CN111663199B - A kind of preparation method of graphene modified PET blended fiber - Google Patents

Abstract

The present invention relates to the field of chemical fibers. Aiming at the problem of poor dispersion in the process of graphene-modified fibers in the prior art, a preparation method of graphene-modified PET blended fibers is disclosed, which includes the following preparation steps: 1) using cationic Graphene modified by modifier; 2) Preparation of modified graphene slices: blending modified cationic graphene, modifier and PET slice powder; 3) Melting: melting PET slices and graphene modified slices; 4) Blending: Two kinds of spinning melts are sprayed from the composite spinneret to form blended fibers; 5) Post-processing: cooling, oiling, stretching and winding the above blended fibers. By improving the dispersion of graphene sheets, the uniformity of graphene in the composite fiber can be improved, and the composite fiber of graphene modified PET with excellent performance can be achieved, so that the fiber itself has good mechanical properties; by slicing the graphene masterbatch Spinning with PET chip composite spinneret to prepare four-leaf clover composite fiber.

Description

A kind of preparation method of graphene modified PET blended fiber

technical field

The invention relates to the field of chemical fibers, in particular to a method for preparing graphene-modified PET blended fibers.

Background technique

Graphene is a new type of carbon material with excellent properties such as thermal conductivity, electrical conductivity, and good mechanical strength. It is praised by researchers at home and abroad as the most potential material in the 21st century. Because graphene has many outstanding properties, it is widely used in various fields such as chemistry, composite fibers, and catalyst carriers. my country is rich in graphite reserves, and has formed a series of comprehensive industries, such as mining, processing, and quality purification. Now my country's annual output of graphite has become the first in the world, about half of the world's total output, and the research and preparation process of graphene is also constantly developing, improving, and maturing. Therefore, graphene is used in the modification of composite materials. where the trend lies.

Polyester (PET) is the largest and most widely used synthetic fiber variety in the world, accounting for more than 60% of the world's synthetic fiber output. PET has the advantages of high strength, excellent physical and mechanical properties, and good stability. It is a thermoplastic resin with excellent comprehensive properties and is widely used in various fields, such as fibers, packaging, containers, plastics, etc. However, because the PET molecular chain contains a rigid benzene ring, the antistatic performance of PET is poor, which greatly limits the application of PET. There is static electricity on the clothes, and a large amount of dust will be adsorbed on the surface of the clothes, causing it to stain the clothes and affect the quality of the product. Moreover, the electrification of clothing will cause electric sparks to be generated between the clothing and the human body, which greatly affects the comfort of the clothing. More importantly, static electricity in clothing is prone to danger during processing, and even fire and explosion may occur in severe cases, affecting the personal safety of processing personnel. In order to give full play to the advantages of PET, such as low cost and high performance, it is of great significance to develop modified PET polyester fibers.

In recent years, the use of graphene and polymer composites to prepare functional fibers with conductivity, antibacterial and far-infrared properties has become an important direction of current research. However, while using graphene to improve the functional properties of fibers, there is a problem of poor dispersion of graphene. Technical problems, and the resulting modified fiber strength is low.

Patent No. CN201710138437.5, patent name "a graphene-tencel composite fiber and its preparation method" The invention discloses a graphene-tencel composite fiber and its preparation method. The graphene-tencel composite fiber is made by oxidation Graphene solution and cellulose pulp are added with NMMO (N-methylmorpholine-N oxide) and water, mixed, dissolved, filtered, spun by dry spray wet process, and then finished by silk thread and graphene oxide finishing solution prepared. The tencel composite fiber contains graphene, and the following steps are adopted: preparation of spinning solution, spinning, and yarn graphene finishing.

Its disadvantage is that in the process of preparing graphene polyurethane solution, graphene sheets are prone to secondary agglomeration, resulting in poor dispersion of graphene.

Contents of the invention

The present invention is to overcome the problem of poor dispersion in the process of graphene modified fiber in the prior art, and provides a preparation method of graphene modified PET blended fiber. On the one hand, by improving the dispersion of graphene sheet itself To improve the uniformity of graphene distribution in the composite fiber, to achieve the composite fiber of graphene modified PET with excellent performance, the fiber itself has good mechanical properties; on the other hand, by cutting the graphene masterbatch and PET chips are spun with a composite spinneret to produce a graphene-modified composite fiber that combines high elasticity, high refolding, high oil absorption, high impact resistance, antistatic, antibacterial, and far-infrared properties of polyester. The preparation process is simple and the cost is saved.

In order to achieve the above object, the present invention adopts the following technical solutions:

A preparation method of graphene modified PET blended fiber, comprising the following preparation steps:

1) modify graphene with cationic modifier;

2) Preparation of modified graphene slices: blending modified cationic graphene, modifier and PET slice powder, and then granulating through a twin-screw extruder to obtain graphene modified slices;

3) melting: melting the dried PET chip and graphene modified chip screw extruder respectively to obtain PET spinning melt and graphene modified chip spinning melt;

4) Blending: the two kinds of spinning melts are respectively entered into the two-component composite spinning assembly through respective corresponding pipes for spinning, and the two kinds of spinning melts are ejected from the composite spinneret to form blended fibers;

5) Post-processing: After the above-mentioned blended fibers are cooled, oiled, stretched and shaped, and wound, the finished product is obtained.

The invention uses modified graphene slices and PET slices as two components, and then adopts a specially designed composite spinneret to prepare a modified graphene composite fiber with a four-leaf clover skin core structure. The modified graphene slices have good antistatic, antibacterial, and far-infrared properties, and the PET slices maintain high elasticity, high refolding, high oil absorption, and high impact resistance; the modified graphene composite fiber transverse The cross-section is four-leaf clover-shaped, and the surface of the polyester component contains modified graphene components at even intervals, which has the characteristics of high strength and good elasticity. The modified graphene components at intervals are evenly distributed around the polyester component, making The composite fiber has the performance advantages of the polyester component and the modified graphene component at the same time, and the preparation cost is low.

Preferably, the cationic modifier in step 1) is DMSO and tributylphosphine containing long carbon chains.

There are cationic groups in the above-mentioned cationic modifier, and the cationic groups replace the functional groups on the graphene oxide, so that the graphene has cations, and the dispersion effect between the graphenes with cations is better. Graphene not only has better dispersibility, but also makes the subsequent spinning fibers have better moisture absorption and perspiration effects.

