CN110306250B - Long-acting anti-static composite nylon fabric and preparation method thereof - Google Patents
Long-acting anti-static composite nylon fabric and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a long-acting anti-static composite polyamide fabric and a preparation method thereof. Then the long-acting antistatic composite nylon fiber can be prepared by carrying out in-situ copolymerization, melt spinning and weaving on the polyamide fiber and caprolactam. According to the invention, only a trace amount of graphene and a small amount of carbon black are added, so that the traditional chinlon has an excellent antistatic effect, and the product has the advantages of good spinnability, stable performance, low cost, small industrialization difficulty and obvious practical value.
Description
Technical Field
The invention belongs to the field of chemical fiber fabrics, and particularly relates to a long-acting anti-static composite nylon fabric and a preparation method thereof.
Background
In daily life, two objects made of different materials are separated after being contacted, and then static electricity can be generated, because one object loses certain charges and then is positively charged, and the other object obtains negative charges, and the charges are difficult to be simply neutralized and gradually accumulated to form static electricity. The most important ways of forming static electricity in daily life are three ways, friction, induction and conduction. Static electricity itself is a very common phenomenon, but when the static electricity is accumulated and violently released, the phenomena of circuit breakdown, information interference, fire, electric shock and the like are easily caused, so that the human body is discomfortable at light weight, the dust adsorption is increased to dirty the environment, and electromagnetic signals are interfered at heavy weight to cause dizziness and headache, breakdown electronic components and even cause explosion and fire.
The primary method of eliminating static electricity is to increase the conductivity of the material, allowing excess charge to be transferred or neutralized from the surface of the object. The conductive additives commonly used at present include metal fibers, carbon fibers, composite conductive fibers, conductive polymers, nano carbon particles, and the like, and from the viewpoint of cost performance, the conductive material with a porous nano carbon structure, carbon black, is the most competitive antistatic additive material. Many researches and reports prove that the carbon black can effectively improve the antistatic effect of the high polymer material, however, the effect can be realized only by adding the carbon black only with high additive amount (more than 5%), and under the condition of the high additive amount, the mechanical property of the composite material is likely to be influenced, and due to the existence of the carbon black cluster, the composite material processed into materials such as fiber and film has the defects of poor product uniformity, low strength and the like.
Graphene is a newly discovered star material in recent years, has numerous unequally-used properties such as mechanical properties, electrical properties, thermal properties, optical properties, catalysis, semiconductors and the like, and is considered to be an industrial monosodium glutamate material which can cause industrial upgrading. Due to the ultrahigh electrical conductivity of graphene, the preparation of antistatic or conductive materials by adding graphene to other materials has become a popular problem in recent years. The method is limited by a plurality of factors such as cost, preparation difficulty and environmental friendliness, the single use of graphene is not an optimal choice, and the high conductivity of graphene and the low cost of carbon black are combined, so that the method is probably a shortcut for preparing the antistatic composite material. CN103832997A graphene/carbon black composite material, preparation method and application thereof adopts a graphite oxide and carbon black compounding mode to prepare the conductive composite powder, however, the preparation is complex, the cost is high, and the industrialization difficulty is large. CN107516740A "a rock black and graphene powder composite conductive agent and its preparation" adopts the method of adding carbon black into the preparation process of graphite oxide to obtain the composite conductive agent, but the oxidizing agent of graphite oxide itself may damage the carbon black structure, and the conductivity of the composite powder is difficult to ensure. CN106147185, "conductive polycarbonate-based pellet containing multi-dimensional carbon nanomaterial, and preparation method and application thereof", blends carbon black, graphene and carbon nanotube with polycarbonate to achieve the purpose of forming a conductive network together with a multi-dimensional carbon material, however, this method cannot avoid aggregation of the carbon material and cannot perform spinning treatment. How to optimize the raw materials of the graphene and the carbon black and the preparation process, the use amounts of the graphene and the carbon black are reduced to the maximum extent, and the molecular level dispersion is realized, which is a precondition for realizing the preparation of the anti-static composite nylon fabric and is also a big problem which is difficult to solve at present.
Disclosure of Invention
The invention aims to provide a long-acting anti-static composite nylon fabric and a preparation method thereof, aiming at the defects of the prior art. In the fibers forming the fabric, graphene and carbon black are uniformly dispersed in a nylon 6 matrix in a copolymerization mode to form a conductive network, so that the conductivity can be kept not to be attenuated even after long-term use and washing, and the fabric has high durability.
