CN111663199A - Preparation method of graphene modified PET (polyethylene terephthalate) blend fiber - Google Patents
Preparation method of graphene modified PET (polyethylene terephthalate) blend fiber Download PDFInfo
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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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/34—Core-skin structure; Spinnerette packs therefor
-
- 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
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
-
- 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
- D01F1/103—Agents inhibiting growth of microorganisms
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
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- Mechanical Engineering (AREA)
- Artificial Filaments (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to the field of chemical fibers, and discloses a preparation method of graphene modified PET (polyethylene terephthalate) blend fibers aiming at the problem of poor dispersibility of graphene modified fibers in the prior art, which comprises the following preparation steps: 1) modifying graphene with a cationic modifier; 2) preparing a graphene modified slice: blending modified cationic graphene, a modifier and PET slice powder; 3) melting: melting the PET slices and the graphene modified slices; 4) blending: two spinning melts are sprayed out from a composite spinneret to form blended fibers; 5) and (3) post-treatment: and cooling, oiling, stretching, shaping and winding the blended fiber. The dispersibility of the graphene lamellar layer is improved, so that the uniformity of graphene in the composite fiber is improved, the graphene modified PET composite fiber with excellent performance is achieved, and the fiber has good mechanical properties; the clover-shaped composite fiber is prepared by spinning a graphene master batch slice and a PET slice composite spinneret plate.
Description
Technical Field
The invention relates to the field of chemical fibers, in particular to a preparation method of graphene modified PET (polyethylene terephthalate) blend fibers.
Background
Graphene is a novel carbon material, has excellent properties such as thermal conductivity, electrical conductivity and good mechanical strength, and is known as the most potential material in the 21 st century by researchers at home and abroad. Graphene has a wide range of outstanding properties and is widely used in various fields such as chemistry, composite fibers, catalyst carriers and the like. China has abundant graphite reserves, and has formed a series of comprehensive industries such as mining, processing, quality purification and the like. Nowadays, the annual output of graphite in China is the first in the world and is about half of the total world output, and the research and preparation process of graphene is continuously developed, advanced and mature, so that the graphene is used for modifying composite materials and is the trend of development.
Polyester (PET) is the most widely used synthetic fiber variety with the largest world output, and accounts for more than 60% of the world synthetic fiber output. PET has the advantages of high strength, excellent physical and mechanical properties, good stability, etc., and is a thermoplastic resin with excellent comprehensive properties, which is widely used in various fields, such as fibers, packaging, containers, plastics, etc. However, because the molecular chain of PET contains rigid group benzene ring, the antistatic property of PET is poor, and the application of PET is greatly limited. There is static electricity on the clothes and a large amount of dust is adsorbed on the surface of the clothes, causing it to stain the clothes and affect the quality of the product. Moreover, electric sparks are generated between the garment and a human body due to the fact that the garment is electrified, and the comfort degree of the garment is greatly influenced. More importantly, the clothes with static electricity are easy to generate danger in the processing process, even fire and explosion can happen in serious cases, and the personal safety of processing personnel is influenced. In order to fully exert the advantages of PET, such as low cost and high performance, the development of the modified PET polyester fiber has very important significance.
In recent years, the preparation of functional fibers with conductive, antibacterial and far infrared characteristics by compounding graphene and polymers is an important direction of current research, but the technical problem of poor dispersion of graphene exists when the functional characteristics of the fibers are improved by adopting graphene, and the strength of the obtained modified fibers is low.
The invention discloses a graphene tencel composite fiber and a preparation method thereof, and the graphene tencel composite fiber is prepared by adding NMMO (N-methylmorpholine-N oxide) and water into a graphene oxide solution and cellulose pulp, mixing, dissolving, filtering, spinning by a dry-jet wet process, and finishing by silk threads and a graphene oxide finishing liquid. The tencel composite fiber contains graphene, and the method comprises the following steps: preparing a spinning solution, spinning, and finishing the yarn with graphene.
The method has the defects that in the process of preparing the graphene polyurethane solution, secondary aggregation is easy to occur on graphene sheet layers, so that the dispersibility of graphene is poor.
Disclosure of Invention
The invention aims to overcome the problem of poor dispersibility in the process of graphene modified fibers in the prior art, and provides a preparation method of graphene modified PET blended fibers, on one hand, the dispersibility of graphene sheets is improved, so that the distribution uniformity of graphene in composite fibers is improved, and the graphene modified PET composite fibers with excellent performance are obtained, and the fibers have good mechanical properties; on the other hand, the graphene modified composite fiber integrating the performances of high elasticity, high renaturation, high oil absorption, high impact resistance, static resistance, bacteria resistance, far infrared performance and the like of the terylene is prepared by spinning the graphene master batch slice and the PET slice composite spinneret plate, the preparation process is simple, and the cost is saved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of graphene modified PET blended fiber comprises the following preparation steps:
1) modifying graphene with a cationic modifier;
2) preparing a graphene modified slice: blending modified cationic graphene, a modifier and PET slice powder, and granulating by using a double-screw extruder to obtain graphene modified slices;
3) melting: respectively melting the dried PET slices and the graphene modified slice by screw extruders to obtain a PET spinning melt and a graphene modified slice spinning melt;
4) blending: the two spinning melts respectively enter the two-component composite spinning assembly through respective corresponding pipelines to be spun, and the two spinning melts are sprayed out from a composite spinneret plate to form a blended fiber;
5) and (3) post-treatment: and cooling, oiling, stretching, shaping and winding the blended fiber to obtain a finished product.
According to the invention, modified graphene slices and PET slices are used as two components, and then a specially designed composite spinneret plate is adopted, so that the modified graphene composite fiber with a clover skin-core structure is prepared. The modified graphene slice has good antistatic, antibacterial and far infrared properties, and the PET slice keeps high elasticity, high renaturation, high oil absorption and high impact resistance; the cross section of the modified graphene composite fiber is in a clover shape, the surface of the polyester component is wrapped with the modified graphene component at uniform intervals, the modified graphene composite fiber has the characteristics of high strength and good elasticity, and the spaced modified graphene component is uniformly distributed around the polyester component, so that the composite fiber has the performance advantages of the polyester component and the modified graphene component, and the preparation cost is low.
Preferably, the cationic modifier in step 1) is DMSO and/or tributylphosphine containing a long carbon chain.
