CN117966294A - Fiber and preparation method thereof - Google Patents
Fiber and preparation method thereof Download PDFInfo
- Publication number
- CN117966294A CN117966294A CN202410369977.4A CN202410369977A CN117966294A CN 117966294 A CN117966294 A CN 117966294A CN 202410369977 A CN202410369977 A CN 202410369977A CN 117966294 A CN117966294 A CN 117966294A
- Authority
- CN
- China
- Prior art keywords
- monomer
- fiber
- dihydrazide
- hydrazide
- chain segment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 117
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 171
- 229920000642 polymer Polymers 0.000 claims abstract description 39
- 238000009987 spinning Methods 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical group C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000001263 acyl chlorides Chemical group 0.000 claims abstract description 17
- 238000006116 polymerization reaction Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 22
- 239000011230 binding agent Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical group ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 9
- 125000000623 heterocyclic group Chemical group 0.000 claims description 9
- 239000003495 polar organic solvent Substances 0.000 claims description 7
- 239000006227 byproduct Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 4
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 3
- FJVIHKKXPLPDSV-UHFFFAOYSA-N 4-phenoxybenzene-1,2-diamine Chemical compound C1=C(N)C(N)=CC=C1OC1=CC=CC=C1 FJVIHKKXPLPDSV-UHFFFAOYSA-N 0.000 claims description 3
- 150000001491 aromatic compounds Chemical group 0.000 claims description 3
- 150000004984 aromatic diamines Chemical group 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 3
- 229920006231 aramid fiber Polymers 0.000 abstract description 22
- 238000004043 dyeing Methods 0.000 abstract description 8
- 239000004753 textile Substances 0.000 abstract description 3
- 239000000543 intermediate Substances 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 26
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000007788 liquid Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 239000004760 aramid Substances 0.000 description 10
- 229920003235 aromatic polyamide Polymers 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000004744 fabric Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 150000007522 mineralic acids Chemical class 0.000 description 6
- 150000007524 organic acids Chemical class 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000000670 limiting effect Effects 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000002798 polar solvent Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 238000002166 wet spinning Methods 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000036961 partial effect Effects 0.000 description 3
- 229920000889 poly(m-phenylene isophthalamide) Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- -1 aryl amide Chemical class 0.000 description 2
- ALHNLFMSAXZKRC-UHFFFAOYSA-N benzene-1,4-dicarbohydrazide Chemical compound NNC(=O)C1=CC=C(C(=O)NN)C=C1 ALHNLFMSAXZKRC-UHFFFAOYSA-N 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 235000012255 calcium oxide Nutrition 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 238000011143 downstream manufacturing Methods 0.000 description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical group OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009954 braiding Methods 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical group O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- DIHKMUNUGQVFES-UHFFFAOYSA-N n,n,n',n'-tetraethylethane-1,2-diamine Chemical compound CCN(CC)CCN(CC)CC DIHKMUNUGQVFES-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Artificial Filaments (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention relates to a fiber and a preparation method thereof, which belong to the technical field of textile printing and dyeing, and the preparation method comprises the following steps: selecting a binary hydrazide monomer, and reacting the first monomer with a second monomer to prepare a high polymer intermediate containing a hydrazide acyl chloride chain segment and an aryl amide chain segment; spinning the polymer intermediate to obtain a nascent fiber; and heating and post-treating the nascent fiber to obtain the fiber containing oxadiazole groups. Compared with the prior aramid fiber, the fiber has the problems of poor high-temperature dimensional stability, wearing comfort, poor dyeability and the like, and has greatly improved size stability under a high-temperature state.
Description
Technical Field
The invention relates to the technical field of textile printing and dyeing, in particular to a fiber and a preparation method thereof.
Background
Poly (m-PHENYLENE ISOPHTHALAMIDE), PMIA for short, which is prepared into fiber with decomposition temperature up to 500 deg.C, long-term use temperature higher than 230 deg.C, limiting oxygen index higher than 29, excellent high-temperature acid-base resistance, electric insulation and good textile processing property, is widely used in the fields of protective clothing, high-temperature filter material, electric appliance industry and composite material, and is an indispensable strategic important material in national economic development. However, meta-aramid fiber molecules are arranged in a zigzag manner, wherein amide groups belong to flexible connection points, and the meta-aramid fiber molecules can generate, vibrate, rotate and rearrange at high temperature, so that the aramid fiber molecules have remarkable thermal shrinkage when the temperature changes, and the meta-aramid fiber molecules are not favorable for stable size at high temperature, so that the improvement of the high temperature resistance of the aramid fiber molecules is further limited.
Meanwhile, as the molecular structure of the aramid fiber is regular, the crystallinity is high and the molecular chain lacks active functional groups, dye or pigment molecules are difficult to permeate into the structure of the aramid fiber, and the polymerized aramid fiber molecules are difficult to combine with the dye or pigment molecules, so that the aramid fiber and the prepared fabric are difficult to dye, and the application of the aramid fiber modified fiber in the field of high-temperature resistant protection is a short plate.
In addition, meta-aramid fiber has the disadvantage of low water absorption (4-5%) and poor wearing comfort.
Thus, there is a need in the art to further improve the high temperature dimensional stability, wearing comfort and dyeability of meta-aramid.
Disclosure of Invention
In view of the above analysis, the present invention aims to provide a fiber and a preparation method thereof, which are used for improving at least one of the problems of poor high-temperature dimensional stability, poor wearing comfort, poor dyeability and the like of the existing fiber.
The aim of the invention is mainly realized by the following technical scheme:
a method of making a fiber comprising:
Step 1: selecting a binary hydrazide monomer, and reacting the first monomer with a second monomer to prepare a high polymer intermediate containing a hydrazide acyl chloride chain segment and an aryl amide chain segment;
Step 2: spinning the polymer intermediate to obtain a nascent fiber;
step 3: and heating and post-treating the nascent fiber to obtain the fiber containing oxadiazole groups.
