CN113881080B - High-heat-conductivity low-dielectric film based on sandwich structure and preparation method thereof - Google Patents

High-heat-conductivity low-dielectric film based on sandwich structure and preparation method thereof Download PDF

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CN113881080B
CN113881080B CN202111188240.5A CN202111188240A CN113881080B CN 113881080 B CN113881080 B CN 113881080B CN 202111188240 A CN202111188240 A CN 202111188240A CN 113881080 B CN113881080 B CN 113881080B
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bnss
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CN113881080A (en
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褚中洋
李唯真
李珂菁
甘文君
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Shanghai University of Engineering Science
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Abstract

The invention relates to the technical field of polymer composite material processing, in particular to a high-heat-conductivity low-dielectric film based on a sandwich structure and a preparation method thereof. The invention uses ball milling method to strip and functionalize h-BN to obtain BNSS-NH 2 The method comprises the steps of carrying out a first treatment on the surface of the The MWCNTs-COOH is connected with the MWCNTs-COOH through covalent bonds, a spin-coating film forming and hot pressing process is utilized to form a highly oriented heat conduction path, and meanwhile, the low dielectric constant and the low dielectric loss are kept, so that the high-heat-conductivity low-dielectric film based on the sandwich structure is prepared. The preparation method provided by the invention has the advantages of easily available raw materials, simple process and low preparation cost.

Description

High-heat-conductivity low-dielectric film based on sandwich structure and preparation method thereof
Technical Field
The invention relates to the technical field of polymer composite material processing, in particular to a high-heat-conductivity low-dielectric film based on a sandwich structure and a preparation method thereof.
Background
In recent years, miniaturization and integration have become a trend of electronic devices. As electronic device power continues to increase, the amount of heat generated also increases dramatically. The large amount of heat can have a certain impact on the stability and lifetime of the electronic device. Therefore, the development of high-performance thermal management materials is critical to the improvement of heat dissipation of electronic devices, and the effective and timely discharge of heat generated by the electronic devices has obviously become an important research direction in the field of thermal management.
Thermal interface materials have been widely used in the field of thermal management to fill micro-voids and rugged surface holes created when a heating element contacts a heat sink element, thereby reducing thermal resistance during heat transfer. When the heating element is in direct contact with the heat dissipation element, only a small portion of the apparent area between the heating element and the heat dissipation element is actually contacted due to the roughness of the surface, and the surface area of the heating element and the heat dissipation element is about 10%. The remaining areas are separated by gaps filled with air. Air is poor in heat conductivity, is a poor conductor, and has a heat conductivity of only 0.024 W.m -1 K -1 . The presence of these air gaps causes a sharp rise in interfacial thermal resistance at the two interfaces, severely impeding heat transfer. The large amount of heat can only be dissipated through the actual contact points, but the small amount of contact points results in the accumulation of large amounts of heat, creating a serious thermal bottleneck. This will reduce the working efficiency of the electronic device, affecting the reliability, stability and lifetime of the electronic device. The high-heat-conductivity thermal interface material is filled between the two interfaces, so that a gap between the two interfaces can be filled, and air is discharged. Thereby increasing the effective contact area and improving the thermal contact between the two interfaces. A large number of effective heat conduction channels are established, and the interface thermal resistance is greatly reduced, so that heat is rapidly discharged.
With the development of aviation and aerospace technology, higher requirements are put on advanced resin matrix composite materials, and the materials are required to have high heat resistance, high thermal conductivity and excellent insulation and mechanical properties. Polyimide-based polymers have been attracting attention because of their excellent thermal stability, mechanical properties and dielectric properties. However, the aromatic heterocyclic main chains in the aromatic heterocyclic main chains are in a polar and unbent structure, have high symmetry, are often obtained by a thermosetting phase imidization process, have the characteristics of difficult dissolution, difficult melting and the like, and cause difficulty in processing.
Disclosure of Invention
Aiming at the defects of the prior heat conduction film technology, the invention aims to provide a high heat conduction low dielectric film based on a sandwich structure and a preparation method thereof, namely a high heat conduction insulating film based on the cooperation of a sandwich structure and highly oriented multidimensional heat conduction filler and a preparation method thereof. The preparation process is simple, the raw materials are common, and the cost is low.