Preferably, in step 2), the modifier used is one or more of cetyltrimethylammonium bromide, sodium lauryl sulfate, ethylenediamine and polyvinylpyrrolidone.

The addition of the modifier makes the mixing uniformity between the modified cationic graphene and the PET chip powder better, prevents the secondary agglomeration of the modified cationic graphene in the molten PET, and the binding force between the two components is stronger , the fluidity between the resulting mixed solutions is better.

Preferably, in step 2), the proportion of modified cationic graphene in the blend is 1%-5%, the proportion of PET chip powder is 98.9%-94%, and the proportion of modifier is 0.1%-1.

Preferably, the two components in the blended fiber in step 4) have a sheath-core structure, including PET spinning (A) in the middle and graphene modified spinning (B) arranged at intervals around it.

Preferably, the cross-section of the blended fiber is four-leaf clover.

The cross-section of the four-leaf clover fiber greatly increases the contact area between the two material components, making the blended fiber have good mechanical properties while ensuring excellent antistatic ability, and can reduce the proportion of modified graphene in the fiber. Effectively reduce the production cost.

Preferably, the PET chips have an intrinsic viscosity of 0.65±0.2 dL/g and a melting point of 240-265°C.

As a preference, when using a twin-screw extruder for melt granulation in step 3), the temperatures in the first to fifth zones of the screw are 245-255°C, 260-270°C, 265-275°C, 265-275°C, 260- 270°C.

If the screw temperature is lower than this range, the granulation will be poor; if the screw temperature is higher, it will easily cause chip degradation and affect the subsequent processing and fiber quality.

As a preference, in step 4), the mass ratio of the modified graphene chip to the PET chip is 20:80-40:60; the screw temperature of the two-component composite spinning assembly is 280-310°C, and the double The box temperature of the component composite spinning assembly is 275-295°C.

If the temperature of the box is low, the spinning condition will be poor and it is easy to break the end; if the temperature of the box is high, the fiber strength will be low and the performance will be reduced.

Preferably, the temperature of the first hot roller is 70-90° C., the temperature of the second hot roller is 130-180° C., and the draw ratio is 3.0-4.0 during stretching and setting in step 5).

The temperature of the hot roll and the draw ratio are controlled within the above range, which can make the fiber have better strength and proper elongation at break.

Therefore, the present invention has following beneficial effect:

(1) Provide a preparation method of graphene-modified PET blended fiber, by improving the dispersion of graphene sheet itself, to improve the uniformity of graphene distribution in the composite fiber, to achieve graphene modification with excellent performance The composite fiber of PET is that the fiber itself has good mechanical properties;

(2) By spinning graphene masterbatch slices and PET slices with a composite spinneret, a skin-core structure with a four-leaf clover structure is prepared, thereby making a polyester with high elasticity, high complexability, high oil absorption, and high impact resistance. The graphene-modified composite fiber with antistatic, antibacterial, far-infrared properties and other properties has a simple preparation process and saves costs.

Description of drawings

Fig. 1 is a 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 Example

A kind of preparation method of graphene modified PET blended fiber, comprises the following steps:

1) Preparation of modified graphene: Add graphite and sodium nitrate to a round bottom flask under ice bath conditions, pour concentrated sulfur and stir to form a paste, slowly add potassium permanganate, control the temperature not to exceed 20°C, and stir for 1.5 -2h. Then the temperature was raised to 35-40°C and kept for 2-2.5h. Add distilled water dropwise and raise the temperature to 98-100°C, at which time a golden yellow suspension appears. Add hydrogen peroxide while hot, pour into distilled water, and ultrasonically disperse for 1-1.2 hours to obtain a graphene oxide mixture. Slowly add the cationic modifier DMSO and tributylphosphine containing long carbon chains to the above mixture, and stir for 10-15 minutes to obtain Reddish-brown precipitate, separated by centrifugation, alternately washed with hydrochloric acid solution and distilled water for 3-5 times, and vacuum freeze-dried for 22-24 hours to obtain a brown complex; ultrasonically disperse the complex in distilled water, add hydrazine hydrate solution, and dry in oil at 78-80°C The reaction was stirred in the bath for 10-12h. After the reaction is completed, the system is a black suspension, washed alternately with hydrochloric acid solution and distilled water for 3-5 times, and vacuum freeze-dried to obtain black powdery modified graphene;

2) Preparation of modified graphene slices: after drying the modified graphene and PET slice powders respectively, adding the graphene powder, PET slice powder, and modifier into a high-speed disperser for sufficient dispersion and mixing. Add the mixed powder into a twin-screw extruder for melt extrusion and granulation to obtain graphene-modified PET chips; the proportion of modified cationic graphene in the blend is 1%-5%, and the proportion of PET chip powder is 95% to 98.9%, the proportion of modifier is 0.1%-1%; the temperature of the first to fifth zone of the twin-screw extruder is 245-255°C, 260-270°C, 265-275°C, 265- 275°C, 260-270°C;

3) Melting: According to the mass ratio of 20:80-40:60, the graphene-modified PET chips and the PET chips are dried separately and then melted by a screw extruder (280-310°C), and the obtained graphene-modified PET chips are spun Melt and PET chip spinning melt;

4) Blending: Two kinds of spinning melts enter the two-component composite spinning assembly through their respective corresponding pipes for spinning (the temperature of the spinning box is 275-295°C), and the two spinning melts are fed from a special composite jet The wire plate is sprayed to form filaments;

5) Post-treatment: After cooling, oiling, stretching and setting and winding the filaments (the temperature of the first hot roller is 70-90°C, the temperature of the second hot roller is 130-180°C; the draw ratio is 3.0-4.0 ; side blowing wind speed 0.7-1.0m/s), to obtain modified graphene composite fiber; two kinds of components in the modified graphene composite fiber are combined in a skin-core type, and the fiber cross section is a four-leaf clover type.

Wherein, the intrinsic viscosity of the PET chip is 0.65±0.2dL/g, the melting point is 240-265°C, and the water content of the dry chip is less than 50ppm.

Example 1

A kind of preparation method of graphene modified PET blended fiber, comprises the following steps:

1) Preparation of modified graphene: Add graphite and sodium nitrate to a round bottom flask under ice bath conditions, pour concentrated sulfur into it and stir to form a paste, slowly add potassium permanganate, control the temperature at 15°C, and stir for 1.8h . Then the temperature was raised to 37°C and kept for 2.3h. Distilled water was added dropwise, and the temperature was raised to 99°C, at which point a golden yellow suspension appeared. Add hydrogen peroxide while hot, pour into distilled water, and ultrasonically disperse for 1.1h to obtain a graphene oxide mixture. Slowly add the cationic modifier DMSO and tributylphosphine containing long carbon chains to the above mixture, and stir for 12min to obtain a reddish-brown precipitate. Centrifuge, wash alternately with hydrochloric acid solution and distilled water for 4 times, vacuum freeze-dry for 23 hours to obtain a brown complex; ultrasonically disperse the complex in distilled water, add hydrazine hydrate solution, and stir in an oil bath at 79°C for 11 hours. After the reaction was completed, the system was a black suspension, which was alternately washed 4 times with hydrochloric acid solution and distilled water, and vacuum freeze-dried to obtain black powdery modified graphene;

2) Preparation of modified graphene slices: after drying the modified graphene and PET slice powders respectively, adding the graphene powder, PET slice powder, and modifier into a high-speed disperser for sufficient dispersion and mixing. Add the mixed powder into a twin-screw extruder for melt extrusion and granulation to obtain graphene-modified PET chips; the proportion of modified cationic graphene in the blend is 3%, and the proportion of PET chip powder is 96.5%. , the proportion of the modifier is 0.5%; the temperatures of the first to fifth zones of the twin-screw extruder are 250°C, 265°C, 270°C, 270°C, and 265°C respectively;

3) Melting: According to the mass ratio of 50:50, the graphene-modified PET chips and PET chips are dried separately and then melted by a screw extruder (300 ° C), and the obtained graphene-modified PET chip spinning melt and PET chip spinning silk melt;

4) Blending: Two kinds of spinning melts enter the two-component composite spinning assembly through their respective corresponding pipes for spinning (the temperature of the spinning box is 280°C), and the two spinning melts are fed from a special composite spinneret Spray to form filaments;

5) Post-treatment: After cooling, oiling, stretching and winding the filaments (the temperature of the first hot roller is 75°C, the temperature of the second hot roller is 150°C; the draw ratio is 3.5; the wind speed of side blowing is 0.8m /s), obtain the modified graphene composite fiber; two kinds of components in the modified graphene composite fiber are combined in a skin-core type, and the fiber cross section is a four-leaf clover type.

The specification of the self-crimping composite filament prepared by the above process is 100dtex/36f.

Example 2

The setting and working principle of this embodiment are the same as that of Embodiment 1, the difference is that:

A kind of preparation method of graphene modified PET blended fiber, comprises the following steps:

1) Preparation of modified graphene: Add graphite and sodium nitrate to a round bottom flask under ice bath conditions, pour concentrated sulfur and stir to form a paste, slowly add potassium permanganate, control the temperature not to exceed 20°C, and stir for 1.5 -2h. Then the temperature was raised to 35-40°C and kept for 2-2.5h. Add distilled water dropwise and raise the temperature to 98-100°C, at which time a golden yellow suspension appears. Add hydrogen peroxide while hot, pour into distilled water, and ultrasonically disperse for 1-1.2 hours to obtain a graphene oxide mixture. Slowly add the cationic modifier DMSO and tributylphosphine containing long carbon chains to the above mixture, and stir for 10-15 minutes to obtain Reddish-brown precipitate, separated by centrifugation, alternately washed with hydrochloric acid solution and distilled water for 3-5 times, and vacuum freeze-dried for 22-24 hours to obtain a brown complex; ultrasonically disperse the complex in distilled water, add hydrazine hydrate solution, and dry in oil at 78-80°C The reaction was stirred in the bath for 10-12h. After the reaction is completed, the system is a black suspension, washed alternately with hydrochloric acid solution and distilled water for 3-5 times, and vacuum freeze-dried to obtain black powdery modified graphene;

2) Preparation of modified graphene slices: after drying the modified graphene and PET slice powders respectively, adding the graphene powder, PET slice powder, and modifier into a high-speed disperser for sufficient dispersion and mixing. Add the mixed powder into a twin-screw extruder for melt extrusion and granulation to obtain graphene-modified PET chips; the proportion of modified cationic graphene in the blend is 1%-5%, and the proportion of PET chip powder is 95% to 98.9%, the proportion of modifier is 0.1%-1%; the temperature of the first to fifth zone of the twin-screw extruder is 245-255°C, 260-270°C, 265-275°C, 265- 275°C, 260-270°C;

3) Melting: According to the mass ratio of 20:80-40:60, the graphene-modified PET chips and the PET chips are dried separately and then melted by a screw extruder (280-310°C), and the obtained graphene-modified PET chips are spun Melt and PET chip spinning melt;

4) Blending: Two kinds of spinning melts enter the two-component composite spinning assembly through their respective corresponding pipes for spinning (the temperature of the spinning box is 275-295°C), and the two spinning melts are fed from a special composite jet The wire plate is sprayed to form filaments;

5) Post-treatment: After cooling, oiling, stretching and winding the filaments (the temperature of the first hot roller is 70°C, the temperature of the second hot roller is 180°C; the draw ratio is 3.0-4.0; the wind speed of side blowing 0.7-1.0m/s), obtain the modified graphene composite fiber; two kinds of components in the modified graphene composite fiber are combined in a sheath-core type, and the cross-section of the fiber is a four-leaf clover type.

The specification of the self-crimping composite filament prepared by the above process is 100dtex/24f.

Example 3

The setting and working principle of this embodiment are the same as that of Embodiment 1, the difference is that:

A kind of preparation method of graphene modified PET blended fiber, comprises the following steps:

1) Preparation of modified graphene: Add graphite and sodium nitrate to a round bottom flask under ice bath conditions, pour concentrated sulfur and stir to form a paste, slowly add potassium permanganate, control the temperature not to exceed 20°C, and stir for 1.5 -2h. Then the temperature was raised to 35-40°C and kept for 2-2.5h. Add distilled water dropwise and raise the temperature to 98-100°C, at which time a golden yellow suspension appears. Add hydrogen peroxide while hot, pour into distilled water, and ultrasonically disperse for 1-1.2 hours to obtain a graphene oxide mixture. Slowly add the cationic modifier DMSO and tributylphosphine containing long carbon chains to the above mixture, and stir for 10-15 minutes to obtain Reddish-brown precipitate, separated by centrifugation, alternately washed with hydrochloric acid solution and distilled water for 3-5 times, and vacuum freeze-dried for 22-24 hours to obtain a brown complex; ultrasonically disperse the complex in distilled water, add hydrazine hydrate solution, and dry in oil at 78-80°C The reaction was stirred in the bath for 10-12h. After the reaction is completed, the system is a black suspension, washed alternately with hydrochloric acid solution and distilled water for 3-5 times, and vacuum freeze-dried to obtain black powdery modified graphene;

2) Preparation of modified graphene slices: after drying the modified graphene and PET slice powders respectively, adding the graphene powder, PET slice powder, and modifier into a high-speed disperser for sufficient dispersion and mixing. Add the mixed powder into a twin-screw extruder for melt extrusion and granulation to obtain graphene-modified PET chips; the proportion of modified cationic graphene in the blend is 1%-5%, and the proportion of PET chip powder is 95% to 98.9%, the proportion of modifier is 0.1%-1%; the temperature of the first to fifth zone of the twin-screw extruder is 245-255°C, 260-270°C, 265-275°C, 265- 275°C, 260-270°C;

3) Melting: According to the mass ratio of 20:80-40:60, the graphene-modified PET chips and the PET chips are dried separately and then melted by a screw extruder (280-310°C), and the obtained graphene-modified PET chips are spun Melt and PET chip spinning melt;

4) Blending: Two kinds of spinning melts enter the two-component composite spinning assembly through their respective corresponding pipes for spinning (the temperature of the spinning box is 275-295°C), and the two spinning melts are fed from a special composite jet The wire plate is sprayed to form filaments;

5) Post-treatment: After cooling, oiling, stretching and winding the filaments (the temperature of the first hot roller is 90°C, the temperature of the second hot roller is 130°C; the draw ratio is 3.0-4.0; the wind speed of side blowing 0.7-1.0m/s), obtain the modified graphene composite fiber; two kinds of components in the modified graphene composite fiber are combined in a sheath-core type, and the cross-section of the fiber is a four-leaf clover type.

The specification of the self-crimping composite filament prepared by the above process is 100dtex/36f.

Example 4

The setting and working principle of this embodiment are the same as that of Embodiment 1, the difference is that:

A kind of preparation method of graphene modified PET blended fiber, comprises the following steps:

1) Preparation of modified graphene: Add graphite and sodium nitrate to a round bottom flask under ice bath conditions, pour concentrated sulfur and stir to form a paste, slowly add potassium permanganate, control the temperature not to exceed 20°C, and stir for 1.5 -2h. Then the temperature was raised to 35-40°C and kept for 2-2.5h. Add distilled water dropwise and raise the temperature to 98-100°C, at which time a golden yellow suspension appears. Add hydrogen peroxide while hot, pour into distilled water, and ultrasonically disperse for 1-1.2 hours to obtain a graphene oxide mixture. Slowly add the cationic modifier DMSO and tributylphosphine containing long carbon chains to the above mixture, and stir for 10-15 minutes to obtain Reddish-brown precipitate, separated by centrifugation, alternately washed with hydrochloric acid solution and distilled water for 3-5 times, and vacuum freeze-dried for 22-24 hours to obtain a brown complex; ultrasonically disperse the complex in distilled water, add hydrazine hydrate solution, and dry in oil at 78-80°C The reaction was stirred in the bath for 10-12h. After the reaction is completed, the system is a black suspension, washed alternately with hydrochloric acid solution and distilled water for 3-5 times, and vacuum freeze-dried to obtain black powdery modified graphene;

2) Preparation of modified graphene slices: after drying the modified graphene and PET slice powders respectively, adding the graphene powder, PET slice powder, and modifier into a high-speed disperser for sufficient dispersion and mixing. Add the mixed powder into a twin-screw extruder for melt extrusion and granulation to obtain graphene-modified PET chips; the proportion of modified cationic graphene in the blend is 1%-5%, and the proportion of PET chip powder is 95% to 98.9%, the proportion of modifier is 0.1%-1%; the temperature of the first to fifth zone of the twin-screw extruder is 245-255°C, 260-270°C, 265-275°C, 265- 275°C, 260-270°C;

3) Melting: According to the mass ratio of 20:80-40:60, the graphene-modified PET chips and the PET chips are dried separately and then melted by a screw extruder (280-310°C), and the obtained graphene-modified PET chips are spun Melt and PET chip spinning melt;

4) Blending: Two kinds of spinning melts enter the two-component composite spinning assembly through their respective corresponding pipes for spinning (the temperature of the spinning box is 275-295°C), and the two spinning melts are fed from a special composite jet The wire plate is sprayed to form filaments;

5) Post-treatment: After cooling, oiling, stretching and winding the filaments (the temperature of the first hot roller is 80°C, the temperature of the second hot roller is 170°C; the draw ratio is 3.0-4.0; the wind speed of side blowing 0.7-1.0m/s), obtain the modified graphene composite fiber; two kinds of components in the modified graphene composite fiber are combined in a sheath-core type, and the cross-section of the fiber is a four-leaf clover type.

The specification of the self-crimping composite filament prepared by the above process is 100dtex/24f.

Example 5

The setting and working principle of this embodiment are the same as that of Embodiment 1, the difference is that:

A kind of preparation method of graphene modified PET blended fiber, comprises the following steps:

1) Preparation of modified graphene: Add graphite and sodium nitrate to a round bottom flask under ice bath conditions, pour concentrated sulfur and stir to form a paste, slowly add potassium permanganate, control the temperature not to exceed 20°C, and stir for 1.5 -2h. Then the temperature was raised to 35-40°C and kept for 2-2.5h. Add distilled water dropwise and raise the temperature to 98-100°C, at which time a golden yellow suspension appears. Add hydrogen peroxide while hot, pour into distilled water, and ultrasonically disperse for 1-1.2 hours to obtain a graphene oxide mixture. Slowly add the cationic modifier DMSO and tributylphosphine containing long carbon chains to the above mixture, and stir for 10-15 minutes to obtain Reddish-brown precipitate, separated by centrifugation, alternately washed with hydrochloric acid solution and distilled water for 3-5 times, and vacuum freeze-dried for 22-24 hours to obtain a brown complex; ultrasonically disperse the complex in distilled water, add hydrazine hydrate solution, and dry in oil at 78-80°C The reaction was stirred in the bath for 10-12h. After the reaction is completed, the system is a black suspension, washed alternately with hydrochloric acid solution and distilled water for 3-5 times, and vacuum freeze-dried to obtain black powdery modified graphene;