Preferably, the first monomer comprises an amino group and the second monomer comprises a formyl group; preferably, the first monomer is an aromatic diamine monomer and the second monomer is a diacid chloride monomer.
Preferably, the first monomer is one or more of m-phenylenediamine, p-phenylenediamine and 3, 4-diaminodiphenyl ether; and/or the second monomer is isophthaloyl dichloride or a mixture of isophthaloyl dichloride and terephthaloyl dichloride.
Preferably, the dibasic hydrazide monomer is an aromatic compound containing two primary hydrazides; preferably, the dihydrazide monomer is an aromatic dihydrazide; further preferably, the dihydrazide monomer is one or more of isophthalhydrazide and terephthalhydrazide.
Preferably, the monomer with the substituent group in the meta-position structure in the first monomer and the dihydrazide monomer accounts for 80-100% of the total molar weight of the first monomer and the dihydrazide monomer, and the monomer with the substituent group in the para-position structure in the first monomer and the dihydrazide monomer accounts for 0-20% of the total molar weight of the first monomer and the dihydrazide monomer.
Preferably, the molar ratio of the substituent groups in the first monomer and the dihydrazide monomer to the para-structure monomer is less than or equal to 10 percent.
Preferably, the molar ratio of the substituent meta-structure monomer in the second monomer is not more than 5%.
Preferably, the second monomer is added two or more times in step 1, comprising the steps of:
S101, dissolving a binary hydrazide monomer and a first monomer in a polar organic solvent;
S102, adding a second monomer into the mixed system in S101 for multiple times, performing multiple times of prepolymerization, adding an acid-binding agent after the prepolymerization, precipitating and separating a reaction product of the acid-binding agent and a prepolymerization byproduct, and then continuing to add the second monomer for polymerization to obtain a polymer intermediate containing a hydrazide acyl chloride chain segment and an aryl amide chain segment.
Preferably, the polar organic solvent in the step 101 is any one of N-dimethylacetamide, dimethylformamide and N-methylpyrrolidone.
A fiber prepared by the fiber preparation method comprises an aromatic structure and a heterocyclic structure for connecting the aromatic structure.
Preferably, the fiber comprises the following structure (i):
（Ⅰ）。
compared with the prior art, the invention has at least one of the following beneficial effects:
(1) The fiber has low heat shrinkage rate, which is lower than 2% at 400 ℃ and is far lower than 4-7% of meta-aramid fiber, thereby improving the dimensional stability of the protective woven garment in a high-temperature state.
(2) The fiber of the invention has strong hygroscopicity and good hydrophilicity, which is up to 6-12% and is higher than 4-5% of meta-aramid fiber. Comfort is improved when a person wears a fabric made using the fiber.
(3) The heat resistance and glass transition temperature of the product are higher than 280 ℃, so that the long-term use temperature can reach 250 ℃ and is higher than 220 ℃ of meta-aramid.
(4) The flame retardance of the product is high, the limiting oxygen index reaches 30-32%, and the relative meta-position aramid fiber is further improved by 28-29%.
(5) The meta-aramid fiber product of the invention has no reduction of the relative strength and elongation at break of the fiber, no reduction of the processability in the downstream processing field, and is very suitable for processing such as spinning.
(6) The product of the invention has obviously improved K/S value relative to meta-aramid dyeability, is convenient for dyeing and coloring after spinning, and has the K/S value of more than 1, preferably 1-8.
In the invention, the technical schemes can be mutually combined to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, like reference numerals being used to designate like parts throughout the drawings;
FIG. 1 is a flow chart of a fiber preparation process in one embodiment of the present invention.
Detailed Description
The following detailed description of preferred embodiments of the invention is made in connection with the accompanying drawings, which form a part hereof, and together with the description of the embodiments of the invention, are used to explain the principles of the invention and are not intended to limit the scope of the invention.
In one aspect of the deficiencies of the prior art, the present invention discloses a fiber comprising an aromatic structure and a heterocyclic structure for attachment of the aromatic structure.
Specifically, the fibers may be obtained by incorporating heterocyclic structures into the aramid molecules.
It can be understood that the invention introduces a heterocyclic structure into the traditional aramid fiber molecule, and improves the high temperature resistance, the thermal stability, the high temperature mechanical strength and the dyeability of the fiber molecule.
In particular, the heterocyclic structure is a rigid structure in which all atoms are coplanar.
Specifically, the number of the constituent atoms of the heterocyclic structure is more than or equal to 5, and at least two double bonds are contained.
In particular, the heterocyclic structure may be an oxadiazole structure.
Preferably, the heterocyclic structure may be a connection structure of benzene rings in the modified aramid molecule.
Specifically, the fiber includes:
（Ⅰ）。
It can be understood that the benzene rings in (I) are connected through the oxadiazole structure, all atoms in the oxadiazole are coplanar, and all atoms in the oxadiazole vibrate and rotate in the same plane when the temperature is changed, so that the degree of freedom is obviously reduced compared with that of the traditional aramid fiber.
In another aspect, the invention discloses a method of making a fiber comprising:
Preparing an aryl polymer intermediate comprising a hydrazide acyl chloride segment; and spinning the aryl polymer intermediate and then carrying out heat treatment to obtain the fiber containing the oxadiazole group.
It can be understood that the fiber containing oxadiazole groups has strong rigidity and difficult spinning and forming; according to the invention, a softer hydrazide acyl chloride chain segment is introduced into a spinning raw material, and the hydrazide acyl chloride chain segment is treated to obtain the oxadiazole group after spinning is finished, so that the defect that the fiber of the oxadiazole group is difficult to spin and form is overcome.