In the present invention, hexagonal boron nitride or referred to simply as "h-BN", boron nitride nanoplatelets or referred to simply as "BNSs", triammonium phosphate, triad of water or referred to simply as "(NH) 3 PO 4 ·3H 2 O ", dichloromethane or abbreviated as" DCM ", polyetherimide or abbreviated as" PEI ", carboxylated multi-walled carbon nanotubes or abbreviated as" MWCNTs-COOH ", 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride or abbreviated as" EDC ", N-hydroxysuccinimide or abbreviated as" NHS ".
The aim of the invention can be achieved by the following technical scheme:
the first object of the invention is to provide a preparation method of a high-heat-conductivity low-dielectric film based on a sandwich structure, which comprises the following steps:
(1) Weighing h-BN and (NH) 3 PO 4 ·3H 2 O, stripping and functionalizing the h-BN to obtain BNSS-NH 2 ；
(2) Dispersing MWCNTs-COOH, EDC and NHS in DCM, stirring and adding BNSS-NH obtained in step (1) 2 Obtaining BNSs@MWCNTs after reacting in a nitrogen environment;
(3) Weighing PEI powder and dissolving in DCM to obtain PEI solution;
(4) Weighing BNSs@MWCNTs obtained in the step (2), and uniformly mixing the PEI solution and the BNSs@MWCNTs to obtain a first mixed solution;
(5) Weighing BNSs-NH 2 obtained in the step (1), and uniformly mixing the PEI solution with the BNSs-NH 2 to obtain a second mixed solution;
(6) Dripping the first mixed solution on a glass sheet of a coater, and spin-coating to form a film; then the second mixed solution is taken for continuous spin coating, and films similar to a sandwich structure are alternately and repeatedly formed;
(7) And carrying out hot pressing treatment on the film.
In one embodiment of the present invention, in the step (1), the specific steps of stripping and functionalizing the h-BN are:
(11) Weighing h-BN sum (NH) 3 PO 4 ·3H 2 O is added into a ball milling tank for ball milling;
(12) Washing the ball milled BNSs to remove (NH) 3 PO 4 ·3H 2 O；
(13) Crushing the solution obtained in the step 2);
(14) Centrifuging to obtain supernatant, and removing unpeeled h-BN;
(15) The lower precipitate was again centrifuged and repeated 3 times, and finally the dispersion solvent was changed to DCM.
In one embodiment of the present invention, in step 1), the ball milling conditions are: 560-720r/min;
preferably, the ball milling condition is 640r/min.
In one embodiment of the invention, in step 1), the ball milling time is 20h.
In one embodiment of the invention, in step 2), the ball milled BNNSs are washed with deionized water until the pH is 7.
In one embodiment of the invention, in step 3), the cells are broken with a point-to-point cytobreaker at a power of 500W for 1 hour.
In one embodiment of the invention, in step 4), the centrifugation is carried out for 10 minutes at a speed of 1500-2500rpm;
preferably, the rotational speed is 2000rpm during centrifugation.
In one embodiment of the invention, in step 5), the centrifugation is carried out for 10 minutes at a speed of 6000 to 9000rpm;
preferably, in step 5), the rotational speed is 8000rpm during centrifugation.
In one embodiment of the present invention, in step (1), h-BN is combined with (NH) 3 PO 4 ·3H 2 The mass ratio of O is as follows: 1:25-100; preferably, h-BN is combined with (NH) 3 PO 4 ·3H 2 The mass ratio of O is 1:25.
in one embodiment of the present invention, in step (2), MWCNTs-COOH and BNSS-NH 2 The mass ratio is 1:1-2; preferablyIn the above, MWCNTs-COOH and BNSs-NH 2 The mass ratio is 1:2.
in one embodiment of the present invention, in step (2), the bnnss@mwcnts are covalently linked.
In one embodiment of the present invention, in step (3), the mass ratio of PEI to DCM is 1:10.
in one embodiment of the invention, in the steps (3) to (5), the solution is uniformly mixed by ultrasonic, and the ultrasonic power is 200-400W;
preferably, the ultrasonic power is 300W.
In one embodiment of the present invention, in step (6), spin coating conditions are:
1)1000rpm，20s；
2)3000rpm，20s；
3)7000rpm，10s。
in one embodiment of the present invention, in the step (6), the number of the interlayers is 5 layers, and 1.0mL of the spin coating solution is taken.
In one embodiment of the invention, after obtaining the film resembling a sandwich structure in step (6), the film is transferred to an oven for vacuum solvent removal.
In one embodiment of the invention, the temperature of the oven is set to 80 ℃, and the time for removing the solvent in vacuum is 30min-1h;
preferably, the time for removing the solvent in vacuo is 1h.
