CN114000219B - Water-repellent and oil-repellent meta-aramid and preparation method thereof - Google Patents
Water-repellent and oil-repellent meta-aramid and preparation method thereof Download PDFInfo
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- CN114000219B CN114000219B CN202111275875.9A CN202111275875A CN114000219B CN 114000219 B CN114000219 B CN 114000219B CN 202111275875 A CN202111275875 A CN 202111275875A CN 114000219 B CN114000219 B CN 114000219B
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- 239000005871 repellent Substances 0.000 title claims abstract description 97
- 239000004760 aramid Substances 0.000 title claims abstract description 40
- 229920003235 aromatic polyamide Polymers 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000011737 fluorine Substances 0.000 claims abstract description 74
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 74
- 229920000642 polymer Polymers 0.000 claims abstract description 54
- 238000001035 drying Methods 0.000 claims abstract description 47
- 238000009998 heat setting Methods 0.000 claims abstract description 38
- 229920006231 aramid fiber Polymers 0.000 claims abstract description 34
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 26
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 238000002166 wet spinning Methods 0.000 claims abstract description 22
- 229940018564 m-phenylenediamine Drugs 0.000 claims abstract description 21
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 76
- 238000000034 method Methods 0.000 claims description 45
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 30
- 229920000889 poly(m-phenylene isophthalamide) Polymers 0.000 claims description 26
- 238000009987 spinning Methods 0.000 claims description 21
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 16
- 239000000920 calcium hydroxide Substances 0.000 claims description 16
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 16
- ZPSUIVIDQHHIFH-UHFFFAOYSA-N 3-(trifluoromethyl)-4-[2-(trifluoromethyl)phenyl]benzene-1,2-diamine Chemical group FC(F)(F)C1=C(N)C(N)=CC=C1C1=CC=CC=C1C(F)(F)F ZPSUIVIDQHHIFH-UHFFFAOYSA-N 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- -1 m-phenylene isophthalamide chloride Chemical compound 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000001112 coagulating effect Effects 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- YCGKJPVUGMBDDS-UHFFFAOYSA-N 3-(6-azabicyclo[3.1.1]hepta-1(7),2,4-triene-6-carbonyl)benzamide Chemical class NC(=O)C1=CC=CC(C(=O)N2C=3C=C2C=CC=3)=C1 YCGKJPVUGMBDDS-UHFFFAOYSA-N 0.000 abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 25
- 239000004744 fabric Substances 0.000 abstract description 21
- 239000000178 monomer Substances 0.000 abstract description 6
- 230000035699 permeability Effects 0.000 abstract description 4
- 238000005507 spraying Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 42
- 230000008569 process Effects 0.000 description 35
- 239000000835 fiber Substances 0.000 description 28
- 150000004985 diamines Chemical class 0.000 description 23
- 229910052757 nitrogen Inorganic materials 0.000 description 21
- 230000015271 coagulation Effects 0.000 description 17
- 238000005345 coagulation Methods 0.000 description 17
- 230000009194 climbing Effects 0.000 description 16
- 238000006386 neutralization reaction Methods 0.000 description 16
- 230000001276 controlling effect Effects 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 5
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000002940 repellent Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- BEKFRNOZJSYWKZ-UHFFFAOYSA-N 4-[2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(N)C=C1 BEKFRNOZJSYWKZ-UHFFFAOYSA-N 0.000 description 1
- LACZRKUWKHQVKS-UHFFFAOYSA-N 4-[4-[4-amino-2-(trifluoromethyl)phenoxy]phenoxy]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1C(F)(F)F LACZRKUWKHQVKS-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000005007 epoxy-phenolic resin Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
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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
Landscapes
- 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)
- Polyamides (AREA)
Abstract
The invention provides a water-repellent and oil-repellent meta-aramid fiber and a preparation method thereof, wherein the preparation process is as follows: adding fluorine-containing monomers and isophthaloyl dichloride into an organic solvent according to a certain proportion, and carrying out polycondensation reaction to obtain a fluorine-containing oligomer; then adding m-phenylenediamine and m-phthaloyl chloride into an organic solvent according to a certain proportion, and carrying out polycondensation reaction to obtain the poly-m-phthaloyl m-phenylenediamine. Mixing the two polymers, adding isophthaloyl dichloride, and obtaining fluorine modified poly-m-phenylene isophthalamide after the polymer viscosity reaches the requirement. And then preparing the water-repellent and oil-repellent meta-aramid precursor through wet spinning, washing the precursor, drying and heat setting to prepare the water-repellent and oil-repellent meta-aramid. After the meta-aramid fiber 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 gap structure of the fabric.
Description
Technical Field
The invention belongs to the technical field of meta-aramid fibers, and relates to a water-repellent and oil-repellent meta-aramid fiber 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, work such as organization self-rescue, mutual rescue and rescue are good, working environment is outdoor often, strain weather changes and severe environment are needed, and the clothing is regulated by national relevant standards, and has the performances of flame retardance, high temperature resistance, corrosion resistance, static electricity resistance, friction resistance and the like. The meta-aramid fiber has excellent high temperature resistance, flame retardance, mechanical property, electrical insulation and good textile processability, is widely applied to the fields of protective clothing, high-temperature filter materials and composite materials, and is an important basic material of emergency rescue clothing. The presence of amide bonds in the fiber makes it unfavorable for use in humid environments, and is subject to moisture and mold. Therefore, the meta-aramid fiber has water and oil repellent performance, so that the emergency rescue suit can be kept dry and clean in water and heavily polluted environments, the safety and comfort of rescue workers on rescue sites are further improved, and the service life of the emergency rescue suit is prolonged.
