CN114381827A - Preparation method of low-cost polyethylene-based carbon fiber - Google Patents
Preparation method of low-cost polyethylene-based carbon fiber Download PDFInfo
- Publication number
- CN114381827A CN114381827A CN202210228157.4A CN202210228157A CN114381827A CN 114381827 A CN114381827 A CN 114381827A CN 202210228157 A CN202210228157 A CN 202210228157A CN 114381827 A CN114381827 A CN 114381827A
- Authority
- CN
- China
- Prior art keywords
- fiber
- polyethylene
- carbon fiber
- low
- based carbon
- 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.)
- Pending
Links
Images
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
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
The invention discloses a preparation method of low-cost polyethylene-based carbon fiber, which comprises the steps of firstly stirring and uniformly mixing polyethylene, an ultraviolet light initiator, a cross-linking agent and a stabilizing agent, fully dispersing, and then carrying out melt spinning to obtain ultraviolet light-sensitive PE fiber; then, drawing and annealing the ultraviolet-sensitive PE fiber to enhance the mechanical property of the fiber; then adopting an ultraviolet light source for irradiation to convert the linear or slightly branched chain type macromolecules into a three-dimensional reticular structure; finally, carrying out carbonization treatment to obtain the low-cost PE-based carbon fiber. The invention adopts the ultraviolet irradiation mode to crosslink PE macromolecules, shortens the stabilization treatment period of the PE-based carbon fiber precursor, improves the production efficiency of carbon fibers, avoids the use of high-energy rays and high-temperature concentrated sulfuric acid, has the advantages of low production cost, low energy consumption, short process period, environmental protection and the like of the carbon fibers, and is easy for industrial implementation.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a preparation method of low-cost polyethylene-based carbon fibers.
Background
Carbon Fiber (CF) is a high-performance fiber composed of more than 90% of carbon elements, has the characteristics of high strength, high modulus, high temperature resistance and the like, and is widely used in the fields of aerospace, rail transit, marine equipment, pressure vessels, building bridges, wind power blades, sports and leisure articles and the like.
There are three main types of precursors (precursors) of carbon fibers: polyacrylonitrile (PAN), asphalt and regenerated cellulose fiber, wherein PAN carbon fiber has the advantages of high strength and high modulus, accounts for 90% of the total carbon fiber yield, but the carbon yield is only 45%, the PAN carbon fiber is formed by adopting a solution spinning method, the production cost is high due to coagulation bath concentration, waste solvent recovery treatment and the like, and the PAN carbon fiber is difficult to meet the application requirements of large scale and low cost in the fields of wind power generation, new energy automobile frames, high-pressure gas cylinders, drilling platforms, sports equipment and the like.
Polyethylene (PE) is one of five synthetic resins, and is also the variety with the largest capacity and the largest import quantity in the synthetic resins in China. PE-based carbon fibers offer advantages over traditional PAN-CF in price and supply, such as high carbon yield (about 70%), excellent processability and very competitive cost. However, PE has a low melting point (130-135 ℃) and needs to be carbonized after stabilization treatment to obtain carbon fibers. At present, the PE precursor fiber is mainly subjected to concentrated sulfuric acid and high-temperature sulfonation treatment or electron beam irradiation crosslinking assisted concentrated sulfuric acid sulfonation. The electron beam irradiation equipment is expensive and 5-10 times of the ultraviolet irradiation equipment, and high-energy rays have great potential safety hazards to the personal safety and health of operators. The sulfonation and crosslinking process of concentrated sulfuric acid is long, and a large amount of toxic SOx gas is generated, so that the problems of environment and safety are caused.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of low-cost polyethylene-based carbon fiber.
The invention provides a preparation method of low-cost polyethylene-based carbon fiber, which is characterized by comprising the following steps:
(1) preparing ultraviolet light sensitive PE fiber: uniformly stirring and mixing polyethylene, an ultraviolet light initiator, a cross-linking agent and a stabilizing agent, fully dispersing, and performing melt spinning to obtain ultraviolet light-sensitive PE fibers;
(2) drawing treatment and annealing treatment: carrying out drafting treatment and annealing treatment on the ultraviolet light sensitive PE fiber obtained in the step (1), improving the orientation degree of the fiber, eliminating internal stress, and enhancing the mechanical property of the fiber to obtain the treated ultraviolet light sensitive PE fiber;
(3) ultraviolet crosslinking: irradiating the treated ultraviolet sensitive PE fiber obtained in the step (2) by adopting an ultraviolet light source to convert linear or slightly branched macromolecules into a three-dimensional network structure to obtain a cross-linked PE fiber;
(4) carbonizing: and carbonizing the cross-linked PE fiber to obtain the low-cost PE-based carbon fiber.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, the PE macromolecules are crosslinked in an ultraviolet irradiation mode, the stabilization period is only 10-600 s, the stabilization treatment period of the PE-based carbon fiber precursor is shortened, the production efficiency of carbon fibers is improved, the use of high-energy rays and high-temperature concentrated sulfuric acid is avoided, the carbon fiber preparation method has the advantages of low production cost, low energy consumption, short process period, environmental friendliness and the like, can meet the requirements of large-scale use in the fields of new energy automobiles, wind power blades, sports leisure articles and the like, and is easy for industrial implementation.