Specifically, the preparation of the fiber comprises the following steps:
Step 1: selecting a binary hydrazide monomer, and reacting the first monomer with a second monomer to prepare a high polymer intermediate containing a hydrazide acyl chloride chain segment and an aryl amide chain segment;
Step 2: spinning the polymer intermediate to obtain a nascent fiber;
step 3: and heating and post-treating the nascent fiber to obtain the fiber containing oxadiazole groups.
In the implementation, step 1 generates a corresponding hydrazide acyl chloride chain segment through the reaction of hydrazide and acyl chloride; simultaneously, the first monomer reacts with acyl chloride to generate an aryl amide segment;
step2, spinning and forming the polymer intermediate prepared in the step 1 to obtain nascent fibers;
And step 3, heating the hydrazide acyl chloride chain segment in the nascent fiber, and then converting the hydrazide acyl chloride chain segment into an oxadiazole group to obtain the fiber.
Specifically, step 1 is performed in a polar organic solvent.
Specifically, the polar organic solvent may be selected from any one of N-dimethylacetamide, dimethylformamide (DMF), and N-methylpyrrolidone, which has good solubility to the raw material monomer and does not react with any raw material monomer.
Preferably, the step 1 preparation comprises: and (3) carrying out one-time prepolymerization according to the insufficient quantity of the second monomer, separating an impurity product after each prepolymerization to promote the forward reaction, and further adding the second monomer according to the complete reaction stoichiometric ratio or the near complete reaction stoichiometric ratio for polymerization to prepare the polymer intermediate.
It should be noted that, the reaction byproducts are generated simultaneously when the dihydrazide monomer, the first monomer and the second monomer are synthesized by reaction, and when the reaction byproducts accumulate to a certain extent in the system, the reaction is inhibited from proceeding forward, and the polymer chain growth and the final fiber performance are affected. The invention adopts a prepolymerization-post polymerization process of adding the second monomer twice or more, after prepolymerization, an acid binding agent is added to combine with reaction byproducts, and the combined products are separated from a solution system, so that the aim of promoting forward combination of the reaction is fulfilled.
Specifically, the acid-binding agent includes an inorganic acid-binding agent and an organic acid-binding agent.
Preferably, the acid-binding agent is an inorganic acid-binding agent.
Specifically, the inorganic acid-binding agent is one or more of ammonia gas, calcium hydroxide, calcium oxide, ammonium carbonate and ammonium bicarbonate
Specifically, the organic acid-binding agent includes any one of diethylamine and triethylamine.
It should be noted that the inorganic acid-binding agent has obvious advantages over the organic acid-binding agent: on the one hand, the organic acid-binding agent is dissolved in a synthetic solvent system and is relatively difficult to separate; on the other hand, the reaction of the organic acid binding agent and hydrochloric acid is reversible, is unstable at high temperature, can be decomposed during heating polymerization, and is difficult to achieve a good acid binding effect; in addition, since the polymer has better crystallinity, the surface of the fiber is regular and compact after the polymer is precipitated into filaments, and the inside of the fiber is difficult to clean thoroughly, so that partial organic acid-binding agent is easy to remain in the fiber to influence the performance of the fiber.
The inorganic acid binding agent contains ammonia gas or the decomposition product is ammonia gas, on one hand, ammonia gas and the like are insoluble in a solvent system, and ammonia gas or carbon dioxide generated by heating redundant raw materials is easily separated in a heating and decompression mode and the like, so that the inorganic acid binding agent fully reacts with hydrogen chloride, and meanwhile, redundant ammonia gas residues and raw material impurities are avoided; on the other hand, ammonia gas is insoluble with ammonium chloride which is a hydrogen chloride product and an organic polar solvent system, and is easy to remove in a precipitation mode, so that new impurity introduction is avoided.
In addition, the second monomer is added for multiple times, so that the second monomer with higher activity is prevented from being decomposed, reacting with impurities and volatilizing; on the other hand, the reaction rate is convenient to control by adding for many times, and the uneven reaction degree of the polymerization reaction caused by uneven mass transfer is reduced.
Specifically, the first monomer comprises an amino group and the second monomer comprises a formyl group.
Preferably, the first monomer is an aromatic diamine monomer and the second monomer is a diacid chloride monomer.
Preferably, the first monomer may be one or more of m-phenylenediamine, p-phenylenediamine, 3, 4-diaminodiphenyl ether.
Specifically, the binary hydrazide monomer is an aromatic compound containing two primary hydrazides.
Preferably, the dihydrazide monomer is an aromatic dihydrazide.
Preferably, the binary hydrazide monomer is one or more of isophthalhydrazide and terephthalhydrazide.
Preferably, the monomer with the substituent group in the meta-position structure in the first monomer and the dihydrazide monomer accounts for 80-100% of the total molar weight of the first monomer and the dihydrazide monomer, and the monomer with the substituent group in the para-position structure in the first monomer and the dihydrazide monomer accounts for 0-20% of the total molar weight of the first monomer and the dihydrazide monomer.
Preferably, the mol ratio of the substituent groups in the first monomer and the binary hydrazide monomer to the para-structure monomer is less than or equal to 10 percent.
Preferably, the second monomer is isophthaloyl dichloride or a mixture of isophthaloyl dichloride and terephthaloyl dichloride.
Preferably, the molar proportion of the substituent meta-structure monomer in the second monomer is not more than 5%.
Specifically, the molar ratio of the first monomer to the dihydrazide monomer is 0-100: 0-100.
Preferably, the ratio of the total molar amount of the first monomer to the dihydrazide monomer and the molar amount of the second monomer is 1: (0.95-1.05).
By way of example, taking NH 2NHCO-Aq-CONHNH2 as a general formula of a dihydrazide monomer, taking m-phenylenediamine as a first monomer, taking m-phthaloyl chloride as a second monomer, taking m-phthaloyl hydrazine as a dihydrazide monomer, and integrally reacting the dihydrazide monomer, the first monomer and the second monomer as follows:
；
Wherein n represents the number of polymer constituent units; (I) represents a polymer constituent unit formed by reacting a first monomer with a second monomer,/> (II) represents a macromolecular intermediate composition unit formed by the reaction of a dihydrazide monomer and a second monomer, a represents the number of macromolecular structural units formed by the reaction of the dihydrazide monomer, n-a represents the number of macromolecular structural units formed by the reaction of the first monomer, and Aq is any one of phenyl and naphthyl in an aromatic group; the two structural units (I) and (II) in the high molecular structural unit are randomly distributed:
specifically, the number ratio of the two structural units (I) to (II) in the polymer intermediate is as follows: 0-99.99:0.01-100.
Specifically, the second monomer is added twice or more in the step 1, comprising the following steps:
S101, dissolving a binary hydrazide monomer and a first monomer in a polar organic solvent;
S102, adding a second monomer into the mixed system in S101 for multiple times, performing multiple times of prepolymerization, adding an acid-binding agent after the prepolymerization, precipitating and separating a reaction product of the acid-binding agent and a prepolymerization byproduct, and then continuing to add the second monomer for polymerization to obtain a polymer intermediate containing a hydrazide acyl chloride chain segment and an aryl amide chain segment.
Specifically, the polar organic solvent in the step 101 is any one of N-dimethylacetamide, dimethylformamide and N-methylpyrrolidone.
Specifically, in step S102, the pre-polymerization is mainly that the reaction of the first monomer, the dihydrazide monomer and the second monomer generates a small molecule prepolymer and the small molecule prepolymer is randomly copolymerized to generate a long chain prepolymer, and the second monomer is taken as isophthaloyl dichloride as an example, and the pre-polymerization main reaction equation is satisfied:
；
Wherein R represents a structure of the first monomer or the dihydrazide monomer after removing two primary amino groups; as an example, using toluenediamine as the first monomer and isophthalhydrazide as the dihydrazide monomer, R represents a benzene ring or a dicarboxylic acid hydrazide in which two meta hydrogens are removed ; M represents the amount of the polymetaphthaloyl structure in the long chain prepolymer or the amount of the second monomer is consumed in the first stage.
Specifically, in the step S102, the post-polymerization mainly includes that as the second monomer is continuously added, the second monomer reacts with the first monomer or the end group of the dihydrazide monomer of the prepolymer molecule to realize long-chain prepolymer connection and long-chain growth; taking the second monomer as isophthaloyl dichloride as an example, the post-polymerization main reaction equation satisfies:
；
Wherein n represents the number of the polymer intermediate structural units; p represents the consumption of a second monomer amount during the post-polymerization stage for the preparation of PMIA molecules having a number of structural units n; Represents the p+1th long-chain prepolymer, and the number of the polymetaphenylene diformyl structures of different long-chain prepolymers can be the same or different; r represents the structure of the first monomer or the dihydrazide monomer after removing two primary amino groups.
Preferably, the prepolymerization polymerization temperature is-20 ℃ to 20 ℃, for example, -20 ℃, -15 ℃, -10 ℃, -5 ℃, 0 ℃,5 ℃, 10 ℃, 15 ℃ and 20 ℃.
The product has larger viscosity average molecular weight and better mechanical strength in the range; the reaction time is 0.05 h-1 h.
Further preferably, the prepolymerization polymerization temperature is-15 ℃ to 10 ℃.
Preferably, the post-polymerization temperature is 20 ℃ to 50 ℃, for example, 25 ℃,30 ℃, 35 ℃,40 ℃, 45 ℃ and 50 ℃; the reaction time is 0.05 h-2 h.
It is noted that the prepolymerization temperature is lower than-20 ℃, the reaction speed is low, and the efficiency of the whole process can be reduced; the pre-polymerization temperature is higher than 20 ℃ or the post-polymerization temperature is higher than 50 ℃, the side reaction is increased, the linearity of the high polymer molecules is destroyed, the molecular weight is lower, the viscosity is lower, the spinnability is reduced, and the fiber strength and the elongation at break are reduced; the post polymerization temperature is higher than the pre polymerization temperature.
Specifically, the mass ratio range of the dihydrazide monomer in the dihydrazide monomer and the first monomer is: 0.01% -100%.
Specifically, the mass concentration of the polymer intermediate solution in the step S102 is 13-25%.
Specifically, the mass ratio range of the dihydrazide monomer to the first monomer in the step 1 is as follows: 100-0.01: 0 to 99.99.
Specifically, step 2 includes:
S201: taking the prepared polar solvent solution of the polymer intermediate as spinning solution, and carrying out pre-spinning slurry pretreatment to remove impurities;
S202: spinning the pretreated spinning solution to obtain the nascent fiber.
Specifically, the pre-spinning slurry pretreatment in S201 includes: neutralization, filtration and deaeration.
The neutralizing agent is selected from: inorganic base, or organic amine.
Preferably, the inorganic base is one or more of calcium oxide, calcium hydroxide, sodium hydroxide, lithium hydroxide and liquid ammonia.
The organic amine is one or more of diethylamine, triethylamine and tetraethyl ethylenediamine.
Specifically, the filtration pressure is 0.3mpa to 0.8mpa.
Specifically, vacuum defoaming is adopted for defoaming, and the vacuum degree is 0.1 Kpa-20 Kpa.
Specifically, wet spinning is preferable in step 2, and the spinning pressure is set to 0.2 to 2MPa, for example, 0.2MPa, 0.3MPa, 0.5MPa, 0.6MPa, 0.8MPa, 0.9MPa, 1.0MPa, 1.2MPa, 1.3MPa, 1.5MPa, 1.6MPa, 1.8MPa, 1.9MPa, 2.0MPa.
Specifically, the post-treatment is further included after the primary fiber is formed in the step 2: plasticizing, stretching, washing and drying.
Specifically, the specific method and process conditions for plasticizing and stretching are as follows: the fibers are passed through a plurality of rollers of varying speeds in sequence so that the speed of the fibers as they leave the stretcher is greater than the speed of the fibers as they enter the stretcher, thereby achieving the stretching effect.
In particular, the fibers are immersed in the plasticizing liquid or rinsed by the plasticizing liquid when in two multi-roll machines of different speeds.
Specifically, the plasticizing liquid is a mixed liquid of a polar solvent, inorganic salt and water.
Preferably, the plasticizing liquid is DMAC (dimethylacetamide) aqueous solution, and the mass ratio is as follows: DMAC: water= (15-45): (85-55), immersing or spraying the plasticizing liquid on the tows, wherein the contact length of the plasticizing liquid and the tows is 0.3-10 m, and the temperature of the plasticizing liquid is 30-90 ℃.
It will be appreciated that the effect of plasticising and stretching is: under the action of plasticizing liquid, the polymer is swelled to a certain extent by the action of solvent, and the polymer can slide mutually to a certain extent under the action of external force, so as to achieve the drawing aim of the molecular in the fiber along the axial orientation of the fiber.
Specifically, the fiber absorbs the plasticizing liquid in the plasticizing and stretching process, so that substances such as polar solvent, inorganic salt and the like remain in the plasticizing liquid; the physical and mechanical properties of the fiber are affected by the substances, and the impurity substances are removed by water washing, the solvent is recovered, so that the material consumption is reduced; the specific method for water washing comprises the following steps: the fiber is washed with water in a multistage countercurrent immersion or leaching mode by using multistage water washing.
Specifically, the specific method and process conditions for drying are as follows: drying the fiber bundles by means of a multi-stage hot roller hot plate or a hot cavity and the like, wherein when the fibers pass through the surface of the heat equipment, heat is transferred from machinery to the fibers, the temperature of the fiber bundles rises, and moisture in the fiber bundles is heated and evaporated, so that the drying effect is achieved; the equipment such as the hot roller or the hot plate can be heated by using an electric resistor, a heating medium (such as heat conducting oil) or steam and the like.
Specifically, the dynamic viscosity of the polymer intermediate solution in the step 3 is 1 ten thousand to 10 ten thousand per centipoise.
Specifically, in step 3, an in-line heat treatment and a continuous heat treatment may be employed for the heat post-treatment to obtain the aramid modified fiber containing oxadiazole groups.
Specifically, the in-line heat treatment includes:
Firstly, carrying out pretreatment stretching at 180-280 ℃ with a stretching ratio of 100-550%;
And then carrying out 100% -150% shaping treatment at the temperature of 280-400 ℃.
Specifically, the batch heat treatment method includes:
The nascent fiber is washed with water and dried, and then cut off for relaxation heat treatment.
Specifically, the relaxation heat treatment includes: heat treatment in a high temperature heat treatment furnace, blast or vacuum environment.
Specifically, the relaxation heat treatment time is 20 min-20 h, and the temperature is 250-400 ℃.
Specifically, in the step3, the nascent fiber is heated and post-treated to obtain the aramid modified fiber containing oxadiazole groups, which comprises the following steps: the hydrazide acyl chloride chain segment in the nascent fiber removes water molecules to generate oxadiazole groups.
The reaction process satisfies the following conditions:
；
Wherein R 'may be a benzene ring and the position of the oxadiazole group to which R' is attached may be meta or para.
Compared with the prior art, in the step 3 of heating post-treatment, the bishydrazide bond in the high polymer chain is subjected to condensation reaction, each chain segment is stripped of one water molecule, the bishydrazide bond simultaneously forms an oxadiazole ring, and meanwhile, the molecular chain segments are oriented along the fiber axis direction and regularly stacked with other molecular chain segments for crystallization; forming a perfect structure of the fiber, and endowing the fiber with heat resistance and good dry heat shrinkage performance; the introduction of the oxadiazole ring greatly improves the hydrophilicity of the fiber and the hygroscopicity of the fiber; thereby improving the wearing comfort of the fabric made of the fibers.
Specifically, the spinning hydrodynamic viscosity of the fiber is 1 ten thousand to 10 ten thousand per centipoise; the glass transition temperature of the fiber is 270-390 ℃; the relative strength of the fiber is 3.5-5 cN/dtex; the breaking elongation of the fiber is 10% -40%; the CV value of the fiber is 8% -15%.
In order to better illustrate the invention, the following examples and comparative examples are further provided:
example 1
The embodiment discloses a preparation method of a fiber:
(1) Preparing a high molecular intermediate: adding a binary hydrazide reaction monomer and a first monomer into a proper amount of N-dimethylacetamide solvent according to a molar ratio of 50:50, controlling the polymerization temperature and time of a second monomer with a set dosage at-10-0 ℃ in a pre-polymerization stage, controlling the temperature at 30-50 ℃ in a post-polymerization stage for 1h, and controlling the solute mass concentration in a polymer intermediate solution to 20% in 2 h; specific compositions of the dihydrazide reaction monomer, the first monomer and the second monomer are shown in Table 1a and Table 1b.
(2) Spinning the polymer intermediate solution:
Filtering the polymer intermediate solution, filtering at 0.3Mpa, defoaming, wet spinning at 1Mpa, and depositing to obtain the final product. The precipitation solution is a mixed solution of N-dimethylacetamide, calcium chloride and water (the mass ratio is 45:25:30).
