CN114000219A - Water-repellent and oil-repellent meta-aramid fiber and preparation method thereof - Google Patents

Water-repellent and oil-repellent meta-aramid fiber and preparation method thereof Download PDF

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CN114000219A
CN114000219A CN202111275875.9A CN202111275875A CN114000219A CN 114000219 A CN114000219 A CN 114000219A CN 202111275875 A CN202111275875 A CN 202111275875A CN 114000219 A CN114000219 A CN 114000219A
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repellent
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water
oil
aramid
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CN114000219B (en
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关振虹
冷向阳
李丹
宋西全
高东
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YANTAI TAYHO ADVANCED MATERIALS CO Ltd
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    • 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
    • D01F6/80—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
    • 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
    • D01F6/80—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides
    • D01F6/805—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides from aromatic copolyamides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear

Abstract

The invention provides water-repellent and oil-repellent meta-aramid and a preparation method thereof, wherein the preparation process comprises the following steps: adding a fluorine-containing monomer and isophthaloyl dichloride into an organic solvent according to a certain proportion, and carrying out polycondensation reaction to obtain a fluorine-containing oligomer; adding m-phenylenediamine and isophthaloyl chloride into an organic solvent according to a certain proportion, and carrying out polycondensation reaction to obtain the polyisophthaloyl m-phenylenediamine. Mixing the two polymers, adding isophthaloyl dichloride, and obtaining the fluorine modified polyisophthaloyl metaphenylene diamine after the viscosity of the polymer meets the requirement. Then the water-repellent and oil-repellent meta-aramid protofilament is prepared by wet spinning, and the protofilament is dried and heat-set after being washed to prepare the water-repellent and oil-repellent meta-aramid. After the meta-aramid with hydrophobicity and oleophobicity is woven into the fabric, the fabric can keep dry in a dynamic water spraying environment, but the air permeability of the fabric can be ensured due to the void structure of the fabric.

Description

Water-repellent and oil-repellent meta-aramid fiber and preparation method thereof
Technical Field
The invention belongs to the technical field of meta-aramid, and relates to water-repellent and oil-repellent meta-aramid and a preparation method thereof.
Background
Emergency rescue personnel need to deal with the prevention and emergency treatment of emergencies, disaster-stricken personnel and public and private property rescue, organize the work such as self-rescue, mutual rescue and rescue after being good, the working environment is often outdoor, the weather change and the severe environment need to be met, and the clothes worn by the emergency rescue personnel are standardized by the relevant national standards and have the performances of flame retardance, high temperature resistance, corrosion resistance, static resistance, friction resistance and the like. The meta-aramid fiber has excellent high temperature resistance, flame retardance, mechanical properties, electrical insulativity and good textile processability, is widely applied to the fields of protective clothing, high-temperature filtering materials and composite materials, and is an important basic material of emergency rescue clothing. The presence of amide linkages in the fibers makes them undesirable for use in humid environments, susceptible to moisture and mildew. Therefore, the meta-aramid fiber is endowed with the water and oil repellent performance, the emergency rescue suit can be kept dry and clean in the water and heavy polluted environment, the safety and comfort of rescue workers on the rescue site are further improved, and the service life of the emergency rescue suit is prolonged.
At present, the water and oil repellent performance of common garment materials mainly comes from an after-finishing method, and the process has the problems of long flow, poor uniformity, more generated sewage, obvious reduction of the water and oil repellent performance after multiple times of washing and the like. The patent on the water and oil repellency generated by the meta-aramid fabric after-treatment is reported. The water and oil repellent function problem is solved from the fiber source, the post-treatment process can be omitted, the stability and uniformity of the function are ensured, and the performance is kept unchanged in the using and washing processes. The preparation method of the meta-aramid fiber with the water and oil repellent function is also reported at present.
In order to solve the problem of high-temperature hydrolysis resistance of the meta-aramid filter material, patent CN102628222A discloses that a filter material blank is immersed in a finishing liquid mainly comprising polytetrafluoroethylene emulsion and epoxy phenolic resin, and then is subjected to low-temperature pre-drying and high-temperature cross-linking baking to form a coated and uniformly dispersed polytetrafluoroethylene film on the surface of the filter material fiber, so as to isolate water vapor from contacting the fiber, and the retention rate of transverse and longitudinal breaking strength after hydrolysis treatment at high temperature is not less than 100%. The method carries out post-finishing treatment on the meta-aramid fiber filter material, the formed film layer has a waterproof function, meanwhile, the penetration of water vapor is prevented, the air permeability of the filter material is reduced, and the film layer has a certain thickness and is not suitable for the treatment of the meta-aramid fiber fabric for clothing. The clothing is worn on the body, and is required to have air permeability and certain comfort, and the fabric is not air permeable or too hard, so that the clothing is not suitable for wearing.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the water-repellent and oil-repellent meta-aramid fiber and the preparation method thereof, which solve the problem of how to repel water and oil from the source of the meta-aramid fiber and simultaneously keep the performance of the meta-aramid fiber unchanged in the process of washing the fabric with water.
The invention is realized by the following technical scheme:
a preparation method of water-repellent and oil-repellent meta-aramid comprises
(1) Adding a fluorine-containing diamine monomer and isophthaloyl dichloride into an organic solvent, and performing polycondensation reaction to obtain a fluorine-containing oligomer system;
(2) adding m-phenylenediamine and isophthaloyl chloride into an organic solvent, and performing polycondensation reaction to obtain a polyisophthaloyl m-phenylenediamine system;
(3) mixing the fluorine-containing oligomer system obtained by the reaction in the step (1) with the polyisophthaloyl metaphenylene diamine system obtained by the reaction in the step (2), adding isophthaloyl dichloride, and adding a neutralizing agent when the viscosity of the polymer reaches 40-100 Pa.S to obtain fluorine modified polyisophthaloyl metaphenylene diamine;
(4) solidifying and forming the fluorine modified poly (m-phenylene isophthalamide) obtained by the reaction in the step (3) in a coagulating bath through wet spinning to prepare water-repellent and oil-repellent meta-aramid precursor fibers, washing the precursor fibers, drying and heat setting to prepare the water-repellent and oil-repellent meta-aramid;
in the step (1), the molar ratio of the fluorine-containing diamine monomer to the isophthaloyl dichloride is 1.01: 1-1.05: 1;
in the step (2), the molar ratio of m-phenylenediamine to isophthaloyl dichloride is 1.01: 1-1.05: 1;
the amount of the isophthaloyl dichloride added in the step (3) accounts for 10-30% of the total mass of the isophthaloyl dichloride in the steps (1), (2) and (3).