2) Preparation of modified graphene slices: after drying the modified graphene and PET slice powders respectively, adding the graphene powder, PET slice powder, and modifier into a high-speed disperser for sufficient dispersion and mixing. Add the mixed powder into a twin-screw extruder for melt extrusion and granulation to obtain graphene-modified PET chips; the proportion of modified cationic graphene in the blend is 1%-5%, and the proportion of PET chip powder is 95% to 98.9%, the proportion of modifier is 0.1%-1%; the temperature of the first to fifth zone of the twin-screw extruder is 245-255°C, 260-270°C, 265-275°C, 265- 275°C, 260-270°C;

3) Melting: According to the mass ratio of 20:80-40:60, the graphene-modified PET chips and the PET chips are dried separately and then melted by a screw extruder (280-310°C), and the obtained graphene-modified PET chips are spun Melt and PET chip spinning melt;

4) Blending: Two kinds of spinning melts enter the two-component composite spinning assembly through their respective corresponding pipes for spinning (the temperature of the spinning box is 275-295°C), and the two spinning melts are fed from a special composite jet The wire plate is sprayed to form filaments;

5) Post-treatment: After cooling, oiling, stretching and winding the filaments (the temperature of the first hot roller is 85°C, the temperature of the second hot roller is 160°C; the draw ratio is 3.0-4.0; the wind speed of side blowing 0.7-1.0m/s), obtain the modified graphene composite fiber; two kinds of components in the modified graphene composite fiber are combined in a sheath-core type, and the cross-section of the fiber is a four-leaf clover type.

The specification of the self-crimping composite filament prepared by the above process is 100dtex/36f.

Comparative Example 1 (the difference with Example 1 is that the graphene content exceeds the preferred ratio in the graphene-modified PET chip, and the proportion of graphene is 7%.)

The setting and working principle of this comparative example are the same as that of Example 1, as follows:

A kind of preparation method of graphene modified PET blended fiber, comprises the following steps:

1) Preparation of modified graphene: Add graphite and sodium nitrate to a round bottom flask under ice bath conditions, pour concentrated sulfur into it and stir to form a paste, slowly add potassium permanganate, control the temperature at 15°C, and stir for 1.8h . Then the temperature was raised to 37°C and kept for 2.3h. Distilled water was added dropwise, and the temperature was raised to 99°C, at which point a golden yellow suspension appeared. Add hydrogen peroxide while hot, pour into distilled water, and ultrasonically disperse for 1.1h to obtain a graphene oxide mixture. Slowly add the cationic modifier DMSO and tributylphosphine containing long carbon chains to the above mixture, and stir for 12min to obtain a reddish-brown precipitate. Centrifuge, wash alternately with hydrochloric acid solution and distilled water for 4 times, vacuum freeze-dry for 23 hours to obtain a brown complex; ultrasonically disperse the complex in distilled water, add hydrazine hydrate solution, and stir in an oil bath at 79°C for 11 hours. After the reaction was completed, the system was a black suspension, which was alternately washed 4 times with hydrochloric acid solution and distilled water, and vacuum freeze-dried to obtain black powdery modified graphene;

2) Preparation of modified graphene slices: after drying the modified graphene and PET slice powders respectively, adding the graphene powder, PET slice powder, and modifier into a high-speed disperser for sufficient dispersion and mixing. Add the mixed powder into a twin-screw extruder for melt extrusion and granulation to obtain graphene-modified PET chips; the proportion of modified cationic graphene in the blend is 7%, and the proportion of PET chip powder is 92%. , the modifier accounted for 1%; the temperatures of the first to fifth zones of the twin-screw extruder were 250°C, 265°C, 270°C, 270°C, and 265°C;

3) Melting: According to the mass ratio of 50:50, the graphene-modified PET chips and PET chips are dried separately and then melted by a screw extruder (300 ° C), and the obtained graphene-modified PET chip spinning melt and PET chip spinning silk melt;

4) Blending: Two kinds of spinning melts enter the two-component composite spinning assembly through their respective corresponding pipes for spinning (the temperature of the spinning box is 280°C), and the two spinning melts are fed from a special composite spinneret Spray to form filaments;

5) Post-treatment: After cooling, oiling, stretching and winding the filaments (the temperature of the first hot roller is 75°C, the temperature of the second hot roller is 150°C; the draw ratio is 3.5; the wind speed of side blowing is 0.8m /s), obtain the modified graphene composite fiber; two kinds of components in the modified graphene composite fiber are combined in a skin-core type, and the fiber cross section is a four-leaf clover type.

The specification of the self-crimping composite filament prepared by the above process is 100dtex/36f.

Comparative Example 2 (the difference from Example 1 is that sheath-core composite spinning is carried out, and the fiber structure is concentric.)

The setting and working principle of this comparative example are the same as that of Example 1, the difference is that:

A kind of preparation method of graphene modified PET blended fiber, comprises the following steps:

1) Preparation of modified graphene: Add graphite and sodium nitrate to a round bottom flask under ice bath conditions, pour concentrated sulfur into it and stir to form a paste, slowly add potassium permanganate, control the temperature at 15°C, and stir for 1.8h . Then the temperature was raised to 37°C and kept for 2.3h. Distilled water was added dropwise, and the temperature was raised to 99°C, at which point a golden yellow suspension appeared. Add hydrogen peroxide while hot, pour into distilled water, and ultrasonically disperse for 1.1h to obtain a graphene oxide mixture. Slowly add the cationic modifier DMSO and tributylphosphine containing long carbon chains to the above mixture, and stir for 12min to obtain a reddish-brown precipitate. Centrifuge, wash alternately with hydrochloric acid solution and distilled water for 4 times, vacuum freeze-dry for 23 hours to obtain a brown complex; ultrasonically disperse the complex in distilled water, add hydrazine hydrate solution, and stir in an oil bath at 79°C for 11 hours. After the reaction was completed, the system was a black suspension, which was alternately washed 4 times with hydrochloric acid solution and distilled water, and vacuum freeze-dried to obtain black powdery modified graphene;

