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CN114182386A - Functionalized graphene-polyester composite fiber and preparation method thereof - Google Patents

Functionalized graphene-polyester composite fiber and preparation method thereof Download PDF

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Publication number
CN114182386A
CN114182386A CN202111559538.2A CN202111559538A CN114182386A CN 114182386 A CN114182386 A CN 114182386A CN 202111559538 A CN202111559538 A CN 202111559538A CN 114182386 A CN114182386 A CN 114182386A
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graphene
hyperbranched
polyarylate
preparation
functionalized graphene
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孙国锋
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    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88Monocomponent 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
    • D01F6/92Monocomponent 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
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/10Other agents for modifying properties

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  • 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)

Abstract

The invention relates to the technical field of polyester, and discloses a functionalized graphene-polyester composite fiber, wherein a molecular chain of hyperbranched polyarylate grafted on the surface of graphene contains an aryl polyester structure, the hyperbranched polyarylate has good similar compatibility with arylate groups in polyethylene glycol terephthalate, and hydroxyl at the tail end of the hyperbranched polyarylate and the polyethylene glycol terephthalate form intermolecular hydrogen bonds, so that the functionalized graphene and the polyethylene glycol terephthalate have excellent interface acting force and compatibility, the hyperbranched polyarylate has a unique three-dimensional branched network structure, forms organic-inorganic hybrid ions with graphene, remarkably improves the breaking elongation and mechanical strength of polyester fiber, forms physical crosslinking sites in the polyester fiber, and blocks the chain segment motion of a PET polyester molecular chain, the thermal decomposition temperature and the thermal stability of the polyester fiber are improved.