The cationic modifier is provided with a cationic group, and the cationic group replaces a functional group on graphene oxide, so that graphene is provided with cations, the dispersion effect among the graphene with the cations is better, and the addition of the cationic with points enables the subsequent spinning fibers to have better moisture absorption and sweat releasing effects besides better dispersion of the graphene.
Preferably, in step 2), the modifier is one or more of cetyl trimethyl ammonium bromide, sodium dodecyl sulfate, ethylenediamine and polyvinylpyrrolidone.
The addition of the modifier enables the mixing uniformity between the modified cationic graphene and the PET slice powder to be better, prevents the modified cationic graphene from secondary agglomeration in the molten PET, and enables the bonding force between the two components to be stronger and the fluidity of the obtained mixed solution to be better.
Preferably, in the step 2), the proportion of the modified cationic graphene, the proportion of the PET chip powder and the proportion of the modifier in the mixture is 1% -5%, 98.9% -94% and 0.1% -1%.
Preferably, the two components in the blended fiber in the step 4) are in a skin-core structure, and the two components comprise a middle PET spinning (A) and a peripheral graphene modified spinning (B) which are arranged at intervals.
Preferably, the cross section of the blended fiber is clover type.
The clover-type fiber section greatly increases the contact area between two material components, so that the blended fiber has good mechanical properties while ensuring excellent antistatic capacity, the proportion of the modified graphene in the fiber can be reduced, and the production cost is effectively reduced.
Preferably, the PET chips have an intrinsic viscosity of 0.65. + -. 0.2dL/g, a melting point of 240-.
Preferably, when a twin-screw extruder is used for melt granulation in the step 3), the temperatures of the first zone to the fifth zone of the screw are 245-.
If the temperature of the screw is lower than the range, the molding is poor during granulation; if the temperature of the screw is higher, the slicing degradation is easy to cause, and the fiber quality in subsequent processing is influenced.
Preferably, in the step 4), the mass ratio of the graphene modified slices to the PET slices is 20:80-40: 60; the screw temperature of the two-component composite spinning assembly is 280-310 ℃, and the box temperature of the two-component composite spinning assembly is 275-295 ℃.
The spinning condition is poor and the end is easy to break when the temperature of the box body is low; the box body temperature is higher, and then fibre intensity is lower, and the performance reduces.
Preferably, the temperature of the first hot roll is 70-90 ℃, the temperature of the second hot roll is 130-180 ℃ and the stretching ratio is 3.0-4.0 during the stretching and setting in the step 5).
The temperature of the hot roller and the stretching ratio are controlled within the above ranges, so that the fiber has better strength and proper elongation at break.
Therefore, the invention has the following beneficial effects:
(1) the preparation method of the graphene modified PET blended fiber is provided, the dispersity of graphene sheets is improved, the distribution uniformity of graphene in the composite fiber is improved, the graphene modified PET composite fiber with excellent performance is achieved, and the fiber has good mechanical properties;
(2) the sheath-core structure of the clover structure is prepared by spinning the graphene master batch slice and the PET slice composite spinneret plate, so that the graphene modified composite fiber integrating the properties of high elasticity, high renaturation, high oil absorption, high impact resistance, static resistance, bacteria resistance, far infrared performance and the like of the terylene is prepared, the preparation process is simple, and the cost is saved.
Drawings
Fig. 1 is a cross-sectional view of a composite spinneret.
Fig. 2 is a schematic cross-sectional view of a composite fiber.
In the figure: A. PET spinning, B, graphene modified spinning.
Detailed Description
General examples
A preparation method of graphene modified PET blended fiber comprises the following steps:
1) preparing modified graphene: adding graphite and sodium nitrate into a round-bottom flask under the ice bath condition, pouring concentrated sulfur, stirring to form paste, slowly adding potassium permanganate, controlling the temperature not to exceed 20 ℃, and stirring for 1.5-2 h. Then the temperature is raised to 35 to 40 ℃ and kept for 2 to 2.5 hours. Distilled water was added dropwise and the temperature was raised to 98-100 ℃ at which a golden yellow suspension appeared. Adding hydrogen peroxide while hot, pouring into distilled water, performing ultrasonic dispersion for 1-1.2h to obtain a graphene oxide mixture, slowly adding a cationic modifier DMSO and/or tributylphosphine containing a long carbon chain into the mixture, stirring for 10-15min to obtain a reddish brown precipitate, performing centrifugal separation, alternately washing for 3-5 times by using a hydrochloric acid solution and distilled water, and performing vacuum freeze drying for 22-24h to obtain a brown compound; ultrasonically dispersing the compound in distilled water, adding a hydrazine hydrate solution, and stirring and reacting in an oil bath at 78-80 ℃ for 10-12 h. After the reaction is finished, the system is a black suspension, alternately washed for 3-5 times by hydrochloric acid solution and distilled water, and subjected to vacuum freeze drying to obtain black powdery modified graphene;
2) preparing a graphene modified slice: respectively drying the modified graphene and the PET slice powder, and adding the graphene powder, the PET slice powder and the modifier into a high-speed dispersion machine for fully dispersing and mixing. Adding the mixed powder into a double-screw extruder for melt extrusion granulation to obtain graphene modified PET slices; in the blend, the modified cationic graphene accounts for 1-5%, the PET slice powder accounts for 95-98.9%, and the modifier accounts for 0.1-1%; the temperatures of the first zone to the fifth zone of the screw of the double-screw extruder are respectively 245-255 ℃, 260-270 ℃, 265-275 ℃ and 260-270 ℃;
3) melting: respectively drying the graphene modified PET slices and the PET slices according to the mass ratio of 20:80-40:60, and then melting the dried graphene modified PET slices and the PET slices by a screw extruder (280-;
4) blending: the two spinning melts respectively enter the two-component composite spinning assembly through respective corresponding pipelines to carry out spinning (the temperature of a spinning box body is 275-;
5) and (3) post-treatment: cooling, oiling, stretching, shaping and winding the strand silk (the temperature of a first hot roller is 70-90 ℃, the temperature of a second hot roller is 130-180 ℃, the stretching ratio is 3.0-4.0, and the side blowing air speed is 0.7-1.0m/s) to obtain the modified graphene composite fiber; the two components in the modified graphene composite fiber are combined in a sheath-core mode, and the cross section of the fiber is clover-shaped.
Wherein the intrinsic viscosity of the PET slice is 0.65 +/-0.2 dL/g, the melting point is 240-265 ℃, and the water content of the dry slice is less than 50 ppm.
Example 1
A preparation method of graphene modified PET blended fiber comprises the following steps:
1) preparing modified graphene: under the ice-bath condition, adding graphite and sodium nitrate into a round-bottom flask, pouring concentrated sulfur, stirring to form paste, slowly adding potassium permanganate, controlling the temperature to be 15 ℃, and stirring for 1.8 h. Then the temperature is raised to 37 ℃ and kept for 2.3 h. Distilled water was added dropwise and the temperature was raised to 99 ℃ at which time a golden yellow suspension appeared. Adding hydrogen peroxide while hot, pouring into distilled water, performing ultrasonic dispersion for 1.1h to obtain a graphene oxide mixture, slowly adding a cationic modifier DMSO and/or tributylphosphine containing a long carbon chain into the mixture, stirring for 12min to obtain a reddish brown precipitate, performing centrifugal separation, alternately washing for 4 times by using a hydrochloric acid solution and distilled water, and performing vacuum freeze drying for 23h to obtain a brown compound; ultrasonically dispersing the compound in distilled water, adding a hydrazine hydrate solution, and stirring and reacting for 11 hours in an oil bath at 79 ℃. After the reaction is finished, the system is a black suspension, alternately washed for 4 times by hydrochloric acid solution and distilled water, and subjected to vacuum freeze drying to obtain black powdery modified graphene;
2) preparing a graphene modified slice: respectively drying the modified graphene and the PET slice powder, and adding the graphene powder, the PET slice powder and the modifier into a high-speed dispersion machine for fully dispersing and mixing. Adding the mixed powder into a double-screw extruder for melt extrusion granulation to obtain graphene modified PET slices; in the blend, the modified cationic graphene accounts for 3%, the PET chip powder accounts for 96.5%, and the modifier accounts for 0.5%; the temperatures of the first zone and the fifth zone of the screw of the double-screw extruder are respectively 250 ℃, 265 ℃, 270 ℃ and 265 ℃;
3) melting: respectively drying the graphene modified PET slices and the PET slices according to the mass ratio of 50:50, and then melting the dried graphene modified PET slices and the PET slices by a screw extruder (300 ℃) to obtain a graphene modified PET slice spinning melt and a PET slice spinning melt;
4) blending: the two spinning melts respectively enter a two-component composite spinning assembly through respective corresponding pipelines to be spun (the temperature of a spinning box body is 280 ℃), and the two spinning melts are sprayed out from a special composite spinneret plate to form filaments;
5) and (3) post-treatment: cooling, oiling, stretching, shaping and winding the strand silk (the temperature of a first hot roller is 75 ℃, the temperature of a second hot roller is 150 ℃, the stretching ratio is 3.5, and the air speed of cross air blowing is 0.8m/s) to obtain the modified graphene composite fiber; the two components in the modified graphene composite fiber are combined in a sheath-core mode, and the cross section of the fiber is clover-shaped.
The self-curling composite filament prepared by the process has the specification of 100dtex/36 f.
Example 2
The present embodiment is the same as embodiment 1 in arrangement and operation principle, and the difference is that:
a preparation method of graphene modified PET blended fiber comprises the following steps:
1) preparing modified graphene: adding graphite and sodium nitrate into a round-bottom flask under the ice bath condition, pouring concentrated sulfur, stirring to form paste, slowly adding potassium permanganate, controlling the temperature not to exceed 20 ℃, and stirring for 1.5-2 h. Then the temperature is raised to 35 to 40 ℃ and kept for 2 to 2.5 hours. Distilled water was added dropwise and the temperature was raised to 98-100 ℃ at which a golden yellow suspension appeared. Adding hydrogen peroxide while hot, pouring into distilled water, performing ultrasonic dispersion for 1-1.2h to obtain a graphene oxide mixture, slowly adding a cationic modifier DMSO and/or tributylphosphine containing a long carbon chain into the mixture, stirring for 10-15min to obtain a reddish brown precipitate, performing centrifugal separation, alternately washing for 3-5 times by using a hydrochloric acid solution and distilled water, and performing vacuum freeze drying for 22-24h to obtain a brown compound; ultrasonically dispersing the compound in distilled water, adding a hydrazine hydrate solution, and stirring and reacting in an oil bath at 78-80 ℃ for 10-12 h. After the reaction is finished, the system is a black suspension, alternately washed for 3-5 times by hydrochloric acid solution and distilled water, and subjected to vacuum freeze drying to obtain black powdery modified graphene;
2) preparing a graphene modified slice: respectively drying the modified graphene and the PET slice powder, and adding the graphene powder, the PET slice powder and the modifier into a high-speed dispersion machine for fully dispersing and mixing. Adding the mixed powder into a double-screw extruder for melt extrusion granulation to obtain graphene modified PET slices; in the blend, the modified cationic graphene accounts for 1-5%, the PET slice powder accounts for 95-98.9%, and the modifier accounts for 0.1-1%; the temperatures of the first zone to the fifth zone of the screw of the double-screw extruder are respectively 245-255 ℃, 260-270 ℃, 265-275 ℃ and 260-270 ℃;
3) melting: respectively drying the graphene modified PET slices and the PET slices according to the mass ratio of 20:80-40:60, and then melting the dried graphene modified PET slices and the PET slices by a screw extruder (280-;
4) blending: the two spinning melts respectively enter the two-component composite spinning assembly through respective corresponding pipelines to carry out spinning (the temperature of a spinning box body is 275-;
5) and (3) post-treatment: cooling, oiling, stretching, shaping and winding the strand silk (the temperature of a first hot roller is 70 ℃, the temperature of a second hot roller is 180 ℃, the stretching ratio is 3.0-4.0, and the side-blown air speed is 0.7-1.0m/s) to obtain the modified graphene composite fiber; the two components in the modified graphene composite fiber are combined in a sheath-core mode, and the cross section of the fiber is clover-shaped.
The self-crimping composite filament prepared by the process has the specification of 100dtex/24 f.
Example 3
The present embodiment is the same as embodiment 1 in arrangement and operation principle, and the difference is that:
a preparation method of graphene modified PET blended fiber comprises the following steps:
1) preparing modified graphene: adding graphite and sodium nitrate into a round-bottom flask under the ice bath condition, pouring concentrated sulfur, stirring to form paste, slowly adding potassium permanganate, controlling the temperature not to exceed 20 ℃, and stirring for 1.5-2 h. Then the temperature is raised to 35 to 40 ℃ and kept for 2 to 2.5 hours. Distilled water was added dropwise and the temperature was raised to 98-100 ℃ at which a golden yellow suspension appeared. Adding hydrogen peroxide while hot, pouring into distilled water, performing ultrasonic dispersion for 1-1.2h to obtain a graphene oxide mixture, slowly adding a cationic modifier DMSO and/or tributylphosphine containing a long carbon chain into the mixture, stirring for 10-15min to obtain a reddish brown precipitate, performing centrifugal separation, alternately washing for 3-5 times by using a hydrochloric acid solution and distilled water, and performing vacuum freeze drying for 22-24h to obtain a brown compound; ultrasonically dispersing the compound in distilled water, adding a hydrazine hydrate solution, and stirring and reacting in an oil bath at 78-80 ℃ for 10-12 h. After the reaction is finished, the system is a black suspension, alternately washed for 3-5 times by hydrochloric acid solution and distilled water, and subjected to vacuum freeze drying to obtain black powdery modified graphene;
2) preparing a graphene modified slice: respectively drying the modified graphene and the PET slice powder, and adding the graphene powder, the PET slice powder and the modifier into a high-speed dispersion machine for fully dispersing and mixing. Adding the mixed powder into a double-screw extruder for melt extrusion granulation to obtain graphene modified PET slices; in the blend, the modified cationic graphene accounts for 1-5%, the PET slice powder accounts for 95-98.9%, and the modifier accounts for 0.1-1%; the temperatures of the first zone to the fifth zone of the screw of the double-screw extruder are respectively 245-255 ℃, 260-270 ℃, 265-275 ℃ and 260-270 ℃;
3) melting: respectively drying the graphene modified PET slices and the PET slices according to the mass ratio of 20:80-40:60, and then melting the dried graphene modified PET slices and the PET slices by a screw extruder (280-;
4) blending: the two spinning melts respectively enter the two-component composite spinning assembly through respective corresponding pipelines to carry out spinning (the temperature of a spinning box body is 275-;
5) and (3) post-treatment: cooling, oiling, stretching, shaping and winding the strand silk (the temperature of a first hot roller is 90 ℃, the temperature of a second hot roller is 130 ℃, the stretching ratio is 3.0-4.0, and the side-blown air speed is 0.7-1.0m/s) to obtain the modified graphene composite fiber; the two components in the modified graphene composite fiber are combined in a sheath-core mode, and the cross section of the fiber is clover-shaped.
The self-curling composite filament prepared by the process has the specification of 100dtex/36 f.
Example 4
The present embodiment is the same as embodiment 1 in arrangement and operation principle, and the difference is that:
a preparation method of graphene modified PET blended fiber comprises the following steps:
1) preparing modified graphene: adding graphite and sodium nitrate into a round-bottom flask under the ice bath condition, pouring concentrated sulfur, stirring to form paste, slowly adding potassium permanganate, controlling the temperature not to exceed 20 ℃, and stirring for 1.5-2 h. Then the temperature is raised to 35 to 40 ℃ and kept for 2 to 2.5 hours. Distilled water was added dropwise and the temperature was raised to 98-100 ℃ at which a golden yellow suspension appeared. Adding hydrogen peroxide while hot, pouring into distilled water, performing ultrasonic dispersion for 1-1.2h to obtain a graphene oxide mixture, slowly adding a cationic modifier DMSO and/or tributylphosphine containing a long carbon chain into the mixture, stirring for 10-15min to obtain a reddish brown precipitate, performing centrifugal separation, alternately washing for 3-5 times by using a hydrochloric acid solution and distilled water, and performing vacuum freeze drying for 22-24h to obtain a brown compound; ultrasonically dispersing the compound in distilled water, adding a hydrazine hydrate solution, and stirring and reacting in an oil bath at 78-80 ℃ for 10-12 h. After the reaction is finished, the system is a black suspension, alternately washed for 3-5 times by hydrochloric acid solution and distilled water, and subjected to vacuum freeze drying to obtain black powdery modified graphene;
2) preparing a graphene modified slice: respectively drying the modified graphene and the PET slice powder, and adding the graphene powder, the PET slice powder and the modifier into a high-speed dispersion machine for fully dispersing and mixing. Adding the mixed powder into a double-screw extruder for melt extrusion granulation to obtain graphene modified PET slices; in the blend, the modified cationic graphene accounts for 1-5%, the PET slice powder accounts for 95-98.9%, and the modifier accounts for 0.1-1%; the temperatures of the first zone to the fifth zone of the screw of the double-screw extruder are respectively 245-255 ℃, 260-270 ℃, 265-275 ℃ and 260-270 ℃;
3) melting: respectively drying the graphene modified PET slices and the PET slices according to the mass ratio of 20:80-40:60, and then melting the dried graphene modified PET slices and the PET slices by a screw extruder (280-;
4) blending: the two spinning melts respectively enter the two-component composite spinning assembly through respective corresponding pipelines to carry out spinning (the temperature of a spinning box body is 275-;
5) and (3) post-treatment: cooling, oiling, stretching, shaping and winding the strand silk (the temperature of a first hot roller is 80 ℃, the temperature of a second hot roller is 170 ℃, the stretching ratio is 3.0-4.0, and the air speed of cross air blowing is 0.7-1.0m/s) to obtain the modified graphene composite fiber; the two components in the modified graphene composite fiber are combined in a sheath-core mode, and the cross section of the fiber is clover-shaped.
The self-crimping composite filament prepared by the process has the specification of 100dtex/24 f.
