CN112538264A - Electromagnetic shielding plastic and preparation method thereof - Google Patents
Electromagnetic shielding plastic and preparation method thereof Download PDFInfo
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- CN112538264A CN112538264A CN202011215953.1A CN202011215953A CN112538264A CN 112538264 A CN112538264 A CN 112538264A CN 202011215953 A CN202011215953 A CN 202011215953A CN 112538264 A CN112538264 A CN 112538264A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/02—Polythioethers; Polythioether-ethers
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
- H05K9/009—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive fibres, e.g. metal fibres, carbon fibres, metallised textile fibres, electro-conductive mesh, woven, non-woven mat, fleece, cross-linked
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The invention discloses an electromagnetic shielding plastic which is characterized by being prepared from the following raw materials in parts by weight: 25-35 parts of vinyl modified hyperbranched polydiphenyl diamino disulfide, 10-15 parts of modified graphene nano fiber containing vinyl fluorine-silicon structure, 60-80 parts of sulfonated polyphenylene sulfide, 0.5-1 part of initiator and 0.3-0.5 part of phosphorus pentoxide. The invention also provides a preparation method of the electromagnetic shielding plastic. The electromagnetic shielding plastic provided by the invention has the advantages of good comprehensive performance, obvious electromagnetic shielding effect, good mechanical property and performance stability, excellent weather resistance and long service life.
Description
Technical Field
The invention relates to the technical field of functional polymer materials, in particular to electromagnetic shielding plastic and a preparation method thereof.
Background
With the development of modern science and technology and the wide application of modern electronics and communication technology, the quality of life of people is gradually improved, in order to ensure information safety and prevent information leakage and interference, the number of objects needing electromagnetic shielding is increased, the shielding degree is enhanced, and the requirements on shielding time and space are increased. The electromagnetic shielding material not only can play a role in guaranteeing information safety, but also can effectively control the harm and hidden danger of electromagnetic waves to human health, and is an important means for shielding electromagnetic wave interference.
The existing electromagnetic shielding material is generally made of metal material, although the metal material has the electromagnetic shielding function, the metal material has the defects of complex processing, high cost, heavy weight and unsuitability for precise instruments because the shape is not easy to form. Whereas conventional plastics can give a satisfactory appearance without electromagnetic shielding. In order to endow the plastic with an electromagnetic shielding function, the plastic is mostly prepared by adopting a single conductive filler, has the defects of large resistance and poor corrosion resistance, and can not meet the use requirement due to serious reduction of mechanical properties in a long time of the electromagnetic shielding energy-saving filler; in addition, due to the problems of compatibility of the conductive filler with the plastic matrix, dispersibility of the conductive filler, processing conditions and the like, the overall performance and performance stability of the finally obtained material are poor.
For example, the chinese patent application No. 201710507824.1 discloses a low-resistance composite electromagnetic shielding plastic, which comprises the following components in parts by weight: 60-80 parts of matrix resin, 10-30 parts of carbon black, 10-20 parts of asphalt-based chopped graphite fiber, 5-10 parts of surface treating agent, 20-30 parts of toughening modifier and 3-8 parts of antioxidant. According to the low-resistance composite electromagnetic shielding plastic, through scientific material selection and raw material proportion and surface treatment on the filling material, the electromagnetic shielding resistance frequency and the mechanical property of the electromagnetic shielding plastic are effectively improved, the resistivity of the composite plastic is greatly reduced, the comprehensive performance is excellent, and the market prospect is wide. However, the filler has a large addition amount, so that the comprehensive performance of the plastic is poor, and the compatibility between the filler and the matrix resin needs to be further improved, so that the performance stability is poor and the service life is short.
The field needs an electromagnetic shielding plastic with good comprehensive performance, obvious electromagnetic shielding effect, good mechanical property and performance stability and long service life.
Disclosure of Invention
The invention aims to provide the electromagnetic shielding plastic with good comprehensive performance, obvious electromagnetic shielding effect, good mechanical property and performance stability, excellent weather resistance and long service life; meanwhile, the invention also provides a preparation method of the electromagnetic shielding plastic, and the preparation method has the advantages of simple process, low energy consumption, small dependence on equipment, high production efficiency and finished product qualification rate, is suitable for continuous large-scale production, and has higher economic value and social value.
