CN114086277A - Cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite fiber and preparation method thereof - Google Patents
Cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite fiber and preparation method thereof Download PDFInfo
- Publication number
- CN114086277A CN114086277A CN202111548468.0A CN202111548468A CN114086277A CN 114086277 A CN114086277 A CN 114086277A CN 202111548468 A CN202111548468 A CN 202111548468A CN 114086277 A CN114086277 A CN 114086277A
- Authority
- CN
- China
- Prior art keywords
- resistant
- graphene composite
- cutting
- wear
- chemical corrosion
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 124
- 239000002131 composite material Substances 0.000 title claims abstract description 95
- 239000000835 fiber Substances 0.000 title claims abstract description 80
- 238000005520 cutting process Methods 0.000 title claims abstract description 51
- 239000000126 substance Substances 0.000 title claims abstract description 51
- 238000005260 corrosion Methods 0.000 title claims abstract description 50
- 230000007797 corrosion Effects 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 50
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000007872 degassing Methods 0.000 claims abstract description 32
- 229920000642 polymer Polymers 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000009987 spinning Methods 0.000 claims abstract description 27
- 229920000137 polyphosphoric acid Polymers 0.000 claims abstract description 25
- 238000005406 washing Methods 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 20
- GAKFXHZPQGSWHQ-UHFFFAOYSA-N 4,6-diaminobenzene-1,3-diol;hydrochloride Chemical compound Cl.NC1=CC(N)=C(O)C=C1O GAKFXHZPQGSWHQ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000005303 weighing Methods 0.000 claims abstract description 9
- 238000004804 winding Methods 0.000 claims abstract description 9
- ICXAPFWGVRTEKV-UHFFFAOYSA-N 2-[4-(1,3-benzoxazol-2-yl)phenyl]-1,3-benzoxazole Chemical compound C1=CC=C2OC(C3=CC=C(C=C3)C=3OC4=CC=CC=C4N=3)=NC2=C1 ICXAPFWGVRTEKV-UHFFFAOYSA-N 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000005299 abrasion Methods 0.000 claims 1
- 229920000927 poly(p-phenylene benzobisoxazole) Polymers 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000002166 wet spinning 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
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
-
- 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
Abstract
The invention discloses a cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite fiber and a preparation method thereof, wherein the method comprises the following steps: step 1, weighing raw materials in proportion; step 2, putting the mixed materials of terephthalic acid, 4, 6-diaminoresorcinol hydrochloride, polyphosphoric acid and phosphorus pentoxide into a dry degassing kettle for reaction, and then reacting in the degassing kettle to obtain a PBO prepolymer; step 3, mixing the PBO prepolymer and the graphene powder, conveying the mixture to a double-screw extruder, and carrying out post-polymerization reaction to obtain a graphene composite PBO polymer; step 4, spinning: and spinning by adopting the graphene composite PBO polymer, drafting and washing, and finally drying and winding. The invention also provides the cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite fiber prepared by the method. The composite fiber prepared by the invention has the characteristics of high elongation, cutting resistance, wear resistance and heavy chemical corrosion resistance, and other indexes are excellent and balanced.
Description
Technical Field
The invention relates to a graphene composite poly-p-phenylene benzobisoxazole fiber with high cutting resistance, wear resistance and chemical corrosion resistance and a preparation method thereof, and particularly relates to a graphene composite fiber with cutting resistance, wear resistance and chemical corrosion resistance and a preparation method thereof.
Background
Graphene is a single-layer carbon atom material stripped from graphite, and a single-layer two-dimensional honeycomb lattice structure is formed by tightly packing carbon atoms, and is known to be the material with the thinnest thickness, the hardest texture and the best conductivity. Graphene has excellent mechanical, optical and electrical properties and a very stable structure, researchers have not found that graphene has a missing carbon atom, the linkage between carbon atoms is very flexible, and is harder than diamond, the strength is 100 times higher than that of the world's best steel, if graphene is used for making a packaging bag, the graphene can bear about two tons of articles, the graphene is almost completely transparent, but is very compact, waterproof and airtight, helium gas with the minimum atomic size cannot pass through the graphene, the graphene has good conductivity, the movement speed of electrons in graphene reaches 1/300 of the light speed, the conductivity exceeds that of any traditional conductive material, the chemical properties are similar to the surface of graphite, various atoms and molecules can be adsorbed and desorbed, and the graphene also has the capability of resisting strong acid and strong alkali.