Preferably, the organic solvent is one of N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), and N-methylpyrrolidone (NMP).
Preferably, the reaction temperature of the step (1) is 0-30 ℃, and the reaction temperature of the step (2) is-20-10 ℃.
Preferably, the neutralizing agent of step (3) is one of calcium hydroxide, ammonia and calcium carbonate.
Preferably, the concentration of the solvent of the coagulation bath for wet spinning is 55-65%.
Preferably, the spinning washing temperature in the step (4) is 50-80 ℃; and (3) drying at 120-180 ℃ in the spinning process of the step (4) until the water content of the meta-aramid fiber is less than 5%.
Preferably, the heat setting temperature in the step (4) is 250-400 ℃, and the heat stretching multiple is 1.2-6 times.
Preferably, the viscosity of the fluorine-containing oligomer obtained in the step (1) is 0.5-20 Pa.s; the viscosity of the polyisophthaloyl metaphenylene diamine obtained in the step (2) is 20-40 Pa.s.
The water-repellent and oil-repellent meta-aramid fiber is prepared by the preparation method.
Preferably, the water-repellent and oil-repellent modified meta-aramid fiber has a chemical structural formula I:
Figure BDA0003329281510000031
wherein: m is more than or equal to 5 and less than or equal to 20, n is more than or equal to 100 and less than or equal to 200,
r' is
Figure BDA0003329281510000032
and-NO2In the above-mentioned manner, the first and second substrates are,
r' is
Figure BDA0003329281510000033
and-NO2One of (1);
r comprises
Figure BDA0003329281510000034
One of (1);
a water-repellent and oil-repellent meta-aramid fiber has a chemical structural formula II:
Figure BDA0003329281510000041
wherein: x is more than or equal to 5 and less than or equal to 20, and y is more than or equal to 100 and less than or equal to 200;
a water-repellent and oil-repellent meta-aramid fiber has a chemical structural formula III as follows:
Figure BDA0003329281510000042
wherein: x is more than or equal to 5 and less than or equal to 20, y is more than or equal to 100 and less than or equal to 200,
r comprises
Figure BDA0003329281510000043
One kind of (1).
Compared with the prior art, the invention has the following beneficial technical effects:
the invention discloses water-repellent and oil-repellent meta-aramid, wherein fluorine-containing groups are introduced into molecular chains of the meta-aramid, so that the fluorine groups can be uniformly distributed on the surface of fibers, fluorine has natural hydrophobicity and oleophobicity, and the fluorine groups on the surface of the fibers can endow the fibers with hydrophobicity and oleophobicity. After the hydrophobic and oleophobic fibers are woven into the fabric, the fabric can be kept dry in a dynamic water spraying environment, but the air permeability of the fabric can be ensured due to the void structure of the fabric. This is different from traditional waterproof surface fabric, and traditional waterproof surface fabric is through the after-treatment technique, adheres to the waterproof layer of a layer compactness on the surface fabric, and the hole in the surface fabric is sealed, and steam also can't pass through, and the steam in the clothing can't distribute away, makes the people have "vexed" sensation in the in-process of wearing. In addition, because the water and oil repellent performance of the fiber is derived from the fiber, the performance can be permanently maintained without being weakened by the falling off of the effective components in the wearing and washing processes.
The invention also discloses a preparation method of the water-repellent and oil-repellent meta-aramid, which takes isophthaloyl dichloride, m-phenylenediamine and fluorine-containing diamine as monomers and adopts low-temperature polycondensation in an organic solvent to prepare a fluorine modified polyisophthaloyl metaphenylene diamine spinning solution. The aromatic diamine containing fluorine groups has high purity and can meet the actual production requirement. Because of the strong electron-withdrawing action of fluorine, the diamine monomer introduced with fluorine groups has higher activation energy with m-phthaloyl chloride polycondensation reaction, and is different from the conventional m-phenylenediamine and m-phthaloyl chloride low-temperature polycondensation conditions, the block copolymerization method is adopted, and the fluorine-containing groups are uniformly introduced into a polymerization molecular chain by two-step polymerization, so that the introduction amount of the fluorine groups is ensured, and the effectiveness and the durability of the water and oil repellent performance of the fiber are also ensured.
Drawings
FIG. 1 is a contact angle test of a fluorine-modified meta-aramid in example 10;
figure 2 is a contact angle test of unmodified meta-aramid in a comparative example.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The technical scheme adopted by the invention is that the fluorine-containing m-phenylenediamine is dissolved in an organic solvent, isophthaloyl dichloride (IPC) is added, and condensation polymerization is carried out at a certain temperature to obtain fluorine-containing oligomer; m-phenylenediamine (MPD) and isophthaloyl chloride (IPC) are subjected to low-temperature polycondensation in an organic solvent to obtain a polyisophthaloyl m-phenylenediamine polymer; and adding IPC after the two are mixed, stopping the reaction after the solution viscosity meets the requirement, and obtaining the fluorine modified polyisophthaloyl metaphenylene diamine polymer.
A water-repellent and oil-repellent modified meta-aramid fiber has a chemical structural formula I:
Figure BDA0003329281510000051
wherein: m is more than or equal to 5 and less than or equal to 20, n is more than or equal to 100 and less than or equal to 200,
r 'and R' comprise
Figure BDA0003329281510000052
One or more of the components (A) and (B),
r comprises
Figure BDA0003329281510000053
One kind of (1).
A water-repellent and oil-repellent modified meta-aramid fiber has a chemical structural formula II:
Figure BDA0003329281510000061
wherein: x is more than or equal to 5 and less than or equal to 20, and y is more than or equal to 100 and less than or equal to 200.
A water-repellent and oil-repellent modified meta-aramid fiber has a chemical structural formula III as follows:
Figure BDA0003329281510000062
wherein: x is more than or equal to 5 and less than or equal to 20, y is more than or equal to 100 and less than or equal to 200, R comprises
Figure BDA0003329281510000063
Figure BDA0003329281510000064
One kind of (1).