In order to achieve the purpose, the invention adopts the technical scheme that the electromagnetic shielding plastic is characterized by being prepared from the following raw materials in parts by weight: 25-35 parts of vinyl modified hyperbranched polydiphenyl diamino disulfide, 10-15 parts of modified graphene nano fiber containing vinyl fluorine-silicon structure, 60-80 parts of sulfonated polyphenylene sulfide, 0.5-1 part of initiator and 0.3-0.5 part of phosphorus pentoxide.
Preferably, the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile.
Preferably, the sulfonated polyphenylene sulfide is the sulfonated polyphenylene sulfide prepared according to the preparation method of example 1 of CN 105694455A.
Preferably, the preparation method of the vinyl-containing fluorosilicone structure modified graphene nanofiber comprises the following steps:
step I, dispersing graphene nanofibers in an organic solvent, adding a silane coupling agent KH560, and carrying out reflux stirring reaction at 60-80 ℃ for 3-5 hours to obtain an intermediate product;
and step II, adding (2Z) -4-oxo-4- [3- (trifluoromethyl) -5, 6-dihydro- [1,2,4] triazolo [4,3-a ] pyrazine-7 (8H) -yl ] -1- (2,4, 5-trifluorophenyl) but-2-ene-2-amine and an alkaline catalyst into the intermediate product prepared in the step I, stirring and reacting for 4-6 hours at 35-45 ℃, centrifuging to remove the solvent, washing for 3-7 times with water, continuing to centrifuge, and finally freeze-drying to remove water to obtain the modified graphene nanofiber containing the vinyl fluorosilicone structure.
Preferably, the mass ratio of the graphene nanofibers, the organic solvent and the silane coupling agent KH560 in the step I is (3-5): (15-25): 0.4-0.8.
The organic solvent suitable for the technical scheme of the present invention is not particularly limited as long as it can make the raw materials better dispersed uniformly and can be advantageously used in the technical scheme of the present invention; in one embodiment of the present invention, the organic solvent is any one of ethanol, dichloromethane, acetone, and tetrahydrofuran.
Preferably, the mass ratio of the intermediate product in the step II, the (2Z) -4-oxo-4- [3- (trifluoromethyl) -5, 6-dihydro- [1,2,4] triazolo [4,3-a ] pyrazin-7 (8H) -yl ] -1- (2,4, 5-trifluorophenyl) but-2-en-2-amine and the basic catalyst is (20-30): 0.3-0.5: 0.5-0.8.
Preferably, the alkaline catalyst is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
Preferably, the diameter of the graphene nanofiber is 200-400nm, and the length-diameter ratio is (10-14): 1.
Preferably, the preparation method of the vinyl modified hyperbranched polydiphenyl diamino disulfide comprises the following steps: adding hyperbranched poly (diphenyl diamino disulfide), N-diisopropylethylamine, 4-vinylaniline and a polymerization inhibitor into N-methylpyrrolidone in a three-neck flask with a condenser pipe, stirring in an ice bath for 2h under the atmosphere of inert gas, heating to 40-50 ℃, stirring for 2-3h, heating to 85-95 ℃, stirring for 6-8h, cooling to room temperature, precipitating and filtering with a large amount of water, washing with diethyl ether and acetone for 3-6 times respectively, and removing residual solvent by rotary evaporation to obtain the vinyl modified hyperbranched poly (diphenyl diamino disulfide).
Preferably, the mass ratio of the hyperbranched polydiphenyl diamino disulfide to the N, N-diisopropylethylamine to the 4-vinylaniline to the polymerization inhibitor to the N-methylpyrrolidone is (3-5): 1-2): 0.3-0.5):0.1: (15-25).
Preferably, the hyperbranched polydiphenylenediamine is a hyperbranched polydiphenylenediamine prepared in example 3 with reference to CN 107887573B.
Preferably, the polymerization inhibitor is at least one of chloranil and 1, 4-naphthoquinone; the inert gas is any one of helium, neon, argon and nitrogen.
Another objective of the present invention is to provide a method for preparing the electromagnetic shielding plastic, which is characterized by comprising the following steps: uniformly mixing the raw materials in parts by weight to obtain a mixture, adding the mixture into a double-screw extruder, and carrying out melt extrusion to obtain the electromagnetic shielding plastic.