PBO (poly-p-phenylene benzobisoxazole) fibers are high performance organic fibers developed by american-road chemical company in cooperation with japan eastern textile company. The organic fiber reinforced material is the organic fiber reinforced material with the highest specific strength and specific modulus at present, and has wide application prospect in military high-technology fields of space flight, aviation, weapon equipment and the like such as rocket engine shells, space flight detection, war chariot armor protection and the like. In recent years, in order to keep pace with the advanced world level and shorten the gap with developed countries in the world, the research on the development and application of domestic PBO fibers is continuously carried out in China under the background of the localization of military key raw materials. However, the PBO fiber has poor ultraviolet resistance and cutting resistance, so that the wide application range in the industry is influenced.
Disclosure of Invention
The invention aims to provide a graphene composite poly (p-phenylene benzobisoxazole) fiber and a preparation method thereof, which solve the problems of low elongation at break, no wear resistance, no corrosion resistance and the like of the poly (p-phenylene benzobisoxazole) fiber in the prior art, and enable the fiber to have the characteristics of high elongation, cutting resistance, wear resistance and heavy chemical corrosion resistance.
In order to achieve the above object, the present invention provides a method for preparing a graphene composite fiber with cutting resistance, wear resistance and chemical corrosion resistance, wherein the method comprises: step 1, weighing raw materials in proportion; step 2, prepolymerization: putting a material obtained by mixing terephthalic acid, 4, 6-diaminoresorcinol hydrochloride, polyphosphoric acid and phosphorus pentoxide into a dry degassing kettle for reaction, and then reacting in the degassing kettle to obtain a PBO prepolymer; step 3, post-polymerization: mixing the PBO prepolymer obtained in the step (2) with graphene powder, conveying the mixture to a double-screw extruder, and carrying out post-polymerization reaction to obtain a graphene composite PBO polymer; step 4, spinning: and (3) spinning the graphene composite PBO polymer obtained in the step (3), drafting and washing, and finally drying and winding to obtain the cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite poly-p-phenylene benzobisoxazole fiber.
The preparation method of the cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite fiber comprises the following steps of preparing the graphene composite poly-p-phenylene benzobisoxazole fiber, wherein the tensile strength of the graphene composite poly-p-phenylene benzobisoxazole fiber is 5.4-5.8GPa, the elongation at break of the graphene composite poly-p-phenylene benzobisoxazole fiber is 3.5-4.5%, the tensile modulus of the graphene composite poly-p-phenylene benzobisoxazole fiber is 140-180GPa, and the density of the graphene composite fiber is 1.53-1.54g/cm 3.
In the preparation method of the graphene composite fiber with cutting resistance, wear resistance and chemical corrosion resistance, in the step 2, the molar ratio of terephthalic acid to 4, 6-diaminoresorcinol hydrochloride, polyphosphoric acid and phosphorus pentoxide is (1.0-1.02): 1: (1.0-5.0): (2.5-6.0).
In the step 2, the materials are put into a dry degassing kettle, and subjected to degassing reaction at a temperature of 50-110 ℃ for 10-15h, and then subjected to further reaction in a degassing kettle at a temperature of 120-150 ℃ for 1-5h to obtain the PBO prepolymer.
In the preparation method of the graphene composite fiber with cutting resistance, wear resistance and chemical corrosion resistance, in the step 2, the solid content of the PBO prepolymer is 10-15% by mass.
In the step 3, the PBO prepolymer and the graphene powder are mixed and then conveyed to a double-screw extruder, post-polymerization reaction is carried out at the temperature of 150-.