The water and oil repellency of the conventional garment fabric mainly comes from the after-finishing method, and the process has the problems of long flow, poor uniformity, more sewage generation, obvious reduction of the water and oil repellency after multiple water washes, and the like. The patent for generating water and oil repellency by post-finishing treatment of meta-aramid fabrics is rarely reported. The problem of water and oil repellent function is solved from the fiber source, the post-treatment procedure 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 meta-aramid fiber with water and oil repellent function is also recently reported.
In order to solve the problem of high-temperature hydrolysis resistance of meta-aramid fiber filter materials, patent CN102628222A is to immerse a filter material blank in a finishing liquid mainly comprising polytetrafluoroethylene emulsion and epoxy phenolic resin, and then to pre-bake at low temperature and crosslink-bake at high temperature, so that a coated and uniformly dispersed polytetrafluoroethylene film is formed on the surface of filter material fibers, water vapor is isolated from contacting the fibers, and the retention rate of transverse and longitudinal breaking strength is more than or equal to 100% after hydrolysis treatment at high temperature. The method has the advantages that the meta-aramid filter material is subjected to after-treatment, the formed film layer has a waterproof function, meanwhile, the penetration of water vapor is blocked, 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 meta-aramid fabrics for clothing. The clothing is worn on the body, has air permeability and certain comfort, and is not suitable for wearing because the fabric is airtight or too hard.
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, solves the problem of how to repel water and oil from the meta-aramid fiber source, and simultaneously keeps the performance of the meta-aramid fiber unchanged in the water washing process of the fabric.
The invention is realized by the following technical scheme:
a preparation method of water-repellent and oil-repellent meta-aramid comprises the following steps of
(1) Adding fluorine-containing diamine monomer and isophthaloyl dichloride into an organic solvent, and carrying out polycondensation reaction to obtain a fluorine-containing oligomer system;
(2) Adding m-phenylenediamine and m-phthaloyl chloride into an organic solvent, and performing polycondensation reaction to obtain a poly m-phthaloyl m-phenylenediamine system;
(3) Mixing the fluorine-containing oligomer system obtained by the reaction in the step (1) and the poly (m-phenylene isophthalamide) obtained by the reaction in the step (2), adding m-phenylene isophthalamide chloride, and adding a neutralizer to obtain fluorine-modified poly (m-phenylene isophthalamide) when the viscosity of the polymer reaches 40-100 Pa.S;
(4) Condensing 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 obtain water-repellent and oil-repellent meta-aramid precursor, washing the precursor, drying and heat setting to obtain the water-repellent and oil-repellent meta-aramid;
the molar ratio of the fluorine-containing diamine monomer to the isophthaloyl dichloride in the step (1) is 1.01:1-1.05:1;
the molar ratio of the m-phenylenediamine to the isophthaloyl dichloride in the step (2) 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 step (1), the step (2) and the step (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 to-10 ℃.
Preferably, the neutralizing agent in step (3) is one of calcium hydroxide, ammonia and calcium carbonate.
Preferably, the concentration of the solvent in the wet spinning coagulation bath is 55-65%.
Preferably, the spinning water washing temperature in the step (4) is 50-80 ℃; and (3) in the spinning process of the step (4), the drying temperature is 120-180 ℃, and the meta-aramid fiber is dried until the moisture content 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; and (3) the viscosity of the poly (m-phenylene isophthalamide) obtained in the step (2) is 20-40 Pa.s.
The water-repellent and oil-repellent meta-aramid is prepared by the preparation method.
Preferably, the water-repellent and oil-repellent modified meta-aramid has a chemical structural formula:
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' isand-NO 2 In one of the above-mentioned processes,
r' isand-NO 2 One of the following;
r comprisesOne of the following;
a water-repellent and oil-repellent meta-aramid fiber has a chemical structural formula II:
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;
a water-repellent and oil-repellent meta-aramid fiber has a chemical structural formula III:
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 comprisesOne of them.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention discloses a water-repellent and oil-repellent meta-aramid fiber, wherein fluorine-containing groups are introduced into a molecular chain of the meta-aramid fiber, so that the fluorine groups can be uniformly distributed on the surface of the fiber, fluorine has natural hydrophobicity and oleophobicity, and the fluorine groups on the surface of the fiber can endow the fiber with the hydrophobicity and oleophobicity. After the fiber with hydrophobicity and oleophobic property is woven into the fabric, the fabric can keep the dryness of the fabric in a dynamic water spraying environment, but the air permeability of the fabric can be ensured by the gap structure of the fabric. Unlike traditional waterproof fabric, the traditional waterproof fabric is formed by attaching a compact waterproof layer on the surface of the fabric through a finishing technology, the pores in the fabric are closed, water vapor cannot pass through, and water vapor in the garment cannot be emitted, so that people feel 'stuffy' in the wearing process. In addition, since the water-and oil-repellent properties of the fibers are derived from the fibers themselves, the properties are not impaired by the falling-off of the active ingredient during wear and washing, and can be permanently maintained.