The preparation process of the water-repellent and oil-repellent meta-aramid comprises the following steps:
step 1, adding a fluorine-containing diamine monomer into an organic solvent at room temperature in a nitrogen drying environment, mechanically stirring at a rotating speed of 300-1000 r/min for dissolving, and cooling a system to 0-10 ℃ to form a diamine solution; the organic solvent is one of DMF, DMAc and NMP. And adding IPC into the diamine solution, wherein the molar ratio of the fluorine-containing diamine to the IPC is 1.01-1.05: 1, and in the adding process of the IPC, controlling the reaction temperature to be 0-30 ℃, and reacting for 30-90 min to form a fluorine-containing oligomer solution, wherein the solution viscosity is 0.5-20 pas.
Step 2, adding MPD into an organic solvent at room temperature in a nitrogen drying environment, wherein the molar ratio of MPD to the fluorine-containing diamine in the step 1 is 10-40: 1, mechanically stirring and dissolving at a rotating speed of 300-1000 r/min, and cooling a system to-20-10 ℃ to form an MPD solution; one of the DMF, DMAc and NMP is preferably in accordance with step 1. And adding IPC into the MPD solution, wherein the molar ratio of MPD to IPC is 1.01-1.05: 1, controlling the reaction temperature to be-20 to-10 ℃ in the IPC adding process, heating the whole system to-1 to 3 ℃ after reacting for 10 to 30min, preferably 0 ℃, and forming a polyisophthaloyl metaphenylene diamine polymer solution with the viscosity of 20 to 40 Pa.s.
And 3, mixing the solutions prepared in the steps 1 and 2, controlling the temperature to be 5-20 ℃, slowly adding IPC, and finishing the polycondensation reaction when a pole climbing phenomenon occurs. Adding a neutralizing agent into a reaction system, adjusting the pH value of the whole system to 6-8, and ensuring that the temperature of the whole system cannot exceed 80 ℃ in the process of adding the neutralizing agent so as to prevent side reaction; and (3) after neutralization reaction, preparing a fluorine modified polyisophthaloyl metaphenylene diamine polymer solution with the viscosity of 40-100 Pa.s. The amount of the isophthaloyl dichloride added in the step 3 accounts for 10-30% of the total amount of acyl chloride (the total amount of the isophthaloyl dichloride added in the 3 steps); the neutralizing agent in the step 3 is one of calcium hydroxide, ammonia and calcium carbonate.
Step 4, coagulating and forming the prepared fluorine modified poly (m-phenylene isophthalamide) polymer solution in a coagulating bath through wet spinning to prepare water-repellent and oil-repellent meta-aramid precursor fibers, wherein the technological parameters of the wet spinning refer to patent CN200910259778, and the water-repellent and oil-repellent modified meta-aramid precursor fibers are repeatedly washed, dried and heat-set to prepare the water-repellent and oil-repellent meta-aramid; the concentration of the wet spinning coagulating bath is 55-65%, the drying temperature is 120-180 ℃, the fiber is dried until the water content of the fiber is less than 5%, the heat setting temperature is 250-450 ℃, the heat stretching multiple is 1.2-6 times, and the fiber is heat-set until the fiber is stably formed.
The invention is further described below with reference to specific examples:
example 1
7.9g of 2, 2' -bis (trifluoromethyl) diaminobiphenyl and 467ml of DMAc were added to a 1L four-necked flask at room temperature under a nitrogen dry atmosphere, mechanically stirred at 800r/min until dissolved, and then the system was cooled to 10 ℃. To the diamine solution was added IPC 4.0 g. And in the IPC adding process, the reaction temperature is controlled to be 5 ℃, and after reaction for 90min, a fluorine-containing oligomer solution is formed, wherein the solution viscosity is 0.5 pas.
At room temperature, under a nitrogen drying environment, 106.6g of MPDA is added into 1L of DMAc, and after the mixture is mechanically stirred and dissolved at the rotating speed of 800r/min, the system is cooled to-10 ℃ to form an MPDA solution. Then adding 158.5g of IPC into the MPDA solution, controlling the reaction temperature to be-15 ℃ in the adding process, heating the whole system to 0 ℃ after reacting for 30min to form polyisophthaloyl metaphenylene diamine polymer solution with the viscosity of 39 Pa.s.
The solutions prepared in the two steps were mixed in a 2L four-necked flask, the temperature was controlled at 10 ℃ and about 40.6g of IPC was added slowly, and when a rod climbing phenomenon occurred, the polycondensation reaction was terminated. Calcium hydroxide is added into the reaction system, the temperature of the whole system is slowly raised to 50 ℃, and the pH value of the whole system is adjusted to 7.69. Neutralizing to obtain the fluorine modified polyisophthaloyl metaphenylene diamine polymer solution with the viscosity of 63 Pa.s.
And (2) carrying out wet spinning on the prepared fluorine modified polyisophthaloyl metaphenylene diamine polymer solution to prepare water-repellent and oil-repellent meta-aramid precursor fibers, wherein the concentration of a spinning coagulation bath is 55%, the drying temperature is 130 ℃, the heat setting temperature is 275 ℃, the heat stretching multiple is 3.5 times, and the fibers are heat-set until stable molding is achieved.
Example 2
10.4g of 2, 2' -bis (trifluoromethyl) diaminobiphenyl and 477ml of DMAc were charged into a 1L four-necked flask at room temperature under a nitrogen dry atmosphere, mechanically stirred at a rotation speed of 800r/min until dissolved, and then the system was cooled to 10 ℃. 5.2g of IPC was added to the diamine solution. And in the IPC adding process, controlling the reaction temperature to be 5 ℃, and reacting for 90min to form a fluorine-containing oligomer solution with the solution viscosity of 3 pas.
At room temperature, under a nitrogen drying environment, adding 105.7g of MPDA into 1L of DMAc, mechanically stirring at a rotating speed of 800r/min for dissolving, and cooling the system to-10 ℃ to form an MPDA solution; . 157.2g of IPC is added into the MPDA solution, the reaction temperature is controlled to be-15 ℃ in the adding process, the whole system is heated to 0 ℃ after reaction for 30min, and the polyisophthaloyl metaphenylene diamine polymer solution with the viscosity of 40 pas is formed.