The preparation method of the cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite fiber comprises the step of dissolving the graphene composite PBO polymer in a polyphosphoric acid/phosphorus pentoxide solvent system, wherein the intrinsic viscosity is 15-35 dL/g.
In the preparation method of the cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite fiber, in the step 3, the amount of the PBO prepolymer is 30-35% and the amount of the graphene powder is 65-70% by mass percentage.
In the step 4, the spinning speed is 40-200m/min, the diameter of a spinneret orifice is 0.10-0.25mm, the speed ratio of a guide roller to a drawing machine is 1.01-1.05:1, the tension between drawing and washing is less than or equal to 500cN, and the tension between multi-stage rotary drum rollers adopted in the washing procedure is less than or equal to 300 cN.
The invention also provides the cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite fiber prepared by the method.
The preparation method can prepare the poly-p-phenylene benzobisoxazole graphene composite fiber with high elongation, cutting resistance, wear resistance and heavy chemical corrosion resistance, and the fiber has high elongation at break, so that the composite fiber has more excellent bulletproof and impact-resistant properties, and is particularly suitable for the field of bulletproof. And the fiber is suitable for industrial scale production. Tests prove that the cutting resistance grade of the PBO fiber modified by the graphene can reach 5 American standard, 0 wear resistance grade and no peeling after soaking the fiber in 240h of strong acid and strong alkali solution.
Detailed Description
The following further describes embodiments of the present invention.
The invention provides a preparation method of a cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite fiber, which comprises the following steps: step 1, weighing raw materials in proportion; step 2, prepolymerization: putting a material obtained by mixing terephthalic acid, 4, 6-diaminoresorcinol hydrochloride, polyphosphoric acid and phosphorus pentoxide into a dry degassing kettle for reaction, and then reacting in the degassing kettle to obtain a PBO prepolymer; step 3, post-polymerization: mixing the PBO prepolymer obtained in the step (2) with graphene powder, conveying the mixture to a double-screw extruder, and carrying out post-polymerization reaction to obtain a graphene composite PBO polymer; step 4, spinning: and (3) spinning the graphene composite PBO polymer obtained in the step (3), drafting and washing, and finally drying and winding to obtain the cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite poly (p-phenylene benzobisoxazole) fiber.
The obtained graphene composite poly-p-phenylene benzobisoxazole fiber is high-elongation graphene composite poly-p-phenylene benzobisoxazole fiber, the tensile strength of bundle yarns of the graphene composite poly-p-phenylene benzobisoxazole fiber is 5.4-5.8GPa, the elongation at break of the graphene composite poly-p-phenylene benzobisoxazole fiber is 3.5-4.5%, the tensile modulus of the bundle yarns of the graphene composite poly-p-phenylene benzobisoxazole fiber is 140-180GPa, and the density of the bundle yarns of the graphene composite poly-p-phenylene benzobisoxazole fiber is 1.53-1.54g/cm3。
In the step 2, the molar ratio of terephthalic acid to 4, 6-diaminoresorcinol hydrochloride, polyphosphoric acid and phosphorus pentoxide is (1.0-1.02): 1: (1.0-5.0): (2.5-6.0).
In the step 2, the materials are put into a dry degassing kettle, degassing reaction is carried out for 10-15h at the temperature of 50-110 ℃, and then reaction is carried out for 1-5h in the degassing kettle at the temperature of 120-150 ℃ to obtain the PBO prepolymer.
The solids content of the resulting PBO prepolymer was 10-15% by mass.
And 3, mixing the PBO prepolymer and the graphene powder by a metering pump, conveying the mixture to a double-screw extruder, carrying out post-polymerization reaction at the temperature of 150-200 ℃, and keeping the material in the screw extruder for 5-30min to obtain the graphene composite PBO polymer.
The obtained graphene composite PBO polymer is dissolved in a polyphosphoric acid/phosphorus pentoxide solvent system, and the intrinsic viscosity is 15-35 dL/g.
