CN106432722A - High-performance fiber and preparation method thereof - Google Patents
High-performance fiber and preparation method thereof Download PDFInfo
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- CN106432722A CN106432722A CN201610911204.XA CN201610911204A CN106432722A CN 106432722 A CN106432722 A CN 106432722A CN 201610911204 A CN201610911204 A CN 201610911204A CN 106432722 A CN106432722 A CN 106432722A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920006253 high performance fiber Polymers 0.000 title description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000000835 fiber Substances 0.000 claims abstract description 49
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 claims abstract description 22
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000002166 wet spinning Methods 0.000 claims abstract description 7
- 238000004132 cross linking Methods 0.000 claims abstract description 6
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 5
- 150000001412 amines Chemical class 0.000 claims abstract description 5
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 14
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000009987 spinning Methods 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 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 6
- 239000007789 gas Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000007142 ring opening reaction Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- CJOJIAKIRLKBOO-UHFFFAOYSA-N dimethyl 2-hydroxybenzene-1,4-dicarboxylate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C(O)=C1 CJOJIAKIRLKBOO-UHFFFAOYSA-N 0.000 claims description 3
- 230000020477 pH reduction Effects 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 230000006835 compression Effects 0.000 claims 1
- 238000007906 compression Methods 0.000 claims 1
- WOZVHXUHUFLZGK-UHFFFAOYSA-N terephthalic acid dimethyl ester Natural products COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- QUDZAFKCASPJLX-UHFFFAOYSA-N 2-aminophenol;hydron;chloride Chemical compound Cl.NC1=CC=CC=C1O QUDZAFKCASPJLX-UHFFFAOYSA-N 0.000 abstract description 2
- 229920000927 poly(p-phenylene benzobisoxazole) Polymers 0.000 abstract description 2
- -1 poly(p-phenylenebenzobisoxazole) Polymers 0.000 abstract 2
- 238000007669 thermal treatment Methods 0.000 abstract 2
- 239000000463 material Substances 0.000 description 6
- 238000005979 thermal decomposition reaction Methods 0.000 description 5
- CDOWNLMZVKJRSC-UHFFFAOYSA-N 2-hydroxyterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(O)=C1 CDOWNLMZVKJRSC-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000005411 Van der Waals force Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- 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 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000011158 industrial composite Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
Classifications
-
- 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
-
- 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
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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)
- Artificial Filaments (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention relates to a modified poly(p-phenylenebenzobisoxazole) (PBO) fiber and a preparation method thereof. According to the fiber, the main problem of poor pressure resistance of the PBO fiber is solved. The preparation method comprises the steps of reacting by virtue of 2-hydroxyl dimethyl terephthalate, an amine source and paraformaldehyde as raw materials so as to prepare terephthalic acid containing an oxazine side group, reacting by virtue of o-amino-phenol hydrochloride, terephthalic acid and terephthalic acid containing the oxazine side group as raw materials so as to prepare modified PBO containing the oxazine side group, carrying out dry-jet wet spinning method to an obtain original benzoxazine grafted modified PBO fiber, and carrying out thermal treatment and benzoxazine open loop crosslinking on the original benzoxazine grafted modified PBO fiber, so as to obtain the modified PBO fiber. The preparation method has the advantages that by introducing an oxazine structure to the side groups of PBO molecular chains, the tensile property of the fiber is hardly influenced; and oxazine is subjected to open loop crosslinking during the thermal treatment of the fiber, and the PBO molecular chains are chemically crosslinked, so that the pressure resistance of the fiber can be substantially improved.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to a high-performance fiber and a preparation method thereof, in particular to a benzoxazine grafted modified poly-p-Phenylene Benzobisoxazole (PBO) fiber and a preparation method thereof.
