CN113416402B - Polycarbonate composite resin and film and preparation method thereof - Google Patents
Polycarbonate composite resin and film and preparation method thereof Download PDFInfo
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Abstract
The invention provides a polycarbonate composite resin and a film and a preparation method thereof, which comprises the steps of dissolving aluminum nitrate and nickel nitrate in water, carrying out hydrothermal reaction to obtain a precursor, and carrying out heat treatment to obtain an aluminum-nickel oxide composite material; then mixing the aluminum-nickel oxide composite material with graphene, and carrying out modification treatment on (trimethoxysilyl) methyl propionate to obtain a modified composite material; then adding the modified composite material into the aqueous acrylic resin emulsion to prepare gel; then 2- (4-fluorophenyl) thiophene and gel are used as raw materials to carry out polymerization reaction to obtain a polymerization product; and finally, mixing, melting and extruding the polycarbonate and the polymerization product to obtain the composite resin. The polycarbonate film prepared by the composite resin has simple processing technology, good wear resistance and antistatic property, and can meet the use requirements of various electronic products.
Description
Technical Field
The invention relates to the technical field of film processing, in particular to a polycarbonate composite resin, a polycarbonate composite film and a preparation method thereof.
Background
Polycarbonate (PC) is one of five widely used engineering plastics, is colorless and transparent, has light transmittance of more than 90 percent, is known to have excellent impact strength and creep resistance, and is very suitable to be used as an optical material. Because of the excellent performance of PC, the product and its blending material are widely used in the industries of electronics, electrical appliances, machinery, automobiles, textile, light industry, construction and the like.
However, the surface of the polycarbonate resin is not wear-resistant, so that the development and application of the polycarbonate resin are limited. At present, the wear resistance and mechanical property of polycarbonate are improved by adding inorganic or organic fillers, but the effect is not particularly obvious. Moreover, when the filler content is more than 15%, a significant decrease in light transmittance of the polycarbonate tends to result.
In addition, polycarbonate is widely applied to electric and electronic parts and mobile phone screens, and the requirements of the products on antistatic property are high, so that in daily life and production, dust collection and electric shock can be caused by electrostatic accumulation, and even explosion and other serious accidents can be caused after sparks are generated. However, polycarbonate itself has good electrical insulation properties, and in order to make it antistatic, it is most common to add a filler such as conductive graphite or metal particles to reduce surface resistance and charge concentration. However, the problem of uneven dispersion often exists in the addition of the filler, the compatibility in a system is poor, and the mechanical property of a product is influenced finally.
Patent application CN106166880A discloses an antistatic polycarbonate film, which comprises, from bottom to top, a first conductive layer, a polycarbonate base layer, a second conductive layer, and a wear-resistant layer, wherein the first conductive layer and the second conductive layer are polycarbonate layers attached with carbon nanotubes respectively; the wear-resistant layer is a polycarbonate layer attached with a friction-resistant agent. The patent application adopts the method of coating processing to realize the improvement of wearability and antistatic properties, and the construction is complicated, and moreover, the coating drops and also leads to disappearance of correlation properties after long-term use, uses and experiences not good enough.
Disclosure of Invention
The invention aims to provide a polycarbonate composite resin, a polycarbonate composite film and a preparation method thereof, which have good wear resistance and antistatic property.
In order to achieve the purpose, the invention is realized by the following scheme:
1. a preparation method of polycarbonate composite resin comprises the following specific steps:
(1) Firstly, dissolving aluminum nitrate and nickel nitrate in water, carrying out hydrothermal reaction to obtain a precursor, and then carrying out heat treatment to obtain an aluminum-nickel oxide composite material;
(2) Then mixing the aluminum-nickel oxide composite material with graphene, and carrying out modification treatment on (trimethoxysilyl) methyl propionate to obtain a modified composite material; then adding the modified composite material into the aqueous acrylic resin emulsion to prepare gel;
(3) Then 2- (4-fluorophenyl) thiophene and gel are used as raw materials to carry out polymerization reaction to obtain a polymerization product;
(4) And finally, mixing, melting and extruding the polycarbonate and the polymerization product to obtain the polycarbonate composite resin.
Preferably, in the step (1), the molar ratio of the aluminum nitrate to the nickel nitrate is 1:1, the amount of water is 7 to 9 times of the weight of the aluminum nitrate.
Preferably, in the step (1), the hydrothermal reaction process conditions are as follows: hydrothermal reaction at 110-120 deg.c for 4-6 hr.