The purpose of the invention is realized by the following technical scheme: a long-acting anti-static composite nylon fabric is woven by graphene modified nylon, wherein the graphene modified nylon at least comprises single-layer graphene grafted with nylon 6 molecules, nano carbon black and free nylon 6, and the nano carbon black is attached to two surfaces of a single-layer graphene sheet; the nano carbon black comprises high-DBP value nano carbon black and low-DBP value nano carbon black, the addition amount of the low-DBP value nano carbon black is 3-5 times that of the high-DBP value nano carbon black, and the mass ratio of the nano carbon black to graphene is 1.5-3.2: 0.04 to 0.24; the mass content of the graphene in the fabric is 0.04-0.24%; the number average molecular weight of the free nylon 6 is 12000-40000.
Further, low-DBP-value nano-carbon black is enriched at defect sites within the single-layer graphene sheets.
Furthermore, the DBP value of the high-DBP-value nano carbon black in the step (2) is 360-400, and the DBP value of the low-DBP-value nano carbon black is 200-280.
A preparation method of a long-acting anti-static composite nylon fabric comprises the following steps:
(1) adding 5 parts by mass of the aqueous dispersion of the modified graphene and 0.05-0.3 part by mass of the molecular weight regulator into 100 parts by mass of caprolactam melt, and uniformly stirring at a high speed (300-500 rpm) at 80 ℃ to form a dispersion. The modified graphene is single-layer graphene with carboxyl, hydroxyl and other oxygen-containing functional groups on the surface, and the carbon-oxygen ratio is 2.5-6; the mass concentration of the modified graphene aqueous dispersion is 1-6%;
(2) mixing the low-DBP-value nano carbon black and the high-DBP-value nano carbon black according to the proportion of 3-5: 1, adding the mixture into the mixed solution obtained in the step (1), and dispersing the mixture through an emulsification homogenizer at the temperature of 80 ℃, wherein the total weight of the mixed nano carbon black is 1.5-3.2 parts by mass;
(3) under the protection of nitrogen, heating the dispersion liquid obtained in the step (2) to 250-270 ℃ in a polycondensation reaction kettle, and reacting for 3 hours under the pressure of 0.1-0.5 MPa; then reacting for 4 hours under vacuum to obtain a polymer melt; finally, carrying out water-cooling granulation on the polymer melt to obtain an anti-static composite nylon slice;
(4) and (4) spinning the slices obtained in the step (3) at a high speed, and weaving to obtain the long-acting anti-static composite nylon fabric. The melt temperature is 250-320 ℃, the continuous spinning speed is 1000-4000 m/min, and the drawing multiple is 4-6 times.
Furthermore, the DBP value of the high-DBP-value nano carbon black in the step (2) is 360-400, and the DBP value of the low-DBP-value nano carbon black is 200-280.
The invention has the beneficial effects that:
(1) the composite structure of the nano carbon black and the graphene with different structure degrees is ingeniously designed. Firstly, because the carbon black is in a nano-scale size, the carbon black can be selectively enriched on the surface of the modified graphene in a caprolactam melt to form a composite structure. Secondly, the carbon black with the low DBP value has a low structure degree, namely a compact structure and a few porous structures, can repair the surface defects of the modified graphene, improves the intrinsic conductivity of the modified graphene, and the carbon black with the high DBP value has a more extended microstructure and developed gaps, can extend outwards when being attached to the surface of the modified graphene, and is beneficial to interface charge transfer and formation of a conductive network. According to the invention, the optimal formula is obtained by repeatedly adjusting the proportion of the modified graphene, the high-DBP carbon black and the low-DBP carbon black, and the antistatic effect of the composite fiber is finally realized (Table 1).
(2) The nano carbon black is uniformly attached to the surface of the single-layer modified graphene, and is uniformly dispersed in the caprolactam melt by virtue of rich oxygen-containing functional groups on the surface of the modified graphene. In the in-situ polymerization process, the caprolactam and the oxygen-containing functional groups generate covalent grafting reaction, so that stacking among graphene sheets is prevented, the graphene-carbon black composite structure can realize molecular level dispersion, and the covalent grafting enables charge transfer on a phase interface to be easier and is beneficial to reduction of conductivity. In addition, the uniform dispersion of the graphene is beneficial to the continuous preparation of the composite fiber, the high continuity and the high stability are still maintained even under the high-speed spinning, and the product quality is good.
(3) The graphene and the carbon black are uniformly dispersed in the nylon 6 matrix in a copolymerization mode, and form a conductive network, so that the conductivity can be kept not to be attenuated even after long-term use and washing, and the high-durability graphene/carbon black composite material has high durability.
