CN117364273A - Preparation method of transverse reinforced PBO (Poly-p-phenylene oxide) fiber - Google Patents
Preparation method of transverse reinforced PBO (Poly-p-phenylene oxide) fiber Download PDFInfo
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- CN117364273A CN117364273A CN202311307048.2A CN202311307048A CN117364273A CN 117364273 A CN117364273 A CN 117364273A CN 202311307048 A CN202311307048 A CN 202311307048A CN 117364273 A CN117364273 A CN 117364273A
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- 239000000835 fiber Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 title description 2
- 238000007872 degassing Methods 0.000 claims abstract description 57
- 238000009987 spinning Methods 0.000 claims abstract description 31
- 239000002002 slurry Substances 0.000 claims abstract description 27
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 26
- CGRRUFNHHQCLDZ-UHFFFAOYSA-N 5-hydroxypyridine-2-carboxylic acid Chemical compound OC(=O)C1=CC=C(O)C=N1 CGRRUFNHHQCLDZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 18
- 230000009467 reduction Effects 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims description 90
- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 77
- 239000003054 catalyst Substances 0.000 claims description 68
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 68
- 239000007790 solid phase Substances 0.000 claims description 45
- 229920000642 polymer Polymers 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 239000007788 liquid Substances 0.000 claims description 29
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 28
- 239000004954 Polyphthalamide Substances 0.000 claims description 21
- 239000012752 auxiliary agent Substances 0.000 claims description 21
- 229920006375 polyphtalamide Polymers 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- GAKFXHZPQGSWHQ-UHFFFAOYSA-N 4,6-diaminobenzene-1,3-diol;hydrochloride Chemical group Cl.NC1=CC(N)=C(O)C=C1O GAKFXHZPQGSWHQ-UHFFFAOYSA-N 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 229910017318 Mo—Ni Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 230000000379 polymerizing effect Effects 0.000 claims description 7
- 229910017313 Mo—Co Inorganic materials 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 abstract description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 9
- 230000002787 reinforcement Effects 0.000 abstract description 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 150000001299 aldehydes Chemical class 0.000 description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 125000003172 aldehyde group Chemical group 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 229920000271 Kevlar® Polymers 0.000 description 3
- 239000004761 kevlar Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 150000003504 terephthalic acids Chemical group 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a preparation method of a transverse reinforced PBO fiber, which comprises the following steps: preparing raw materials; degassing and prepolymerizing; hydrogenation reduction; preparing TPA slurry; post-polymerization; spinning and forming; according to the preparation method of the PBO fiber with the transverse reinforcement, 2-carboxyl-5-hydroxypyridine is introduced, anchor point quantity for forming hydrogen bonds can be provided, hydrogenation reduction reaction is carried out on aldehyde in an-R group after pre-polymerization occurs, the generated hydroxyl groups can form the hydrogen bonds among molecular chains, and the bonding strength among the molecular chains of the PBO fiber is enhanced, so that the transverse strength of the fiber is improved.
Description
Technical Field
The invention relates to the technical field of PBO fiber preparation, in particular to a preparation method of a transverse reinforced PBO fiber.
Background
The PBO is used as the 21 st century super-performance fiber, has very excellent physical and mechanical properties and chemical properties, has the strength and modulus which are 2 times that of Kevlar (Kevlar) fiber and has the heat-resistant and flame-retardant performance of meta-aramid fiber, and the physical and chemical properties are completely superior to those of Kevlar fiber which is in the leading position in the field of high-performance fiber.
The molecular chain of the PBO fiber is rod-shaped and has high longitudinal crystallinity, so that the tensile strength is higher, but the transverse strength of the PBO fiber is lower, and the PBO fiber is easy to longitudinally split due to the defect of a sheath-core structure in the fiber processing process, so that the compression performance of the PBO fiber is poor.
Disclosure of Invention
The invention aims to overcome the problems existing in the existing PBO fiber preparation process, 2-carboxyl-5-hydroxypyridine is introduced into the transverse reinforced PBO fiber preparation method, the anchor point amount for forming hydrogen bonds can be provided, and after the pre-polymerization occurs, the aldehyde in the-R group is subjected to hydrogenation reduction reaction, and the generated hydroxyl groups can form hydrogen bonds among molecular chains to strengthen the bonding strength among the molecular chains of the PBO fiber, so that the transverse strength of the fiber is improved.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a method of preparing a transverse reinforced PBO fiber comprising the steps of:
step (A), raw material preparation:
weighing 8-18% of a first monomer, 0.5-2% of phosphorus pentoxide, 6-15% of a second monomer, 0.5-5% of a third monomer, 50-85% of polyphosphoric acid, 0.03-0.1% of a solid phase catalyst and 0.5-2% of polyphthalamide according to mass ratio;
step (B), degassing and prepolymerizing:
adding the first monomer, phosphorus pentoxide, third monomer, second monomer accounting for 80-90% of the total mass ratio and polyphosphoric acid accounting for 70-90% of the total mass ratio into a degassing reaction kettle for reaction, and continuously stirring under the degassing condition to obtain a prepolymer;
step (C), hydrogenation reduction:
adding a solid phase catalyst into a degassing reaction kettle, stirring at 150-300rpm, then introducing hydrogen, maintaining the degassing reaction kettle under a certain pressure condition, reacting for 4-10h, and standing and defoaming for a period of time under a vacuumizing condition to obtain a prepolymer;
step (D), TPA slurry preparation:
mixing and preparing the second monomer with the rest mass ratio, polyphosphoric acid and polyphthalamide with all mass ratios under a certain temperature condition to obtain TPA slurry;
step (E), post polymerization:
filtering the prepolymer obtained in the step (C) through a filter screen under the heat preservation condition, mixing the filtered prepolymer with TPA slurry obtained in the step (D), and then, continuously polymerizing in a double-screw extruder, wherein the final phosphorus pentoxide concentration is controlled to be 75-90%, so as to obtain PBO (poly (propylene oxide)) polymer liquid;
step (F), spinning and forming:
before spinning, filtering the PBO polymer liquid through a candle core filter, and forming the filtered PBO polymer liquid through a spinning process to obtain the transverse reinforced PBO fiber.