In the step 3, the amount of the PBO prepolymer is 30-35% and the amount of the graphene powder is 65-70% by mass percentage.
In the step 4, the spinning speed is 40-200m/min, the diameter of a spinneret orifice is 0.10-0.25mm, the speed ratio of a guide roller to a drawing machine is 1.01-1.05:1, the tension between drawing and washing is less than or equal to 500cN, and the tension between multi-stage rotary drum rollers adopted in the washing procedure is less than or equal to 300 cN.
The equipment used in the present invention is known to those skilled in the art.
The invention also provides the cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite fiber prepared by the method.
The cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite fiber and the preparation method thereof provided by the invention are further described in the following with reference to the examples.
Example 1
A preparation method of a cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite fiber comprises the following steps:
step 1, weighing the raw materials in proportion.
Step 2, prepolymerization: the mixed materials of terephthalic acid, 4, 6-diaminoresorcinol hydrochloride, polyphosphoric acid and phosphorus pentoxide are put into a dry degassing kettle, and subjected to degassing reaction for 10-15h at the temperature of 50-110 ℃, and then subjected to further reaction for 1-5h at the temperature of 120-150 ℃ in the degassing kettle to obtain the PBO prepolymer. The solids content in the PBO prepolymer was 10% by mass.
The molar ratio of terephthalic acid to 4, 6-diaminoresorcinol hydrochloride, polyphosphoric acid and phosphorus pentoxide is (1.0-1.02): 1: (1.0-5.0): (2.5-6.0).
Step 3, post-polymerization: and (3) mixing the PBO prepolymer obtained in the step (2) with graphene powder, conveying the mixture to a double-screw extruder, carrying out post-polymerization reaction at the temperature of 150-200 ℃, and allowing the materials to stay in the screw extruder for 5-30min to obtain the graphene composite PBO polymer.
The obtained graphene composite PBO polymer is dissolved in a polyphosphoric acid/phosphorus pentoxide solvent system, and the intrinsic viscosity is 15-35 dL/g.
The dosage of the PBO prepolymer is 30% and the dosage of the graphene powder is 70% in percentage by mass.
Step 4, spinning: and (3) spinning the graphene composite PBO polymer obtained in the step (3), drafting and washing, and finally drying and winding to obtain the cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite poly-p-phenylene benzobisoxazole fiber.
In the step 4, the spinning speed is 40-200m/min, the diameter of a spinneret orifice is 0.10-0.25mm, the speed ratio of a guide roller to a drawing machine is 1.01-1.05:1, the tension between drawing and washing is less than or equal to 500cN, and the tension between multi-stage rotary drum rollers adopted in the washing procedure is less than or equal to 300 cN.
The obtained graphene composite poly-p-phenylene benzobisoxazole fiber has the tensile strength of 5.4-5.8GPa, the elongation at break of 3.5-4.5%, the tensile modulus of 140-180GPa and the density of 1.53-1.54g/cm3。
The embodiment also provides the cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite fiber prepared by the method.
Example 2
A preparation method of a cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite fiber comprises the following steps:
step 1, weighing the raw materials in proportion.
Step 2, prepolymerization: the mixed materials of terephthalic acid, 4, 6-diaminoresorcinol hydrochloride, polyphosphoric acid and phosphorus pentoxide are put into a dry degassing kettle, and subjected to degassing reaction for 10-15h at the temperature of 50-110 ℃, and then subjected to further reaction for 1-5h at the temperature of 120-150 ℃ in the degassing kettle to obtain the PBO prepolymer. The solid content in the PBO prepolymer was 12% by mass.
The molar ratio of terephthalic acid to 4, 6-diaminoresorcinol hydrochloride, polyphosphoric acid and phosphorus pentoxide is (1.0-1.02): 1: (1.0-5.0): (2.5-6.0).
Step 3, post-polymerization: and (3) mixing the PBO prepolymer obtained in the step (2) with graphene powder, conveying the mixture to a double-screw extruder, carrying out post-polymerization reaction at the temperature of 150-200 ℃, and allowing the materials to stay in the screw extruder for 5-30min to obtain the graphene composite PBO polymer.