In one embodiment of the invention, in the step (7), the hot pressing condition is 250-280 ℃, 10-20MPa, 10-30min;
preferably, the hot pressing condition is 280 ℃,15MPa and 15min.
The second purpose of the invention is to provide a high-heat-conductivity low-dielectric film based on a sandwich structure, which is provided with a BNSs@MWCNTs highly oriented heat-conducting channel structure in the in-plane direction formed by spin coating and hot pressing processes.
The technical scheme principle of the invention is as follows:
(1) Principle of stripping and functionalization of BN using physical ball milling:
the mechanical ball milling stripping method is realized by a physical machineThe h-BN is peeled off layer by mechanical action. In the ball milling process, h-BN receives strong shearing force and impact force, and under the action of the shearing force and the impact force, van der Waals force between the sheet layers is destroyed, so that h-BN stripping is realized. Meanwhile, the B atom site is fully exposed due to strong physical action, so that the functionalization of the h-BN is realized. While (NH) 3 PO 4 ·3H 2 O acts as a ball milling aid during ball milling. The ball milling device has the functions of buffering and lubricating in the ball milling process, reduces impact of grinding balls and related abrasion and pollution, avoids generating BNSs with smaller size under strong shearing force, and minimizes damage to the crystal structure in the h-BN plane. And amino groups are introduced to realize the functionalization of BNSs.
(2) Preparation principle of highly oriented BNSs@MWCNTs/PEI high-heat-conductivity insulating film:
1) BNSs-NH after stripping 2 The MWCNTs-COOH and the matrix have better dispersibility in the matrix and better interface compatibility with the matrix, and the multi-dimensional filler is compounded, so that a heat conduction path is formed in the system, and the heat conduction performance is improved.
2) Compared with other film forming methods, the spin coating film forming process can not only take away a part of low-boiling organic solvent due to high-speed rotation in the spin coating process, but also uniformly distribute the heat conducting filler in the matrix.
3) In microelectronic packaging and radio communication technologies, thermal management materials are also required to have low dielectric constants and low dielectric losses in order to reduce parasitic capacitance, signal delay and power consumption, BNSs-NH in the present highly thermally conductive insulating films 2 And PEI is used as an insulating layer to effectively block migration of carriers in BNSs@MWCNTs/PEI, so that the BNSs@MWCNTs/PEI has low dielectric constant and low dielectric loss.
4) Finally, the hot pressing process firstly enables BNSs@MWCNTs to form a highly oriented structure in the in-plane direction, and secondly enables the film to form a stacked structure similar to cement-brick, so that interface thermal resistance is reduced, and heat conduction performance and mechanical performance are improved.
Because the molecular main chain of the polyetherimide resin (PEI) contains ether bonds and meta-position substitution structures and isopropyl structures, the polyetherimide resin has excellent solubility and film forming property, and the thermoplastic film material prepared based on the polyetherimide resin has wide application prospect.
The high-heat-conductivity low-dielectric film based on the sandwich structure and the preparation method thereof are provided, wherein BNSs are added into a ball milling auxiliary agent (NH) in the first step 3 PO 4 ·3H 2 Under the action of O, physical ball milling stripping is carried out, and the effect is that under the condition of adding BNSs with the same quality, BNSs with more thin layers exist in a system through stripping, so that the efficiency of improving the heat conducting performance of the composite material by the BNSs is increased, and the BNSs are synchronously functionalized by virtue of the synergistic effect of ball milling auxiliary agents, so that the dispersion of the BNSs and the interfacial compatibility of the BNSs with a matrix are helped.
Compared with the prior art, the invention has the following beneficial effects:
(1) The preparation method is simple, the raw materials are easy to obtain, and the production cost is low.
(2) The film prepared by the method has a sandwich-like sandwich structure, and the excellent low dielectric insulation performance is effectively maintained.
(3) The film prepared by the method has a cement-brick-like stacked structure, so that the composite material film has high heat conduction and excellent mechanical properties (E' is 2502MPa and T) g 229 c).
(4) The film prepared by the method can greatly improve the heat conduction performance of the composite material, and the heat conduction coefficient in the in-plane direction can be improved to 6.88W/mK, which is 40.4 times that of pure PEI.
(5) The multidimensional composite filler highly oriented structure prepared by the method can avoid the damage of mechanical properties of the composite material caused by excessive addition of inorganic filler.
(6) The filler has low price and small addition amount, and can meet the economic benefit.
Drawings
Figure 1 is the XRD pattern of comparative example 3 and example 2.
FIG. 2 is an infrared thermal image of BNSs@MWCNTs/PEI composite films of comparative example 1 and example 2 and the film surface temperature versus time.
FIG. 3 is a graph showing the dielectric constants of the composite films of comparative examples 1, 2 and example 2
Fig. 4 is a schematic diagram of dielectric loss of the composite films of comparative examples 1, 2 and example 2.
Detailed Description
The invention provides a preparation method of a high-heat-conductivity low-dielectric film based on a sandwich structure, which comprises the following steps:
(1) Weighing h-BN and (NH) 3 PO 4 ·3H 2 O, stripping and functionalizing the h-BN to obtain BNSS-NH 2 ；
(2) Dispersing MWCNTs-COOH, EDC and NHS in DCM, stirring and adding BNSS-NH obtained in step (1) 2 Obtaining BNSs@MWCNTs after reacting in a nitrogen environment;
(3) Weighing PEI powder and dissolving in DCM to obtain PEI solution;
(4) Weighing BNSs@MWCNTs obtained in the step (2), and uniformly mixing the PEI solution and the BNSs@MWCNTs to obtain a first mixed solution;
(5) Weighing BNSs-NH obtained in the step (1) 2 Mixing PEI solution with BNSs-NH 2 Uniformly mixing to obtain a second mixed solution;
(6) Dripping the first mixed solution on a glass sheet of a coater, and spin-coating to form a film; then the second mixed solution is taken for continuous spin coating, and films similar to a sandwich structure are alternately and repeatedly formed;
(7) And carrying out hot pressing treatment on the film.
In one embodiment of the present invention, in the step (1), the specific steps of stripping and functionalizing the h-BN are:
(11) Weighing h-BN sum (NH) 3 PO 4 ·3H 2 O is added into a ball milling tank for ball milling;
(12) Washing the ball milled BNSs to remove (NH) 3 PO 4 ·3H 2 O；
(13) Crushing the solution obtained in the step (2);
(14) Centrifuging to obtain supernatant, and removing unpeeled h-BN;
(15) The lower precipitate was again centrifuged and repeated 3 times, and finally the dispersion solvent was changed to DCM.
In one embodiment of the present invention, in step 1), the ball milling conditions are: 560-720r/min;
preferably, the ball milling condition is 640r/min.
In one embodiment of the invention, in step 1), the ball milling time is 20h.
In one embodiment of the invention, in step 2), the ball milled BNNSs are washed with deionized water until the pH is 7.
In one embodiment of the invention, in step 3), the cells are broken with a point-to-point cytobreaker at a power of 500W for 1 hour.
In one embodiment of the invention, in step 4), the centrifugation is carried out for 10 minutes at a speed of 1500-2500rpm;
preferably, the rotational speed is 2000rpm during centrifugation.
In one embodiment of the invention, in step 5), the centrifugation is carried out for 10 minutes at a speed of 6000 to 9000rpm;
preferably, in step 5), the rotational speed is 8000rpm during centrifugation.
In one embodiment of the present invention, in step (1), h-BN is combined with (NH) 3 PO 4 ·3H 2 The mass ratio of O is as follows: 1:25-100.
Preferably, h-BN is combined with (NH) 3 PO 4 ·3H 2 The mass ratio of O is as follows: 1:25.
in one embodiment of the present invention, in step (2), MWCNTs-COOH and BNSS-NH 2 The mass ratio is 1:1-2;
preferably, MWCNTs-COOH and BNSs-NH 2 The mass ratio is 1:2.
in one embodiment of the present invention, in step (2), the bnnss@mwcnts are covalently linked.
In one embodiment of the present invention, in step (3), the mass ratio of PEI to DCM is 1:10.
in one embodiment of the invention, in the steps (3) to (5), the solution is uniformly mixed by ultrasonic, and the ultrasonic power is 200-400W;
preferably, the ultrasonic power is 300W.
In one embodiment of the present invention, in step (6), spin coating conditions are:
1)1000rpm，20s；
2)3000rpm，20s；
3)7000rpm，10s。
in one embodiment of the present invention, in the step (6), the number of the interlayers is 5 layers, and 1.0mL of the spin coating solution is taken.
In one embodiment of the invention, after obtaining the film resembling a sandwich structure in step (6), the film is transferred to an oven for vacuum solvent removal.
