CN112647155A - Preparation method of PIPD (Poly ethylene-propylene-diene monomer) coated PBO (Poly ethylene-propylene-diene monomer) composite fiber and spinning equipment thereof - Google Patents
Preparation method of PIPD (Poly ethylene-propylene-diene monomer) coated PBO (Poly ethylene-propylene-diene monomer) composite fiber and spinning equipment thereof Download PDFInfo
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- CN112647155A CN112647155A CN202011497862.1A CN202011497862A CN112647155A CN 112647155 A CN112647155 A CN 112647155A CN 202011497862 A CN202011497862 A CN 202011497862A CN 112647155 A CN112647155 A CN 112647155A
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- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 38
- 238000010438 heat treatment Methods 0.000 claims description 35
- 238000006116 polymerization reaction Methods 0.000 claims description 25
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 23
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000009826 distribution Methods 0.000 claims description 13
- 238000004321 preservation Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 10
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- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 9
- 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 description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 8
- HOWDQPJMFFMJSR-UHFFFAOYSA-N pyridine-2,3,4,5-tetramine Chemical compound NC1=CN=C(N)C(N)=C1N HOWDQPJMFFMJSR-UHFFFAOYSA-N 0.000 claims description 8
- 238000007872 degassing Methods 0.000 claims description 7
- 230000001112 coagulating effect Effects 0.000 claims description 6
- JKXCZYCVHPKTPK-UHFFFAOYSA-N hydrate;trihydrochloride Chemical compound O.Cl.Cl.Cl JKXCZYCVHPKTPK-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 claims 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 abstract description 3
- 239000003063 flame retardant Substances 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000002657 fibrous material Substances 0.000 abstract description 2
- 238000009736 wetting Methods 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 19
- 230000001276 controlling effect Effects 0.000 description 19
- 239000007789 gas Substances 0.000 description 19
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 19
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- 230000014759 maintenance of location Effects 0.000 description 8
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
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- 238000004381 surface treatment Methods 0.000 description 3
- 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 description 2
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- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/10—Filtering or de-aerating the spinning solution or melt
- D01D1/106—Filtering
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/34—Core-skin structure; Spinnerette packs therefor
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
The invention provides a preparation method of a PIPD coated PBO composite fiber and spinning equipment thereof, relating to the technical field of composite fiber materials, wherein the preparation method comprises the following steps: preparing a PIPD/PPA polymer solution; preparing a PBO/PPA polymer solution; conveying the polymer solution; preparing primary raw silk; the PBO/PPA polymer solution is conveyed to an inner side cavity of the spinning assembly through a first feed inlet of the spinning assembly and is sprayed out from an inner side hole of the PBO spinneret plate to form a core layer with a skin-core structure; the PIPD/PPA polymer solution is conveyed to the annular cavity of the spinning assembly through a second feeding hole, and is sprayed out from a spinneret orifice of a PIPD spinneret plate to form a skin layer with a skin-core structure, and finally, the filaments sprayed out from the combined spinneret plate form primary filaments; stretching, solidifying, washing and drying. The PIPD coated PBO composite fiber prepared by the invention improves the weather resistance, the wetting property and the bonding property with a resin matrix of the PBO fiber on the basis of not reducing the excellent mechanical property, high temperature resistance and flame retardant property of the PBO fiber.
Description
Technical Field
The invention relates to the technical field of composite fiber materials, in particular to a preparation method of a PIPD coated PBO composite fiber and spinning equipment thereof.
Background
PBO is a conjugated aromatic heterocyclic rigid rod-like liquid crystal polymer, which is fully named as poly-p-phenylene benzobisoxazole. The thermoplastic elastomer has the biggest characteristics of tensile strength of up to 5.8GPa, elastic modulus of up to 280GPa, thermal decomposition temperature of 650 ℃ in air, limiting oxygen index LOI of 68, and excellent heat resistance, flame retardancy and impact resistance. PBO fiber and its composite material have been widely used in the aerospace field. PBO fibers (poly-p-phenylene benzobisoxazole fibers) have a drawback of poor light resistance and influence on the strength of the fibers by ultraviolet irradiation, and thus should be protected from light when used. The defects of poor weather resistance and weak ultraviolet resistance of the PBO fiber limit the application of the PBO fiber in the field of weather-resistant materials, so that the high-strength high-modulus high-temperature resistance of the PBO fiber cannot be better exerted. In addition, the PBO fiber composite material without surface treatment has lower interlaminar shear strength than aramid fiber composite material and compression resistanceThe strength and dyeing property are also poor. The molecular structure of PBO fibers is shown below:
PIPD is known under the full name of poly [2, 5-dihydroxy-1, 4-phenylenepyridobisimidazole ], developed by Aksu Nobel Research, the Netherlands as a new rigid rod-like polymer fiber (trade name M5). The M5 fiber has excellent mechanical properties, the tensile strength and the elastic modulus are respectively 5.3GPa and 330GPa, and the heat resistance and the flame retardant property are excellent. A large number of polar groups on the macromolecular chain form a unique two-dimensional hydrogen bond network structure, so that the axial compression strength of the prepared fiber is up to 1.7GPa, which is 5.7 times that of the PBO fiber. The excellent interfacial adhesion property of the M5 fiber and the resin matrix enables the composite material to have wide application prospect in the field of composite materials. The molecular structure of PIPD fibers is shown below:
the applicant has found that the prior art has at least the following technical problems: at present, the processing methods for the weather resistance of the PBO fiber are more, and mainly comprise a pigment covering method, a light stabilizer method and the like, but the methods have the defects of complex processing technology, uneven cross section modification or certain loss of the mechanical property of the fiber. Therefore, it is desirable to provide a method for improving the weatherability of PBO fibers to enhance the application of PBO fibers in the field of composites.