2) Preparation of modified graphene slices: after drying the modified graphene and PET slice powders respectively, adding the graphene powder, PET slice powder, and modifier into a high-speed disperser for sufficient dispersion and mixing. Add the mixed powder into a twin-screw extruder for melt extrusion and granulation to obtain graphene-modified PET chips; the proportion of modified cationic graphene in the blend is 3%, and the proportion of PET chip powder is 96.5%. , the proportion of the modifier is 0.5%; the temperatures of the first to fifth zones of the twin-screw extruder are 250°C, 265°C, 270°C, 270°C, and 265°C respectively;

3) Melting: According to the mass ratio of 50:50, the graphene-modified PET chips and PET chips are dried separately and then melted by a screw extruder (300 ° C), and the obtained graphene-modified PET chip spinning melt and PET chip spinning silk melt;

4) Blending: The two spinning melts enter the two-component composite spinning assembly through their corresponding pipes for spinning (the temperature of the spinning box is 280 ° C), and the two spinning melts are fed from the skin-core composite spinning assembly Sprayed from the spinneret to form filaments;

5) Post-treatment: After cooling, oiling, stretching and winding the filaments (the temperature of the first hot roller is 75°C, the temperature of the second hot roller is 150°C; the draw ratio is 3.5; the wind speed of side blowing is 0.8m /s), obtain the modified graphene composite fiber; two kinds of components in the modified graphene composite fiber are combined in a skin-core type, and the fiber cross section has a concentric circular structure.

The specification of the self-crimping composite filament prepared by the above process is 100dtex/36f.

Comparative example 3 (difference from the embodiment is that the temperature of the spinning box body and the temperature of the hot roll exceed the optimal range during the spinning process; the temperature of the spinning box body is 305 ° C, the temperature of the first hot roll is 105 ° C; the temperature of the second hot roll is 185°C.)

A kind of preparation method of graphene modified PET blended fiber, comprises the following steps:

1) Preparation of modified graphene: Add graphite and sodium nitrate to a round bottom flask under ice bath conditions, pour concentrated sulfur into it and stir to form a paste, slowly add potassium permanganate, control the temperature at 15°C, and stir for 1.8h . Then the temperature was raised to 37°C and kept for 2.3h. Distilled water was added dropwise, and the temperature was raised to 99°C, at which point a golden yellow suspension appeared. Add hydrogen peroxide while hot, pour into distilled water, and ultrasonically disperse for 1.1h to obtain a graphene oxide mixture. Slowly add the cationic modifier DMSO and tributylphosphine containing long carbon chains to the above mixture, and stir for 12min to obtain a reddish-brown precipitate. Centrifuge, wash alternately with hydrochloric acid solution and distilled water for 4 times, vacuum freeze-dry for 23 hours to obtain a brown complex; ultrasonically disperse the complex in distilled water, add hydrazine hydrate solution, and stir in an oil bath at 79°C for 11 hours. After the reaction was completed, the system was a black suspension, which was alternately washed 4 times with hydrochloric acid solution and distilled water, and vacuum freeze-dried to obtain black powdery modified graphene;

2) Preparation of modified graphene slices: after drying the modified graphene and PET slice powders respectively, adding the graphene powder, PET slice powder, and modifier into a high-speed disperser for sufficient dispersion and mixing. Add the mixed powder into a twin-screw extruder for melt extrusion and granulation to obtain graphene-modified PET chips; the proportion of modified cationic graphene in the blend is 3%, and the proportion of PET chip powder is 96.5%. , the proportion of the modifier is 0.5%; the temperatures of the first to fifth zones of the twin-screw extruder are 250°C, 265°C, 270°C, 270°C, and 265°C respectively;

3) Melting: According to the mass ratio of 50:50, the graphene-modified PET chips and PET chips are dried separately and then melted by a screw extruder (300 ° C), and the obtained graphene-modified PET chip spinning melt and PET chip spinning silk melt;

4) Blending: Two kinds of spinning melts enter the two-component composite spinning assembly through their respective corresponding pipes for spinning (the temperature of the spinning box is 305°C), and the two spinning melts are fed from a special composite spinneret Spray to form filaments;

5) Post-treatment: After cooling, oiling, stretching and setting and winding of the filaments (the temperature of the first hot roller is 105°C, the temperature of the second hot roller is 185°C; the draw ratio is 3.5; the wind speed of side blowing is 0.8m /s), obtain the modified graphene composite fiber; two kinds of components in the modified graphene composite fiber are combined in a skin-core type, and the fiber cross section is a four-leaf clover type.

The specification of the self-crimping composite filament prepared by the above process is 100dtex/36f.

Comparative example 4 (the difference with embodiment is, do not carry out cationic modification to graphene.)

A kind of preparation method of graphene modified PET blended fiber, comprises the following steps:

1) Preparation of graphene slices: after drying the graphene and PET slice powders respectively, adding the graphene powder, PET slice powders, and modifiers into a high-speed disperser for sufficient dispersion and mixing. Add the mixed powder into a twin-screw extruder for melt extrusion and granulation to obtain graphene-modified PET chips; the proportion of modified cationic graphene in the blend is 1%-5%, and the proportion of PET chip powder is 95% to 98.9%, the proportion of modifier is 0.1%-1%; the temperature of the first to fifth zone of the twin-screw extruder is 245-255°C, 260-270°C, 265-275°C, 265- 275°C, 260-270°C;

2) Melting: According to the mass ratio of 50:50, the graphene-modified PET chips and PET chips are dried separately and then melted (300° C.) by a screw extruder, and the obtained graphene-modified PET chips spinning melt and PET chips are spun silk melt;

3) Blending: Two kinds of spinning melts enter the two-component composite spinning assembly through their respective corresponding pipes for spinning (the temperature of the spinning box is 280°C), and the two kinds of spinning melts are fed from a special composite spinneret Spray to form filaments;

4) Post-treatment: After cooling, oiling, stretching and setting and winding the filaments (the temperature of the first hot roller is 75°C, the temperature of the second hot roller is 150°C; the draw ratio is 3.5; the wind speed of side blowing is 0.8m /s), obtain the modified graphene composite fiber; two kinds of components in the modified graphene composite fiber are combined in a skin-core type, and the fiber cross section is a four-leaf clover type.

The specification of the self-crimping composite filament prepared by the above process is 100dtex/36f.

Comparative Example 5 (The difference from the examples is that 1.3-dimethyl phthalate-5-sodium sulfonate is used for cationic modification.)

A kind of preparation method of graphene modified PET blended fiber, comprises the following steps:

1) Preparation of modified graphene: Add graphite and sodium nitrate to a round bottom flask under ice bath conditions, pour concentrated sulfur into it and stir to form a paste, slowly add potassium permanganate, control the temperature at 15°C, and stir for 1.8h . Then the temperature was raised to 37°C and kept for 2.3h. Distilled water was added dropwise, and the temperature was raised to 99°C, at which point a golden yellow suspension appeared. Add hydrogen peroxide while hot, pour into distilled water, and ultrasonically disperse for 1.1h to obtain a graphene oxide mixture. Slowly add the cationic modifier 1.3-dimethylphthalate-5-sodium sulfonate to the above mixture, and stir for 12min to obtain The reddish-brown precipitate was separated by centrifugation, washed alternately with hydrochloric acid solution and distilled water 4 times, and vacuum freeze-dried for 23 hours to obtain a brown complex; the complex was ultrasonically dispersed in distilled water, added with hydrazine hydrate solution, and stirred in an oil bath at 79°C for 11 hours. After the reaction was completed, the system was a black suspension, which was alternately washed 4 times with hydrochloric acid solution and distilled water, and vacuum freeze-dried to obtain black powdery modified graphene;

2) Preparation of modified graphene slices: after drying the modified graphene and PET slice powders respectively, adding the graphene powder, PET slice powder, and modifier into a high-speed disperser for sufficient dispersion and mixing. Add the mixed powder into a twin-screw extruder for melt extrusion and granulation to obtain graphene-modified PET chips; the proportion of modified cationic graphene in the blend is 3%, and the proportion of PET chip powder is 96.5%. , the proportion of the modifier is 0.5%; the temperatures of the first to fifth zones of the twin-screw extruder are 250°C, 265°C, 270°C, 270°C, and 265°C respectively;

3) Melting: According to the mass ratio of 50:50, the graphene-modified PET chips and PET chips are dried separately and then melted by a screw extruder (300 ° C), and the obtained graphene-modified PET chip spinning melt and PET chip spinning silk melt;

4) Blending: Two kinds of spinning melts enter the two-component composite spinning assembly through their respective corresponding pipes for spinning (the temperature of the spinning box is 280°C), and the two spinning melts are fed from a special composite spinneret Spray to form filaments;

5) Post-treatment: After cooling, oiling, stretching and winding the filaments (the temperature of the first hot roller is 75°C, the temperature of the second hot roller is 150°C; the draw ratio is 3.5; the wind speed of side blowing is 0.8m /s), obtain the modified graphene composite fiber; two kinds of components in the modified graphene composite fiber are combined in a skin-core type, and the fiber cross section is a four-leaf clover type.

The specification of the self-crimping composite filament prepared by the above process is 100dtex/36f.

Comparative example 6 (the difference with embodiment is, does not add modifying agent when blending.)

1) Preparation of modified graphene: Add graphite and sodium nitrate to a round bottom flask under ice bath conditions, pour concentrated sulfur into it and stir to form a paste, slowly add potassium permanganate, control the temperature at 15°C, and stir for 1.8h . Then the temperature was raised to 37°C and kept for 2.3h. Distilled water was added dropwise, and the temperature was raised to 99°C, at which point a golden yellow suspension appeared. Add hydrogen peroxide while hot, pour into distilled water, and ultrasonically disperse for 1.1h to obtain a graphene oxide mixture. Slowly add the cationic modifier DMSO and tributylphosphine containing long carbon chains to the above mixture, and stir for 12min to obtain a reddish-brown precipitate. Centrifuge, wash alternately with hydrochloric acid solution and distilled water for 4 times, vacuum freeze-dry for 23 hours to obtain a brown complex; ultrasonically disperse the complex in distilled water, add hydrazine hydrate solution, and stir in an oil bath at 79°C for 11 hours. After the reaction was completed, the system was a black suspension, which was alternately washed 4 times with hydrochloric acid solution and distilled water, and vacuum freeze-dried to obtain black powdery modified graphene;

2) Preparation of modified graphene slices: after drying the modified graphene and PET slice powders respectively, adding the graphene powder and PET slice powders into a high-speed disperser for sufficient dispersion and mixing. Add the mixed powder into a twin-screw extruder for melt extrusion and granulation to obtain graphene-modified PET chips; the proportion of modified cationic graphene in the blend is 3%, and the proportion of PET chip powder is 96.5%. , the proportion of the modifier is 0.5%; the temperatures of the first to fifth zones of the twin-screw extruder are 250°C, 265°C, 270°C, 270°C, and 265°C respectively;

3) Melting: According to the mass ratio of 50:50, the graphene-modified PET chips and PET chips are dried separately and then melted by a screw extruder (300 ° C), and the obtained graphene-modified PET chip spinning melt and PET chip spinning silk melt;

4) Blending: Two kinds of spinning melts enter the two-component composite spinning assembly through their respective corresponding pipes for spinning (the temperature of the spinning box is 280°C), and the two spinning melts are fed from a special composite spinneret Spray to form filaments;

5) Post-treatment: After cooling, oiling, stretching and winding the filaments (the temperature of the first hot roller is 75°C, the temperature of the second hot roller is 150°C; the draw ratio is 3.5; the wind speed of side blowing is 0.8m /s), obtain the modified graphene composite fiber; two kinds of components in the modified graphene composite fiber are combined in a skin-core type, and the fiber cross section is a four-leaf clover type.

The specification of the self-crimping composite filament prepared by the above process is 100dtex/36f.

The evaluation parameters of the composite spun fibers obtained in Examples 1-5 and Comparative Examples 1-6 are shown in Table 1.

The filaments prepared in the above examples were tested for the strength of the composite fiber fabric according to "GB/T-14337 Filament Tensile Performance Test Method", and the water absorption of the composite fiber fabric was tested according to "GB/T12703.4-2010". The conductivity of the composite fiber fabric was tested according to "GBT 1410-2006". According to the textile industry standard of the People's Republic of China FZT 54042-2011, when the fiber volume specific resistance is 105-108Ω·cm, the fiber It has excellent antistatic performance and is a superior product. See Table 1 for details.