(3) Post-treating the nascent fiber:
Plasticizing and stretching the nascent fiber, immersing the tow in plasticizing liquid for 2.5 meters at 50 ℃; the plasticizing liquid is DMAC (dimethylacetamide) aqueous solution, and the mass ratio is as follows: DMAC: water = 35:65. then spray water washing is used, and the mixture is dried by a hot roller heated by saturated steam.
(4) And (3) fiber forming:
The specific components are shown in tables 1a and 1b using an in-line heat treatment.
This example discloses a fiber made by the method described above, with specific parameters as shown in table 2.
Example 2
The embodiment discloses a preparation method of a fiber:
(1) Preparing a high molecular intermediate: adding a binary hydrazide reaction monomer and a first monomer into a proper amount of N-dimethylacetamide solvent according to a molar ratio of 95:5, controlling the polymerization temperature and time of the second monomer with a set dosage at 20 ℃ in a pre-polymerization stage, controlling the polymerization temperature at 0.05 h in a post-polymerization stage at 30 ℃, controlling the solute mass concentration in a polymer intermediate solution at 0.05 h; specific compositions of the dihydrazide reaction monomer, the first monomer and the second monomer are shown in Table 1a and Table 1b.
(2) Spinning the polymer intermediate solution:
Filtering the polymer intermediate solution, filtering at 0.3Mpa, defoaming, wet spinning at 1Mpa, and depositing to obtain the final product. The precipitation solution is a mixed solution of N-dimethylacetamide, calcium chloride and water (the mass ratio is 45:25:30).
(3) Post-treating the nascent fiber:
Plasticizing and stretching the nascent fiber, immersing the tow in plasticizing liquid, wherein the immersed length is 2.5 meters, and the temperature is 50 ℃; the plasticizing liquid is DMAC (dimethylacetamide) aqueous solution, and the mass ratio is as follows: DMAC: water = 35:65. then spray water washing is used, and the mixture is dried by a hot roller heated by saturated steam.
(4) And (3) fiber forming:
The specific components are shown in tables 1a and 1b using an in-line heat treatment.
This example discloses a fiber made by the method described above, with specific parameters as shown in table 2.
Example 3
The embodiment discloses a preparation method of a fiber:
(1) Preparing a high molecular intermediate: adding a binary hydrazide reaction monomer and a first monomer into a proper amount of N-dimethylacetamide solvent according to a molar ratio of 10:90, controlling the polymerization temperature and time of a second monomer with a set dosage at-5 ℃ in a pre-polymerization stage, controlling the polymerization temperature at 40 ℃ in a post-polymerization stage for 1h, and controlling the solute mass concentration in a polymer intermediate solution to be 20%; specific compositions of the dihydrazide reaction monomer, the first monomer and the second monomer are shown in Table 1a and Table 1b.
(2) Spinning the polymer intermediate solution:
Filtering the polymer intermediate solution, filtering at 0.4Mpa, defoaming, wet spinning at 1Mpa, and depositing to obtain the final product. The precipitation solution is a mixed solution of N-dimethylacetamide, calcium chloride and water (the mass ratio is 45:25:30).
(3) Post-treating the nascent fiber:
Plasticizing and stretching the nascent fiber, immersing the tow in plasticizing liquid, wherein the immersed length is 2.5 meters, and the temperature is 50 ℃; the plasticizing liquid is DMAC (dimethylacetamide) aqueous solution, and the mass ratio is as follows: DMAC: water = 35:65. then spray water washing is used, and the mixture is dried by a hot roller heated by saturated steam.
(4) And (3) fiber forming:
The specific components are shown in tables 1a and 1b using an in-line heat treatment.
This example discloses a fiber made by the method described above, with specific parameters as shown in table 2.
Example 4-example 9 and comparative example were set, and example 1 was repeated except that the parameters in tables 1a and 1b were changed.
The main raw material compositions of the above examples and comparative examples are shown in tables 1a and 1 b:
Table 1a part of the main raw material composition of examples and comparative examples
Note that: in the tables "-" indicates that the component is absent or the process conditions are not implemented.
Table 1b part of the main raw material composition of examples and comparative examples
Note that: in the tables "-" indicates that the component is absent or the process conditions are not implemented.
The process parameters of the above examples and comparative examples are shown in table 2:
table 2 part of the process parameters of examples and comparative examples
Note that: in the tables "-" indicates that the component is absent or the process conditions are not implemented.
The polymer intermediates and fibers prepared in the above examples and comparative examples were tested,
The relative strength, elongation at break and CV value detection method are carried out according to the GB/T14337 rule, and the pre-tension is (0.0750+/-0.0075) cN/dtex;
the dyeability K/S value test method is to test by using a Datacolor SF-600 type color meter according to a D65 light source and under the condition of 10-degree visual field:
(1) Firstly, weaving undyed blank fibers and dip-dyed fibers into a tubular fabric by using a CEF598 dyeing test braiding machine, and cutting the tubular fabric into a 5X5cm sample; wherein, the dyeing uses 2% mass fraction disperse deep blue 79 dyeing solution, the bath ratio is 1:50, and the flow dyeing is carried out according to the procedures of dip dyeing at 25 ℃,10min, 130 ℃,70min, heat preservation and 65 ℃ and water washing;
(2) Starting the color meter and calibrating with undyed blank fiber fabric sample, setting aperture and mirror surface under test condition, taking different 5 points on the fabric with D65 and 10 degree field of view, measuring reflectivity R of each point, taking average value, and formulating Calculating a K/S value;
The hydrophilicity is characterized by the moisture regain, and the test is carried out according to the GB/T6503-2008 chemical fiber moisture regain test method;
limiting oxygen index test method according to FZ/T50017-2011;
The dry heat shrinkage rate test method at 400 ℃ is tested according to FZ/T50004-2011, and the test temperature is 400 ℃ and the test time is 15min;
The viscosity of the spinning solution adopts the relative viscosity eta as the ratio of the dynamic viscosity of the spinning solution to the dynamic viscosity of the pure solvent at the same temperature; dynamic viscosity the dynamic viscosity is measured by using GB/T10247-2008 viscosity measurement standard;
The above results are shown in tables 3a and 3 b:
table 3a data relating to partial dope and fiber properties
Note that: in the tables "-" indicates that the component is absent or the process conditions are not implemented.