Disclosure of Invention
The invention aims to provide a preparation method of a PIPD coated PBO composite fiber and spinning equipment thereof, which aim to solve the technical problem of poor weather resistance of the PBO fiber and achieve the aims of improving the weather resistance of the PBO fiber and the application performance of the PBO fiber in a composite material. The technical effects that can be produced by the preferred technical scheme in the technical schemes provided by the invention are described in detail in the following.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention provides a preparation method of a PIPD coated PBO composite fiber, which comprises the following steps:
A. preparing a PIPD/PPA polymer solution;
adding 2, 5-dihydroxyterephthalic acid, a trihydrochloride monohydrate of tetraaminopyridine, polyphosphoric acid and phosphorus pentoxide into a polymerization kettle for reaction to obtain a PIPD/PPA polymer solution;
B. preparing a PBO/PPA polymer solution;
adding terephthalic acid, 4, 6-diaminoresorcinol hydrochloride, polyphosphoric acid and phosphorus pentoxide into a polymerization kettle for reaction to obtain a PBO/PPA polymer solution;
C. conveying the polymer solution;
respectively conveying the PIPD/PPA polymer solution obtained in the step A and the PBO/PPA polymer solution obtained in the step B to a twin-screw extruder through metering pumps, wherein the mass ratio of the PIPD/PPA polymer solution to the PBO/PPA polymer solution is 1:1-10 are respectively conveyed into independent double-screw extruders;
D. preparing primary raw silk;
conveying the PIPD/PPA polymer solution and the PBO/PPA polymer solution which are further polymerized and degassed by independent twin-screw extruders in the step C into a spinning assembly, wherein the PBO/PPA polymer solution is conveyed to an inner cavity of the spinning assembly through a first feed port of the spinning assembly and is ejected from an inner hole of a PBO spinneret to form a core layer of a sheath-core structure; the PIPD/PPA polymer solution is conveyed to the annular cavity of the spinning assembly through a second feeding hole and is ejected from a spinneret orifice of a PIPD spinneret to form a skin layer of a skin-core structure, and a core layer formed by the PBO/PPA polymer solution and the skin layer formed by the PIPD/PPA polymer solution form a primary filament from a filament ejected from a combined spinneret;
E. stretching, solidifying, washing and drying;
and D, stretching the primary yarn obtained in the step D, and obtaining the PIPD coated PBO composite fiber after coagulating bath, water washing and drying.
According to a preferred embodiment, in step a, the molar ratio of 2, 5-dihydroxyterephthalic acid to the monohydrochloride monohydrate of tetraaminopyridine is from 1 to 1.05: 1; the solid content of the polymer in the polymer system of the step A is 11-20%, and the content of the phosphorus pentoxide in the polymer system is 80-86%.
According to a preferred embodiment, in step a, said polymerization step comprises:
controlling the stirring speed to be 8-10r/min and the temperature to be 80-90 ℃, stirring for 2-3h, and removing 80-90% HCl gas;
heating to 100 ℃ and 110 ℃, rotating at the speed of 15-20r/min, vacuumizing to remove 9-19% HCl gas, and keeping the temperature for 8-12 h;
heating to 130 ℃ and 150 ℃, keeping the rotating speed at 25-30r/min, and reacting for 3 hours in a heat preservation way;
heating to 180 ℃ and 200 ℃, keeping the rotating speed at 25-30r/min, and reacting for 3-5h under the condition of heat preservation to obtain the PIPD/PPA polymer solution.
According to a preferred embodiment, in step B, the molar ratio of terephthalic acid to 4, 6-diaminoresorcinol hydrochloride is in the range of 1 to 1.05: 1, the polymer solid content in the polymer system of the step B is 11% -20%, and the phosphorus pentoxide content in the polymer system is 80% -87%.
According to a preferred embodiment, in step B, said polymerization step comprises:
controlling the stirring speed to be 8-10r/min and the temperature to be 80-90 ℃, stirring for 2-3h, and removing 80-90% HCl gas;
heating to 100 ℃, rotating at the speed of 15-20r/min, vacuumizing to remove 9-19% of HCl gas, and keeping the temperature for 6-10 h;
heating to 110 ℃ and 120 ℃, keeping the rotating speed at 25-30r/min, and reacting for 3-5 h;
heating to 135 ℃ and 150 ℃, keeping the rotating speed at 25-30r/min, and reacting for 3-5 h;
heating to 160 ℃ and 180 ℃, controlling the rotating speed at 30-35r/min, and carrying out heat preservation reaction for 5h to obtain the PBO/PPA polymer solution.
According to a preferred embodiment, in step C, said step of delivering the polymer solution comprises: adjusting the stirring direction of the polymerization kettle to be reverse rotation, controlling the rotating speed of a metering pump to be 10-30r/min, controlling the pipeline temperature to be 160-200 ℃, respectively conveying the PIPD/PPA polymer solution and the PBO/PPA polymer solution into independent double-screw extruders, respectively carrying out secondary polymerization reaction, and discharging residual 1-5% HCl gas in materials.
According to a preferred embodiment, in the step D, a vacuum device is connected to a degassing port of a screw of the double-screw extruder, and the vacuum degree is-0.09 MPa-0.098 MPa; the precision of a double-screw machine head filtering device of the double-screw extruder is 5-20 mu m, the screw temperature is 160-210 ℃, and the rotating speed is 10-30 r/min; the spinning temperature is 190-220 ℃.
According to a preferred embodiment, in step D, the following steps are further included: the PBO/PPA polymer solution enters a spinning assembly from a first feed inlet, then sequentially enters an inner feeding pressing block, an inner distributing plate and an inner filter screen of the spinning assembly, and is sprayed out from an inner hole of a PBO spinneret plate to form a core layer with a skin-core structure;
in step D, the method further comprises the steps of: enabling the PIPD/PPA polymer solution to enter a spinning assembly from a second feeding hole, sequentially entering an annular feeding pressing block, an annular filter screen and a PIPD/PPA polymer solution distribution hole on the outer side of a PBO spinneret plate of the spinning assembly, and then spraying out from a spinneret hole of the PIPD spinneret plate to form a skin layer with a skin-core structure, wherein a core layer formed by the PBO/PPA polymer solution and the skin layer formed by the PIPD/PPA polymer solution are finally formed into primary yarns from yarns sprayed out of the PIPD spinneret plate of the combined spinneret plate;
the spin pack assembly enables the PBO/PPA polymer solution and the PIPD/PPA polymer solution to each remain separate prior to forming the raw filaments.
According to a preferred embodiment, in step E, the drawing comprises drawing the filaments under conditions of an air gap length of 8-20cm and a draw ratio of 50-110, and the water washing comprises a water bath with deionized water at 20-80 ℃.
The invention also provides spinning equipment for completing the preparation method of the PIPD-coated PBO composite fiber, which comprises a spinning assembly, wherein the spinning assembly comprises an annular sleeve, an annular feeding pressing block is sleeved outside the annular sleeve, an inner feeding pressing block and an inner side distribution plate are sequentially arranged inside the annular sleeve from top to bottom, an inner filter screen is sleeved inside the annular sleeve and below the inner side distribution plate, an annular filter screen is sleeved outside the annular sleeve and below the annular feeding pressing block, one end of the annular sleeve is embedded into a first O-shaped groove of a PBO spinneret plate, a metal adjusting gasket and the PIPD spinneret plate are sequentially arranged below the PBO spinneret plate to form a pre-assembly part, an assembly sleeve is sleeved outside the pre-assembly part, and the other end of the annular sleeve is embedded into a second O-shaped groove of an assembly cover plate, aligning the screw holes on the assembly cover plate with the screw holes on the assembly sleeve to realize the fastening connection between the assembly cover plate and the assembly sleeve through fastening bolts; the assembly cover plate is provided with a first feeding hole and a second feeding hole which are independent, the first feeding hole is communicated with the inner cavity of the annular sleeve, and the second feeding hole is communicated with the outer annular cavity of the annular sleeve;
the PBO spinneret plate comprises an outer side hole and an inner side hole, the outer side hole of the PBO spinneret plate is a PIPD/PPA polymer solution distribution hole, and the inner side hole of the PBO spinneret plate is a spinneret hole of a PBO/PPA polymer solution; the spinneret orifices of the PIPD spinneret plate are consistent with the distribution of the holes on the inner side of the PBO spinneret plate.