(2) The prepared cross-linked PE fiber can tolerate the high temperature of 900-2400 ℃, and the excellent thermodynamic stability is kept in the carbonization process.
(3) The preparation process of the carbon fiber is green and environment-friendly, and accords with the national green low-carbon development strategy. The carbon fiber precursor preparation has zero solvent consumption and zero sulfide emission in the stabilization process.
(4) The average diameter of the PE-based carbon fiber prepared by the method is 5-15 mu m, and the density is 1.7-2.5 g/cm3The carbon fiber has the advantages of 1.2-5.0 GPa of tensile strength, 80-350 GPa of tensile modulus and 1-3% of elongation at break, and the obtained carbon fiber has excellent performance.
Drawings
FIG. 1 is an electron microscope image of the apparent morphology of a low-cost PE-based carbon fiber prepared in example 1 of the present invention;
FIG. 2 is an electron microscope image of the cross-sectional morphology of the low-cost PE-based carbon fiber prepared in example 1 of the present invention;
FIG. 3 is an electron microscope image of the cross-sectional morphology of the low-cost PE-based carbon fiber prepared in example 1 of the present invention;
FIG. 4 is an electron microscope image of the apparent morphology of the low-cost PE-based carbon fiber prepared in example 2 of the present invention;
FIG. 5 is an electron microscope image of the apparent morphology of the low-cost PE-based carbon fiber prepared in example 3 of the present invention;
Detailed Description
Specific examples of the present invention are given below. The specific examples are only intended to illustrate the invention in further detail and do not limit the scope of protection of the claims of the present application.
The invention provides a preparation method (method for short) of low-cost polyethylene-based carbon fiber, which is characterized by comprising the following steps:
(1) preparing ultraviolet light sensitive PE fiber: fully drying polyethylene particles, an ultraviolet light initiator, a cross-linking agent and a stabilizing agent, adding the materials into a high-speed mixer, uniformly stirring and mixing the materials, fully dispersing the materials, and adding the materials into a melt extruder for melt spinning to obtain ultraviolet light sensitive PE fibers;
preferably, in the step (1), the mass ratio of each component is as follows: 89.0-99.69 wt% of polyethylene granules, 0.1-5.0 wt% of ultraviolet initiator, 0.2-5.0 wt% of cross-linking agent and 0.01-1.0 wt% of stabilizer, wherein the sum of the mass of each component is 100%.
The function of the ultraviolet light initiator is as follows: absorbing certain wavelength of ultraviolet light energy to generate free radicals, thereby initiating the crosslinking of the PE monomer. The function of the cross-linking agent is: the quantum efficiency of the ultraviolet initiator is improved, the rate of the crosslinking reaction is accelerated, and the crosslinking uniformity is improved. The light stabilizer has the functions of: absorb ultraviolet rays and convert them into harmless heat energy; the heat stabilizer has the functions of: can slow down the reaction, maintain chemical equilibrium, prevent light, thermal or oxidative decomposition, etc.
Preferably, in the step (1), the melt spinning temperature is 150-220 ℃.
Preferably, in the step (1), the polyethylene is one of Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), High Density Polyethylene (HDPE), cross-linked polyethylene (XLPE) or ultraviolet cross-linked polyethylene (UXPE). When UV-crosslinked polyethylene is used, no UV-initiator may be added.
Preferably, in the step (1), the ultraviolet photoinitiator is one of Hexachlorobenzene (HCB), chlorendic anhydride (HET), Benzophenone (BP), 4-chlorobenzophenone (4-CBP), 4 '-dichlorobenzophenone (4,4' -DBP), 2-methylanthraquinone (2-MAQ), 2-ethylanthraquinone (2-EAQ), 2-chloroanthraquinone (2-CAQ), tetrachlorobenzoquinone (p-CA), dibenzyl sulfide (BS), phenyl sulfoxide (BSO), 4-acetylbiphenyl (4-AB), Anthrone (AT), Sandoray (TM) 1000, Chloroanhydride (CA), 4-nitrobenzophenone (4-NBP) or 2-chlorophenol ketone (2-CBP); preferably hexachlorobenzene, chlorendic anhydride, benzophenone, 4-chlorobenzophenone or 4,4' -dichlorobenzophenone.
Preferably, in the step (1), the crosslinking agent is one of triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), trimethylolpropane triacrylate (TMPTA), pentaerythritol triallyl acrylate (PETA), tetraarm polyethylene glycol-acrylate (4-APEGA), Neopentyl Glycol Diacrylate (NGD), trimethylolpropane trimethacrylate (TMOT), polydipentaerythritol hexaacrylate (DPAH), pentaerythritol triacrylate (PAT), 1, 5-pentanediol diacrylate (1,5-PDD), trimethylolpropane triacrylate (TEPT), dipropylene glycol diacrylate (DPGD), 1, 4-butanediol dimethacrylate (1,4-BDD), or Ethylene Glycol Diacrylate (EGD); triallyl cyanurate, triallyl isocyanurate, trimethylolpropane triacrylate or pentaerythritol triallyl propionate are preferred.
Preferably, in step (1), the stabilizer comprises a light stabilizer and a heat stabilizer; the light stabilizer is one of Chimassorb81, Tinuvin 770, Tinuvin 622, Chimassorb 944, Uvinul 3039, Uvinul 3035, Chimassorb 2020 or Tinuvin B97; the heat stabilizer is one of antioxidant 1010, antioxidant 1012, antioxidant 2246, antioxidant 3052, antioxidant XH-245 or antioxidant 412S.