Table 3b data relating to partial dope and fiber properties
Note that: in the tables "-" indicates that the component is absent or the process conditions are not implemented.
The results show that: the fiber of the invention has low heat shrinkage rate, which is lower than 2% at 400 ℃, and is far lower than 4-7% of that of meta-aramid (such as comparative example 1), thereby improving the dimensional stability of the protective clothing at high temperature.
The fiber of the invention has strong hygroscopicity, good hydrophilicity and high moisture regain which is up to 6-12 percent and is higher than 4-5 percent of meta-aramid fiber. Comfort is improved when a person wears a fabric made using the fiber.
The heat resistance of the product is that the glass transition temperature is more than 280 ℃, the long-term use temperature reaches 250 ℃ and is higher than 220 ℃ of meta-aramid.
The flame retardance of the product is high, and the limiting oxygen index is up to 30-32% which is higher than that of meta-aramid fiber by 28-29%.
The product of the invention has obviously improved K/S value relative to meta-aramid dyeability, which can reach more than 1, preferably 1-8.
As can be seen from comparative example 1 and comparative example 1, the CV value of the product of the invention is reduced to a certain extent relative to meta-aramid fiber, which is helpful for the stability of fiber performance.
The meta-aramid fiber product of the invention has no reduction of the relative strength and elongation at break of the fiber, no reduction of the processability in the downstream processing field, and is very suitable for processing such as spinning.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention.
Claims (10)
1. A method of making a fiber comprising:
Step 1: selecting a binary hydrazide monomer, and reacting the first monomer with a second monomer to prepare a high polymer intermediate containing a hydrazide acyl chloride chain segment and an aryl amide chain segment; the first monomer is an aromatic diamine monomer, and the second monomer is a binary acyl chloride monomer;
Step 2: spinning the polymer intermediate to obtain a nascent fiber;
step 3: and heating and post-treating the nascent fiber to obtain the fiber containing oxadiazole groups.
2. The method of making a fiber according to claim 1, wherein the first monomer is one or more of m-phenylenediamine, p-phenylenediamine, 3, 4-diaminodiphenyl ether; and/or the second monomer is isophthaloyl dichloride or a mixture of isophthaloyl dichloride and terephthaloyl dichloride.
3. The method of claim 1, wherein the dihydrazide monomer is an aromatic compound containing two primary hydrazides.
4. A method of making a fiber according to claim 3 wherein the dihydrazide monomer is an aromatic dihydrazide.
5. The fiber preparation method according to claim 1, wherein the monomer with the substituent in the meta structure in the first monomer and the dihydrazide monomer accounts for 80-100% of the total molar amount of the first monomer and the dihydrazide monomer, and the monomer with the substituent in the para structure in the first monomer and the dihydrazide monomer accounts for 0-20% of the total molar amount of the first monomer and the dihydrazide monomer.
6. The method for preparing the fiber according to claim 1, wherein the substituent in the first monomer and the dihydrazide monomer is a molar ratio of the para-structure monomer which is less than or equal to 10 percent.
7. The fiber preparation method according to claim 1, wherein the molar ratio of the substituent meta-structure monomer in the second monomer is not more than 5%.
8. The method of preparing a fiber according to claim 1, wherein the adding of the second monomer in step 1 is performed two or more times, comprising the steps of:
S101, dissolving a binary hydrazide monomer and a first monomer in a polar organic solvent;
S102, adding a second monomer into the mixed system in S101 for multiple times, performing multiple times of prepolymerization, adding an acid-binding agent after the prepolymerization, precipitating and separating a reaction product of the acid-binding agent and a prepolymerization byproduct, and then continuing to add the second monomer for polymerization to obtain a polymer intermediate containing a hydrazide acyl chloride chain segment and an aryl amide chain segment.
9. A fiber prepared by the fiber preparation method of any one of claims 1 to 8, comprising an aromatic structure and a heterocyclic structure for linking the aromatic structure.