(4) The addition of the graphene and the carbon black can also endow the nylon fiber with properties which are not possessed by the nylon fiber originally, such as far infrared emission, antibiosis, ultraviolet resistance and the like.
(5) The content of graphene in the fiber is only 0.04-0.24%, the total addition of the nano carbon black is only 1.2-3.2%, the addition of an adult is obviously lower than that of like products and reported values in the market, the cost is low, and the industrial production is easy to realize.
In conclusion, the composite fiber obtained by the method is simple to prepare, excellent in antistatic performance, good in durability and low in cost, has remarkable advantages compared with the traditional fiber, and has wide market prospect and application value.
Drawings
Fig. 1 is a partial structural schematic diagram of a composite fiber, wherein 1 is a single-layer graphene sheet grafted with nylon 6, and 2 is free nylon 6.
Fig. 2 is a schematic view of the microscopic composition of the composite fiber, in which 1 is a single-layer graphene sheet, 2 is a grafted nylon 6 molecule, 3 is a defect on the graphene surface, 4 is low-structure carbon black, and 5 is high-structure carbon black.
Fig. 3 is a scanning electron microscope photograph of a graphene-carbon black composite structure deposited on a porous substrate after composite fibers are dissolved.
Detailed Description
Firstly, mixing single-layer modified graphene and caprolactam melt to uniformly disperse the modified graphene in the caprolactam monomer. And then adding nano carbon black with different DBP values, and carrying out high-speed shearing dispersion together, wherein the carbon black is selectively adsorbed on the surface of the modified graphene to form a composite structure in the process, and the composite carbon structure can be dispersed in a single-layer form under the shearing action without agglomeration. And then, heating the system, carrying out ring opening and polycondensation reaction, carrying out covalent grafting on the oxygen-containing functional group on the surface of the modified graphene and the nylon 6 molecule, reducing the defects and the functional groups on the surface of the modified graphene to a certain degree under heating, and finally obtaining the nano composite structure shown in figure 1, wherein a scanning electron microscope image of the structure is shown in figure 3. The carbon black with low structure degree on the graphene sheet has the purposes of repairing defects and improving the conductivity, and the carbon black with high structure degree increases the interface effect of graphene and nylon and is beneficial to the construction of a conductive network (figure 2). The obtained composite slice can be used for obtaining a composite fiber product with long-acting antistatic property through high-speed continuous spinning.
In the following embodiments, modified graphene with a carbon-oxygen ratio of 2.5-6 is adopted, and the weight loss rate after a polymerization process at 250 ℃ is usually about 20%.
The present invention is described in detail by the following embodiments, which are only used for further illustration of the present invention and should not be construed as limiting the scope of the present invention, and the non-essential changes and modifications made by the person skilled in the art according to the above disclosure are within the scope of the present invention.
Example 1:
(1) adding 5 parts by mass of the aqueous dispersion of the modified graphene and 0.05 part by mass of the molecular weight regulator into 100 parts by mass of the caprolactam melt, and uniformly stirring at 300rpm at 80 ℃ to form a dispersion. The modified graphene is a single-layer graphene with carboxyl, hydroxyl and other oxygen-containing functional groups on the surface, the carbon-oxygen ratio is 2.5, and the mass concentration of the modified graphene aqueous dispersion is 1%;
(2) mixing 0.3 part of high-DBP-value nano carbon black and 1.2 parts of low-DBP-value nano carbon black, adding the mixture into the mixed solution obtained in the step (1), and performing high-speed shearing dispersion at 80 ℃ by using an emulsifying homogenizer; wherein the DBP value of the high DBP value nano carbon black is 360, and the DBP value of the low DBP value carbon black is 240;
(3) under the protection of nitrogen, heating the dispersion liquid obtained in the step (2) to 250 ℃ in a polycondensation reaction kettle, and reacting for 3 hours under 0.1 MPa; then reacting for 4 hours under vacuum to obtain a polymer melt; finally, carrying out water-cooling granulation on the polymer melt to obtain an anti-static composite nylon slice;
(4) and (4) spinning the slices obtained in the step (3) at a high speed, and weaving to obtain the long-acting anti-static composite nylon fabric. The melt temperature was 270 ℃, the continuous spinning speed was 4000 m/min, and the draft multiple was 6 times.
