Bamboo charcoal surface modification method, device and nylon carrier bamboo charcoal masterbatch preparation method

Abstract

The invention relates to the technical field of artificial fibers, and provides a bamboo charcoal surface modification method, device and nylon carrier bamboo charcoal masterbatch preparation method, comprising the following steps: putting bamboo charcoal powder into a closed reaction chamber and evacuating the chamber; introducing oxidizing gas into the reaction chamber; discharging in the reaction chamber to generate an electric field, ionizing the oxidizing gas into a plasma state, and generating excited oxygen atoms; the carbon atom in the bamboo charcoal powder reacts with an excited oxygen atom, and simultaneously captures a hydrogen atom from the surface of the bamboo charcoal to generate a hydroxyl compound; the hydroxyl compound reacts again with an excited oxygen atom to generate a carboxyl group on the surface of the bamboo charcoal, and obtains carboxyl-modified bamboo charcoal powder. In this way, the invention obtains carboxyl-modified bamboo charcoal powder by ionizing the oxidizing gas to generate excited oxygen atoms. By grafting hyperbranched nylon on the surface of the modified bamboo charcoal, the compatibility of the bamboo charcoal particles and the nylon matrix is ​​increased; and the agglomeration of the bamboo charcoal particles is reduced.

Description

Technical Field

[0001] The invention belongs to the technical field of artificial fibers, and in particular relates to a bamboo charcoal surface modification method and device and a nylon carrier bamboo charcoal masterbatch preparation method. Background Art

[0002] Bamboo charcoal fiber is a functional fiber that combines bamboo charcoal with textile fiber. After the bamboo charcoal is carbonized at high temperature, it is crushed into micron-sized bamboo charcoal particles, and then mixed with raw materials such as nylon and spun to make it.

[0003] When bamboo charcoal is used in spinning, it is usually first made into a high-concentration masterbatch with nylon, and then mixed with nylon for spinning. The bamboo charcoal content can be precisely controlled, making the ratio of spinning materials more flexible, reducing dust in the spinning workshop, and reducing production environmental pollution.

[0004] As an inorganic filler, bamboo charcoal has poor compatibility with nylon. When manufacturing high-concentration masterbatch with nylon as the carrier, it is difficult to evenly disperse it into the nylon matrix, which affects the spinning stability, fiber strength and appearance of the fiber.

[0005] In summary, the prior art obviously has inconveniences and defects in practical use, so it is necessary to improve it. Summary of the invention

[0006] In view of the above defects, the present invention mainly provides a bamboo charcoal surface modification method to solve the technical problem of poor compatibility between bamboo charcoal and nylon.

[0007] In order to solve the above problems, the present invention provides a bamboo charcoal surface modification method, comprising the following steps:

[0008] S1, placing dry bamboo charcoal powder into a sealed reaction chamber; and exhausting the air and moisture in the reaction chamber;

[0009] S2, introducing an oxidizing gas into the reaction chamber; the pressure of the oxidizing gas is 50-500 kPa;

[0010] S3, discharge in the reaction chamber to generate an electric field; the discharge power is 100-1000 W, and the discharge time is 10-100 min; the following reactions occur in sequence in the reaction chamber:

[0011] The oxidizing gas is ionized into a plasma state, producing excited oxygen atoms;

[0012] The carbon atom in the bamboo charcoal powder reacts with an excited oxygen atom and simultaneously captures a hydrogen atom from the surface of the bamboo charcoal to generate a hydroxyl compound;

[0013] The hydroxy compound reacts again with an excited oxygen atom to generate a carboxyl group on the surface of the bamboo charcoal to obtain carboxyl-modified bamboo charcoal powder.

[0014] According to the bamboo charcoal surface modification method of the present invention, the air and moisture in the reaction chamber of step S1 are evacuated by first introducing nitrogen into the reaction chamber to replace the air and moisture in the chamber, and then evacuating the nitrogen; this method is repeated 2-4 times.

[0015] According to the bamboo charcoal surface modification method of the present invention, the pressure of the oxidizing gas in step S2 is 200 kPa-400 kPa; the discharge power in step S3 is 400 W-800 W, and the discharge time is 40-80 min.

[0016] According to the bamboo charcoal surface modification method of the present invention, the oxidizing gas is oxygen, carbon dioxide or a mixed gas of the two.

[0017] According to the bamboo charcoal surface modification method of the present invention, the bamboo charcoal powder in step S1 is dried at 100° C. to 110° C. for 12 to 24 hours before being placed in the reaction chamber to remove adsorbed moisture.

[0018] A modification device for performing the bamboo charcoal surface modification method, comprising:

[0019] A reactor having a reaction chamber for containing bamboo charcoal powder;

[0020] A gas storage cylinder, connected to the reactor, used to store the oxidizing gas and input the oxidizing gas into the reaction chamber;

[0021] A power source electrically connected to two electrode rods extending into the reaction chamber; the two electrode rods generate an electric field in the reaction chamber;

[0022] The vacuum pump is connected to the reactor and is used to evacuate the reaction chamber to exhaust the air and moisture in the reaction chamber.

[0023] According to the modification device of the present invention, the gas storage bottle and the vacuum pump are both connected to the reactor via a control valve.

[0024] A method for preparing nylon carrier bamboo charcoal masterbatch comprises the following steps:

[0025] Z1, mixing the carboxyl-modified bamboo charcoal powder and hyperbranched nylon prepared by the bamboo charcoal surface modification method or modification device, and placing the mixture into a microwave reactor; the hyperbranched nylon having terminal amine groups;

[0026] Z2, microwave heating, carboxyl modified bamboo charcoal powder and hyperbranched nylon undergo grafting reaction to generate hyperbranched nylon grafted bamboo charcoal;

[0027] The power of microwave heating is: 1000 W~5000 W, and the reaction time is: 30 min~300 min;

[0028] Z3, putting the hyperbranched nylon grafted bamboo charcoal, antioxidant 1010 and nylon material into a high-speed mixer at a predetermined weight ratio, and mixing for 15 min;

[0029] By weight, the hyperbranched nylon grafted bamboo charcoal is 50%, the antioxidant 1010 is 1%, and the rest is nylon material;

[0030] Z4, putting the mixed material into a twin-screw extruder for melting, mixing and granulation to obtain nylon carrier bamboo charcoal masterbatch;

[0031] The extrusion temperature of the twin-screw extruder is: 200℃~300℃, and the screw speed is: 100 rpm.

[0032] According to the preparation method of nylon carrier bamboo charcoal masterbatch of the present invention, the power of microwave heating in step Z2 is: 2000W~4000W, and the reaction time is: 100 min~200 min.

[0033] According to the preparation method of nylon carrier bamboo charcoal masterbatch of the present invention, the nylon material is one or more of nylon 6, nylon 66, nylon 11, nylon 12, nylon 1010, nylon 610 and nylon 56.

[0034] In summary, the bamboo charcoal surface modification method of the present invention ionizes the oxidizing gas to generate excited oxygen atoms (O ∗ ); after that, the excited oxygen atom (O ∗ ) reacts with the carbon atom (C) in the bamboo charcoal and simultaneously captures a hydrogen atom (H) from the surface of the bamboo charcoal to generate a hydroxyl compound (C-OH). Afterwards, the hydroxyl compound (C-OH) reacts with an excited oxygen atom (O ∗ ) reaction, a carboxyl group (-COOH) is generated on the surface of bamboo charcoal, and carboxyl-modified bamboo charcoal powder is obtained. The present invention also provides a modification device and a method for preparing nylon carrier bamboo charcoal masterbatch. By grafting hyperbranched nylon on the surface of bamboo charcoal, the compatibility of bamboo charcoal particles and nylon matrix is ​​increased; the steric repulsion effect of the grafted chain segment is utilized to reduce the agglomeration of bamboo charcoal particles. The dispersibility of bamboo charcoal particles is improved, so that they can be evenly dispersed in the nylon matrix. The stability of subsequent spinning using masterbatch is improved, the fiber strength is increased, and the appearance quality is improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 It is a structural schematic diagram of the modification device of the present invention;

[0036] Figure 2 It is a schematic diagram of the grafting reaction of the method for preparing nylon carrier bamboo charcoal masterbatch of the present invention;

[0037] In the figure: 1-reactor, 11-control valve; 2-bamboo charcoal powder, 3-gas storage bottle, 4-power supply, 41-electrode rod; 5-vacuum pump. DETAILED DESCRIPTION

[0038] See also Figure 1 The present invention provides a bamboo charcoal surface modification method, comprising the following steps:

[0039] S1, placing dry bamboo charcoal powder into a sealed reaction chamber; then evacuating the reaction chamber to discharge air and moisture in the reaction chamber;

[0040] Optionally, the bamboo charcoal powder in step S1 is dried at 100° C. to 110° C. for 12 to 24 h before being placed in the reaction chamber to remove adsorbed moisture;

[0041] As a preferred solution, in step S1, after bamboo charcoal powder is placed in the reaction chamber, nitrogen is first introduced to replace the air and moisture in the chamber, and then vacuum is drawn to extract the nitrogen in the reaction chamber. The air and moisture in the reaction chamber can be fully discharged to avoid affecting the subsequent reaction.

[0042] Further, nitrogen is introduced to replace the air in the cavity, and then vacuum is drawn; the operation is repeated multiple times, such as 2-4 times, so that the air and moisture in the cavity are completely discharged.

[0043] S2, introducing oxidizing gas into the reaction chamber; the pressure of the oxidizing gas is 50-500 kPa; preferably, the pressure of the present invention is 200 kPa-400 kPa,

[0044] S3, discharge in the reaction chamber generates an electric field, ionizing the oxidizing gas into a plasma state and generating excited oxygen atoms; the discharge power is 100 to 1000 W, and the discharge time is 10 to 100 min;

[0045] As a preferred embodiment, the discharge power of step S3 of the present invention is 400 W to 800 W, and the discharge time is 40 to 80 min. The concentration of excited oxygen atoms generated is appropriate to ensure the subsequent reaction.

[0046] The carbon atom (C) in the bamboo charcoal powder and an excited oxygen atom (O ∗ ) reaction, and at the same time, it captures a hydrogen atom (H) from the surface of bamboo charcoal to generate a hydroxyl compound (C-OH);

[0047] The hydroxyl compound (C-OH) reacts again with an excited oxygen atom to generate a carboxyl group (-COOH) on the surface of the bamboo charcoal to obtain carboxyl-modified bamboo charcoal powder.

[0048] As an embodiment, the oxidizing gas of the present invention is oxygen (O2), carbon dioxide (CO2) or a mixture of the two;

[0049] The oxygen (O2) molecules of the present invention are ionized to generate excited oxygen atoms (O ∗ ) is:

[0050] An oxygen molecule receives a positive charge in an electric field, generating positively charged oxygen ions (O2 + ):O2+e + →O2 + ;

[0051] A positively charged oxygen ion (O2 + ), decomposed into an oxygen ion (O + ) and an excited oxygen atom (O ∗ ):O2 + →O + +O ∗ ;

[0052] Or an oxygen (O2) molecule can be directly decomposed into two excited oxygen atoms (O ∗ ):O2→2O ∗ ;

[0053] The carbon dioxide (CO2) of the present invention is ionized to generate excited oxygen atoms (O ∗ ) is:

[0054] A carbon dioxide molecule (CO2) receives a positive charge in an electric field, generating a positively charged carbon dioxide ion (CO2 + ):CO2+e + →CO2 + ;

[0055] A positively charged carbon dioxide ion (CO2 + ), decomposed into carbon monoxide ions (CO + ) and an excited oxygen atom (O∗): CO2 + →CO + +O ∗ ;

[0056] As an embodiment, the particle size of the modified bamboo charcoal powder of the present invention does not exceed 5 μm;

[0057] The bamboo charcoal surface modification method of the present invention comprises the following steps: ionizing the oxidizing gas to generate excited oxygen atoms (O ∗ ); after that, the excited oxygen atom (O ∗ ) reacts with the carbon atom (C) in the bamboo charcoal and simultaneously captures a hydrogen atom (H) from the surface of the bamboo charcoal to generate a hydroxyl compound (C-OH). Afterwards, the hydroxyl compound (C-OH) reacts with an excited oxygen atom (O∗ ) reaction to generate a carboxyl group (-COOH) on the surface of bamboo charcoal to obtain carboxyl-modified bamboo charcoal powder.

[0058] See also Figure 1 The present invention also provides a modification device for performing the bamboo charcoal surface modification method, comprising:

[0059] The reactor 1 has a reaction chamber for containing the bamboo charcoal powder 2;

[0060] A power source 4, electrically connected to two electrode rods 41 extending into the reaction chamber; the two electrode rods 41 generate an electric field in the reaction chamber;

[0061] A gas storage cylinder 3, connected to the reactor 1, for storing the oxidizing gas; and for inputting the oxidizing gas into the reaction chamber;

[0062] Optionally, the present invention has two gas storage cylinders 3, storing oxygen and carbon dioxide respectively. A single oxidizing gas can be input into the reaction chamber alone, or a mixed oxidizing gas of oxygen and carbon dioxide can be input into the reaction chamber in proportion.

[0063] A vacuum pump 5 connected to the reactor 1 and used to evacuate the reaction chamber;

[0064] As an embodiment, the gas storage bottle 3 and the vacuum pump 5 are both connected to the reactor 1 via a control valve 11, so as to facilitate the control of the amount of oxidizing gas introduced and the vacuum degree of the reaction chamber.

[0065] Optionally, a nitrogen bottle is also included to store nitrogen; during the operation of evacuating the air and moisture in the reaction chamber, nitrogen can be filled into the chamber to replace the air and moisture.

[0066] The present invention also provides a method for preparing nylon carrier bamboo charcoal masterbatch, comprising the following steps:

[0067] Z1, mixing the carboxyl-modified bamboo charcoal powder and hyperbranched nylon, and placing the mixture into a microwave reactor; the hyperbranched nylon having terminal amine groups;

[0068] Z2, see Figure 2 , microwave heating, carboxyl modified bamboo charcoal powder and hyperbranched nylon undergo grafting reaction to generate hyperbranched nylon grafted bamboo charcoal;

[0069] The power of microwave heating is: 1000 W~5000 W, and the reaction time is: 30 min~300 min;

[0070] As a preferred embodiment, the microwave heating power of Z2 of the present invention is: 2000 W ~ 4000 W, and the reaction time is: 100 min ~ 200 min;

[0071] The carboxyl group of the bamboo charcoal powder undergoes an amidation reaction with the terminal amine group of the hyperbranched nylon, so that the hyperbranched nylon is grafted onto the surface of the bamboo charcoal.

[0072] Better yet, nitrogen is continuously introduced during the reaction process, and the generated water molecules are carried out by the nitrogen, thereby promoting the amidation reaction to proceed in the positive direction.

[0073] Microwaves have a promoting effect on the amidation reaction occurring on the surface of bamboo charcoal. Bamboo charcoal particles can form microwave "hot spots" on the surface under the radiation of microwaves. These "hot spots" can increase the reaction temperature in local areas, promote the movement and diffusion of hyperbranched nylon molecules, and thus accelerate the combination of carboxyl groups and terminal amine groups. The microwaves of the present invention not only produce thermal effects, but also induce non-thermal effects, such as producing polarization effects to change the interaction force between molecules, making the reaction faster and more efficient.

[0074] Z3, putting the hyperbranched nylon grafted bamboo charcoal, antioxidant 1010 and nylon material into a high-speed mixer at a predetermined weight ratio, and mixing for 15 min;

[0075] By weight, the hyperbranched nylon grafted bamboo charcoal is 50%, the antioxidant 1010 is 1%, and the rest is nylon material;

[0076] Z4, putting the mixed material into a twin-screw extruder for melting, mixing and granulation to obtain nylon carrier bamboo charcoal masterbatch;

[0077] The extrusion temperature of the twin-screw extruder is: 200℃~300℃, and the screw speed is: 100 rpm;

[0078] As an embodiment, the nylon material is one or more of nylon 6, nylon 66, nylon 11, nylon 12, nylon 1010, nylon 610 and nylon 56.

[0079] The method for preparing nylon carrier bamboo charcoal masterbatch of the present invention increases the compatibility of bamboo charcoal particles and nylon matrix by grafting hyperbranched nylon on the surface of bamboo charcoal; at the same time, the steric repulsion effect of the grafted chain segment is utilized to reduce the agglomeration of bamboo charcoal particles. The dispersibility of bamboo charcoal particles is improved so that the particles can be evenly dispersed in the nylon matrix. The stability of subsequent spinning using the masterbatch is improved, the fiber strength is increased, and the appearance quality is improved.

[0080] Compared with linear polymers, hyperbranched nylon has a highly branched structure, which reduces its viscosity and has excellent lubrication. When manufacturing nylon carrier bamboo charcoal masterbatch, it can promote melt plasticization, improve fluidity, and facilitate the processing and molding of the masterbatch.

[0081] The inventors used the aforementioned bamboo charcoal surface modification method to prepare a plurality of modified bamboo charcoal powder samples. The prepared samples used the aforementioned nylon carrier bamboo charcoal masterbatch preparation method to prepare a plurality of masterbatch example samples;

[0082] At the same time, unmodified bamboo charcoal powder was used to prepare comparative samples using the above-mentioned nylon carrier bamboo charcoal masterbatch preparation method. Each embodiment and comparative sample was observed by scanning electron microscope (SEM), and the particle size of bamboo charcoal in the nylon carrier was detected to verify the compatibility of bamboo charcoal in the masterbatch with nylon material.

[0083] Specific experimental parameters and test results are shown in Table 1. (Note: Table 1 only lists the changed parameters. The same components and steps can be found in the previous text and will not be repeated here.) From the test results, the particle size of the bamboo charcoal in the nylon carrier prepared by using the modified bamboo charcoal powder is significantly reduced. This shows that the bamboo charcoal particles in the masterbatch are compatible with nylon and are evenly dispersed.

[0084]

[0085] In summary, the present invention provides a method for modifying the surface of bamboo charcoal, wherein the oxidizing gas is ionized to generate excited oxygen atoms (O ∗ ); after that, the excited oxygen atom (O ∗ ) reacts with the carbon atom (C) in the bamboo charcoal and simultaneously captures a hydrogen atom (H) from the surface of the bamboo charcoal to generate a hydroxyl compound (C-OH). Afterwards, the hydroxyl compound (C-OH) reacts with an excited oxygen atom (O ∗ ) reaction, a carboxyl group (-COOH) is generated on the surface of bamboo charcoal, and carboxyl-modified bamboo charcoal powder is obtained. The invention provides a modification device and a method for preparing a nylon carrier bamboo charcoal masterbatch. By grafting hyperbranched nylon on the surface of bamboo charcoal, the compatibility of bamboo charcoal particles and nylon matrix is ​​increased; the steric repulsion effect of the grafted chain segment is utilized to reduce the agglomeration of bamboo charcoal particles. The dispersibility of bamboo charcoal particles is improved, so that they can be evenly dispersed in the nylon matrix. The stability of subsequent spinning using masterbatch is improved, the fiber strength is increased, and the appearance quality is improved.

[0086] Of course, the present invention may have many other embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art may make various corresponding changes and modifications based on the present invention, but these corresponding changes and modifications should all fall within the scope of protection of the claims attached to the present invention.

Claims

1. A method for preparing nylon carrier bamboo charcoal masterbatch, characterized in that: Including bamboo charcoal surface modification method; The bamboo charcoal surface modification method comprises the following steps: S1, placing dry bamboo charcoal powder into a sealed reaction chamber; and exhausting the air and moisture in the reaction chamber; S2, introducing an oxidizing gas into the reaction chamber; the pressure of the oxidizing gas is 50-500 kPa; S3, discharge in the reaction chamber to generate an electric field; the discharge power is 100-1000 W, and the discharge time is 10-100 min; the following reactions occur in sequence in the reaction chamber: The oxidizing gas is ionized into a plasma state, producing excited oxygen atoms; The carbon atom in the bamboo charcoal powder reacts with an excited oxygen atom and simultaneously captures a hydrogen atom from the surface of the bamboo charcoal to generate a hydroxyl compound; The hydroxy compound reacts again with an excited oxygen atom to generate a carboxyl group on the surface of the bamboo charcoal to obtain carboxyl-modified bamboo charcoal powder; The method for preparing nylon carrier bamboo charcoal masterbatch also includes the following steps: Z1, mixing carboxyl-modified bamboo charcoal powder prepared by the bamboo charcoal surface modification method and hyperbranched nylon, and placing the mixture into a microwave reactor; the hyperbranched nylon having terminal amine groups; Z2, microwave heating, carboxyl-modified bamboo charcoal powder and hyperbranched nylon undergo grafting reaction to generate hyperbranched nylon-grafted bamboo charcoal; The power of microwave heating is: 1000 W~5000 W, and the reaction time is: 30 min~300 min; Z3, putting the hyperbranched nylon grafted bamboo charcoal, antioxidant 1010 and nylon material into a high-speed mixer at a predetermined weight ratio, and mixing for 15 min; By weight, the hyperbranched nylon grafted bamboo charcoal is 50%, the antioxidant 1010 is 1%, and the rest is nylon material; Z4, putting the mixed material into a twin-screw extruder for melting, mixing and granulation to obtain nylon carrier bamboo charcoal masterbatch; The extrusion temperature of the twin-screw extruder is: 200℃~300℃, and the screw speed is: 100 rpm.

2. The method for preparing nylon carrier bamboo charcoal masterbatch according to claim 1, characterized in that: The method for exhausting the air and moisture in the reaction chamber in step S1 is: firstly, nitrogen is introduced into the reaction chamber to replace the air and moisture in the chamber, and then vacuum is drawn to exhaust the nitrogen; this method is repeated 2-4 times.

3. The method for preparing nylon carrier bamboo charcoal masterbatch according to claim 1, characterized in that: The pressure of the oxidizing gas in step S2 is 200 kPa to 400 kPa; the discharge power in step S3 is 400 W to 800 W, and the discharge time is 40 to 80 min.

4. The method for preparing nylon carrier bamboo charcoal masterbatch according to claim 1, characterized in that: The oxidizing gas is oxygen, carbon dioxide or a mixture of the two.

5. The method for preparing nylon carrier bamboo charcoal masterbatch according to claim 1, characterized in that: Before being placed in the reaction chamber, the bamboo charcoal powder in step S1 is dried at 100° C. to 110° C. for 12 to 24 hours to remove adsorbed moisture.

6. The method for preparing nylon carrier bamboo charcoal masterbatch according to any one of claims 1 to 5, characterized in that: Also included is a modification device for executing the bamboo charcoal surface modification method; The modification device comprises: A reactor having a reaction chamber for containing bamboo charcoal powder; A gas storage cylinder connected to the reactor and used for storing the oxidizing gas and inputting the oxidizing gas into the reaction chamber; A power source electrically connected to two electrode rods extending into the reaction chamber; the two electrode rods generate an electric field in the reaction chamber; The vacuum pump is connected to the reactor and is used to evacuate the reaction chamber to exhaust the air and moisture in the reaction chamber.

7. The method for preparing nylon carrier bamboo charcoal masterbatch according to claim 6, characterized in that: The gas storage bottle and the vacuum pump are both connected to the reactor via a control valve.

8. The method for preparing nylon carrier bamboo charcoal masterbatch according to claim 1, characterized in that: The power of the microwave heating in step Z2 is 2000 W to 4000 W, and the reaction time is 100 min to 200 min.

9. The method for preparing nylon carrier bamboo charcoal masterbatch according to claim 1, characterized in that: The nylon material is one or more of nylon 6, nylon 66, nylon 11, nylon 12, nylon 1010, nylon 610 and nylon 56.

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