(2) Drawing treatment and annealing treatment: carrying out drafting treatment and annealing treatment on the ultraviolet light sensitive PE fiber obtained in the step (1), improving the orientation degree of the fiber, eliminating internal stress, and enhancing the mechanical property of the fiber to obtain the treated ultraviolet light sensitive PE fiber; the drawing treatment and the annealing treatment can be carried out synchronously, and can also be carried out in sequence in any order (namely drawing first and then annealing, or annealing first and then drawing);
preferably, in the step (2), the drawing treatment process is as follows: the fiber is subjected to drafting treatment at 100-120 ℃, so that the orientation degree of macromolecular chains in a low-order area of the fiber along the axial direction of the fiber is improved, the change of density and crystallinity structure is accompanied, the number of molecular chains bearing external tension of the fiber is increased as a result of the drafting, the breaking strength of the fiber is obviously improved, the extensibility is reduced, the wear resistance and the fatigue strength to various types of deformation are also obviously improved, and the drafting multiple is 1-5 times.
Preferably, in the step (2), the annealing treatment process is as follows: annealing treatment is carried out on the fiber at 120-150 ℃ for 10-60 min, internal stress is eliminated, growth of macromolecules in a crystal region is more complete, and strength and toughness of the fiber are improved.
(3) Ultraviolet crosslinking: irradiating the treated ultraviolet-sensitive PE fiber obtained in the step (2) by adopting an ultraviolet light source of 2-30 kW for 10-600 s, so that linear or slightly branched macromolecules are converted into a three-dimensional network structure, the strength, the heat resistance and other properties are improved, if no crosslinking reaction is carried out, the PE fiber is melted during high-temperature calcination, and the irradiation temperature is between room temperature and 150 ℃, so that a crosslinked PE fiber is obtained;
(4) carbonizing: and carbonizing the cross-linked PE fiber at 900-2400 ℃ for 5-60 min in a nitrogen atmosphere, wherein the heating rate is 1-5 ℃/min, and thus the low-cost PE-based carbon fiber is obtained.
Example 1
(1) Fully drying 98 wt% of HDPE granules, 1.0 wt% of ultraviolet initiator 4-CBP, 0.5 wt% of cross-linking agent TAIC and 0.5 wt% of stabilizer antioxidant 1010, adding the dried materials into a high-speed mixer, uniformly stirring and mixing, and then adding the mixture into a melt extruder for spinning at the spinning temperature of 210 ℃ to obtain ultraviolet-sensitive PE fibers;
(2) drafting the fiber at 120 ℃ and stretching by 3 times; annealing at 130 ℃ for 30min to obtain the treated ultraviolet-sensitive PE fiber;
(3) irradiating the treated ultraviolet sensitive PE fiber for 300s by adopting an ultraviolet light source with the light intensity of 20kW at the irradiation temperature of 60 ℃ to obtain a crosslinked PE fiber;
(4) and carbonizing the cross-linked PE fiber at 1000 ℃ for 10min in a nitrogen atmosphere, wherein the heating rate is 5 ℃/min, and thus the low-cost PE-based carbon fiber is obtained.
The average diameter of the PE-based carbon fiber was 10 μm, and the density was 1.8g/cm3The tensile strength is 1.8GPa, the tensile modulus is 180GPa, the elongation at break is 1.2%, and the performance of the obtained carbon fiber meets the requirements of the carbon fiber.
As can be seen from fig. 2 and 3, the obtained carbon fiber has a circular shape and a morphology structure typical of carbon fiber.
Example 2
(1) After being fully dried, 98.2 wt% of LLDPE granules, 1.0 wt% of ultraviolet initiator 4-CBP, 0.5 wt% of cross-linking agent TAIC and 0.3 wt% of stabilizer Chimassorb81 are added into a high-speed mixer to be uniformly stirred and mixed, and then are added into a melt extruder to be spun at the spinning temperature of 200 ℃ to obtain ultraviolet sensitive PE fibers;
(2) drafting the fiber at 100 ℃ and stretching by 2 times; annealing at 120 deg.C for 30min to obtain treated ultraviolet sensitive PE fiber;
(3) irradiating the treated ultraviolet sensitive PE fiber for 150s by adopting an ultraviolet light source with the light intensity of 25kW, wherein the irradiation temperature is room temperature, and obtaining a cross-linked PE fiber;
(4) and carbonizing the cross-linked PE fiber at 900 ℃ for 5min in a nitrogen atmosphere, wherein the heating rate is 5 ℃/min, and thus the low-cost PE-based carbon fiber is obtained.
The average diameter of the PE-based carbon fiber was 11 μm, and the density was 2.1g/cm3The tensile strength is 1.5GPa, the tensile modulus is 160GPa, the elongation at break is 1.4%, and the performance of the obtained carbon fiber meets the requirements of the carbon fiber.