Preferably, in step (A),
the first monomer is 4, 6-diamino resorcinol hydrochloride;
the second monomer is a derivative of terephthalic acid;
the third monomer is 2-carboxyl-5-hydroxypyridine.
Preferably, in step (A),
the solid phase catalyst comprises a catalyst and an auxiliary agent;
wherein the catalyst accounts for 60-80% of the total mass of the solid phase catalyst, and the auxiliary agent accounts for 20-40% of the total mass of the solid phase catalyst;
and the solid phase catalyst accounts for 0.03-0.08% of the total mass of the first monomer and the second monomer.
Preferably, the catalyst is Mo-Ni or Mo-Co;
the auxiliary agent is Si or P.
Preferably, the step (B) and the degassing and prepolymerizing specifically comprise the following steps:
(B1) Adding the first monomer, phosphorus pentoxide, third monomer, second monomer accounting for 80-90% of the total mass ratio and polyphosphoric acid accounting for 70-90% of the total mass ratio into a degassing reaction kettle, and reacting for 15-24h at 50-150 ℃;
(B2) The degassing reaction kettle is kept at the pressure of 20-50pa under the degassing condition, and stirred for 3-8h at the stirring speed of 50-100rpm, so as to obtain the prepolymer with the intrinsic viscosity of 2-8 dl/g.
Preferably, the step (C) and the hydrogenation reduction specifically comprise the following steps:
(C1) Adding a catalyst accounting for 60-80% of the total mass of the solid phase catalyst and an auxiliary agent accounting for 20-40% of the total mass of the solid phase catalyst into a degassing reaction kettle, and stirring at 150-300rpm;
(C2) Introducing hydrogen at 40-80deg.C, maintaining the degassing reaction kettle at 3-4Mpa, and reacting for 4-10 hr;
(C3) Then, under the condition of vacuumizing, the pressure is kept at 30-40pa, and after standing and defoaming for 10-20 hours, the prepolymer with the intrinsic viscosity of 3-8dl/g is obtained.
Preferably, in step (D), the second monomer and the polyphthalamide are mixed and formulated at a temperature of 80-100 ℃.
Preferably, the step (E) and the post-polymerization specifically comprise the following steps:
(E1) Filtering the prepolymer obtained in the step (C3) through a filter screen under the heat-preserving condition to obtain a filtered prepolymer;
(E2) Mixing the filtered prepolymer with TPA slurry obtained in the step (D), and then, continuously polymerizing in a twin-screw extruder, wherein the temperature is kept at 180-300 ℃, and the total mole ratio of the first monomer to the second monomer is 1-1.2: the total mass of the 1, 2-carboxyl-5-hydroxypyridine is 2-5% of the total mole of the first monomer and the second monomer;
(E3) Controlling the final phosphorus pentoxide concentration between 75 and 90 percent to obtain the PBO polymer solution with the intrinsic viscosity of 20 to 30 dl/g.
Preferably, in the step (E1), the filter screen is a 100-200 mesh filter screen.
Preferably, the step (F) and the spinning forming specifically comprise the following steps:
(F1) Filtering the PBO polymer liquid obtained in the step (E3) through a candle core filter with a minimum pore diameter of 30 microns before spinning to obtain a filtered PBO polymer liquid;
(F2) And forming the filtered PBO polymer liquid through a spinning process to obtain the transverse reinforced PBO fiber.
The beneficial effects of the invention are as follows: according to the preparation method of the PBO fiber with the transverse reinforcement, 2-carboxyl-5-hydroxypyridine is introduced, anchor point quantity for forming hydrogen bonds can be provided, hydrogenation reduction reaction is carried out on aldehyde in an-R group after pre-polymerization occurs, the generated hydroxyl groups can form the hydrogen bonds among molecular chains, and the bonding strength among the molecular chains of the PBO fiber is enhanced, so that the transverse strength of the fiber is improved.