The solutions prepared in the two steps were mixed in a 2L four-necked flask, the temperature was controlled at 10 ℃ and about 40.6g of IPC was added slowly, and when a rod climbing phenomenon occurred, the polycondensation reaction was terminated. Calcium hydroxide is added into the reaction system, the temperature of the whole system is slowly raised to 50 ℃, and the pH value of the whole system is adjusted to 7.91. Neutralizing to obtain the fluorine modified polyisophthaloyl metaphenylene diamine polymer solution with the viscosity of 66 Pa.s.
And (2) carrying out wet spinning on the prepared fluorine modified polyisophthaloyl metaphenylene diamine polymer solution to prepare water-repellent and oil-repellent meta-aramid precursor fibers, wherein the concentration of a spinning coagulation bath is 55%, the drying temperature is 130 ℃, the heat setting temperature is 275 ℃, the heat stretching multiple is 3.5 times, and the fibers are heat-set until stable molding is achieved.
Example 3
12.4g of 2, 2' -bis (trifluoromethyl) diaminobiphenyl and 485ml of DMAc were charged into a 1L four-necked flask at room temperature under a nitrogen-dry atmosphere, mechanically stirred at a rotation speed of 800r/min until dissolved, and then the system was cooled to 10 ℃. 6.2g of IPC was added to the diamine solution. And in the IPC adding process, controlling the reaction temperature to be 5 ℃, and reacting for 90min to form a fluorine-containing oligomer solution with the solution viscosity of 4 pas.
At room temperature, under a nitrogen drying environment, adding 105g of MPDA into 1L of DMAc, mechanically stirring at a rotating speed of 800r/min for dissolving, and cooling the system to-10 ℃ to form an MPDA solution; . And adding 156.2g of IPC into the MPDA solution, controlling the reaction temperature to be-15 ℃ in the adding process, heating the whole system to 0 ℃ after reacting for 30min to form polyisophthaloyl metaphenylene diamine polymer solution with the viscosity of 35 pas.
The solutions prepared in the two steps were mixed in a 2L four-necked flask, the temperature was controlled at 10 ℃ and about 40.6g of IPC was added slowly, and when a rod climbing phenomenon occurred, the polycondensation reaction was terminated. Calcium hydroxide is added into the reaction system, the whole system is slowly heated to 50 ℃, and the pH value of the whole system is adjusted to 7.80. Neutralizing to obtain the fluorine modified polyisophthaloyl metaphenylene diamine polymer solution with the viscosity of 61 Pa.s.
And (2) carrying out wet spinning on the prepared fluorine modified polyisophthaloyl metaphenylene diamine polymer solution to prepare water-repellent and oil-repellent meta-aramid precursor fibers, wherein the concentration of a spinning coagulation bath is 55%, the drying temperature is 130 ℃, the heat setting temperature is 275 ℃, the heat stretching multiple is 3.5 times, and the fibers are heat-set until stable molding is achieved.
Example 4
15.4g of 2, 2' -bis (trifluoromethyl) diaminobiphenyl and 496ml of DMAc were charged into a 1L four-necked flask at room temperature under a nitrogen-dry atmosphere, mechanically stirred at a rotation speed of 800r/min until dissolved, and then the system was cooled to 10 ℃. 7.7g of IPC was further added to the diamine solution. And in the IPC adding process, controlling the reaction temperature to be 5 ℃, and reacting for 90min to form a fluorine-containing oligomer solution with the solution viscosity of 6 pas.
Adding 104g of MPDA into 1L of DMAc at room temperature under a nitrogen drying environment, mechanically stirring at the rotating speed of 800r/min for dissolving, and cooling the system to-10 ℃ to form an MPDA solution; . And then 154.7g of IPC is added into the MPDA solution, in the adding process, the reaction temperature is controlled to be-15 ℃, the whole system is heated to 0 ℃ after reaction for 30min, and the polyisophthaloyl metaphenylene diamine polymer solution with the viscosity of 37 Pa.s is formed.
The solutions prepared in the two steps were mixed in a 2L four-necked flask, the temperature was controlled at 10 ℃ and about 40.6g of IPC was added slowly, and when a rod climbing phenomenon occurred, the polycondensation reaction was terminated. Calcium hydroxide is added into the reaction system, the temperature of the whole system is slowly raised to 50 ℃, and the pH value of the whole system is adjusted to 7.83. Neutralizing to obtain the fluorine modified polyisophthaloyl metaphenylene diamine polymer solution with the viscosity of 67 Pa.s.
And (2) carrying out wet spinning on the prepared fluorine modified polyisophthaloyl metaphenylene diamine polymer solution to prepare water-repellent and oil-repellent meta-aramid precursor fibers, wherein the concentration of a spinning coagulation bath is 55%, the drying temperature is 130 ℃, the heat setting temperature is 275 ℃, the heat stretching multiple is 3.5 times, and the fibers are heat-set until stable molding is achieved.
Example 5
20.2g of 2, 2' -bis (trifluoromethyl) diaminobiphenyl and 510ml of DMAc were charged into a 1L four-necked flask at room temperature under a nitrogen-dry atmosphere, mechanically stirred at a rotation speed of 800r/min to be dissolved, and then the system was cooled to 10 ℃. To the diamine solution was added IPC 10.2 g. And in the IPC adding process, controlling the reaction temperature to be 5 ℃, and reacting for 90min to form a fluorine-containing oligomer solution with the solution viscosity of 7 pas.
Adding 102.7g of MPDA into 1L of DMAc at room temperature in a nitrogen drying environment, mechanically stirring at the rotating speed of 800r/min for dissolving, and cooling the system to-10 ℃ to form an MPDA solution; . And adding 152.3g of IPC into the MPDA solution, controlling the reaction temperature to be-15 ℃ in the adding process, heating the whole system to 0 ℃ after reacting for 30min to form a polyisophthaloyl metaphenylene diamine polymer solution with the viscosity of 31Pa s.
The solutions prepared in the two steps were mixed in a 2L four-necked flask, the temperature was controlled at 10 ℃ and about 40.6g of IPC was added slowly, and when a rod climbing phenomenon occurred, the polycondensation reaction was terminated. Calcium hydroxide is added into the reaction system, the temperature of the whole system is slowly raised to 50 ℃, and the pH value of the whole system is adjusted to 7.71. Neutralizing to obtain the fluorine modified polyisophthaloyl metaphenylene diamine polymer solution with the viscosity of 63 Pa.s.