Example 3
(1) Fully drying 93.9 wt% of UXPE granules, 0.1 wt% of ultraviolet initiator 4-CBP, 5.0 wt% of cross-linking agent TMPTA and 1.0 wt% of stabilizer antioxidant XH-245, adding into a high-speed mixer, stirring and mixing uniformly, then adding into a melt extruder for spinning, wherein the spinning temperature is 220 ℃, and obtaining the ultraviolet-sensitive PE fiber;
(2) drafting the fiber at 120 ℃ and stretching by 3 times; annealing at 150 ℃ for 30min to obtain the treated ultraviolet-sensitive PE fiber;
(3) irradiating the treated ultraviolet sensitive PE fiber for 150s by adopting an ultraviolet light source with the light intensity of 20kW, wherein the irradiation temperature is 130 ℃, and obtaining a cross-linked PE fiber;
(4) and carbonizing the cross-linked PE fiber at 900 ℃ for 30min in a nitrogen atmosphere, wherein the heating rate is 3 ℃/min, and thus the low-cost PE-based carbon fiber is obtained.
The average diameter of the PE-based carbon fiber was 11 μm, and the density was 2.1g/cm3The tensile strength is 2.0GPa, the tensile modulus is 220GPa, the elongation at break is 1.4%, and the performance of the obtained carbon fiber meets the requirements of the carbon fiber.
Example 4
(1) Fully drying 98.9 wt% of LDPE (Low-Density polyethylene) granules, 0.5 wt% of ultraviolet initiator BP (Back propagation), 0.2 wt% of cross-linking agent TAC and 0.4 wt% of stabilizer antioxidant 2246, adding the dried materials into a high-speed mixer, uniformly stirring and mixing, adding the mixture into a melt extruder, and spinning at the spinning temperature of 200 ℃ to obtain ultraviolet-sensitive PE (polyethylene) fibers;
(2) drafting the fiber at 100 ℃ and stretching by 1 time; annealing at 120 deg.C for 30min to obtain treated ultraviolet sensitive PE fiber;
(3) irradiating the treated ultraviolet sensitive PE fiber for 300s by adopting an ultraviolet light source with the light intensity of 30kW, wherein the irradiation temperature is room temperature, and obtaining a cross-linked PE fiber;
(4) and carbonizing the cross-linked PE fiber at 900 ℃ for 5min in a nitrogen atmosphere, wherein the heating rate is 1 ℃/min, and thus the low-cost PE-based carbon fiber is obtained.
The average diameter of the PE-based carbon fiber is 15 μm, and the density is 2.5g/cm3The tensile strength is 1.2GPa, the tensile modulus is 90GPa, the elongation at break is 3.0 percent, and the performance of the obtained carbon fiber meets the requirement of the carbon fiber.
Example 5
(1) After being fully dried, 98.2 wt% of LDPE granules, 1.0 wt% of ultraviolet initiator 4,4' -DBP, 0.5 wt% of cross-linking agent PETA and 0.3 wt% of stabilizer Tinuvin 770 are added into a high-speed mixer to be uniformly stirred and mixed, and then are added into a melt extruder to be spun at the spinning temperature of 200 ℃ to obtain the ultraviolet sensitive PE fiber;
(2) drafting the fiber at 100 ℃ and stretching by 3 times; annealing at 120 deg.C for 30min to obtain treated ultraviolet sensitive PE fiber;
(3) irradiating the treated ultraviolet sensitive PE fiber for 400s by adopting an ultraviolet light source with the light intensity of 10kW at the irradiation temperature of 100 ℃ to obtain a crosslinked PE fiber;
(4) and carbonizing the cross-linked PE fiber at 1000 ℃ for 10min in a nitrogen atmosphere, wherein the heating rate is 5 ℃/min, and thus the low-cost PE-based carbon fiber is obtained.
The average diameter of the PE-based carbon fiber was 10 μm, and the density was 2.1g/cm3The tensile strength is 1.3GPa, the tensile modulus is 85GPa, the elongation at break is 1.6%, and the performance of the obtained carbon fiber meets the requirements of the carbon fiber.
Example 6
(1) Fully drying 98 wt% of LDPE (Low-Density polyethylene) granules, 1.0 wt% of 2-MAQ (ultraviolet initiator), 0.5 wt% of 4-APEGA (cross-linking agent) and 0.5 wt% of antioxidant XH-245, adding into a high-speed mixer, stirring and mixing uniformly, then adding into a melt extruder for spinning, wherein the spinning temperature is 200 ℃, and obtaining the ultraviolet-sensitive PE fiber;
(2) drafting the fiber at 110 ℃ and stretching by 3 times; annealing at 130 ℃ for 30min to obtain the treated ultraviolet-sensitive PE fiber;
(3) irradiating the treated ultraviolet sensitive PE fiber for 400s by adopting an ultraviolet light source with the light intensity of 10kW at the irradiation temperature of 60 ℃ to obtain a crosslinked PE fiber;
(4) and carbonizing the cross-linked PE fiber at 1000 ℃ for 10min in a nitrogen atmosphere, wherein the heating rate is 5 ℃/min, and thus the low-cost PE-based carbon fiber is obtained.
The average diameter of the PE-based carbon fiber was 10 μm, and the density was 2.2g/cm3The tensile strength is 1.4GPa, the tensile modulus is 105GPa, the elongation at break is 1.5%, and the performance of the obtained carbon fiber meets the requirements of the carbon fiber.