Table 1 Main preparation process and fiber physical index

Conclusion: In conjunction with the above-mentioned examples and the comparative examples of Table 1, it can be seen that the present application uses blended modified graphene PET chips and PET chips as two components and then melts and extrudes them respectively through a screw extruder to enter a two-component Composite spinning equipment and specially designed fan-blade composite spinneret hole, after cooling, oiling, drafting, heat setting and winding, the mechanical properties of the obtained fiber have reached the relevant standard requirements. Due to the appropriate component ratio, excellent spinneret design, and excellent spinning process, the composite fiber obtained has the characteristics of high strength and good moisture absorption and perspiration. The graphene components are evenly dispersed without agglomeration, and the fiber is also It has good antistatic properties and is a high value-added fiber.

Taking Example 1, the water absorption test was carried out, and the measured value was 228%, meeting the standard requirement of ≥200%, and the rest of the examples also all met the standard.

The difference between Comparative Example 1 and Example 1 is that the addition ratio of modified graphene is too high during blending, so that graphene cannot be fully dispersed uniformly, and partial agglomeration occurs, which is not conducive to its subsequent processing, and cannot exert its resistance. Electrostatic performance, moisture absorption and perspiration ability, and various mechanical properties of fibers have declined.

The difference between Comparative Example 2 and Example 1 is that the obtained fiber does not use a specially designed four-leaf clover spinneret, so although the obtained fiber has good antistatic properties, its strength is significantly reduced, and more graphene is used. The cost is higher and cannot be compared with the fiber obtained in Example 1.

The difference between Comparative Example 3 and Example 1 is that the obtained fiber has a higher spinning temperature, resulting in partial degradation, the obtained fiber cannot have strength, and because the winding temperature is too high, the obtained fiber is poorly formed and cannot meet the following requirements. Processing and other steps, the resulting fiber performance is poor.

The difference between Comparative Example 4 and Example 1 is that graphene is not cationic modified, although the resulting fiber has antistatic properties, its mechanical properties and antistatic properties are lower than those used in Example 1 using cationic modification of graphene. It can be seen that cationic modification of graphene can better disperse the graphene evenly without agglomeration, so that the fiber has excellent performance.

The difference between Comparative Example 5 and Example 1 is that instead of using DMSO and tributylphosphine containing long carbon chains, the conventional modifier 1.3-dimethyl phthalate-5-sodium sulfonate is used to modify the graphene cationic. It can be seen that the performance indicators of the modified graphene composite fiber after modification are lower than those obtained by using the cationic modifier DMSO and the fiber containing long carbon chain tributylphosphine. This is because dimethyl isophthalate -5-Sodium sulfonate is generally used for modification of conventional polyester, because it has a benzene ring, and there may be a force between it and graphene, so it cannot be modified very well, so the effect is poor.

The difference between Comparative Example 6 and Example 1 is that no modifier was added when the modified graphene PET slices were blended, and the properties of the resulting fibers were quite different. This is because the addition of modifiers can make the dispersion effect of graphene Even better, so the antistatic effect and strength of the fibers obtained without modifiers are lower than those obtained with modifiers.

From the data of Examples 1-5 and Comparative Examples 1-6, it can be seen that only the schemes within the scope of the claims of the present invention can meet the above requirements in all aspects, and obtain the optimal synthesis scheme. However, changes in the ratio, replacement/addition or subtraction of raw materials, or changes in the order of feeding will all have corresponding negative effects.

Raw materials used in the present invention, equipment, if not specified, are commonly used raw materials, equipment in this area; Method used in the present invention, if not specified, are conventional methods in this area.

The above are only preferred embodiments of the present invention, and do not limit the present invention in any way. All simple modifications, changes and equivalent transformations made to the above embodiments according to the technical essence of the present invention still belong to the technical solution of the present invention. scope of protection.

Claims (6)

1. a preparation method of graphene modified PET blended fiber, is characterized in that, comprises following preparation steps: 1) Modification of graphene with a cationic modifier; the cationic modifier is DMSO and tributylphosphine containing long carbon chains; 2) Preparation of modified graphene slices: blend modified cationic graphene, modifier and PET slice powder, and then granulate graphene modified slices through a twin-screw extruder; modified cationic slices in the blend The proportion of graphene is 1%~5%, the proportion of PET chip powder is 95%~98.9%, and the proportion of modifier is 0.1%~1%; 3) Melting: melting the dried PET chips and graphene-modified chips with a screw extruder to obtain PET spinning melt and graphene-modified chip spinning melt; 4) Blending: the two kinds of spinning melts enter the two-component composite spinning assembly through their respective corresponding pipes for spinning, and the two spinning melts are sprayed out from the composite spinneret to form blended fibers; the two-component The box temperature of the composite spinning assembly is 275~295°C; the cross-section of the blended fiber is a four-leaf clover; the two components in the blended fiber have a sheath-core structure, including PET spinning (A) and Graphene modified spinning arranged at intervals around (B); 5) Post-processing: After cooling, oiling, stretching and setting and winding the above-mentioned blended fibers, the finished product is obtained; when stretching and setting, the temperature of the first hot roller is 70~90°C, and the temperature of the second hot roller is 130~180°C . 2. the preparation method of a kind of graphene-modified PET blended fiber according to claim 1, is characterized in that, in step 2), used modifier is cetyltrimethylammonium bromide, dodecane One or more of sodium sulfate, ethylenediamine and polyvinylpyrrolidone. 3. The preparation method of a graphene-modified PET blended fiber according to claim 1, wherein the intrinsic viscosity of the PET chips is 0.65±0.2dL/g, and the melting point is 240-265°C. 4. the preparation method of a kind of graphene-modified PET blended fiber according to claim 1, it is characterized in that, when using twin-screw extruder to carry out melting granulation in step 3), the temperature of screw rod one zone to five zone respectively 245~255℃, 260~270℃, 265~275℃, 265~275℃, 260~270℃. 5. the preparation method of a kind of graphene modified PET blended fiber according to claim 1, is characterized in that, in step 4), described graphene modified chip and PET chip mass ratio are 20:80～40: 60; the screw temperature of the two-component composite spinning assembly is 280-310°C. 6. The preparation method of a graphene-modified PET blended fiber according to claim 1, characterized in that, in step 5), the draw ratio is 3.0-4.0 when stretching and setting.

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