Based on the technical scheme, the preparation method of the PIPD coated PBO composite fiber at least has the following technical effects:
1. the preparation method is carried out through two mutually independent polymerization, conveying and spinning process routes, and the molecular structures of the PIPD and the PBO are similar, so that the spinning temperature control and the dry-jet wet spinning process are consistent, and the prepared PIPD-coated PBO composite fiber improves the weather resistance, the wetting property and the bonding property with a resin matrix on the basis of not reducing the excellent mechanical property, the high temperature resistance and the flame retardant property of the PBO fiber. The strength of the PIPD coated PBO composite fiber prepared by the preparation method reaches 31.3cN/dtex-33.5cN/dtex, and the strength retention rate is more than 87% when the fiber is irradiated for 100 hours under ultraviolet light. The PIPD coated PBO composite fiber prepared by the invention improves the strength retention rate of the PBO fiber in the application of composite materials and improves the application performance of the PBO fiber.
2. Compared with the prior art for improving the surface performance of the PBO fiber, the preparation method of the invention does not add any organic pigment, light stabilizer and other substances, does not influence the spinnability, molecular weight and mechanical property of the polymer, avoids the problem of unstable fiber quality caused by doping, is suitable for large-scale production, simultaneously complements the advantages of the two fibers, reduces the secondary damage to fiber cortex caused by winding and friction in the surface treatment process of the fiber, cancels a fussy surface treatment process, and improves the treatment efficiency.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic diagram of the construction of a spin pack assembly of the present invention;
FIG. 2 is an assembled exploded schematic view of the spin pack assembly of the present invention;
FIG. 3 is a schematic view of the construction of the components of the spin pack assembly of the present invention;
FIG. 4 is a schematic diagram of the structure of a PBO spinneret of the present invention;
FIG. 5 is a schematic diagram of a PIPD spinneret configuration according to the present invention;
fig. 6 and 7 are schematic diagrams of the assembly of the combined spinneret plate of the PBO spinneret plate and PIPD spinneret plate of the present invention.
Reference numerals: 1-a first feed port; 2-a second feed port; 3-fastening screws; 4-a component cover plate; 5-a second O-shaped groove; 6-an annular sleeve; 7-ring-shaped feeding briquettes; 8-inner side feeding briquetting; 9-inner distribution plate; 10-ring filter screen; 11-inner filter screen; 12-a first O-groove; 13-PBO spinneret; 14-PIPD/PPA polymer solution dispense orifice; 15-metal adjusting shim; 16-PIPD spinneret; 17-an assembly sleeve;
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
In the description of the present invention, it is to be noted that, unless otherwise specified, "a plurality" means two or more; the terms "upper", "lower", "left", "right", "inner", "outer", "front", "rear", "head", "tail", and the like, indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, are only for convenience in describing and simplifying the description, and do not indicate or imply that the device or element referred to must have a particular orientation, be constructed in a particular orientation, and be operated, and thus, should not be construed as limiting the invention. Furthermore, the terms "first," "second," "third," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should also be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; may be directly connected or indirectly connected through an intermediate. The specific meaning of the above terms in the present invention can be understood as appropriate to those of ordinary skill in the art.
The invention provides a preparation method of a PIPD coated PBO composite fiber, which comprises the following steps:
A. preparing a PIPD/PPA polymer solution;
mixing 2, 5-dihydroxyterephthalic acid (DHTA), tetraaminopyridine trihydrochloride monohydrate (TAP), polyphosphoric acid (PPA) and phosphorus pentoxide (P)2O5) Adding the mixture into a polymerization kettle for reaction to obtain a PIPD/PPA polymer solution.
Preferably, in step a, the molar ratio of 2, 5-dihydroxyterephthalic acid (DHTA) to the tris-hydrochloride monohydrate (TAP) of tetraaminopyridine is from 1 to 1.05: 1. polyphosphoric Acid (PPA) and phosphorus pentoxide (P)2O5) The solid content of the polymer in the polymer system of the step A is 11-20 percent and the content of the phosphorus pentoxide in the polymer system is 80-86 percent.
Preferably, in step a, the polymerization step comprises:
controlling the stirring speed to be 8-10r/min and the temperature to be 80-90 ℃, stirring for 2-3h, and removing 80-90% HCl gas;
heating to 100 ℃ and 110 ℃, rotating at the speed of 15-20r/min, vacuumizing to remove 9-19% HCl gas, and keeping the temperature for 8-12 h;
heating to 130 ℃ and 150 ℃, keeping the rotating speed at 25-30r/min, and reacting for 3 hours in a heat preservation way;
heating to 180 ℃ and 200 ℃, keeping the rotating speed at 25-30r/min, and reacting for 3-5h under the condition of heat preservation to obtain the PIPD/PPA polymer solution.
B. Preparing a PBO/PPA polymer solution;
mixing Terephthalic Acid (TA), 4, 6-diaminoresorcinol hydrochloride (DAR), polyphosphoric acid (PPA) and phosphorus pentoxide (P)2O5) Adding the mixture into a polymerization kettle for reaction to obtain PBO/PPA polymer solution.
Preferably, in step B, the molar ratio of Terephthalic Acid (TA) to 4, 6-diaminoresorcinol hydrochloride (DAR) is 1-1.05: 1. polyphosphoric Acid (PPA) and phosphorus pentoxide (P)2O5) The solid content of the polymer in the polymer system in the step B is 11-20 percent and the content of phosphorus pentoxide in the polymer system is 80-87 percent.
Preferably, in step B, the polymerization step comprises:
controlling the stirring speed to be 8-10r/min and the temperature to be 80-90 ℃, stirring for 2-3h, and removing 80-90% HCl gas;
heating to 100 ℃, rotating at the speed of 15-20r/min, vacuumizing to remove 9-19% of HCl gas, and keeping the temperature for 6-10 h;
heating to 110 ℃ and 120 ℃, keeping the rotating speed at 25-30r/min, and reacting for 3-5 h;
heating to 135 ℃ and 150 ℃, keeping the rotating speed at 25-30r/min, and reacting for 3-5 h;
heating to 160 ℃ and 180 ℃, controlling the rotating speed at 30-35r/min, and carrying out heat preservation reaction for 5h to obtain the PBO/PPA polymer solution.