Example 7
(1) After being fully dried, 98.2 wt% of LDPE granules, 1.0 wt% of ultraviolet initiator 4-AB, 0.5 wt% of crosslinking agent NGD and 0.3 wt% of stabilizer antioxidant 2246 are added into a high-speed mixer to be uniformly stirred and mixed, and then the mixture is added into a melt extruder to be spun at the spinning temperature of 200 ℃ to obtain the ultraviolet sensitive PE fiber;
(2) drafting the fiber at 100 ℃ and stretching by 3 times; annealing at 130 ℃ for 20min to obtain the treated ultraviolet-sensitive PE fiber;
(3) irradiating the treated ultraviolet sensitive PE fiber for 600s by adopting an ultraviolet light source with the light intensity of 15kW, wherein the irradiation temperature is room temperature, and obtaining a cross-linked PE fiber;
(4) and carbonizing the cross-linked PE fiber at 900 ℃ for 10min in a nitrogen atmosphere, wherein the heating rate is 5 ℃/min, and thus the low-cost PE-based carbon fiber is obtained.
The average diameter of the PE-based carbon fiber was 11 μm, and the density was 2.2g/cm3The tensile strength is 1.2GPa, the tensile modulus is 90GPa, the elongation at break is 1.6%, and the performance of the obtained carbon fiber meets the requirements of the carbon fiber.
Example 8
(1) After being fully dried, 98.6 wt% of LLDPE granules, 1.0 wt% of ultraviolet initiator BSO, 0.3 wt% of cross-linking agent 1,5-PDD and 0.1 wt% of stabilizer Tinuvin 622 are added into a high-speed mixer to be uniformly stirred and mixed, and then are added into a melt extruder to be spun at the spinning temperature of 205 ℃ to obtain the ultraviolet sensitive PE fiber;
(2) drafting the fiber at 100 ℃ and stretching by 2 times; annealing at 120 deg.C for 30min to obtain treated ultraviolet sensitive PE fiber;
(3) irradiating the treated ultraviolet sensitive PE fiber for 100s by adopting an ultraviolet light source with the light intensity of 25kW, wherein the irradiation temperature is room temperature, and obtaining a cross-linked PE fiber;
(4) and carbonizing the cross-linked PE fiber at 900 ℃ for 50min in a nitrogen atmosphere, wherein the heating rate is 3 ℃/min, and thus the low-cost PE-based carbon fiber is obtained.
The average diameter of the PE-based carbon fiber was 10 μm, and the density was 1.9g/cm3Tensile strength of 1.6GPa, tensile modulus of 150GPa, and breakThe elongation is 1.5%, and the performance of the obtained carbon fiber meets the requirement of the carbon fiber.
Example 9
(1) Fully drying 98.2 wt% of LLDPE granules, 1.0 wt% of ultraviolet initiator 4-CBP, 0.5 wt% of cross-linking agent EGD and 0.3 wt% of stabilizer Chimassorb 2020, adding into a high-speed mixer, stirring and mixing uniformly, then adding into a melt extruder for spinning, wherein the spinning temperature is 200 ℃, and obtaining ultraviolet sensitive PE fibers;
(2) drafting the fiber at 120 ℃ and stretching by 3 times; annealing at 120 deg.C for 30min to obtain treated ultraviolet sensitive PE fiber;
(3) irradiating the treated ultraviolet sensitive PE fiber for 400s by adopting an ultraviolet light source with the light intensity of 15kW at the irradiation temperature of 60 ℃ to obtain a crosslinked PE fiber;
(4) and carbonizing the cross-linked PE fiber at 900 ℃ for 10min in a nitrogen atmosphere, wherein the heating rate is 5 ℃/min, and thus the low-cost PE-based carbon fiber is obtained.
The average diameter of the PE-based carbon fiber was 8 μm, and the density was 1.8g/cm3The tensile strength is 5.0GPa, the tensile modulus is 210GPa, the elongation at break is 1.4%, and the obtained carbon fiber has excellent performance.
Example 10
(1) After being fully dried, 98 wt% of LLDPE granules, 1.0 wt% of ultraviolet initiator 2-EAQ, 0.5 wt% of crosslinking agent NGD and 0.5 wt% of stabilizer Uvinul 3039 are added into a high-speed mixer to be uniformly stirred and mixed, and then are added into a melt extruder to be spun at the spinning temperature of 200 ℃ to obtain ultraviolet sensitive PE fibers;
(2) drafting the fiber at 110 ℃ and stretching by 3 times; annealing at 130 ℃ for 30min to obtain the treated ultraviolet-sensitive PE fiber;
(3) irradiating the treated ultraviolet sensitive PE fiber for 600s by adopting an ultraviolet light source with the light intensity of 10kW at the irradiation temperature of 60 ℃ to obtain a crosslinked PE fiber;
(4) and carbonizing the cross-linked PE fiber at 1000 ℃ for 10min in a nitrogen atmosphere, wherein the heating rate is 5 ℃/min, and thus the low-cost PE-based carbon fiber is obtained.
Average diameter of PE-based carbon fiber 10 μm, density 2.0g/cm3The tensile strength is 1.8GPa, the tensile modulus is 170GPa, the elongation at break is 1.5%, and the obtained carbon fiber has excellent performance.
