CN109943051B - Polycarbonate material with electromagnetic shielding effect and preparation method thereof - Google Patents
Polycarbonate material with electromagnetic shielding effect and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of polycarbonate material preparation, and particularly discloses a polycarbonate material with an electromagnetic shielding effect and a preparation method thereof. The preparation method of the polycarbonate with the electromagnetic shielding effect comprises the following steps: (1) adding carbon nanotubes and nylon 6T into an organic solvent, performing ultrasonic treatment, after uniform dispersion, placing the mixture into a container for casting to form a film, and performing vacuum drying at the temperature of 55-65 ℃ for 1-2 hours to obtain a PA6T/MWNT composite film; (2) placing the PA6T/MWNT composite membrane in electroplating solution containing nickel salt for electroplating to obtain a PA6T/MWNT/Ni composite membrane; (3) and (3) melting and blending the PA6T/MWNT/Ni composite film and polycarbonate at 230-250 ℃, and extruding by using an extruding device to obtain the polycarbonate material with the electromagnetic shielding effect. Experiments show that the polycarbonate material prepared by the invention has excellent mechanical property, conductivity and electromagnetic shielding effectiveness.
Description
Technical Field
The invention relates to the technical field of preparation of polycarbonate materials, in particular to a polycarbonate material with an electromagnetic shielding effect and a preparation method thereof.
Background
Polycarbonate (PC for short) is a high molecular polymer containing carbonate groups in its molecular chain, and is widely used in the industrial fields of electronics, electric appliances, communication equipment, and the like. When polycarbonate plastic is used in the fields of electronics, electrical and communication equipment, electromagnetic waves can act on electronic components due to the interference of the electronic components to the outside, and an interfered phenomenon is generated. In order to reduce the electromagnetic interference phenomenon, the corresponding devices usually employ a component made of conductive material to shield the magnetic field of the electric field. Therefore, the polycarbonate with the electromagnetic shielding effect is developed, and particularly the polycarbonate with the high-performance electromagnetic shielding effect has wide application prospect.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a polycarbonate material with an electromagnetic shielding effect, wherein the polycarbonate material prepared by the method has an excellent electromagnetic shielding effect.
The technical problem to be solved by the invention is realized by the following technical scheme:
a preparation method of a polycarbonate material with electromagnetic shielding effect comprises the following steps:
(1) adding carbon nanotubes and nylon 6T into an organic solvent, performing ultrasonic treatment, after uniform dispersion, placing the mixture into a container for casting to form a film, and performing vacuum drying at the temperature of 55-65 ℃ for 1-2 hours to obtain a PA6T/MWNT composite film;
(2) placing the PA6T/MWNT composite membrane in electroplating solution containing nickel salt for electroplating to obtain a PA6T/MWNT/Ni composite membrane;
(3) and (3) melting and blending the PA6T/MWNT/Ni composite film and polycarbonate at 230-250 ℃, and extruding by using an extruding device to obtain the polycarbonate material with the electromagnetic shielding effect.
Preferably, the ratio of the carbon nanotubes to the nylon 6T in the step (1) is 1: 3 to 5.
Preferably, the carbon nanotubes in step (1) are multi-walled carbon nanotubes; the organic solvent is chloroform.
Preferably, the plating solution containing a nickel salt described in step (2) contains the following components: 100-120 g/L of nickel sulfate; 30-40 g/L of sodium sulfate; 30-40 g/L of sodium citrate; 10-20 g/L of sodium acetate; 10-20 g/L of sodium hypophosphite.
Most preferably, the plating solution containing a nickel salt described in step (2) contains the following components: 110g/L of nickel sulfate; 35g/L of sodium sulfate; 34g/L of sodium citrate; 15g/L of sodium acetate; 15g/L of sodium hypophosphite.
More preferably, the electroplating solution containing the nickel salt contains 20-30 g/L of an auxiliary agent, and the auxiliary agent is prepared by the following method:
dissolving dodecyl dimethyl tertiary amine and 1, 3-dichloro-2-propanol in an organic solvent according to the molar ratio of 2:1, then adding a catalyst, reacting at 110-140 ℃ for 12-24 h, concentrating and drying to obtain the auxiliary agent.
Still more preferably, the organic solvent in the preparation of the adjuvant is methanol, and the catalyst is potassium iodide; the dosage ratio of the total weight of the dodecyl dimethyl tertiary amine and the 1, 3-dichloro-2-propanol to the organic solvent is 1 g: 2-5 mL; the weight ratio of the total weight of the dodecyl dimethyl tertiary amine and the 1, 3-dichloro-2-propanol to the catalyst is 100: 1-2.
Preferably, the plating conditions in step (2) are: controlling the current density to be 3-4 ASD and the electroplating time to be 20-40 min.
Most preferably, the plating conditions in step (2) are: the current density was controlled to 3.5ASD and the plating time was 30 min.
Preferably, the dosage ratio of the PA6T/MWNT/Ni composite membrane to the polycarbonate in the step (3) is 1-5: 100.
Preferably, the extruding device in the step (3) is a twin-screw extruder.
The invention also provides the polycarbonate material with the electromagnetic shielding effect prepared by the preparation method.
Has the advantages that: (1) the preparation method comprises the steps of wrapping multi-walled carbon nanotubes (MWNT) with nylon 6T (PA6T), preparing a PA6T/MWNT composite film in a solution blending mode, plating a layer of nickel material on the PA6T/MWNT composite film in an electroplating mode to prepare a PA6T/MWNT/Ni composite film, and melting and blending the PA6T/MWNT/Ni composite film and Polycarbonate (PC) to prepare a polycarbonate material with an electromagnetic shielding effect; from the above, the invention provides a brand new preparation method of polycarbonate material; the prepared polycarbonate material also has brand-new raw material composition. (2) Because the processing temperature of the nylon 6T used in the invention is higher than that of PC, PA6T is used as a reinforcing phase for loading metal Ni, PC is used as a continuous phase, and the film is firstly formed and then the electroplating is carried out, so that the dispersibility of the filler in the polymer is improved, the high dispersibility of the filler in the polymer is realized, the phenomenon of conductivity attenuation caused by nonuniform dispersion is greatly reduced, and the high conductivity of the surface of the final bar is realized. (3) MWNT and metal Ni are used as common conductive fillers, a binary compound filler is formed by using PA6T as a bridge through solution blending and electroplating processes, a conductive network system is built together, and high conductive performance of the low-filler in the polymer is realized to form a high electromagnetic shielding network system. (4) In addition, in the electroplating process, an auxiliary agent synthesized by a brand-new method is added into the electroplating solution, so that the electromagnetic shielding effect of the prepared polycarbonate material is further improved.
Detailed Description
The present invention is further explained below with reference to specific examples, which are not intended to limit the present invention in any way.
EXAMPLE 1 preparation of polycarbonate Material
(1) Adding multi-wall carbon nanotubes and nylon 6T (PA6T sold by Mitsui corporation of Japan as RA230 NK) into chloroform, performing ultrasonic treatment, uniformly dispersing, placing into a container, casting into a film, and performing vacuum drying at 60 ℃ for 1h to obtain a PA6T/MWNT composite film;
the dosage ratio of the multi-walled carbon nanotube to the nylon 6T to the chloroform in the step is 1 g: 4 g: 30 mL;
(2) placing the PA6T/MWNT composite membrane in electroplating solution containing nickel salt for electroplating to obtain a PA6T/MWNT/Ni composite membrane;
the plating solution containing a nickel salt described in this step contains the following components: 110g/L of nickel sulfate; 35g/L of sodium sulfate; 34g/L of sodium citrate; 15g/L of sodium acetate; 15g/L of sodium hypophosphite; the electroplating conditions are as follows: controlling the current density to be 3.5ASD and the electroplating time to be 30 min;
(3) melting and blending PA6T/MWNT/Ni composite film and polycarbonate (polycarbonate with 1302HP-09 of Korean LG company), and extruding by a double-screw extruder to obtain the polycarbonate material with electromagnetic shielding effect;
in the step, the dosage ratio of the PA6T/MWNT/Ni composite membrane to the polycarbonate is 3: 100.
EXAMPLE 2 preparation of polycarbonate Material
(1) Adding multi-wall carbon nanotubes and nylon 6T (PA6T sold by Mitsui corporation of Japan as RA230 NK) into chloroform, performing ultrasonic treatment, uniformly dispersing, placing into a container, casting into a film, and vacuum drying at 55 ℃ for 1.5h to obtain a PA6T/MWNT composite film;
the dosage ratio of the multi-walled carbon nanotube to the nylon 6T to the chloroform in the step is 1 g: 3 g: 40 mL; (ii) a
(2) Placing the PA6T/MWNT composite membrane in electroplating solution containing nickel salt for electroplating to obtain a PA6T/MWNT/Ni composite membrane;
the plating solution containing a nickel salt described in this step contains the following components: 100g/L of nickel sulfate; 40g/L of sodium sulfate; 40g/L of sodium citrate; 10g/L of sodium acetate; 10g/L of sodium hypophosphite; the electroplating conditions are as follows: controlling the current density to be 4ASD and the electroplating time to be 40 min;
(3) melting and blending PA6T/MWNT/Ni composite film and polycarbonate (polycarbonate with 1302HP-09 of Korean LG company), and extruding by a double-screw extruder to obtain the polycarbonate material with electromagnetic shielding effect;
in the step, the dosage ratio of the PA6T/MWNT/Ni composite membrane to the polycarbonate is 2: 100.
EXAMPLE 3 preparation of polycarbonate Material
(1) Adding multi-wall carbon nanotubes and nylon 6T (PA6T sold by Mitsui corporation of Japan as RA230 NK) into chloroform, performing ultrasonic treatment, uniformly dispersing, placing into a container, casting into a film, and performing vacuum drying at 65 ℃ for 1h to obtain a PA6T/MWNT composite film;
the dosage ratio of the multi-walled carbon nanotube to the nylon 6T to the chloroform in the step is 1 g: 5 g: 40 mL;
(2) placing the PA6T/MWNT composite membrane in electroplating solution containing nickel salt for electroplating to obtain a PA6T/MWNT/Ni composite membrane;
the plating solution containing a nickel salt described in this step contains the following components: 120g/L of nickel sulfate; 30g/L of sodium sulfate; 30g/L of sodium citrate; 20g/L of sodium acetate; 20g/L of sodium hypophosphite; the electroplating conditions are as follows: controlling the current density to be 3ASD and the electroplating time to be 40 min;
(3) melting and blending PA6T/MWNT/Ni composite film and polycarbonate (polycarbonate with 1302HP-09 of Korean LG company), and extruding by a double-screw extruder to obtain the polycarbonate material with electromagnetic shielding effect;
in the step, the dosage ratio of the PA6T/MWNT/Ni composite membrane to the polycarbonate is 4: 100.
EXAMPLE 4 preparation of polycarbonate Material
(1) Adding multi-wall carbon nanotubes and nylon 6T (PA6T sold by Mitsui corporation of Japan as RA230 NK) into chloroform, performing ultrasonic treatment, uniformly dispersing, placing into a container, casting into a film, and performing vacuum drying at 60 ℃ for 1h to obtain a PA6T/MWNT composite film;
the dosage ratio of the multi-walled carbon nanotube to the nylon 6T to the chloroform in the step is 1: 4: 25 mL;
(2) placing the PA6T/MWNT composite membrane in electroplating solution containing nickel salt for electroplating to obtain a PA6T/MWNT/Ni composite membrane;
the plating solution containing a nickel salt described in this step contains the following components: 110g/L of nickel sulfate; 35g/L of sodium sulfate; 34g/L of sodium citrate; 15g/L of sodium acetate; 15g/L of sodium hypophosphite; 15g/L of auxiliary agent; the electroplating conditions are as follows: controlling the current density to be 3.5ASD and the electroplating time to be 30 min;
the auxiliary agent is prepared by the following method: dissolving dodecyl dimethyl tertiary amine and 1, 3-dichloro-2-propanol in methanol according to the molar ratio of 2:1, adding a catalyst potassium iodide, reacting at 130 ℃ for 16 hours, concentrating and drying to obtain the auxiliary agent; the dosage ratio of the total weight of the dodecyl dimethyl tertiary amine and the 1, 3-dichloro-2-propanol to the methanol is 1 g: 4 mL; the weight ratio of the total weight of the dodecyl dimethyl tertiary amine and the 1, 3-dichloro-2-propanol to the catalyst potassium iodide is 100: 1.5;
(3) melting and blending PA6T/MWNT/Ni composite film and polycarbonate (polycarbonate with 1302HP-09 of Korean LG company), and extruding by a double-screw extruder to obtain the polycarbonate material with electromagnetic shielding effect;
in the step, the dosage ratio of the PA6T/MWNT/Ni composite membrane to the polycarbonate is 3: 100.
Example 4 is different from example 1 in that no auxiliary agent was added to the plating solution in example 1, and an auxiliary agent was added to the plating solution in example 4.
Experimental example 1
The polycarbonate materials prepared in examples 1 to 4 were subjected to the following criteria to prepare test specimens and to perform the relevant performance tests.
The tensile strength (23 ℃) is tested with reference to the standard ASTM D638; testing flexural modulus with reference to ASTM D790; notched Izod impact strength (23 ℃ C.) according to ASTM D256; testing the surface resistance of the sample by using a surface resistance tester; electromagnetic shielding was tested according to ASTM D4935; the specific test results are shown in table 1.
TABLE 1 Property test results for polycarbonate materials
As can be seen from the performance test data in Table 1, the polycarbonate materials prepared in examples 1 to 4 have excellent mechanical properties, conductivity and electromagnetic shielding effectiveness. In particular, the polycarbonate material prepared in the embodiment 4 has electromagnetic shielding effectiveness far higher than that of the polycarbonate materials prepared in the embodiments 1 to 3, and can be applied to the application field with high electromagnetic shielding requirements; the fact also shows that the electromagnetic shielding effectiveness of the prepared polycarbonate material can be further greatly improved by adding the auxiliary agent prepared by the invention into the electroplating solution in the electroplating step.
Claims (9)
1. A preparation method of a polycarbonate material with electromagnetic shielding effect is characterized by comprising the following steps:
(1) adding carbon nanotubes and nylon 6T into an organic solvent, performing ultrasonic treatment, after uniform dispersion, placing the mixture into a container for casting to form a film, and performing vacuum drying at the temperature of 55-65 ℃ for 1-2 hours to obtain a PA6T/MWNT composite film;
(2) placing the PA6T/MWNT composite membrane in electroplating solution containing nickel salt for electroplating to obtain a PA6T/MWNT/Ni composite membrane;
(3) melting and blending the PA6T/MWNT/Ni composite film and polycarbonate at 230-250 ℃, and extruding by an extruding device to obtain the polycarbonate material with the electromagnetic shielding effect;
the electroplating solution containing nickel salt in the step (2) comprises the following components: 100-120 g/L of nickel sulfate; 30-40 g/L of sodium sulfate; 30-40 g/L of sodium citrate; 10-20 g/L of sodium acetate; 10-20 g/L of sodium hypophosphite;
the electroplating solution containing the nickel salt further comprises 20-30 g/L of an auxiliary agent, and the auxiliary agent is prepared by the following method:
dissolving dodecyl dimethyl tertiary amine and 1, 3-dichloro-2-propanol in an organic solvent according to the molar ratio of 2:1, then adding a catalyst, reacting at 110-140 ℃ for 12-24 h, concentrating and drying to obtain the auxiliary agent.
2. The method for preparing polycarbonate material with electromagnetic shielding effect as claimed in claim 1, wherein the ratio of the carbon nanotubes to nylon 6T in step (1) is 1: 3 to 5.
3. The method for preparing a polycarbonate material with electromagnetic shielding effect as claimed in claim 1, wherein the organic solvent in step (1) is chloroform.
4. The method for preparing polycarbonate material with electromagnetic shielding effect as claimed in claim 1, wherein the electroplating solution containing nickel salt in step (2) comprises the following components: 110g/L of nickel sulfate; 35g/L of sodium sulfate; 34g/L of sodium citrate; 15g/L of sodium acetate; 15g/L of sodium hypophosphite.
5. The method for preparing polycarbonate material with electromagnetic shielding effect as claimed in claim 1, wherein the electroplating conditions in step (2) are as follows: controlling the current density to be 3-4 ASD and the electroplating time to be 20-40 min.
6. The method for preparing polycarbonate material with electromagnetic shielding effect as claimed in claim 5, wherein the electroplating conditions in step (2) are as follows: the current density was controlled to 3.5ASD and the plating time was 30 min.
7. The method for preparing a polycarbonate material with electromagnetic shielding effect according to claim 1, wherein the dosage ratio of the PA6T/MWNT/Ni composite film to the polycarbonate in the step (3) is 1-5: 100.
8. The method for preparing polycarbonate material with electromagnetic shielding effect as claimed in claim 1, wherein the extruding device in step (3) is a twin-screw extruder.
9. The polycarbonate material with electromagnetic shielding effect prepared by the preparation method of any one of claims 1 to 8.
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