The invention also discloses a preparation method of the water-repellent and oil-repellent meta-aramid fiber, which takes m-phthaloyl chloride, m-phenylenediamine and fluorine-containing diamine as monomers, and adopts low-temperature polycondensation in an organic solvent to prepare fluorine-modified poly-m-phthaloyl-m-phenylenediamine spinning solution. The aromatic diamine containing fluorine group has high purity industrial products and can meet the actual production requirement. Because of the strong electron-withdrawing effect of fluorine, the polycondensation reaction activation energy of the diamine monomer with introduced fluorine groups and the isophthaloyl dichloride is higher, and is different from the conventional low-temperature polycondensation condition of the isophthaloyl dichloride and the isophthaloyl dichloride, so that a block copolymerization method is adopted, the fluorine-containing groups are uniformly introduced into a polymerization molecular chain by two-step polymerization, the introduction amount of the fluorine groups is ensured, and the effectiveness and durability of the water and oil repellency of the fiber are also ensured.
Drawings
FIG. 1 is a contact angle test of the fluorine modified meta-aramid fiber of example 10;
fig. 2 is a contact angle test of the unmodified meta-aramid of the comparative example.
Detailed Description
The invention will now be described in further detail with reference to specific examples, which are intended to illustrate, but not to limit, the invention.
The invention adopts the technical scheme that fluorine-containing m-phenylenediamine is dissolved in an organic solvent, m-phthaloyl chloride (IPC) is added, and the mixture is polycondensed at a certain temperature to obtain fluorine-containing oligomer; the method comprises the steps of (1) performing low-temperature polycondensation on m-phenylenediamine (MPD) and m-phthaloyl chloride (IPC) in an organic solvent to obtain a poly-m-phthaloyl m-phenylenediamine polymer; and mixing the two materials, adding IPC, stopping the reaction after the solution viscosity reaches the requirement, and obtaining the fluorine modified poly (m-phenylene isophthalamide) polymer.
The water-repellent and oil-repellent modified meta-aramid has a chemical structural formula:
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' includeOne or more of the above-mentioned materials,
r comprisesOne of them.
The water-repellent and oil-repellent modified meta-aramid has a chemical structural formula II:
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.
The water-repellent and oil-repellent modified meta-aramid has a chemical structural formula III:
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, and R comprises One of them.
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 under a nitrogen drying environment, mechanically stirring and dissolving at a rotating speed of 300-1000 r/min, and cooling the 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 controlling the reaction temperature to be 0-30 ℃ in the process of adding the IPC, and reacting for 30-90 min to form a fluorine-containing oligomer solution with the solution viscosity of 0.5-20 Pa.s.
Step 2, adding MPD into an organic solvent in a nitrogen drying environment at room temperature, wherein the molar ratio of MPD to the fluorine-containing diamine in the step 1 is 10-40:1, mechanically stirring and dissolving at the rotating speed of 300-1000 r/min, and cooling the system to-20 to-10 ℃ to form MPD solution; one of DMF, DMAc and NMP is preferably consistent with step 1. And adding IPC into the MPD solution, wherein the molar ratio of the MPD to the IPC is 1.01-1.05:1, controlling the reaction temperature to be-20 to-10 ℃ in the IPC adding process, and heating the whole system to-1-3 ℃, preferably 0 ℃ after reacting for 10-30 min to form the poly (m-phenylene isophthalamide) polymer solution with the viscosity of 20-40 Pa.s.
And step 3, mixing the solutions prepared in the step 1 and the step 2, controlling the temperature to be 5-20 ℃, slowly adding IPC, and finishing the polycondensation reaction when the pole climbing phenomenon occurs. Adding a neutralizing agent into a reaction system, and adjusting the pH value of the whole system to 6-8, wherein the temperature of the whole system is required to be ensured not to exceed 80 ℃ in the process of adding the neutralizing agent so as to prevent side reactions; after the neutralization reaction, the fluorine modified poly (m-phenylene isophthalamide) polymer solution is prepared, and the viscosity is 40-100 Pa.s. The amount of the added isophthaloyl dichloride in the step 3 accounts for 10% -30% of the total amount of the acyl chlorides (the total amount of the added isophthaloyl dichloride in the step 3); the neutralizer in the step 3 is one of calcium hydroxide, ammonia and calcium carbonate.
Step 4, solidifying and forming the prepared fluorine modified poly (m-phenylene isophthalamide) polymer solution in a coagulating bath through wet spinning to obtain a water-repellent and oil-repellent meta-aramid precursor, wherein the technological parameters of the wet spinning refer to patent CN200910259778, and repeatedly washing, drying and heat-setting the water-repellent and oil-repellent modified meta-aramid precursor to obtain the water-repellent and oil-repellent meta-aramid; the concentration of the wet spinning coagulation bath is 55-65%, the drying temperature is 120-180 ℃, the fiber moisture content is less than 5%, the heat setting temperature is 250-450 ℃, the heat stretching multiple is 1.2-6 times, and the heat setting fiber is stably formed.
The invention is further described with reference to the following 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 nitrogen-dry conditions, mechanically stirred at 800r/min until dissolved, and the system was cooled to 10 ℃. To the diamine solution was then added 4.0g of IPC. In the IPC adding process, the reaction temperature is controlled to be 5 ℃, and after the reaction is carried out for 90min, the fluorine-containing oligomer solution is formed, and the solution viscosity is 0.5 Pa.s.
106.6g of MPDA was added to 1L of DMAc at room temperature under nitrogen dry conditions, and after dissolution by mechanical stirring at 800r/min, the system was cooled to-10℃to form an MPDA solution. And then 158.5g of IPC is added into the MPDA solution, the reaction temperature is controlled to be minus 15 ℃ in the adding process, the whole system is heated to 0 ℃ after the reaction is carried out for 30min, and the poly m-phenylene isophthalamide polymer solution with the viscosity of 39 Pa.s is formed.
The solutions prepared in the two steps are mixed in a 2L four-mouth bottle, the temperature is controlled to be 10 ℃, about 40.6g of IPC is slowly added, and when the pole climbing phenomenon occurs, the polycondensation reaction is finished. 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 7.69. After the neutralization reaction, the fluorine modified poly (m-phenylene isophthalamide) polymer solution is prepared, and the viscosity is 63 Pa.s.
The prepared fluorine modified poly m-phenylene isophthalamide polymer solution is subjected to wet spinning to obtain the water-repellent and oil-repellent meta-aramid fiber precursor, 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 heat setting fiber is stably molded.
Example 2
10.4g of 2,2' -bis (trifluoromethyl) diaminobiphenyl and 477ml of DMAc were added to a 1L four-necked flask at room temperature under nitrogen-drying conditions, mechanically stirred at 800r/min until dissolved, and the system was cooled to 10 ℃. To the diamine solution was then added 5.2g of IPC. In the IPC adding process, the reaction temperature is controlled to be 5 ℃, and after the reaction is carried out for 90min, the fluorine-containing oligomer solution is formed, and the solution viscosity is 3 Pa.s.
Under the room temperature and nitrogen drying environment, 105.7g of MPDA is added into 1L of DMAc, and after the MPDA is mechanically stirred and dissolved at the rotating speed of 800r/min, the system is cooled to-10 ℃ to form MPDA solution; . Then adding 157.2g of IPC into the MPDA solution, controlling the reaction temperature to be-15 ℃ in the adding process, and heating the whole system to 0 ℃ after reacting for 30min to form the poly m-phenylene isophthalamide polymer solution with the viscosity of 40 Pa.s.
The solutions prepared in the two steps are mixed in a 2L four-mouth bottle, the temperature is controlled to be 10 ℃, about 40.6g of IPC is slowly added, and when the pole climbing phenomenon occurs, the polycondensation reaction is finished. 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 7.91. After the neutralization reaction, the fluorine modified poly (m-phenylene isophthalamide) polymer solution is prepared, and the viscosity is 66 Pa.s.
The prepared fluorine modified poly m-phenylene isophthalamide polymer solution is subjected to wet spinning to obtain the water-repellent and oil-repellent meta-aramid fiber precursor, 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 heat setting fiber is stably molded.
Example 3
12.4g of 2,2' -bis (trifluoromethyl) diaminobiphenyl and 485ml of DMAc were added to a 1L four-necked flask at room temperature under nitrogen-drying conditions, mechanically stirred at 800r/min until dissolved, and the system was cooled to 10 ℃. 6.2g of IPC was then added to the diamine solution. In the IPC adding process, the reaction temperature is controlled to be 5 ℃, and after the reaction is carried out for 90min, the fluorine-containing oligomer solution is formed, and the solution viscosity is 4 Pa.s.
Under the room temperature and nitrogen drying environment, adding 105g of MPDA into 1L of DMAc, mechanically stirring and dissolving at the rotating speed of 800r/min, and cooling the system to-10 ℃ to form MPDA solution; . 156.2g of IPC is added into the MPDA solution, the reaction temperature is controlled to be minus 15 ℃ in the adding process, the whole system is heated to 0 ℃ after the reaction is carried out for 30min, and the poly m-phenylene isophthalamide polymer solution with the viscosity of 35 Pa.s is formed.
The solutions prepared in the two steps are mixed in a 2L four-mouth bottle, the temperature is controlled to be 10 ℃, about 40.6g of IPC is slowly added, and when the pole climbing phenomenon occurs, the polycondensation reaction is finished. 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. After the neutralization reaction, the fluorine modified poly (m-phenylene isophthalamide) polymer solution is prepared, and the viscosity is 61 Pa.s.
The prepared fluorine modified poly m-phenylene isophthalamide polymer solution is subjected to wet spinning to obtain the water-repellent and oil-repellent meta-aramid fiber precursor, 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 heat setting fiber is stably molded.
Example 4
15.4g of 2,2' -bis (trifluoromethyl) diaminobiphenyl and 496ml of DMAc were added to a 1L four-necked flask at room temperature under nitrogen-dry conditions, mechanically stirred at 800r/min until dissolved, and the system was cooled to 10 ℃. 7.7g of IPC was then added to the diamine solution. In the IPC adding process, the reaction temperature is controlled to be 5 ℃, and after the reaction is carried out for 90min, the fluorine-containing oligomer solution is formed, and the solution viscosity is 6 Pa.s.
Under the room temperature and nitrogen drying environment, adding 104g of MPDA into 1L of DMAc, mechanically stirring and dissolving at the rotating speed of 800r/min, and cooling the system to-10 ℃ to form MPDA solution; . 154.7g of IPC is added into the MPDA solution, the reaction temperature is controlled to be minus 15 ℃ in the adding process, the whole system is heated to 0 ℃ after the reaction is carried out for 30min, and the poly m-phenylene isophthalamide polymer solution with the viscosity of 37 Pa.s is formed.
The solutions prepared in the two steps are mixed in a 2L four-mouth bottle, the temperature is controlled to be 10 ℃, about 40.6g of IPC is slowly added, and when the pole climbing phenomenon occurs, the polycondensation reaction is finished. 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 7.83. After the neutralization reaction, the fluorine modified poly (m-phenylene isophthalamide) polymer solution is prepared, and the viscosity is 67 Pa.s.
The prepared fluorine modified poly m-phenylene isophthalamide polymer solution is subjected to wet spinning to obtain the water-repellent and oil-repellent meta-aramid fiber precursor, 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 heat setting fiber is stably molded.
Example 5
20.2g of 2,2' -bis (trifluoromethyl) diaminobiphenyl and 510ml of DMAc were added to a 1L four-necked flask at room temperature under nitrogen-drying conditions, mechanically stirred at 800r/min until dissolved, and the system was cooled to 10 ℃. To the diamine solution was then added 10.2g of IPC. In the IPC adding process, the reaction temperature is controlled to be 5 ℃, and after the reaction is carried out for 90min, the fluorine-containing oligomer solution is formed, and the solution viscosity is 7 Pa.s.
102.7g of MPDA is added into 1L of DMAc under the condition of room temperature and nitrogen drying, and after the MPDA is mechanically stirred and dissolved at the rotating speed of 800r/min, the system is cooled to-10 ℃ to form MPDA solution; . And adding 152.3g of IPC into the MPDA solution, controlling the reaction temperature to be-15 ℃ in the adding process, and heating the whole system to 0 ℃ after reacting for 30min to form the poly m-phenylene isophthalamide polymer solution with the viscosity of 31 Pa.s.
The solutions prepared in the two steps are mixed in a 2L four-mouth bottle, the temperature is controlled to be 10 ℃, about 40.6g of IPC is slowly added, and when the pole climbing phenomenon occurs, the polycondensation reaction is finished. 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 7.71. After the neutralization reaction, the fluorine modified poly (m-phenylene isophthalamide) polymer solution is prepared, and the viscosity is 63 Pa.s.
The prepared fluorine modified poly m-phenylene isophthalamide polymer solution is subjected to wet spinning to obtain the water-repellent and oil-repellent meta-aramid fiber precursor, 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 heat setting fiber is stably molded.
Example 6
29.5g of 2,2' -bis (trifluoromethyl) diaminobiphenyl and 570ml of DMAc were added to a 1L four-necked flask at room temperature under nitrogen-drying conditions, mechanically stirred at 800r/min until dissolved, and the system was cooled to 10 ℃. To the diamine solution was then added 14.8g of IPC. In the IPC adding process, the reaction temperature is controlled to be 5 ℃, and after the reaction is carried out for 90min, the fluorine-containing oligomer solution is formed, and the solution viscosity is 9 Pa.s.
99.5g of MPDA is added into 1L of DMAc under the condition of room temperature and nitrogen drying, and after the MPDA is mechanically stirred and dissolved at the rotating speed of 800r/min, the system is cooled to-10 ℃ to form MPDA solution; . Adding 147.7g of IPC into the MPDA solution, controlling the reaction temperature to be-15 ℃ in the adding process, and heating the whole system to 0 ℃ after reacting for 30min to form the poly m-phenylene isophthalamide polymer solution with the viscosity of 30 Pa.s.
The solutions prepared in the two steps are mixed in a 2L four-mouth bottle, the temperature is controlled to be 10 ℃, about 40.6g of IPC is slowly added, and when the pole climbing phenomenon occurs, the polycondensation reaction is finished. 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 7.68. After the neutralization reaction, the fluorine modified poly (m-phenylene isophthalamide) polymer solution is prepared, and the viscosity is 67 Pa.s.
The prepared fluorine modified poly m-phenylene isophthalamide polymer solution is subjected to wet spinning to obtain the water-repellent and oil-repellent meta-aramid fiber precursor, 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 heat setting fiber is stably molded.
Example 7
21.0g of 2,2' -bis (trifluoromethyl) diaminobiphenyl and 510ml of DMAc were added to a 1L four-necked flask at room temperature under nitrogen-drying conditions, mechanically stirred at 800r/min until dissolved, and the system was cooled to 10 ℃. To the diamine solution was then added 10.2g of IPC. In the IPC adding process, the reaction temperature is controlled to be 5 ℃, and after the reaction is carried out for 90min, the fluorine-containing oligomer solution is formed, and the solution viscosity is 5 Pa.s.
Under the room temperature and nitrogen drying environment, 106.5g of MPDA is added into 1L of DMAc, and after the MPDA is mechanically stirred and dissolved at the rotating speed of 800r/min, the system is cooled to-10 ℃ to form MPDA solution; . And adding 152.3g of IPC into the MPDA solution, controlling the reaction temperature to be-15 ℃ in the adding process, and heating the whole system to 0 ℃ after reacting for 30min to form the poly m-phenylene isophthalamide polymer solution with the viscosity of 30 Pa.s.
The solutions prepared in the two steps are mixed in a 2L four-mouth bottle, the temperature is controlled to be 10 ℃, about 40.6g of IPC is slowly added, and when the pole climbing phenomenon occurs, the polycondensation reaction is finished. 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 7.58. After the neutralization reaction, the fluorine modified poly (m-phenylene isophthalamide) polymer solution is prepared, and the viscosity is 70 Pa.s.
The prepared fluorine modified poly m-phenylene isophthalamide polymer solution is subjected to wet spinning to obtain the water-repellent and oil-repellent meta-aramid fiber precursor, 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 heat setting fiber is stably molded.
Example 8
20.8g of 2,2' -bis (trifluoromethyl) diaminobiphenyl and 510ml of DMAc were added to a 1L four-necked flask at room temperature under nitrogen-drying conditions, mechanically stirred at 800r/min until dissolved, and the system was cooled to 10 ℃. To the diamine solution was then added 10.2g of IPC. In the IPC adding process, the reaction temperature is controlled to be 5 ℃, and after the reaction is carried out for 90min, the fluorine-containing oligomer solution is formed, and the solution viscosity is 7 Pa.s.