Example 11
(1) After being fully dried, 98.2 wt% of HDPE particles, 1.0 wt% of ultraviolet initiator 4-CBP, 0.5 wt% of cross-linking agent PETA and 0.3 wt% of stabilizer Tinuvin 770 are added into a high-speed mixer to be uniformly stirred and mixed, and then are added into a melt extruder to be spun, wherein the spinning temperature is 210 ℃, so that the ultraviolet sensitive PE fiber is obtained;
(2) drafting the fiber at 100 ℃ and stretching by 2 times; annealing at 130 ℃ for 30min to obtain the treated ultraviolet-sensitive PE fiber;
(3) irradiating the treated ultraviolet sensitive PE fiber for 300s by adopting an ultraviolet light source with the light intensity of 25kW, wherein the irradiation temperature is room temperature, and obtaining a cross-linked PE fiber;
(4) and carbonizing the cross-linked PE fiber at 900 ℃ for 60min in a nitrogen atmosphere, wherein the heating rate is 3 ℃/min, and thus the low-cost PE-based carbon fiber is obtained.
The average diameter of the PE-based carbon fiber was 12 μm, and the density was 2.1g/cm3The tensile strength is 1.4GPa, the tensile modulus is 120GPa, the elongation at break is 1.6%, and the performance of the obtained carbon fiber meets the requirements of the carbon fiber.
Example 12
(1) Fully drying 98 wt% of HDPE granules, 1.0 wt% of ultraviolet initiator BP, 0.5 wt% of cross-linking agent TAIC and 0.5 wt% of stabilizer antioxidant 1010, adding into a high-speed mixer, stirring and mixing uniformly, then adding into a melt extruder, spinning at the spinning temperature of 220 ℃, and obtaining ultraviolet-sensitive PE fibers;
(2) drafting the fiber at 110 ℃ and stretching by 3 times; annealing at 120 deg.C for 30min to obtain treated ultraviolet sensitive PE fiber;
(3) irradiating the treated ultraviolet sensitive PE fiber for 600s by adopting an ultraviolet light source with the light intensity of 10kW at the irradiation temperature of 60 ℃ to obtain a crosslinked PE fiber;
(4) and carbonizing the cross-linked PE fiber at 2400 ℃ for 5min in a nitrogen atmosphere, and heating at the rate of 5 ℃/min to obtain the low-cost PE-based carbon fiber.
The average diameter of the PE-based carbon fiber was 10 μm, and the density was 1.8g/cm3The tensile strength is 2.0GPa, the tensile modulus is 350GPa, the elongation at break is 1.4%, and the obtained carbon fiber has excellent performance.
Example 13
(1) Fully drying 98.3 wt% of HDPE particles, 1.0 wt% of ultraviolet initiator 4-CBP, 0.5 wt% of cross-linking agent TAIC and 0.2 wt% of stabilizer antioxidant 1010, adding the materials into a high-speed mixer, uniformly stirring and mixing, and then adding the materials into a melt extruder for spinning at the spinning temperature of 215 ℃ to obtain ultraviolet-sensitive PE fibers;
(2) drafting the fiber at 110 ℃ and stretching by 3 times; annealing at 120 deg.C for 60min to obtain treated ultraviolet sensitive PE fiber;
(3) irradiating the treated ultraviolet sensitive PE fiber for 600s by adopting an ultraviolet light source with the light intensity of 2kW at the irradiation temperature of 60 ℃ to obtain a crosslinked PE fiber;
(4) and carbonizing the cross-linked PE fiber at 1000 ℃ for 30min in a nitrogen atmosphere, wherein the heating rate is 5 ℃/min, and thus the low-cost PE-based carbon fiber is obtained.
The average diameter of the PE-based carbon fiber was 10 μm, and the density was 1.9g/cm3The tensile strength is 1.9GPa, the tensile modulus is 210GPa, the elongation at break is 1.0 percent, and the obtained carbon fiber has excellent performance.
Comparative example 1
(1) After being fully dried, 98.65 wt% of LDPE (low-density polyethylene) particles, 0.05 wt% of ultraviolet initiator 4-NBP (N-bromosuccinimide), 1.0 wt% of crosslinking agent 1,5-PDD (polyethylene glycol) and 0.3 wt% of stabilizer Tinuvin B97 are added into a high-speed mixer to be uniformly stirred and mixed, and then the mixture is added into a melt extruder to be spun at the spinning temperature of 200 ℃ to obtain the ultraviolet sensitive PE fiber;
(2) drafting the fiber at 100 ℃ and stretching by 1 time; annealing at 120 deg.C for 30min to obtain treated ultraviolet sensitive PE fiber;
(3) irradiating the treated ultraviolet sensitive PE fiber for 300s by adopting an ultraviolet light source with the light intensity of 30kW, wherein the irradiation temperature is room temperature, and obtaining a cross-linked PE fiber;
(4) and carbonizing the cross-linked PE fibers at 900 ℃ for 5min in a nitrogen atmosphere at the heating rate of 1 ℃/min, and not obtaining the PE-based carbon fibers after carbonization. The failure to obtain carbon fibers may be due to insufficient crosslinking of the PE fibers during crosslinking, insufficient network formation, and melting of the crosslinked PE fibers during high temperature calcination.