C. Conveying the polymer solution;
and B, respectively conveying the PIPD/PPA polymer solution obtained in the step A and the PBO/PPA polymer solution obtained in the step B to a double-screw extruder through a metering pump, wherein the PIPD/PPA polymer solution and the PBO/PPA polymer solution are respectively conveyed to the independent double-screw extruder according to the mass ratio of 1: 1-10.
Preferably, in step C, the step of delivering the polymer solution comprises:
adjusting the stirring direction of the polymerization kettle to be reverse rotation, controlling the rotating speed of a metering pump to be 10-30r/min, controlling the temperature of a pipeline to be 160-200 ℃, respectively conveying the PIPD/PPA polymer solution and the PBO/PPA polymer solution into independent double-screw extruders to respectively carry out secondary polymerization reaction, further improving the molecular weight of the polymer, and discharging residual 1-5% of HCl gas in the materials under the strong shearing and vacuum effects of the double screws.
D. Preparing primary raw silk;
conveying the PIPD/PPA polymer solution and the PBO/PPA polymer solution which are further polymerized and degassed by the independent double-screw extruder in the step C into a spinning assembly, wherein the PBO/PPA polymer solution is conveyed to an inner cavity of the spinning assembly through a first feed port 1 of the spinning assembly and is ejected out of an inner hole of a PBO spinneret plate 13 to form a core layer with a skin-core structure; the PIPD/PPA polymer solution is fed through the second feed port 2 into the annular chamber of the spin pack and exits the orifices of the PIPD spinneret 16 to form a sheath of sheath-core structure, a core of PBO/PPA polymer solution and a sheath of PIPD/PPA solution from the filaments exiting the combined spinneret to form the nascent filaments.
Preferably, in the step D, a degassing port of a screw of the double-screw extruder is connected with a vacuum device, and the vacuum degree is-0.09 MPa-0.098 MPa; releasing hydrogen chloride gas encapsulated in the slurry. The precision of a double-screw machine head filtering device of the double-screw extruder is 5-20 mu m, the screw temperature is 160-210 ℃, and the rotating speed is 10-30 r/min; the spinning temperature is 190-220 ℃.
Preferably, in step D, the method further comprises the following steps: the PBO/PPA polymer solution enters a spinning assembly from a first feed inlet 1, then sequentially enters a feeding pressing block 8, an inner side distributing plate 9 and an inner filter screen 11 on the inner side of the spinning assembly, and is sprayed out from an inner side hole of a PBO spinneret plate 13 to form a core layer with a skin-core structure;
in step D, the method further comprises the steps of: enabling the PIPD/PPA polymer solution to enter a spinning assembly from a second feeding hole 2, then sequentially entering an annular feeding pressing block 7, an annular filter screen 10 and a PIPD/PPA polymer solution distribution hole on the outer side of a PBO spinneret plate 13 of the spinning assembly, and then spraying out from a spinneret hole of a PIPD spinneret plate 16 to form a skin layer with a skin-core structure, wherein a core layer formed by the PBO/PPA polymer solution and the skin layer formed by the PIPD/PPA solution finally form a primary filament from a filament sprayed out from the PIPD spinneret plate 16 of the combined spinneret plate;
the spin pack assembly of the present invention enables the PBO/PPA polymer solution and the PIPD/PPA polymer solution to be separated prior to forming the raw filaments.
E. Stretching, solidifying, washing and drying;
and D, stretching the primary yarn obtained in the step D, and obtaining the PIPD coated PBO composite fiber after coagulating bath, water washing and drying.
Preferably, in step E, the drawing comprises drawing the spun yarn at a draw ratio of 50 to 110 with an air gap length of 8 to 20cm, and the water washing comprises water washing with deionized water at 20 to 80 ℃. And cutting and sampling the obtained PIPD-coated PBO composite fiber by using a blade, and observing the section thicknesses of the skin layer and the core layer of the fiber by using a scanning electron microscope.
As shown in fig. 1 to 7, the present invention further provides a spinning apparatus for performing the above-mentioned manufacturing method of the PIPD-coated PBO composite fiber, the spinning apparatus includes a spinning assembly, the spinning assembly includes an annular sleeve 6, an annular feeding compact 7 is sleeved outside the annular sleeve 6, an inner feeding compact 8 and an inner distribution plate 9 are sequentially disposed inside the annular sleeve 6 from top to bottom, an inner filtering screen 11 is sleeved inside the annular sleeve 6 and below the inner distribution plate 9, an annular filtering screen 10 is sleeved outside the annular sleeve 6 and below the annular feeding compact 7, one end of the annular sleeve 6 is embedded in a first O-shaped groove 12 of the PBO spinneret 13, a metal adjusting gasket 15 and a PIPD spinneret 16 are sequentially mounted below the PBO spinneret 13 to form a pre-assembly, an assembly sleeve 17 is sleeved outside the pre-assembly, the other end of the annular sleeve 6 is embedded in the second O-shaped groove 5 of the component cover plate 4 and aligns the screw holes on the component cover plate 4 with the screw holes on the component sleeve 17 to achieve a fastening connection between the component cover plate 4 and the component sleeve 17 by means of the fastening bolts 3. The component cover plate 4 is respectively provided with a first feeding hole 1 and a second feeding hole 3 which are independent, the first feeding hole 1 is communicated with the inner cavity of the annular sleeve 6, and the second feeding hole 3 is communicated with the outer annular cavity of the annular sleeve 6.
Preferably, the combined spinneret of the present invention includes a PBO spinneret 13 and a PIPD spinneret 16 as shown in fig. 4 to 7. The PBO spinneret 13 includes outer holes and inner holes, as shown in FIG. 4A 1-A4, the outer holes of the PBO spinneret 13 are PIPD/PPA polymer solution dispensing holes 14, the inner holes of the PBO spinneret 13 are PBO/PPA polymer solution dispensing holes, preferably, the outer holes are arranged in 4 rings, 60-120 holes per ring, the inner holes are arranged in 1-4 rings, and 10-40 holes per ring. The orifices of the PIPD spinneret 16 are aligned with the inside hole distribution of the PBO spinneret 13 as shown in fig. 5B 1-B4. As shown in figures 6 and 7, when two spinneret plates are combined, the skin thickness of the fiber can be adjusted through the difference of the thicknesses of the metal adjusting gaskets 15, and the skin thickness of the blended fiber is directly influenced.
The technical solution of the present invention will be described in detail with reference to examples 1 to 15.