And (2) carrying out wet spinning on the prepared fluorine modified polyisophthaloyl metaphenylene diamine polymer solution to prepare water-repellent and oil-repellent meta-aramid precursor fibers, wherein the concentration of a spinning coagulation bath is 55%, the drying temperature is 130 ℃, the heat setting temperature is 275 ℃, the heat stretching multiple is 3.5 times, and the fibers are heat-set until stable molding is achieved.
Example 6
29.5g of 2, 2' -bis (trifluoromethyl) diaminobiphenyl and 570ml of DMAc were charged into a 1L four-necked flask at room temperature under a nitrogen-dry atmosphere, mechanically stirred at a rotation speed of 800r/min to be dissolved, and then the system was cooled to 10 ℃. To the diamine solution was added IPC 14.8 g. And in the IPC adding process, controlling the reaction temperature to be 5 ℃, and reacting for 90min to form a fluorine-containing oligomer solution with the solution viscosity of 9 pas.
At room temperature, under a nitrogen drying environment, adding 99.5g of MPDA into 1L of DMAc, mechanically stirring at a rotating speed of 800r/min for dissolving, and cooling the system to-10 ℃ to form an MPDA solution; . And adding 147.7g of IPC into the MPDA solution, controlling the reaction temperature to be-15 ℃ in the adding process, heating the whole system to 0 ℃ after reacting for 30min to form the polyisophthaloyl metaphenylene diamine polymer solution with the viscosity of 30 Pa.s.
The solutions prepared in the two steps were mixed in a 2L four-necked flask, the temperature was controlled at 10 ℃ and about 40.6g of IPC was added slowly, and when a rod climbing phenomenon occurred, the polycondensation reaction was terminated. Calcium hydroxide is added into the reaction system, the temperature of the whole system is slowly raised to 50 ℃, and the pH value of the whole system is adjusted to 7.68. Neutralizing to obtain the fluorine modified polyisophthaloyl metaphenylene diamine polymer solution with the viscosity of 67 Pa.s.
And (2) carrying out wet spinning on the prepared fluorine modified polyisophthaloyl metaphenylene diamine polymer solution to prepare water-repellent and oil-repellent meta-aramid precursor fibers, wherein the concentration of a spinning coagulation bath is 55%, the drying temperature is 130 ℃, the heat setting temperature is 275 ℃, the heat stretching multiple is 3.5 times, and the fibers are heat-set until stable molding is achieved.
Example 7
21.0g of 2, 2' -bis (trifluoromethyl) diaminobiphenyl and 510ml of DMAc were charged into a 1L four-necked flask at room temperature under a nitrogen-dry atmosphere, mechanically stirred at a rotation speed of 800r/min to be dissolved, and then the system was cooled to 10 ℃. To the diamine solution was added IPC 10.2 g. And in the IPC adding process, controlling the reaction temperature to be 5 ℃, and reacting for 90min to form a fluorine-containing oligomer solution with the solution viscosity of 5 pas.
At room temperature, under the nitrogen drying environment, adding 106.5g of MPDA into 1L of DMAc, mechanically stirring at the rotating speed of 800r/min for dissolving, and cooling the system to-10 ℃ to form an MPDA solution; . And adding 152.3g of IPC into the MPDA solution, controlling the reaction temperature to be-15 ℃ in the adding process, heating the whole system to 0 ℃ after reacting for 30min to form a polyisophthaloyl metaphenylene diamine polymer solution with the viscosity of 30 pas.
The solutions prepared in the two steps were mixed in a 2L four-necked flask, the temperature was controlled at 10 ℃ and about 40.6g of IPC was added slowly, and when a rod climbing phenomenon occurred, the polycondensation reaction was terminated. Calcium hydroxide is added into the reaction system, the temperature of the whole system is slowly raised to 50 ℃, and the pH value of the whole system is adjusted to 7.58. Neutralizing to obtain the fluorine modified polyisophthaloyl metaphenylene diamine polymer solution with the viscosity of 70 pas.
And (2) carrying out wet spinning on the prepared fluorine modified polyisophthaloyl metaphenylene diamine polymer solution to prepare water-repellent and oil-repellent meta-aramid precursor fibers, wherein the concentration of a spinning coagulation bath is 55%, the drying temperature is 130 ℃, the heat setting temperature is 275 ℃, the heat stretching multiple is 3.5 times, and the fibers are heat-set until stable molding is achieved.
Example 8
20.8g of 2, 2' -bis (trifluoromethyl) diaminobiphenyl and 510ml of DMAc were charged into a 1L four-necked flask at room temperature under a nitrogen-dry atmosphere, mechanically stirred at a rotation speed of 800r/min to be dissolved, and then the system was cooled to 10 ℃. To the diamine solution was added IPC 10.2 g. And in the IPC adding process, controlling the reaction temperature to be 5 ℃, and reacting for 90min to form a fluorine-containing oligomer solution with the solution viscosity of 7 pas.
At room temperature, under a nitrogen drying environment, adding 105.4g of MPDA into 1L of DMAc, mechanically stirring at a rotating speed of 800r/min for dissolving, and cooling the system to-10 ℃ to form an MPDA solution; . And adding 152.3g of IPC into the MPDA solution, controlling the reaction temperature to be-15 ℃ in the adding process, heating the whole system to 0 ℃ after reacting for 30min to form polyisophthaloyl metaphenylene diamine polymer solution with the viscosity of 33 Pa.s.
The solutions prepared in the two steps were mixed in a 2L four-necked flask, the temperature was controlled at 10 ℃ and about 40.6g of IPC was added slowly, and when a rod climbing phenomenon occurred, the polycondensation reaction was terminated. Calcium hydroxide is added into the reaction system, the temperature of the whole system is slowly raised to 50 ℃, and the pH value of the whole system is adjusted to 7.77. Neutralizing to obtain the fluorine modified polyisophthaloyl metaphenylene diamine polymer solution with the viscosity of 71 pas.
And (2) carrying out wet spinning on the prepared fluorine modified polyisophthaloyl metaphenylene diamine polymer solution to prepare water-repellent and oil-repellent meta-aramid precursor fibers, wherein the concentration of a spinning coagulation bath is 55%, the drying temperature is 130 ℃, the heat setting temperature is 275 ℃, the heat stretching multiple is 3.5 times, and the fibers are heat-set until stable molding is achieved.
