CN113737303A - Organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber and preparation method thereof - Google Patents
Organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber and preparation method thereof Download PDFInfo
- Publication number
- CN113737303A CN113737303A CN202111105366.1A CN202111105366A CN113737303A CN 113737303 A CN113737303 A CN 113737303A CN 202111105366 A CN202111105366 A CN 202111105366A CN 113737303 A CN113737303 A CN 113737303A
- Authority
- CN
- China
- Prior art keywords
- montmorillonite
- polyethylene glycol
- glycol modified
- reaction
- toughened
- 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.)
- Withdrawn
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 49
- 230000032683 aging Effects 0.000 title claims abstract description 35
- 229910017059 organic montmorillonite Inorganic materials 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims description 6
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical class O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 176
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 154
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 145
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 47
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 42
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 claims abstract description 41
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 32
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000012964 benzotriazole Substances 0.000 claims abstract description 25
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229940014800 succinic anhydride Drugs 0.000 claims abstract description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 105
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 57
- 239000002904 solvent Substances 0.000 claims description 52
- 238000006243 chemical reaction Methods 0.000 claims description 50
- 238000009987 spinning Methods 0.000 claims description 47
- 238000003756 stirring Methods 0.000 claims description 46
- 238000001035 drying Methods 0.000 claims description 43
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 36
- 238000005406 washing Methods 0.000 claims description 34
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 18
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 125000002252 acyl group Chemical group 0.000 claims description 13
- 238000006467 substitution reaction Methods 0.000 claims description 12
- 238000005886 esterification reaction Methods 0.000 claims description 11
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims description 10
- DPJCXCZTLWNFOH-UHFFFAOYSA-N 2-nitroaniline Chemical compound NC1=CC=CC=C1[N+]([O-])=O DPJCXCZTLWNFOH-UHFFFAOYSA-N 0.000 claims description 9
- 239000004709 Chlorinated polyethylene Substances 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 229960001701 chloroform Drugs 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000005457 ice water Substances 0.000 claims description 9
- 235000010288 sodium nitrite Nutrition 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 8
- 238000007142 ring opening reaction Methods 0.000 claims description 5
- 238000005660 chlorination reaction Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 7
- 239000011159 matrix material Substances 0.000 abstract description 7
- 230000006750 UV protection Effects 0.000 abstract description 6
- 230000035882 stress Effects 0.000 abstract description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 abstract 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 42
- 239000005020 polyethylene terephthalate Substances 0.000 description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 15
- 229920000728 polyester Polymers 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 229920000620 organic polymer Polymers 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 229920000891 common polymer Polymers 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- -1 polyethylene terephthalate Polymers 0.000 description 2
- 239000012763 reinforcing filler Substances 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 208000013201 Stress fracture Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Images
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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- 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
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Artificial Filaments (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to the technical field of PET (polyethylene glycol terephthalate) fibers, and discloses an organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber, wherein chlorinated montmorillonite reacts with polyethylene glycol to obtain polyethylene glycol modified montmorillonite, the polyethylene glycol modified montmorillonite reacts with succinic anhydride to obtain carboxylated polyethylene glycol modified montmorillonite, the carboxylated polyethylene glycol modified montmorillonite is modified by thionyl chloride to obtain acyl chloride-based polyethylene glycol modified montmorillonite, the acyl chloride-based polyethylene glycol modified montmorillonite further reacts with a benzotriazole derivative to obtain benzotriazole-based polyethylene glycol modified montmorillonite, the montmorillonite can absorb stress, the polyethylene glycol long chain can enhance the flexibility of a PET matrix, the toughness of the composite PET fiber is further improved, meanwhile, the montmorillonite can absorb and scatter ultraviolet light, the benzotriazole group can convert high-energy ultraviolet light into heat energy, and the mechanical property, the ultraviolet resistance and the aging resistance of the composite PET fiber are greatly improved by combining the advantages of montmorillonite, the polyethylene glycol and the benzotriazole, The comprehensive properties of ultraviolet resistance and the like further expand the application field of PET.
Description
Technical Field
The invention relates to the technical field of PET (polyethylene terephthalate) fibers, in particular to an organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber and a preparation method thereof.
Background
With the continuous damage of the atmospheric layer, more and more ultraviolet rays are projected on the surface of the earth, the high-energy ultraviolet rays irradiate the skin of human being for a long time and cause great harm to the health of people, so that the ultraviolet-resistant fabric is gradually concerned, and the research heat is aroused in the world, and the polyester fiber (PET) has the characteristics of good wrinkle resistance, high shape retention, strong elasticity and the like, and has great application value in the field of clothing fiber, but the polyester fiber matrix does not have the ultraviolet resistance and can not shield the ultraviolet rays, the strength of the polyester fiber is not high enough, the phenomena of thread breakage, pulling crack and the like are easy to occur, the further development of the polyester fiber is greatly limited, so that the traditional polyester fiber is modified at will, and the filling modification is a common polymer modification means, namely, the epoxy resin and the filling modification means are common polymer modification means, Organic polymer materials such as PET and the like are filled with inorganic nano materials such as titanium dioxide, montmorillonite and the like with excellent performances such as high strength, ultraviolet absorption and the like, or organic polymer materials such as polyvinyl alcohol, polyethylene glycol and the like with toughening and reinforcing performances, and the effect of improving the comprehensive performance of the organic polymer materials is achieved by combining the advantages of the organic and inorganic materials.
