickle, volatilizing a solvent in hot air, solidifying and forming, stretching and heat setting; the content of ferric salt in the polyacrylic acid spinning solution is 2.5-3.0wt%, the content of ethanol is 2.5-7.5wt%, and the ferric salt is ferrous salt and/or ferric salt;
the tensile strength of the polyacrylic fiber is 0.41-0.99cN/dtex, the elongation at break is 83.08-132.13%, the shrinkage in water is 14.43-30.47%, the dissolution in water is 17.72-22.37%, the catalytic activity is 5-10min, and the average iron ion leaching concentration is 2.08-4.76mg/L.
2. The method for preparing the polyacrylic acid fiber by dry spinning according to claim 1, wherein the polyacrylic acid spinning solution consists of 10-15wt% of polyacrylic acid, 9-18wt% of formamide, 2.5-7.5wt% of ethanol, 2.5-3.0wt% of ferric salt and the balance of water.
3. The method for preparing the polyacrylic acid fiber by dry spinning according to claim 1, wherein the polyacrylic acid is an acrylic acid-maleic anhydride copolymer, and is obtained by polymerizing acrylic acid and maleic anhydride in a mass ratio of 90:10-97.5:2.5 under the action of an initiator.
4. The method for preparing the polyacrylic acid fiber by dry spinning according to claim 1, wherein the ferric salt is ferrous chloride or a mixture of ferrous chloride and ferric chloride in a molar ratio of 7:3-9:1.
5. The method for preparing the polyacrylic fiber by dry spinning according to claim 1, wherein the temperature for volatilizing the solvent in hot air and solidifying and forming is 40-80 ℃ for 1-5h.
6. A method for preparing polyacrylic fibers by dry spinning according to claim 1, wherein the stretching is performed in air.
7. A method for preparing polyacrylic fiber by dry spinning according to claim 1, wherein the multiple of stretching is 4-6.
8. The method for preparing the polyacrylic fiber by dry spinning according to claim 1, wherein the heat setting temperature is 60-140 ℃ and the time is 1.5-12h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311715232.0A CN117431652B (en) | 2023-12-14 | 2023-12-14 | Method for preparing polyacrylic fiber through dry spinning |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311715232.0A CN117431652B (en) | 2023-12-14 | 2023-12-14 | Method for preparing polyacrylic fiber through dry spinning |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117431652A CN117431652A (en) | 2024-01-23 |
| CN117431652B true CN117431652B (en) | 2024-03-22 |
Family
ID=89553659
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311715232.0A Active CN117431652B (en) | 2023-12-14 | 2023-12-14 | Method for preparing polyacrylic fiber through dry spinning |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117431652B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1090895A (en) * | 1992-08-19 | 1994-08-17 | 钟纺株式会社 | high hygroscopicity fibre |
| CN105002587A (en) * | 2015-08-04 | 2015-10-28 | 浙江中烟工业有限责任公司 | Organic-inorganic nanofibers composite tow and preparation method and application thereof |
| CN113083372A (en) * | 2021-05-17 | 2021-07-09 | 天津工业大学 | Preparation method of heterogeneous oxidation reaction catalytic fiber |
| CN115557790A (en) * | 2022-11-11 | 2023-01-03 | 中国人民解放军国防科技大学 | Elastic SiC ceramic sponge material and preparation method and application thereof |
-
2023
- 2023-12-14 CN CN202311715232.0A patent/CN117431652B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1090895A (en) * | 1992-08-19 | 1994-08-17 | 钟纺株式会社 | high hygroscopicity fibre |
| CN105002587A (en) * | 2015-08-04 | 2015-10-28 | 浙江中烟工业有限责任公司 | Organic-inorganic nanofibers composite tow and preparation method and application thereof |
| CN113083372A (en) * | 2021-05-17 | 2021-07-09 | 天津工业大学 | Preparation method of heterogeneous oxidation reaction catalytic fiber |
| CN115557790A (en) * | 2022-11-11 | 2023-01-03 | 中国人民解放军国防科技大学 | Elastic SiC ceramic sponge material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117431652A (en) | 2024-01-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100557098C (en) | A kind of manufacture method of polyacrylonitrile base carbon fiber precursors | |
| JP3933712B2 (en) | Acrylonitrile-based precursor fiber for carbon fiber, method for producing the same, and carbon fiber obtained from the precursor fiber | |
| Yamashiki et al. | New class of cellulose fiber spun from the novel solution of cellulose by wet spinning method | |
| CN102517671B (en) | Method for preparing carbon fiber precursor by two-step process of aqueous suspension and solution polymerization | |
| CN100570026C (en) | The manufacture method of polyacrylonitrile base carbon fiber precursors | |
| KR20150083796A (en) | Process for the production of acrylic fibers | |
| CN102953153B (en) | A kind of preparation method of polyacrylonitrile-based carbon fibre | |
| US4143200A (en) | Synthetic filaments and fibres with high moisture absorption and water retention capacity | |
| CN1743517A (en) | Method for preparing copolymerized acrylonitrile high water-absorption fiber | |
| CN117431652B (en) | Method for preparing polyacrylic fiber through dry spinning | |
| CN109137117A (en) | The method of the low swelling capacity polyacrylonitrile as-spun fibre of dry-jet wet-spinning | |
| CN117403341B (en) | Preparation method of polyacrylic fiber with high stretching ratio | |
| US5286844A (en) | Method of purifying polyacrylonitrile | |
| JP3728862B2 (en) | Water-absorbing acrylic fiber | |
| US4185059A (en) | Process for the preparation of hydrophilic fibres and filaments from synthetic polymers | |
| CN102953138A (en) | Manufacturing method for polyacrylonitrile-based carbon fiber protofilament | |
| JPH0586970B2 (en) | ||
| KR100224474B1 (en) | A manufacturing method for polyvinyl alcohol fiber with high absorptiveness and intensivity | |
| JP3041655B2 (en) | Acrylonitrile fiber and method for producing the same | |
| CN102953156A (en) | Manufacturing method for polyacrylonitrile-based carbon fiber | |
| CN218893770U (en) | Acrylonitrile-acrylic acid polymer dissolving equipment | |
| CN116876093B (en) | Polyacrylamide/graphene composite fiber and preparation method thereof | |
| CN1039337C (en) | Purification method of polyacrylonitrile | |
| JP3104049B2 (en) | Method for purifying polymer solution and method for producing polymer | |
| CN117983075A (en) | Polyacrylonitrile-based conductive ultrafiltration membrane for water treatment and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |