CN112853533B - Castor oil-based functional polyamide fiber with ultralow-temperature toughness and preparation method thereof - Google Patents
Castor oil-based functional polyamide fiber with ultralow-temperature toughness and preparation method thereof Download PDFInfo
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 136
- 229920002647 polyamide Polymers 0.000 title claims abstract description 136
- 239000000835 fiber Substances 0.000 title claims abstract description 43
- 239000004359 castor oil Substances 0.000 title claims abstract description 19
- 235000019438 castor oil Nutrition 0.000 title claims abstract description 19
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims description 28
- 239000002657 fibrous material Substances 0.000 claims abstract description 24
- 238000009987 spinning Methods 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims description 87
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 238000001125 extrusion Methods 0.000 claims description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 229920002292 Nylon 6 Polymers 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- ALPIESLRVWNLAX-UHFFFAOYSA-N hexane-1,1-dithiol Chemical compound CCCCCC(S)S ALPIESLRVWNLAX-UHFFFAOYSA-N 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- 230000006835 compression Effects 0.000 claims description 2
- 238000007906 compression Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229920005594 polymer fiber Polymers 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000002074 melt spinning Methods 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 6
- 125000004185 ester group Chemical group 0.000 description 5
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 239000011846 petroleum-based material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- MRHPRDYMSACWSG-UHFFFAOYSA-N 1,3-diaminopropan-1-ol Chemical compound NCCC(N)O MRHPRDYMSACWSG-UHFFFAOYSA-N 0.000 description 1
- ANLABNUUYWRCRP-UHFFFAOYSA-N 1-(4-nitrophenyl)cyclopentane-1-carbonitrile Chemical compound C1=CC([N+](=O)[O-])=CC=C1C1(C#N)CCCC1 ANLABNUUYWRCRP-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920003188 Nylon 3 Polymers 0.000 description 1
- 229920001007 Nylon 4 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- ZXKINMCYCKHYFR-UHFFFAOYSA-N aminooxidanide Chemical compound [O-]N ZXKINMCYCKHYFR-UHFFFAOYSA-N 0.000 description 1
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- LSACYLWPPQLVSM-UHFFFAOYSA-N isobutyric acid anhydride Chemical compound CC(C)C(=O)OC(=O)C(C)C LSACYLWPPQLVSM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- XPQPWPZFBULGKT-UHFFFAOYSA-N undecanoic acid methyl ester Natural products CCCCCCCCCCC(=O)OC XPQPWPZFBULGKT-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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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
-
- 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
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/12—Stretch-spinning methods
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyamides (AREA)
Abstract
The invention discloses castor oil-based functional polyamide fiber with ultralow temperature toughness, and relates to the technical field of low-temperature fiber materials, wherein the fiber is formed by spinning functional polyamide, and the structural formula of the functional polyamide is as follows:
wherein n is more than or equal to 5 and less than or equal to 5000, R1Is composed of
The repeating unit of (1). R2Is composed of
The invention has the beneficial effects that: the castor oil based functional polyamide fiber has excellent mechanical properties at room temperature and extremely cold temperature, and compared with the traditional polymer fiber material, the castor oil based functional polyamide fiber has the advantage that the mechanical properties of the castor oil based functional polyamide fiber are further enhanced at the temperature of-100 ℃. The mechanical property parameters at-100 ℃ are: the elastic modulus is 100-1200 MPa, the tensile breaking stress is 50-1500 MPa, the tensile breaking strain is 50-1000%, and the toughness is 200-one-shot 600MJ/m3。
Description
Technical Field
The invention relates to the technical field of low-temperature fiber materials, in particular to castor oil-based functional polyamide fiber with ultralow-temperature toughness and a preparation method thereof.
Background
With the development of society, people can not live away from the existence of polymer materials. The properties of polymeric materials are therefore of great interest. The fiber material prepared from the synthetic polymer is widely applied to the fields of textile, safety protection and the like. However, polymer fibers having excellent room temperature properties generally have problems of poor toughness, brittleness, and the like at low temperatures due to the characteristic problems of the polymer itself. However, materials used in extremely cold temperature areas such as outer space and polar regions have extremely high requirements on cold resistance. This also results in many polymer fiber materials not being usable in these extremely cold temperature areas.
At present, polymer fiber materials used in extremely cold temperature areas such as outer space and the like generally originate from fossil resources. However, with the increasing exhaustion of fossil resources and the increasing environmental pollution, the preparation of fiber materials with excellent mechanical properties at extremely cold temperatures by using biomass resources is of great significance. At present, the performance of polymer materials prepared by using biomass resources is generally in a large gap compared with petroleum-based materials. Therefore, the preparation of biomass fiber materials with ultrahigh toughness at room temperature and extremely cold temperature by using biomass resources is still a great challenge.
At present, the low-temperature resistant fibers in the market are mainly petroleum-based materials, and have the problem of poor toughness at room temperature. The traditional polymer material generally has the problems of poor performance, incapability of use and the like at low temperature. The patent application with the publication number of CN110437611A discloses a reinforced and toughened ultralow temperature resistant nylon composite material and a preparation method and application thereof, but the impact strength of the composite material at the temperature of 50 ℃ below zero is only 15KJ/m2The polymer fiber in the prior art is difficult to have ultrahigh toughness at the same time under the conditions of room temperature and ultralow temperature.
Disclosure of Invention
The invention aims to solve the technical problem that the polymer fiber in the prior art is difficult to have ultrahigh toughness under the conditions of room temperature and ultralow temperature.
The invention solves the technical problems through the following technical means:
the ultralow-temperature-toughness castor oil-based functional polyamide fiber is formed by spinning functional polyamide, and the structural formula of the functional polyamide is as follows:
Has the advantages that: the castor oil based functional polyamide fiber has excellent mechanical properties at room temperature and extremely cold temperature, and compared with the traditional polymer fiber material, the castor oil based functional polyamide fiber has the advantage that the mechanical properties of the castor oil based functional polyamide fiber are further enhanced at the temperature of-100 ℃. The mechanical property parameters at-100 ℃ are: the elastic modulus is 100-1200 MPa, the tensile breaking stress is 50-1500 MPa, the tensile breaking strain is 50-1000%, and the toughness is 200-one-shot 600MJ/m3And the method can be well applied to special areas such as outer space, polar regions and the like.
The invention also provides a preparation method of the castor oil-based functional polyamide fiber with ultralow temperature toughness, which comprises the following steps: and (3) putting the functional polyamide into a fiber forming machine for melt spinning.
Has the advantages that: the preparation method has the advantages of simple preparation steps, high yield, no need of blending and suitability for large-scale preparation, and the prepared fiber material has good mechanical properties at room temperature and low temperature, and has the toughness of 200-600MJ/m at ultralow temperature of-100 DEG C3。
Preferably, the fiber forming machine is a melt spinning machine.
Preferably, the preparation method of the ultralow-temperature tough castor oil-based functional polyamide fiber comprises the following steps:
(1) vacuum drying the functional polyamide at 60 ℃ for 8-24 h;
(2) and (3) putting the dried functional polyamide into a melt spinning machine, carrying out melt spinning, gradually increasing the partition temperature of the melt spinning machine, and then carrying out extrusion molding.
Preferably, the diameter of the filament outlet of the melt spinning machine is 0.05-1 mm.
Preferably, the zone temperatures of the melt spinning machine are respectively as follows: the first zone is 80-120 ℃, the second zone is 100-.
Preferably, the zone temperatures of the melt spinning machine are respectively as follows: the first zone is 80 ℃, the second zone is 110 ℃, the third zone is 130 ℃, the fourth zone is 140 ℃, the screw speed is 30rpm/s, the extrusion pressure is 1Mpa, and the fiber drafting speed is 20m/min during fiber extrusion molding.
Preferably, the zone temperatures of the melt spinning machine are respectively as follows: the first zone is 90 ℃, the second zone is 120 ℃, the third zone is 140 ℃, the fourth zone is 160 ℃, the diameter of a filament outlet of the melt spinning machine is 0.05-1mm, the screw speed is 30rpm when the fiber is extruded and molded, the extrusion pressure is 1Mpa, and the fiber drafting speed is 20 m/min.
Preferably, the zone temperatures of the melt spinning machine are respectively as follows: the first zone is 100 ℃, the second zone is 120 ℃, the third zone is 140 ℃, the fourth zone is 180 ℃, the screw speed is 30rpm/s, the extrusion pressure is 1Mpa, and the fiber drafting speed is 20m/min during fiber extrusion molding.
Preferably, the zone temperatures of the melt spinning machine are respectively as follows: the first zone is 90 ℃, the second zone is 120 ℃, the third zone is 140 ℃, the fourth zone is 180 ℃, the screw speed is 50rpm/s, the extrusion pressure is 2Mpa, and the fiber drafting speed is 10m/min during fiber extrusion molding.
Has the advantages that: the mechanical property of the fiber is influenced by the spinning parameters, the obtained fiber has excellent mechanical property at room temperature after the spinning temperature, the screw speed, the extrusion pressure and the fiber drafting speed are adjusted, the mechanical strength is obviously further improved to 140MPa and the strain is 300 percent under the condition of ultralow temperature of 100 ℃, and the toughness reaches 310MJ/m3。
The invention has the advantages that: the castor oil based functional polyamide fiber has excellent mechanical properties at room temperature and extremely cold temperature, and compared with the traditional polymer fiber material (such as nylon 6, the low temperature resistance is generally-20 ℃ to-40 ℃, the embrittlement temperature of nylon 66 is-30 ℃), the tensile toughness of the fiber at-100 ℃ is further enhanced. The mechanical property parameters at-100 ℃ are as follows: the elastic modulus is 100-1200 MPa, the tensile breaking stress is 50-1500 MPa, the tensile breaking strain is 50-1000%, and the toughness is 200-one-shot 600MJ/m3。
The preparation method has simple preparation steps, and the prepared fiber material has the toughness of 200-600MJ/m at the ultralow temperature of-100 DEG C3。
The spinning parameters influence the mechanical properties of the fiber, and the spinning temperature are adjustedAfter the rod speed, the extrusion pressure and the fiber drafting speed are reached, the obtained fiber has excellent mechanical property at room temperature, the mechanical strength is obviously further improved to 140MPa at the ultralow temperature of 100 ℃, the strain is 300 percent, and the toughness reaches 310MJ/m3。
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a functional polyamide monomer 1 in example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of a functional polyamide monomer 2 in example 1 of the present invention;
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of a functional polyamide monomer 3 in example 1 of the present invention;
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of the functional polyamide monomer 4 in example 1 of the present invention;
FIG. 5 is a nuclear magnetic resonance hydrogen spectrum of the functional polyamide monomer 5 in example 1 of the present invention;
FIG. 6 is a nuclear magnetic resonance hydrogen spectrum of the functional polyamide monomer 6 in example 1 of the present invention;
FIG. 7 is a nuclear magnetic resonance hydrogen spectrum of the functional polyamide monomer 7 in example 1 of the present invention;
FIG. 8 is a differential scanning calorimetry chart of a functional polyamide according to example 2 to example 7 of the present invention;
FIG. 9 is a room temperature mechanical tensile curve of the functional polyamide in examples 2 to 7 of the present invention;
FIG. 10 is a room temperature mechanical tensile curve for fibers of examples 8-11 of the present invention;
FIG. 11 is a photomicrograph of a fiber of example 11 of the present invention;
FIG. 12 is a graph showing the mechanical tensile curve of the fiber at ultra-low temperature of-100 ℃ in example 11 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
In the following examples, azobisisobutyronitrile was purified by recrystallization, and tetrahydrofuran was purified by distillation.
Example 1
Preparation of functional polyamide monomers
(1) Preparation of functional polyamide monomer 1, comprising the following steps:
80g of methyl undecylenate, 5g of 1, 3-diamino-propanol were added to 20ml of tetrahydrofuran. Introducing shielding gas for half an hour, heating at 40 ℃, adding 3ml of sodium methoxide, reacting for 20 hours at 40 ℃, and recrystallizing to obtain white powdery solid, namely the hydroxy amide monomer, which is named as functional polyamide monomer 1.
The structural formula of the functional polyamide monomer 1 is as follows:
The NMR spectrum of the functional polyamide monomer 1 is shown in FIG. 1, and the presence of an amide bond can be indicated by a peak at 3.35 ppm. And the peak at 3.78ppm indicates the presence of hydroxyl groups. It was found that the functional polyamide monomer 1 was successfully prepared.
(2) The preparation of the functional polyamide monomer 2 comprises the following steps:
48g of functional polyamide monomer 1, 15g of acetic anhydride and 80mg of dimethylaminopyridine are placed in 15ml of tetrahydrofuran to be mixed, the mixture reacts for 18 hours at the temperature of 50 ℃ to obtain a clear solution, and the clear solution is purified to obtain the functional polyamide monomer which is named as functional polyamide monomer 2.