In one embodiment of the invention, the temperature of the oven is set to 80 ℃, and the time for removing the solvent in vacuum is 30min-1h;
preferably, the time for removing the solvent in vacuo is 1h.
In one embodiment of the invention, in the step (8), the hot pressing condition is 250-280 ℃, 10-20MPa, 10-30min;
preferably, the hot pressing condition is 280 ℃,15MPa and 15min.
The invention provides a high-heat-conductivity low-dielectric film based on a sandwich structure, which is provided with a BNSs@MWCNTs highly oriented heat-conducting channel structure in an in-plane direction formed by spin coating and hot pressing processes.
The invention will now be described in detail with reference to the drawings and specific examples.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used in this specification includes any and all combinations of one or more of the associated listed items.
The experimental methods used in the following examples are conventional methods unless otherwise specified.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified. Table 1 shows the main reagents and raw materials of the present invention.
TABLE 1 Main reagents and raw materials
Figure BDA0003300170320000081
Example 1
The embodiment provides a high-heat-conductivity low-dielectric film based on a sandwich structure and a preparation method thereof, and the method comprises the following steps:
(1) h-BN and (NH) 3 PO 4 ·3H 2 And stripping and functionalizing the h-BN by using a physical ball milling method. The method comprises the following specific steps:
1) Weighing the following components in percentage by mass: 25 h-BN & lt (NH) 3 PO 4 ·3H 2 O is added into a ball milling tank, and ball milling is carried out for 20 hours at the rotating speed of 640 r/min;
2) Dispersing ball-milled BNSs in deionized water, and washing with deionized water for multiple times to remove residual (NH) in the solution 3 PO 4 ·3H 2 O, until the pH value is 7;
3) Crushing the obtained uniformly dispersed solution for 1 hour under the power of 500W by using a point-to-point cytoclasis instrument;
4) Centrifuging at 2000rpm for 10min, collecting supernatant, and removing non-stripped h-BN;
5) Centrifugation was performed at 8000rpm for 10min and the pellet was removed, repeated 3 times, and the dispersion was solvent-exchanged for DCM.
(2) Weighing 1g of MWCNTs-COOH,0.5g of EDC and 0.3g of NHS, mixing and dispersing in DCM solvent, stirring the mixed solution in a three-neck flask for 30min, and then adding 1g of BNSS-NH in the step (1) 2 And (3) reacting for 12 hours in a nitrogen environment, and obtaining the covalently linked BNSs@MWCNTs after the reaction.
(3) 4.2g PEI powder was weighed into 42mL DCM solution and sonicated to dissolve completely.
(4) Weighing 0.8g of BNSs@MWCNTs obtained in the step (2), mixing with the solution obtained in the step (3), and carrying out ultrasonic dispersion and uniform mixing to obtain a first mixed solution.
(5) 3.4g PEI powder was weighed into 34mL DCM solution and sonicated to dissolve completely.
(6) Weighing 1.6g of BNSS-NH obtained in the step (1) 2 Mixing with the solution in the step (5), and uniformly dispersing and mixing by ultrasonic to obtain a second mixed solution.
(7) 1mL of the first mixed solution is dripped on a glass sheet of a coating machine at one time, spin coating is carried out to form a film, then 1mL of the second mixed solution is continuously spin coated, a sandwich-like sandwich structure is alternately and repeatedly formed, the total spin coating is carried out for 5 times, and the spin coating conditions are as follows:
1)1000rpm，20s；
2)3000rpm，20s；
3)7000rpm，10s。
(8) The film was then transferred to an 80 ℃ oven for solvent removal in vacuo for 1h.
(9) Finally, hot-pressing the film for 15min at 280 ℃ and 15 MPa.
Example 2
The embodiment provides a high-heat-conductivity low-dielectric film based on a sandwich structure and a preparation method thereof, and the method comprises the following steps:
(1) h-BN and (NH) 3 PO 4 ·3H 2 And stripping and functionalizing the h-BN by using a physical ball milling method. The method comprises the following specific steps:
1) Weighing the following components in percentage by mass: 25 h-BN & lt (NH) 3 PO 4 ·3H 2 O is added into a ball milling tank, and ball milling is carried out for 20 hours at the rotating speed of 640 r/min;
2) Dispersing ball-milled BNSs in deionized water, and washing with deionized water for multiple times to remove residual (NH) in the solution 3 PO 4 ·3H 2 O, until the pH value is 7;
3) Crushing the obtained uniformly dispersed solution for 1 hour under the power of 500W by using a point-to-point cytoclasis instrument;
4) Centrifuging at 2000rpm for 10min, collecting supernatant, and removing non-stripped h-BN;
5) Centrifugation was performed at 8000rpm for 10min and the pellet was removed, repeated 3 times, and the dispersion was solvent-exchanged for DCM.