Example 1:
the preparation method of the PBO fiber with excellent weather resistance of the embodiment 1 is specifically completed by the following steps:
the preparation method of the PIPD/PPA and PBO/PPA polymer solution is specifically completed according to the following steps:
A. a PIPD/PPA polymer solution was prepared.
a. 165.93kg of P2O5Polyphosphoric Acid (PPA) with a mass concentration of 80-83%, 25kg (93.825mol) of the trihydrochloride monohydrate (TAP) of tetraaminopyridine, 18.584kg (93.825mol) of 2, 5-dihydroxyterephthalic acid (DHTA) and 10.37kg of P2O5Putting into a 500L polymerization kettle at a time;
b. stirring at the stirring speed of 8-10r/min and the temperature of 80-90 ℃ for 2-3h to remove HCl gas;
c. heating to 100-110 ℃, controlling the rotating speed at 15-20r/min, vacuumizing to remove HCl gas, and keeping the temperature for 8-12 h;
d. heating to 130-150 ℃, keeping the temperature and reacting for 3h, wherein the rotating speed is 25-30 r/min;
e. heating to 180-200 ℃, controlling the rotating speed to be 25-30r/min, and reacting for 3-5h under the condition of heat preservation to obtain the PIPD/PPA polymer solution.
B. PBO/PPA polymer solutions were prepared.
a. 138.471kg of P2O5Polyphosphoric Acid (PPA) with a mass concentration of 80-83%, 4, 6-diaminoresorcinol hydrochloride (DAR) with a mass concentration of 25kg (117.37mol), Terephthalic Acid (TA) with a mass concentration of 19.4835kg (117.37mol) and phosphorus pentoxide (P) with a mass concentration of 34.659kg2O5) Putting into a 500L polymerization kettle at a time;
b. stirring at the stirring speed of 8-10r/min and the temperature of 80-90 ℃ for 2-3h to remove HCl gas;
c. heating to 100 ℃, controlling the rotating speed at 15r/min-20r/min, vacuumizing to remove HCl gas, and keeping the temperature for 6-10 h;
d. heating to 110-120 ℃, keeping the temperature and reacting for 3-5h, wherein the rotating speed is 25-30 r/min;
e. heating to 135-150 ℃, keeping the temperature and reacting for 3-5h, wherein the rotating speed is 25-30 r/min;
f. heating to 160-180 ℃, controlling the rotating speed to be 30-35r/min, and reacting for 5 hours under the condition of heat preservation to obtain the PBO/PPA polymer solution.
C. And (4) conveying the polymer solution.
Respectively conveying the PIPD/PPA polymer solution obtained in the step A and the PBO/PPA polymer solution obtained in the step B to a twin-screw extruder through metering pumps, wherein the polymer solutions are mixed according to the mass ratio of 1:1-10 are respectively fed into independent twin-screw extruders.
Secondly, carrying out further polymerization reaction and degassing on the PIPD/PBO polymer solution obtained in the step C by a double-screw extruder with a vacuum degassing device, and conveying the solution into a spinning assembly, wherein the thickness of a metal adjusting gasket in the spinning assembly is 0.5mm, the PBO/PPA polymer solution enters a cavity on the inner side of the assembly from a first feed inlet, the PIPD/PPA polymer solution enters an annular cavity of the assembly from a second feed inlet on the assembly, the degassing port of the screw is connected with the vacuum device, the vacuum degree is-0.09 MPa-0.098 MPa, the precision of a double-screw handpiece filtering device is 5-20um, the temperature of the screw is 160-210 ℃, and the rotating speed is 10-30 r/min; the spinning temperature is 190-220 ℃, a core layer is formed by an A1 type spinneret plate with the inner side aperture of 0.11-0.45 mm, and a raw silk with a skin-core structure is formed by a B1 type spinneret plate with the aperture of 0.20-0.60 mm, wherein the number of holes is 15-40.
Spinning the as-spun yarn under the conditions that the length of an air gap is 8-20cm and the stretching ratio is 50-110, and obtaining the PIPD coated PBO composite fiber No. 1 after coagulating bath, deionized water washing bath at 20-50 ℃ and drying.
Example 2:
the present embodiment 2 differs from embodiment 1 in that:
in the step C, the PIPD/PPA polymer solution obtained in the step A and the PBO/PPA polymer solution obtained in the step B are processed by an A2 type spinneret plate with the aperture of 0.11mm-0.45mm to form a core layer, and then processed by a B2 type spinneret plate with the aperture of 0.20mm-0.60mm to form a primary yarn with a skin-core structure, wherein the total number of holes of the two rings is 40-70. Thus obtaining the PIPD coated PBO composite fiber 2 #. The rest is the same as in example 1.
Example 3:
this example 3 differs from examples 1 and 2 in that:
in the step C, the PIPD/PPA polymer solution obtained in the step A and the PBO/PPA polymer solution obtained in the step B are processed by an A3 type spinneret plate with the aperture of 0.11mm-0.45mm to form a core layer, and then processed by a B3 type spinneret plate with the aperture of 0.20mm-0.60mm to form a primary yarn with a skin-core structure, wherein the total number of the three rings is 70-100. Thus obtaining the PIPD coated PBO composite fiber No. 3. The other steps are the same as in examples 1 and 2.
Example 4:
this example 4 differs from examples 1 to 3 in that:
in the step C, the PIPD/PPA polymer solution obtained in the step A and the PBO/PPA polymer solution obtained in the step B are processed by an A4 type spinneret plate with the aperture of 0.11mm-0.45mm to form a core layer, and then processed by a B4 type spinneret plate with the aperture of 0.20mm-0.60mm to form a primary yarn with a skin-core structure, wherein the total number of four rings is 100-150. Thus obtaining the PIPD coated PBO composite fiber No. 4. The others are the same as in examples 1 to 3.
Example 5:
this example 5 differs from examples 1 to 4 in that:
and C, enabling the PIPD/PPA polymer solution obtained in the step A and the PBO/PPA polymer solution obtained in the step B to pass through an A2 type spinneret plate with the aperture of 0.11mm-0.45mm to form a core layer, and then passing through a B2 type spinneret plate with the aperture of 0.20mm-0.60mm to form a primary yarn with a skin-core structure, wherein the total number of holes of the two rings is 40-70, and the thickness of the metal regulating gasket of the component is 1 mm. Thus obtaining the PIPD coated PBO composite fiber No. 5. The others are the same as in examples 1 to 4.
Example 6:
this example 6 differs from examples 1 to 5 in that:
and C, enabling the PIPD/PPA polymer solution obtained in the step A and the PBO/PPA polymer solution obtained in the step B to pass through an A2 type spinneret plate with the aperture of 0.11mm-0.45mm to form a core layer, and then passing through a B2 type spinneret plate with the aperture of 0.20mm-0.60mm to form a primary yarn with a skin-core structure, wherein the total number of holes of the two rings is 40-70, and the thickness of the metal regulating gasket of the component is 2 mm. Thus obtaining the PIPD coated PBO composite fiber 6 #. The others are the same as in examples 1 to 5.
