CN117867686A - Dyeing method without changing mechanical properties of poly (p-phenylene benzobisoxazole) fiber - Google Patents
Dyeing method without changing mechanical properties of poly (p-phenylene benzobisoxazole) fiber Download PDFInfo
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- 239000000835 fiber Substances 0.000 title claims abstract description 98
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000004043 dyeing Methods 0.000 title claims abstract description 26
- 229920000927 poly(p-phenylene benzobisoxazole) Polymers 0.000 title claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 76
- 238000010438 heat treatment Methods 0.000 claims abstract description 50
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims abstract description 47
- 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 42
- 229920000137 polyphosphoric acid Polymers 0.000 claims abstract description 36
- 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 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 26
- 238000009987 spinning Methods 0.000 claims abstract description 23
- 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
- 239000000049 pigment Substances 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 30
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000002861 polymer material Substances 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 239000004973 liquid crystal related substance Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 9
- 239000006229 carbon black Substances 0.000 description 4
- 238000001338 self-assembly Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical class [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 2
- 238000006384 oligomerization reaction Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical group C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/22—Polybenzoxazoles
-
- 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
- D01F1/04—Pigments
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
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- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to a dyeing method without changing the mechanical properties of poly (p-phenylene benzobisoxazole), which comprises the following steps: adding 4, 6-diaminoresorcinol hydrochloride, phosphorus pentoxide, terephthalic acid and pigment phthalocyanine into a reaction device filled with polyphosphoric acid, and carrying out gradient heating and stirring reaction at the temperature of 45-145 ℃ to obtain PBO prepolymer solution; the PBO prepolymer solution is conveyed to a double-screw extruder, high polymerization is completed in the double-screw extruder, and then the PBO prepolymer solution is conveyed to a spinning metering pump to prepare the high-performance PBO fiber.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a dyeing method without changing the mechanical properties of poly (p-Phenylene Benzobisoxazole) (PBO) fibers.
Background
Poly (p-Phenylene Benzobisoxazole) (PBO) fibers can be prepared by solution polycondensation of 4, 6-diaminoresorcinol hydrochloride (DAR) and terephthalic acid (TPA) in polyphosphoric acid (PPA) followed by liquid crystal spinning. By liquid crystal spinning technology, rigid rod-like molecules in PBO molecules are almost completely aligned along the fiber axis to form a highly aligned ordered structure. The PBO fiber has high strength, high modulus and high heat resistance, and is widely applied to the fields of advanced structure composite materials such as aerospace, military and the like.
The PBO fibers themselves are golden or yellowish-brown. The dyeing of the PBO fibers can meet different application fields of the fibers, and particularly, the application of the PBO fibers in military camouflage and other aspects is realized. However, the macromolecular structure of the PBO fiber has no active group, the fiber structure is very compact, and the conventional synthetic fiber dyeing processing method is difficult to dye. If titanium dioxide, carbon black, cobalt green and other pigments are added for dyeing, the original structure of the fiber and the high molecular orientation along the fiber axis can be destroyed, and the performance of the fiber is reduced. Therefore, a new method for dyeing PBO fibers suitable for industrial production is needed, so that the dyed PBO fibers are more colorful and the mechanical properties of the fibers are not affected.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the dyeing method without changing the mechanical properties of the poly (p-Phenylene Benzobisoxazole) (PBO) fiber, wherein the phthalocyanine pigment which can be dissolved in polyphosphoric acid is added into a PBO prepolymerization system, and the problem of difficult dyeing of the PBO fiber in the prior art can be solved by matching with a gradient heating mode in the prepolymerization process, meanwhile, the mechanical properties of the PBO fiber can be ensured, and the application scene of the PBO fiber is greatly expanded.
The technical scheme of the invention is as follows:
adding 4, 6-diamino resorcinol hydrochloride, phosphorus pentoxide, terephthalic acid and phthalocyanine pigment into a reaction device filled with polyphosphoric acid, and carrying out gradient heating and stirring reaction at the temperature of 45-145 ℃ to obtain PBO prepolymer solution; the PBO prepolymer solution was fed into a twin screw extruder where the high polymerization was completed and then fed into a spinning metering pump to produce high performance PBO fibers.
Preferably, the phthalocyanine pigments are unsubstituted phthalocyanines and phthalocyanine derivatives dissolved in polyphosphoric acid. The phthalocyanine pigment has good solubility in polyphosphoric acid which is a solvent for PBO polymerization reaction, phthalocyanine molecules have a planar structure similar to that of the PBO molecules, and the structural formula of the phthalocyanine is as follows:
wherein M can be iron, cobalt, copper or the like, and R can be phenyl, pyridyl, methyl or the like.
Preferably, the addition amount of 0 < phthalocyanine is less than or equal to 25 per mill of the mass of polyphosphoric acid.
Preferably, the raw materials used in the dyeing method comprise 1 to 5 parts of polyphosphoric acid, 0.2 to 1 part of 4, 6-diaminoresorcinol hydrochloride, 0.4 to 2 parts of phosphorus pentoxide and 0.2 to 1 part of terephthalic acid.
Preferably, the specific process of gradient heating is as follows: heating to 45-65 ℃ and stirring for reaction for 6-8h, heating to 65-125 ℃ and stirring for reaction for 4-6h, heating to 125-145 ℃ and stirring for reaction for 2-4h, thus obtaining PBO prepolymer solution.
Preferably, the forward rotation/reverse rotation of the stirring paddles is switched every 10-60min in the prepolymerization stage, and the stirring speed of the stirring paddles is 10-100r/min.
Preferably, the temperature is set to 150-200 ℃ when the rotating speed of the screw extruder is controlled to 10-50 r/min.
Preferably, the specific preparation of the PBO prepolymer is as follows: introducing nitrogen into a reaction device filled with polyphosphoric acid, adding 4, 6-diaminoresorcinol hydrochloride and phosphorus pentoxide, and then carrying out oil bath heating reaction to exhaust hydrogen chloride; after the hydrogen chloride is exhausted, adding the monomer terephthalic acid and the phthalocyanine pigment, and carrying out gradient heating and stirring reaction at the temperature of 45-145 ℃ to prepare the PBO prepolymer. Further preferably, the oil bath is heated to 45-65 ℃ and stirred for reaction for 6-10h.
Preferably, the material is held in the twin-screw extruder for a residence time of 90 minutes.
According to the invention, the phthalocyanine pigment which can be dissolved in polyphosphoric acid is added into a PBO prepolymerization system, the polyphosphoric acid solvated phthalocyanine molecules have a planar structure similar to PBO, the phthalocyanine molecules are tightly combined on a PBO molecular chain through pi-pi interaction, meanwhile, as the phthalocyanine molecules are smaller than the PBO molecules on a fiber shaft but larger than the PBO molecules in a transverse direction, the plane of the phthalocyanine molecules is more easily aligned with the flowing direction of the polyphosphoric acid, and the benzene ring and the oxazole ring of the PBO can be guided and oriented to the radial direction of the fiber, so that the PBO fiber modulus is improved; by controlling the temperature gradient of the prepolymerization reaction, the polymerization rate of the PBO is slowed down in the early stage, so that sufficient time is provided for the self-assembly of phthalocyanine/PBO oligomerization molecules through the conjugate physical effect, the next phthalocyanine molecules are convenient to fully play the template effect, the phthalocyanine/PBO micromolecules are combined together through the self-assembly in the oligomerization stage, and then the PBO molecule chain is continuously polymerized and grown, so that the phthalocyanine is more uniformly dispersed in the molecular dimension, the radial dimension of the PBO macromolecule is better guided, the strength of the PBO fiber is improved, if the polymerization degree of the PBO molecule is high, the phthalocyanine molecules are difficult to be uniformly doped into the PBO molecule chain in the molecular dimension, and if the phthalocyanine molecules singly form aggregates, the process is equivalent to introducing impurities into a system, and the strength of the prepared fiber is reduced.
The dyeing method of the poly (p-Phenylene Benzobisoxazole) (PBO) fiber provided by the invention has the advantages that the PBO fiber can be uniformly dyed, the original structure of the PBO fiber is not damaged, the mechanical property of the PBO fiber is not reduced, and the application scene of the PBO fiber is greatly expanded.
Drawings
FIG. 1 is a schematic reaction diagram of a prior art terephthalic acid process for preparing PBO homopolymer.
Detailed Description
The invention will be further illustrated by the following examples, which will allow a person skilled in the art to more fully understand the invention, but which are not intended to limit the invention in any way.
Among the following selected polyphosphoric acids: p is more than or equal to 85.0 percent 2 O 5 The content is less than or equal to 90.0 percent.
Example 15 Process for the preparation of a non-substituted, non-metallic Phthalocyanine dyed PBO fiber (specifically speaking, a center-metal-free and substituent-free Phthalocyanine)
Adding 5.024Kg of polyphosphoric acid solvent, 1.09Kg of 4, 6-diaminoresorcinol hydrochloride and 1.931Kg of phosphorus pentoxide into a polymerization reaction kettle which is filled with nitrogen (the nitrogen is filled for removing oxygen), heating an oil bath to 45 ℃ and stirring for reaction for 8 hours to remove hydrogen chloride (a gas guide tube is used for filling the discharged hydrogen chloride into a sodium hydroxide solution); adding 0.025Kg of unsubstituted nonmetallic phthalocyanine (accounting for 5 per mill of the mass ratio of polyphosphoric acid) and 0.850Kg of monomer terephthalic acid after hydrogen chloride is exhausted, gradually heating to 65 ℃ after the addition, stirring and reacting for 6 hours, heating to 125 ℃ and stirring and reacting for 4 hours, heating to 145 ℃ and stirring and reacting for 2 hours, wherein the stirring speed of a stirring paddle is 50r/min, and switching forward rotation/reverse rotation of the stirring paddle every 20min to obtain a dyed PBO prepolymer solution; then conveying the PBO prepolymer solution into a double-screw extruder, wherein the rotating speed of the screw extruder is 30r/min, the temperature is set to 180 ℃, the retention time of the materials in the double-screw extruder is 90min, and the high polymerization is completed in the double-screw extruder; and then the fiber is conveyed to a spinning metering pump, and PBO molecules are highly oriented on a fiber shaft due to high-power stretching of a liquid crystal spinning method, so that the high-performance PBO fiber is prepared, a finished product is green, and the tensile modulus of the finished product is tested to be 162GPa.
Example 2 preparation of 10% by weight of unsubstituted non-metallic Phthalocyanine dyed PBO fiber (specifically speaking, center-metal-free and substituent-free Phthalocyanine)
Adding 5.024Kg of polyphosphoric acid solvent and 1.09Kg of 4, 6-diaminoresorcinol hydrochloride and 1.931Kg of phosphorus pentoxide into a polymerization reaction kettle filled with nitrogen, heating an oil bath to 45 ℃ and stirring for reaction for 8 hours to remove hydrogen chloride (a gas guide tube introduces the discharged hydrogen chloride into a sodium hydroxide solution); adding 0.050Kg of unsubstituted nonmetallic phthalocyanine (accounting for 10 per mill of the mass ratio of polyphosphoric acid) and 0.850Kg of monomer terephthalic acid after discharging hydrogen chloride, gradually heating to 65 ℃ after the addition, stirring and reacting for 6 hours, heating to 125 ℃ and stirring and reacting for 4 hours, heating to 145 ℃ and stirring and reacting for 2 hours, wherein the stirring speed of a stirring paddle is 50r/min, and switching forward rotation/reverse rotation of the stirring paddle every 20min to obtain a dyed PBO prepolymer solution; then conveying the PBO prepolymer solution into a double-screw extruder, wherein the rotating speed of the screw extruder is 30r/min, the temperature is set to 180 ℃, the retention time of the materials in the double-screw extruder is 90min, and the high polymerization is completed in the double-screw extruder; and then the fiber is conveyed to a spinning metering pump, and PBO molecules are highly oriented on a fiber shaft due to high-power stretching of a liquid crystal spinning method, so that the high-performance PBO fiber is prepared, a finished product is green, and the tensile modulus of the fiber is tested to be 167GPa.
Example 3 preparation of 15% by weight of unsubstituted non-metallic Phthalocyanine dyed PBO fiber (specifically speaking, center-metal-free and substituent-free Phthalocyanine)
Adding 5.024Kg of polyphosphoric acid solvent and 1.09Kg of 4, 6-diaminoresorcinol hydrochloride and 1.931Kg of phosphorus pentoxide into a polymerization reaction kettle filled with nitrogen, heating an oil bath to 45 ℃ and stirring for reaction for 8 hours to remove hydrogen chloride (a gas guide tube introduces the discharged hydrogen chloride into a sodium hydroxide solution); adding 0.075Kg of unsubstituted nonmetallic phthalocyanine (accounting for 15 per mill of the mass ratio of polyphosphoric acid) and 0.850Kg of monomer terephthalic acid after hydrogen chloride is exhausted, gradually heating to 65 ℃ after the addition, stirring and reacting for 6 hours, heating to 125 ℃ and stirring and reacting for 4 hours, heating to 145 ℃ and stirring and reacting for 2 hours, wherein the stirring speed of a stirring paddle is 50r/min, and switching the stirring paddles to rotate positively/negatively every 20min to obtain a dyed PBO prepolymer solution; then conveying the PBO prepolymer solution into a double-screw extruder, wherein the rotating speed of the screw extruder is 30r/min, the temperature is set to 180 ℃, the retention time of the materials in the double-screw extruder is 90min, and the high polymerization is completed in the double-screw extruder; and then the fiber is conveyed to a spinning metering pump, and PBO molecules are highly oriented on a fiber shaft due to high-power stretching of a liquid crystal spinning method, so that the high-performance PBO fiber is prepared, a finished product is green, and the tensile modulus of the finished product is tested to be 174GPa.
Example 4 preparation of 20% of unsubstituted non-Metal Phthalocyanine dyed PBO fiber (specifically speaking, center-metal-free and substituent-free Phthalocyanine)
Adding 5.024Kg of polyphosphoric acid solvent and 1.09Kg of 4, 6-diaminoresorcinol hydrochloride and 1.931Kg of phosphorus pentoxide into a polymerization reaction kettle filled with nitrogen, heating an oil bath to 45 ℃ and stirring for reaction for 8 hours to remove hydrogen chloride (a gas guide tube introduces the discharged hydrogen chloride into a sodium hydroxide solution); adding 0.100Kg of unsubstituted nonmetallic phthalocyanine (accounting for 20 per mill of the mass ratio of polyphosphoric acid) and 0.850Kg of monomer terephthalic acid after hydrogen chloride is exhausted, gradually heating to 65 ℃ after the addition, stirring and reacting for 6 hours, heating to 125 ℃ and stirring and reacting for 4 hours, heating to 145 ℃ and stirring and reacting for 2 hours, wherein the stirring speed of a stirring paddle is 50r/min, and switching the stirring paddles to rotate forward/reverse every 20min to obtain a dyed PBO prepolymer solution; then conveying the PBO prepolymer solution into a double-screw extruder, wherein the rotating speed of the screw extruder is 30r/min, the temperature is set to 180 ℃, the retention time of the materials in the double-screw extruder is 90min, and the high polymerization is completed in the double-screw extruder; and then the fiber is conveyed to a spinning metering pump, and PBO molecules are highly oriented on a fiber shaft due to high-power stretching of a liquid crystal spinning method, so that the high-performance PBO fiber is prepared, the finished product is green, and the tensile modulus of the finished product is tested to be 166GPa.
Example 5 preparation of 25% by weight of unsubstituted non-metallic Phthalocyanine dyed PBO fiber (specifically speaking, center-metal-free and substituent-free Phthalocyanine)
Adding 5.024Kg of polyphosphoric acid solvent and 1.09Kg of 4, 6-diaminoresorcinol hydrochloride and 1.931Kg of phosphorus pentoxide into a polymerization reaction kettle filled with nitrogen, heating an oil bath to 45 ℃ and stirring for reaction for 8 hours to remove hydrogen chloride (a gas guide tube introduces the discharged hydrogen chloride into a sodium hydroxide solution); adding 0.0125Kg of unsubstituted nonmetallic phthalocyanine (accounting for 25 per mill of the mass ratio of polyphosphoric acid) and 0.850Kg of monomer terephthalic acid after hydrogen chloride is exhausted, gradually heating to 65 ℃ after the addition, stirring and reacting for 6 hours, heating to 125 ℃ and stirring and reacting for 4 hours, heating to 145 ℃ and stirring and reacting for 2 hours, wherein the stirring speed of a stirring paddle is 50r/min, and switching forward rotation/reverse rotation of the stirring paddle every 20min to obtain a dyed PBO prepolymer solution; then conveying the PBO prepolymer solution into a double-screw extruder, wherein the rotating speed of the screw extruder is 30r/min, the temperature is set to 180 ℃, the retention time of the materials in the double-screw extruder is 90min, and the high polymerization is completed in the double-screw extruder; and then the fiber is conveyed to a spinning metering pump, and PBO molecules are highly oriented on a fiber shaft due to high-power stretching of a liquid crystal spinning method, so that the high-performance PBO fiber is prepared, a finished product is green, and the tensile modulus of the finished product is tested to be 146GPa.
Example 6 preparation of 15% substituted copper phthalocyanine dyed PBO fiber (specifically speaking, a substituted-free phthalocyanine with copper as the center metal)
Adding 5.024Kg of polyphosphoric acid solvent and 1.09Kg of 4, 6-diaminoresorcinol hydrochloride and 1.931Kg of phosphorus pentoxide into a polymerization reaction kettle filled with nitrogen, heating an oil bath to 45 ℃ and stirring for reaction for 8 hours to remove hydrogen chloride (a gas guide tube introduces the discharged hydrogen chloride into a sodium hydroxide solution); adding 0.075Kg of unsubstituted copper phthalocyanine (accounting for 15 per mill of the mass ratio of polyphosphoric acid) and 0.850Kg of monomer terephthalic acid after hydrogen chloride is exhausted, gradually heating to 65 ℃ after the addition, stirring and reacting for 6 hours, heating to 125 ℃ and stirring and reacting for 4 hours, heating to 145 ℃ and stirring and reacting for 2 hours, wherein the stirring speed of a stirring paddle is 50r/min, and switching forward rotation/reverse rotation of the stirring paddle every 20min to obtain a dyed PBO prepolymer solution; then conveying the PBO prepolymer solution into a double-screw extruder, wherein the rotating speed of the screw extruder is 30r/min, the temperature is set to 180 ℃, the retention time of the materials in the double-screw extruder is 90min, and the high polymerization is completed in the double-screw extruder; and then the fiber is conveyed to a spinning metering pump, and PBO molecules are highly oriented on a fiber shaft due to high-power stretching of a liquid crystal spinning method, so that the high-performance PBO fiber is prepared, a finished product is blue, and the tensile modulus of the finished product is tested to be 172GPa.
Comparative example 1 method for preparing PBO fiber by terephthalic acid method (as shown in FIG. 1)
Adding 5.024Kg of polyphosphoric acid solvent and 1.09Kg of 4, 6-diaminoresorcinol hydrochloride and 1.931Kg of phosphorus pentoxide into a polymerization reaction kettle filled with nitrogen, heating an oil bath to 45 ℃ and stirring for reaction for 8 hours to remove hydrogen chloride (a gas guide tube introduces the discharged hydrogen chloride into a sodium hydroxide solution); adding 0.850Kg of monomer terephthalic acid after hydrogen chloride is discharged, gradually heating to 65 ℃ after the addition, stirring and reacting for 6 hours, heating to 125 ℃ and stirring and reacting for 4 hours, heating to 145 ℃ and stirring and reacting for 2 hours, wherein the stirring speed of a stirring paddle is 50r/min, and switching the forward rotation/reverse rotation of the stirring paddle every 20min to obtain a prepolymer solution; then conveying the PBO prepolymer solution into a double-screw extruder, wherein the rotating speed of the screw extruder is 30r/min, the temperature is set to 180 ℃, the retention time of the materials in the double-screw extruder is 90min, and the high polymerization is completed in the double-screw extruder; and then the fiber is conveyed to a spinning metering pump, and PBO molecules are highly oriented on a fiber shaft due to high-power stretching of a liquid crystal spinning method, so that the high-performance PBO fiber is prepared, the finished product is golden yellow, and the tensile modulus of the finished product is tested to be 161GPa. Comparative example 2 preparation of 15% carbon black dyed PBO fibre
Adding 5.024Kg of polyphosphoric acid solvent and 1.09Kg of 4, 6-diaminoresorcinol hydrochloride and 1.931Kg of phosphorus pentoxide into a polymerization reaction kettle filled with nitrogen, heating an oil bath to 45 ℃ and stirring for reaction for 8 hours to remove hydrogen chloride (a gas guide tube introduces the discharged hydrogen chloride into a sodium hydroxide solution); adding 0.075Kg of carbon black (accounting for 15 per mill of the mass ratio of the polyphosphoric acid) after discharging hydrogen chloride, and 0.850Kg of monomer terephthalic acid, gradually heating to 65 ℃ after the addition, stirring and reacting for 6 hours, heating to 125 ℃ and stirring and reacting for 4 hours, heating to 145 ℃ and stirring and reacting for 2 hours, wherein the stirring speed of a stirring paddle is 50r/min, and switching the forward/reverse rotation of the stirring paddle every 20min to obtain a pre-polymerization solution. Then conveying the PBO prepolymer solution into a double-screw extruder, wherein the rotating speed of the screw extruder is 30r/min, the temperature is set to 180 ℃, the retention time of the materials in the double-screw extruder is 90min, and the high polymerization is completed in the double-screw extruder; and then the fiber is conveyed to a spinning metering pump, and PBO molecules are highly oriented on a fiber shaft due to high-power stretching of a liquid crystal spinning method, so that the high-performance PBO fiber is prepared, a finished product is black, and the tensile modulus of the fiber is tested to be 119GPa.
Comparative example 3 preparation of 15% of unsubstituted non-metallic phthalocyanine dyed PBO fibers (specifically speaking, center metal-free and substituent-free phthalocyanine, prepolymerization stage without low temperature self-assembly process)
Adding 5.024Kg of polyphosphoric acid solvent and 1.09Kg of 4, 6-diaminoresorcinol hydrochloride and 1.931Kg of phosphorus pentoxide into a polymerization reaction kettle filled with nitrogen, heating an oil bath to 45 ℃ and stirring for reaction for 8 hours to remove hydrogen chloride (a gas guide tube introduces the discharged hydrogen chloride into a sodium hydroxide solution); adding 0.075Kg of unsubstituted nonmetallic phthalocyanine (accounting for 15 per mill of the mass ratio of polyphosphoric acid) after hydrogen chloride is exhausted, and 0.850Kg of monomer terephthalic acid, heating to 145 ℃ after the addition, stirring and reacting for 6 hours, wherein the stirring speed of a stirring paddle is 50r/min, and switching forward rotation/reverse rotation of the stirring paddle every 20min to obtain a dyeing PBO pre-polymerization solution; then conveying the PBO prepolymer solution into a double-screw extruder, wherein the rotating speed of the screw extruder is 30r/min, the temperature is set to 180 ℃, the retention time of the materials in the double-screw extruder is 90min, and the high polymerization is completed in the double-screw extruder; and then the fiber is conveyed to a spinning metering pump, and PBO molecules are highly oriented on a fiber shaft due to high-power stretching of a liquid crystal spinning method, so that the high-performance PBO fiber is prepared, a finished product is green, and the tensile modulus of the finished product is tested to be 137GPa.
Comparative example 1 is a prior art terephthalic acid process for making PBO fibers, the tensile modulus of PBO fibers dyed by examples 1-6 is even higher than that of PBO fibers of comparative example 1; comparative example 2 the tensile modulus of PBO fibers dyed with carbon black was significantly reduced compared to the fibers of comparative example 1 and examples 1-6; comparative example 2 the tensile modulus of the fibers was significantly lower than the fibers of comparative example 1 and examples 1-6 using conventional reaction temperatures and times during the prepolymerization stage. As is obvious from comparative examples 1-3, the invention can solve the problem of difficult dyeing of PBO fiber in the prior art by adopting the specific gradient heating mode in the process of the cooperation of phthalocyanine pigment and prepolymerization, can also ensure the mechanical property of the PBO fiber, and greatly expands the application scene of the PBO fiber
The dyeing method of the poly (p-Phenylene Benzobisoxazole) (PBO) fiber provided by the invention has the advantages that the PBO fiber can be uniformly dyed, the original structure of the PBO fiber is not damaged, the mechanical property of the PBO fiber is not reduced, and the application scene of the PBO fiber is greatly expanded.
Claims (10)
1. A dyeing method without changing the mechanical properties of poly (p-phenylene benzobisoxazole) fiber is characterized in that 4, 6-diaminoresorcinol hydrochloride, phosphorus pentoxide, terephthalic acid and phthalocyanine pigment are added into a reaction device filled with polyphosphoric acid, and the mixture is heated up in a gradient way and stirred at the temperature of 45-145 ℃ to react to obtain PBO prepolymer solution; the PBO prepolymer solution was fed into a twin screw extruder where the high polymerization was completed and then fed into a spinning metering pump to produce high performance PBO fibers.
2. The dyeing method without changing the mechanical properties of the poly (p-phenylene benzobisoxazole) fiber according to claim 1, wherein the phthalocyanine pigment is a phthalocyanine and a phthalocyanine derivative dissolved in polyphosphoric acid.
3. The dyeing method without changing the mechanical properties of the poly (p-phenylene benzobisoxazole) fiber according to claim 1 or 2, wherein the addition amount of 0 < phthalocyanine is less than or equal to 25 per mill of the mass of polyphosphoric acid.
4. The dyeing method without changing the mechanical properties of the poly (p-phenylene benzobisoxazole) fiber according to claim 1, wherein the raw materials used in the dyeing method comprise 1-5 parts of polyphosphoric acid, 0.2-1 part of 4, 6-diaminoresorcinol hydrochloride, 0.4-2 parts of phosphorus pentoxide and 0.2-1 part of terephthalic acid.
5. The dyeing method without changing the mechanical properties of the poly (p-phenylene benzobisoxazole) fiber according to claim 1, wherein the specific process of gradient heating is as follows: heating to 45-65 ℃ and stirring for reaction for 6-8h, heating to 65-125 ℃ and stirring for reaction for 4-6h, heating to 125-145 ℃ and stirring for reaction for 2-4h, thus obtaining PBO prepolymer solution.
6. The dyeing method without changing the mechanical properties of the poly (p-phenylene benzobisoxazole) fiber according to claim 1, wherein the stirring paddle is switched to forward/reverse rotation every 10-60min in the prepolymerization stage, and the stirring speed is 10-100r/min.
7. The dyeing method without changing the mechanical properties of the poly (p-phenylene benzobisoxazole) fiber according to claim 1, wherein the temperature is set to 150-200 ℃ when the rotating speed of the screw extruder is controlled to 10-50 r/min.
8. The dyeing method without changing the mechanical properties of the poly (p-phenylene benzobisoxazole) fiber according to claim 1, wherein the preparation of the PBO prepolymer is specifically as follows: introducing nitrogen into a reaction device filled with polyphosphoric acid, adding 4, 6-diaminoresorcinol hydrochloride and phosphorus pentoxide, and then carrying out oil bath heating reaction to exhaust hydrogen chloride; then adding monomer terephthalic acid and phthalocyanine pigment, heating up in a gradient way at the temperature of 45-145 ℃ and stirring for reaction to prepare the PBO prepolymer.
9. The dyeing method without changing the mechanical properties of the poly (p-phenylene benzobisoxazole) fiber according to claim 8, wherein the oil bath is heated to 45-65 ℃ and stirred for 6-10h.
10. The dyeing method without changing the mechanical properties of the poly (p-phenylene benzobisoxazole) fiber according to claim 1, wherein the residence time of the material in the twin-screw extruder is 30 to 120 minutes.
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