Drawings
FIG. 1 is a flow chart of a method of making a transverse reinforced PBO fiber of the present invention;
FIG. 2 is a structural formula of a first monomer, a second monomer, and a third monomer of the present invention;
FIG. 3 is a linear structure of the second monomer of the present invention wherein the R group contains an aldehyde group;
FIG. 4 is a prepolymerization equation of the first monomer, the second monomer and the third monomer of the present invention.
Detailed Description
The invention will be further described with reference to the drawings.
As shown in fig. 1, the method for preparing the transverse-reinforced PBO fiber of the present invention, comprising the steps of,
step (A), raw material preparation:
weighing 8-18% of a first monomer, 0.5-2% of phosphorus pentoxide, 6-15% of a second monomer, 0.5-5% of a third monomer, 50-85% of polyphosphoric acid, 0.03-0.1% of a solid phase catalyst and 0.5-2% of polyphthalamide according to mass ratio
In the step (A), the step (B),
the first monomer is 4, 6-diamino resorcinol hydrochloride;
the second monomer is a derivative of terephthalic acid;
the third monomer is 2-carboxyl-5-hydroxypyridine;
the solid phase catalyst comprises a catalyst and an auxiliary agent;
wherein the catalyst accounts for 60-80% of the total mass of the solid phase catalyst, and the auxiliary agent accounts for 20-40% of the total mass of the solid phase catalyst;
and the solid phase catalyst accounts for 0.03-0.08% of the total mass of the first monomer and the second monomer;
the catalyst is Mo-Ni or Mo-Co;
the auxiliary agent is Si or P;
step (B), degassing and prepolymerizing, which specifically comprises the following steps:
(B1) Adding the first monomer, phosphorus pentoxide, third monomer, second monomer accounting for 80-90% of the total mass ratio and polyphosphoric acid accounting for 70-90% of the total mass ratio into a degassing reaction kettle, and reacting for 15-24h at 50-150 ℃;
as shown in fig. 2, the structural formulas of the first monomer, the second monomer and the third monomer are shown, wherein the R group in the second monomer is a linear structure containing aldehyde group, and one of the following fig. 3;
as shown in fig. 4, fig. 4 is a prepolymerization equation of a first monomer, a second monomer, and a third monomer;
(B2) The degassing reaction kettle is kept at the pressure of 20-50pa under the degassing condition, and stirred for 3-8h at the stirring speed of 50-100rpm, so as to obtain the prepolymer with the intrinsic viscosity of 2-8 dl/g.
Step (C), hydrogenation reduction, specifically comprising the following steps:
(C1) Adding a catalyst accounting for 60-80% of the total mass of the solid phase catalyst and an auxiliary agent accounting for 20-40% of the total mass of the solid phase catalyst into a degassing reaction kettle, and stirring at 150-300rpm;
(C2) Introducing hydrogen at 40-80deg.C, maintaining the degassing reaction kettle at 3-4Mpa, and reacting for 4-10 hr;
(C3) Then, under the condition of vacuumizing, maintaining the pressure at 30-40pa, standing and defoaming for 10-20 hours to obtain a prepolymer with the intrinsic viscosity of 3-8 dl/g;
step (D), TPA slurry preparation:
mixing and preparing the rest parts by weight of a second monomer, polyphosphoric acid and polyphthalamide with all mass ratios at a certain temperature to obtain TPA slurry;
in the step (D), the temperature of the mixture preparation of the second monomer and the polyphthalamide is 80-100 DEG C
Step (E) and post polymerization, specifically comprising the following steps:
(E1) Filtering the prepolymer obtained in the step (C3) through a filter screen under the heat-preserving condition to obtain a filtered prepolymer;
in the step (E1), the filter screen is a 100-200-mesh filter screen;
(E2) Mixing the filtered prepolymer with TPA slurry obtained in the step (D), and then, continuously polymerizing in a twin-screw extruder, wherein the temperature is kept at 180-300 ℃, and the total mole ratio of the first monomer to the second monomer is 1-1.2: the total weight part of the 1, 2-carboxyl-5-hydroxypyridine is 2-5% of the total mole of the first monomer and the second monomer;
(E3) Controlling the final phosphorus pentoxide concentration to be 75-90%, and obtaining PBO polymer solution with the intrinsic viscosity of 20-30 dl/g;
the polyphosphoric acid in the normal state exists in the state of hydrated phosphorus pentoxide, the hydrated phosphorus pentoxide can be decomposed into phosphorus pentoxide and water, and the three substances are reversible reaction equilibrium processes under certain conditions; the polyphosphoric acid disclosed by the invention is taken as a solvent of a polymerization system, the equilibrium state can be broken, phosphorus pentoxide appears in the polymerization system, the viscosity of the polymerization solution is a key index for measuring the spinnability of the polymerization solution, in the PBO polymerization solution, the viscosity of the polymerization solution (or the reaction degree of the polymerization solution) is often measured by using the relative value of the concentration of the phosphorus pentoxide, and the concentration of the phosphorus pentoxide is controlled to be 75-90% which is the degree of better spinnability of the viscosity of the polymerization solution;
step (F), spinning and forming, which specifically comprises the following steps:
(F1) Filtering the PBO polymer liquid obtained in the step (E3) through a candle core filter with a minimum pore diameter of 30 microns before spinning to obtain a filtered PBO polymer liquid;
(F2) And forming the filtered PBO polymer liquid through a spinning process to obtain the transverse reinforced PBO fiber.