Under the room temperature and nitrogen drying environment, 105.4g of MPDA is added into 1L of DMAc, and after the MPDA is mechanically stirred and dissolved at the rotating speed of 800r/min, the system is cooled to-10 ℃ to form MPDA solution; . And adding 152.3g of IPC into the MPDA solution, controlling the reaction temperature to be-15 ℃ in the adding process, and heating the whole system to 0 ℃ after reacting for 30min to form the poly m-phenylene isophthalamide polymer solution with the viscosity of 33 Pa.s.
The solutions prepared in the two steps are mixed in a 2L four-mouth bottle, the temperature is controlled to be 10 ℃, about 40.6g of IPC is slowly added, and when the pole climbing phenomenon occurs, the polycondensation reaction is finished. 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 7.77. After the neutralization reaction, the fluorine modified poly (m-phenylene isophthalamide) polymer solution is prepared, and the viscosity is 71 Pa.s.
The prepared fluorine modified poly m-phenylene isophthalamide polymer solution is subjected to wet spinning to obtain the water-repellent and oil-repellent meta-aramid fiber precursor, 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 heat setting fiber is stably molded.
Example 9
20.6g of 2,2' -bis (trifluoromethyl) diaminobiphenyl and 510ml of DMAc were added to a 1L four-necked flask at room temperature under nitrogen-drying conditions, mechanically stirred at 800r/min until dissolved, and the system was cooled to 10 ℃. To the diamine solution was then added 10.2g of IPC. In the IPC adding process, the reaction temperature is controlled to be 5 ℃, and after the reaction is carried out for 90min, the fluorine-containing oligomer solution is formed, and the solution viscosity is 6 Pa.s.
104.4g of MPDA is added into 1L of DMAc under the condition of room temperature and nitrogen drying, and after the MPDA is mechanically stirred and dissolved at the rotating speed of 800r/min, the system is cooled to-10 ℃ to form MPDA solution; . And adding 152.3g of IPC into the MPDA solution, controlling the reaction temperature to be-15 ℃ in the adding process, and heating the whole system to 0 ℃ after reacting for 30min to form the poly m-phenylene isophthalamide polymer solution with the viscosity of 37 Pa.s.
The solutions prepared in the two steps are mixed in a 2L four-mouth bottle, the temperature is controlled to be 10 ℃, about 40.6g of IPC is slowly added, and when the pole climbing phenomenon occurs, the polycondensation reaction is finished. 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 7.71. After the neutralization reaction, the fluorine modified poly (m-phenylene isophthalamide) polymer solution is prepared, and the viscosity is 69 Pa.s.
The prepared fluorine modified poly m-phenylene isophthalamide polymer solution is subjected to wet spinning to obtain the water-repellent and oil-repellent meta-aramid fiber precursor, 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 heat setting fiber is stably molded.
Example 10
20.4g of 2,2' -bis (trifluoromethyl) diaminobiphenyl and 510ml of DMAc were added to a 1L four-necked flask at room temperature under nitrogen-drying conditions, mechanically stirred at 800r/min until dissolved, and the system was cooled to 10 ℃. To the diamine solution was then added 10.2g of IPC. In the IPC adding process, the reaction temperature is controlled to be 5 ℃, and after the reaction is carried out for 90min, the fluorine-containing oligomer solution is formed, and the solution viscosity is 5 Pa.s.
Under the room temperature and nitrogen drying environment, 103.4g of MPDA is added into 1L of DMAc, and after the MPDA is mechanically stirred and dissolved at the rotating speed of 800r/min, the system is cooled to-10 ℃ to form MPDA solution; . And adding 152.3g of IPC into the MPDA solution, controlling the reaction temperature to be-15 ℃ in the adding process, and heating the whole system to 0 ℃ after reacting for 30min to form the poly m-phenylene isophthalamide polymer solution with the viscosity of 30 Pa.s.
The solutions prepared in the two steps are mixed in a 2L four-mouth bottle, the temperature is controlled to be 10 ℃, about 40.6g of IPC is slowly added, and when the pole climbing phenomenon occurs, the polycondensation reaction is finished. 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. After the neutralization reaction, the fluorine modified poly (m-phenylene isophthalamide) polymer solution is prepared, and the viscosity is 72 Pa.s.
The prepared fluorine modified poly m-phenylene isophthalamide polymer solution is subjected to wet spinning to obtain the water-repellent and oil-repellent meta-aramid fiber precursor, 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 heat setting fiber is stably molded.
Example 11
21.3g of 2, 2-bis (4-aminophenyl) hexafluoropropane and 510ml of DMAc were added to a 1L four-necked flask at room temperature under nitrogen dry conditions, mechanically stirred at 800r/min until dissolved, and the system was cooled to 10 ℃. To the diamine solution was then added 10.2g of IPC. In the IPC adding process, the reaction temperature is controlled to be 5 ℃, and after the reaction is carried out for 90min, the fluorine-containing oligomer solution is formed, and the solution viscosity is 8 Pa.s.
Under the room temperature and nitrogen drying environment, 103.4g of MPDA is added into 1L of DMAc, and after the MPDA is mechanically stirred and dissolved at the rotating speed of 800r/min, the system is cooled to-10 ℃ to form MPDA solution; . And adding 152.3g of IPC into the MPDA solution, controlling the reaction temperature to be-15 ℃ in the adding process, and heating the whole system to 0 ℃ after reacting for 30min to form the poly m-phenylene isophthalamide polymer solution with the viscosity of 36 Pa.s.