Montmorillonite, a nano-dimension silicate sheet layer with negative charges on the surface, has good adsorbability, dimensional stability and gas barrier property, and in recent years, the application of montmorillonite as a functional reinforcing filler is gradually developed by people, but the montmorillonite on the nano layer surface is easy to agglomerate, and can not be stably dispersed when the addition amount in the organic polymer material matrix is higher, moreover, the ultraviolet shielding performance of the montmorillonite is relatively common, and the performance can be greatly improved without adding a small amount of montmorillonite, therefore, montmorillonite needs to be modified, the surface of montmorillonite is organically modified by using a silane coupling agent, and then an organic functional group with special performance is introduced through an active functional group of the silane coupling agent, can improve the strength and the breadth of the montmorillonite used as the functional reinforcing filler and provide great convenience for the further application of the montmorillonite.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides an organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber and a preparation method thereof, and solves the problems that the traditional polyester fiber is poor in strength and does not have anti-ultraviolet aging performance.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: the preparation method of the organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber comprises the following steps:
(1) adding a deionized water solvent, nano-montmorillonite and 3-chloropropyl triethoxysilane with the mass ratio of 100: 180-;
(2) adding an absolute ethyl alcohol solvent and chlorinated montmorillonite into a three-neck flask, uniformly dispersing by ultrasonic, adding potassium hydroxide and n-tetrabutylammonium sulfate, placing the mixture in an ice-water bath, stirring for 5-15min, continuously adding polyethylene glycol into the system for substitution reaction, centrifuging after the reaction is finished, distilling under reduced pressure to remove the solvent, filtering, purifying and drying to obtain polyethylene glycol modified montmorillonite;
(3) adding a toluene solvent and polyethylene glycol modified montmorillonite into a three-neck bottle, ultrasonically dispersing uniformly, continuously adding succinic anhydride, transferring into an oil bath pot, raising the temperature to perform ring-opening esterification reaction, filtering, washing, centrifuging and drying a product to obtain carboxylated polyethylene glycol modified montmorillonite;
(4) adding a toluene solvent and carboxylated polyethylene glycol modified montmorillonite into a three-neck bottle, ultrasonically dispersing uniformly, then continuously adding thionyl chloride, transferring into an oil bath pot, raising the temperature to perform acyl chlorination reaction, and after the reaction is finished, distilling under reduced pressure to remove the solvent, washing and drying to obtain acyl chlorinated polyethylene glycol modified montmorillonite;
(5) reacting o-nitroaniline, sodium nitrite, resorcinol, sodium hydroxide and zinc powder to obtain the benzotriazole derivative with the molecular formula of C12H9N3O2；
(6) Adding a trichloromethane solvent and acyl chloride polyethylene glycol modified montmorillonite into a three-necked bottle, ultrasonically dispersing uniformly, adding a benzotriazole derivative and sodium hydroxide, stirring until the benzotriazole derivative and the sodium hydroxide are completely dissolved, carrying out esterification reaction, and centrifuging, washing and drying after the reaction is finished to obtain benzotriazole-based polyethylene glycol modified montmorillonite;
(7) adding a dichloromethane solvent, PET and benzotriazole-based polyethylene glycol modified montmorillonite into a reactor, stirring to form a uniform spinning solution, pouring the uniform spinning solution into a high-speed spinning machine for spinning, transferring the uniform spinning solution to a drawing machine for drawing, and obtaining the organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber.
Preferably, the mass ratio of the montmorillonite chloride, the potassium hydroxide, the n-tetrabutylammonium sulfate and the polyethylene glycol in the step (2) is 100:40-80:0.6-1.4: 260-540.
Preferably, the temperature of the substitution reaction in the step (2) is 15-35 ℃, and the reaction is carried out for 20-30h under the condition of constant-temperature stirring in the nitrogen atmosphere.
Preferably, the mass ratio of the polyethylene glycol modified montmorillonite to the succinic anhydride in the step (3) is 100: 25-50.
Preferably, the temperature of the ring opening esterification reaction in the step (3) is 100-120 ℃, and the reaction is carried out for 4-10h under constant temperature reflux in a nitrogen atmosphere.
Preferably, the mass ratio of the carboxylated polyethylene glycol modified montmorillonite to the thionyl chloride in the step (4) is 100: 120-280.
Preferably, the temperature of the acyl chlorination reaction in the step (4) is 70-90 ℃, and the reaction is carried out for 20-30h under the stirring of nitrogen atmosphere.
Preferably, in the step (6), the mass ratio of the acyl chloride polyethylene glycol modified montmorillonite to the benzotriazole derivative to the sodium hydroxide is 100:15-35: 6-12.
Preferably, the temperature of the esterification reaction in the step (6) is 15-35 ℃, and the reaction is carried out for 2-6h under the condition of constant-temperature stirring in the nitrogen atmosphere.
Preferably, the mass ratio of the PET to the benzotriazole-based polyethylene glycol modified montmorillonite in the step (7) is 100: 2-6.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the surface of montmorillonite modified by 3-chloropropyltriethoxysilane contains a large amount of chlorine atoms, and the montmorillonite is subjected to substitution reaction with hydroxyl in polyethylene glycol under the combined action of a catalyst n-tetrabutylammonium sulfate and acid-binding agent potassium hydroxide to obtain polyethylene glycol modified montmorillonite, the residual hydroxyl in the molecular chain of the polyethylene glycol modified montmorillonite can be subjected to ring-opening esterification reaction with succinic anhydride to obtain carboxylated polyethylene glycol modified montmorillonite, carboxyl in the carboxylated polyethylene glycol modified montmorillonite is modified into acyl chloride through modification of thionyl chloride to obtain acyl chloride-based polyethylene glycol modified montmorillonite, and the acyl chloride-based polyethylene glycol modified montmorillonite is further subjected to esterification reaction with para-position phenolic hydroxyl in a benzotriazole derivative under the action of acid-binding agent sodium hydroxide to obtain benzotriazole-based polyethylene glycol modified montmorillonite, and is modified by chemical bonds, organic molecules such as chlorine atoms, polyethylene glycol, carboxyl, acyl chloride groups, benzotriazole groups and the like are covalently grafted on the surface of the montmorillonite, and the application range of the montmorillonite is further improved by combining the excellent properties of the organic molecules, so that convenience is brought to the further application of the montmorillonite.
The organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber is prepared by adding benzotriazole-based polyethylene glycol modified montmorillonite into a PET matrix, spinning through a high-speed spinning machine to obtain the organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber, wherein the high strength and dimensional stability of montmorillonite enable the PET matrix to absorb a large amount of stress when being subjected to external force, and cracks generated by stress fracture can be prevented from further expanding, so that the mechanical properties such as tensile strength, impact strength and the like of the composite PET fiber are enhanced, polyethylene glycol long chains grafted on the surface of montmorillonite have good flexibility, and after forming a mutual winding network structure with the PET matrix, the flexibility of the PET matrix can be greatly enhanced, and when being subjected to external force, the flexible network can absorb a large amount of deformation work, so that the toughness of the composite PET fiber is further improved, in addition, montmorillonite is used as a silicate mineral, can absorb ultraviolet light, and can scatter high-energy ultraviolet light to the air through a higher specific surface area, so that the ultraviolet resistance of the composite PET fiber is improved to a certain extent, meanwhile, a benzotriazole group grafted on the surface of montmorillonite can form a chelated six-membered ring in a molecule under the irradiation of ultraviolet light, namely, the ultraviolet light with high energy is converted into heat energy required in chemical reaction, so that the ultraviolet resistance of the composite PET fiber is further improved, by combining the advantages of montmorillonite, polyethylene glycol and benzotriazole, the comprehensive performances of the composite PET fiber, such as mechanics, ultraviolet resistance and the like, are greatly improved, and the application field of PET is further expanded.
Drawings
FIG. 1 is a schematic representation of the reaction of chlorinated montmorillonite and polyethylene glycol.
FIG. 2 is a schematic diagram of the reaction of polyethylene glycol modified montmorillonite and succinic anhydride.
FIG. 3 is a schematic diagram of the reaction of carboxylated polyethylene glycol modified montmorillonite and thionyl chloride.
FIG. 4 is a reaction scheme of acyl chloride polyethylene glycol modified montmorillonite and benzotriazole derivative.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: an organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber is prepared by the following steps:
(1) adding a deionized water solvent, nano-montmorillonite and 3-chloropropyl triethoxysilane with the mass ratio of 100: 180-;
(2) adding an absolute ethanol solvent and montmorillonite chloride into a three-neck flask, uniformly dispersing by ultrasonic, adding potassium hydroxide and n-tetrabutylammonium sulfate, stirring in an ice-water bath for 5-15min, continuously adding polyethylene glycol into the system for substitution reaction, wherein the mass ratio of the montmorillonite chloride to the potassium hydroxide to the n-tetrabutylammonium sulfate to the polyethylene glycol is 100:40-80:0.6-1.4:260 and 540, reacting at 15-35 ℃ for 20-30h in a nitrogen atmosphere, centrifuging after the reaction is finished, distilling under reduced pressure to remove the solvent, filtering, purifying and drying to obtain polyethylene glycol modified montmorillonite;
(3) adding a toluene solvent and polyethylene glycol modified montmorillonite into a three-neck flask, uniformly dispersing by ultrasonic, continuously adding succinic anhydride, wherein the mass ratio of the polyethylene glycol modified montmorillonite to the succinic anhydride is 100:25-50, transferring the mixture into an oil bath pot, reacting for 4-10h at the temperature of 120 ℃ in a nitrogen atmosphere, filtering, washing, centrifuging and drying a product to obtain carboxylated polyethylene glycol modified montmorillonite;
(4) adding a toluene solvent and carboxylated polyethylene glycol modified montmorillonite into a three-neck flask, carrying out uniform ultrasonic dispersion, continuing adding thionyl chloride, wherein the mass ratio of the carboxylated polyethylene glycol modified montmorillonite to the thionyl chloride is 100:120-280, transferring the mixture into an oil bath pot, stirring and reacting for 20-30h at 70-90 ℃ in a nitrogen atmosphere, and after the reaction is finished, carrying out reduced pressure distillation to remove the solvent, washing and drying to obtain acyl chlorinated polyethylene glycol modified montmorillonite;
(5) reacting o-nitroaniline, sodium nitrite, resorcinol, sodium hydroxide and zinc powder to obtain the benzotriazole derivative with the molecular formula of C12H9N3O2；
(6) Adding a trichloromethane solvent and acyl chloride polyethylene glycol modified montmorillonite into a three-necked bottle, ultrasonically dispersing uniformly, adding a benzotriazole derivative and sodium hydroxide, wherein the mass ratio of the acyl chloride polyethylene glycol modified montmorillonite to the benzotriazole derivative to the sodium hydroxide is 100:15-35:6-12, stirring until the acyl chloride polyethylene glycol modified montmorillonite, the benzotriazole derivative and the sodium hydroxide are completely dissolved, reacting for 2-6h at 15-35 ℃ in a nitrogen atmosphere, centrifuging, washing and drying after the reaction is finished, so as to obtain benzotriazole-based polyethylene glycol modified montmorillonite;
(7) adding a dichloromethane solvent, PET and benzotriazole-based polyethylene glycol modified montmorillonite with the mass ratio of 100:2-6 into a reactor, stirring until uniform spinning solution is formed, pouring the spinning solution into a high-speed spinning machine for spinning, transferring the spinning solution onto a drawing machine for drawing, and obtaining the organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber.
Example 1
(1) Adding a deionized water solvent, nano-montmorillonite and 3-chloropropyl triethoxysilane in a mass ratio of 100:180 into a three-necked bottle, ultrasonically dispersing uniformly, adjusting the pH of the solution to 6 by using hydrochloric acid, transferring the solution into an oil bath pot, stirring at a constant temperature of 50 ℃ for reaction for 2 hours, centrifuging, washing and drying the product to obtain chlorinated montmorillonite;
(2) adding an absolute ethyl alcohol solvent and montmorillonite chloride into a three-neck flask, uniformly dispersing by ultrasonic, adding potassium hydroxide and n-tetrabutylammonium sulfate, stirring for 5min in an ice-water bath, continuously adding polyethylene glycol into the system for substitution reaction, wherein the mass ratio of the montmorillonite chloride to the potassium hydroxide to the n-tetrabutylammonium sulfate to the polyethylene glycol is 100:40:0.6:260, reacting for 20h at 15 ℃ in a nitrogen atmosphere, centrifuging after the reaction is finished, distilling under reduced pressure to remove the solvent, filtering, purifying and drying to obtain polyethylene glycol modified montmorillonite;
(3) adding a toluene solvent and polyethylene glycol modified montmorillonite into a three-neck flask, uniformly dispersing by ultrasonic, continuously adding succinic anhydride, wherein the mass ratio of the polyethylene glycol modified montmorillonite to the succinic anhydride is 100:25, transferring the mixture into an oil bath pot, reacting for 4 hours at 100 ℃ in a nitrogen atmosphere, filtering, washing, centrifuging and drying a product to obtain carboxylated polyethylene glycol modified montmorillonite;
(4) adding a toluene solvent and carboxylated polyethylene glycol modified montmorillonite into a three-neck flask, carrying out uniform ultrasonic dispersion, then continuously adding thionyl chloride, wherein the mass ratio of the carboxylated polyethylene glycol modified montmorillonite to the thionyl chloride is 100:120, transferring the mixture into an oil bath pot, carrying out stirring reaction for 20 hours at 70 ℃ in a nitrogen atmosphere, carrying out reduced pressure distillation after the reaction is finished to remove the solvent, washing and drying to obtain acyl chlorinated polyethylene glycol modified montmorillonite;
(5) reacting o-nitroaniline, sodium nitrite, resorcinol, sodium hydroxide and zinc powder to obtain the benzotriazole derivative with the molecular formula of C12H9N3O2；
(6) Adding a trichloromethane solvent and acyl chloride polyethylene glycol modified montmorillonite into a three-necked bottle, ultrasonically dispersing uniformly, adding a benzotriazole derivative and sodium hydroxide, wherein the mass ratio of the acyl chloride polyethylene glycol modified montmorillonite to the benzotriazole derivative to the sodium hydroxide is 100:15:6, stirring until the acyl chloride polyethylene glycol modified montmorillonite, the benzotriazole derivative and the sodium hydroxide are completely dissolved, reacting for 2 hours at 15 ℃ in a nitrogen atmosphere, centrifuging, washing and drying after the reaction is finished, so as to obtain benzotriazole-based polyethylene glycol modified montmorillonite;
(7) adding a dichloromethane solvent, PET and benzotriazole-based polyethylene glycol modified montmorillonite with the mass ratio of 100:2 into a reactor, stirring until uniform spinning solution is formed, pouring the spinning solution into a high-speed spinning machine for spinning, transferring the spinning solution to a drawing machine for drawing, and obtaining the organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber.
Example 2
(1) Adding a deionized water solvent, nano-montmorillonite and 3-chloropropyl triethoxysilane in a mass ratio of 100:240 into a three-necked bottle, ultrasonically dispersing uniformly, adjusting the pH of the solution to 7 by hydrochloric acid, transferring the solution into an oil bath pot, stirring at a constant temperature of 55 ℃ for reaction for 3 hours, centrifuging, washing and drying the product to obtain chlorinated montmorillonite;
(2) adding an absolute ethyl alcohol solvent and montmorillonite chloride into a three-neck flask, uniformly dispersing by ultrasonic, adding potassium hydroxide and n-tetrabutylammonium sulfate, stirring for 6min in an ice-water bath, continuously adding polyethylene glycol into the system for substitution reaction, wherein the mass ratio of the montmorillonite chloride to the potassium hydroxide to the n-tetrabutylammonium sulfate to the polyethylene glycol is 100:50:0.8:330, reacting for 22h at 20 ℃ in a nitrogen atmosphere, centrifuging after the reaction is finished, distilling under reduced pressure to remove the solvent, filtering, purifying and drying to obtain polyethylene glycol modified montmorillonite;
(3) adding a toluene solvent and polyethylene glycol modified montmorillonite into a three-neck flask, uniformly dispersing by ultrasonic, continuously adding succinic anhydride, wherein the mass ratio of the polyethylene glycol modified montmorillonite to the succinic anhydride is 100:30, transferring the mixture into an oil bath pot, reacting for 5 hours at 105 ℃ in a nitrogen atmosphere, filtering, washing, centrifuging and drying a product to obtain carboxylated polyethylene glycol modified montmorillonite;
(4) adding a toluene solvent and carboxylated polyethylene glycol modified montmorillonite into a three-neck flask, carrying out uniform ultrasonic dispersion, then continuously adding thionyl chloride, wherein the mass ratio of the carboxylated polyethylene glycol modified montmorillonite to the thionyl chloride is 100:160, transferring the mixture into an oil bath pot, carrying out stirring reaction for 22 hours at 75 ℃ in a nitrogen atmosphere, carrying out reduced pressure distillation after the reaction is finished to remove the solvent, washing and drying to obtain acyl chlorinated polyethylene glycol modified montmorillonite;
(5) reacting o-nitroaniline, sodium nitrite, resorcinol, sodium hydroxide and zinc powder to obtain the benzotriazole derivative with the molecular formula of C12H9N3O2；
(6) Adding a trichloromethane solvent and acyl chloride polyethylene glycol modified montmorillonite into a three-necked bottle, ultrasonically dispersing uniformly, adding a benzotriazole derivative and sodium hydroxide, wherein the mass ratio of the acyl chloride polyethylene glycol modified montmorillonite to the benzotriazole derivative to the sodium hydroxide is 100:20:7.5, stirring until the acyl chloride polyethylene glycol modified montmorillonite, the benzotriazole derivative and the sodium hydroxide are completely dissolved, reacting for 3 hours at 20 ℃ in a nitrogen atmosphere, centrifuging, washing and drying after the reaction is finished, so as to obtain benzotriazole-based polyethylene glycol modified montmorillonite;
(7) adding a dichloromethane solvent, PET and benzotriazole-based polyethylene glycol modified montmorillonite with the mass ratio of 100:3 into a reactor, stirring until uniform spinning solution is formed, pouring the spinning solution into a high-speed spinning machine for spinning, transferring the spinning solution to a drawing machine for drawing, and obtaining the organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber.
Example 3
(1) Adding a deionized water solvent, nano-montmorillonite and 3-chloropropyl triethoxysilane in a mass ratio of 100:290 into a three-necked bottle, ultrasonically dispersing uniformly, adjusting the pH of the solution to 7 by hydrochloric acid, transferring the solution into an oil bath pot, stirring at a constant temperature of 60 ℃ for reaction for 4 hours, centrifuging, washing and drying the product to obtain chlorinated montmorillonite;
(2) adding an absolute ethyl alcohol solvent and montmorillonite chloride into a three-neck flask, ultrasonically dispersing uniformly, adding potassium hydroxide and n-tetrabutylammonium sulfate, stirring for 10min in an ice-water bath, continuously adding polyethylene glycol into the system for substitution reaction, wherein the mass ratio of the montmorillonite chloride to the potassium hydroxide to the n-tetrabutylammonium sulfate to the polyethylene glycol is 100:60:1:400, reacting for 25h at 25 ℃ in a nitrogen atmosphere, centrifuging after the reaction is finished, distilling under reduced pressure to remove the solvent, filtering, purifying and drying to obtain polyethylene glycol modified montmorillonite;
(3) adding a toluene solvent and polyethylene glycol modified montmorillonite into a three-neck flask, uniformly dispersing by ultrasonic, continuously adding succinic anhydride, wherein the mass ratio of the polyethylene glycol modified montmorillonite to the succinic anhydride is 100:38, transferring the mixture into an oil bath pot, reacting for 6 hours at 110 ℃ in a nitrogen atmosphere, filtering, washing, centrifuging and drying a product to obtain carboxylated polyethylene glycol modified montmorillonite;
(4) adding a toluene solvent and carboxylated polyethylene glycol modified montmorillonite into a three-neck flask, carrying out uniform ultrasonic dispersion, then continuously adding thionyl chloride, wherein the mass ratio of the carboxylated polyethylene glycol modified montmorillonite to the thionyl chloride is 100:200, transferring the mixture into an oil bath pot, carrying out stirring reaction for 25 hours at 80 ℃ in a nitrogen atmosphere, carrying out reduced pressure distillation after the reaction is finished to remove the solvent, washing and drying to obtain acyl chlorinated polyethylene glycol modified montmorillonite;
(5) reacting o-nitroaniline, sodium nitrite, resorcinol, sodium hydroxide and zinc powder to obtain the benzotriazole derivative with the molecular formula of C12H9N3O2；
(6) Adding a trichloromethane solvent and acyl chloride polyethylene glycol modified montmorillonite into a three-necked bottle, ultrasonically dispersing uniformly, adding a benzotriazole derivative and sodium hydroxide, wherein the mass ratio of the acyl chloride polyethylene glycol modified montmorillonite to the benzotriazole derivative to the sodium hydroxide is 100:25:9, stirring until the acyl chloride polyethylene glycol modified montmorillonite, the benzotriazole derivative and the sodium hydroxide are completely dissolved, reacting for 4 hours at 25 ℃ in a nitrogen atmosphere, centrifuging, washing and drying after the reaction is finished, so as to obtain benzotriazole-based polyethylene glycol modified montmorillonite;
(7) adding a dichloromethane solvent, PET and benzotriazole-based polyethylene glycol modified montmorillonite with the mass ratio of 100:4 into a reactor, stirring until uniform spinning solution is formed, pouring the spinning solution into a high-speed spinning machine for spinning, transferring the spinning solution to a drawing machine for drawing, and obtaining the organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber.
Example 4
(1) Adding a deionized water solvent, nano-montmorillonite and 3-chloropropyl triethoxysilane in a mass ratio of 100:350 into a three-necked bottle, ultrasonically dispersing uniformly, adjusting the pH of the solution to 7 by using hydrochloric acid, transferring the solution into an oil bath pot, stirring at a constant temperature of 65 ℃ for reaction for 5 hours, centrifuging, washing and drying the product to obtain chlorinated montmorillonite;
(2) adding an absolute ethyl alcohol solvent and montmorillonite chloride into a three-neck flask, uniformly dispersing by ultrasonic, adding potassium hydroxide and n-tetrabutylammonium sulfate, stirring in an ice-water bath for 12min, continuously adding polyethylene glycol into the system for substitution reaction, wherein the mass ratio of the montmorillonite chloride to the potassium hydroxide to the n-tetrabutylammonium sulfate to the polyethylene glycol is 100:70:1.2:470, reacting for 28h at 30 ℃ in a nitrogen atmosphere, centrifuging after the reaction is finished, distilling under reduced pressure to remove the solvent, filtering, purifying and drying to obtain polyethylene glycol modified montmorillonite;
(3) adding a toluene solvent and polyethylene glycol modified montmorillonite into a three-neck flask, uniformly dispersing by ultrasonic, continuously adding succinic anhydride, wherein the mass ratio of the polyethylene glycol modified montmorillonite to the succinic anhydride is 100:44, transferring the mixture into an oil bath pot, reacting for 8 hours at 115 ℃ in a nitrogen atmosphere, filtering, washing, centrifuging and drying a product to obtain carboxylated polyethylene glycol modified montmorillonite;
(4) adding a toluene solvent and carboxylated polyethylene glycol modified montmorillonite into a three-neck flask, carrying out uniform ultrasonic dispersion, then continuously adding thionyl chloride, wherein the mass ratio of the carboxylated polyethylene glycol modified montmorillonite to the thionyl chloride is 100:240, transferring the mixture into an oil bath pot, carrying out stirring reaction for 28 hours at 85 ℃ in a nitrogen atmosphere, carrying out reduced pressure distillation after the reaction is finished to remove the solvent, washing and drying to obtain acyl chlorinated polyethylene glycol modified montmorillonite;
(5) reacting o-nitroaniline, sodium nitrite, resorcinol, sodium hydroxide and zinc powder to obtain the benzotriazole derivative with the molecular formula of C12H9N3O2；
(6) Adding a trichloromethane solvent and acyl chloride polyethylene glycol modified montmorillonite into a three-necked bottle, ultrasonically dispersing uniformly, adding a benzotriazole derivative and sodium hydroxide, wherein the mass ratio of the acyl chloride polyethylene glycol modified montmorillonite to the benzotriazole derivative to the sodium hydroxide is 100:30:10.5, stirring until the acyl chloride polyethylene glycol modified montmorillonite, the benzotriazole derivative and the sodium hydroxide are completely dissolved, reacting for 5 hours at 30 ℃ in a nitrogen atmosphere, centrifuging, washing and drying after the reaction is finished, so as to obtain benzotriazole-based polyethylene glycol modified montmorillonite;
(7) adding a dichloromethane solvent, PET and benzotriazole-based polyethylene glycol modified montmorillonite with the mass ratio of 100:5 into a reactor, stirring until uniform spinning solution is formed, pouring the spinning solution into a high-speed spinning machine for spinning, transferring the spinning solution to a drawing machine for drawing, and obtaining the organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber.
Example 5
(1) Adding a deionized water solvent, nano-montmorillonite and 3-chloropropyl triethoxysilane in a mass ratio of 100:400 into a three-necked bottle, ultrasonically dispersing uniformly, adjusting the pH of the solution to 8 by using hydrochloric acid, transferring the solution into an oil bath pot, stirring at a constant temperature of 70 ℃ for reacting for 6 hours, centrifuging, washing and drying the product to obtain chlorinated montmorillonite;
(2) adding an absolute ethyl alcohol solvent and montmorillonite chloride into a three-neck flask, uniformly dispersing by ultrasonic, adding potassium hydroxide and n-tetrabutylammonium sulfate, stirring for 15min in an ice-water bath, continuously adding polyethylene glycol into the system for substitution reaction, wherein the mass ratio of the montmorillonite chloride to the potassium hydroxide to the n-tetrabutylammonium sulfate to the polyethylene glycol is 100:80:1.4:540, reacting for 30h at 35 ℃ in a nitrogen atmosphere, centrifuging after the reaction is finished, distilling under reduced pressure to remove the solvent, filtering, purifying and drying to obtain polyethylene glycol modified montmorillonite;
(3) adding a toluene solvent and polyethylene glycol modified montmorillonite into a three-neck flask, uniformly dispersing by ultrasonic, continuously adding succinic anhydride, wherein the mass ratio of the polyethylene glycol modified montmorillonite to the succinic anhydride is 100:50, transferring the mixture into an oil bath pot, reacting for 10 hours at 120 ℃ in a nitrogen atmosphere, filtering, washing, centrifuging and drying a product to obtain carboxylated polyethylene glycol modified montmorillonite;
(4) adding a toluene solvent and carboxylated polyethylene glycol modified montmorillonite into a three-neck flask, ultrasonically dispersing uniformly, then continuously adding thionyl chloride, wherein the mass ratio of the carboxylated polyethylene glycol modified montmorillonite to the thionyl chloride is 100:280, transferring the mixture into an oil bath pot, stirring and reacting for 30 hours at 90 ℃ in a nitrogen atmosphere, and after the reaction is finished, distilling under reduced pressure to remove the solvent, washing and drying to obtain acyl chlorinated polyethylene glycol modified montmorillonite;
(5) prepared from o-nitroaniline, sodium nitrite, resorcinol, and hydrogen oxygenSodium hydroxide reacts with zinc powder to obtain benzotriazole derivative with molecular formula of C12H9N3O2；
(6) Adding a trichloromethane solvent and acyl chloride polyethylene glycol modified montmorillonite into a three-necked bottle, ultrasonically dispersing uniformly, adding a benzotriazole derivative and sodium hydroxide, wherein the mass ratio of the acyl chloride polyethylene glycol modified montmorillonite to the benzotriazole derivative to the sodium hydroxide is 100:35:12, stirring until the acyl chloride polyethylene glycol modified montmorillonite, the benzotriazole derivative and the sodium hydroxide are completely dissolved, reacting for 6 hours at 35 ℃ in a nitrogen atmosphere, centrifuging, washing and drying after the reaction is finished, so as to obtain benzotriazole-based polyethylene glycol modified montmorillonite;
(7) adding a dichloromethane solvent, PET and benzotriazole-based polyethylene glycol modified montmorillonite with the mass ratio of 100:6 into a reactor, stirring until uniform spinning solution is formed, pouring the spinning solution into a high-speed spinning machine for spinning, transferring the spinning solution to a drawing machine for drawing, and obtaining the organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber.
Comparative example 1
(1) Adding a deionized water solvent, nano-montmorillonite and 3-chloropropyl triethoxysilane in a mass ratio of 100:120 into a three-necked bottle, ultrasonically dispersing uniformly, adjusting the pH of the solution to 6 by using hydrochloric acid, transferring the solution into an oil bath pot, stirring at a constant temperature of 50 ℃ for reaction for 1 hour, centrifuging, washing and drying the product to obtain chlorinated montmorillonite;
(2) adding an absolute ethyl alcohol solvent and montmorillonite chloride into a three-neck flask, ultrasonically dispersing uniformly, adding potassium hydroxide and n-tetrabutylammonium sulfate, placing the mixture into an ice water bath, stirring for 2min, continuously adding polyethylene glycol into the system for substitution reaction, wherein the mass ratio of the montmorillonite chloride to the potassium hydroxide to the n-tetrabutylammonium sulfate to the polyethylene glycol is 100:30:0.4:190, reacting for 18h at 15 ℃ in a nitrogen atmosphere, centrifuging after the reaction is finished, distilling under reduced pressure to remove the solvent, filtering, purifying and drying to obtain polyethylene glycol modified montmorillonite;
(3) adding a toluene solvent and polyethylene glycol modified montmorillonite into a three-neck flask, uniformly dispersing by ultrasonic, continuously adding succinic anhydride, wherein the mass ratio of the polyethylene glycol modified montmorillonite to the succinic anhydride is 100:18, transferring the mixture into an oil bath pot, reacting for 3 hours at 100 ℃ in a nitrogen atmosphere, filtering, washing, centrifuging and drying a product to obtain carboxylated polyethylene glycol modified montmorillonite;
(4) adding a toluene solvent and carboxylated polyethylene glycol modified montmorillonite into a three-neck flask, carrying out uniform ultrasonic dispersion, then continuously adding thionyl chloride, wherein the mass ratio of the carboxylated polyethylene glycol modified montmorillonite to the thionyl chloride is 100:80, transferring the mixture into an oil bath pot, carrying out stirring reaction for 18 hours at 70 ℃ in a nitrogen atmosphere, carrying out reduced pressure distillation after the reaction is finished to remove the solvent, washing and drying to obtain acyl chlorinated polyethylene glycol modified montmorillonite;
(5) reacting o-nitroaniline, sodium nitrite, resorcinol, sodium hydroxide and zinc powder to obtain the benzotriazole derivative with the molecular formula of C12H9N3O2；
(6) Adding a trichloromethane solvent and acyl chloride polyethylene glycol modified montmorillonite into a three-necked bottle, ultrasonically dispersing uniformly, adding a benzotriazole derivative and sodium hydroxide, wherein the mass ratio of the acyl chloride polyethylene glycol modified montmorillonite to the benzotriazole derivative to the sodium hydroxide is 100:10:4.5, stirring until the acyl chloride polyethylene glycol modified montmorillonite, the benzotriazole derivative and the sodium hydroxide are completely dissolved, reacting for 1h at 15 ℃ in a nitrogen atmosphere, centrifuging, washing and drying after the reaction is finished, so as to obtain benzotriazole-based polyethylene glycol modified montmorillonite;
(7) adding a dichloromethane solvent, PET and benzotriazole-based polyethylene glycol modified montmorillonite with the mass ratio of 100:1 into a reactor, stirring until uniform spinning solution is formed, pouring the spinning solution into a high-speed spinning machine for spinning, transferring the spinning solution to a drawing machine for drawing, and obtaining the organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber.
And testing the tensile strength and the elongation at break of the organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber by using a BLD-1028A tensile strength testing machine and the tensile strength and the elongation at break of the organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber after being irradiated by ultraviolet rays for 60 hours.
And testing the impact strength of the organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber and the impact strength of the organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber after being irradiated by ultraviolet rays for 60 hours by using an HH300-500J impact strength tester.
Claims (10)
1. An organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber is characterized in that: the preparation method of the organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber comprises the following steps:
(1) adding nano-montmorillonite and 3-chloropropyl triethoxysilane with the mass ratio of 100:180-400 into a deionized water solvent, ultrasonically dispersing uniformly, adjusting the pH of the solution to 6-8 by using hydrochloric acid, transferring the solution into an oil bath pot, stirring at a constant temperature of 50-70 ℃ for reaction for 2-6h, centrifuging, washing and drying the product to obtain chlorinated montmorillonite;
(2) adding chlorinated montmorillonite into an absolute ethyl alcohol solvent, performing ultrasonic dispersion uniformly, adding potassium hydroxide and n-tetrabutylammonium sulfate, stirring in an ice-water bath, adding polyethylene glycol for substitution reaction, centrifuging after the reaction is finished, performing reduced pressure distillation, filtering and drying to obtain polyethylene glycol modified montmorillonite;
(3) adding polyethylene glycol modified montmorillonite into a toluene solvent, uniformly dispersing by ultrasonic, continuously adding succinic anhydride, transferring to an oil bath pot, raising the temperature to perform ring-opening esterification reaction, filtering, washing, centrifuging and drying a product to obtain carboxylated polyethylene glycol modified montmorillonite;
(4) adding carboxylated polyethylene glycol modified montmorillonite into a toluene solvent, adding thionyl chloride after ultrasonic dispersion is uniform, transferring the mixture into an oil bath pot, raising the temperature to perform acyl chlorination reaction, and after the reaction is finished, performing reduced pressure distillation, washing and drying to obtain acyl chlorinated polyethylene glycol modified montmorillonite;
(5) prepared from o-nitroaniline, sodium nitrite, resorcinol, sodium hydroxide and zinc powderReacting to obtain benzotriazole derivative with molecular formula C12H9N3O2；
(6) Adding acyl chloride polyethylene glycol modified montmorillonite into a trichloromethane solvent, adding a benzotriazole derivative and sodium hydroxide after uniform ultrasonic dispersion, transferring the mixture into an oil bath pot for esterification, and centrifuging, washing and drying after the reaction is finished to obtain benzotriazole-based polyethylene glycol modified montmorillonite;
(7) adding PET and benzotriazole-based polyethylene glycol modified montmorillonite into a dichloromethane solvent, stirring to form a uniform spinning solution, pouring the uniform spinning solution into a high-speed spinning machine for spinning, transferring the uniform spinning solution onto a drawing machine for drawing, and obtaining the organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber.
2. The organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber as claimed in claim 1, which is characterized in that: the mass ratio of the chlorinated montmorillonite to the potassium hydroxide to the n-tetrabutylammonium sulfate to the polyethylene glycol in the step (2) is 100:40-80:0.6-1.4: 260-.
3. The organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber as claimed in claim 1, which is characterized in that: the temperature of the substitution reaction in the step (2) is 15-35 ℃, and the reaction is carried out for 20-30h under the condition of constant-temperature stirring in the nitrogen atmosphere.