Example 1: the second monomer is 2, 5-dipropionaldehyde terephthalic acid, a third monomer and a solid phase catalyst are not added, the preparation method of the transverse reinforced PBO fiber comprises the following steps,
step (A), raw material preparation:
weighing 15% of 4, 6-diaminoresorcinol hydrochloride, 0.8% of phosphorus pentoxide, 13% of 2, 5-dipropionate terephthalic acid, 70% of polyphosphoric acid and 1.2% of polyphthalamide according to the mass ratio;
step (B), degassing and prepolymerizing, which specifically comprises the following steps:
(B1) Adding 4, 6-diaminoresorcinol hydrochloride, phosphorus pentoxide, 2, 5-dipropionate terephthalic acid accounting for 90% of the total mass ratio and polyphosphoric acid accounting for 90% of the total mass ratio into a degassing reaction kettle, and reacting for 24 hours at the temperature of 150 ℃;
(B2) The pressure in the degassing reactor was maintained at 50pa under degassing conditions and stirred at a stirring speed of 100rpm for 5 hours to obtain a prepolymer having an intrinsic viscosity of 3 dl/g.
Step (D), TPA slurry preparation:
mixing and preparing the rest mass ratio of 2, 5-dipropyl aldehyde terephthalic acid, polyphosphoric acid and all mass ratio of polyphthalamide at the temperature of 100 ℃ to obtain TPA slurry;
step (E) and post polymerization, specifically comprising the following steps:
(E1) Filtering the prepolymer obtained in the step (C3) through a filter screen under the heat-preserving condition to obtain a filtered prepolymer;
(E2) And (2) mixing the filtered prepolymer with TPA slurry obtained in the step (D), and then, continuously polymerizing in a twin-screw extruder at a temperature of 250 ℃, wherein the total molar ratio of 2, 5-dipropionate terephthalic acid to polyphthalamide is 1:1, a step of;
(E3) Controlling the final phosphorus pentoxide concentration to be 80%, and obtaining PBO polymer liquid 1 with the intrinsic viscosity of 7 dl/g;
step (F), spinning and forming, which specifically comprises the following steps:
(F1) Filtering the PBO polymer liquid 1 obtained in the step (E3) through a candle core filter with a minimum pore diameter of 30 microns before spinning to obtain a filtered PBO polymer liquid 1;
(F2) Forming the filtered PBO polymer liquid 1 through a spinning process to obtain a transverse reinforced PBO fiber sample 1;
example 2: the second monomer is 2, 5-dipropionate terephthalic acid, the preparation method of the transverse reinforced PBO fiber comprises the following steps,
step (A), raw material preparation:
weighing 16% of 4, 6-diaminoresorcinol hydrochloride, 0.7% of phosphorus pentoxide, 12% of 2, 5-dipropionate terephthalic acid, 2% of 2-carboxyl-5-hydroxypyridine, 68% of polyphosphoric acid, 0.08% of solid phase catalyst and 1.22% of polyphthalamide according to parts by weight;
the solid phase catalyst comprises a catalyst and an auxiliary agent;
wherein the catalyst accounts for 80% of the total mass of the solid phase catalyst, and the auxiliary agent accounts for 20% of the total mass of the solid phase catalyst;
and the solid phase catalyst accounts for 0.08 percent of the total mass of the 4, 6-diaminoresorcinol hydrochloride and the 2, 5-dipropionate terephthalic acid;
the catalyst is Mo-Ni;
the auxiliary agent is Si;
step (B), degassing and prepolymerizing, which specifically comprises the following steps:
(B1) Adding 4, 6-diaminoresorcinol hydrochloride, phosphorus pentoxide, 2-carboxyl-5-hydroxypyridine, 2, 5-dipropyl aldehyde terephthalic acid accounting for 90% of the total mass ratio and polyphosphoric acid accounting for 90% of the total mass ratio into a degassing reaction kettle, and reacting for 24 hours at the temperature of 150 ℃;
(B2) The pressure in the degassing reactor was maintained at 50pa under degassing conditions and stirred at a stirring speed of 100rpm for 5 hours to obtain a prepolymer having an intrinsic viscosity of 3 dl/g.