Example 5
The present embodiment is the same as embodiment 1 in arrangement and operation principle, and the difference is that:
a preparation method of graphene modified PET blended fiber comprises the following steps:
1) preparing modified graphene: adding graphite and sodium nitrate into a round-bottom flask under the ice bath condition, pouring concentrated sulfur, stirring to form paste, slowly adding potassium permanganate, controlling the temperature not to exceed 20 ℃, and stirring for 1.5-2 h. Then the temperature is raised to 35 to 40 ℃ and kept for 2 to 2.5 hours. Distilled water was added dropwise and the temperature was raised to 98-100 ℃ at which a golden yellow suspension appeared. Adding hydrogen peroxide while hot, pouring into distilled water, performing ultrasonic dispersion for 1-1.2h to obtain a graphene oxide mixture, slowly adding a cationic modifier DMSO and/or tributylphosphine containing a long carbon chain into the mixture, stirring for 10-15min to obtain a reddish brown precipitate, performing centrifugal separation, alternately washing for 3-5 times by using a hydrochloric acid solution and distilled water, and performing vacuum freeze drying for 22-24h to obtain a brown compound; ultrasonically dispersing the compound in distilled water, adding a hydrazine hydrate solution, and stirring and reacting in an oil bath at 78-80 ℃ for 10-12 h. After the reaction is finished, the system is a black suspension, alternately washed for 3-5 times by hydrochloric acid solution and distilled water, and subjected to vacuum freeze drying to obtain black powdery modified graphene;
2) preparing a graphene modified slice: respectively drying the modified graphene and the PET slice powder, and adding the graphene powder, the PET slice powder and the modifier into a high-speed dispersion machine for fully dispersing and mixing. Adding the mixed powder into a double-screw extruder for melt extrusion granulation to obtain graphene modified PET slices; in the blend, the modified cationic graphene accounts for 1-5%, the PET slice powder accounts for 95-98.9%, and the modifier accounts for 0.1-1%; the temperatures of the first zone to the fifth zone of the screw of the double-screw extruder are respectively 245-255 ℃, 260-270 ℃, 265-275 ℃ and 260-270 ℃;
3) melting: respectively drying the graphene modified PET slices and the PET slices according to the mass ratio of 20:80-40:60, and then melting the dried graphene modified PET slices and the PET slices by a screw extruder (280-;
4) blending: the two spinning melts respectively enter the two-component composite spinning assembly through respective corresponding pipelines to carry out spinning (the temperature of a spinning box body is 275-;
5) and (3) post-treatment: cooling, oiling, stretching, shaping and winding the strand silk (the temperature of a first hot roller is 85 ℃, the temperature of a second hot roller is 160 ℃, the stretching ratio is 3.0-4.0, and the side-blown air speed is 0.7-1.0m/s) to obtain the modified graphene composite fiber; the two components in the modified graphene composite fiber are combined in a sheath-core mode, and the cross section of the fiber is clover-shaped.
The self-curling composite filament prepared by the process has the specification of 100dtex/36 f.
Comparative example 1 (different from example 1 in that the content of graphene in the graphene-modified PET chip exceeds the preferred ratio and the ratio of graphene is 7%)
This comparative example is the same as example 1 in terms of setup and working principle:
a preparation method of graphene modified PET blended fiber comprises the following steps:
1) preparing modified graphene: under the ice-bath condition, adding graphite and sodium nitrate into a round-bottom flask, pouring concentrated sulfur, stirring to form paste, slowly adding potassium permanganate, controlling the temperature to be 15 ℃, and stirring for 1.8 h. Then the temperature is raised to 37 ℃ and kept for 2.3 h. Distilled water was added dropwise and the temperature was raised to 99 ℃ at which time a golden yellow suspension appeared. Adding hydrogen peroxide while hot, pouring into distilled water, performing ultrasonic dispersion for 1.1h to obtain a graphene oxide mixture, slowly adding a cationic modifier DMSO and/or tributylphosphine containing a long carbon chain into the mixture, stirring for 12min to obtain a reddish brown precipitate, performing centrifugal separation, alternately washing for 4 times by using a hydrochloric acid solution and distilled water, and performing vacuum freeze drying for 23h to obtain a brown compound; ultrasonically dispersing the compound in distilled water, adding a hydrazine hydrate solution, and stirring and reacting for 11 hours in an oil bath at 79 ℃. After the reaction is finished, the system is a black suspension, alternately washed for 4 times by hydrochloric acid solution and distilled water, and subjected to vacuum freeze drying to obtain black powdery modified graphene;
2) preparing a graphene modified slice: respectively drying the modified graphene and the PET slice powder, and adding the graphene powder, the PET slice powder and the modifier into a high-speed dispersion machine for fully dispersing and mixing. Adding the mixed powder into a double-screw extruder for melt extrusion granulation to obtain graphene modified PET slices; in the blend, the modified cationic graphene accounts for 7%, the PET chip powder accounts for 92%, and the modifier accounts for 1%; the temperatures of the first zone and the fifth zone of the screw of the double-screw extruder are respectively 250 ℃, 265 ℃, 270 ℃ and 265 ℃;
3) melting: respectively drying the graphene modified PET slices and the PET slices according to the mass ratio of 50:50, and then melting the dried graphene modified PET slices and the PET slices by a screw extruder (300 ℃) to obtain a graphene modified PET slice spinning melt and a PET slice spinning melt;
4) blending: the two spinning melts respectively enter a two-component composite spinning assembly through respective corresponding pipelines to be spun (the temperature of a spinning box body is 280 ℃), and the two spinning melts are sprayed out from a special composite spinneret plate to form filaments;
5) and (3) post-treatment: cooling, oiling, stretching, shaping and winding the strand silk (the temperature of a first hot roller is 75 ℃, the temperature of a second hot roller is 150 ℃, the stretching ratio is 3.5, and the air speed of cross air blowing is 0.8m/s) to obtain the modified graphene composite fiber; the two components in the modified graphene composite fiber are combined in a sheath-core mode, and the cross section of the fiber is clover-shaped.
The self-curling composite filament prepared by the process has the specification of 100dtex/36 f.