Example 9
20.6g of 2, 2' -bis (trifluoromethyl) diaminobiphenyl and 510ml of DMAc were charged into a 1L four-necked flask at room temperature under a nitrogen-dry atmosphere, mechanically stirred at a rotation speed of 800r/min to be dissolved, and then the system was cooled to 10 ℃. To the diamine solution was added IPC 10.2 g. And in the IPC adding process, controlling the reaction temperature to be 5 ℃, and reacting for 90min to form a fluorine-containing oligomer solution with the solution viscosity of 6 pas.
Adding 104.4g of MPDA into 1L of DMAc at room temperature in a nitrogen drying environment, mechanically stirring at the rotating speed of 800r/min for dissolving, and cooling the system to-10 ℃ to form an MPDA solution; . And adding 152.3g of IPC into the MPDA solution, controlling the reaction temperature to be-15 ℃ in the adding process, heating the whole system to 0 ℃ after reacting for 30min to form polyisophthaloyl metaphenylene diamine polymer solution with the viscosity of 37 pas.
The solutions prepared in the two steps were mixed in a 2L four-necked flask, the temperature was controlled at 10 ℃ and about 40.6g of IPC was added slowly, and when a rod climbing phenomenon occurred, the polycondensation reaction was terminated. Calcium hydroxide is added into the reaction system, the temperature of the whole system is slowly raised to 50 ℃, and the pH value of the whole system is adjusted to 7.71. Neutralizing to obtain the fluorine modified polyisophthaloyl metaphenylene diamine polymer solution with the viscosity of 69 pas.
And (2) carrying out wet spinning on the prepared fluorine modified polyisophthaloyl metaphenylene diamine polymer solution to prepare water-repellent and oil-repellent meta-aramid precursor fibers, wherein the concentration of a spinning coagulation bath is 55%, the drying temperature is 130 ℃, the heat setting temperature is 275 ℃, the heat stretching multiple is 3.5 times, and the fibers are heat-set until stable molding is achieved.
Example 10
20.4g of 2, 2' -bis (trifluoromethyl) diaminobiphenyl and 510ml of DMAc were charged into a 1L four-necked flask at room temperature under a nitrogen-dry atmosphere, mechanically stirred at a rotation speed of 800r/min until dissolved, and then the system was cooled to 10 ℃. To the diamine solution was added IPC 10.2 g. And in the IPC adding process, controlling the reaction temperature to be 5 ℃, and reacting for 90min to form a fluorine-containing oligomer solution with the solution viscosity of 5 pas.
Adding 103.4g of MPDA into 1L of DMAc at room temperature in a nitrogen drying environment, mechanically stirring at the rotating speed of 800r/min for dissolving, and cooling the system to-10 ℃ to form an MPDA solution; . And adding 152.3g of IPC into the MPDA solution, controlling the reaction temperature to be-15 ℃ in the adding process, heating the whole system to 0 ℃ after reacting for 30min to form a polyisophthaloyl metaphenylene diamine polymer solution with the viscosity of 30 pas.
The solutions prepared in the two steps were mixed in a 2L four-necked flask, the temperature was controlled at 10 ℃ and about 40.6g of IPC was added slowly, and when a rod climbing phenomenon occurred, the polycondensation reaction was terminated. Calcium hydroxide is added into the reaction system, the whole system is slowly heated to 50 ℃, and the pH value of the whole system is adjusted to 7.85. And (3) after neutralization reaction, preparing a fluorine modified polyisophthaloyl metaphenylene diamine polymer solution with the viscosity of 72 pas.
And (2) carrying out wet spinning on the prepared fluorine modified polyisophthaloyl metaphenylene diamine polymer solution to prepare water-repellent and oil-repellent meta-aramid precursor fibers, wherein the concentration of a spinning coagulation bath is 55%, the drying temperature is 130 ℃, the heat setting temperature is 275 ℃, the heat stretching multiple is 3.5 times, and the fibers are heat-set until stable molding is achieved.
Example 11
21.3g of 2, 2-bis (4-aminophenyl) hexafluoropropane and 510ml of DMAc were charged into a 1L four-necked flask at room temperature under a nitrogen dry atmosphere, mechanically stirred at 800r/min to be dissolved, and then the system was cooled to 10 ℃. To the diamine solution was added IPC 10.2 g. And in the IPC adding process, controlling the reaction temperature to be 5 ℃, and reacting for 90min to form a fluorine-containing oligomer solution with the solution viscosity of 8 pas.
Adding 103.4g of MPDA into 1L of DMAc at room temperature in a nitrogen drying environment, mechanically stirring at the rotating speed of 800r/min for dissolving, and cooling the system to-10 ℃ to form an MPDA solution; . And adding 152.3g of IPC into the MPDA solution, controlling the reaction temperature to be-15 ℃ in the adding process, heating the whole system to 0 ℃ after reacting for 30min to form polyisophthaloyl metaphenylene diamine polymer solution with the viscosity of 36 Pa.s.
The solutions prepared in the two steps were mixed in a 2L four-necked flask, the temperature was controlled at 10 ℃ and about 40.6g of IPC was added slowly, and when a rod climbing phenomenon occurred, the polycondensation reaction was terminated. Calcium hydroxide is added into the reaction system, the whole system is slowly heated to 50 ℃, and the pH value of the whole system is adjusted to 7.85. Neutralizing to obtain the fluorine modified polyisophthaloyl metaphenylene diamine polymer solution with the viscosity of 80 Pa.s.
And (2) carrying out wet spinning on the prepared fluorine modified polyisophthaloyl metaphenylene diamine polymer solution to prepare water-repellent and oil-repellent meta-aramid precursor fibers, wherein the concentration of a spinning coagulation bath is 55%, the drying temperature is 130 ℃, the heat setting temperature is 275 ℃, the heat stretching multiple is 3.5 times, and the fibers are heat-set until stable molding is achieved.
Example 12
33.03g of 2, 2-bis [4- (4-aminophenoxy) ] hexafluoropropane and 510ml of DMAc were charged into a 1L four-necked flask at room temperature under a nitrogen dry atmosphere, mechanically stirred at 800r/min to be dissolved, and then the system was cooled to 10 ℃. To the diamine solution was added IPC 10.2 g. And in the IPC adding process, controlling the reaction temperature to be 5 ℃, and reacting for 90min to form a fluorine-containing oligomer solution with the solution viscosity of 7 pas.