Preferably, in the step (1), the heat treatment process conditions are as follows: heat treatment is carried out for 5 to 7 hours at 480 to 520 ℃.
Preferably, in the step (2), the mass ratio of the aluminum-nickel oxide composite material to the graphene to the methyl (trimethoxysilyl) propionate is 1: 0.01-0.02: 5 to 7.
Preferably, in the step (2), the specific method of modification treatment is: firstly, uniformly mixing an aluminum-nickel oxide composite material with graphene, then adding the mixture into a toluene solution of (trimethoxysilyl) methyl propionate, stirring and reacting for 6-8 hours at the temperature of 80-90 ℃, filtering, washing and drying to obtain the modified composite material; wherein the toluene solution of (trimethoxysilyl) methyl propionate is obtained by adding (trimethoxysilyl) methyl propionate into toluene which is 5-7 times of the weight of (trimethoxysilyl) methyl propionate and uniformly oscillating by ultrasonic waves.
Preferably, in step (2), the gel is prepared as follows: adding the modified composite material into aqueous acrylic resin emulsion with the weight of 4-5 times of that of the modified composite material, stirring at 55-65 ℃ until sol is formed, naturally cooling to 25 ℃, and standing for 8-10 hours to obtain the gel.
Preferably, the specific method of step (3) is as follows, in parts by weight: adding 1 part of gel into 8-10 parts of 0.1-0.2 mol/L hydrochloric acid solution, and dispersing the gel uniformly by ultrasonic oscillation to form hydrochloric acid suspension; then slowly adding 2-3 parts of 2- (4-fluorophenyl) thiophene into the hydrochloric acid suspension at a constant speed, carrying out ultrasonic oscillation, and placing in an ice water bath; slowly dropwise adding a hydrochloric acid solution of ammonium persulfate while stirring, stirring and reacting for 15-20 hours at the temperature of 0-5 ℃, performing suction filtration, alternately washing with absolute ethyl alcohol and deionized water, and drying to obtain the polymerization product; wherein the hydrochloric acid solution of ammonium persulfate is obtained by dissolving 0.001-0.002 part of ammonium persulfate in 0.006-0.008 part of 0.1-0.2 mol/L hydrochloric acid solution.
More preferably, the feeding time of the 2- (4-fluorophenyl) thiophene is 20 to 30 minutes.
Further preferably, the process conditions of the ultrasonic oscillation are as follows: ultrasonic oscillation at 400-500W for 10-15 min.
Preferably, in the step (4), the mass ratio of the polycarbonate to the polymerization product is 100:0.3 to 0.5.
Preferably, in the step (4), the melt extrusion is realized by a twin-screw extruder, the screw speed of the extruder is 300-400 r/min, and the temperature from the feed inlet to the head is 260 ℃, 257 ℃, 248 ℃, 270 ℃, 265 ℃ and 262 ℃.
2. The polycarbonate composite resin obtained by the preparation method.
3. A polycarbonate film prepared by using the polycarbonate composite resin.
4. The preparation method of the polycarbonate film comprises the steps of heating the polycarbonate composite resin to be molten, flowing out of the polycarbonate composite resin to the roll surface of a calender roll, and rolling to obtain the polycarbonate film with the thickness of 0.1-0.2 mm.
The invention has the beneficial effects that:
dissolving aluminum nitrate and nickel nitrate in water, carrying out hydrothermal reaction to obtain a precursor, and carrying out heat treatment to obtain an aluminum-nickel oxide composite material; then mixing the aluminum-nickel oxide composite material with graphene, and carrying out modification treatment on (trimethoxysilyl) methyl propionate to obtain a modified composite material; then adding the modified composite material into the aqueous acrylic resin emulsion to prepare gel; then 2- (4-fluorophenyl) thiophene and gel are used as raw materials to carry out polymerization reaction to obtain a polymerization product; and finally, mixing, melting and extruding the polycarbonate and the polymerization product to obtain the polycarbonate composite resin. The polycarbonate film prepared by the composite resin has simple processing technology, good wear resistance and antistatic property, and can meet the use requirements of various electronic products.
The aluminum-nickel oxide composite material and the graphene have certain conductivity, and the prepared modified composite material has conductivity.
The mixture of the aluminum-nickel oxide composite material and the graphene is modified by (trimethoxysilyl) methyl propionate, and then an ester group is introduced. The ester exchange reaction occurs in the process of mixing, melting and extruding the polycarbonate and the polymerization product, so that the compatibility between the polycarbonate and the polymerization product is improved, and the mechanical property of the product is ensured.