Description

Functionalized graphene-polyester composite fiber and preparation method thereof
Technical Field
The invention relates to the technical field of polyester, in particular to a functionalized graphene-polyester composite fiber and a preparation method thereof.
Background
The synthetic fiber is one of three macromolecular materials, wherein the polyethylene terephthalate PET polyester fiber has strong solvent resistance and excellent electrical insulation property, and is widely applied to the aspects of electronic appliances, clothing fabrics and the like.
The utilization of inorganic nanoparticles such as graphene to modify PET fibers is a research hotspot, and graphene and PET fibers can be compounded by adopting ways such as blended spinning, grafting in-situ polymerization and the like, and a blended spinning method is adopted, because the compatibility of the graphene and the PET is poor, the graphene and the PET can be separated from each other after blending and spinning, and can damage the crystallinity of PET and influence the comprehensive performance of PET fibers, the hyperbranched polymer has a three-dimensional branched structure, is not easy to tangle among molecules, has low viscosity and good flow property, the hyperbranched polyurethane/PTT elastic fiber has excellent elasticity and hydrophilic hygroscopicity, so that hyperbranched polymers can be combined with graphene to cooperatively modify PET fibers.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides the functionalized graphene-polyester composite fiber and the preparation method thereof, which improve the compatibility and the interface bonding force between graphene and PET fibers and enhance the mechanical property and the thermal stability of the composite fiber.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a functionalized graphene-polyester composite fiber is prepared by the following steps:
(1) adding N, N-dimethylformamide, dimethylolpropionic acid and terephthalyl alcohol into a reaction bottle, introducing nitrogen and adding p-toluenesulfonic acid, heating to 120-140 ℃ for reaction for 6-18 h, cooling in an ice water bath after reaction, adding distilled water to precipitate, filtering, washing the product with distilled water and ethanol, and preparing the hyperbranched polyarylate with the hydroxyl at the tail end.
(2) Adding graphene oxide into thionyl chloride for reaction to prepare graphene containing acyl chloride, then adding graphene containing acyl chloride and hyperbranched polyarylate into an N, N-dimethylformamide solvent, performing ultrasonic dispersion, then dropwise adding a catalyst triethylamine, wherein the mass ratio of the graphene containing acyl chloride, the hyperbranched polyarylate and the triethylamine is 100:250-400:60-120, heating for reflux reaction, cooling in an ice water bath after reaction, adding distilled water to precipitate, filtering, washing products with distilled water and ethanol, and preparing the hyperbranched polyarylate grafted functionalized graphene.
(3) Adding the functionalized graphene and the polyethylene glycol terephthalate into a double-screw extruder, carrying out melt blending and extrusion granulation, carrying out melt spinning to obtain composite nascent fiber, and carrying out hot traction and stretching to obtain the functionalized graphene-polyester composite fiber.
Preferably, the mass ratio of the dimethylolpropionic acid to the terephthalic acid to the p-toluenesulfonic acid in the step (1) is 100:90-105: 3.5-5.
Preferably, the temperature of the reflux reaction in the step (2) is 80-120 ℃, and the reaction time is 24-48 h.
Preferably, the mass ratio of the functionalized graphene to the polyethylene terephthalate in the step (3) is 0.2-1: 100.
Preferably, the spinning speed of the melt spinning in the step (3) is 10-20 m/s, the spinning temperature is 290-310 ℃, the speed of the hot drawing is 3-4.5 m/s, and the drawing multiple is 3-4 times.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
according to the functionalized graphene-polyester composite fiber, a molecular chain of hyperbranched polyarylate synthesized from dimethylolpropionic acid and terephthalyl alcohol contains an aryl polyester structure, and the tail end of the hyperbranched polyarylate contains active hydroxyl, and the tail end of the hyperbranched polyarylate is subjected to esterification reaction with an acyl chloride group on the surface of graphene under the catalysis of triethylamine to obtain hyperbranched polyarylate grafted functionalized graphene, so that the hyperbranched polyarylate is chemically modified on the surface of the graphene.
The functional graphene and the polyethylene terephthalate (PET) are utilized to carry out blending spinning, the molecular chain of the hyperbranched polyarylate grafted on the surface of the graphene contains an aryl polyester structure, the aromatic polyester structure has good similar compatibility with the arylate group in the polyethylene terephthalate, and the hydroxyl at the tail end of the hyperbranched polyarylate and the polyethylene terephthalate form intermolecular hydrogen bonds, so that the functional graphene and the polyethylene terephthalate have excellent interface acting force and compatibility, the blending spinning can be carried out well, the problem that the mechanical property of the polyester fiber is influenced because the hydroxyl at the tail end of the hyperbranched polyarylate and the polyethylene terephthalate are easy to be separated is solved, the hyperbranched polyarylate has a unique three-dimensional branched network structure, forms organic-inorganic hybrid ions with the graphene, the breaking elongation and the mechanical strength of the polyester fiber are remarkably improved, and the functional graphene forms physical crosslinking sites in the polyester fiber, the chain segment movement of the PET polyester molecular chain is hindered, and the energy required by the thermal decomposition of the polyester fiber is increased, so that the thermal decomposition temperature and the thermal stability of the polyester fiber are improved.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a functionalized graphene-polyester composite fiber is prepared by the following steps:
(1) adding N, N-dimethylformamide, dimethylolpropionic acid and p-xylene glycol into a reaction bottle, introducing nitrogen and adding p-toluenesulfonic acid, wherein the mass ratio of dimethylolpropionic acid to p-xylene glycol to p-toluenesulfonic acid is 100:90-105:3.5-5, heating to 120-140 ℃, reacting for 6-18 h, cooling in an ice water bath after reaction, adding distilled water to precipitate, filtering, washing products with distilled water and ethanol, and preparing the hyperbranched polyarylate with the hydroxyl at the tail end.
(2) Adding graphene oxide into thionyl chloride for reaction to prepare graphene containing acyl chloride, then adding graphene containing acyl chloride and hyperbranched polyarylate into an N, N-dimethylformamide solvent, performing ultrasonic dispersion, then dropwise adding a catalyst triethylamine, wherein the mass ratio of the graphene containing acyl chloride, the hyperbranched polyarylate and the triethylamine is 100:250-400:60-120, heating to 80-120 ℃, performing reflux reaction for 24-48 h, cooling in an ice water bath after the reaction, adding distilled water to precipitate, filtering, washing the product with distilled water and ethanol, and thus obtaining the functionalized graphene grafted with the hyperbranched polyarylate.
(3) Adding the functionalized graphene and the polyethylene glycol terephthalate with the mass ratio of 0.2-1:100 into a double-screw extruder, carrying out melt blending and extrusion granulation, carrying out melt spinning with the spinning speed of 10-20 m/s to obtain composite nascent fiber, and then carrying out hot drawing and stretching with the speed of 3-4.5 m/s and the drawing multiple of 3-4 times to obtain the functionalized graphene-polyester composite fiber.
Preparing the functionalized graphene-polyester composite fiber into a fiber membrane of 12cm multiplied by 1 cm multiplied by 0.1 cm, and testing the tensile property of the composite fiber according to the standard of GB/T14337-2008.
The functionalized graphene-polyester composite fiber is prepared into a fiber membrane of 2cm multiplied by 0.1 cm, the fiber membrane is placed in an LF type TGA thermogravimetric analyzer, and the thermal stability of the composite fiber is tested according to the standard of GB/T37631-2019.
Example 1
(1) Adding N, N-dimethylformamide, dimethylolpropionic acid and p-xylene glycol into a reaction bottle, introducing nitrogen and adding p-toluenesulfonic acid, wherein the mass ratio of dimethylolpropionic acid to p-xylene glycol to p-toluenesulfonic acid is 100:90:3.5, heating to 120 ℃, reacting for 6 h, placing in an ice water bath for cooling after reaction, adding distilled water to precipitate, filtering, washing the product with distilled water and ethanol, and preparing the hyperbranched polyarylate with the hydroxyl at the tail end.
(2) Adding graphene oxide into thionyl chloride, reacting to obtain graphene containing acyl chloride, then adding graphene containing acyl chloride and hyperbranched polyarylate into an N, N-dimethylformamide solvent, performing ultrasonic dispersion, then dropwise adding a catalyst triethylamine, wherein the mass ratio of the graphene containing acyl chloride to the hyperbranched polyarylate to the triethylamine is 100:250:60, heating to 80 ℃, performing reflux reaction for 24 hours, cooling in an ice water bath after reaction, adding distilled water to precipitate, filtering, washing products with distilled water and ethanol, and thus obtaining the hyperbranched polyarylate grafted functionalized graphene.
(3) Adding functionalized graphene and polyethylene glycol terephthalate with the mass ratio of 0.2:100 into a double-screw extruder, carrying out melt blending, extruding and granulating, carrying out melt spinning with the spinning speed of 10 m/s to obtain composite nascent fiber, then carrying out hot traction and stretching with the speed of 3 m/s and the traction multiple of 3 times to obtain the functionalized graphene-polyester composite fiber, wherein the tensile strength is 56.7 MPa, the elongation at break is 75.2%, and the initial thermal decomposition temperature (T) is higher than that of the composite nascent fiber5%) The temperature was 409.2 ℃.
Example 2
(1) Adding N, N-dimethylformamide, dimethylolpropionic acid and p-xylene glycol into a reaction bottle, introducing nitrogen and adding p-toluenesulfonic acid, wherein the mass ratio of dimethylolpropionic acid to p-xylene glycol to p-toluenesulfonic acid is 100:95:4, heating to 120 ℃, reacting for 18 h, placing in an ice water bath for cooling after reaction, adding distilled water to precipitate, filtering, and washing a product with distilled water and ethanol to obtain the hyperbranched polyarylate with the hydroxyl at the tail end.
(2) Adding graphene oxide into thionyl chloride, reacting to obtain graphene containing acyl chloride, then adding graphene containing acyl chloride and hyperbranched polyarylate into an N, N-dimethylformamide solvent, performing ultrasonic dispersion, then dropwise adding a catalyst triethylamine, wherein the mass ratio of the graphene containing acyl chloride to the hyperbranched polyarylate to the triethylamine is 100:300:80, heating to 100 ℃, performing reflux reaction for 48 hours, cooling in an ice water bath after reaction, adding distilled water to precipitate, filtering, washing products with distilled water and ethanol, and thus obtaining the hyperbranched polyarylate grafted functionalized graphene.