Comparative example 2 (difference from example 1 in that sheath-core composite spinning is performed, and the fiber structure is concentric circular.) this comparative example is the same as example 1 in arrangement and operation principle, except that:
a preparation method of graphene modified PET blended fiber comprises the following steps:
1) preparing modified graphene: under the ice-bath condition, adding graphite and sodium nitrate into a round-bottom flask, pouring concentrated sulfur, stirring to form paste, slowly adding potassium permanganate, controlling the temperature to be 15 ℃, and stirring for 1.8 h. Then the temperature is raised to 37 ℃ and kept for 2.3 h. Distilled water was added dropwise and the temperature was raised to 99 ℃ at which time a golden yellow suspension appeared. Adding hydrogen peroxide while hot, pouring into distilled water, performing ultrasonic dispersion for 1.1h to obtain a graphene oxide mixture, slowly adding a cationic modifier DMSO and/or tributylphosphine containing a long carbon chain into the mixture, stirring for 12min to obtain a reddish brown precipitate, performing centrifugal separation, alternately washing for 4 times by using a hydrochloric acid solution and distilled water, and performing vacuum freeze drying for 23h to obtain a brown compound; ultrasonically dispersing the compound in distilled water, adding a hydrazine hydrate solution, and stirring and reacting for 11 hours in an oil bath at 79 ℃. After the reaction is finished, the system is a black suspension, alternately washed for 4 times by hydrochloric acid solution and distilled water, and subjected to vacuum freeze drying to obtain black powdery modified graphene;
2) preparing a graphene modified slice: respectively drying the modified graphene and the PET slice powder, and adding the graphene powder, the PET slice powder and the modifier into a high-speed dispersion machine for fully dispersing and mixing. Adding the mixed powder into a double-screw extruder for melt extrusion granulation to obtain graphene modified PET slices; in the blend, the modified cationic graphene accounts for 3%, the PET chip powder accounts for 96.5%, and the modifier accounts for 0.5%; the temperatures of the first zone and the fifth zone of the screw of the double-screw extruder are respectively 250 ℃, 265 ℃, 270 ℃ and 265 ℃;
3) melting: respectively drying the graphene modified PET slices and the PET slices according to the mass ratio of 50:50, and then melting the dried graphene modified PET slices and the PET slices by a screw extruder (300 ℃) to obtain a graphene modified PET slice spinning melt and a PET slice spinning melt;
4) blending: the two spinning melts respectively enter a two-component composite spinning assembly through respective corresponding pipelines to be spun (the temperature of a spinning box body is 280 ℃), and the two spinning melts are sprayed out from a sheath-core composite spinning assembly by a spinneret plate to form filaments;
5) and (3) post-treatment: cooling, oiling, stretching, shaping and winding the strand silk (the temperature of a first hot roller is 75 ℃, the temperature of a second hot roller is 150 ℃, the stretching ratio is 3.5, and the air speed of cross air blowing is 0.8m/s) to obtain the modified graphene composite fiber; two components in the modified graphene composite fiber are combined in a skin-core mode, and the cross section of the fiber is of a concentric circular structure.
The self-curling composite filament prepared by the process has the specification of 100dtex/36 f.
Comparative example 3 (different from the examples in that the spinning beam temperature and the hot roll temperature were out of the optimum range during spinning; spinning beam temperature 305 ℃, first hot roll temperature 105 ℃, second hot roll temperature 185 ℃.)
A preparation method of graphene modified PET blended fiber comprises the following steps:
1) preparing modified graphene: under the ice-bath condition, adding graphite and sodium nitrate into a round-bottom flask, pouring concentrated sulfur, stirring to form paste, slowly adding potassium permanganate, controlling the temperature to be 15 ℃, and stirring for 1.8 h. Then the temperature is raised to 37 ℃ and kept for 2.3 h. Distilled water was added dropwise and the temperature was raised to 99 ℃ at which time a golden yellow suspension appeared. Adding hydrogen peroxide while hot, pouring into distilled water, performing ultrasonic dispersion for 1.1h to obtain a graphene oxide mixture, slowly adding a cationic modifier DMSO and/or tributylphosphine containing a long carbon chain into the mixture, stirring for 12min to obtain a reddish brown precipitate, performing centrifugal separation, alternately washing for 4 times by using a hydrochloric acid solution and distilled water, and performing vacuum freeze drying for 23h to obtain a brown compound; ultrasonically dispersing the compound in distilled water, adding a hydrazine hydrate solution, and stirring and reacting for 11 hours in an oil bath at 79 ℃. After the reaction is finished, the system is a black suspension, alternately washed for 4 times by hydrochloric acid solution and distilled water, and subjected to vacuum freeze drying to obtain black powdery modified graphene;
2) preparing a graphene modified slice: respectively drying the modified graphene and the PET slice powder, and adding the graphene powder, the PET slice powder and the modifier into a high-speed dispersion machine for fully dispersing and mixing. Adding the mixed powder into a double-screw extruder for melt extrusion granulation to obtain graphene modified PET slices; in the blend, the modified cationic graphene accounts for 3%, the PET chip powder accounts for 96.5%, and the modifier accounts for 0.5%; the temperatures of the first zone and the fifth zone of the screw of the double-screw extruder are respectively 250 ℃, 265 ℃, 270 ℃ and 265 ℃;
3) melting: respectively drying the graphene modified PET slices and the PET slices according to the mass ratio of 50:50, and then melting the dried graphene modified PET slices and the PET slices by a screw extruder (300 ℃) to obtain a graphene modified PET slice spinning melt and a PET slice spinning melt;
4) blending: the two spinning melts respectively enter the two-component composite spinning assembly through respective corresponding pipelines to be spun (the temperature of a spinning box body is 305 ℃), and the two spinning melts are sprayed out from a special composite spinneret plate to form filaments;
5) and (3) post-treatment: cooling, oiling, stretching, shaping and winding the strand silk (the temperature of a first hot roller is 105 ℃, the temperature of a second hot roller is 185 ℃, the stretching ratio is 3.5, and the air speed of cross air blowing is 0.8m/s) to obtain the modified graphene composite fiber; the two components in the modified graphene composite fiber are combined in a sheath-core mode, and the cross section of the fiber is clover-shaped.
The self-curling composite filament prepared by the process has the specification of 100dtex/36 f.
Comparative example 4 (different from the examples in that graphene was not cation-modified.)
A preparation method of graphene modified PET blended fiber comprises the following steps:
1) preparing graphene slices: respectively drying the graphene and PET slice powder, and adding the graphene powder, the PET slice powder and the modifier into a high-speed dispersion machine for fully dispersing and mixing. Adding the mixed powder into a double-screw extruder for melt extrusion granulation to obtain graphene modified PET slices; in the blend, the modified cationic graphene accounts for 1-5%, the PET slice powder accounts for 95-98.9%, and the modifier accounts for 0.1-1%; the temperatures of the first zone to the fifth zone of the screw of the double-screw extruder are respectively 245-255 ℃, 260-270 ℃, 265-275 ℃ and 260-270 ℃;
2) melting: respectively drying the graphene modified PET slices and the PET slices according to the mass ratio of 50:50, and then melting the dried graphene modified PET slices and the PET slices by a screw extruder (300 ℃) to obtain a graphene modified PET slice spinning melt and a PET slice spinning melt;
3) blending: the two spinning melts respectively enter a two-component composite spinning assembly through respective corresponding pipelines to be spun (the temperature of a spinning box body is 280 ℃), and the two spinning melts are sprayed out from a special composite spinneret plate to form filaments;
4) and (3) post-treatment: cooling, oiling, stretching, shaping and winding the strand silk (the temperature of a first hot roller is 75 ℃, the temperature of a second hot roller is 150 ℃, the stretching ratio is 3.5, and the air speed of cross air blowing is 0.8m/s) to obtain the modified graphene composite fiber; the two components in the modified graphene composite fiber are combined in a sheath-core mode, and the cross section of the fiber is clover-shaped.