On the other hand, the aluminum-nickel oxide composite material and the graphene both have certain wear resistance, and are introduced into a polycarbonate system through the modification treatment, so that the compatibility is good, and the wear resistance of the product is synergistically improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a polycarbonate film comprises the following specific steps:
(1) Firstly, dissolving aluminum nitrate and nickel nitrate in water, carrying out hydrothermal reaction to obtain a precursor, and then carrying out heat treatment to obtain an aluminum-nickel oxide composite material;
(2) Then mixing the aluminum-nickel oxide composite material with graphene, and carrying out modification treatment on (trimethoxysilyl) methyl propionate to obtain a modified composite material; then adding the modified composite material into the aqueous acrylic resin emulsion to prepare gel;
(3) Then 2- (4-fluorophenyl) thiophene and gel are used as raw materials to carry out polymerization reaction to obtain a polymerization product;
(4) Then mixing, melting and extruding the polycarbonate and the polymerization product to obtain the polycarbonate composite resin.
(5) And finally, heating the polycarbonate composite resin to be molten, flowing out to the roll surface of a calender roll, and calendering to prepare a polycarbonate film with the thickness of 0.1 mm.
In the step (1), the molar ratio of the aluminum nitrate to the nickel nitrate is 1:1, the amount of water is 9 times of the weight of the aluminum nitrate.
In the step (1), the process conditions of the hydrothermal reaction are as follows: and carrying out hydrothermal reaction at 110 ℃ for 6 hours.
In the step (1), the heat treatment process conditions are as follows: heat treatment at 480 ℃ for 7 hours.
In the step (2), the mass ratio of the aluminum-nickel oxide composite material to the graphene to the methyl (trimethoxysilyl) propionate is 1:0.01:7.
in the step (2), the specific method of the modification treatment is as follows: uniformly mixing an aluminum-nickel oxide composite material with graphene, adding the mixture into a toluene solution of (trimethoxysilyl) methyl propionate, stirring and reacting for 8 hours at 80 ℃, filtering, washing and drying to obtain the modified composite material; wherein the toluene solution of (trimethoxysilyl) methyl propionate is prepared by adding (trimethoxysilyl) methyl propionate into toluene 5 times of the weight of (trimethoxysilyl) methyl propionate, and uniformly oscillating with ultrasonic wave.
In the step (2), the preparation method of the gel is as follows: adding the modified composite material into 5 times of the aqueous acrylic resin emulsion, stirring at 55 ℃ until sol is formed, naturally cooling to 25 ℃, and standing for 10 hours to obtain the gel.
The specific method of the step (3) is as follows: firstly, adding 1kg of gel into 8kg of 0.2mol/L hydrochloric acid solution, and uniformly dispersing the gel by ultrasonic oscillation to form hydrochloric acid suspension; then, adding 2kg of 2- (4-fluorophenyl) thiophene into the hydrochloric acid suspension slowly at a constant speed, carrying out ultrasonic oscillation, and placing in an ice-water bath; slowly dropwise adding a hydrochloric acid solution of ammonium persulfate while stirring, stirring at 5 ℃ for reaction for 15 hours, performing suction filtration, alternately washing with absolute ethyl alcohol and deionized water, and drying to obtain the polymerization product; wherein the hydrochloric acid solution of ammonium persulfate is obtained by dissolving 0.002kg of ammonium persulfate in 0.006kg of 0.2mol/L hydrochloric acid solution.
The 2- (4-fluorophenyl) thiophene feed time was 20 minutes.
The process conditions of ultrasonic oscillation are as follows: 500W ultrasonic oscillation is carried out for 10 minutes.
In the step (4), the mass ratio of the polycarbonate to the polymerization product is 100:0.5.
in the step (4), a double-screw extruder is adopted to realize melt extrusion, the screw rotating speed of the extruder is 300 revolutions per minute, and the temperature from a feed inlet to a machine head is 260 ℃, 257 ℃, 248 ℃, 270 ℃, 265 ℃ and 262 ℃ in sequence.
Example 2
A preparation method of a polycarbonate film comprises the following specific steps:
(1) Firstly, dissolving aluminum nitrate and nickel nitrate in water, carrying out hydrothermal reaction to obtain a precursor, and then carrying out heat treatment to obtain an aluminum-nickel oxide composite material;
(2) Then mixing the aluminum-nickel oxide composite material with graphene, and carrying out modification treatment on (trimethoxysilyl) methyl propionate to obtain a modified composite material; then adding the modified composite material into the aqueous acrylic resin emulsion to prepare gel;
(3) Then 2- (4-fluorophenyl) thiophene and gel are used as raw materials to carry out polymerization reaction to obtain a polymerization product;
(4) Then mixing, melting and extruding the polycarbonate and the polymerization product to obtain the polycarbonate composite resin.
(5) And finally, heating the polycarbonate composite resin to be molten, flowing out to the roll surface of a calender roll, and calendering to prepare a polycarbonate film with the thickness of 0.2 mm.
In the step (1), the molar ratio of the aluminum nitrate to the nickel nitrate is 1:1, the amount of water is 7 times of the weight of the aluminum nitrate.
In the step (1), the process conditions of the hydrothermal reaction are as follows: and carrying out hydrothermal reaction at 120 ℃ for 4 hours.
In the step (1), the heat treatment process conditions are as follows: heat treatment at 520 ℃ for 5 hours.
In the step (2), the mass ratio of the aluminum-nickel oxide composite material to the graphene to the methyl (trimethoxysilyl) propionate is 1:0.02:5.
in the step (2), the specific method of modification treatment is as follows: uniformly mixing an aluminum-nickel oxide composite material with graphene, adding the mixture into a toluene solution of (trimethoxysilyl) methyl propionate, stirring and reacting for 6 hours at 90 ℃, filtering, washing and drying to obtain the modified composite material; wherein the toluene solution of (trimethoxysilyl) methyl propionate is prepared by adding (trimethoxysilyl) methyl propionate into toluene 7 times the weight of the (trimethoxysilyl) methyl propionate, and uniformly oscillating with ultrasonic wave.
In the step (2), the preparation method of the gel is as follows: adding the modified composite material into 4 times of the weight of the aqueous acrylic resin emulsion, stirring at 65 ℃ until sol is formed, naturally cooling to 25 ℃, and standing for 8 hours to obtain the gel.
The specific method of the step (3) is as follows: adding 1kg of gel into 10kg of 0.1mol/L hydrochloric acid solution, and uniformly dispersing the gel by ultrasonic oscillation to form hydrochloric acid suspension; then, slowly adding 3kg of 2- (4-fluorophenyl) thiophene into the hydrochloric acid suspension at a constant speed, oscillating by ultrasonic waves, and placing in an ice water bath; slowly dropwise adding a hydrochloric acid solution of ammonium persulfate while stirring, stirring at 0 ℃ for reaction for 20 hours, performing suction filtration, alternately washing with absolute ethyl alcohol and deionized water, and drying to obtain the polymerization product; wherein the hydrochloric acid solution of ammonium persulfate is obtained by dissolving 0.001kg of ammonium persulfate in 0.008kg of 0.1mol/L hydrochloric acid solution.
The charging time of 2- (4-fluorophenyl) thiophene was 30 minutes.
The process conditions of ultrasonic oscillation are as follows: the 400W ultrasonic wave was oscillated for 15 minutes.
In the step (4), the mass ratio of the polycarbonate to the polymerization product is 100:0.3.
in the step (4), a double-screw extruder is adopted to realize melt extrusion, the screw rotating speed of the extruder is 400 r/min, and the temperatures from a feed inlet to a machine head are 260 ℃, 257 ℃, 248 ℃, 270 ℃, 265 ℃ and 262 ℃ in sequence.
Example 3
A preparation method of a polycarbonate film comprises the following specific steps:
(1) Firstly, dissolving aluminum nitrate and nickel nitrate in water, carrying out hydrothermal reaction to obtain a precursor, and then carrying out heat treatment to obtain an aluminum-nickel oxide composite material;
(2) Then mixing the aluminum-nickel oxide composite material with graphene, and carrying out modification treatment on (trimethoxysilyl) methyl propionate to obtain a modified composite material; adding the modified composite material into the aqueous acrylic resin emulsion to prepare gel;
(3) Then 2- (4-fluorophenyl) thiophene and gel are used as raw materials to carry out polymerization reaction to obtain a polymerization product;
(4) Then mixing, melting and extruding the polycarbonate and the polymerization product to obtain the polycarbonate composite resin.
(5) And finally, heating the polycarbonate composite resin to be molten, flowing out to the roll surface of a calender roll, and calendering to prepare a polycarbonate film with the thickness of 0.15 mm.
In the step (1), the molar ratio of the aluminum nitrate to the nickel nitrate is 1:1, the amount of water is 8 times of the weight of the aluminum nitrate.
In the step (1), the process conditions of the hydrothermal reaction are as follows: hydrothermal reaction at 115 deg.c for 5 hr.
In the step (1), the heat treatment process conditions are as follows: heat treatment at 500 ℃ for 6 hours.
In the step (2), the mass ratio of the aluminum-nickel oxide composite material to the graphene to the methyl (trimethoxysilyl) propionate is 1:0.015:6.
in the step (2), the specific method of modification treatment is as follows: firstly, uniformly mixing an aluminum-nickel oxide composite material with graphene, then adding the mixture into a toluene solution of (trimethoxysilyl) methyl propionate, stirring and reacting for 7 hours at 85 ℃, filtering, washing and drying to obtain the modified composite material; wherein the toluene solution of (trimethoxysilyl) methyl propionate is prepared by adding (trimethoxysilyl) methyl propionate into toluene 6 times of the weight of the (trimethoxysilyl) methyl propionate and uniformly oscillating by ultrasonic waves.
In the step (2), the preparation method of the gel is as follows: adding the modified composite material into aqueous acrylic resin emulsion with the weight of 4.5 times of that of the modified composite material, stirring at 60 ℃ until sol is formed, naturally cooling to 25 ℃, and standing for 9 hours to obtain the gel.
The specific method of the step (3) is as follows: adding 1kg of gel into 9kg of 0.15mol/L hydrochloric acid solution, and uniformly dispersing the gel by ultrasonic oscillation to form hydrochloric acid suspension; then 2.5kg of 2- (4-fluorophenyl) thiophene is slowly added into the hydrochloric acid suspension at a constant speed, and the suspension is placed in an ice water bath after ultrasonic oscillation; slowly dropwise adding a hydrochloric acid solution of ammonium persulfate while stirring, stirring at 2 ℃ for reacting for 18 hours, performing suction filtration, alternately washing with absolute ethyl alcohol and deionized water, and drying to obtain the polymerization product; wherein the hydrochloric acid solution of ammonium persulfate is obtained by dissolving 0.0015kg of ammonium persulfate in 0.007kg of 0.15mol/L hydrochloric acid solution.
The feed time of 2- (4-fluorophenyl) thiophene was 25 minutes.
The process conditions of ultrasonic oscillation are as follows: the 500W ultrasonic wave was oscillated for 12 minutes.
In the step (4), the mass ratio of the polycarbonate to the polymerization product is 100:0.4.
in the step (4), a double-screw extruder is adopted to realize melt extrusion, the screw rotating speed of the extruder is 400 r/min, and the temperatures from a feed inlet to a machine head are 260 ℃, 257 ℃, 248 ℃, 270 ℃, 265 ℃ and 262 ℃ in sequence.
Comparative example 1
A preparation method of a polycarbonate film comprises the following specific steps:
(1) Carrying out modification treatment on graphene by using (trimethoxysilyl) methyl propionate to obtain modified graphene; adding the modified graphene into the aqueous acrylic resin emulsion to prepare gel;
(2) Then 2- (4-fluorophenyl) thiophene and gel are used as raw materials to carry out polymerization reaction to obtain a polymerization product;
(3) Then mixing, melting and extruding the polycarbonate and the polymerization product to obtain the polycarbonate composite resin.
(4) And finally, heating the polycarbonate composite resin to be molten, flowing out to the roll surface of a calender roll, and calendering to prepare a polycarbonate film with the thickness of 0.1 mm.
In the step (1), the mass ratio of the graphene to the methyl (trimethoxysilyl) propionate is 1.01:7.
in the step (1), the specific method of modification treatment is as follows: firstly, adding graphene into a toluene solution of (trimethoxysilyl) methyl propionate, stirring and reacting for 8 hours at 80 ℃, filtering, washing and drying to obtain the modified graphene; wherein the toluene solution of (trimethoxysilyl) methyl propionate is prepared by adding (trimethoxysilyl) methyl propionate into toluene 5 times of the weight of (trimethoxysilyl) methyl propionate, and uniformly oscillating with ultrasonic wave.
In the step (1), the preparation method of the gel is as follows: adding modified graphene into 5 times of aqueous acrylic resin emulsion by weight, stirring at 55 ℃ until sol is formed, naturally cooling to 25 ℃, and standing for 10 hours to obtain the gel.
The specific method of the step (2) is as follows: firstly, adding 1kg of gel into 8kg of 0.2mol/L hydrochloric acid solution, and uniformly dispersing the gel by ultrasonic oscillation to form hydrochloric acid suspension; then, slowly adding 2kg of 2- (4-fluorophenyl) thiophene into the hydrochloric acid suspension at a constant speed, oscillating by ultrasonic waves, and placing in an ice-water bath; slowly dropwise adding a hydrochloric acid solution of ammonium persulfate while stirring, stirring at 5 ℃ for reaction for 15 hours, performing suction filtration, alternately washing with absolute ethyl alcohol and deionized water, and drying to obtain the polymerization product; wherein the hydrochloric acid solution of ammonium persulfate is obtained by dissolving 0.002kg of ammonium persulfate in 0.006kg of 0.2mol/L hydrochloric acid solution.
The 2- (4-fluorophenyl) thiophene feed time was 20 minutes.
The process conditions of ultrasonic oscillation are as follows: 500W ultrasonic oscillation is carried out for 10 minutes.
In the step (3), the mass ratio of the polycarbonate to the polymerization product is 100:0.5.
in the step (3), a double-screw extruder is adopted to realize melt extrusion, the screw rotating speed of the extruder is 300 revolutions per minute, and the temperatures from a feed inlet to a machine head are 260 ℃, 257 ℃, 248 ℃, 270 ℃, 265 ℃ and 262 ℃ in sequence.
Comparative example 2
A preparation method of a polycarbonate film comprises the following specific steps:
(1) Firstly, dissolving aluminum nitrate and nickel nitrate in water, carrying out hydrothermal reaction to obtain a precursor, and then carrying out heat treatment to obtain an aluminum-nickel oxide composite material;
(2) Then mixing the aluminum-nickel oxide composite material with graphene to obtain a mixture, and then adding the mixture into the aqueous acrylic resin emulsion to prepare gel;
(3) Then 2- (4-fluorophenyl) thiophene and gel are used as raw materials to carry out polymerization reaction to obtain a polymerization product;
(4) Then mixing, melting and extruding the polycarbonate and the polymerization product to obtain the polycarbonate composite resin.
(5) And finally, heating the polycarbonate composite resin to be molten, flowing out to the roll surface of a calender roll, and calendering to prepare a polycarbonate film with the thickness of 0.1 mm.
In the step (1), the molar ratio of the aluminum nitrate to the nickel nitrate is 1:1, the amount of water is 9 times of the weight of the aluminum nitrate.
In the step (1), the process conditions of the hydrothermal reaction are as follows: hydrothermal reaction at 110 deg.c for 6 hr.
In the step (1), the heat treatment process conditions are as follows: heat treatment at 480 ℃ for 7 hours.
In the step (2), the mass ratio of the aluminum-nickel oxide composite material to the graphene is 1:0.01.
in the step (2), the preparation method of the gel is as follows: adding the mixture into 5 times of the weight of the aqueous acrylic resin emulsion, stirring at 55 ℃ until sol is formed, naturally cooling to 25 ℃, and standing for 10 hours to obtain the gel.
The specific method of the step (3) is as follows: firstly, adding 1kg of gel into 8kg of 0.2mol/L hydrochloric acid solution, and uniformly dispersing the gel by ultrasonic oscillation to form hydrochloric acid suspension; then, slowly adding 2kg of 2- (4-fluorophenyl) thiophene into the hydrochloric acid suspension at a constant speed, oscillating by ultrasonic waves, and placing in an ice-water bath; slowly dropwise adding a hydrochloric acid solution of ammonium persulfate while stirring, stirring at 5 ℃ for reaction for 15 hours, performing suction filtration, alternately washing with absolute ethyl alcohol and deionized water, and drying to obtain the polymerization product; wherein the hydrochloric acid solution of ammonium persulfate is obtained by dissolving 0.002kg of ammonium persulfate in 0.006kg of 0.2mol/L hydrochloric acid solution.
The 2- (4-fluorophenyl) thiophene feed time was 20 minutes.
The process conditions of ultrasonic oscillation are as follows: 500W ultrasonic oscillation is carried out for 10 minutes.
In the step (4), the mass ratio of the polycarbonate to the polymerization product is 100:0.5.
in the step (4), a double-screw extruder is adopted to realize melt extrusion, the screw rotating speed of the extruder is 300 revolutions per minute, and the temperature from a feed inlet to a machine head is 260 ℃, 257 ℃, 248 ℃, 270 ℃, 265 ℃ and 262 ℃ in sequence.
Comparative example 3
A preparation method of a polycarbonate film comprises the following specific steps:
(1) Firstly, dissolving aluminum nitrate and nickel nitrate in water, carrying out hydrothermal reaction to obtain a precursor, and then carrying out heat treatment to obtain an aluminum-nickel oxide composite material;
(2) Then mixing the aluminum-nickel oxide composite material with graphene, and carrying out modification treatment on (trimethoxysilyl) methyl propionate to obtain a modified composite material;
(3) Then, taking 2- (4-fluorophenyl) thiophene and the modified composite material as raw materials, and carrying out polymerization reaction to obtain a polymerization product;
(4) Then mixing, melting and extruding the polycarbonate and the polymerization product to obtain the polycarbonate composite resin.
(5) And finally, heating the polycarbonate composite resin to be molten, flowing out to the roll surface of a calender roll, and calendering to prepare a polycarbonate film with the thickness of 0.1 mm.
In the step (1), the molar ratio of the aluminum nitrate to the nickel nitrate is 1:1, the amount of water is 9 times of the weight of the aluminum nitrate.
In the step (1), the process conditions of the hydrothermal reaction are as follows: hydrothermal reaction at 110 deg.c for 6 hr.
In the step (1), the heat treatment process conditions are as follows: heat treatment at 480 ℃ for 7 hours.
In the step (2), the mass ratio of the aluminum-nickel oxide composite material to the graphene to the methyl (trimethoxysilyl) propionate is 1:0.01:7.
in the step (2), the specific method of modification treatment is as follows: uniformly mixing an aluminum-nickel oxide composite material with graphene, adding the mixture into a toluene solution of (trimethoxysilyl) methyl propionate, stirring and reacting for 8 hours at 80 ℃, filtering, washing and drying to obtain the modified composite material; wherein the toluene solution of (trimethoxysilyl) methyl propionate is prepared by adding (trimethoxysilyl) methyl propionate into toluene 5 times of the weight of (trimethoxysilyl) methyl propionate, and uniformly oscillating with ultrasonic wave.
The specific method of the step (3) is as follows: firstly, adding 1kg of modified composite material into 8kg of 0.2mol/L hydrochloric acid solution, and uniformly dispersing the modified composite material by ultrasonic oscillation to form hydrochloric acid suspension; then, slowly adding 2kg of 2- (4-fluorophenyl) thiophene into the hydrochloric acid suspension at a constant speed, oscillating by ultrasonic waves, and placing in an ice-water bath; slowly dropwise adding a hydrochloric acid solution of ammonium persulfate while stirring, stirring at 5 ℃ for reaction for 15 hours, performing suction filtration, alternately washing with absolute ethyl alcohol and deionized water, and drying to obtain the polymerization product; wherein the hydrochloric acid solution of ammonium persulfate is obtained by dissolving 0.002kg of ammonium persulfate in 0.006kg of 0.2mol/L hydrochloric acid solution.
The 2- (4-fluorophenyl) thiophene feed time was 20 minutes.
The process conditions of ultrasonic oscillation are as follows: 500W ultrasonic oscillation is carried out for 10 minutes.
In the step (4), the mass ratio of the polycarbonate to the polymerization product is 100:0.5.
in the step (4), a double-screw extruder is adopted to realize melt extrusion, the screw rotating speed of the extruder is 300 revolutions per minute, and the temperatures from a feed inlet to a machine head are 260 ℃, 257 ℃, 248 ℃, 270 ℃, 265 ℃ and 262 ℃ in sequence.
Test examples
The films obtained in examples 1 to 3 or comparative examples 1 to 3 were subjected to the performance test, and the results are shown in tables 1 and 2.
Wherein, the mechanical properties comprise: the tensile strength is tested by using a universal electronic experiment machine, and the reference is GB/T1040.3-2006; impact strength, see ASTM D256-2010.
The wear resistance is referred to GB/T3960-2016.
And antistatic property, surface resistivity is measured by adopting a surface resistance tester, and reference is made to GB/T1410-2006.
TABLE 1 comparison of mechanical Properties
| Tensile Strength (MPa) | Impact strength (J/m) | |
| Example 1 | 92.3 | 983 |
| Example 2 | 92.8 | 985 |
| Example 3 | 93.7 | 988 |
| Comparative example 1 | 75.4 | 889 |
| Comparative example 2 | 64.1 | 762 |
| Comparative example 3 | 80.2 | 920 |
TABLE 2 abrasion resistance and antistatic Properties comparison
| Amount of abrasion (mg) | Surface resistivity (omega/sq) | |
| Example 1 | 0.3 | 1.1×10 5 |
| Example 2 | 0.3 | 9.5×10 4 |
| Example 3 | 0.2 | 7.7×10 4 |
| Comparative example 1 | 1.8 | 6.3×10 8 |
| Comparative example 2 | 0.9 | 1.8×10 7 |
| Comparative example 3 | 0.8 | 4.2×10 9 |
As can be seen from tables 1 and 2, the films obtained in examples 1 to 3 have excellent mechanical properties, and have excellent abrasion resistance and antistatic properties.
Comparative example 1 omits the aluminum-nickel oxide composite material, the mechanical property, the wear resistance and the antistatic property of the product are obviously poor, which shows that the product and the graphene have synergistic interaction; comparative example 2 (trimethoxysilyl) methyl propionate modification treatment was omitted, the mechanical properties of the product were significantly deteriorated, and the abrasion resistance and antistatic properties were also deteriorated to some extent, probably due to poor compatibility; comparative example 3 omits the process of preparing gel from the aqueous acrylic resin emulsion, the antistatic property of the product is obviously deteriorated, the mechanical property and the wear resistance are also deteriorated, which shows that the formation of a conductive path is influenced because hydrogen bonds are not formed, and other properties are also influenced.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (4)
1. The preparation method of the polycarbonate composite resin is characterized by comprising the following specific steps of:
(1) Firstly, dissolving aluminum nitrate and nickel nitrate in water, carrying out hydrothermal reaction to obtain a precursor, and then carrying out heat treatment to obtain an aluminum-nickel oxide composite material;
(2) Then mixing the aluminum-nickel oxide composite material with graphene, and carrying out modification treatment on (trimethoxysilyl) methyl propionate to obtain a modified composite material; adding the modified composite material into the aqueous acrylic resin emulsion to prepare gel;
(3) Then 2- (4-fluorophenyl) thiophene and gel are used as raw materials to carry out polymerization reaction to obtain a polymerization product;
(4) Finally, mixing, melting and extruding the polycarbonate and the polymerization product to obtain the polycarbonate composite resin;
wherein, in the step (1), the process conditions of the hydrothermal reaction are as follows: hydrothermal reaction at 110-120 deg.c for 4-6 hr;
wherein, in the step (1), the heat treatment process conditions are as follows: heat treatment is carried out for 5 to 7 hours at 480 to 520 ℃;
in the step (2), the mass ratio of the aluminum-nickel oxide composite material to the graphene to the methyl (trimethoxysilyl) propionate is 1: 0.01-0.02: 5 to 7;
in the step (2), the specific method of modification treatment is as follows: firstly, uniformly mixing an aluminum-nickel oxide composite material with graphene, then adding the mixture into a toluene solution of (trimethoxysilyl) methyl propionate, stirring and reacting for 6-8 hours at the temperature of 80-90 ℃, filtering, washing and drying to obtain the modified composite material; wherein the toluene solution of (trimethoxysilyl) methyl propionate is obtained by adding (trimethoxysilyl) methyl propionate into toluene 5-7 times of the weight of (trimethoxysilyl) methyl propionate and uniformly oscillating with ultrasonic waves;
wherein, in the step (2), the preparation method of the gel is as follows: firstly, adding the modified composite material into aqueous acrylic resin emulsion with the weight 4-5 times that of the modified composite material, stirring at 55-65 ℃ until sol is formed, naturally cooling to 25 ℃, and standing for 8-10 hours to obtain gel;
wherein the specific method of the step (3) comprises the following steps in parts by weight: adding 1 part of gel into 8-10 parts of 0.1-0.2 mol/L hydrochloric acid solution, and uniformly dispersing the gel by ultrasonic oscillation to form hydrochloric acid suspension; then slowly adding 2-3 parts of 2- (4-fluorophenyl) thiophene into the hydrochloric acid suspension at a constant speed, carrying out ultrasonic oscillation, and placing in an ice water bath; slowly dropwise adding a hydrochloric acid solution of ammonium persulfate while stirring, stirring and reacting for 15-20 hours at the temperature of 0-5 ℃, performing suction filtration, alternately washing with absolute ethyl alcohol and deionized water, and drying to obtain the polymerization product; wherein the hydrochloric acid solution of ammonium persulfate is obtained by dissolving 0.001-0.002 part of ammonium persulfate in 0.006-0.008 part of 0.1-0.2 mol/L hydrochloric acid solution.
2. A polycarbonate composite resin obtained by the production method according to claim 1.
3. A polycarbonate film prepared by using the polycarbonate composite resin as defined in claim 2.
4. A process for producing a polycarbonate film as defined in claim 3, wherein the polycarbonate composite resin is heated to melt, flowed out onto the surface of a calender roll, and rolled to a thickness of 0.1 to 0.2 mm.
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