The structural formula of the functional polyamide monomer 2 is as follows:
The NMR spectrum of the functional polyamide monomer 2 is shown in FIG. 2, and the presence of an ester group peak was observed at 4.75 ppm. The newly appearing methyl peak can be seen from the peak at 1.95 ppm. Indicating that the monomer was successfully prepared.
(3) The preparation of the functional polyamide monomer 3 comprises the following steps:
48g of functional polyamide monomer 1, 20g of benzoic anhydride and 80mg of dimethylaminopyridine are placed in 15ml of tetrahydrofuran to be mixed, reaction is carried out for 18 hours at 60 ℃, clear solution is obtained, and the functional polyamide monomer obtained through purification is named as functional polyamide monomer 3.
The structural formula of the functional polyamide monomer 3 is as follows:
The NMR spectrum of the functional polyamide monomer 3 is shown in FIG. 3, and the presence of an ester group peak was observed at 4.75 ppm. The newly appeared peaks of benzene rings were observed from the peaks at 7.4ppm, 7.5ppm and 7.98 ppm. Indicating that functional polyamide monomer 3 was successfully prepared.
(4) The preparation of the functional polyamide monomer 4 comprises the following steps:
40g of functional polyamide monomer 1, 12g of butyric anhydride and 80mg of dimethylaminopyridine are placed in 10ml of tetrahydrofuran to be mixed, and react for 16 hours at 55 ℃ to obtain a clear solution, and the functional polyamide monomer obtained by purification is named as functional polyamide monomer 4.
The structural formula of the functional polyamide monomer 4 is as follows:
The NMR spectrum of the functional polyamide monomer 4 is shown in FIG. 4, and the presence of an ester group peak was observed at 4.75 ppm. The newly appearing methyl peak can be seen from the peak at 0.9 ppm. Indicating that functional polyamide monomer 4 was successfully prepared.
(5) Preparation of functional polyamide monomer 5, comprising the steps of:
30g of functional polyamide monomer 1, 10g of isobutyric anhydride and 40mg of dimethylaminopyridine are placed in 10ml of tetrahydrofuran to be mixed, and the mixture reacts for 24 hours at 65 ℃ to obtain a clear solution, and the functional polyamide monomer obtained through purification is named as functional polyamide monomer 5.
The structural formula of the functional polyamide monomer 5 is as follows:
The NMR spectrum of the functional polyamide monomer 5 is shown in FIG. 5, and the presence of an ester group peak was observed at 4.75 ppm. The newly appearing methylene peak and methyl peak are seen from the peaks at 2.56ppm and 1.1 ppm. Indicating that functional polyamide monomer 5 was successfully prepared.
(6) Preparation of functional polyamide monomer 6, comprising the steps of:
30g of the functional polyamide monomer 1, 80mg of dimethylaminopyridine and 12g of triethylamine were mixed and dissolved in 15ml of tetrahydrofuran, and 12g of acryloyl chloride was added dropwise to the mixture. Reacting for 18 hours at 60 ℃ to obtain a clear solution, and purifying to obtain the functional polyamide monomer named as functional polyamide monomer 6.
The structural formula of the functional polyamide monomer 6 is as follows:
The NMR spectrum of the functional polyamide monomer 6 is shown in FIG. 6, and the presence of an ester group peak was observed at 4.9 ppm. The presence of new double bonds can be seen from the newly appearing peaks at 5.92pp, 6.2ppm and 6.48 ppm. Indicating that functional polyamide monomer 6 was successfully prepared.
(7) The preparation of the functional polyamide monomer 7 comprises the following steps:
30g of functional polyamide monomer 6, 4g of imidazole, 3g of 1-methylimidazole and 5g of triethylamine are placed in 20ml of NN-dimethylformamide to be mixed, the mixture reacts for 48 hours at 65 ℃ to obtain a clear solution, and the clear solution is purified to obtain the functional polyamide monomer named as functional polyamide monomer 7.