The self-curling composite filament prepared by the process has the specification of 100dtex/36 f.
Comparative example 5 (difference from example in cationic modification with sodium 1, 3-benzenedicarboxyl dimethyl-5-sulfonate.)
A preparation method of graphene modified PET blended fiber comprises the following steps:
1) preparing modified graphene: under the ice-bath condition, adding graphite and sodium nitrate into a round-bottom flask, pouring concentrated sulfur, stirring to form paste, slowly adding potassium permanganate, controlling the temperature to be 15 ℃, and stirring for 1.8 h. Then the temperature is raised to 37 ℃ and kept for 2.3 h. Distilled water was added dropwise and the temperature was raised to 99 ℃ at which time a golden yellow suspension appeared. Adding hydrogen peroxide while hot, pouring into distilled water, performing ultrasonic dispersion for 1.1h to obtain a graphene oxide mixture, slowly adding a cationic modifier 1.3-dimethyl phthalate-5-sodium sulfonate into the mixture, stirring for 12min to obtain a reddish brown precipitate, performing centrifugal separation, alternately washing for 4 times by using a hydrochloric acid solution and distilled water, and performing vacuum freeze drying for 23h to obtain a brown compound; ultrasonically dispersing the compound in distilled water, adding a hydrazine hydrate solution, and stirring and reacting for 11 hours in an oil bath at 79 ℃. After the reaction is finished, the system is a black suspension, alternately washed for 4 times by hydrochloric acid solution and distilled water, and subjected to vacuum freeze drying to obtain black powdery modified graphene;
2) preparing a graphene modified slice: respectively drying the modified graphene and the PET slice powder, and adding the graphene powder, the PET slice powder and the modifier into a high-speed dispersion machine for fully dispersing and mixing. Adding the mixed powder into a double-screw extruder for melt extrusion granulation to obtain graphene modified PET slices; in the blend, the modified cationic graphene accounts for 3%, the PET chip powder accounts for 96.5%, and the modifier accounts for 0.5%; the temperatures of the first zone and the fifth zone of the screw of the double-screw extruder are respectively 250 ℃, 265 ℃, 270 ℃ and 265 ℃;
3) melting: respectively drying the graphene modified PET slices and the PET slices according to the mass ratio of 50:50, and then melting the dried graphene modified PET slices and the PET slices by a screw extruder (300 ℃) to obtain a graphene modified PET slice spinning melt and a PET slice spinning melt;
4) blending: the two spinning melts respectively enter a two-component composite spinning assembly through respective corresponding pipelines to be spun (the temperature of a spinning box body is 280 ℃), and the two spinning melts are sprayed out from a special composite spinneret plate to form filaments;
5) and (3) post-treatment: cooling, oiling, stretching, shaping and winding the strand silk (the temperature of a first hot roller is 75 ℃, the temperature of a second hot roller is 150 ℃, the stretching ratio is 3.5, and the air speed of cross air blowing is 0.8m/s) to obtain the modified graphene composite fiber; the two components in the modified graphene composite fiber are combined in a sheath-core mode, and the cross section of the fiber is clover-shaped.
The self-curling composite filament prepared by the process has the specification of 100dtex/36 f.
Comparative example 6 (different from the examples in that no modifier was added at the time of blending.)
1) Preparing modified graphene: under the ice-bath condition, adding graphite and sodium nitrate into a round-bottom flask, pouring concentrated sulfur, stirring to form paste, slowly adding potassium permanganate, controlling the temperature to be 15 ℃, and stirring for 1.8 h. Then the temperature is raised to 37 ℃ and kept for 2.3 h. Distilled water was added dropwise and the temperature was raised to 99 ℃ at which time a golden yellow suspension appeared. Adding hydrogen peroxide while hot, pouring into distilled water, performing ultrasonic dispersion for 1.1h to obtain a graphene oxide mixture, slowly adding a cationic modifier DMSO and/or tributylphosphine containing a long carbon chain into the mixture, stirring for 12min to obtain a reddish brown precipitate, performing centrifugal separation, alternately washing for 4 times by using a hydrochloric acid solution and distilled water, and performing vacuum freeze drying for 23h to obtain a brown compound; ultrasonically dispersing the compound in distilled water, adding a hydrazine hydrate solution, and stirring and reacting for 11 hours in an oil bath at 79 ℃. After the reaction is finished, the system is a black suspension, alternately washed for 4 times by hydrochloric acid solution and distilled water, and subjected to vacuum freeze drying to obtain black powdery modified graphene;
2) preparing a graphene modified slice: and respectively drying the modified graphene and the PET slice powder, and adding the graphene powder and the PET slice powder into a high-speed dispersion machine for full dispersion and mixing. Adding the mixed powder into a double-screw extruder for melt extrusion granulation to obtain graphene modified PET slices; in the blend, the modified cationic graphene accounts for 3%, the PET chip powder accounts for 96.5%, and the modifier accounts for 0.5%; the temperatures of the first zone and the fifth zone of the screw of the double-screw extruder are respectively 250 ℃, 265 ℃, 270 ℃ and 265 ℃;
3) melting: respectively drying the graphene modified PET slices and the PET slices according to the mass ratio of 50:50, and then melting the dried graphene modified PET slices and the PET slices by a screw extruder (300 ℃) to obtain a graphene modified PET slice spinning melt and a PET slice spinning melt;
4) blending: the two spinning melts respectively enter a two-component composite spinning assembly through respective corresponding pipelines to be spun (the temperature of a spinning box body is 280 ℃), and the two spinning melts are sprayed out from a special composite spinneret plate to form filaments;
5) and (3) post-treatment: cooling, oiling, stretching, shaping and winding the strand silk (the temperature of a first hot roller is 75 ℃, the temperature of a second hot roller is 150 ℃, the stretching ratio is 3.5, and the air speed of cross air blowing is 0.8m/s) to obtain the modified graphene composite fiber; the two components in the modified graphene composite fiber are combined in a sheath-core mode, and the cross section of the fiber is clover-shaped.
The self-curling composite filament prepared by the process has the specification of 100dtex/36 f.
The evaluation parameter indexes of the composite spun fibers obtained in examples 1 to 5 and comparative examples 1 to 6 are shown in Table 1.