The obtained graphene composite PBO polymer is dissolved in a polyphosphoric acid/phosphorus pentoxide solvent system, and the intrinsic viscosity is 15-35 dL/g.
The dosage of the PBO prepolymer is 32% and the dosage of the graphene powder is 68% in percentage by mass.
Step 4, spinning: and (3) spinning the graphene composite PBO polymer obtained in the step (3), drafting and washing, and finally drying and winding to obtain the cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite poly-p-phenylene benzobisoxazole fiber.
In the step 4, the spinning speed is 40-200m/min, the diameter of a spinneret orifice is 0.10-0.25mm, the speed ratio of a guide roller to a drawing machine is 1.01-1.05:1, the tension between drawing and washing is less than or equal to 500cN, and the tension between multi-stage rotary drum rollers adopted in the washing procedure is less than or equal to 300 cN.
The obtained graphene composite poly-p-phenylene benzobisoxazole fiber has the tensile strength of 5.4-5.8GPa, the elongation at break of 3.5-4.5%, the tensile modulus of 140-180GPa and the density of 1.53-1.54g/cm3。
The embodiment also provides the cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite fiber prepared by the method.
Example 3
A preparation method of a cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite fiber comprises the following steps:
step 1, weighing the raw materials in proportion.
Step 2, prepolymerization: the mixed materials of terephthalic acid, 4, 6-diaminoresorcinol hydrochloride, polyphosphoric acid and phosphorus pentoxide are put into a dry degassing kettle, and subjected to degassing reaction for 10-15h at the temperature of 50-110 ℃, and then subjected to further reaction for 1-5h at the temperature of 120-150 ℃ in the degassing kettle to obtain the PBO prepolymer. The solids content in the PBO prepolymer was 13% by mass.
The molar ratio of terephthalic acid to 4, 6-diaminoresorcinol hydrochloride, polyphosphoric acid and phosphorus pentoxide is (1.0-1.02): 1: (1.0-5.0): (2.5-6.0).
Step 3, post-polymerization: and (3) mixing the PBO prepolymer obtained in the step (2) with graphene powder, conveying the mixture to a double-screw extruder, carrying out post-polymerization reaction at the temperature of 150-200 ℃, and allowing the materials to stay in the screw extruder for 5-30min to obtain the graphene composite PBO polymer.
The obtained graphene composite PBO polymer is dissolved in a polyphosphoric acid/phosphorus pentoxide solvent system, and the intrinsic viscosity is 15-35 dL/g.
The using amount of the PBO prepolymer is 33% and the using amount of the graphene powder is 67% in percentage by mass.
Step 4, spinning: and (3) spinning the graphene composite PBO polymer obtained in the step (3), drafting and washing, and finally drying and winding to obtain the cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite poly-p-phenylene benzobisoxazole fiber.
In the step 4, the spinning speed is 40-200m/min, the diameter of a spinneret orifice is 0.10-0.25mm, the speed ratio of a guide roller to a drawing machine is 1.01-1.05:1, the tension between drawing and washing is less than or equal to 500cN, and the tension between multi-stage rotary drum rollers adopted in the washing procedure is less than or equal to 300 cN.
The obtained graphene composite poly-p-phenylene benzobisoxazole fiber has the tensile strength of 5.4-5.8GPa, the elongation at break of 3.5-4.5%, the tensile modulus of 140-180GPa and the density of 1.53-1.54g/cm3。
The embodiment also provides the cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite fiber prepared by the method.
Example 4
A preparation method of a cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite fiber comprises the following steps:
step 1, weighing the raw materials in proportion.
Step 2, prepolymerization: the mixed materials of terephthalic acid, 4, 6-diaminoresorcinol hydrochloride, polyphosphoric acid and phosphorus pentoxide are put into a dry degassing kettle, and subjected to degassing reaction for 10-15h at the temperature of 50-110 ℃, and then subjected to further reaction for 1-5h at the temperature of 120-150 ℃ in the degassing kettle to obtain the PBO prepolymer. The solid content in the PBO prepolymer was 14% by mass.