Adding 103.4g of MPDA into 1L of DMAc at room temperature in a nitrogen drying environment, mechanically stirring at the rotating speed of 800r/min for dissolving, and cooling the system to-10 ℃ to form an MPDA solution; . And adding 152.3g of IPC into the MPDA solution, controlling the reaction temperature to be-15 ℃ in the adding process, heating the whole system to 0 ℃ after reacting for 30min to form polyisophthaloyl metaphenylene diamine polymer solution with the viscosity of 33 Pa.s.
The solutions prepared in the two steps were mixed in a 2L four-necked flask, the temperature was controlled at 10 ℃ and about 40.6g of IPC was added slowly, and when a rod climbing phenomenon occurred, the polycondensation reaction was terminated. Calcium carbonate is added into the reaction system, the whole system is slowly heated to 50 ℃, and the pH value of the whole system is adjusted to 7.85. Neutralizing to obtain the fluorine modified polyisophthaloyl metaphenylene diamine polymer solution with the viscosity of 79 pas.
And (2) carrying out wet spinning on the prepared fluorine modified polyisophthaloyl metaphenylene diamine polymer solution to prepare water-repellent and oil-repellent meta-aramid precursor fibers, wherein the concentration of a spinning coagulation bath is 55%, the drying temperature is 130 ℃, the heat setting temperature is 275 ℃, the heat stretching multiple is 3.5 times, and the fibers are heat-set until stable molding is achieved.
Example 13
27.29g of 1, 4-bis- (4 '-amino-2' -trifluoromethylphenoxy) benzene and 510ml of DMF were charged into a 1L four-necked flask at room temperature under a nitrogen-dry atmosphere, mechanically stirred at 1000r/min until dissolved, and then the system was cooled to 0 ℃. To the diamine solution was added IPC 10.2 g. And in the IPC adding process, the reaction temperature is controlled to be 30 ℃, and after reaction for 30min, a fluorine-containing oligomer solution is formed, wherein the solution viscosity is 15 pas.
Adding 103.4g of MPDA into 1L of DMF at room temperature in a nitrogen drying environment, mechanically stirring at the rotating speed of 1000r/min for dissolving, and cooling the system to-20 ℃ to form an MPDA solution; . And adding 152.3g of IPC into the MPDA solution, controlling the reaction temperature to be-10 ℃ in the adding process, heating the whole system to 0 ℃ after reacting for 10min to form polyisophthaloyl metaphenylene diamine polymer solution with the viscosity of 39 Pa.s.
The solutions prepared in the two steps were mixed in a 2L four-necked flask, the temperature was controlled at 20 ℃ and about 40.6g of IPC was added slowly, and when a rod climbing phenomenon occurred, the polycondensation reaction was terminated. Adding ammonia into the reaction system, slowly heating the whole system to 50 ℃, and adjusting the pH value of the whole system to 7.85. And (3) after neutralization reaction, preparing a fluorine modified polyisophthaloyl metaphenylene diamine polymer solution with the viscosity of 85 pas.
And (2) carrying out wet spinning on the prepared fluorine modified polyisophthaloyl metaphenylene diamine polymer solution to prepare water-repellent and oil-repellent meta-aramid precursor fibers, wherein the concentration of a spinning coagulation bath is 65%, the drying temperature is 180 ℃, the heat setting temperature is 400 ℃, the heat stretching multiple is 1.2 times, and the fibers are heat-set until stable molding is achieved.
Example 14
22.5g of 3,3 '-diamino-5, 5' -bis (trifluoromethyl) diaminobiphenyl and 510ml of NMP were added to a 1L four-necked flask at room temperature under a nitrogen-dry atmosphere, mechanically stirred at a rotation speed of 300r/min until dissolved, and then the system was cooled to 10 ℃. To the diamine solution was added IPC 10.2 g. And in the IPC adding process, controlling the reaction temperature to be 0 ℃, and reacting for 90min to form a fluorine-containing oligomer solution with the solution viscosity of 20 pas.
Adding 103.4g of MPDA into 1L of NMP at room temperature in a nitrogen drying environment, mechanically stirring at the rotating speed of 300r/min for dissolving, and cooling the system to-20 ℃ to form an MPDA solution; . And adding 152.3g of IPC into the MPDA solution, controlling the reaction temperature to be-20 ℃ in the adding process, heating the whole system to 3 ℃ after reacting for 30min to form polyisophthaloyl metaphenylene diamine polymer solution with the viscosity of 40 pas.
The solutions prepared in the two steps were mixed in a 2L four-necked flask, the temperature was controlled at 5 ℃ and about 40.6g of IPC was added slowly, and when a rod climbing phenomenon occurred, the polycondensation reaction was terminated. Calcium hydroxide is added into the reaction system, the temperature of the whole system is slowly raised to 50 ℃, and the pH value of the whole system is adjusted to 7.90. Neutralizing to obtain the fluorine modified polyisophthaloyl metaphenylene diamine polymer solution with the viscosity of 100 pas.
And (2) carrying out wet spinning on the prepared fluorine modified polyisophthaloyl metaphenylene diamine polymer solution to prepare water-repellent and oil-repellent meta-aramid precursor fibers, wherein the concentration of a spinning coagulation bath is 65%, the drying temperature is 120 ℃, the heat setting temperature is 250 ℃, the heat stretching multiple is 6 times, and the fibers are heat-set until stable molding is achieved.
Comparative example
At room temperature, under the dry environment of nitrogen, adding 109.2g of MPDA into 1435ml of DMAc, mechanically stirring at the rotating speed of 800r/min for dissolving, and cooling the system to-10 ℃ to form an MPDA solution; . And adding 162.4g of IPC into the MPDA solution, controlling the reaction temperature to be-15 ℃ in the adding process, heating the whole system to 0 ℃ after reacting for 30min to form polyisophthaloyl metaphenylene diamine polymer solution with the viscosity of 35 pas. Then, about 40.6g of IPC is slowly added, the temperature of the system is controlled at 10 ℃, and when a pole climbing phenomenon occurs, the polycondensation reaction is finished. Calcium hydroxide is added into the reaction system, the temperature of the whole system is slowly raised to 50 ℃, and the pH value of the whole system is adjusted to 7.59. Neutralizing to obtain the fluorine modified polyisophthaloyl metaphenylene diamine polymer solution with the viscosity of 70 pas.