The melt extrusion process suitable for the present invention is not particularly limited as long as melt extrusion of the compounded material can be favorably used in the present invention.
The preparation method of the electromagnetic shielding plastic provided by the invention is simple in process, low in energy consumption, small in equipment dependence, high in production efficiency and finished product qualification rate, suitable for continuous large-scale production, and high in economic value and social value.
The electromagnetic shielding plastic provided by the invention overcomes the defects that the existing electromagnetic shielding material is generally made of metal materials, the metal materials have an electromagnetic shielding function, but the processing is complex, the cost is high, the weight is heavy, in addition, the appearance is not easy to form, and the electromagnetic shielding plastic is not suitable for precise instruments; the defects of large resistance and poor corrosion resistance caused by the fact that the traditional plastic can meet the appearance of people and does not have an electromagnetic shielding function are overcome, and the plastic is mostly prepared by adopting single conductive filler to endow the electromagnetic shielding function, and the mechanical property is seriously reduced when the electromagnetic shielding filler is used for a long time, so that the use requirement cannot be met; in addition, due to the problems of compatibility of the conductive filler and the plastic matrix, dispersibility of the conductive filler, processing conditions and the like, the finally obtained material has the defects of poor comprehensive performance and performance stability; through the synergistic effect of the components, the prepared electromagnetic shielding material has the advantages of good comprehensive performance, obvious electromagnetic shielding effect, good mechanical property and performance stability, excellent weather resistance and long service life.
According to the electromagnetic shielding plastic provided by the invention, the added vinyl modified hyperbranched poly (diphenyl diamine disulfide) and the vinyl containing vinyl fluorine-silicon structure modified graphene nanofiber have copolymerization crosslinking reaction under the action of an initiator in the melt extrusion process, and sulfonic groups on sulfonated polyphenylene sulfide and benzene rings on the vinyl modified hyperbranched poly (diphenyl diamine disulfide) have chemical reaction under the catalysis of phosphorus pentoxide to form a three-dimensional network structure, so that the comprehensive performance and the performance stability of the plastic are effectively improved.
According to the electromagnetic shielding plastic provided by the invention, the added vinyl modified hyperbranched polydiphenyl diamino disulfide and graphene nanofibers have a synergistic effect, so that the electromagnetic shielding effect of the plastic is remarkable, and the electromagnetic shielding active ingredients enter a molecular main chain through chemical bonds, so that the performance stability is better, the electromagnetic shielding effect is better, the processability of the plastic can be improved due to the introduction of the hyperbranched polydiphenyl diamino disulfide structure, and the mechanical strength of the plastic can be further improved due to the introduction of the graphene nanofiber structure.
The invention provides an electromagnetic shielding plastic, modified graphene nano-fiber containing vinyl fluorine-silicon structure is modified by (2Z) -4-oxo-4- [3- (trifluoromethyl) -5, 6-dihydro- [1,2,4] triazolo [4,3-a ] pyrazine-7 (8H) -group ] -1- (2,4, 5-trifluorophenyl) butyl-2-ene-2-amine and a silane coupling agent KH560, ethoxy silicon group on the silane coupling agent is in bridging connection with the graphene nano-fiber, epoxy group on the silane coupling agent is in bridging connection with (2Z) -4-oxo-4- [3- (trifluoromethyl) -5, 6-dihydro- [1,2,4] triazolo [ 4), 3-a ] pyrazin-7 (8H) -yl ] -1- (2,4, 5-trifluorophenyl) but-2-en-2-amine, with ring opening; the (2Z) -4-oxo-4- [3- (trifluoromethyl) -5, 6-dihydro- [1,2,4] triazolo [4,3-a ] pyrazine-7 (8H) -yl ] -1- (2,4, 5-trifluorophenyl) but-2-ene-2-amine is a medical impurity, is low in cost and provides a new application for medical waste, and the fluorine-containing triazole pyrazine structure on the fluorine-containing triazole pyrazine can effectively improve the weather resistance and flame retardance of plastics.
Detailed Description
The following detailed description of preferred embodiments of the invention will be made.
The electromagnetic shielding plastic is characterized by being prepared from the following raw materials in parts by weight: 25-35 parts of vinyl modified hyperbranched polydiphenyl diamino disulfide, 10-15 parts of modified graphene nano fiber containing vinyl fluorine-silicon structure, 60-80 parts of sulfonated polyphenylene sulfide, 0.5-1 part of initiator and 0.3-0.5 part of phosphorus pentoxide.
Preferably, the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile.
Preferably, the sulfonated polyphenylene sulfide is the sulfonated polyphenylene sulfide prepared according to the preparation method of example 1 of CN 105694455A.
Preferably, the preparation method of the vinyl-containing fluorosilicone structure modified graphene nanofiber comprises the following steps:
step I, dispersing graphene nanofibers in an organic solvent, adding a silane coupling agent KH560, and carrying out reflux stirring reaction at 60-80 ℃ for 3-5 hours to obtain an intermediate product;
and step II, adding (2Z) -4-oxo-4- [3- (trifluoromethyl) -5, 6-dihydro- [1,2,4] triazolo [4,3-a ] pyrazine-7 (8H) -yl ] -1- (2,4, 5-trifluorophenyl) but-2-ene-2-amine and an alkaline catalyst into the intermediate product prepared in the step I, stirring and reacting for 4-6 hours at 35-45 ℃, centrifuging to remove the solvent, washing for 3-7 times with water, continuing to centrifuge, and finally freeze-drying to remove water to obtain the modified graphene nanofiber containing the vinyl fluorosilicone structure.
Preferably, the mass ratio of the graphene nanofibers, the organic solvent and the silane coupling agent KH560 in the step I is (3-5): (15-25): 0.4-0.8.
The organic solvent suitable for the technical scheme of the present invention is not particularly limited as long as it can make the raw materials better dispersed uniformly and can be advantageously used in the technical scheme of the present invention; in one embodiment of the present invention, the organic solvent is any one of ethanol, dichloromethane, acetone, and tetrahydrofuran.
Preferably, the mass ratio of the intermediate product in the step II, the (2Z) -4-oxo-4- [3- (trifluoromethyl) -5, 6-dihydro- [1,2,4] triazolo [4,3-a ] pyrazin-7 (8H) -yl ] -1- (2,4, 5-trifluorophenyl) but-2-en-2-amine and the basic catalyst is (20-30): 0.3-0.5: 0.5-0.8.
Preferably, the alkaline catalyst is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
Preferably, the diameter of the graphene nanofiber is 200-400nm, and the length-diameter ratio is (10-14): 1.
Preferably, the preparation method of the vinyl modified hyperbranched polydiphenyl diamino disulfide comprises the following steps: adding hyperbranched poly (diphenyl diamino disulfide), N-diisopropylethylamine, 4-vinylaniline and a polymerization inhibitor into N-methylpyrrolidone in a three-neck flask with a condenser pipe, stirring in an ice bath for 2h under the atmosphere of inert gas, heating to 40-50 ℃, stirring for 2-3h, heating to 85-95 ℃, stirring for 6-8h, cooling to room temperature, precipitating and filtering with a large amount of water, washing with diethyl ether and acetone for 3-6 times respectively, and removing residual solvent by rotary evaporation to obtain the vinyl modified hyperbranched poly (diphenyl diamino disulfide).
Preferably, the mass ratio of the hyperbranched polydiphenyl diamino disulfide to the N, N-diisopropylethylamine to the 4-vinylaniline to the polymerization inhibitor to the N-methylpyrrolidone is (3-5): 1-2): 0.3-0.5):0.1: (15-25).
Preferably, the hyperbranched polydiphenylenediamine is a hyperbranched polydiphenylenediamine prepared in example 3 with reference to CN 107887573B.
Preferably, the polymerization inhibitor is at least one of chloranil and 1, 4-naphthoquinone; the inert gas is any one of helium, neon, argon and nitrogen.
Another objective of the present invention is to provide a method for preparing the electromagnetic shielding plastic, which is characterized by comprising the following steps: uniformly mixing the raw materials in parts by weight to obtain a mixture, adding the mixture into a double-screw extruder, and carrying out melt extrusion to obtain the electromagnetic shielding plastic.
The melt extrusion process suitable for the present invention is not particularly limited as long as melt extrusion of the compounded material can be favorably used in the present invention.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
(1) the preparation method of the electromagnetic shielding plastic provided by the invention is simple in process, low in energy consumption, small in equipment dependence, high in production efficiency and finished product qualification rate, suitable for continuous large-scale production, and high in economic value and social value.
(2) The electromagnetic shielding plastic provided by the invention overcomes the defects that the existing electromagnetic shielding material is generally made of metal materials, the metal materials have an electromagnetic shielding function, but the processing is complex, the cost is high, the weight is heavy, in addition, the appearance is not easy to form, and the electromagnetic shielding plastic is not suitable for precise instruments; the defects of large resistance and poor corrosion resistance caused by the fact that the traditional plastic can meet the appearance of people and does not have an electromagnetic shielding function are overcome, and the plastic is mostly prepared by adopting single conductive filler to endow the electromagnetic shielding function, and the mechanical property is seriously reduced when the electromagnetic shielding filler is used for a long time, so that the use requirement cannot be met; in addition, due to the problems of compatibility of the conductive filler and the plastic matrix, dispersibility of the conductive filler, processing conditions and the like, the finally obtained material has the defects of poor comprehensive performance and performance stability; through the synergistic effect of the components, the prepared electromagnetic shielding material has the advantages of good comprehensive performance, obvious electromagnetic shielding effect, good mechanical property and performance stability, excellent weather resistance and long service life.
(3) According to the electromagnetic shielding plastic provided by the invention, the added vinyl modified hyperbranched poly (diphenyl diamine disulfide) and the vinyl containing vinyl fluorine-silicon structure modified graphene nanofiber have copolymerization crosslinking reaction under the action of an initiator in the melt extrusion process, and sulfonic groups on sulfonated polyphenylene sulfide and benzene rings on the vinyl modified hyperbranched poly (diphenyl diamine disulfide) have chemical reaction under the catalysis of phosphorus pentoxide to form a three-dimensional network structure, so that the comprehensive performance and the performance stability of the plastic are effectively improved.
(4) According to the electromagnetic shielding plastic provided by the invention, the added vinyl modified hyperbranched polydiphenyl diamino disulfide and graphene nanofibers have a synergistic effect, so that the electromagnetic shielding effect of the plastic is remarkable, and the electromagnetic shielding active ingredients enter a molecular main chain through chemical bonds, so that the performance stability is better, the electromagnetic shielding effect is better, the processability of the plastic can be improved due to the introduction of the hyperbranched polydiphenyl diamino disulfide structure, and the mechanical strength of the plastic can be further improved due to the introduction of the graphene nanofiber structure.
(5) The invention provides an electromagnetic shielding plastic, modified graphene nano-fiber containing vinyl fluorine-silicon structure is modified by (2Z) -4-oxo-4- [3- (trifluoromethyl) -5, 6-dihydro- [1,2,4] triazolo [4,3-a ] pyrazine-7 (8H) -group ] -1- (2,4, 5-trifluorophenyl) butyl-2-ene-2-amine and a silane coupling agent KH560, ethoxy silicon group on the silane coupling agent is in bridging connection with the graphene nano-fiber, epoxy group on the silane coupling agent is in bridging connection with (2Z) -4-oxo-4- [3- (trifluoromethyl) -5, 6-dihydro- [1,2,4] triazolo [ 4), 3-a ] pyrazin-7 (8H) -yl ] -1- (2,4, 5-trifluorophenyl) but-2-en-2-amine, with ring opening; the (2Z) -4-oxo-4- [3- (trifluoromethyl) -5, 6-dihydro- [1,2,4] triazolo [4,3-a ] pyrazine-7 (8H) -yl ] -1- (2,4, 5-trifluorophenyl) but-2-ene-2-amine is a medical impurity, is low in cost and provides a new application for medical waste, and the fluorine-containing triazole pyrazine structure on the fluorine-containing triazole pyrazine can effectively improve the weather resistance and flame retardance of plastics.
Example 1
Embodiment 1 provides an electromagnetic shielding plastic, which is characterized by being prepared from the following raw materials in parts by weight: 25 parts of vinyl modified hyperbranched polydiphenyl diamino disulfide, 10 parts of modified graphene nano fiber containing vinyl fluorine-silicon structure, 60 parts of sulfonated polyphenylene sulfide, 0.5 part of initiator and 0.3 part of phosphorus pentoxide; the initiator is azobisisobutyronitrile.
The preparation method of the vinyl-containing fluorosilicone structure modified graphene nanofiber comprises the following steps:
step I, dispersing graphene nanofibers in an organic solvent, adding a silane coupling agent KH560 into the organic solvent, and carrying out reflux stirring reaction for 3 hours at the temperature of 60 ℃ to obtain an intermediate product;
and step II, adding (2Z) -4-oxo-4- [3- (trifluoromethyl) -5, 6-dihydro- [1,2,4] triazolo [4,3-a ] pyrazine-7 (8H) -yl ] -1- (2,4, 5-trifluorophenyl) but-2-ene-2-amine and an alkaline catalyst into the intermediate product prepared in the step I, stirring and reacting for 4 hours at 35 ℃, centrifuging to remove the solvent, washing for 3 times, continuing to centrifuge, and finally freeze-drying to remove water to obtain the vinyl fluorosilicone structure modified graphene nanofiber.
In the step I, the mass ratio of the graphene nanofibers to the organic solvent to the silane coupling agent KH560 is 3:15: 0.4; the organic solvent is tetrahydrofuran.
The mass ratio of the intermediate product in the step II, the (2Z) -4-oxo-4- [3- (trifluoromethyl) -5, 6-dihydro- [1,2,4] triazolo [4,3-a ] pyrazin-7 (8H) -yl ] -1- (2,4, 5-trifluorophenyl) but-2-ene-2-amine and the basic catalyst is 20:0.3: 0.5; the alkaline catalyst is sodium hydroxide.
The diameter of the graphene nanofiber is 200nm, and the length-diameter ratio of the graphene nanofiber is 10: 1.
The preparation method of the vinyl modified hyperbranched polydiphenyldiaminedisulfide comprises the following steps: adding hyperbranched polydiphenyl diamino disulfide, N-diisopropylethylamine, 4-vinylaniline and a polymerization inhibitor into N-methylpyrrolidone in a three-neck flask with a condenser pipe, stirring in ice bath for 2h under the atmosphere of inert gas, heating to 40 ℃, stirring for 2h, heating to 85 ℃, stirring for 6h, cooling to room temperature, precipitating and filtering with a large amount of water, washing with diethyl ether and acetone for 3 times respectively, and removing residual solvent by rotary evaporation to obtain vinyl modified hyperbranched polydiphenyl diamino disulfide; the mass ratio of the hyperbranched polydiphenyldiamino disulfide to the N, N-diisopropylethylamine to the 4-vinylaniline to the polymerization inhibitor to the N-methylpyrrolidone is 3:1:0.3:0.1: 15; the polymerization inhibitor is tetrachlorobenzoquinone; the inert gas is nitrogen.
The preparation method of the electromagnetic shielding plastic is characterized by comprising the following steps of: uniformly mixing the raw materials in parts by weight to obtain a mixture, adding the mixture into a double-screw extruder, and carrying out melt extrusion to obtain the electromagnetic shielding plastic; the melt extrusion temperature was 330 ℃.
Example 2
Embodiment 2 provides an electromagnetic shielding plastic, which is basically the same as embodiment 1 in formulation and preparation method, except that the electromagnetic shielding plastic is prepared from the following raw materials in parts by weight: 27 parts of vinyl modified hyperbranched polydiphenyl diamino disulfide, 11 parts of modified graphene nano fiber containing vinyl fluorine-silicon structure, 65 parts of sulfonated polyphenylene sulfide, 0.6 part of initiator and 0.35 part of phosphorus pentoxide.
Example 3
Embodiment 3 provides an electromagnetic shielding plastic, which has a formula and a preparation method substantially the same as those of embodiment 1, except that the electromagnetic shielding plastic is prepared from the following raw materials in parts by weight: 30 parts of vinyl modified hyperbranched polydiphenyl diamino disulfide, 13 parts of modified graphene nano fiber containing vinyl fluorine-silicon structure, 70 parts of sulfonated polyphenylene sulfide, 0.75 part of initiator and 0.4 part of phosphorus pentoxide.
Example 4
Embodiment 4 provides an electromagnetic shielding plastic, which has a formula and a preparation method substantially the same as those of embodiment 1, except that the electromagnetic shielding plastic is prepared from the following raw materials in parts by weight: 33 parts of vinyl modified hyperbranched polydiphenyl diamino disulfide, 14 parts of modified graphene nano fiber containing vinyl fluorine-silicon structure, 75 parts of sulfonated polyphenylene sulfide, 0.9 part of initiator and 0.45 part of phosphorus pentoxide.
Example 5
Embodiment 5 provides an electromagnetic shielding plastic, which has a formula and a preparation method substantially the same as those of embodiment 1, except that the electromagnetic shielding plastic is prepared from the following raw materials in parts by weight: 35 parts of vinyl modified hyperbranched polydiphenyl diamino disulfide, 15 parts of modified graphene nano fiber containing vinyl fluorine-silicon structure, 80 parts of sulfonated polyphenylene sulfide, 1 part of initiator and 0.5 part of phosphorus pentoxide.
Comparative example 1
Comparative example 1 provides an electromagnetic shielding plastic, the formulation and preparation method of which are substantially the same as those of example 1, except that the vinyl-containing fluorosilicone structure modified graphene nanofiber is not added.
Comparative example 2
Comparative example 2 provides an electro-magnetic shielding plastic, the formulation and preparation method of which are substantially the same as those of example 1, except that no vinyl-modified hyperbranched polydiphenyldiamminedisulfide was added.
Comparative example 3
Comparative example 3 provides an electromagnetic shielding plastic, the formulation and preparation method of which are substantially the same as those of example 1, except that the vinyl-modified hyperbranched polydiphenylenediamine is replaced with hyperbranched polydiphenylenediamine disulfide.
Comparative example 4
Comparative example 4 provides an electromagnetic shielding plastic, the formulation and preparation method of which are substantially the same as those of example 1, except that the preparation of the vinyl fluorosilicone structure modified graphene nanofiber does not include step ii.
The materials described in examples 1-5 and comparative examples 1-4 were tested for performance, the results are shown in Table 1, and the test methods are as follows:
(1) tensile strength: the test was performed according to GB/T1040.1-2006.
(2) Impact of the gap of the simply supported beam: the test was carried out according to GB 1043-79.
(3) Limiting oxygen index: the test was performed according to GB/T2406-1993.
(4) Weather resistance: the carbon arc lamp aging test is carried out according to GB/T16422.4-1996, and a continuous 720-hour illumination test is adopted, wherein the blackboard temperature is (65 +/-3) DEG C, and the relative humidity is (50 +/-5)%. The tensile strength retention of the product was measured, and the tensile strength retention was defined as the post-aging tensile strength/pre-aging tensile strength × 100%.
(5) Electromagnetic shielding efficiency: the test was carried out according to GB/T30142-2013.
As can be seen from Table 1, the electromagnetic shielding plastic disclosed in the embodiment of the invention has better mechanical properties, weather resistance, flame retardancy and electromagnetic shielding effect, which are the result of the synergistic effect of the raw materials.
TABLE 1 Properties of samples of examples and comparative examples
| Item | Tensile strength | Impact of simply supported beam gap | Limiting oxygen index | Weather resistance | Electromagnetic shielding efficiency |
| Unit of | MPa | KJ/m2 | % | % | dB |
| Example 1 | 83 | 7.5 | 32 | 98.3 | >69 |
| Example 2 | 85 | 7.7 | 34 | 98.5 | >71 |
| Example 3 | 88 | 7.9 | 36 | 98.9 | >71 |
| Example 4 | 90 | 8.2 | 37 | 99.2 | >72 |
| Example 5 | 91 | 8.4 | 38 | 99.5 | >73 |
| Comparative example 1 | 67 | 6.1 | 27 | 95.67 | >60 |
| Comparative example 2 | 73 | 6.4 | 28 | 96.75 | >62 |
| Comparative example 3 | 77 | 6.9 | 31 | 96.53 | >66 |
| Comparative example 4 | 79 | 7.0 | 30 | 97.41 | >67 |
The above-mentioned embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (10)
1. The electromagnetic shielding plastic is characterized by being prepared from the following raw materials in parts by weight: 25-35 parts of vinyl modified hyperbranched polydiphenyl diamino disulfide, 10-15 parts of modified graphene nano fiber containing vinyl fluorine-silicon structure, 60-80 parts of sulfonated polyphenylene sulfide, 0.5-1 part of initiator and 0.3-0.5 part of phosphorus pentoxide.