The filaments prepared in the above examples were tested for strength of the composite fiber fabric according to the GB/T-14337 filament tensile property test method, and for water absorption of the composite fiber fabric according to the GB/T12703.4-2010; the conductivity of the composite fiber fabric is tested according to GBT 1410 and 2006, and according to the textile industry standard FZT 54042 and 2011 of the people's republic of China, the fiber has excellent antistatic performance and is an excellent product when the volume specific resistance of the fiber is 105-108 ohm. See in particular table 1.
TABLE 1 Main preparation Process and fiber physical index
And (4) conclusion: it can be seen by combining the above examples and the comparative examples in table 1 that, in the present application, the modified graphene PET chips and the PET chips are blended as two components and then respectively melt-extruded through the screw extruder, and the two components enter the two-component composite spinning device and the specially designed fan-blade type composite spinneret holes, and the sprayed melt is cooled, oiled, drawn, heat-set and wound, so that the mechanical properties of the obtained fiber meet the relevant standard requirements.
The water absorption test of example 1 was carried out, and the measured value was 228%, which meets the standard requirement of not less than 200%, and the other examples also meet the standard.
The difference between the comparative example 1 and the example 1 is that the addition ratio of the modified graphene is too high during blending, so that the graphene cannot be fully and uniformly dispersed, a partial agglomeration phenomenon occurs, the subsequent processing is not facilitated, the antistatic performance and the moisture absorption and sweat releasing capacity of the fiber cannot be exerted, and the mechanical properties of the fiber are reduced.
The difference between the comparative example 2 and the example 1 is that the obtained fiber does not use a specially designed clover type spinneret, so that the obtained fiber has good antistatic performance, but the strength is remarkably reduced, and the cost is higher due to the use of more graphene, which cannot be compared with the fiber obtained in the example 1.
The difference between the comparative example 3 and the example 1 is that the obtained fiber has high spinning temperature, so that the fiber is partially degraded, the obtained fiber cannot have strength, and the obtained fiber has poor forming property due to the high winding temperature, cannot meet the following processing steps and the like, and has poor performance.
The comparative example 4 is different from the example 1 in that the graphene is not subjected to cationic modification, and the obtained fiber has antistatic performance, but the mechanical properties and the antistatic performance of the fiber are lower than those of the fiber obtained by modifying the graphene by using cations in the example 1, so that the graphene can be better dispersed uniformly by the cationic modification, no agglomeration occurs, and the fiber has excellent performance.
Comparative example 5 is different from example 1 in that the graphene is not cationically modified by DMSO and/or tributyl phosphine containing a long carbon chain but by the conventional modifier 1.3-dimethyl phthalate-5-sodium sulfonate, and it can be seen that the performance indexes of the modified graphene composite fiber are lower than those of the fiber obtained by using the cationic modifier DMSO and/or tributyl phosphine containing a long carbon chain, because dimethyl isophthalate-5-sodium sulfonate is generally used for conventional polyester modification and cannot be modified well due to the fact that the sodium sulfonate has a benzene ring and a force may exist between the sodium sulfonate and the graphene, so the effect is poor.
The difference between the comparative example 6 and the example 1 is that the modified graphene PET chips are prepared without adding the modifying agent, and the obtained fibers have larger performance difference, because the dispersing effect of the graphene can be better by adding the modifying agent, so that the indexes of the antistatic effect and the strength of the fibers obtained without adding the modifying agent are lower than those of the fibers obtained with adding the modifying agent.
From the data of examples 1 to 5 and comparative examples 1 to 6, it is clear that only the protocols within the scope of the claims of the present invention are able to satisfy the above requirements in all respects and lead to an optimized synthesis protocol. The change of the mixture ratio, the replacement/addition/subtraction of raw materials or the change of the feeding sequence can bring corresponding negative effects.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. A preparation method of graphene modified PET blended fiber is characterized by comprising the following preparation steps:
1) modifying graphene with a cationic modifier;
2) preparing a graphene modified slice: blending modified cationic graphene, a modifier and PET slice powder, and granulating by using a double-screw extruder to obtain graphene modified slices;
3) melting: respectively melting the dried PET slices and the graphene modified slice by screw extruders to obtain a PET spinning melt and a graphene modified slice spinning melt;
4) blending: the two spinning melts respectively enter the two-component composite spinning assembly through respective corresponding pipelines to be spun, and the two spinning melts are sprayed out from a composite spinneret plate to form a blended fiber;
5) and (3) post-treatment: and cooling, oiling, stretching, shaping and winding the blended fiber to obtain a finished product.
2. The preparation method of the graphene-modified PET blended fiber according to claim 1, wherein the cationic modifier in the step 1) is DMSO and/or tributylphosphine containing a long carbon chain.
3. The method for preparing the graphene modified PET blended fiber according to claim 1, wherein in the step 2), the modifier is one or more of cetyl trimethyl ammonium bromide, sodium dodecyl sulfate, ethylenediamine and polyvinylpyrrolidone.
4. The preparation method of the graphene modified PET blended fiber according to claim 1, wherein in the step 2), the modified cationic graphene accounts for 1% -5%, the PET slice powder accounts for 95% -98.9%, and the modifier accounts for 0.1% -1%.
5. The preparation method of the graphene modified PET blended fiber according to claim 1, wherein two components in the blended fiber in the step 4) are of a skin-core structure, and the two components comprise a middle PET spun yarn (A) and a peripheral graphene modified spun yarn (B) which are arranged at intervals.
6. The preparation method of the graphene modified PET blended fiber according to claim 1 or 5, wherein the cross section of the blended fiber is clover-shaped.
7. The preparation method of the graphene-modified PET blended fiber according to claim 1, wherein the intrinsic viscosity of the PET slices is 0.65 +/-0.2 dL/g, and the melting point is 240-265 ℃.
8. The preparation method of the graphene modified PET blended fiber according to claim 1, wherein when a twin-screw extruder is used for melt granulation in the step 3), the temperatures of the first zone to the fifth zone of the screw are 245-255 ℃, 260-270 ℃, 265-275 ℃ and 260-270 ℃.
9. The preparation method of the graphene modified PET blended fiber according to claim 1, wherein in the step 4), the mass ratio of the graphene modified slice to the PET slice is 20:80-40: 60; the screw temperature of the two-component composite spinning assembly is 280-310 ℃, and the box body temperature of the two-component composite spinning assembly is 275-295 ℃.
10. The preparation method of the graphene modified PET blended fiber according to claim 1, wherein the temperature of the first hot roller is 70-90 ℃, the temperature of the second hot roller is 130-180 ℃, and the stretching ratio is 3.0-4.0 during stretching and setting in the step 5).
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