The molar ratio of terephthalic acid to 4, 6-diaminoresorcinol hydrochloride, polyphosphoric acid and phosphorus pentoxide is (1.0-1.02): 1: (1.0-5.0): (2.5-6.0).
Step 3, post-polymerization: and (3) mixing the PBO prepolymer obtained in the step (2) with graphene powder, conveying the mixture to a double-screw extruder, carrying out post-polymerization reaction at the temperature of 150-200 ℃, and allowing the materials to stay in the screw extruder for 5-30min to obtain the graphene composite PBO polymer.
The obtained graphene composite PBO polymer is dissolved in a polyphosphoric acid/phosphorus pentoxide solvent system, and the intrinsic viscosity is 15-35 dL/g.
The dosage of the PBO prepolymer is 34% and the dosage of the graphene powder is 66% in percentage by mass.
Step 4, spinning: and (3) spinning the graphene composite PBO polymer obtained in the step (3), drafting and washing, and finally drying and winding to obtain the cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite poly-p-phenylene benzobisoxazole fiber.
In the step 4, the spinning speed is 40-200m/min, the diameter of a spinneret orifice is 0.10-0.25mm, the speed ratio of a guide roller to a drawing machine is 1.01-1.05:1, the tension between drawing and washing is less than or equal to 500cN, and the tension between multi-stage rotary drum rollers adopted in the washing procedure is less than or equal to 300 cN.
The obtained graphene composite poly-p-phenylene benzobisoxazole fiber has the tensile strength of 5.4-5.8GPa, the elongation at break of 3.5-4.5%, the tensile modulus of 140-180GPa and the density of 1.53-1.54g/cm3。
The embodiment also provides the cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite fiber prepared by the method.
Example 5
A preparation method of a cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite fiber comprises the following steps:
step 1, weighing the raw materials in proportion.
Step 2, prepolymerization: the mixed materials of terephthalic acid, 4, 6-diaminoresorcinol hydrochloride, polyphosphoric acid and phosphorus pentoxide are put into a dry degassing kettle, and subjected to degassing reaction for 10-15h at the temperature of 50-110 ℃, and then subjected to further reaction for 1-5h at the temperature of 120-150 ℃ in the degassing kettle to obtain the PBO prepolymer. The solid content in the PBO prepolymer was 15% by mass.
The molar ratio of terephthalic acid to 4, 6-diaminoresorcinol hydrochloride, polyphosphoric acid and phosphorus pentoxide is (1.0-1.02): 1: (1.0-5.0): (2.5-6.0).
Step 3, post-polymerization: and (3) mixing the PBO prepolymer obtained in the step (2) with graphene powder, conveying the mixture to a double-screw extruder, carrying out post-polymerization reaction at the temperature of 150-200 ℃, and allowing the materials to stay in the screw extruder for 5-30min to obtain the graphene composite PBO polymer.
The obtained graphene composite PBO polymer is dissolved in a polyphosphoric acid/phosphorus pentoxide solvent system, and the intrinsic viscosity is 15-35 dL/g.
The dosage of the PBO prepolymer is 35% and the dosage of the graphene powder is 65% in percentage by mass.
Step 4, spinning: and (3) spinning the graphene composite PBO polymer obtained in the step (3), drafting and washing, and finally drying and winding to obtain the cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite poly-p-phenylene benzobisoxazole fiber.
In the step 4, the spinning speed is 40-200m/min, the diameter of a spinneret orifice is 0.10-0.25mm, the speed ratio of a guide roller to a drawing machine is 1.01-1.05:1, the tension between drawing and washing is less than or equal to 500cN, and the tension between multi-stage rotary drum rollers adopted in the washing procedure is less than or equal to 300 cN.
The obtained graphene composite poly-p-phenylene benzobisoxazole fiber has the tensile strength of 5.4-5.8GPa, the elongation at break of 3.5-4.5%, the tensile modulus of 140-180GPa and the density of 1.53-1.54g/cm3。
The embodiment also provides the cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite fiber prepared by the method.
The invention provides a cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite fiber and a preparation method thereof, wherein a poly-p-phenylene benzobisoxazole polymer with the intrinsic viscosity of 15-35dL/g is used as a raw material, and the graphene PBO fiber is prepared in a spinning mode of dry-jet wet spinning. The obtained composite fiber has the characteristics of high elongation, cutting resistance, wear resistance and heavy chemical corrosion resistance, has the same excellent and balanced other indexes, has more excellent bulletproof and impact resistance, is particularly suitable for the field of bulletproof, fills up the domestic blank, and is suitable for industrial mass production.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, the scope of the invention should be determined from the following claims.
Claims (10)
1. A preparation method of a cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite fiber is characterized by comprising the following steps:
step 1, weighing raw materials in proportion;
step 2, prepolymerization: putting a material obtained by mixing terephthalic acid, 4, 6-diaminoresorcinol hydrochloride, polyphosphoric acid and phosphorus pentoxide into a dry degassing kettle for reaction, and then reacting in the degassing kettle to obtain a PBO prepolymer;
step 3, post-polymerization: mixing the PBO prepolymer obtained in the step (2) with graphene powder, conveying the mixture to a double-screw extruder, and carrying out post-polymerization reaction to obtain a graphene composite PBO polymer;
step 4, spinning: and (3) spinning the graphene composite PBO polymer obtained in the step (3), drafting and washing, and finally drying and winding to obtain the cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite poly-p-phenylene benzobisoxazole fiber.
2. The method for preparing the cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite fiber as claimed in claim 1, wherein the graphene composite poly-p-phenylene benzobisoxazole fiber has a tensile strength of 5.4-5.8GPa, an elongation at break of 3.5-4.5%, a tensile modulus of 140-180GPa, a density of 1.53-1.54g/cm3。
3. The method for preparing the cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite fiber according to claim 1, wherein in the step 2, the molar ratio of terephthalic acid to 4, 6-diaminoresorcinol hydrochloride, polyphosphoric acid and phosphorus pentoxide is (1.0-1.02): 1: (1.0-5.0): (2.5-6.0).
4. The method for preparing the cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite fiber as claimed in claim 3, wherein in the step 2, the material is put into a dry degassing kettle, degassing reaction is carried out for 10-15h at a temperature of 50-110 ℃, and then reaction is carried out for 1-5h at a temperature of 120-150 ℃ in the degassing kettle, so as to obtain the PBO prepolymer.
5. The method for preparing the cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite fiber according to claim 4, wherein in the step 2, the solid content of the PBO prepolymer is 10-15% by mass.
6. The method for preparing the cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite fiber as claimed in claim 1, wherein in the step 3, the PBO prepolymer and the graphene powder are mixed and then are conveyed to a double-screw extruder, a post-polymerization reaction is carried out at the temperature of 150-200 ℃, and the residence time of the materials in the screw extruder is 5-30min, so as to obtain the graphene composite PBO polymer.
7. The method for preparing the cutting-resistant, wear-resistant, and chemical corrosion-resistant graphene composite fiber according to claim 6, wherein the graphene composite PBO polymer is soluble in a polyphosphoric acid/phosphorus pentoxide solvent system and has an intrinsic viscosity of 15-35 dL/g.
8. The preparation method of the cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite fiber according to claim 6, wherein in the step 3, the amount of the PBO prepolymer is 30-35% and the amount of the graphene powder is 65-70% by mass percentage.
9. The method for preparing the cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite fiber according to claim 1, wherein in the step 4, the spinning speed is 40-200m/min, the diameter of a spinneret orifice is 0.10-0.25mm, the speed ratio of a guide roller to a drawing machine is 1.01-1.05:1, the tension between drawing and washing is less than or equal to 500cN, and the tension between multi-stage rotary drum rollers adopted in the washing procedure is less than or equal to 300 cN.
10. A graphene composite fiber resistant to cutting, abrasion and chemical corrosion prepared by the method of any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111548468.0A CN114086277A (en) | 2021-12-17 | 2021-12-17 | Cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite fiber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111548468.0A CN114086277A (en) | 2021-12-17 | 2021-12-17 | Cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite fiber and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114086277A true CN114086277A (en) | 2022-02-25 |
Family
ID=80307553
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111548468.0A Pending CN114086277A (en) | 2021-12-17 | 2021-12-17 | Cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite fiber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114086277A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103014901A (en) * | 2012-12-12 | 2013-04-03 | 哈尔滨工业大学 | Preparation method of graphene/PBO (Poly-P-Phenylene Benzobisoxazazole) composite fiber |
| KR20140108360A (en) * | 2013-02-25 | 2014-09-11 | 금오공과대학교 산학협력단 | Graphene-reinforced Poly(p-phenylene benzobisoxazole) composites and process for producing the same |
-
2021
- 2021-12-17 CN CN202111548468.0A patent/CN114086277A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103014901A (en) * | 2012-12-12 | 2013-04-03 | 哈尔滨工业大学 | Preparation method of graphene/PBO (Poly-P-Phenylene Benzobisoxazazole) composite fiber |
| KR20140108360A (en) * | 2013-02-25 | 2014-09-11 | 금오공과대학교 산학협력단 | Graphene-reinforced Poly(p-phenylene benzobisoxazole) composites and process for producing the same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9512290B2 (en) | Reinforced polymeric articles | |
| CA1182004A (en) | Sized carbon fibers and thermoplastic polyester based composite structures employing the same | |
| KR101985849B1 (en) | Carbon fiber prepreg or carbon fiber - reinforced plastic, and materials including the same | |
| EP2963165B1 (en) | Composite fiber, fabric, knitted article, and composite material | |
| US20240120128A1 (en) | Conductive compositions of conductive polymer and metal coated fiber | |
| EP3564287B1 (en) | Aramid-based epoxy resin and preparation method thereof | |
| Chang et al. | Structure–property relationship of polyimide fibers containing ether groups | |
| Akato et al. | High performance fibers from aramid polymers | |
| Ashadujjaman et al. | Enhancing the mechanical properties of natural jute yarn suitable for structural applications | |
| Jeong et al. | Preparation, structure and properties of poly (p-phenylene benzobisoxazole) composite fibers reinforced with graphene | |
| CN114086273A (en) | Graphene anti-ultraviolet anti-cutting high-stretch-resistance composite fiber and preparation method thereof | |
| Song et al. | Construction of bio-based ramie fabric/epoxy resin composites with high flame retardant and mechanical performances | |
| CN114086277A (en) | Cutting-resistant, wear-resistant and chemical corrosion-resistant graphene composite fiber and preparation method thereof | |
| EP3293296B1 (en) | Spun yarn comprising carbon staple fibers and method of preparing the same | |
| Jassal et al. | Aramid fibers | |
| CN113337909A (en) | Creep-resistant polyester industrial yarn and preparation method thereof | |
| Tian et al. | A novel ternary composite of polyurethane/polyaniline/nanosilica with antistatic property and excellent mechanical strength: preparation and mechanism | |
| JP5589971B2 (en) | Molding material | |
| CN106396429A (en) | Glass structure, and train with glass structure | |
| CN115522276A (en) | Preparation method of conductive and reinforced PBT fiber | |
| CN112941704B (en) | Preparation method of three-dimensional spacer fabric reinforced porous composite material | |
| CN113737528A (en) | Degradable resin carbon fiber sizing agent | |
| CN113005604A (en) | Preparation method of three-dimensional spacer fabric reinforced porous composite material | |
| CN206219445U (en) | Glass structure and the train with it | |
| CN1245434C (en) | Poly-benzobisoxazole polymer containing hydroxyl group and process for preparing same |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220225 |