4. The organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber as claimed in claim 1, which is characterized in that: the mass ratio of the polyethylene glycol modified montmorillonite to the succinic anhydride in the step (3) is 100: 25-50.
5. The organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber as claimed in claim 1, which is characterized in that: the temperature of the ring opening esterification reaction in the step (3) is 100-120 ℃, and the reaction is carried out for 4-10h under constant temperature reflux in a nitrogen atmosphere.
6. The organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber as claimed in claim 1, which is characterized in that: the mass ratio of the carboxylated polyethylene glycol modified montmorillonite to the thionyl chloride in the step (4) is 100: 120-280.
7. The organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber as claimed in claim 1, which is characterized in that: the temperature of the acyl chlorination reaction in the step (4) is 70-90 ℃, and the reaction is carried out for 20-30h under the stirring of nitrogen atmosphere.
8. The organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber as claimed in claim 1, which is characterized in that: in the step (6), the mass ratio of the acyl chloride polyethylene glycol modified montmorillonite to the benzotriazole derivative to the sodium hydroxide is 100:15-35: 6-12.
9. The organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber as claimed in claim 1, which is characterized in that: the temperature of the esterification reaction in the step (6) is 15-35 ℃, and the esterification reaction is carried out for 2-6h under the condition of constant-temperature stirring in the nitrogen atmosphere.
10. The organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber as claimed in claim 1, which is characterized in that: the mass ratio of the PET to the benzotriazole-based polyethylene glycol modified montmorillonite in the step (7) is 100: 2-6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111105366.1A CN113737303A (en) | 2021-09-22 | 2021-09-22 | Organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111105366.1A CN113737303A (en) | 2021-09-22 | 2021-09-22 | Organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113737303A true CN113737303A (en) | 2021-12-03 |
Family
ID=78740172
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111105366.1A Withdrawn CN113737303A (en) | 2021-09-22 | 2021-09-22 | Organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113737303A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114516746A (en) * | 2022-03-31 | 2022-05-20 | 黄伟 | Radiation-proof diatom board and preparation method thereof |
| CN114685890A (en) * | 2021-12-19 | 2022-07-01 | 徐州苏力德木业有限公司 | Functionalized montmorillonite flame-retardant modified polypropylene composite board and preparation method thereof |
-
2021
- 2021-09-22 CN CN202111105366.1A patent/CN113737303A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114685890A (en) * | 2021-12-19 | 2022-07-01 | 徐州苏力德木业有限公司 | Functionalized montmorillonite flame-retardant modified polypropylene composite board and preparation method thereof |
| CN114685890B (en) * | 2021-12-19 | 2023-09-12 | 徐州苏力德木业有限公司 | Functionalized montmorillonite flame-retardant modified polypropylene composite board and preparation method thereof |
| CN114516746A (en) * | 2022-03-31 | 2022-05-20 | 黄伟 | Radiation-proof diatom board and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113737303A (en) | Organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber and preparation method thereof | |
| Hoyos et al. | Cellulose nanofibrils extracted from fique fibers as bio-based cement additive | |
| CN105968717B (en) | A kind of preparation of carbon fiber/graphite alkene/carbon nano tube/epoxy resin prepreg and carbon fibre composite | |
| Jung et al. | High strength epoxy nanocomposites reinforced by epoxy functionalized aramid nanofibers | |
| CN105603717B (en) | A kind of surface modification of aramid fiber and preparation method thereof | |
| CN105906842B (en) | A kind of modified graphene oxide and epoxy resin composite material and preparation method thereof | |
| CN103865295B (en) | Method for polymer surface modification of hollow glass micro-bead | |
| Tang et al. | Flexible conductive polypyrrole nanocomposite membranes based on bacterial cellulose with amphiphobicity | |
| CN109705377B (en) | Nano-cellulose-enhanced photo-crosslinking polyvinyl alcohol hydrogel and preparation method and application thereof | |
| CN104262881A (en) | Method for preparing high-strength double-network nano silicon dioxide composite hydrogel | |
| Fang et al. | Disintegrable, transparent and mechanically robust high-performance antimony tin oxide/nanocellulose/polyvinyl alcohol thermal insulation films | |
| CN106430159B (en) | Pi bond is conjugated the tough highly conductive bionic laminar graphene composite material preparation method of integration | |
| CN114059347B (en) | Surface modification method for improving combination property of ultra-high molecular weight polyethylene fiber and matrix resin | |
| Cheng et al. | Hydrothermal synthesis of nanocellulose-based fluorescent hydrogel for mercury ion detection | |
| CN109336415B (en) | Method for carrying out fiber surface modification on basalt fiber by using silicon carbon black | |
| CN102251386B (en) | Environmentally friendly modified bast fiber containing functional structure, and preparation method thereof | |
| Shih et al. | Development of eco-friendly modified cellulose nanofiber reinforced polystyrene nanocomposites: Thermal, mechanical, and optical properties | |
| CN109956465B (en) | Preparation method of long-chain conjugated pi-bond crosslinked ultra-tough high-conductivity graphene composite film | |
| KR102659609B1 (en) | Carbon fiber coating method and carbon fiber woven fabric produced through the method | |
| CN1282792C (en) | Sol-gel anti-ultraviolet finishing method for cotton fabric | |
| CN109810349A (en) | A kind of anticorrosive impact resistance septic tank composite material and preparation method | |
| Li et al. | Effects of surface treatment on the properties of wheat straw fiber-reinforced rHDPE composites | |
| CN111944174A (en) | Method for improving interfacial adhesion of ultrahigh molecular weight polyethylene fibers and epoxy resin | |
| Abed et al. | Preparation of a novel composite based polyester nonwovens with high mechanical resistance and wash fastness properties | |
| Qu et al. | Developing multifunctional and environmental-friendly hot-pressed peanut meal protein adhesive based on peanut waste |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20211203 |