The structural formula of the functional polyamide monomer 7 is as follows:
The nuclear magnetic resonance hydrogen spectrum of the functional polyamide monomer 7 is shown in fig. 7: the presence of an ester peak was observed at 4.8 ppm. The newly appearing methylene peak is seen from the peak at 7.58 ppm. Indicating that functional polyamide monomer 7 was successfully prepared.
Example 2
The preparation of functional polyamide includes the following steps:
21.2g of a functional polyamide monomer 2, 3.9g of a functional polyamide monomer 1, 1.6g of a functional polyamide monomer 3, 0.7g of a functional polyamide monomer 4, 0.3g of a functional polyamide monomer 7, 0.15g of a functional polyamide monomer 5, 9.3g of 3, 6-dioxa-1, 8-dithiol, and 400mg of azobisisobutyronitrile catalyst and 60ml of tetrahydrofuran were charged into a reaction vessel. Argon was introduced for 15 minutes, and then the mixture was placed in a 50 ℃ oil bath to react for 36 hours. And then purifying to obtain the functional polyamide named as functional polyamide 1.
The chemical formula of the functional polyamide 1 is as follows:
Example 3
The preparation of functional polyamide includes the following steps:
this embodiment is different from embodiment 2 in that: the addition amount of the functional polyamide monomer 2 was 18.3g, and the addition amount of the functional polyamide monomer 1 was 6.3g, and the obtained functional polyamide was named functional polyamide 2.
Example 4
The preparation of functional polyamide includes the following steps:
this embodiment is different from embodiment 2 in that: the addition amount of the functional polyamide monomer 2 was 15.6g, and the addition amount of the functional polyamide monomer 1 was 8.8g, and the obtained functional polyamide was named functional polyamide 3.
Example 5
The preparation of functional polyamide includes the following steps:
this embodiment is different from embodiment 2 in that: the addition amount of the functional polyamide monomer 2 was 10.3g, and the addition amount of the functional polyamide monomer 7 was 6g, and the obtained functional polyamide was named functional polyamide 4.
Example 6
The preparation of functional polyamide includes the following steps:
this embodiment is different from embodiment 4 in that: the 3, 6-dioxa-1, 8-dithiol was replaced with hexanedithiol, and the resulting functional polyamide was designated as functional polyamide 5.
The chemical formula of the functional polyamide 5 is as follows:
Example 7
This embodiment is different from embodiment 3 in that: the 3, 6-dioxa-1, 8-dithiol was replaced with hexanedithiol, and the resulting functional polyamide was designated as functional polyamide 6.
The functional polyamides obtained in examples 2 to 7 were melt-tableted to prepare films, respectively, and the obtained samples were subjected to thermal tests, wherein differential scanning calorimetry curves thereof are shown in FIG. 8, and it can be seen that the thermal properties of the functional polyamides can be controlled by varying the contents of the respective monomers.
The functional polyamides obtained in examples 2 to 7 were melt-tableted to prepare films, and dumbbell-shaped test pieces having a length of 15mm, a width of 2mm and a thickness of 0.2mm were cut for mechanical testing at a tensile rate of 10mm/min, and the stress-strain curves thereof are shown in FIG. 9. In FIG. 9, example 7 had a strength of 40MPa, a strain of 480% and a toughness of 120MJ/m3. It can be seen from the figure that the functional polyamide prepared from the castor oil based derivative has excellent mechanical properties, wherein the functional polyamide 6 in example 7 has the best overall mechanical properties, and therefore, is used for preparing fibers.
Example 8
Preparation of a fibrous material comprising the steps of:
500 parts by weight of prepared functional polyamide 6 is put in a vacuum oven at 60 ℃ for drying for 8 hours, and is pretreated for standby; and then putting the pretreated functional polyamide 1 into a spinning machine, wherein the diameter of a filament outlet of the spinning machine is 0.3mm, the temperature of a first zone is 80 ℃ preheating temperature, the temperature of a second zone and a third zone are 110 ℃ and 130 ℃ compression temperature respectively, the temperature of a fourth zone is 140 ℃ extrusion temperature, and a fiber material is prepared under the conditions of 30rpm screw rotating speed, 20m/min drafting speed and 1MPa extrusion pressure and named as a fiber material 1.
Example 9
This embodiment is different from embodiment 8 in that: and adjusting the parameters of the spinning machine, wherein the temperature of the first zone is 90 ℃, the temperature of the second zone is 120 ℃, the temperature of the third zone is 140 ℃, and the temperature of the fourth zone is 160 ℃, so as to prepare the fiber material, namely the fiber material 2.