(3) Adding functionalized graphene and polyethylene glycol terephthalate with the mass ratio of 0.4:100 into a double-screw extruder, carrying out melt blending, extruding and granulating, carrying out melt spinning with the spinning speed of 15 m/s to obtain composite nascent fiber, then carrying out hot traction and stretching with the speed of 3 m/s and the traction multiple of 3.5 times to obtain the functionalized graphene-polyester composite fiber, wherein the tensile strength is 62.0 MPa, the elongation at break is 98.4%, and the initial thermal decomposition temperature (T) is high5%) The temperature was 411.3 ℃.
Example 3
(1) Adding N, N-dimethylformamide, dimethylolpropionic acid and p-xylene glycol into a reaction bottle, introducing nitrogen and adding p-toluenesulfonic acid, wherein the mass ratio of dimethylolpropionic acid to p-xylene glycol to p-toluenesulfonic acid is 100:100:4.5, heating to 120 ℃, reacting for 12 hours, placing in an ice water bath for cooling after reaction, adding distilled water to precipitate, filtering, washing the product with distilled water and ethanol, and preparing the hyperbranched polyarylate with the hydroxyl at the tail end.
(2) Adding graphene oxide into thionyl chloride, reacting to obtain graphene containing acyl chloride, then adding graphene containing acyl chloride and hyperbranched polyarylate into an N, N-dimethylformamide solvent, performing ultrasonic dispersion, then dropwise adding a catalyst triethylamine, wherein the mass ratio of the graphene containing acyl chloride to the hyperbranched polyarylate to the triethylamine is 100:350:100, heating to 100 ℃, performing reflux reaction for 36 hours, cooling in an ice water bath after reaction, adding distilled water to precipitate, filtering, washing products with distilled water and ethanol, and thus obtaining the hyperbranched polyarylate grafted functionalized graphene.
(3) Adding functionalized graphene and polyethylene glycol terephthalate with the mass ratio of 0.7:100 into a double-screw extruder, carrying out melt blending, extruding and granulating, carrying out melt spinning with the spinning speed of 15 m/s to obtain composite nascent fiber, and then carrying out hot traction and stretching with the speed of 4 m/s and the traction multiple of 3.5 times to obtain the functionalized graphene-polyester composite fiber, wherein the tensile strength is 69.1 MPa, the elongation at break is 90.2%, and the initial thermal decomposition temperature (T) is high5%) It was 417.7 ℃.
Example 4
(1) Adding N, N-dimethylformamide, dimethylolpropionic acid and p-xylene glycol into a reaction bottle, introducing nitrogen and adding p-toluenesulfonic acid, wherein the mass ratio of dimethylolpropionic acid to p-xylene glycol is 100:105:5, heating to 140 ℃, reacting for 18 h, placing in an ice water bath for cooling after reaction, adding distilled water to precipitate, filtering, and washing the product with distilled water and ethanol to obtain the hyperbranched polyarylate with the hydroxyl at the tail end.
(2) Adding graphene oxide into thionyl chloride, reacting to obtain graphene containing acyl chloride, then adding graphene containing acyl chloride and hyperbranched polyarylate into an N, N-dimethylformamide solvent, performing ultrasonic dispersion, then dropwise adding a catalyst triethylamine, wherein the mass ratio of the graphene containing acyl chloride to the hyperbranched polyarylate to the triethylamine is 100:400:120, heating to 120 ℃, performing reflux reaction for 48 hours, cooling in an ice water bath after reaction, adding distilled water to precipitate, filtering, washing products with distilled water and ethanol, and thus obtaining the hyperbranched polyarylate grafted functionalized graphene.
(3) Adding functionalized graphene and polyethylene glycol terephthalate with the mass ratio of 1:100 into a double-screw extruder, and carrying out melt blending and extrusionGranulating, carrying out melt spinning at a spinning speed of 20 m/s to obtain composite nascent fiber, and then carrying out hot drawing and stretching at a speed of 4.5 m/s and a drawing multiple of 4 times to obtain functionalized graphene-polyester composite fiber, wherein the tensile strength is 62.2 MPa, the elongation at break is 70.2%, and the initial thermal decomposition temperature (T) is5%) The temperature was 409.5 ℃.
Comparative example 1
(1) Adding N, N-dimethylformamide, dimethylolpropionic acid and p-xylene glycol into a reaction bottle, introducing nitrogen and adding p-toluenesulfonic acid, wherein the mass ratio of dimethylolpropionic acid to p-xylene glycol to p-toluenesulfonic acid is 100:90:3.5, heating to 140 ℃, reacting for 6 h, cooling in an ice water bath after reaction, adding distilled water to precipitate, filtering, washing the product with distilled water and ethanol, and preparing the hyperbranched polyarylate with the hydroxyl at the tail end.
(2) Adding hyperbranched polyarylate and polyethylene glycol terephthalate with the mass ratio of 0.2:100 into a double-screw extruder, carrying out melt blending, extruding and granulating, carrying out melt spinning with the spinning speed of 15 m/s to obtain composite nascent fiber, and carrying out hot drawing with the speed of 3 m/s and the drawing multiple of 4 times to obtain polyester composite fiber, wherein the tensile strength is 48.7 MPa, the elongation at break is 42.0%, and the initial thermal decomposition temperature (T) is5%) The temperature was 404.9 ℃.
Comparative example 2
(1) Adding graphene and polyethylene glycol terephthalate with the mass ratio of 0.4:100 into a double-screw extruder, carrying out melt blending, extruding and granulating, carrying out melt spinning with the spinning speed of 10 m/s to obtain composite nascent fiber, and then carrying out hot drawing and stretching with the speed of 4.5 m/s and the drawing multiple of 3.5 times to obtain the graphene-polyester composite fiber, wherein the tensile strength is 52.1 MPa, the elongation at break is 55.8%, and the initial thermal decomposition temperature (T is the temperature of the polyester fiber) is5%) It was 406.0 ℃.