2. The EMI shielding plastic as set forth in claim 1, wherein said initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile.
3. The electromagnetic shielding plastic of claim 1, wherein the preparation method of the vinyl-containing fluorosilicone structure modified graphene nanofiber comprises the following steps:
step I, dispersing graphene nanofibers in an organic solvent, adding a silane coupling agent KH560, and carrying out reflux stirring reaction at 60-80 ℃ for 3-5 hours to obtain an intermediate product;
and step II, adding (2Z) -4-oxo-4- [3- (trifluoromethyl) -5, 6-dihydro- [1,2,4] triazolo [4,3-a ] pyrazine-7 (8H) -yl ] -1- (2,4, 5-trifluorophenyl) but-2-ene-2-amine and an alkaline catalyst into the intermediate product prepared in the step I, stirring and reacting for 4-6 hours at 35-45 ℃, centrifuging to remove the solvent, washing for 3-7 times with water, continuing to centrifuge, and finally freeze-drying to remove water to obtain the modified graphene nanofiber containing the vinyl fluorosilicone structure.
4. The electromagnetic shielding plastic of claim 3, wherein the mass ratio of the graphene nanofiber, the organic solvent and the silane coupling agent KH560 in step I is (3-5): (15-25): (0.4-0.8); the organic solvent is any one of ethanol, dichloromethane, acetone and tetrahydrofuran.
5. An EMI shielding plastic as claimed in claim 3, wherein the mass ratio of the intermediate product in step II, (2Z) -4-oxo-4- [3- (trifluoromethyl) -5, 6-dihydro- [1,2,4] triazolo [4,3-a ] pyrazin-7 (8H) -yl ] -1- (2,4, 5-trifluorophenyl) but-2-en-2-amine, basic catalyst is (20-30): (0.3-0.5): 0.5-0.8); the alkaline catalyst is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
6. The electromagnetic shielding plastic as claimed in claim 3, wherein the graphene nanofiber has a diameter of 200-400nm and an aspect ratio of (10-14): 1.
7. The electromagnetic shielding plastic of claim 1, wherein the preparation method of the vinyl modified hyperbranched polydiphenylenediamine disulfide comprises the following steps: adding hyperbranched poly (diphenyl diamino disulfide), N-diisopropylethylamine, 4-vinylaniline and a polymerization inhibitor into N-methylpyrrolidone in a three-neck flask with a condenser pipe, stirring in an ice bath for 2h under the atmosphere of inert gas, heating to 40-50 ℃, stirring for 2-3h, heating to 85-95 ℃, stirring for 6-8h, cooling to room temperature, precipitating and filtering with a large amount of water, washing with diethyl ether and acetone for 3-6 times respectively, and removing residual solvent by rotary evaporation to obtain the vinyl modified hyperbranched poly (diphenyl diamino disulfide).
8. The electromagnetic shielding plastic of claim 7, wherein the mass ratio of the hyperbranched polydiphenyldiamminedisulfide, N-diisopropylethylamine, 4-vinylaniline, polymerization inhibitor and N-methylpyrrolidone is (3-5): 1-2): 0.3-0.5):0.1 (15-25).
9. The EMI shielding plastic as claimed in claim 7, wherein said polymerization inhibitor is at least one of chloranil and 1, 4-naphthoquinone; the inert gas is any one of helium, neon, argon and nitrogen.
10. A method for preparing an electromagnetic shielding plastic according to any one of claims 1 to 9, comprising the steps of: uniformly mixing the raw materials in parts by weight to obtain a mixture, adding the mixture into a double-screw extruder, and carrying out melt extrusion to obtain the electromagnetic shielding plastic.
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| CN115262035A (en) * | 2021-04-30 | 2022-11-01 | 中国科学院宁波材料技术与工程研究所 | Graphene nanofiber material and preparation method and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115262035A (en) * | 2021-04-30 | 2022-11-01 | 中国科学院宁波材料技术与工程研究所 | Graphene nanofiber material and preparation method and application thereof |
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