Comparative example 2
(1) Fully drying 92.7 wt% of LLDPE granules, 1.0 wt% of ultraviolet light initiator HCB, 6.0 wt% of cross-linking agent TAC and 0.3 wt% of stabilizer antioxidant 1010, adding the obtained product into a high-speed mixer, uniformly stirring and mixing the obtained product, adding the obtained product into a melt extruder, spinning at the spinning temperature of 200 ℃, and solidifying the LLDPE granules in a screw due to excessive addition of the cross-linking agent, so that the nascent fiber cannot be spun.
Nothing in this specification is said to apply to the prior art.
Claims (10)
1. A method for preparing low-cost polyethylene-based carbon fibers is characterized by comprising the following steps:
(1) preparing ultraviolet light sensitive PE fiber: uniformly stirring and mixing polyethylene, an ultraviolet light initiator, a cross-linking agent and a stabilizing agent, fully dispersing, and performing melt spinning to obtain ultraviolet light-sensitive PE fibers;
(2) drawing treatment and annealing treatment: carrying out drafting treatment and annealing treatment on the ultraviolet light sensitive PE fiber obtained in the step (1), improving the orientation degree of the fiber, eliminating internal stress, and enhancing the mechanical property of the fiber to obtain the treated ultraviolet light sensitive PE fiber;
(3) ultraviolet crosslinking: irradiating the treated ultraviolet sensitive PE fiber obtained in the step (2) by adopting an ultraviolet light source to convert linear or slightly branched macromolecules into a three-dimensional network structure to obtain a cross-linked PE fiber;
(4) carbonizing: and carbonizing the cross-linked PE fiber to obtain the low-cost PE-based carbon fiber.
2. The method for preparing low-cost polyethylene-based carbon fiber according to claim 1, wherein in the step (1), the mass ratio of each component is: 89.0-99.69 wt% of polyethylene, 0.1-5.0 wt% of ultraviolet initiator, 0.2-5.0 wt% of cross-linking agent and 0.01-1.0 wt% of stabilizer, wherein the sum of the mass of the components is 100%; the melt spinning temperature is 150-220 ℃.
3. The method for preparing low-cost polyethylene-based carbon fiber according to claim 1, wherein in the step (1), the polyethylene is one of low density polyethylene, linear low density polyethylene, high density polyethylene, crosslinked polyethylene or ultraviolet light crosslinked polyethylene.
4. The method for preparing low-cost polyvinyl carbon fiber according to claim 1, wherein in the step (1), the UV initiator is one of hexachlorobenzene, chlorendic anhydride, benzophenone, 4-chlorobenzophenone, 4' -dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-chloroanthraquinone, tetrachlorobenzoquinone, dibenzyl sulfide, phenyl sulfoxide, 4-acetylbiphenyl, anthrone, Sandoray (TM) 1000, chloroanhydride, 4-nitrobenzophenone or 2-chlorophenol ketone.
5. The method of preparing a low-cost polyvinylcarbon fiber as claimed in claim 1, wherein the crosslinking agent is one of triallyl cyanurate, triallyl isocyanurate, trimethylolpropane triacrylate, pentaerythritol triallyl acrylate, four-armed polyethylene glycol-acrylate, neopentyl glycol diacrylate, trimethylolpropane trimethacrylate, polydipentaerythritol hexaacrylate, pentaerythritol triacrylate, 1, 5-pentanediol diacrylate, trimethylolpropane triacrylate, dipropylene glycol diacrylate, 1, 4-butanediol dimethacrylate or ethylene glycol diacrylate in step (1).
6. The method for preparing low-cost polyethylene-based carbon fiber according to claim 1, wherein in the step (1), the stabilizer comprises light stabilizer and heat stabilizer; the light stabilizer is one of Chimassorb81, Tinuvin 770, Tinuvin 622, Chimassorb 944, Uvinul 3039, Uvinul 3035, Chimassorb 2020 or Tinuvin B97; the heat stabilizer is one of antioxidant 1010, antioxidant 1012, antioxidant 2246, antioxidant 3052, antioxidant XH-245 or antioxidant 412S.
7. The method for preparing low-cost polyethylene-based carbon fiber according to claim 1, wherein in the step (2), the drawing process is: the fiber is subjected to drafting treatment at 100-120 ℃, so that the orientation degree of macromolecular chains in a low-order area of the fiber along the axial direction of the fiber is improved, the change of density and crystallinity structure is accompanied, the number of molecular chains bearing external tension of the fiber is increased as a result of the drafting, the breaking strength of the fiber is obviously improved, the extensibility is reduced, the wear resistance and the fatigue strength to various types of deformation are also obviously improved, and the drafting multiple is 1-5 times.
8. The method for preparing low-cost polyethylene-based carbon fiber according to claim 1, wherein in the step (2), the annealing process is: annealing treatment is carried out on the fiber at 120-150 ℃ for 10-60 min, internal stress is eliminated, growth of macromolecules in a crystal region is more complete, and strength and toughness of the fiber are improved.
9. The preparation method of the low-cost polyethylene-based carbon fiber according to claim 1, wherein in the step (3), the light intensity of the ultraviolet light source is 2-30 kW, the irradiation temperature is room temperature-150 ℃, and the irradiation time is 10-600 s.