The results are shown in table 1, where table 1 is a comparison of the properties of the PIPD-coated PBO composite fibers prepared in examples 1 to 6, the thickness of the sheath PIPD fiber, the thickness of the core PBO fiber, the resistance to ultraviolet light, and the high humidity and heat environment with the PBO fiber.
TABLE 1 comparison of fiber Properties
As can be seen from Table 1, the strength of the PIPD-coated PBO composite fiber prepared by the preparation method can reach 31.3-33.3cN/dtex, the strength retention rate is 88.9% -91.2% when the fiber is irradiated for 100 hours under ultraviolet light, and the strength retention rate is still 80.9% -82.3% after the fiber is exposed for 700 hours under the atmosphere with the relative humidity of 80%. The retention rate of the strength of the fiber in the composite material is greatly improved.
Example 7:
A. a PIPD/PPA polymer solution was prepared.
a. 165.93kg of P2O5Polyphosphoric Acid (PPA) with a mass concentration of 80-83%, 25kg (93.825mol) of the trihydrochloride monohydrate (TAP) of tetraaminopyridine, 18.584kg (93.825mol) of 2, 5-dihydroxyterephthalic acid (DHTA) and 10.37kg of P2O5Putting into a 500L polymerization kettle at a time;
b. stirring at the stirring speed of 8-10r/min and the temperature of 80-90 ℃ for 2-3h to remove HCl gas;
c. heating to 100-110 ℃, controlling the rotating speed at 15-20r/min, vacuumizing to remove HCl gas, and keeping the temperature for 8-12 h;
d. heating to 130-150 deg.c and rotating at 25-30r/min for reaction for 3 hr.
e. Heating to 180-200 ℃, controlling the rotating speed to be 25-30r/min, and reacting for 3-5h under the condition of heat preservation to obtain the PIPD/PPA polymer solution.
B. Preparation of PBO/PPA Polymer solution
a. 138.471kg of P2O5Polyphosphoric Acid (PPA) with a mass concentration of 80-83%, 4, 6-diaminoresorcinol hydrochloride (DAR) with a mass concentration of 25kg (117.37mol), terephthalic acid with a mass concentration of 19.4835kg (117.37mol)(TA) and 34.659kg of phosphorus pentoxide (P)2O5) Putting into a 500L polymerization kettle at a time;
b. stirring at the stirring speed of 8-10r/min and the temperature of 80-90 ℃ for 2-3h to remove HCl gas;
c. heating to 100 ℃, controlling the rotating speed at 15r/min-20r/min, vacuumizing to remove HCl gas, and keeping the temperature for 6-10 h;
d. heating to 110-120 ℃, keeping the temperature and reacting for 3-5h, wherein the rotating speed is 25-30 r/min;
e. heating to 135-150 ℃, keeping the temperature and reacting for 3-5h, wherein the rotating speed is 25-30 r/min;
f. heating to 160-180 ℃, controlling the rotating speed to be 30-35r/min, and reacting for 5 hours under the condition of heat preservation to obtain the PBO/PPA polymer solution.
C. Respectively conveying the PIPD/PPA polymer solution obtained in the step A and the PBO/PPA polymer solution obtained in the step B to a double-screw extruder through metering pumps, wherein the polymer flow rates are as follows according to the mass ratio of 1:1-10 are respectively fed into independent twin-screw extruders.
Secondly, carrying out further polymerization reaction on the PIPD/PPA polymer solution and the PBO/PPA polymer solution obtained in the step C through a double-screw extruder with a vacuum degassing device, degassing, and conveying the polymer solution into a spinning assembly, wherein the thickness of a metal adjusting gasket in the spinning assembly is 0.5mm, the PBO/PPA polymer solution enters a cavity on the inner side of the assembly from a first feed inlet, the PIPD/PPA polymer solution enters an annular cavity of the assembly from a second feed inlet on the assembly, the degassing port of a screw is connected with the vacuum device, the vacuum degree is-0.09 MPa-0.098 MPa, the precision of a double-screw handpiece filtering device is 5-20um, the temperature of the screw is 160-210 ℃, and the rotating speed is 10-30 r/min; the spinning temperature is 190-220 ℃, a core layer is formed after passing through an A2 type spinneret plate with the aperture of 0.11-0.45 mm, and then a nascent yarn with a skin-core structure is formed after passing through a B2 type spinneret plate with the aperture of 0.20-0.60 mm, wherein the total number of holes of the two rings is 40-70.
Spinning the nascent fiber at the air gap length of 8-20cm and the air gap circular blowing temperature of 70-90 ℃ under the condition that the stretching ratio is 50-110, and obtaining the PIPD coated PBO composite fiber 7# after coagulation bath, deionized water washing bath at 20-50 ℃ and drying.
The circular blowing can uniformly disperse hot air around the unbundled filaments below the spinneret plate, and has the slow cooling effect. In the embodiment, the air gap circular blowing temperature is controlled to be 70-90 ℃, compared with the air gap circular blowing temperature in the embodiments 1-6 which is slowly cooled at room temperature, the spinnability of the polymer can be improved, the phenomenon of filament breakage of a spinneret orifice is reduced, and under the condition, the filament breakage of the fiber is less, and continuous fiber can be obtained.
Example 8:
this example 8 differs from example 7 in that:
spinning the primary yarn in the air gap with the length of 8-20cm, controlling the air gap circular blowing temperature at 70-90 ℃ and the stretching ratio at 50-110, and washing with 20-30% of coagulating bath solution and deionized water at 20-50 ℃. Thus obtaining the PIPD coated PBO composite fiber No. 8.
In the embodiment, the coagulation bath solution of 20-30% of the coagulation bath solution is adopted, compared with the coagulation bath solution with the concentration of 0-10% in the conventional process, the supplement of deionized water can be greatly reduced, the effect of slowly reducing the concentration of phosphoric acid is achieved for the primary yarn, and the spinning process is optimized.
Example 9:
the present embodiment 9 differs from embodiment 8 in that:
the primary raw silk is washed by 20 to 30 percent of coagulating bath solution and deionized water with the temperature of 50 to 80 ℃. Thus obtaining the PIPD coated PBO composite fiber 9 #.
According to the embodiment, the temperature of deionized water washing bath is increased, the concentration of phosphoric acid washed by each level is rapidly balanced by increasing energy consumption, phosphoric acid is washed out to the maximum extent, the phosphorus content in the fiber is reduced to the minimum, and the performance of the fiber is facilitated.
Example 10:
the present embodiment 10 differs from embodiment 7 in that:
the precision of the double-screw filtering device in the second step is 10um-15 um. Thus obtaining the PIPD coated PBO composite fiber 10 #.
Example 11:
this example 11 differs from example 7 in that:
in the second step, the screw temperature is 170-180 ℃. Thus obtaining the PIPD coated PBO composite fiber 11 #.
Example 12:
this example 12 differs from example 7 in that:
in the second step, the spinning temperature is 200-210 ℃. Thus obtaining the PIPD coated PBO composite fiber 12 #.
Example 13:
this example differs from example 7 in that:
in step two, the aperture of the PBO spinneret A2 is 0.15mm-0.3 mm. And obtaining the PIPD coated PBO composite fiber 13 #.
Example 14:
the present embodiment 14 differs from embodiment 7 in that:
in the third step, the length of the primary silk in the air gap is 10cm-15 cm. Thus obtaining the PIPD coated PBO composite fiber No. 14.
Example 15:
this example 15 differs from example 7 in that:
and (3) washing the mixture in deionized water at 40-50 ℃ in the third step. And obtaining the PIPD coated PBO composite fiber 15 #.
The results are shown in table 2, table 2 is a comparison of the performance of the PIPD-coated PBO composite fibers prepared in examples 7 to 15, uv light resistance, and high humidity and heat environment with the PBO fibers.
TABLE 2 comparison of fiber Properties
As can be seen from table 2, the PIPD-coated PBO composite fiber prepared by the preparation method of the optimized process in embodiments 7 to 15 of the present invention has a strength of 32.3 to 33.5cN/dtex, and has a strength retention ratio of 87.4% to 91.2% when irradiated under ultraviolet light for 100 hours, and a strength retention ratio of 78.1% to 82.2% after exposed under an atmosphere with a relative humidity of 80% for 700 hours. The retention rate of the strength of the fiber in the composite material is greatly improved.
The PBO fibers in the tables 1-2 are home-made PBO fibers made by the design Limited company of the Middling morning light chemical industry, and the combination of A-type spinnerets and B-type spinnerets can form a PIPD fiber protective skin layer with the thickness of 1.5-4 mu m, so that the weather resistance of the PBO fibers is greatly improved, and the application of the PBO fibers in the field of composite materials is effectively improved on the basis that the high strength of the PBO fibers is maintained by the PIPD/PBO composite fibers.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. A preparation method of a PIPD coated PBO composite fiber is characterized by comprising the following steps:
A. preparing a PIPD/PPA polymer solution;
adding 2, 5-dihydroxyterephthalic acid, a trihydrochloride monohydrate of tetraaminopyridine, polyphosphoric acid and phosphorus pentoxide into a polymerization kettle for reaction to obtain a PIPD/PPA polymer solution;
B. preparing a PBO/PPA polymer solution;
adding terephthalic acid, 4, 6-diaminoresorcinol hydrochloride, polyphosphoric acid and phosphorus pentoxide into a polymerization kettle for reaction to obtain a PBO/PPA polymer solution;
C. conveying the polymer solution;
respectively conveying the PIPD/PPA polymer solution obtained in the step A and the PBO/PPA polymer solution obtained in the step B to a twin-screw extruder through metering pumps, wherein the mass ratio of the PIPD/PPA polymer solution to the PBO/PPA polymer solution is 1:1-10 are respectively conveyed into independent double-screw extruders;
D. preparing primary raw silk;
conveying the PIPD/PPA polymer solution and the PBO/PPA polymer solution which are further polymerized and degassed by independent twin-screw extruders in the step C into a spinning assembly, wherein the PBO/PPA polymer solution is conveyed to an inner cavity of the spinning assembly through a first feed port (1) of the spinning assembly and is ejected from an inner hole of a PBO spinneret plate (13) to form a core layer of a sheath-core structure; the PIPD/PPA polymer solution is conveyed to the annular cavity of the spinning assembly through a second feeding hole (2) and is ejected from a spinneret orifice of a PIPD spinneret plate (16) to form a skin layer with a skin-core structure, and a core layer formed by the PBO/PPA polymer solution and the skin layer formed by the PIPD/PPA solution form a primary filament from a filament ejected from a combined spinneret plate;
E. stretching, solidifying, washing and drying;
and D, stretching the primary yarn obtained in the step D, and obtaining the PIPD coated PBO composite fiber after coagulating bath, water washing and drying.
2. The method of claim 1, wherein in step a, the molar ratio of 2, 5-dihydroxyterephthalic acid to the monohydrochloride monohydrate of tetraaminopyridine is 1-1.05: 1; the solid content of the polymer in the polymer system of the step A is 11-20%, and the content of the phosphorus pentoxide in the polymer system is 80-86%.
3. The process according to claim 1 or 2, wherein in the step A, the polymerization step comprises:
controlling the stirring speed to be 8-10r/min and the temperature to be 80-90 ℃, stirring for 2-3h, and removing 80-90% HCl gas;
heating to 100 ℃ and 110 ℃, rotating at the speed of 15-20r/min, vacuumizing to remove 9-19% HCl gas, and keeping the temperature for 8-12 h;
heating to 130 ℃ and 150 ℃, keeping the rotating speed at 25-30r/min, and reacting for 3 hours in a heat preservation way;
heating to 180 ℃ and 200 ℃, keeping the rotating speed at 25-30r/min, and reacting for 3-5h under the condition of heat preservation to obtain the PIPD/PPA polymer solution.
4. The method according to claim 1, wherein in step B, the molar ratio of terephthalic acid to 4, 6-diaminoresorcinol hydrochloride is 1 to 1.05: 1, the polymer solid content in the polymer system of the step B is 11% -20%, and the phosphorus pentoxide content in the polymer system is 80% -87%.
5. The method according to claim 1 or 4, wherein in the step B, the polymerization step comprises:
controlling the stirring speed to be 8-10r/min and the temperature to be 80-90 ℃, stirring for 2-3h, and removing 80-90% HCl gas;
heating to 100 ℃, rotating at the speed of 15-20r/min, vacuumizing to remove 9-19% of HCl gas, and keeping the temperature for 6-10 h;
heating to 110 ℃ and 120 ℃, keeping the rotating speed at 25-30r/min, and reacting for 3-5 h;
heating to 135 ℃ and 150 ℃, keeping the rotating speed at 25-30r/min, and reacting for 3-5 h;
heating to 160 ℃ and 180 ℃, controlling the rotating speed at 30-35r/min, and carrying out heat preservation reaction for 5h to obtain the PBO/PPA polymer solution.
6. The method of claim 1, wherein in step C, the step of delivering the polymer solution comprises: adjusting the stirring direction of the polymerization kettle to be reverse rotation, controlling the rotating speed of a metering pump to be 10-30r/min, controlling the pipeline temperature to be 160-200 ℃, respectively conveying the PIPD/PPA polymer solution and the PBO/PPA polymer solution into independent double-screw extruders, respectively carrying out secondary polymerization reaction, and discharging residual 1-5% HCl gas in materials.
7. The preparation method of claim 1, wherein in the step D, a vacuum device is connected to a degassing port of a screw of the twin-screw extruder, and the vacuum degree is-0.09 MPa-0.098 MPa; the precision of a double-screw machine head filtering device of the double-screw extruder is 5-20 mu m, the screw temperature is 160-210 ℃, and the rotating speed is 10-30 r/min; the spinning temperature is 190-220 ℃.
8. The method according to claim 1, further comprising, in step D, the steps of: the PBO/PPA polymer solution enters a spinning assembly from a first feed inlet (1), then sequentially enters an inner side feeding pressing block (8), an inner side distributing plate (9) and an inner filter screen (11) of the spinning assembly, and is sprayed out from an inner side hole of a PBO spinneret plate (13) to form a core layer with a skin-core structure;
in step D, the method further comprises the steps of: enabling the PIPD/PPA polymer solution to enter a spinning assembly from a second feeding hole (2), then sequentially entering an annular feeding pressing block (7), an annular filter screen (10) and a PIPD/PPA polymer solution distribution hole (14) at the outer side of a PBO spinneret plate (13) of the spinning assembly, and then being sprayed out from a spinneret hole of a PIPD spinneret plate (16) to form a skin layer with a skin-core structure, wherein a core layer formed by the PBO/PPA polymer solution and the skin layer formed by the PIPD/PPA polymer solution finally form a primary filament from a filament sprayed out from a PIPD spinneret plate (16) of a combined spinneret plate;
the spin pack assembly enables the PBO/PPA polymer solution and the PIPD/PPA polymer solution to each remain separate prior to forming the raw filaments.
9. The method of claim 1, wherein in step E, the drawing comprises drawing the spun yarn at an air gap length of 8-20cm and a draw ratio of 50-110, and the water washing comprises water washing with deionized water at 20-80 ℃.
10. A spinning apparatus, characterized in that the spinning apparatus is used for completing the preparation method of the PIPD-coated PBO composite fiber according to any one of the preceding claims 1 to 9, the spinning apparatus comprises a spinning assembly, the spinning assembly comprises an annular sleeve (6), an annular feeding pressure block (7) is sleeved outside the annular sleeve (6), an inner feeding pressure block (8) and an inner distributing plate (9) are sequentially arranged inside the annular sleeve (6) from top to bottom, an inner filter screen (11) is sleeved inside the annular sleeve (6) and below the inner distributing plate (9), an annular filter screen (10) is sleeved outside the annular sleeve (6) and below the annular feeding pressure block (7), one end of the annular sleeve (6) is embedded in a first O-shaped groove (12) of a PBO spinneret (13), a metal adjusting gasket (15) and a PIPD spinneret plate (16) are sequentially arranged below the PBO spinneret plate (13) to form a pre-assembly component, a component sleeve (17) is sleeved outside the pre-assembly component, the other end of the annular sleeve (6) is embedded into a second O-shaped groove (5) of the component cover plate (4), screw holes in the component cover plate (4) are aligned with screw holes in the component sleeve (17), and the assembly cover plate (4) is tightly connected with the component sleeve (17) through fastening bolts (3); the assembly cover plate (4) is provided with a first feeding hole (1) and a second feeding hole (2) which are independent, the first feeding hole (1) is communicated with the inner cavity of the annular sleeve (6), and the second feeding hole (2) is communicated with the outer annular cavity of the annular sleeve (6);
the PBO spinneret plate (13) comprises an outer hole and an inner hole, the outer hole of the PBO spinneret plate (13) is a PIPD/PPA polymer solution distribution hole (14), and the inner hole of the PBO spinneret plate (13) is a spinneret hole of the PBO/PPA polymer solution; the spinneret orifices of the PIPD spinneret plate (16) are consistent with the distribution of the holes on the inner side of the PBO spinneret plate (13).
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117364273A (en) * | 2023-10-10 | 2024-01-09 | 江苏亨博复合材料有限公司 | Preparation method of transverse reinforced PBO (Poly-p-phenylene oxide) fiber |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN202297901U (en) * | 2011-10-22 | 2012-07-04 | 东华大学 | High-temperature resistant anti-ultraviolet composite fiber material |
| CN104195658A (en) * | 2014-07-30 | 2014-12-10 | 杭州翔盛高强纤维材料股份有限公司 | UHMWPP and UHMWPE sheath-core composite fiber, special device and spinning method thereof |
| CN104862826A (en) * | 2015-05-28 | 2015-08-26 | 中蓝晨光化工研究设计院有限公司 | Preparation method of PIPD/PBO (poly(dihydroxyphenylene pyridobisimidazole)/poly-p-phenylene ben-zobisthiazole) blend fiber |
| CN106344969A (en) * | 2016-09-26 | 2017-01-25 | 南方医科大学南方医院 | Dental composite-resin high-strength fiber periodontal bundle band and preparation method thereof |
| CN111206298A (en) * | 2020-03-10 | 2020-05-29 | 闽江学院 | Preparation method of skin-core composite structure dope-colored red chinlon 6 fiber |
| CN111519274A (en) * | 2020-01-20 | 2020-08-11 | 浙江新维狮合纤股份有限公司 | Production process of superfine fiber with super-soft bi-component sheath-core structure and superfine fiber thereof |
-
2020
- 2020-12-17 CN CN202011497862.1A patent/CN112647155A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN202297901U (en) * | 2011-10-22 | 2012-07-04 | 东华大学 | High-temperature resistant anti-ultraviolet composite fiber material |
| CN104195658A (en) * | 2014-07-30 | 2014-12-10 | 杭州翔盛高强纤维材料股份有限公司 | UHMWPP and UHMWPE sheath-core composite fiber, special device and spinning method thereof |
| CN104862826A (en) * | 2015-05-28 | 2015-08-26 | 中蓝晨光化工研究设计院有限公司 | Preparation method of PIPD/PBO (poly(dihydroxyphenylene pyridobisimidazole)/poly-p-phenylene ben-zobisthiazole) blend fiber |
| CN106344969A (en) * | 2016-09-26 | 2017-01-25 | 南方医科大学南方医院 | Dental composite-resin high-strength fiber periodontal bundle band and preparation method thereof |
| CN111519274A (en) * | 2020-01-20 | 2020-08-11 | 浙江新维狮合纤股份有限公司 | Production process of superfine fiber with super-soft bi-component sheath-core structure and superfine fiber thereof |
| CN111206298A (en) * | 2020-03-10 | 2020-05-29 | 闽江学院 | Preparation method of skin-core composite structure dope-colored red chinlon 6 fiber |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117364273A (en) * | 2023-10-10 | 2024-01-09 | 江苏亨博复合材料有限公司 | Preparation method of transverse reinforced PBO (Poly-p-phenylene oxide) fiber |
| CN117364273B (en) * | 2023-10-10 | 2024-04-26 | 江苏亨博复合材料有限公司 | Preparation method of transverse reinforced PBO (Poly-p-phenylene oxide) fiber |
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