And (2) carrying out wet spinning on the prepared polyisophthaloyl metaphenylene diamine polymer solution to prepare meta-aramid precursor fibers, wherein the concentration of a spinning coagulating bath is 55%, the drying temperature is 130 ℃, the heat setting temperature is 275 ℃, the heat stretching multiple is 3.5 times, and the fibers are heat-set until stable molding is carried out.
TABLE 1 polymerization conditions and physical properties index of spinning solution for examples and comparative examples
Figure BDA0003329281510000191
TABLE 2 Water and oil repellency test results of fluorine modified meta-aramid
Figure BDA0003329281510000201
TABLE 3 Water and oil repellency of fluorine-modified meta-aramid after 50-time washing
Figure BDA0003329281510000202
TABLE 4 fluorine modified meta-aramid fiber flame retardancy and mechanical Property test results
Figure BDA0003329281510000211
According to the results of the examples, the fluorine-modified meta-aramid has good mechanical properties, the fluorine-modified meta-aramid fabric has excellent water and oil repellency, the fabric of the examples 5, 7, 8, 9 and 10 has the water repellency grade of 9 and the oil repellency grade of 7, and the results are shown in the tables 2 and 4. Fig. 1 is a contact angle test of the modified meta-aramid of example 10 and fig. 2 is a contact angle test of the unmodified meta-aramid of comparative example, showing that the water repellency after fluorine modification is significantly improved.
The meta-aramid fabrics of example 5, example 7, example 8, example 9, example 10 and comparative example were selected, and after 50 water washes, the water and oil repellency rating was tested to remain unchanged, with the results shown in table 3.

Claims (10)

1. A preparation method of water-repellent and oil-repellent meta-aramid is characterized by comprising the following steps:
(1) adding a fluorine-containing diamine monomer and isophthaloyl dichloride into an organic solvent, and performing polycondensation reaction to obtain a fluorine-containing oligomer system;
(2) adding m-phenylenediamine and isophthaloyl chloride into an organic solvent, and performing polycondensation reaction to obtain a polyisophthaloyl m-phenylenediamine system;
(3) mixing the fluorine-containing oligomer system obtained by the reaction in the step (1) with the polyisophthaloyl metaphenylene diamine system obtained by the reaction in the step (2), adding isophthaloyl dichloride, and adding a neutralizing agent when the viscosity of the polymer reaches 40-100 Pa.s to obtain fluorine modified polyisophthaloyl metaphenylene diamine;
(4) solidifying and forming the fluorine modified poly (m-phenylene isophthalamide) obtained by the reaction in the step (3) in a coagulating bath through wet spinning to prepare water-repellent and oil-repellent meta-aramid precursor fibers, washing the precursor fibers, drying and heat setting to prepare the water-repellent and oil-repellent meta-aramid;
in the step (1), the molar ratio of the fluorine-containing diamine monomer to the isophthaloyl dichloride is 1.01: 1-1.05: 1;
in the step (2), the molar ratio of m-phenylenediamine to isophthaloyl dichloride is 1.01: 1-1.05: 1;
the amount of the isophthaloyl dichloride added in the step (3) accounts for 10-30% of the total mass of the isophthaloyl dichloride in the steps (1), (2) and (3).
2. The method for producing a water-and oil-repellent meta-aramid as claimed in claim 1, wherein the organic solvent is one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
3. The preparation method of the water-repellent and oil-repellent meta-aramid fiber according to claim 1, characterized in that the reaction temperature of the step (1) is 0 to 30 ℃ and the reaction temperature of the step (2) is-20 to-10 ℃.
4. The method for preparing water-and oil-repellent meta-aramid according to claim 1, wherein the neutralizing agent of step (3) is one of calcium hydroxide, ammonia and calcium carbonate.
5. The preparation method of the water-repellent and oil-repellent meta-aramid fiber according to claim 1, characterized in that the concentration of the solvent of the wet spinning coagulation bath is 55-65%.
6. The preparation method of the water-repellent and oil-repellent meta-aramid fiber according to claim 1, characterized in that the spinning water washing temperature of the step (4) is 50-80 ℃; and (3) drying at 120-180 ℃ in the spinning process of the step (4) until the water content of the meta-aramid fiber is less than 5%.
7. The preparation method of the water-repellent and oil-repellent meta-aramid fiber according to claim 1, characterized in that the heat setting temperature in the step (4) is 250 to 400 ℃, and the thermal stretching ratio is 1.2 to 6.
8. The preparation method of the water-repellent and oil-repellent meta-aramid fiber according to claim 1, characterized in that the fluorine-containing oligomer obtained in the step (1) has a viscosity of 0.5 to 20 Pa-s; the viscosity of the polyisophthaloyl metaphenylene diamine obtained in the step (2) is 20-40 Pa.s.
9. A water-and oil-repellent meta-aramid fiber characterized by being produced based on the production method described in any one of claims 1 to 8.
10. The water-repellent oil-repellent meta-aramid fiber as claimed in claim 9, wherein the water-repellent oil-repellent modified meta-aramid fiber has a first chemical structural formula:
Figure FDA0003329281500000021
wherein: m is more than or equal to 5 and less than or equal to 20, n is more than or equal to 100 and less than or equal to 200;
r' is-CH3、-OH、
Figure FDA0003329281500000022
-Cl, -Br and-NO2In the above-mentioned manner, the first and second substrates are,
r' is-CH3、-OH、
Figure FDA0003329281500000023
-Cl, -Br and-NO2One of (1);
r is
Figure FDA0003329281500000024
One of (1);
the chemical structural formula II of the water-repellent and oil-repellent meta-aramid is as follows:
Figure FDA0003329281500000031
wherein: x is more than or equal to 5 and less than or equal to 20, and y is more than or equal to 100 and less than or equal to 200;
the chemical structural formula III of the water-repellent and oil-repellent meta-aramid is as follows:
Figure FDA0003329281500000032
wherein: x is more than or equal to 5 and less than or equal to 20, and y is more than or equal to 100 and less than or equal to 200;
r is
Figure FDA0003329281500000033
One kind of (1).
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