10. The fiber of claim 9, comprising the following structure (i):
（Ⅰ）。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410369977.4A CN117966294B (en) | 2024-03-29 | 2024-03-29 | Fiber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410369977.4A CN117966294B (en) | 2024-03-29 | 2024-03-29 | Fiber and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117966294A true CN117966294A (en) | 2024-05-03 |
| CN117966294B CN117966294B (en) | 2024-07-05 |
Family
ID=90857961
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410369977.4A Active CN117966294B (en) | 2024-03-29 | 2024-03-29 | Fiber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117966294B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3642706A (en) * | 1970-03-03 | 1972-02-15 | Monsanto Co | Process for spinning wholly aromatic polyamide filaments |
| US3944522A (en) * | 1971-07-02 | 1976-03-16 | Toray Industries, Inc. | Aromatic polyhydrazide fiber of high modulus and high tenacity |
| ATA784674A (en) * | 1971-11-26 | 1976-11-15 | Monsanto Co | OXADIAZOLE / N-ALKYL HYDRAZIDE MIXED POLYMERIZED FIBERS |
| CN1756789A (en) * | 2003-03-05 | 2006-04-05 | 东丽株式会社 | Aromatic polymer, film, dielectric film and dividing plate |
| CN101735455A (en) * | 2008-11-14 | 2010-06-16 | 无锡华东创新材料研究院 | Method for preparing special aromatic polyoxadiazole and flame-retardant high-temperature resistant polyoxadiazole fiber thereof |
| CN103012307A (en) * | 2012-11-20 | 2013-04-03 | 沈阳航空航天大学 | Asymmetric aromatic diamine containing 1,3,4-oxadiazole structure and preparation method thereof |
| CN104818646A (en) * | 2015-05-22 | 2015-08-05 | 江苏宝德新材料有限公司 | Fiber paper containing p-POD chopped fiber and preparation method of fiber paper |
| CN104894922A (en) * | 2015-05-22 | 2015-09-09 | 江苏宝德新材料有限公司 | Fiber paper containing m-POD precipitation fibers and preparation method and application of fiber paper containing m-POD precipitation fibers |
| CN106700065A (en) * | 2017-02-06 | 2017-05-24 | 四川大学 | Method for preparing heterocyclic aramid solution |
| CN115260491A (en) * | 2022-08-18 | 2022-11-01 | 江西同益高分子材料科技有限公司 | Alkali-degradation-resistant polyimide engineering plastic and preparation method thereof |
| CN116837483A (en) * | 2023-07-21 | 2023-10-03 | 江苏新视界先进功能纤维创新中心有限公司 | Polymer coloring method, spinning solution and colored fiber |
-
2024
- 2024-03-29 CN CN202410369977.4A patent/CN117966294B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3642706A (en) * | 1970-03-03 | 1972-02-15 | Monsanto Co | Process for spinning wholly aromatic polyamide filaments |
| US3944522A (en) * | 1971-07-02 | 1976-03-16 | Toray Industries, Inc. | Aromatic polyhydrazide fiber of high modulus and high tenacity |
| ATA784674A (en) * | 1971-11-26 | 1976-11-15 | Monsanto Co | OXADIAZOLE / N-ALKYL HYDRAZIDE MIXED POLYMERIZED FIBERS |
| CN1756789A (en) * | 2003-03-05 | 2006-04-05 | 东丽株式会社 | Aromatic polymer, film, dielectric film and dividing plate |
| CN101735455A (en) * | 2008-11-14 | 2010-06-16 | 无锡华东创新材料研究院 | Method for preparing special aromatic polyoxadiazole and flame-retardant high-temperature resistant polyoxadiazole fiber thereof |
| CN103012307A (en) * | 2012-11-20 | 2013-04-03 | 沈阳航空航天大学 | Asymmetric aromatic diamine containing 1,3,4-oxadiazole structure and preparation method thereof |
| CN104818646A (en) * | 2015-05-22 | 2015-08-05 | 江苏宝德新材料有限公司 | Fiber paper containing p-POD chopped fiber and preparation method of fiber paper |
| CN104894922A (en) * | 2015-05-22 | 2015-09-09 | 江苏宝德新材料有限公司 | Fiber paper containing m-POD precipitation fibers and preparation method and application of fiber paper containing m-POD precipitation fibers |
| CN106700065A (en) * | 2017-02-06 | 2017-05-24 | 四川大学 | Method for preparing heterocyclic aramid solution |
| CN115260491A (en) * | 2022-08-18 | 2022-11-01 | 江西同益高分子材料科技有限公司 | Alkali-degradation-resistant polyimide engineering plastic and preparation method thereof |
| CN116837483A (en) * | 2023-07-21 | 2023-10-03 | 江苏新视界先进功能纤维创新中心有限公司 | Polymer coloring method, spinning solution and colored fiber |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117966294B (en) | 2024-07-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100531989B1 (en) | Process for producing meta-aromatic polyamide fiber | |
| CA1070447A (en) | Aromatic copolyamides shaped articles therefrom and processes for producing said copolyamides and shaped articles | |
| TW571007B (en) | Meta-type wholly aromatic polyamide filaments and process for producing same | |
| RU2285761C1 (en) | Method of manufacturing high-strength heat-resistant threads from aromatic copolyamide having heterocycles in the chain | |
| WO2007089008A1 (en) | Meta-type fully aromatic polyamide fiber having excellent high-temperature processability and method for production thereof | |
| CN110499542B (en) | Para-aramid fiber and preparation method thereof | |
| JPS636649B2 (en) | ||
| JP2011508100A (en) | Low shrinkage, dyeable MPD-I yarn | |
| CN116695270A (en) | Meta-aramid fiber and molecular weight regulating and controlling method and application thereof | |
| JP5394392B2 (en) | High-speed plasticization of rapid cooling yarn | |
| JP5186008B2 (en) | High-speed production of meta-aramid fiber | |
| JP5227421B2 (en) | One-stage drawing for MPD-I yarn | |
| CN116837483B (en) | Polymer coloring method, spinning solution and colored fiber | |
| CN117966294B (en) | Fiber and preparation method thereof | |
| JP3995532B2 (en) | Method for producing dense meta-type wholly aromatic polyamide fiber | |
| US5250633A (en) | Fibers and fibrets from blends of polybezimidazoles and aromatic polyamides, aromatic polyamide-hydrazides or aromatic polyamides containing heterocyclic linkages | |
| JP2013515768A (en) | Aromatic diamine and method for producing the same, aramid fiber and method for producing the same | |
| CN116575138A (en) | Preparation method of bio-based aromatic polyamide fiber | |
| JP4588032B2 (en) | Improved process of wet spinning for salt-containing aramid polymers | |
| CA1051594A (en) | Aromatic polyamides and their production | |
| CN117005056B (en) | Polymer coloring method, spinning color paste, spinning solution and colored fiber | |
| JP4664794B2 (en) | Method for producing meta-type aromatic polyamide fiber | |
| CN117004018B (en) | Polymer coloring method, spinning solution and colored fiber | |
| JP2003342832A (en) | Method for producing meta-type wholly aromatic polyamide fiber having excellent shrinkage stability | |
| EP0316486B1 (en) | Process for preparing aromatic polyamide fibre and film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |