CN107326474B - Graphene and polyester composite fiber for cord and preparation method thereof - Google Patents
Graphene and polyester composite fiber for cord and preparation method thereof Download PDFInfo
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- CN107326474B CN107326474B CN201710495004.5A CN201710495004A CN107326474B CN 107326474 B CN107326474 B CN 107326474B CN 201710495004 A CN201710495004 A CN 201710495004A CN 107326474 B CN107326474 B CN 107326474B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
Abstract
The invention discloses a graphene polyester composite fiber for cord threads and a preparation method thereof. The graphene polyester composite fiber for the cord is prepared from a graphene/PET nano composite material through drying, pre-crystallization, solid phase polycondensation, cooling and high-speed melt spinning, wherein the graphene/PET nano composite material is prepared by adding fold-spherical graphene oxide and a catalyst into a PET precursor and performing in-situ polycondensation. According to the method, the stacking of graphene oxide in the esterification stage is avoided, so that the graphene has good dispersibility in a polymer matrix, and the PET molecular chain is grafted on the surface of the graphene sheet, so that the force transfer between the graphene and the PET can be effectively realized. The preparation process is simple and effective, the cost can be effectively saved, the breaking strength of the obtained composite fiber is more than 9.0cN/dtex, the elongation at break is 14-18%, and the composite fiber can be used for tire cords and the like.
Description
Technical Field
The invention belongs to the field of fibers, and particularly relates to a graphene polyester composite fiber for a cord and a preparation method thereof.
Background
Polyester is an important variety of synthetic fibers, and is a fiber prepared by taking polyethylene terephthalate (PET) as a raw material and performing spinning and post-treatment. Because of the characteristics of stable chemical property, high mechanical strength, light weight, good thermal stability, good sanitary property, high transparency, easy processing and the like, the fiber is widely applied to textiles such as clothing, bedding, various decorative fabrics, national defense and military special fabrics and the like and other industrial fiber products. Among them, the PET industrial yarn has the characteristics of low cost, high strength and the like, and is widely applied to automobile tires. In order to further improve the strength of the PET industrial yarn, people adopt different means to improve the strength. Patent 201310043077.2 "method for producing melt direct spinning high modulus low shrinkage polyester industrial filament" adopts melt liquid phase tackification, melt direct spinning, two-stage drafting means to obtain high modulus low shrinkage polyester filament, which can be used in the fields of cord thread and the like. Besides improving the spinning process, the strength of the filament can be improved by adding a reinforcing material, and better performance can be obtained.
Conventional reinforcing materials include metallic materials (nanowires, nanoparticles), inorganic fillers (montmorillonite, titanium dioxide, silica, boron nitride, etc.), and carbon materials (carbon black, graphite, etc.). The conventional reinforcing material has two defects, on one hand, a satisfactory effect can be obtained only by needing a very high addition amount, but the high addition amount is accompanied with the reduction of other performances, so that the comprehensive improvement of the performances is difficult to realize, and on the other hand, the reinforcing effect is often single and cannot improve a plurality of performances simultaneously. These problems lead to low cost performance of conventional reinforcing materials, and are not suitable for large-scale popularization. For spinning, the filling reinforcing material must also consider the influence of the dispersion uniformity on the spinning continuity, otherwise, phenomena such as yarn breakage, yarn floating and the like are easily generated, and the continuous production is not facilitated.
Graphene is one of the most interesting new materials in the new century, and has a wide application prospect in many fields due to its ultrahigh specific surface area, excellent mechanical properties, high electrical conductivity, high thermal conductivity, flame retardancy and high barrier property. In the field of composite materials, a small amount of graphene is added, so that multiple properties of the material can be improved, and the material has ultrahigh cost performance, so that the material is widely researched in the aspect of composite materials. However, for continuous spinning, the strong agglomeration of graphene can cause defects in the fiber, so that the phenomena of yarn breakage and broken yarn in the spinning process are increased. Thus, many researchers have tried to suppress stacking of graphene, such as by polymerizing graphene oxide, performing surface modification or adding a dispersant. Patent 201510680473.5 "a method for preparing graphene-polyester nano composite fiber" is to melt, blend, extrude and granulate graphene powder and PET, and then spin. However, the conventional graphene powder is formed by stacking multiple layers of graphene, and the stacking cannot be separated under the mixing action of screw extrusion, so that the spinnability and continuity are seriously affected. Patent 201510688803.5 "a preparation method of military anti-dripping antistatic high-strength flame-retardant polyester" modifies graphene oxide, dries the graphene oxide, and then blends the graphene oxide with PET for granulation and spinning, although the graphene oxide modification effectively reduces agglomeration, the agglomeration of graphene in the dried modified powder cannot be dissociated in the melt extrusion process, which can lead to the blockage of a spinning plate and the phenomenon of yarn breakage. Patent 201610757032.5 graphene polyester monofilament is treated with silane coupling agent, and then blended with PET for extrusion. The coupling agent can improve the interaction between graphene and PET, but cannot change the stacking state of graphene, and the spinning effect is still poor. In conclusion, the problem of graphene stacking cannot be fundamentally solved in the preparation of the graphene-based polyester fiber at the present stage, so that high-speed and continuous spinning is greatly limited.
Disclosure of Invention
The invention aims to provide a graphene polyester composite fiber for cord threads and a preparation method thereof, aiming at the defects of the prior art.
The purpose of the invention is realized by the following technical scheme: the graphene polyester composite fiber for the cord is prepared from a graphene/PET nano composite material through drying, pre-crystallization, solid-phase polycondensation, cooling and high-speed melt spinning. The graphene/PET nano composite material consists of a single-layer graphene sheet and PET, wherein the surface of the graphene sheet is connected with PET molecules through a covalent bond.
Further, the drying temperature is 170-180 ℃, the pre-crystallization temperature is 175-185 ℃, the solid phase polycondensation temperature is 210-220 ℃, the intrinsic viscosity after solid phase polycondensation is 0.9-1.2, the cooling temperature is 60-80 ℃, the spinning temperature is 270-290 ℃, the winding speed is 3000-5000 m/min, and the draw ratio is 1.5-4.
Further, the graphene/PET nanocomposite material is prepared by the following steps:
(1) drying the single-layer graphene oxide dispersion liquid with the size of 1-10 micrometers by an atomization drying method to obtain folded spherical graphene oxide with the carbon-oxygen ratio of 2.5-5;
(2) fully mixing and stirring 100 parts by weight of terephthalic acid, 48-67 parts by weight of ethylene glycol and 0.02 part by weight of sodium acetate, and carrying out esterification reaction at 250 ℃;
(3) and (3) adding 0.117-1.17 parts by weight of pleated spherical graphene oxide obtained in the step (1) and 0.018 parts by weight of catalyst into the esterification product obtained in the step (2), keeping the temperature, stirring for 1-3 hours, then heating to 285 ℃, vacuumizing, reacting until the system does not release heat, and performing water cooling and grain cutting to obtain the graphene/PET nano composite material.
Further, the atomization drying temperature in the step (1) is 130-200 ℃.
Further, the stirring speed in the step (3) is 140-200 r/min.
Further, the catalyst in the step (3) is an antimony-based catalyst, and comprises antimony oxide, inorganic salt and organic compound.
Further, the catalyst in the step (3) is a titanium-based catalyst, and comprises titanium oxide, inorganic salt and organic compound.
Further, the catalyst in the step (3) is a germanium-based catalyst, and comprises germanium oxide, inorganic salt and organic compound.
The invention has the beneficial effects that: (1) the pleating graphene oxide microspheres added after esterification can be gradually unfolded and dissociated into single-layer flaky graphene oxide, and hydroxyl and carboxyl on the surface of the graphene oxide react with PET molecules in a system in the PET polymerization process, so that PET molecular chains are grafted on the surface of the graphene, the compatibility of the two is improved, the stacking is reduced, the addition amount of the graphene is greatly reduced, and the method has high cost performance. In contrast, graphene oxide is added in the esterification stage to thermally reduce the graphene oxide, and the reduced graphene is gradually stacked into aggregates along with the reaction, which is not beneficial to the improvement of performance, and continuous high-speed spinning cannot be performed due to the existence of the aggregates. (2) The graphene oxide is added after esterification, so that the influence on the first esterification process is avoided. For the polymerization process, the introduction of the fold-shaped graphene oxide has no obvious influence on the polymerization process, so that the method is more reasonable in the actual production process, higher in efficiency and lower in cost. (3) The graphene has tackifying capability to the PET melt, and the viscosity of the melt can be controlled within a proper range by selecting a proper carbon-oxygen ratio, size and filling amount of the graphene oxide. (4) After the graphene is added, the composite material can be subjected to high-speed continuous spinning, the obtained fiber is high in breaking strength and breaking elongation, and the heat resistance of the fiber is improved.
Drawings
Fig. 1 is a photograph of a graphene polyester composite fiber for a cord prepared in example 1 of the present invention.
Fig. 2 is an SEM image of pleated spherical graphene oxide prepared by example 1 of the present invention.
Detailed Description
The method for preparing the graphene polyester composite fiber for the cord comprises the following steps:
(1) and drying the single-layer graphene oxide dispersion liquid by an atomization drying method to obtain the folded spherical graphene oxide. The atomization drying temperature is 130-200 ℃. The folded spherical graphene oxide is composed of single-layer folded graphene oxide sheets, the size of each graphene oxide sheet is 1-50 micrometers, and the carbon-oxygen ratio is 2.5-5; (2) fully mixing and stirring 100 parts by weight of terephthalic acid, 48-67 parts by weight of ethylene glycol and 0.02 part by weight of sodium acetate, and carrying out esterification reaction at 250 ℃ until no water is generated; (3) and (3) adding 0.117-1.17 parts by weight of pleated spherical graphene oxide obtained in the step (1) and 0.018 parts by weight of catalyst into the esterification product obtained in the step (2), keeping the temperature, stirring for 1-3 hours, then heating to 285 ℃, vacuumizing, reacting until the system does not release heat, and performing water cooling and grain cutting to obtain the graphene/PET nano composite material. The stirring speed is 140-200 rpm. The catalyst is an antimony catalyst, and comprises antimony oxide, inorganic salt and organic compound. The catalyst is a titanium catalyst and comprises antimony oxide, inorganic salt and organic compounds. The catalyst is an antimony catalyst and comprises germanium oxide, inorganic salt and organic compounds; (4) and (4) drying, pre-crystallizing, solid-phase polycondensation, cooling and high-speed melt spinning the graphene/PET nano composite material obtained in the step (3) to obtain the graphene polyester composite fiber for the cord. The drying temperature is 170-180 ℃, the pre-crystallization temperature is 175-185 ℃, the solid phase polycondensation temperature is 210-220 ℃, the intrinsic viscosity after solid phase polycondensation is 0.9-1.2, the cooling temperature is 60-80 ℃, the spinning temperature is 270-290 ℃, the winding speed is 3000-5000 m/min, and the draw ratio is 1.5-4.
The present invention is described in detail by the following embodiments, which are only used for further illustration of the present invention and should not be construed as limiting the scope of the present invention, and the non-essential changes and modifications made by the person skilled in the art according to the above disclosure are within the scope of the present invention.
Example 1:
(1) drying the single-layer graphene oxide dispersion liquid by an atomization drying method to obtain graphene oxide microspheres, wherein the atomization temperature is 130 ℃, the size of graphene oxide sheets is 1-3 microns, and the carbon-oxygen ratio is 2.5;
(2) fully mixing and stirring 100 parts by mass of terephthalic acid, 53 parts by mass of ethylene glycol and 0.02 part by mass of sodium acetate, and carrying out esterification reaction at 250 ℃ until no water is generated;
(3) and (2) adding 0.117 mass part of pleated spherical graphene oxide obtained in the step (1) and 0.018 mass part of ethylene glycol antimony into the esterification product obtained in the step (2), keeping the temperature and stirring for 2 hours at the stirring speed of 160 r/min, then heating to 285 ℃, vacuumizing, reacting until the system does not release heat, and performing water-cooling granulation to obtain the graphene/PET nano composite material.
(4) And (4) drying, pre-crystallizing, performing solid phase polycondensation, cooling and performing high-speed melt spinning on the composite material obtained in the step (3). The drying temperature is 175 ℃, the pre-crystallization temperature is 180 ℃, the solid phase polycondensation temperature is 215 ℃, the intrinsic viscosity after solid phase polycondensation is 1.1, the cooling temperature is 70 ℃, the spinning temperature is 290 ℃, the winding speed is 4000m/min, and the draw ratio is 3.
The graphene polyester composite fiber for the cord is obtained through the steps, and is shown in figure 1. The SEM image of the obtained pleated graphene oxide is shown in fig. 2, and the specific properties of the obtained graphene/PET composite material are shown in table 1.
Example 2:
(1) drying the single-layer graphene oxide dispersion liquid by an atomization drying method to obtain graphene oxide microspheres, wherein the atomization temperature is 130 ℃, the size of graphene oxide sheets is 6-10 microns, and the carbon-oxygen ratio is 2.5;
(2) fully mixing and stirring 100 parts by mass of terephthalic acid, 53 parts by mass of ethylene glycol and 0.02 part by mass of sodium acetate, and carrying out esterification reaction at 250 ℃ until no water is generated;
(3) and (2) adding 0.117 mass part of pleated spherical graphene oxide obtained in the step (1) and 0.018 mass part of ethylene glycol antimony into the esterification product obtained in the step (2), keeping the temperature and stirring for 2 hours at the stirring speed of 160 r/min, then heating to 285 ℃, vacuumizing, reacting until the system does not release heat, and performing water-cooling granulation to obtain the graphene/PET nano composite material.
(4) And (4) drying, pre-crystallizing, performing solid phase polycondensation, cooling and performing high-speed melt spinning on the composite material obtained in the step (3). The drying temperature is 175 ℃, the pre-crystallization temperature is 180 ℃, the solid phase polycondensation temperature is 215 ℃, the intrinsic viscosity after solid phase polycondensation is 1.1, the cooling temperature is 70 ℃, the spinning temperature is 290 ℃, the winding speed is 4000m/min, and the draw ratio is 3.
The graphene polyester composite fiber for the cord is obtained through the steps, and the specific properties are shown in table 1.
Example 3:
(1) drying the single-layer graphene oxide dispersion liquid by an atomization drying method to obtain graphene oxide microspheres, wherein the atomization temperature is 160 ℃, the size of graphene oxide sheets is 6-10 microns, and the carbon-oxygen ratio is 5;
(2) fully mixing and stirring 100 parts by mass of terephthalic acid, 53 parts by mass of ethylene glycol and 0.02 part by mass of sodium acetate, and carrying out esterification reaction at 250 ℃ until no water is generated;
(3) and (2) adding 0.117 weight part of pleated spherical graphene oxide obtained in the step (1) and 0.018 weight part of ethylene glycol antimony into the esterification product obtained in the step (2), keeping the temperature and stirring for 2 hours at the stirring speed of 160 revolutions per minute, then heating to 285 ℃, vacuumizing, reacting until the system does not release heat, and performing water-cooling granulation to obtain the graphene/PET nano composite material.
(4) And (4) drying, pre-crystallizing, performing solid phase polycondensation, cooling and performing high-speed melt spinning on the composite material obtained in the step (3). The drying temperature is 175 ℃, the pre-crystallization temperature is 180 ℃, the solid phase polycondensation temperature is 215 ℃, the intrinsic viscosity after solid phase polycondensation is 1.1, the cooling temperature is 70 ℃, the spinning temperature is 290 ℃, the winding speed is 4000m/min, and the draw ratio is 3.
The graphene polyester composite fiber for the cord is obtained through the steps, and the specific properties are shown in table 12.
Example 4:
(1) drying the single-layer graphene oxide dispersion liquid by an atomization drying method to obtain graphene oxide microspheres, wherein the atomization temperature is 130 ℃, the size of graphene oxide sheets is 6-10 microns, and the carbon-oxygen ratio is 2.5;
(2) fully mixing and stirring 100 parts by mass of terephthalic acid, 53 parts by mass of ethylene glycol and 0.02 part by mass of sodium acetate, and carrying out esterification reaction at 250 ℃ until no water is generated;
(3) and (2) adding 0.585 part by weight of pleated spherical graphene oxide obtained in the step (1) and 0.018 part by weight of ethylene glycol antimony into the esterification product obtained in the step (2), keeping the temperature and stirring for 2 hours at the stirring speed of 160 r/min, then heating to 285 ℃, vacuumizing, reacting until the system does not release heat, and performing water cooling and grain cutting to obtain the graphene/PET nano composite material.
(4) And (4) drying, pre-crystallizing, performing solid phase polycondensation, cooling and performing high-speed melt spinning on the composite material obtained in the step (3). The drying temperature is 175 ℃, the pre-crystallization temperature is 180 ℃, the solid phase polycondensation temperature is 215 ℃, the intrinsic viscosity after solid phase polycondensation is 1.12, the cooling temperature is 70 ℃, the spinning temperature is 290 ℃, the winding speed is 4000m/min, and the draw ratio is 3.
The graphene polyester composite fiber for the cord is obtained through the steps, and the specific properties are shown in table 1.
Example 5:
(1) drying the single-layer graphene oxide dispersion liquid by an atomization drying method to obtain graphene oxide microspheres, wherein the atomization temperature is 130 ℃, the size of graphene oxide sheets is 6-10 microns, and the carbon-oxygen ratio is 2.5;
(2) fully mixing and stirring 100 parts by mass of terephthalic acid, 53 parts by mass of ethylene glycol and 0.02 part by mass of sodium acetate, and carrying out esterification reaction at 250 ℃ until no water is generated;
(3) adding 1.17 parts by mass of pleated spherical graphene oxide obtained in the step (1) and 0.018 part by mass of ethylene glycol antimony into the esterification product obtained in the step (2), stirring for 2 hours at the stirring speed of 160 revolutions per minute while keeping the temperature, then heating to 285 ℃, vacuumizing, reacting until the system does not release heat, and pelletizing by water cooling to obtain the graphene/PET composite material.
(4) And (4) drying, pre-crystallizing, performing solid phase polycondensation, cooling and performing high-speed melt spinning on the composite material obtained in the step (3). The drying temperature is 175 ℃, the pre-crystallization temperature is 180 ℃, the solid phase polycondensation temperature is 215 ℃, the intrinsic viscosity after solid phase polycondensation is 1.14, the cooling temperature is 70 ℃, the spinning temperature is 290 ℃, the winding speed is 4000m/min, and the draw ratio is 3.
The graphene polyester composite fiber for the cord is obtained through the steps, and the specific properties are shown in table 1.
Comparative example 1:
PET was prepared according to the method of example 1, except that no pleated spherical graphene oxide was added during the preparation. The properties are shown in Table 1.
Comparative example 2:
(1) drying the single-layer graphene oxide dispersion liquid by an atomization drying method to obtain graphene oxide microspheres, wherein the atomization temperature is 130 ℃, the size of graphene oxide sheets is 0.3-0.7 microns, and the carbon-oxygen ratio is 2.5;
(2) fully mixing and stirring 100 parts by mass of terephthalic acid, 53 parts by mass of ethylene glycol and 0.02 part by mass of sodium acetate, and carrying out esterification reaction at 250 ℃ until no water is generated;
(3) and (2) adding 0.117 mass part of pleated spherical graphene oxide obtained in the step (1) and 0.018 mass part of ethylene glycol antimony into the esterification product obtained in the step (2), keeping the temperature and stirring for 2 hours at the stirring speed of 160 r/min, then heating to 285 ℃, vacuumizing, reacting until the system does not release heat, and performing water-cooling granulation to obtain the graphene/PET nano composite material.
(4) And (4) drying, pre-crystallizing, performing solid phase polycondensation, cooling and performing high-speed melt spinning on the composite material obtained in the step (3). The drying temperature is 175 ℃, the pre-crystallization temperature is 180 ℃, the solid phase polycondensation temperature is 215 ℃, the intrinsic viscosity after solid phase polycondensation is 1.1, the cooling temperature is 70 ℃, the spinning temperature is 290 ℃, the winding speed is 4000m/min, and the draw ratio is 3.
The graphene polyester composite fiber for the cord is obtained through the steps, and the specific properties are shown in table 1.
Comparative example 3:
(1) drying the single-layer graphene oxide dispersion liquid by an atomization drying method to obtain graphene oxide microspheres, wherein the atomization temperature is 130 ℃, the size of graphene oxide sheets is 40-45 micrometers, and the carbon-oxygen ratio is 2.5;
(2) fully mixing and stirring 100 parts by mass of terephthalic acid, 53 parts by mass of ethylene glycol and 0.02 part by mass of sodium acetate, and carrying out esterification reaction at 250 ℃ until no water is generated;
(3) and (2) adding 0.117 mass part of pleated spherical graphene oxide obtained in the step (1) and 0.018 mass part of ethylene glycol antimony into the esterification product obtained in the step (2), keeping the temperature and stirring for 2 hours at the stirring speed of 160 r/min, then heating to 285 ℃, vacuumizing, reacting until the system does not release heat, and performing water-cooling granulation to obtain the graphene/PET nano composite material.
(4) And (4) drying, pre-crystallizing, performing solid phase polycondensation, cooling and performing high-speed melt spinning on the composite material obtained in the step (3). The drying temperature is 175 ℃, the pre-crystallization temperature is 180 ℃, the solid phase polycondensation temperature is 215 ℃, the intrinsic viscosity after solid phase polycondensation is 1.31, the cooling temperature is 70 ℃, the spinning temperature is 290 ℃, the winding speed is 4000m/min, and the draw ratio is 3.
Through the steps, the viscosity of the melt is too high, and continuous spinning is difficult.
Comparative example 4:
(1) drying the single-layer graphene oxide dispersion liquid by an atomization drying method to obtain graphene oxide microspheres, wherein the atomization temperature is 220 ℃, the size of graphene oxide sheets is 6-10 microns, and the carbon-oxygen ratio is 10;
(2) fully mixing and stirring 100 parts by mass of terephthalic acid, 53 parts by mass of ethylene glycol and 0.02 part by mass of sodium acetate, and carrying out esterification reaction at 250 ℃ until no water is generated;
(3) and (2) adding 0.117 mass part of pleated spherical graphene oxide obtained in the step (1) and 0.018 mass part of ethylene glycol antimony into the esterification product obtained in the step (2), keeping the temperature and stirring for 2 hours at the stirring speed of 160 r/min, then heating to 285 ℃, vacuumizing, reacting until the system does not release heat, and performing water-cooling granulation to obtain the graphene/PET nano composite material.
(4) And (4) drying, pre-crystallizing, performing solid phase polycondensation, cooling and performing high-speed melt spinning on the composite material obtained in the step (3). The drying temperature is 175 ℃, the pre-crystallization temperature is 180 ℃, the solid phase polycondensation temperature is 215 ℃, the intrinsic viscosity after solid phase polycondensation is 1.1, the cooling temperature is 70 ℃, the spinning temperature is 290 ℃, the winding speed is 4000m/min, and the draw ratio is 3.
Through the steps, the spinning plate is found to have the phenomenon of blockage, the continuity of the spun yarn is poor, and the frequency of yarn breakage is high.
Comparative example 5:
(1) drying the single-layer graphene oxide dispersion liquid by an atomization drying method to obtain graphene oxide microspheres, wherein the atomization temperature is 130 ℃, the size of graphene oxide sheets is 6-10 microns, and the carbon-oxygen ratio is 2.5;
(2) fully mixing and stirring 100 parts by mass of terephthalic acid, 53 parts by mass of ethylene glycol and 0.02 part by mass of sodium acetate, and carrying out esterification reaction at 250 ℃ until no water is generated;
(3) and (2) adding 5.85 parts by mass of pleated spherical graphene oxide obtained in the step (1) and 0.018 part by mass of ethylene glycol antimony into the esterification product obtained in the step (2), keeping the temperature and stirring for 2 hours at the stirring speed of 160 revolutions per minute, then heating to 285 ℃, vacuumizing, reacting until the system does not release heat, and performing water-cooling granulation to obtain the graphene/PET composite material.
(4) And (4) drying, pre-crystallizing, performing solid phase polycondensation, cooling and performing high-speed melt spinning on the composite material obtained in the step (3). The drying temperature is 175 ℃, the pre-crystallization temperature is 180 ℃, the solid phase polycondensation temperature is 215 ℃, the intrinsic viscosity after solid phase polycondensation is 1.37, the cooling temperature is 70 ℃, the spinning temperature is 290 ℃, the winding speed is 4000m/min, and the draw ratio is 3.
Through the steps, the melt viscosity is overhigh, the spinning difficulty is high, and the continuity is poor.
TABLE 1 specific parameters and Properties of the examples
Analysis of comparative example 1, comparative example 2, example 1, example 2, and comparative example 3 revealed that increasing the graphene size in an appropriate range effectively increases the breaking strength of the fiber, while maintaining the carbon-oxygen ratio and the addition amount of the graphene oxide unchanged. The graphene oxide of comparative example 2 is too small in size and cannot be used as an effective reinforcing material, while the graphene oxide of comparative example 3 is too large in size, and the tackifying effect is obvious after the graphene oxide is added into a polymerization system, so that after the melt is tackified in a solid phase polycondensation stage, the viscosity is further increased, the spinning difficulty is increased, and the continuous production is not facilitated. Therefore, the graphene oxide is limited in the size range of 1-10 microns, and the graphene oxide can play a role in enhancing more effectively.
Analysis of comparative examples 1, 2, 3 and 4 shows that the carbon-oxygen ratio is increased, and various indexes of the composite fiber are all increased, because the carbon-oxygen ratio is increased, the defects of graphene are less, the performance of the composite material is better, and the composite material has better performance. However, the carbon-oxygen ratio cannot be too high, otherwise, the bonding force between graphene oxide sheets is too strong, and the graphene oxide sheets still keep a stacked state during polymerization, so that spinning holes are blocked, and continuous production is difficult (comparative example 4).
Analysis of comparative example 1, example 2, example 4, example 5, and comparative example 5 shows that the addition amount of graphene oxide increases, and the breaking strength of the composite fiber also increases significantly, which means that graphene has a reinforcing effect. After too much graphene oxide was added, the viscosity of the system was too high, melt spinnability was greatly reduced after tackification, and continuous production was difficult (comparative example 5).
Example 6:
(1) drying the single-layer graphene oxide dispersion liquid by an atomization drying method to obtain graphene oxide microspheres, wherein the atomization temperature is 130 ℃, the size of a graphene oxide sheet is 3-5 microns, and the carbon-oxygen ratio is 2.5;
(2) fully mixing and stirring 100 parts by mass of terephthalic acid, 53 parts by mass of ethylene glycol and 0.02 part by mass of sodium acetate, and carrying out esterification reaction at 250 ℃ until no water is generated;
(3) and (3) adding 0.95 mass part of pleated spherical graphene oxide obtained in the step (1) and 0.018 mass part of ethylene glycol antimony into the esterification product obtained in the step (2), keeping the temperature and stirring for 3 hours at the stirring speed of 140 r/min, then heating to 285 ℃, vacuumizing, reacting until the system does not release heat, and performing water-cooling granulation to obtain the graphene/PET composite material.
(4) And (4) drying, pre-crystallizing, performing solid phase polycondensation, cooling and performing high-speed melt spinning on the composite material obtained in the step (3). The drying temperature was 170 ℃, the pre-crystallization temperature was 175 ℃, the solid phase polycondensation temperature was 210 ℃, the intrinsic viscosity after solid phase polycondensation was 0.9, the cooling temperature was 60 ℃, the spinning temperature was 290 ℃, the winding speed was 5000m/min, and the draw ratio was 4.
Through testing, the graphene polyester composite fiber for the cord has good mechanical property and electrical property.
Example 7:
(1) drying the single-layer graphene oxide dispersion liquid by an atomization drying method to obtain graphene oxide microspheres, wherein the atomization temperature is 200 ℃, the size of graphene oxide sheets is 3-5 microns, and the carbon-oxygen ratio is 5;
(2) fully mixing and stirring 100 parts by mass of terephthalic acid, 53 parts by mass of ethylene glycol and 0.02 part by mass of sodium acetate, and carrying out esterification reaction at 250 ℃ until no water is generated;
(3) and (3) adding 0.95 mass part of pleated spherical graphene oxide obtained in the step (1) and 0.018 mass part of ethylene glycol antimony into the esterification product obtained in the step (2), keeping the temperature and stirring for 1h at the stirring speed of 200 r/min, then heating to 285 ℃, vacuumizing, reacting until the system does not release heat, and performing water-cooling granulation to obtain the graphene/PET composite material.
(4) And (4) drying, pre-crystallizing, performing solid phase polycondensation, cooling and performing high-speed melt spinning on the composite material obtained in the step (3). The drying temperature was 180 ℃, the pre-crystallization temperature was 185 ℃, the solid phase polycondensation temperature was 220 ℃, the intrinsic viscosity after solid phase polycondensation was 1.2, the cooling temperature was 80 ℃, the spinning temperature was 270 ℃, the winding speed was 3000m/min, and the draw ratio was 1.5.
Through testing, the graphene polyester composite fiber for the cord has good mechanical property and electrical property.
Claims (6)
1. The graphene polyester composite fiber for the cord is characterized in that the fiber is obtained by drying, pre-crystallizing, solid phase polycondensation, cooling and high-speed melt spinning of a graphene/PET nano composite material; the drying temperature is 170-180 ℃, the pre-crystallization temperature is 175-185 ℃, the solid phase polycondensation temperature is 210-220 ℃, the intrinsic viscosity after solid phase polycondensation is 0.9-1.2, the cooling temperature is 60-80 ℃, the spinning temperature is 270-290 ℃, the winding speed is 3000-5000 m/min, and the draw ratio is 1.5-4;
the graphene/PET nano composite material consists of a single-layer graphene sheet and PET, wherein the surface of the graphene sheet is connected with PET molecules through a covalent bond;
the graphene/PET nanocomposite is prepared by the following steps:
(1) drying the single-layer graphene oxide dispersion liquid with the size of 1-10 micrometers by an atomization drying method to obtain folded spherical graphene oxide with the carbon-oxygen ratio of 2.5-5;
(2) fully mixing and stirring 100 parts by weight of terephthalic acid, 48-67 parts by weight of ethylene glycol and 0.02 part by weight of sodium acetate at 250 parts by weightoC, carrying out esterification reaction;
(3) adding 0.117-1.17 parts by weight of pleated spherical graphene oxide obtained in the step (1) and 0.018 parts by weight of catalyst into the esterification product obtained in the step (2), keeping the temperature, stirring for 1-3 hours, and then heating to 285 deg.CoAnd C, vacuumizing, reacting until the system does not release heat, and performing water cooling and grain cutting to obtain the graphene/PET nano composite material.
2. The graphene polyester composite fiber for cord threads according to claim 1, wherein the atomization drying temperature in the step (1) is 130-200%oC。
3. The graphene polyester composite fiber for cords according to claim 1, wherein the stirring speed in the step (3) is 140 to 200 rpm.
4. The graphene polyester composite fiber for cords according to claim 1, wherein the catalyst in the step (3) is an antimony catalyst comprising antimony oxide, inorganic salt and organic compound.
5. The graphene polyester composite fiber for cords according to claim 1, wherein the catalyst in the step (3) is a titanium catalyst comprising titanium oxide, inorganic salt and organic compound.
6. The graphene polyester composite fiber for cords according to claim 1, wherein the catalyst in the step (3) is a germanium-based catalyst comprising germanium oxide, inorganic salt and organic compound.
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| CN201710495004.5A CN107326474B (en) | 2017-06-26 | 2017-06-26 | Graphene and polyester composite fiber for cord and preparation method thereof |
| US16/626,546 US11149129B2 (en) | 2017-06-26 | 2018-02-26 | Graphene composite material and preparation method thereof |
| PCT/CN2018/077169 WO2019000985A1 (en) | 2017-06-26 | 2018-02-26 | Graphene composite material and preparation method therefor |
| BR112019027930-0A BR112019027930B1 (en) | 2017-06-26 | 2018-02-26 | METHOD FOR PREPARING A GRAPHENOPOLYESTER NANOCOMPOSITE MATERIAL |
| KR1020207002385A KR102284847B1 (en) | 2017-06-26 | 2018-02-26 | Graphene composite material and its manufacturing method |
| EP18822649.2A EP3626758B1 (en) | 2017-06-26 | 2018-02-26 | Graphene composite material and preparation method therefor |
| JP2019571324A JP6963040B2 (en) | 2017-06-26 | 2018-02-26 | Method for manufacturing graphene composite material |
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