The solutions prepared in the two steps are mixed in a 2L four-mouth bottle, the temperature is controlled to be 10 ℃, about 40.6g of IPC is slowly added, and when the pole climbing phenomenon occurs, the polycondensation reaction is finished. 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. After the neutralization reaction, the fluorine modified poly (m-phenylene isophthalamide) polymer solution is prepared, and the viscosity is 80 Pa.s.
The prepared fluorine modified poly m-phenylene isophthalamide polymer solution is subjected to wet spinning to obtain the water-repellent and oil-repellent meta-aramid fiber precursor, 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 heat setting fiber is stably molded.
Example 12
33.03g of 2, 2-bis [4- (4-aminophenoxy) ] hexafluoropropane and 510ml of DMAc were added to a 1L four-necked flask at room temperature under nitrogen dry conditions, mechanically stirred at 800r/min until dissolved, and the system was cooled to 10 ℃. To the diamine solution was then added 10.2g of IPC. In the IPC adding process, the reaction temperature is controlled to be 5 ℃, and after the reaction is carried out for 90min, the fluorine-containing oligomer solution is formed, and the solution viscosity is 7 Pa.s.
Under the room temperature and nitrogen drying environment, 103.4g of MPDA is added into 1L of DMAc, and after the MPDA is mechanically stirred and dissolved at the rotating speed of 800r/min, the system is cooled to-10 ℃ to form MPDA solution; . And adding 152.3g of IPC into the MPDA solution, controlling the reaction temperature to be-15 ℃ in the adding process, and heating the whole system to 0 ℃ after reacting for 30min to form the poly m-phenylene isophthalamide polymer solution with the viscosity of 33 Pa.s.
The solutions prepared in the two steps are mixed in a 2L four-mouth bottle, the temperature is controlled to be 10 ℃, about 40.6g of IPC is slowly added, and when the pole climbing phenomenon occurs, the polycondensation reaction is finished. 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. After the neutralization reaction, the fluorine modified poly (m-phenylene isophthalamide) polymer solution is prepared, and the viscosity is 79 Pa.s.
The prepared fluorine modified poly m-phenylene isophthalamide polymer solution is subjected to wet spinning to obtain the water-repellent and oil-repellent meta-aramid fiber precursor, 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 heat setting fiber is stably molded.
Example 13
27.29g of 1, 4-bis- (4 '-amino-2' -trifluoromethylphenoxy) benzene and 510ml of DMF were added to a 1L four-necked flask at room temperature under nitrogen dry conditions, mechanically stirred at 1000r/min until dissolved, and the system was cooled to 0 ℃. To the diamine solution was then added 10.2g of IPC. In the IPC adding process, the reaction temperature is controlled to be 30 ℃, and after the reaction is carried out for 30min, a fluorine-containing oligomer solution is formed, and the solution viscosity is 15 Pa.s.
Under the condition of room temperature and nitrogen drying, 103.4g of MPDA is added into 1L of DMF, and after the MPDA is mechanically stirred and dissolved at the rotating speed of 1000r/min, the system is cooled to-20 ℃ to form MPDA solution; . And adding 152.3g of IPC into the MPDA solution, controlling the reaction temperature to be-10 ℃ in the adding process, and heating the whole system to 0 ℃ after reacting for 10min to form the poly m-phenylene isophthalamide polymer solution with the viscosity of 39 Pa.s.
The solutions prepared in the two steps are mixed in a 2L four-mouth bottle, the temperature is controlled to be 20 ℃, about 40.6g of IPC is slowly added, and when the pole climbing phenomenon occurs, the polycondensation reaction is finished. Ammonia was added to the reaction system, the whole system was slowly warmed to 50 ℃ and the pH of the whole system was adjusted to 7.85. After the neutralization reaction, the fluorine modified poly (m-phenylene isophthalamide) polymer solution is prepared, and the viscosity is 85 Pa.s.
The prepared fluorine modified poly m-phenylene isophthalamide polymer solution is subjected to wet spinning to obtain the water-repellent and oil-repellent meta-aramid fiber precursor, 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 heat setting fiber is stably molded.
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 nitrogen drying, mechanically stirred at 300r/min until dissolved, and the system was cooled to 10 ℃. To the diamine solution was then added 10.2g of IPC. In the IPC adding process, the reaction temperature is controlled to be 0 ℃, and after the reaction is carried out for 90min, the fluorine-containing oligomer solution is formed, and the solution viscosity is 20 Pa.s.
Under the room temperature and nitrogen drying environment, 103.4g of MPDA is added into 1L of NMP, and after the MPDA is mechanically stirred and dissolved at the rotating speed of 300r/min, the system is cooled to-20 ℃ to form MPDA solution; . And adding 152.3g of IPC into the MPDA solution, controlling the reaction temperature to be-20 ℃ in the adding process, and heating the whole system to 3 ℃ after reacting for 30min to form the poly m-phenylene isophthalamide polymer solution with the viscosity of 40 Pa.s.
The solutions prepared in the two steps are mixed in a 2L four-mouth bottle, the temperature is controlled to be 5 ℃, about 40.6g of IPC is slowly added, and when the pole climbing phenomenon occurs, the polycondensation reaction is finished. 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 7.90. After the neutralization reaction, the fluorine modified poly (m-phenylene isophthalamide) polymer solution is prepared, and the viscosity is 100 Pa.s.