[ background of the invention ]
Poly (p-Phenylene Benzobisoxazole) (PBO) is a rigid rod-like molecule containing an oxazole ring structure, typically obtained by polycondensation of 4, 6-diaminoresorcinol hydrochloride (DAR) with terephthalic acid in polyphosphoric acid (PPA). The high-performance PBO fiber can be obtained by adopting a dry-jet wet spinning technology and through the working procedures of spinning, solidification, stretching, washing, drying, heat treatment and the like. PBO fiber is the material with highest tensile strength and tensile modulus in the prior organic synthetic fiber, and has good heat resistance, and the decomposition temperature under nitrogen is as high as 600 ℃. In addition, it is excellent in chemical stability, flame retardancy, dimensional stability and the like. PBO is used in various forms of filament, yarn, short fiber, super short fiber pulp, etc. in different fields, such as aerospace, military industry, fire fighting, industrial composite material, etc.
However, the PBO molecular structure has no polar groups, and the acting force between molecular chains is mainly weak van der waals force, which causes easy slippage between molecular chains, so that the PBO fiber has high tensile strength but low compressive strength of only 0.2-0.4GPa, and cannot meet the use requirements in many occasions. In order to solve the problem, the main method adopted at present is to introduce some polar groups capable of interacting, such as hydroxyl, into the PBO molecular chain, and to increase the intermolecular force of the fibers by using the hydrogen bonding force between the hydroxyl groups on adjacent molecular chains. However, the strength of the force between the polar groups is higher than the van der waals force, but it is still insufficient for the application of PBO fibers. And the introduction of hydroxyl groups can greatly reduce the thermal property of the fiber, and is not favorable for the application of the fiber under the condition of high temperature.
[ summary of the invention ]
The invention aims to overcome the defects of the prior art and provides a benzoxazine grafted and modified PBO polymer fiber and a preparation method thereof.
One of the purposes of the invention is to provide a benzoxazine grafted and modified PBO polymer, which has the structural formula:
wherein n and m are the mole percentages of the two structural units, and n + m is 100%. Wherein n is 80-95% and m is 5-20%.
Wherein,is one of the following:
the second purpose of the invention is to provide a preparation method of a benzoxazine grafted modified PBO polymer, which comprises the following steps:
firstly, 2-hydroxy dimethyl terephthalate, an amine source and paraformaldehyde are used as raw materials to react to prepare the terephthalic acid containing the oxazine side group, and the chemical reaction equation is as follows:
wherein,is one of the following:
here, it is necessary to use dimethyl 2-hydroxyterephthalate but not 2-hydroxyterephthalic acid, because the carboxyl group of 2-hydroxyterephthalic acid undergoes a side reaction with the amine group of the amine source, resulting in a decrease in the yield of the objective product.
And secondly, taking o-aminophenol hydrochloride, terephthalic acid and the oxazine side group-containing terephthalic acid synthesized in the first step as raw materials, and reacting to prepare the modified PBO containing the oxazine side group, wherein the chemical reaction equation is as follows:
where n and m are the mole percentages of the two structures, and n + m is 100%. Wherein n is 80-95% and m is 5-20%.
And thirdly, adopting a dry-jet wet spinning method commonly used for PBO to obtain the original benzoxazine grafted and modified PBO fiber. And then carrying out heat treatment on the original fiber, and carrying out ring-opening crosslinking on benzoxazine to obtain the modified PBO fiber. Dry-jet wet spinning is one of the common spinning methods, and there are many documents relating to this technology.
The specific operation steps are as follows:
(1) adding dimethyl 2-hydroxy terephthalate, paraformaldehyde and dimethyl formamide solvent into a three-neck flask with a stirring and condensing reflux device, heating to 70 ℃, adding an amine source, heating to 100 ℃, and reacting for 10 hours. The system is subjected to precipitation, washing, drying, hydrolysis under alkaline conditions, acidification, precipitation and drying to obtain the terephthalic acid containing the oxazine side group.
(2) Heating and dissolving 4, 6-diaminoresorcinol hydrochloride, terephthalic acid and benzoxazine-side group-containing terephthalic acid in a certain ratio in polyphosphoric acid in a reaction kettle equipped with protective gas and a stirring device, reacting for 6 hours at 120 ℃ under the condition of continuously introducing the protective gas to remove hydrogen chloride, then vacuumizing, and reacting for 26 hours in stages under the vacuum of 140-180 ℃ and 50Pa to obtain the benzoxazine grafted modified PBO polymer.