10. The method for preparing low-cost polyethylene-based carbon fiber according to claim 1, wherein the carbonization is performed in a nitrogen atmosphere in step (4), the carbonization temperature is 900 to 2400 ℃, the carbonization time is 5 to 60min, and the temperature increase rate is 1 to 5 ℃/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210228157.4A CN114381827A (en) | 2022-03-10 | 2022-03-10 | Preparation method of low-cost polyethylene-based carbon fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210228157.4A CN114381827A (en) | 2022-03-10 | 2022-03-10 | Preparation method of low-cost polyethylene-based carbon fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114381827A true CN114381827A (en) | 2022-04-22 |
Family
ID=81205755
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210228157.4A Pending CN114381827A (en) | 2022-03-10 | 2022-03-10 | Preparation method of low-cost polyethylene-based carbon fiber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114381827A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114959950A (en) * | 2022-06-15 | 2022-08-30 | 浙江毅聚新材料有限公司 | Preparation process of carbon fiber |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4070446A (en) * | 1973-02-01 | 1978-01-24 | Sumitomo Chemical Company, Limited | Process for production of carbon fiber |
| WO1992003601A2 (en) * | 1990-08-08 | 1992-03-05 | Allied-Signal Inc. | Carbon fiber and process for its production |
| CN104695039A (en) * | 2015-03-04 | 2015-06-10 | 江苏神鹤科技发展有限公司 | Thermal-resistant anti-cutting ultra-high molecular weight polyethylene fiber and preparation method thereof |
| CN104695038A (en) * | 2015-03-04 | 2015-06-10 | 江苏神鹤科技发展有限公司 | Heat-resisting creep-resisting ultra-high molecular weight polyethylene constant-strength fiber and preparation method thereof |
-
2022
- 2022-03-10 CN CN202210228157.4A patent/CN114381827A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4070446A (en) * | 1973-02-01 | 1978-01-24 | Sumitomo Chemical Company, Limited | Process for production of carbon fiber |
| WO1992003601A2 (en) * | 1990-08-08 | 1992-03-05 | Allied-Signal Inc. | Carbon fiber and process for its production |
| CN104695039A (en) * | 2015-03-04 | 2015-06-10 | 江苏神鹤科技发展有限公司 | Thermal-resistant anti-cutting ultra-high molecular weight polyethylene fiber and preparation method thereof |
| CN104695038A (en) * | 2015-03-04 | 2015-06-10 | 江苏神鹤科技发展有限公司 | Heat-resisting creep-resisting ultra-high molecular weight polyethylene constant-strength fiber and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 严庆: "聚乙烯纤维的紫外光交联", 合成纤维工业, vol. 16, no. 4, pages 15 - 18 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114959950A (en) * | 2022-06-15 | 2022-08-30 | 浙江毅聚新材料有限公司 | Preparation process of carbon fiber |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Choi et al. | Fabrication of low-cost carbon fibers using economical precursors and advanced processing technologies | |
| US11174346B2 (en) | Flame-retardant polyester fiber and its preparation method | |
| CN109320762B (en) | Method for recovering waste thermosetting resin by using microwaves | |
| CN109234850B (en) | Cross-linked modified ultra-high molecular weight polyethylene fiber and preparation method thereof | |
| CN104695038A (en) | Heat-resisting creep-resisting ultra-high molecular weight polyethylene constant-strength fiber and preparation method thereof | |
| CN114381827A (en) | Preparation method of low-cost polyethylene-based carbon fiber | |
| KR20160138775A (en) | Nanocarbon composite carbon fiber with low cost and high performance and their preparation method | |
| CN105063787A (en) | Cross-linked polymer and preparation method thereof | |
| WO2020052360A1 (en) | Method for preparing high-strength and high-modulus polyethylene fiber | |
| CN104818541A (en) | Crosslinked ultrahigh molecular weight polyethylene fiber and wet preparation method thereof | |
| CN104711696A (en) | Heat-resisting antistatic UHMWPE (ultra high molecular weight polyethylene) fiber and preparation method thereof | |
| US11505646B1 (en) | Method for producing high-melt-strength polylactide resin | |
| Jo et al. | Effects of ultraviolet irradiation on stabilization of textile-grade polyacrylonitrile fibers without photo-initiator for preparing carbon fibers | |
| CN113622045B (en) | Glass-like polymer fiber and preparation method thereof | |
| JP2024502395A (en) | Spinning dope, heat-resistant creep-resistant fiber and manufacturing method thereof | |
| Kholkhoev et al. | Polybenzimidazole-based thiol-ene photosensitive composition for DLP 3D printing | |
| US20200332444A1 (en) | Carbon fiber formed from chlorinated polyvinyl chloride, and method for preparing same | |
| CN110038453A (en) | A kind of enhanced PVC hollow fiber ultrafiltration membrane and preparation method | |
| CN107903508B (en) | Aramid fiber reinforced polypropylene micro-foaming composite material and preparation method thereof | |
| CN104846446A (en) | Crosslinked polyethylene fiber with ultrahigh molecular weight and dry preparation method for crosslinked polyethylene fiber | |
| KR102115961B1 (en) | The manufacturing method of carbon fiber | |
| CN111676570B (en) | Antibacterial anti-seepage fabric | |
| CN107189346A (en) | The preparation method of benzoxazine colophony composite | |
| KR20180070294A (en) | Method for separating non-reacted monomer from mixture comprising non-reacted monomer | |
| CN113337107A (en) | Method for composite modification of nylon 6 by nano-alumina |
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 |