Example 10
This embodiment is different from embodiment 8 in that: and (3) adjusting the parameters of the spinning machine, wherein the temperature of the first zone is 100 ℃, the temperature of the second zone is 120 ℃, the temperature of the third zone is 140 ℃, and the temperature of the fourth zone is 180 ℃ to prepare the fiber material, namely the fiber material 3.
Example 11
This embodiment is different from embodiment 10 in that: and (3) adjusting the parameters of the spinning machine, wherein the rotating speed of a screw is 50rpm, the extrusion pressure is 2MPa, and the drafting speed is 10m/min, so that a fiber material is prepared and named as a fiber material 4.
The fibers obtained in examples 8 to 11 were subjected to mechanical tensile tests at room temperature, respectively, and the room temperature mechanical tensile test thereof is shown in FIG. 10, from which it can be seen that the difference in spinning conditions has a great influence on the properties thereof, wherein the fiber material 4 in example 11 has the best mechanical properties at room temperature, has a strength of 70MPa, a strain of 600%, and a toughness of 240MJ/m3. The fiber was observed by a microscope, and the diameter of the spun yarn was about 200um as shown in FIG. 11. The mechanical property of the fiber material 4 of the prepared example 11 is tested at the ultralow temperature of 100 ℃ and the mechanical tensile diagram is shown in figure 12, so that the mechanical strength is obviously improved to 140MPa at the ultralow temperature of 100 ℃ and the strain is 300 percent, and the toughness reaches the astonishing 310MJ/m3And compared with the room temperature, the temperature is greatly improved.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (2)
1. A preparation method of castor oil based functional polyamide fiber with ultralow temperature toughness is characterized by comprising the following steps: the method comprises the following steps:
adding 21.2g of functional polyamide monomer 2, 3.9g of functional polyamide monomer 1, 1.6g of functional polyamide monomer 3, 0.7g of functional polyamide monomer 4, 0.3g of functional polyamide monomer 7, 0.15g of functional polyamide monomer 5, 9.3g of 3, 6-dioxa-1, 8-dithiol, 400mg of azobisisobutyronitrile catalyst and 60ml of tetrahydrofuran into a reaction vessel, introducing argon for 15 minutes, placing the mixture in a 50 ℃ oil bath to react for 36 hours, and then purifying to obtain functional polyamide, which is named as functional polyamide 1;
adding 18.3g of functional polyamide monomer 2, 6.3g of functional polyamide monomer 1, 1.6g of functional polyamide monomer 3, 0.7g of functional polyamide monomer 4, 0.3g of functional polyamide monomer 7, 0.15g of functional polyamide monomer 5, 9.3g of hexanedithiol, 400mg of azobisisobutyronitrile catalyst and 60ml of tetrahydrofuran into a reaction vessel, introducing argon for 15 minutes, placing the mixture in an oil bath kettle at 50 ℃ for reaction for 36 hours, and purifying to obtain functional polyamide, namely functional polyamide 6;
500 parts by weight of prepared functional polyamide 6 is put in a vacuum oven at 60 ℃ for drying for 8 hours, and is pretreated for standby; then putting the pretreated functional polyamide 1 into a spinning machine, wherein the diameter of a filament outlet of the spinning machine is 0.3mm, the temperature of a first zone is 100 ℃ preheating temperature, the compression temperature of a second zone and a third zone is 120 ℃ and 140 ℃ respectively, the extrusion temperature of a fourth zone is 180 ℃, and a fiber material is prepared under the conditions of 50rpm screw rotating speed, 10m/min drafting speed and 2MPa extrusion pressure;
wherein the structural formula of the functional polyamide monomer 1 is as follows:
the structural formula of the functional polyamide monomer 2 is as follows:
The structural formula of the functional polyamide monomer 3 is as follows:
The structural formula of the functional polyamide monomer 4 is as follows:
The structural formula of the functional polyamide monomer 5 is as follows:
The structural formula of the functional polyamide monomer 7 is as follows:
2. The castor oil based functional polyamide fiber with ultralow temperature toughness is characterized in that: the ultra-low temperature flexible castor oil based functional polyamide fiber is prepared by the method for preparing the ultra-low temperature flexible castor oil based functional polyamide fiber according to claim 1.
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