The mixture ratio is as follows: 4, 6-diaminoresorcinol hydrochloride: (terephthalic acid + oxazine side group-containing terephthalic acid) 1:1 (molar ratio)
The mixture ratio is as follows: terephthalic acid: and the benzoxazine-side group-containing terephthalic acid is 80: 20-95: 5 (molar ratio).
The protective gas is nitrogen or argon.
(3) And (3) carrying out dry-jet wet spinning on the solution obtained by polymerization by adopting a common PBO (poly (p-phenylene benzoxide)) dry-jet wet spinning method to obtain the original benzoxazine grafted and modified PBO fiber. And then carrying out tension heat treatment on the original fiber at a certain temperature, and carrying out ring-opening crosslinking on the benzoxazine to obtain the modified PBO fiber.
The heat treatment temperature is 220-300 ℃, and the preferable temperature is 240-260 ℃;
the tension of the heat treatment is 0.1-0.4N, and the preferable tension is 0.2-0.3N;
the heat treatment time is 60-300 s, and the preferable time is 120-180 s.
Compared with the prior art, the invention has the advantages that:
(1) the technology introduces an oxazine structure on the PBO molecular chain side group, and the side group oxazine is subjected to ring-opening crosslinking during heat treatment, so that chemical crosslinking is generated among the PBO molecular chains. Because the strength of the chemical bond is far greater than the strength of the attractive force between hydrogen bonds and polar groups and the strength of Van der Waals force, the intermolecular acting force of the fibers is greatly improved, and the compressive capacity is greatly enhanced.
(2) Because the oxazine is introduced as a side group of the PBO molecule, the main chain is still in a PBO structure, and the main chain mainly bears tensile stress during stretching, the tensile property of the modified PBO fiber is not remarkably reduced compared with that of the PBO fiber.
(3) The high-temperature resistance of the benzoxazine is good. The benzoxazine is introduced into the PBO structure, although the thermal property of the PBO is slightly reduced, the reduction is not much, and the application requirement under the high-temperature condition can be met.
[ description of the drawings ]
FIG. 1 Infrared Spectrum of benzoxazine grafted modified PBO obtained in example 1
[ detailed description ] embodiments
The following provides specific embodiments of the modified PBO fiber of the present invention and a method for preparing the same.
Comparative example 1
In a reaction vessel equipped with a nitrogen blanket and a stirring device, 0.2mol of 4, 6-diaminoresorcinol hydrochloride, 0.2mol of terephthalic acid, 100g of polyphosphoric acid (P)2O5Concentration of 83 wt%), 80g P2O5. Heating the materials in the reaction kettle to 60 ℃ for 1 hour, preliminarily mixing the materials, slowly heating to 70 ℃ under the condition of continuously introducing nitrogen, keeping for 1 hour, continuously heating to 120 ℃ and keeping for 6 hours. And (3) stopping introducing nitrogen, changing into vacuumizing to 50Pa, heating to 140 ℃ for reaction for 8 hours, then heating to 160 ℃ for reaction for 12 hours, and finally heating to 180 ℃ for reaction for 6 hours to obtain the PBO polymer/polyphosphoric acid solution.
Directly taking the obtained PBO polymer/polyphosphoric acid solution as a spinning solution, transferring the PBO polymer/polyphosphoric acid solution into a double-screw extruder, spinning at 180 ℃ by adopting a dry jet spinning process, washing the obtained fiber by using a spinneret plate with the diameter of a spinneret orifice of 0.2mm and the number of spinneret orifices of 120 to fully remove the residual polyphosphoric acid solvent, and drying at 150 ℃ to remove moisture to obtain the PBO fiber.
This comparative example provides an unmodified PBO fiber having the following structure.
The obtained PBO fiber has the tensile strength of 5.5GPa, the thermal decomposition temperature of 595 ℃ in air and the compressive strength of 0.26 GPa.
Example 1
(1) Adding 0.5mol of 2-hydroxy dimethyl terephthalate and 1.1mol of paraformaldehyde into a three-neck flask with a condensing and stirring device, adding 80ml of dimethylformamide serving as a solvent, heating to 70 ℃, adding 0.5mol of aniline after reagents are fully mixed and dissolved, heating to 100 ℃, and reacting for 10 hours. The system is precipitated, washed and dried to obtain the dimethyl terephthalate containing the oxazine side group. And adding 100ml of methanol solution containing 1mol of potassium hydroxide while stirring, heating and refluxing for 7 hours, adding diluted hydrochloric acid for acidification, and drying to obtain the terephthalic acid containing the oxazine side group.
(2) In a reaction kettle equipped with a nitrogen protection and stirring device, 0.2mol of 4, 6-diaminoresorcinol hydrochloride, 0.16mol of terephthalic acid, 0.04mol of terephthalic acid containing oxazine side groups and 100g of polyphosphoric acid (P)2O5Concentration of 83 wt%), 80g P2O5. Wherein the molar ratio n of terephthalic acid to the oxazine side group-containing terephthalic acid is: and m is 80: 20.
Heating the materials in the reaction kettle to 60 ℃ for 1 hour, preliminarily mixing the materials, slowly heating to 70 ℃ under the condition of continuously introducing nitrogen, keeping for 1 hour, continuously heating to 120 ℃ and keeping for 6 hours. And (3) stopping introducing nitrogen, changing into vacuumizing to 50Pa, heating to 140 ℃ for reaction for 8 hours, then heating to 160 ℃ for reaction for 12 hours, and finally heating to 180 ℃ for reaction for 4 hours to obtain the modified PBO polymer/polyphosphoric acid solution.
The molecular structure of the modified PBO in this example is:
the IR spectrum of the modified PBO of this example is shown in FIG. 1.
(3) The modified PBO polymer/polyphosphoric acid solution obtained in the previous step is directly used as spinning solution for spinning, and the spinning process is the same as that of comparative example 1. The obtained original fiber is thermally treated for 150 seconds at 250 ℃ under the tension condition of 0.2N, and the modified PBO fiber is obtained.
The tensile strength of the modified PBO fiber obtained in the embodiment is 4.9GPa, the thermal decomposition temperature in air is 552 ℃, and the compressive strength is 1.7 GPa.
Example 2
The molar ratio of terephthalic acid to oxazine side group-containing terephthalic acid in example 1 was changed to n: and m is 95: 5. Namely 31.54g (0.18mol) of terephthalic acid, 2.99g (0.02mol) of terephthalic acid containing oxazine side groups. The other steps are the same as in example 1.
The molecular structure of the modified PBO in this example is:
the tensile strength of the modified PBO fiber obtained in the embodiment is 5.2GPa, the thermal decomposition temperature in air is 575 ℃, and the compressive strength is 0.9 GPa.
Example 3
The aniline in example 2 was changed to paracyanoaniline, and the charge amount was changed accordingly. The other operation steps were the same as those in example 1.
The molecular structure of the modified PBO in this example is:
the tensile strength of the modified PBO fiber obtained in the embodiment is 5.1GPa, the thermal decomposition temperature in air is 571 ℃, and the compressive strength is 1.3 GPa.
Example 4
The molar ratio of terephthalic acid to oxazine side group-containing terephthalic acid in example 3 was changed to n: and m is 85:15, and the feeding amount is changed correspondingly. The other operation steps were the same as those in example 1.
The molecular structure of the modified PBO in this example is:
the tensile strength of the modified PBO fiber obtained in the embodiment is 5.2GPa, the thermal decomposition temperature in air is 560 ℃ and the compressive strength is 1.9 GPa.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and decorations can be made without departing from the concept of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A benzoxazine grafted and modified PBO polymer has a chemical structural formula as follows:
wherein n and m are the mole percentages of the two structural units, and n + m is 100%. Wherein n is 80-95% and m is 5-20%.
Wherein,is one of the following:
2. a preparation method of benzoxazine grafted modified PBO polymer and fiber is characterized by comprising the following specific operation steps:
(1) adding dimethyl 2-hydroxy terephthalate, paraformaldehyde and dimethyl formamide solvent into a three-neck flask with a stirring and condensing reflux device, heating to 70 ℃, adding an amine source, heating to 100 ℃, and reacting for 10 hours. The system is subjected to precipitation, washing, drying, hydrolysis under alkaline conditions, acidification, precipitation and drying to obtain the terephthalic acid containing the oxazine side group.
(2) Heating and dissolving 4, 6-diaminoresorcinol hydrochloride, terephthalic acid and benzoxazine-side group-containing terephthalic acid in a certain ratio in polyphosphoric acid in a reaction kettle equipped with protective gas and a stirring device, reacting for 6 hours at 120 ℃ under the condition of continuously introducing nitrogen, then vacuumizing, and reacting for 26 hours in stages under the vacuum of 140-180 ℃ and 50Pa to obtain the benzoxazine grafted modified PBO polymer.
(3) And spinning the solution obtained by polymerization by adopting a dry-jet wet spinning method to obtain the original benzoxazine grafted modified PBO fiber. And then carrying out tension heat treatment on the original fiber at a certain temperature, and carrying out ring-opening crosslinking on the benzoxazine to obtain the modified PBO fiber.
3. The method for preparing the benzoxazine-grafted modified PBO polymer and fiber according to claim 2, wherein the weight ratio of terephthalic acid: the molar ratio of the benzoxazine-side group-containing terephthalic acid is 80: 20-95: 5.
4. The method for preparing the benzoxazine-grafted modified PBO polymer and fiber according to claim 2, wherein the protective gas is nitrogen or argon.
5. The preparation method of benzoxazine grafted and modified PBO polymer and fiber according to claim 2, wherein the original fiber obtained by spinning must be subjected to a heat treatment step with tension at a certain temperature to open and crosslink the oxazine ring pendant groups and chemically crosslink molecular chains, so that the modified PBO fiber of the present invention is obtained, and the purpose of improving the compression resistance of the PBO fiber is achieved.
6. The heat treatment step with belt tension at a certain temperature according to claim 5, wherein the heat treatment temperature is 220 to 300 ℃, preferably 240 to 260 ℃.
7. The heat treatment step with a belt tension at a certain temperature according to claim 5, wherein the heat treatment tension is 0.1 to 0.4N, preferably 0.2 to 0.3N.
8. The heat treatment step with belt tension at a certain temperature according to claim 5, wherein the heat treatment time is 60 to 300s, preferably 120 to 180 s.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115584625A (en) * | 2022-11-17 | 2023-01-10 | 成都科宜高分子科技有限公司 | Organic fiber, fiber composite material, preparation method and application thereof |
| 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 |
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| US20110196051A1 (en) * | 2006-02-07 | 2011-08-11 | Samsung Sdi Co., Ltd. | Electrolyte membrane using polybenzoxazine based compound |
| CN102250117A (en) * | 2011-05-11 | 2011-11-23 | 华东理工大学 | Dibenzoxazine containing oxazole ring and preparation method thereof |
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| US20110196051A1 (en) * | 2006-02-07 | 2011-08-11 | Samsung Sdi Co., Ltd. | Electrolyte membrane using polybenzoxazine based compound |
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| KAN ZHANG ET AL.,: "High Performance Crosslinked System Based on Reaction of Benzoxazine", 《 JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY》 * |
| YOUQING LI ET AL.,: "Curing Behavior and Properties of the Cured Resin Based on Bismaleimide, Bisoxazoline, and Oleic Acid Ternary Copolymer", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
| 张涛 等: "抗紫外老化聚对苯撑苯并噁唑（PBO）纤维的制备与表征", 《化学学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115584625A (en) * | 2022-11-17 | 2023-01-10 | 成都科宜高分子科技有限公司 | Organic fiber, fiber composite material, preparation method and application thereof |
| 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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| Publication number | Publication date |
|---|---|
| CN106432722B (en) | 2018-11-16 |
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