Step (C), hydrogenation reduction, specifically comprising the following steps:
(C1) Adding Mo-Ni catalyst accounting for 80 percent of the total mass of the solid phase catalyst and auxiliary Si accounting for 20 percent of the total mass of the solid phase catalyst into a degassing reaction kettle, and stirring at 200rpm;
(C2) Introducing hydrogen at 80 ℃, maintaining the degassing reaction kettle at the pressure of 4Mpa, and reacting for 10 hours;
(C3) Then, under the condition of vacuumizing, maintaining the pressure at 40pa, standing and defoaming for 20 hours to obtain a prepolymer with the intrinsic viscosity of 7 dl/g;
step (D), TPA slurry preparation:
mixing and preparing the rest mass ratio of 2, 5-dipropyl aldehyde terephthalic acid, polyphosphoric acid and all mass ratio of polyphthalamide at the temperature of 100 ℃ to obtain TPA slurry;
step (E) and post polymerization, specifically comprising the following steps:
(E1) Filtering the prepolymer obtained in the step (C3) through a 200-mesh filter screen under the heat-preserving condition to obtain a filtered prepolymer;
(E2) And (2) mixing the filtered prepolymer with TPA slurry obtained in the step (D), and then feeding the mixture into a double-screw extruder for continuous polymerization, wherein the temperature is kept at 250 ℃, and the total mole ratio of the first monomer to the second monomer is 1: the total weight part of the 1, 2-carboxyl-5-hydroxypyridine is 5 percent of the total mole of the first monomer and the second monomer;
(E3) Controlling the final phosphorus pentoxide concentration to be 80%, and obtaining PBO polymer liquid 2 with the intrinsic viscosity of 25 dl/g;
step (F), spinning and forming, which specifically comprises the following steps:
(F1) Filtering the PBO polymer liquid 2 obtained in the step (E3) through a candle core filter with a minimum pore diameter of 30 microns before spinning to obtain filtered PBO polymer liquid 2;
(F2) Forming the filtered PBO polymer liquid 2 through a spinning process to obtain a transverse reinforced PBO fiber sample 2;
example 3: the second monomer is 2, 5-dipropionate terephthalic acid, the preparation method of the transverse reinforced PBO fiber comprises the following steps,
step (A), raw material preparation:
weighing 15% of 4, 6-diaminoresorcinol hydrochloride, 1.3% of phosphorus pentoxide, 11% of 2, 5-dipropyl aldehyde terephthalic acid, 4% of 2-carboxyl-5-hydroxypyridine, 68% of polyphosphoric acid, 0.1% of solid phase catalyst and 0.6% of polyphthalamide according to mass ratio;
the solid phase catalyst comprises a catalyst and an auxiliary agent;
wherein the catalyst accounts for 60% of the total mass of the solid phase catalyst, and the auxiliary agent accounts for 40% of the total mass of the solid phase catalyst;
and the solid phase catalyst accounts for 0.03 percent of the total mass of the 4, 6-diaminoresorcinol hydrochloride and the 2, 5-dipropionate terephthalic acid;
the catalyst is Mo-Ni;
the auxiliary agent is Si;
step (B), degassing and prepolymerizing, which specifically comprises the following steps:
(B1) Adding 4, 6-diaminoresorcinol hydrochloride, phosphorus pentoxide, 2-carboxyl-5-hydroxypyridine, 2, 5-dipropyl aldehyde terephthalic acid accounting for 80% of the total mass ratio and polyphosphoric acid accounting for 70% of the total mass ratio into a degassing reaction kettle, and reacting for 15h at the temperature of 50 ℃;
(B2) The pressure in the degassing reactor was maintained at 20pa under degassing conditions and stirred at 50rpm for 8 hours to obtain a prepolymer having an intrinsic viscosity of 2 dl/g.
Step (C), hydrogenation reduction, specifically comprising the following steps:
(C1) Adding Mo-Ni catalyst accounting for 60 percent of the total mass of the solid phase catalyst and auxiliary Si accounting for 40 percent into a degassing reaction kettle, and stirring at 150rpm;
(C2) Introducing hydrogen at 40 ℃, maintaining the degassing reaction kettle at the pressure of 3Mpa, and reacting for 4 hours;
(C3) Then, under the condition of vacuumizing, maintaining the pressure at 30pa, standing and defoaming for 10 hours to obtain a prepolymer with the intrinsic viscosity of 6 dl/g;
step (D), TPA slurry preparation:
mixing and preparing the rest mass ratio of 2, 5-dipropyl aldehyde terephthalic acid, polyphosphoric acid and all mass ratio of polyphthalamide at 80 ℃ to obtain TPA slurry;
step (E) and post polymerization, specifically comprising the following steps:
(E1) Filtering the prepolymer obtained in the step (C3) through a 100-mesh filter screen under the heat preservation condition to obtain a filtered prepolymer;
(E2) And (2) mixing the filtered prepolymer with TPA slurry obtained in the step (D), and then feeding the mixture into a double-screw extruder for continuous polymerization, wherein the temperature is kept at 180 ℃, and the total mole ratio of the first monomer to the second monomer is 1.1: the total mass of the 1, 2-carboxyl-5-hydroxypyridine is 2 percent of the total mole of the first monomer and the second monomer;
(E3) Controlling the final phosphorus pentoxide concentration to be 75%, and obtaining PBO polymer liquid 3 with the intrinsic viscosity of 20 dl/g;
step (F), spinning and forming, which specifically comprises the following steps:
(F1) Filtering the PBO polymer liquid 3 obtained in the step (E3) through a candle core filter with a minimum pore diameter of 30 microns before spinning to obtain filtered PBO polymer liquid 3;
(F2) Forming the filtered PBO polymer liquid 3 through a spinning process to obtain a transverse reinforced PBO fiber sample 3;
example 4: a process for preparing the transverse reinforced PBO fibers with the second monomer being 2, 5-di (2-butyraldehyde) terephthalic acid, which comprises the steps of,
step (A), raw material preparation:
weighing 10% of 4, 6-diaminoresorcinol hydrochloride, 1.5% of phosphorus pentoxide, 6.8% of 2, 5-di (2-butyraldehyde) terephthalic acid, 0.5% of 2-carboxyl-5-hydroxypyridine, 80% of polyphosphoric acid, 0.05% of solid phase catalyst and 1.15% of polyphthalamide according to mass ratio;
the solid phase catalyst comprises a catalyst and an auxiliary agent;
wherein the catalyst accounts for 70% of the total mass of the solid phase catalyst, and the auxiliary agent accounts for 30% of the total mass of the solid phase catalyst;
and the solid phase catalyst accounts for 0.05% of the total mass of the 4, 6-diaminoresorcinol hydrochloride and the 2, 5-di (2-butyraldehyde) terephthalic acid;
the catalyst is Mo-Co;
the auxiliary agent is Si;
step (B), degassing and prepolymerizing, which specifically comprises the following steps:
(B1) Adding 4, 6-diaminoresorcinol hydrochloride, phosphorus pentoxide, 2-carboxyl-5-hydroxypyridine, 2, 5-di (2-butyraldehyde) terephthalic acid accounting for 85% of the total mass ratio and polyphosphoric acid accounting for 80% of the total mass ratio into a degassing reaction kettle, and reacting for 20h at the temperature of 100 ℃;
(B2) The pressure in the degassing reactor was maintained at 30pa under degassing conditions and stirred at a stirring speed of 70rpm for 5 hours to obtain a prepolymer having an intrinsic viscosity of 2 dl/g.
Step (C), hydrogenation reduction, specifically comprising the following steps:
(C1) Adding a Mo-Co catalyst accounting for 70 percent of the total mass of the solid phase catalyst and an auxiliary Si accounting for 30 percent into a degassing reaction kettle, and stirring at 200rpm;
(C2) Introducing hydrogen at 60 ℃, maintaining the degassing reaction kettle at the pressure of 4Mpa, and reacting for 7h;
(C3) Then, under the condition of vacuumizing, maintaining the pressure at 35pa, standing and defoaming for 15 hours to obtain a prepolymer with the intrinsic viscosity of 7 dl/g;
step (D), TPA slurry preparation:
mixing and preparing the rest 2.5-di (2-butyraldehyde) terephthalic acid, polyphosphoric acid and the total mass proportion of polyphthalamide at 90 ℃ to obtain TPA slurry;
step (E) and post polymerization, specifically comprising the following steps:
(E1) Filtering the prepolymer obtained in the step (C3) through a 100-mesh filter screen under the heat preservation condition to obtain a filtered prepolymer;
(E2) And (2) mixing the filtered prepolymer with TPA slurry obtained in the step (D), and then feeding the mixture into a double-screw extruder for continuous polymerization, wherein the temperature is kept at 200 ℃, and the total mole ratio of the first monomer to the second monomer is 1: the total weight part of the 1, 2-carboxyl-5-hydroxypyridine is 3 percent of the total mole of the first monomer and the second monomer;
(E3) Controlling the final phosphorus pentoxide concentration to be 80%, and obtaining PBO polymer solution 4 with the intrinsic viscosity of 25 dl/g;
step (F), spinning and forming, which specifically comprises the following steps:
(F1) Filtering the PBO polymer solution 4 obtained in the step (E3) through a candle core filter with a minimum pore diameter of 30 microns before spinning to obtain a filtered PBO polymer solution 4;
(F2) Forming the filtered PBO polymer liquid 4 through a spinning process to obtain a transverse reinforced PBO fiber sample 4;
example 5: the second monomer is terephthalic acid, the preparation method of the PBO fiber with transverse reinforcement comprises the following steps,
step (A), raw material preparation:
weighing 15% of 4, 6-diaminoresorcinol hydrochloride, 1.3% of phosphorus pentoxide, 19% of terephthalic acid, 4% of 2-carboxyl-5-hydroxypyridine, 60% of polyphosphoric acid, 0.06% of solid phase catalyst and 0.64% of polyphthalamide according to mass ratio;
step (B), degassing and prepolymerizing, which specifically comprises the following steps:
(B1) Adding 4, 6-diaminoresorcinol hydrochloride, phosphorus pentoxide, 2-carboxyl-5-hydroxypyridine, terephthalic acid accounting for 90% of the total mass ratio and polyphosphoric acid accounting for 90% of the total mass ratio into a degassing reaction kettle, and reacting for 24 hours at the temperature of 150 ℃;
(B2) The pressure in the degassing reactor was maintained at 50pa under degassing conditions and stirred at a stirring speed of 100rpm for 5 hours to obtain a prepolymer having an intrinsic viscosity of 3 dl/g.