Claims (5)

1. A preparation method of functionalized graphene-polyester composite fibers is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) adding N, N-dimethylformamide, dimethylolpropionic acid and terephthalyl alcohol into a reaction bottle, introducing nitrogen and adding p-toluenesulfonic acid, heating to 120-140 ℃ for reaction for 6-18 h, cooling in an ice water bath after the reaction, adding distilled water to precipitate, filtering, washing the product with distilled water and ethanol, and preparing hyperbranched polyarylate with the hydroxyl at the tail end;
(2) adding graphene oxide into thionyl chloride, reacting to obtain graphene containing acyl chloride, then adding graphene containing acyl chloride and hyperbranched polyarylate into an N, N-dimethylformamide solvent, performing ultrasonic dispersion, dropwise adding a catalyst triethylamine, wherein the mass ratio of the graphene containing acyl chloride to the hyperbranched polyarylate to the triethylamine is 100:250-400:60-120, heating for reflux reaction, cooling in an ice water bath after reaction, adding distilled water to precipitate, filtering, washing products with distilled water and ethanol, and preparing the hyperbranched polyarylate grafted functionalized graphene;
(3) adding the functionalized graphene and the polyethylene glycol terephthalate into a double-screw extruder, carrying out melt blending and extrusion granulation, carrying out melt spinning to obtain composite nascent fiber, and carrying out hot traction and stretching to obtain the functionalized graphene-polyester composite fiber.
2. The preparation method of the functionalized graphene-polyester composite fiber according to claim 1, wherein the preparation method comprises the following steps: the mass ratio of the dimethylolpropionic acid to the p-xylene glycol to the p-toluenesulfonic acid in the step (1) is 100:90-105: 3.5-5.
3. The preparation method of the functionalized graphene-polyester composite fiber according to claim 1, wherein the preparation method comprises the following steps: the temperature of the reflux reaction in the step (2) is 80-120 ℃, and the reaction time is 24-48 h.
4. The preparation method of the functionalized graphene-polyester composite fiber according to claim 1, wherein the preparation method comprises the following steps: the mass ratio of the functionalized graphene to the polyethylene terephthalate in the step (3) is 0.2-1: 100.
5. The preparation method of the functionalized graphene-polyester composite fiber according to claim 1, wherein the preparation method comprises the following steps: the spinning speed of the melt spinning in the step (3) is 10-20 m/s, the spinning temperature is 290-310 ℃, the hot drawing speed is 3-4.5 m/s, and the drawing multiple is 3-4 times.
CN202111559538.2A 2021-12-20 2021-12-20 Functionalized graphene-polyester composite fiber and preparation method thereof Withdrawn CN114182386A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116444799A (en) * 2023-04-14 2023-07-18 常州大学 POSS-based polyphosphazene and PET/POSS-based polyphosphazene composite material and preparation method thereof
CN116694143A (en) * 2023-07-06 2023-09-05 安徽强邦新材料股份有限公司 Coating composition with self-repairing characteristic for printing plate and preparation method thereof
CN119800550A (en) * 2025-03-13 2025-04-11 山东杰瑞纺织科技有限公司 A method for preparing graphene-modified nylon fiber

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116444799A (en) * 2023-04-14 2023-07-18 常州大学 POSS-based polyphosphazene and PET/POSS-based polyphosphazene composite material and preparation method thereof
CN116694143A (en) * 2023-07-06 2023-09-05 安徽强邦新材料股份有限公司 Coating composition with self-repairing characteristic for printing plate and preparation method thereof
CN116694143B (en) * 2023-07-06 2024-03-29 安徽强邦新材料股份有限公司 Coating composition with self-repairing characteristic for printing plate and preparation method thereof
CN119800550A (en) * 2025-03-13 2025-04-11 山东杰瑞纺织科技有限公司 A method for preparing graphene-modified nylon fiber

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Application publication date: 20220315