The prepared fluorine modified poly m-phenylene isophthalamide polymer solution is subjected to wet spinning to obtain the water-repellent and oil-repellent meta-aramid fiber precursor, 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 heat setting fiber is stably molded.
Comparative example
109.2g of MPDA is added into 1435ml of DMAc under the condition of room temperature and nitrogen drying, and after the solution is mechanically stirred and dissolved at the rotating speed of 800r/min, the system is cooled to-10 ℃ to form MPDA solution; . 162.4g of IPC is added into MPDA solution, the reaction temperature is controlled to be minus 15 ℃ in the adding process, the whole system is heated to 0 ℃ after the reaction is carried out for 30min, and the poly m-phenylene isophthalamide polymer solution with the viscosity of 35 Pa.s is formed. Then slowly adding about 40.6g of IPC, controlling the system temperature at 10 ℃, and finishing the polycondensation reaction when the pole climbing phenomenon occurs. 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 7.59. After the neutralization reaction, the fluorine modified poly (m-phenylene isophthalamide) polymer solution is prepared, and the viscosity is 70 Pa.s.
And (3) preparing meta-aramid fiber precursor by wet spinning of the prepared poly m-phenylene isophthalamide polymer solution, 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 heat setting fiber is stably formed.
TABLE 1 polymerization conditions and spinning solution physical Properties index for examples and comparative examples
TABLE 2 test results of Water and oil repellency of fluorine modified meta-aramid
TABLE 3 Water and oil repellency after 50 times of washing of fluorine-modified meta-aramid
TABLE 4 flame retardance and mechanical Property test results of fluorine modified meta-aramid
According to the results of examples, the fluorine-modified meta-aramid has good mechanical properties, the fluorine-modified meta-aramid fabric has good water and oil repellency, the fabrics of examples 5, 7, 8, 9 and 10 have water repellency rating of 9, and the oil repellency rating of 7, and the results are shown in tables 2 and 4. Fig. 1 is a contact angle test of the modified meta-aramid in example 10, and fig. 2 is a contact angle test of the meta-aramid which is not neutral in comparative example, and the result shows that the water repellency after fluorine modification is significantly improved.
The meta-aramid fabrics of examples 5, 7, 8, 9, 10 and comparative examples were respectively subjected to 50 water washes and tested to keep their oil and water repellency rating unchanged, and the results are shown in table 3.
Claims (8)
1. The preparation method of the water-repellent and oil-repellent meta-aramid is characterized by comprising the following steps of:
(1) Adding 2,2' -di (trifluoromethyl) diaminobiphenyl and isophthaloyl dichloride into an organic solvent, and performing polycondensation reaction to obtain a fluorine-containing oligomer system, wherein the viscosity of the fluorine-containing oligomer is 0.5-20 Pa.s;
(2) The m-phenylenediamine and m-phthaloyl chloride are added into an organic solvent to undergo a polycondensation reaction to obtain a poly m-phthaloyl m-phenylenediamine system, and the viscosity of the poly m-phthaloyl m-phenylenediamine is 20-40 Pa.s;
(3) Mixing the fluorine-containing oligomer system obtained by the reaction in the step (1) and the poly (m-phenylene isophthalamide) obtained by the reaction in the step (2), adding m-phenylene isophthalamide chloride, and adding a neutralizer to obtain fluorine-modified poly (m-phenylene isophthalamide) when the viscosity of the polymer reaches 40-100 Pa.s;
(4) Condensing and forming the fluorine modified poly (m-phenylene isophthalamide) obtained by the reaction in the step (3) in a coagulating bath through wet spinning, wherein the concentration of a coagulating bath solvent is 55-65%, obtaining a water-repellent and oil-repellent meta-aramid precursor, washing the precursor, drying and heat-setting to obtain the water-repellent and oil-repellent meta-aramid;
the molar ratio of the 2,2' -bis (trifluoromethyl) diaminobiphenyl to the isophthaloyl dichloride in the step (1) is 1.01:1-1.05:1;
the molar ratio of the m-phenylenediamine to the isophthaloyl dichloride in the step (2) 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);
the molar ratio of the 2,2' -bis (trifluoromethyl) diaminobiphenyl to the m-phenylenediamine is 1:15.
2. The method for preparing water-repellent and oil-repellent meta-aramid according to claim 1, wherein the organic solvent is one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
3. The method for preparing water-repellent and oil-repellent meta-aramid according to claim 1, wherein the reaction temperature of the step (1) is 0-30 ℃, and the reaction temperature of the step (2) is-20 to-10 ℃.
4. The method for preparing water-repellent and oil-repellent meta-aramid according to claim 1, wherein the neutralizing agent of the step (3) is one of calcium hydroxide, ammonia and calcium carbonate.
5. The method for preparing water-repellent and oil-repellent meta-aramid according to claim 1, wherein the spinning water-washing temperature of the step (4) is 50-80 ℃; and (3) in the spinning process of the step (4), the drying temperature is 120-180 ℃, and the meta-aramid fiber is dried until the moisture content is less than 5%.
6. The method for preparing water-repellent and oil-repellent meta-aramid according to claim 1, wherein the heat setting temperature in the step (4) is 250-400 ℃ and the heat stretching multiple is 1.2-6 times.
7. A water-and oil-repellent meta-aramid produced based on the production method according to any one of claims 1 to 6.
8. The water-and oil-repellent meta-aramid of claim 7 wherein the chemical structure of the water-and oil-repellent meta-aramid is:
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.
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