In the composite nylon fabric synthesized in this embodiment, the nano-carbon black includes high-DBP-value nano-carbon black and low-DBP-value nano-carbon black, the addition amount of the low-DBP-value nano-carbon black is 4 times that of the high-DBP-value nano-carbon black, and the mass ratio of the nano-carbon black to the graphene is 1.5: 0.04; the mass content of graphene in the fabric is 0.04%.
The test shows that the graphene modified nylon is woven by graphene modified nylon, the graphene modified nylon at least comprises single-layer graphene grafted with nylon 6 molecules, nano carbon black and free nylon 6, and the nano carbon black is attached to two surfaces of a single-layer graphene sheet; the number average molecular weight of the free nylon 6 was 15000.
Specific properties are shown in table 1.
Example 2:
(1) adding 5 parts by mass of the aqueous dispersion of the modified graphene and 0.05 part by mass of the molecular weight regulator into 100 parts by mass of the caprolactam melt, and uniformly stirring at 500rpm at 80 ℃ to form a dispersion. The modified graphene is a single-layer graphene with carboxyl, hydroxyl and other oxygen-containing functional groups on the surface, the carbon-oxygen ratio is 6, and the mass concentration of the modified graphene aqueous dispersion is 3%;
(2) mixing 0.3 part of high-DBP-value nano carbon black and 1.5 parts of low-DBP-value nano carbon black, adding the mixture into the mixed solution obtained in the step (1), and performing high-speed shearing dispersion at 80 ℃ by using an emulsification homogenizer; wherein the DBP value of the high DBP value nano carbon black is 400, and the DBP value of the low DBP value carbon black is 240;
(3) under the protection of nitrogen, heating the dispersion liquid obtained in the step (2) to 260 ℃ in a polycondensation reaction kettle, and reacting for 3 hours under 0.3 MPa; then reacting for 4 hours under vacuum to obtain a polymer melt; finally, carrying out water-cooling granulation on the polymer melt to obtain an anti-static composite nylon slice;
(4) and (4) spinning the slices obtained in the step (3) at a high speed, and weaving to obtain the long-acting anti-static composite nylon fabric. The melt temperature was 300 ℃, the continuous spinning speed was 3000 m/min, and the draft multiple was 4 times.
In the composite nylon fabric synthesized in this embodiment, the nano-carbon black includes high-DBP-value nano-carbon black and low-DBP-value nano-carbon black, the addition amount of the low-DBP-value nano-carbon black is 5 times that of the high-DBP-value nano-carbon black, and the mass ratio of the nano-carbon black to the graphene is 1.8: 0.15; the mass content of the graphene in the fabric is 0.12-0.24%.
The test shows that the graphene modified nylon is woven by graphene modified nylon, the graphene modified nylon at least comprises single-layer graphene grafted with nylon 6 molecules, nano carbon black and free nylon 6, and the nano carbon black is attached to two surfaces of a single-layer graphene sheet; the number average molecular weight of the free nylon 6 was 12000.
Specific properties are shown in table 1.
Example 3:
(1) adding 5 parts by mass of the aqueous dispersion of the modified graphene and 0.3 part by mass of the molecular weight regulator into 100 parts by mass of the caprolactam melt, and uniformly stirring at 500rpm at 80 ℃ to form a dispersion. The modified graphene is a single-layer graphene with carboxyl, hydroxyl and other oxygen-containing functional groups on the surface, the carbon-oxygen ratio is 4, and the mass concentration of the modified graphene aqueous dispersion is 6%;
(2) mixing 0.3 part of high-DBP-value nano carbon black and 1.2 parts of low-DBP-value nano carbon black, adding the mixture into the mixed solution obtained in the step (1), and performing high-speed shearing dispersion at 80 ℃ by using an emulsifying homogenizer; wherein the DBP value of the high DBP value nano carbon black is 380, and the DBP value of the low DBP value carbon black is 280;
(3) under the protection of nitrogen, heating the dispersion liquid obtained in the step (2) to 270 ℃ in a polycondensation reaction kettle, and reacting for 3 hours under 0.5 MPa; then reacting for 4 hours under vacuum to obtain a polymer melt; finally, carrying out water-cooling granulation on the polymer melt to obtain an anti-static composite nylon slice;
(4) and (4) spinning the slices obtained in the step (3) at a high speed, and weaving to obtain the long-acting anti-static composite nylon fabric. The melt temperature was 320 ℃, the continuous spinning speed was 1000 m/min, and the draw down factor was 4 times.
In the composite nylon fabric synthesized in this embodiment, the nano-carbon black includes high-DBP-value nano-carbon black and low-DBP-value nano-carbon black, the addition amount of the low-DBP-value nano-carbon black is 4 times that of the high-DBP-value nano-carbon black, and the mass ratio of the nano-carbon black to the graphene is 1.5: 0.24; the mass content of the graphene in the fabric is 0.24%;
the test shows that the graphene modified nylon is woven by graphene modified nylon, the graphene modified nylon at least comprises single-layer graphene grafted with nylon 6 molecules, nano carbon black and free nylon 6, and the nano carbon black is attached to two surfaces of a single-layer graphene sheet; the number average molecular weight of the free nylon 6 was 19000.
Specific properties are shown in table 1.
Example 4:
(1) adding 5 parts by mass of the aqueous dispersion of the modified graphene and 0.3 part by mass of the molecular weight regulator into 100 parts by mass of the caprolactam melt, and uniformly stirring at 500rpm at 80 ℃ to form a dispersion. The modified graphene is a single-layer graphene with carboxyl, hydroxyl and other oxygen-containing functional groups on the surface, the carbon-oxygen ratio is 4, and the mass concentration of the modified graphene aqueous dispersion is 2%;
(2) mixing 0.8 part of high-DBP-value nano carbon black and 2.4 parts of low-DBP-value nano carbon black, adding the mixture into the mixed solution obtained in the step (1), and performing high-speed shearing dispersion at 80 ℃ by using an emulsification homogenizer; wherein the DBP value of the high DBP value nano carbon black is 380, and the DBP value of the low DBP value carbon black is 200;
(3) under the protection of nitrogen, heating the dispersion liquid obtained in the step (2) to 270 ℃ in a polycondensation reaction kettle, and reacting for 3 hours under 0.5 MPa; then reacting for 4 hours under vacuum to obtain a polymer melt; finally, carrying out water-cooling granulation on the polymer melt to obtain an anti-static composite nylon slice;
(4) and (4) spinning the slices obtained in the step (3) at a high speed, and weaving to obtain the long-acting anti-static composite nylon fabric. The melt temperature was 250 ℃, the continuous spinning speed was 1000 m/min, and the draw down factor was 4 times.
In the composite nylon fabric synthesized in this embodiment, the nano-carbon black includes high-DBP-value nano-carbon black and low-DBP-value nano-carbon black, the addition amount of the low-DBP-value nano-carbon black is 3 times that of the high-DBP-value nano-carbon black, and the mass ratio of the nano-carbon black to the graphene is 3.2: 0.08; the mass content of the graphene in the fabric is 0.08% of nano carbon black;
the test shows that the graphene modified nylon is woven by graphene modified nylon, the graphene modified nylon at least comprises single-layer graphene grafted with nylon 6 molecules, nano carbon black and free nylon 6, and the nano carbon black is attached to two surfaces of a single-layer graphene sheet; the number average molecular weight of the free nylon 6 was 25000.
Specific properties are shown in table 1.
Example 5:
(1) adding 5 parts by mass of the aqueous dispersion of the modified graphene and 0.1 part by mass of the molecular weight regulator into 100 parts by mass of the caprolactam melt, and uniformly stirring at 500rpm at 80 ℃ to form a dispersion. The modified graphene is a single-layer graphene with carboxyl, hydroxyl and other oxygen-containing functional groups on the surface, the carbon-oxygen ratio is 4, and the mass concentration of the modified graphene aqueous dispersion is 0.1%;
(2) mixing 0.3 part of high-DBP-value nano carbon black and 1.2 parts of low-DBP-value nano carbon black, adding the mixture into the mixed solution obtained in the step (1), and performing high-speed shearing dispersion at 80 ℃ by using an emulsifying homogenizer; wherein the DBP value of the high DBP value nano carbon black is 380, and the DBP value of the low DBP value carbon black is 200;
(3) under the protection of nitrogen, heating the dispersion liquid obtained in the step (2) to 270 ℃ in a polycondensation reaction kettle, and reacting for 3 hours under 0.3 MPa; then reacting for 4 hours under vacuum to obtain a polymer melt; finally, carrying out water-cooling granulation on the polymer melt to obtain an anti-static composite nylon slice;
(4) and (4) spinning the slices obtained in the step (3) at a high speed, and weaving to obtain the long-acting anti-static composite nylon fabric. The melt temperature was 280 ℃, the continuous spinning speed was 3000 m/min, and the draw down factor was 6 times.
In the composite nylon fabric synthesized in this embodiment, the nano-carbon black includes high-DBP-value nano-carbon black and low-DBP-value nano-carbon black, the addition amount of the low-DBP-value nano-carbon black is 4 times that of the high-DBP-value nano-carbon black, and the mass ratio of the nano-carbon black to the graphene is 1.5: 0.004; the mass content of graphene in the fabric is 0.004%;
the test shows that the graphene modified nylon is woven by graphene modified nylon, the graphene modified nylon at least comprises single-layer graphene grafted with nylon 6 molecules, nano carbon black and free nylon 6, and the nano carbon black is attached to two surfaces of a single-layer graphene sheet; the number average molecular weight of the free nylon 6 was 25000.
Specific properties are shown in table 1.
Example 6:
(1) adding 5 parts by mass of the aqueous dispersion of the modified graphene and 0.1 part by mass of the molecular weight regulator into 100 parts by mass of the caprolactam melt, and uniformly stirring at 500rpm at 80 ℃ to form a dispersion. The modified graphene is a single-layer graphene with carboxyl, hydroxyl and other oxygen-containing functional groups on the surface, the carbon-oxygen ratio is 4, and the mass concentration of the modified graphene aqueous dispersion is 10%;
(2) mixing 0.3 part of high-DBP-value nano carbon black and 1.2 parts of low-DBP-value nano carbon black, adding the mixture into the mixed solution obtained in the step (1), and performing high-speed shearing dispersion at 80 ℃ by using an emulsifying homogenizer; wherein the DBP value of the high DBP value nano carbon black is 380, and the DBP value of the low DBP value carbon black is 200;
(3) under the protection of nitrogen, heating the dispersion liquid obtained in the step (2) to 270 ℃ in a polycondensation reaction kettle, and reacting for 3 hours under 0.3 MPa; then reacting for 4 hours under vacuum to obtain a polymer melt; finally, carrying out water-cooling granulation on the polymer melt to obtain an anti-static composite nylon slice;
(4) and (4) spinning the slices obtained in the step (3) at a high speed, and weaving to obtain the long-acting anti-static composite nylon fabric. The melt temperature was 280 ℃, the continuous spinning speed was 3000 m/min, and the draw down factor was 6 times.
In the composite nylon fabric synthesized in this embodiment, the nano-carbon black includes high-DBP-value nano-carbon black and low-DBP-value nano-carbon black, the addition amount of the low-DBP-value nano-carbon black is 4 times that of the high-DBP-value nano-carbon black, and the mass ratio of the nano-carbon black to the graphene is 1.5: 0.4; the mass content of graphene in the fabric is 0.4%;
the test shows that the graphene modified nylon is woven by graphene modified nylon, the graphene modified nylon at least comprises single-layer graphene grafted with nylon 6 molecules, nano carbon black and free nylon 6, and the nano carbon black is attached to two surfaces of a single-layer graphene sheet; the number average molecular weight of the free nylon 6 was 40000.
Specific properties are shown in table 1.
Example 7:
(1) adding 5 parts by mass of the aqueous dispersion of the modified graphene and 0.1 part by mass of the molecular weight regulator into 100 parts by mass of the caprolactam melt, and uniformly stirring at 500rpm at 80 ℃ to form a dispersion. The modified graphene is a single-layer graphene with carboxyl, hydroxyl and other oxygen-containing functional groups on the surface, the carbon-oxygen ratio is 4, and the mass concentration of the modified graphene aqueous dispersion is 6%;
(2) adding 1.5 parts of high-DBP-value nano carbon black into the mixed solution obtained in the step (1), and performing high-speed shearing dispersion at 80 ℃ by using an emulsification homogenizer; wherein the DBP value of the high DBP value nano carbon black is 380;
(3) under the protection of nitrogen, heating the dispersion liquid obtained in the step (2) to 270 ℃ in a polycondensation reaction kettle, and reacting for 3 hours under 0.3 MPa; then reacting for 4 hours under vacuum to obtain a polymer melt; finally, carrying out water-cooling granulation on the polymer melt to obtain an anti-static composite nylon slice;
(4) and (4) spinning the slices obtained in the step (3) at a high speed, and weaving to obtain the long-acting anti-static composite nylon fabric. The melt temperature was 280 ℃, the continuous spinning speed was 3000 m/min, and the draw down factor was 6 times.
In the composite nylon fabric synthesized in this embodiment, the nano carbon black is high-DBP-value nano carbon black, and the mass ratio of the nano carbon black to the graphene is 1.5: 0.24; the mass content of the graphene in the fabric is 0.24%;
the test shows that the graphene modified nylon is woven by graphene modified nylon, the graphene modified nylon at least comprises single-layer graphene grafted with nylon 6 molecules, nano carbon black and free nylon 6, and the nano carbon black is attached to two surfaces of a single-layer graphene sheet; the number average molecular weight of the free nylon 6 was 27000.
Specific properties are shown in table 1.
Example 8:
(1) adding 5 parts by mass of the aqueous dispersion of the modified graphene and 0.1 part by mass of the molecular weight regulator into 100 parts by mass of the caprolactam melt, and uniformly stirring at 500rpm at 80 ℃ to form a dispersion. The modified graphene is a single-layer graphene with carboxyl, hydroxyl and other oxygen-containing functional groups on the surface, the carbon-oxygen ratio is 4, and the mass concentration of the modified graphene aqueous dispersion is 6%;
(2) mixing 1.5 parts of low-DBP-value nano carbon black, adding the mixture into the mixed solution obtained in the step (1), and performing high-speed shearing dispersion at 80 ℃ by using an emulsifying homogenizer; wherein the low DBP number carbon black has a DBP number of 200;
(3) under the protection of nitrogen, heating the dispersion liquid obtained in the step (2) to 270 ℃ in a polycondensation reaction kettle, and reacting for 3 hours under 0.3 MPa; then reacting for 4 hours under vacuum to obtain a polymer melt; finally, carrying out water-cooling granulation on the polymer melt to obtain an anti-static composite nylon slice;
(4) and (4) spinning the slices obtained in the step (3) at a high speed, and weaving to obtain the long-acting anti-static composite nylon fabric. The melt temperature was 280 ℃, the continuous spinning speed was 3000 m/min, and the draw down factor was 6 times.
In the composite nylon fabric synthesized in this embodiment, the nano carbon black is low-DBP-value nano carbon black, and the mass ratio of the nano carbon black to the graphene is 1.5: 0.24; the mass content of the graphene in the fabric is 0.24%;
the test shows that the graphene modified nylon is woven by graphene modified nylon, the graphene modified nylon at least comprises single-layer graphene grafted with nylon 6 molecules, nano carbon black and free nylon 6, and the nano carbon black is attached to two surfaces of a single-layer graphene sheet; the number average molecular weight of the free nylon 6 was 22000.
Specific properties are shown in table 1.
Example 9:
(1) adding 5 parts by mass of the aqueous dispersion of the modified graphene and 0.1 part by mass of the molecular weight regulator into 100 parts by mass of the caprolactam melt, and uniformly stirring at 500rpm at 80 ℃ to form a dispersion. The modified graphene is a single-layer graphene with carboxyl, hydroxyl and other oxygen-containing functional groups on the surface, the carbon-oxygen ratio is 4, and the mass concentration of the modified graphene aqueous dispersion is 6%;
(2) mixing 0.3 part of high-DBP-value nano carbon black and 1.2 parts of low-DBP-value nano carbon black, adding the mixture into the mixed solution obtained in the step (1), and performing high-speed shearing dispersion at 80 ℃ by using an emulsifying homogenizer; wherein the DBP value of the high DBP value nano carbon black is 500, and the DBP value of the low DBP value carbon black is 100;
(3) under the protection of nitrogen, heating the dispersion liquid obtained in the step (2) to 270 ℃ in a polycondensation reaction kettle, and reacting for 3 hours under 0.3 MPa; then reacting for 4 hours under vacuum to obtain a polymer melt; finally, carrying out water-cooling granulation on the polymer melt to obtain an anti-static composite nylon slice;
(4) and (4) spinning the slices obtained in the step (3) at a high speed, and weaving to obtain the long-acting anti-static composite nylon fabric. The melt temperature was 280 ℃, the continuous spinning speed was 3000 m/min, and the draw down factor was 6 times.
In the composite nylon fabric synthesized in the embodiment, the mass ratio of the nano carbon black to the graphene is 1.5: 0.24; the mass content of the graphene in the fabric is 0.24%;
the test shows that the graphene modified nylon is woven by graphene modified nylon, the graphene modified nylon at least comprises single-layer graphene grafted with nylon 6 molecules, nano carbon black and free nylon 6, and the nano carbon black is attached to two surfaces of a single-layer graphene sheet; the number average molecular weight of the free nylon 6 was 22000.
Specific properties are shown in table 1.
TABLE 1 relevant parameters and composite fiber Properties of the examples
It can be seen from the comparison of examples 1 to 4 that, under the condition of controlling the addition of the nano carbon black to be constant, the conductivity of the composite fiber can be remarkably improved by increasing the content of the graphene, because the modified graphene has the promotion effect on the dispersibility of the nano carbon black and forms a better phase interface. On the contrary, when the amount of the added graphene is too low (example 5), the dispersibility of the nano carbon black is poor, and the nano carbon black is dissociated in the nylon 6 matrix and combined with each other, an agglomerated structure is formed, so that a conductive network cannot be effectively formed, the spinnability is affected, and the conductivity is seriously reduced. And the addition amount of the graphene is too high (example 6), the mass ratio of the graphene to the carbon black is too high, the carbon black cannot be effectively distributed on the graphene sheet, the repairing effect on the defects of the graphene is poor, so that the conductivity of the graphene is low, the graphene is easy to agglomerate, a stacking phenomenon is formed, a spinneret plate is blocked during spinning, and continuous spinning cannot be performed.
From examples 7 and 8, it can be seen that the effective conductance of the composite fiber cannot be achieved by using either high-DBP nano-carbon black or low-DBP nano-carbon black alone, because of the lack of a mechanism of synergy, the conductivity can be significantly increased with the addition of low-carbon black only by achieving both the effects of "defect repair" and "network formation", otherwise a similar effect can still be achieved by adding a large amount of carbon black. Example 9 selects the nano carbon black with higher DBP value and lower DBP value for compounding, and the effect is still inferior to the result obtained by the claims of the present invention, which is caused by that the nano carbon black with lower DBP value has poor conductive network forming capability and poor modified graphene defect repairing effect, and the nano carbon black with too high DBP value has poor dispersion effect and is easy to agglomerate.
Claims (3)
1. The long-acting anti-static composite nylon fabric is characterized by being woven by graphene modified nylon fibers, wherein the graphene modified nylon fibers at least comprise single-layer graphene grafted with nylon 6 molecules, nano carbon black and free nylon 6, and the nano carbon black is attached to two surfaces of a single-layer graphene sheet; the nano carbon black comprises high-DBP value nano carbon black and low-DBP value nano carbon black, the adding mass of the low-DBP value nano carbon black is 3-5 times that of the high-DBP value nano carbon black, and the mass ratio of the nano carbon black to graphene is 1.5-3.2: 0.04 to 0.24; the mass content of the graphene in the fabric is 0.04% -0.24%; the number average molecular weight of the free nylon 6 is 12000-40000; the DBP value of the high-DBP-value nano carbon black is 360-400, and the DBP value of the low-DBP-value nano carbon black is 200-280.
2. The composite chinlon fabric of claim 1, wherein low-DBP-value nano-carbon black is enriched at defect sites within the single-layer graphene sheet.
3. A preparation method of a long-acting anti-static composite nylon fabric is characterized by comprising the following steps:
(1) adding 5 parts by mass of modified graphene aqueous dispersion and 0.05-0.3 part by mass of molecular weight regulator into 100 parts by mass of caprolactam melt, and stirring and uniformly mixing at a high speed of 300-500 rpm at 80 ℃ to form dispersion; the modified graphene is single-layer graphene with carboxyl and hydroxyl oxygen-containing functional groups on the surface, and the carbon-oxygen ratio is 2.5-6; the mass concentration of the modified graphene aqueous dispersion is 1-6%;
(2) mixing the low-DBP-value nano carbon black and the high-DBP-value nano carbon black according to the mass ratio of 3-5: 1, adding the mixture into the mixed liquid obtained in the step (1), and dispersing the mixture through an emulsification homogenizer at 80 ℃, wherein the total weight of the mixed nano carbon black is 1.5-3.2 parts by mass; the DBP value of the high-DBP-value nano carbon black is 360-400, and the DBP value of the low-DBP-value nano carbon black is 200-280;
(3) under the protection of nitrogen, heating the dispersion liquid obtained in the step (2) to 250-270 ℃ in a polycondensation reaction kettle, and reacting for 3 hours under the pressure of 0.1-0.5 MPa; then reacting for 4 hours under vacuum to obtain a polymer melt; finally, carrying out water-cooling granulation on the polymer melt to obtain an anti-static composite nylon slice;
(4) spinning the slices obtained in the step (3) at a high speed, and weaving to obtain the long-acting anti-static composite nylon fabric; the melt temperature is 250-320 ℃, the continuous spinning speed is 1000-4000 m/min, and the drawing multiple is 4-6 times.
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