Step (C), hydrogenation reduction, specifically comprising the following steps:
(C1) Adding a Mo-Co catalyst accounting for 60 percent of the total mass of the solid phase catalyst and an auxiliary Si accounting for 40 percent into a degassing reaction kettle, and stirring at 150rpm;
(C2) Introducing hydrogen at 60 ℃, maintaining the degassing reaction kettle at the pressure of 4Mpa, and reacting for 7h;
(C3) Then, under the condition of vacuumizing, maintaining the pressure at 30pa, standing and defoaming for 15 hours to obtain a prepolymer with the intrinsic viscosity of 4 dl/g;
step (D), TPA slurry preparation:
mixing and preparing the rest mass ratio of terephthalic acid, polyphosphoric acid and all mass ratio of polyphthalamide at the temperature of 100 ℃ to obtain TPA slurry;
step (E) and post polymerization, specifically comprising the following steps:
(E1) Filtering the prepolymer obtained in the step (C3) through a filter screen under the heat-preserving condition to obtain a filtered prepolymer;
(E2) And (2) mixing the filtered prepolymer with TPA slurry obtained in the step (D), and then, continuously polymerizing in a twin-screw extruder, wherein the temperature is kept at 250 ℃, and the total molar ratio of terephthalic acid to polyphthalamide is 1:1, a step of;
(E3) Controlling the final phosphorus pentoxide concentration to be 80%, and obtaining PBO polymer solution 5 with the intrinsic viscosity of 7 dl/g;
step (F), spinning and forming, which specifically comprises the following steps:
(F1) Filtering the PBO polymer solution 5 obtained in the step (E3) through a candle core filter with a minimum pore diameter of 30 microns before spinning to obtain a filtered PBO polymer solution 5;
(F2) Forming the filtered PBO polymer liquid 5 through a spinning process to obtain a transverse reinforced PBO fiber sample 5;
the test panels were prepared by combining the PBO fiber sample 1, the PBO fiber sample 2, the PBO fiber sample 3, the PBO fiber sample 4 and the PBO fiber sample 5 with a thermoplastic resin in the same process to perform the compression performance test according to ASTM 6641-2016,
the test results are shown in table 1 below:
table 1:
from the test results shown in table 1 above, it is understood that the compressive strength can be reflected laterally by the size of the transverse strength of the fiber under the same conditions of other preparation, and that sample 1 has the smallest compressive strength because the preparation process does not add 2-carboxy-5-hydroxypyridine nor perform the hydrogenation reduction step, and the aldehyde group is not converted into a hydroxyl group capable of forming intermolecular hydrogen bonds, so that the compressive strength is lower; sample 2-sample 4 follows the inventive concept to make fibers, so the overall compressive strength is improved; sample 5 has lower compressive strength because there are no derivatives containing aldehyde groups to which terephthalic acid is added, and there are too few side chain anchor points to be reduced by hydrogenation, but since 2-carboxy-5-hydroxypyridine also has some hydroxyl groups, compressive strength sample 5 will be slightly higher than sample 1, but there will be much fewer side chain hydroxyl groups than sample 2-sample 4, so compressive strength sample 5 is much smaller than sample 2-sample 4;
the purpose of adding 2-carboxyl-5-hydroxypyridine is that the benzene ring is not contained in the pyridine, so that the addition of the pyridine plays a role in changing the bond angle in a molecular chain, and the change of the bond angle does not greatly affect the molecular weight because of the existence of double bonds in the pyridine, so that the steric hindrance between the molecular chains is increased, the possibility of subsequent hydrogenation reduction can be provided, then the second monomer is derived from aldehydes of terephthalic acid, the hydrogenation reaction can reduce aldehyde groups into hydroxyl groups, hydrogen bonds can be formed between the hydroxyl groups, a great proportion of hydrogen bonding force exists between the molecular chains, and the transverse binding force of the prepared fiber is improved;
in summary, the method for preparing the PBO fiber with transverse reinforcement introduces 2-carboxyl-5-hydroxypyridine, which can provide anchor point quantity for forming hydrogen bonds, and after the pre-polymerization, the aldehyde in the-R group is subjected to hydrogenation reduction reaction, and the generated hydroxyl can form hydrogen bonds among molecular chains, so that the bonding strength among the molecular chains of the PBO fiber is enhanced, and the transverse strength of the fiber is improved.
The foregoing has outlined and described the basic principles, features, and advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A method of preparing a transverse reinforced PBO fiber, comprising the steps of:
step (A), raw material preparation:
weighing 8-18% of a first monomer, 0.5-2% of phosphorus pentoxide, 6-15% of a second monomer, 0.5-5% of a third monomer, 50-85% of polyphosphoric acid, 0.03-0.1% of a solid phase catalyst and 0.5-2% of polyphthalamide according to mass ratio;
step (B), degassing and prepolymerizing:
adding the first monomer, phosphorus pentoxide, third monomer, second monomer accounting for 80-90% of the total mass ratio and polyphosphoric acid accounting for 70-90% of the total mass ratio into a degassing reaction kettle for reaction, and continuously stirring under the degassing condition to obtain a prepolymer;
step (C), hydrogenation reduction:
adding a solid phase catalyst into a degassing reaction kettle, stirring at 150-300rpm, then introducing hydrogen, maintaining the degassing reaction kettle under a certain pressure condition, reacting for 4-10h, and standing and defoaming for a period of time under a vacuumizing condition to obtain a prepolymer;
step (D), TPA slurry preparation:
mixing and preparing the second monomer with the rest mass ratio, polyphosphoric acid and polyphthalamide with all mass ratios under a certain temperature condition to obtain TPA slurry;
step (E), post polymerization:
filtering the prepolymer obtained in the step (C) through a filter screen under the heat preservation condition, mixing the filtered prepolymer with TPA slurry obtained in the step (D), and then, continuously polymerizing in a double-screw extruder, wherein the final phosphorus pentoxide concentration is controlled to be 75-90%, so as to obtain PBO (poly (propylene oxide)) polymer liquid;
step (F), spinning and forming:
before spinning, filtering the PBO polymer liquid through a candle core filter, and forming the filtered PBO polymer liquid through a spinning process to obtain the transverse reinforced PBO fiber.
2. A method of making a transverse-reinforced PBO fiber according to claim 1, wherein: in the step (A), the step (B),
the first monomer is 4, 6-diamino resorcinol hydrochloride;
the second monomer is a derivative of terephthalic acid;
the third monomer is 2-carboxyl-5-hydroxypyridine.
3. A method of making a transverse-reinforced PBO fiber according to claim 2, wherein: in the step (A), the step (B),
the solid phase catalyst comprises a catalyst and an auxiliary agent;
wherein the catalyst accounts for 60-80% of the total mass of the solid phase catalyst, and the auxiliary agent accounts for 20-40% of the total mass of the solid phase catalyst;
and the solid phase catalyst accounts for 0.03-0.08% of the total mass of the first monomer and the second monomer.
4. A method of making a transverse-reinforced PBO fiber according to claim 3, wherein: the catalyst is Mo-Ni or Mo-Co;
the auxiliary agent is Si or P.
5. A method of making a transverse-reinforced PBO fiber according to claim 4, wherein: step (B), degassing and prepolymerizing, which specifically comprises the following steps:
(B1) Adding the first monomer, phosphorus pentoxide, third monomer, second monomer accounting for 80-90% of the total mass ratio and polyphosphoric acid accounting for 70-90% of the total mass ratio into a degassing reaction kettle, and reacting for 15-24h at 50-150 ℃;
(B2) The degassing reaction kettle is kept at the pressure of 20-50pa under the degassing condition, and stirred for 3-8h at the stirring speed of 50-100rpm, so as to obtain the prepolymer with the intrinsic viscosity of 2-8 dl/g.
6. A method of making a transverse-reinforced PBO fiber according to claim 5, wherein: step (C), hydrogenation reduction, specifically comprising the following steps:
(C1) Adding a catalyst accounting for 60-80% of the total mass of the solid phase catalyst and an auxiliary agent accounting for 20-40% of the total mass of the solid phase catalyst into a degassing reaction kettle, and stirring at 150-300rpm;
(C2) Introducing hydrogen at 40-80deg.C, maintaining the degassing reaction kettle at 3-4Mpa, and reacting for 4-10 hr;
(C3) Then, under the condition of vacuumizing, the pressure is kept at 30-40pa, and after standing and defoaming for 10-20 hours, the prepolymer with the intrinsic viscosity of 3-8dl/g is obtained.
7. A method of making a transverse-reinforced PBO fiber according to claim 6, wherein: in the step (D), the temperature of the mixed preparation of the second monomer and the polyphthalamide is 80-100 ℃.
8. A method of making a transverse-reinforced PBO fiber according to claim 7, wherein: step (E) and post polymerization, specifically comprising the following steps:
(E1) Filtering the prepolymer obtained in the step (C3) through a filter screen under the heat-preserving condition to obtain a filtered prepolymer;
(E2) Mixing the filtered prepolymer with TPA slurry obtained in the step (D), and then, continuously polymerizing in a twin-screw extruder, wherein the temperature is kept at 180-300 ℃, and the total mole ratio of the first monomer to the second monomer is 1-1.2: the total mass of the 1, 2-carboxyl-5-hydroxypyridine is 2-5% of the total mole of the first monomer and the second monomer;
(E3) Controlling the final phosphorus pentoxide concentration between 75 and 90 percent to obtain the PBO polymer solution with the intrinsic viscosity of 20 to 30 dl/g.
9. A method of making a transverse-reinforced PBO fiber according to claim 8, wherein: in the step (E1), the filter screen is a 100-200 mesh filter screen.
10. A method of making a transverse-reinforced PBO fiber according to claim 9, wherein: step (F), spinning and forming, which specifically comprises the following steps:
(F1) Filtering the PBO polymer liquid obtained in the step (E3) through a candle core filter with a minimum pore diameter of 30 microns before spinning to obtain a filtered PBO polymer liquid;
(F2) And forming the filtered PBO polymer liquid through a spinning process to obtain the transverse reinforced PBO fiber.
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