(2) Weighing 1g of MWCNTs-COOH,0.5g of EDC and 0.3g of NHS, mixing and dispersing in DCM solvent, stirring the mixed solution in a three-neck flask for 30min, and then adding 2g of BNSS-NH in the step (1) 2 And (3) reacting for 12 hours in a nitrogen environment, and obtaining the covalently linked BNSs@MWCNTs after the reaction.
(3) 4.2g PEI powder was weighed into 42mL DCM solution and sonicated to dissolve completely.
(4) Weighing 0.8g of BNSs@MWCNTs obtained in the step (2), mixing with the solution obtained in the step (3), and carrying out ultrasonic dispersion and uniform mixing to obtain a first mixed solution.
(5) 3.4g PEI powder was weighed into 34mL DCM solution and sonicated to dissolve completely.
(6) Weighing 1.6g of BNSS-NH obtained in the step (1) 2 Mixing with the solution in the step (5), and uniformly dispersing and mixing by ultrasonic to obtain a second mixed solution.
(7) 1mL of the first mixed solution is dripped on a glass sheet of a coating machine at one time, spin coating is carried out to form a film, then 1mL of the second mixed solution is continuously spin coated, a sandwich-like sandwich structure is alternately and repeatedly formed, the total spin coating is carried out for 5 times, and the spin coating conditions are as follows:
1)1000rpm，20s；
2)3000rpm，20s；
3)7000rpm，10s。
(8) The film was then transferred to an 80 ℃ oven for solvent removal in vacuo for 1h.
(9) Finally, hot-pressing the film for 15min at 280 ℃ and 15 MPa.
Example 3
The embodiment provides a high-heat-conductivity low-dielectric film based on a sandwich structure and a preparation method thereof, and the method comprises the following steps:
(1) h-BN and (NH) 3 PO 4 ·3H 2 And stripping and functionalizing the h-BN by using a physical ball milling method. The method comprises the following specific steps:
1) Weighing the following components in percentage by mass: h-BN with (NH) of 100 3 PO 4 ·3H 2 O is added into a ball milling tank, and ball milling is carried out for 20 hours at the rotating speed of 640 r/min;
2) Dispersing ball-milled BNSs in deionized water, and washing with deionized water for multiple times to remove residual (NH) in the solution 3 PO 4 ·3H 2 O, until the pH value is 7;
3) Crushing the obtained uniformly dispersed solution for 1 hour under the power of 500W by using a point-to-point cytoclasis instrument;
4) Centrifuging at 2000rpm for 10min, collecting supernatant, and removing non-stripped h-BN;
5) Centrifugation was performed at 8000rpm for 10min and the pellet was removed, repeated 3 times, and the dispersion was solvent-exchanged for DCM.
(2) Weighing 1g of MWCNTs-COOH,0.5g of EDC and 0.3g of NHS, mixing and dispersing in DCM solvent, stirring the mixed solution in a three-neck flask for 30min, and then adding 2g of BNSS-NH in the step (1) 2 And (3) reacting for 12 hours in a nitrogen environment, and obtaining the covalently linked BNSs@MWCNTs after the reaction.
(3) 4.2g PEI powder was weighed into 42mL DCM solution and sonicated to dissolve completely.
(4) Weighing 0.8g of BNSs@MWCNTs obtained in the step (2), mixing with the solution obtained in the step (3), and carrying out ultrasonic dispersion and uniform mixing to obtain a first mixed solution.
(5) 3.4g PEI powder was weighed into 34mL DCM solution and sonicated to dissolve completely.
(6) Weighing 1.6g of BNSS-NH obtained in the step (1) 2 Mixing with the solution in the step (5), and uniformly dispersing and mixing by ultrasonic to obtain a second mixed solution.
(7) 1mL of the first mixed solution is dripped on a glass sheet of a coating machine at one time, spin coating is carried out to form a film, then 1mL of the second mixed solution is continuously spin coated, a sandwich-like sandwich structure is alternately and repeatedly formed, the total spin coating is carried out for 5 times, and the spin coating conditions are as follows:
1)1000rpm，20s；
2)3000rpm，20s；
3)7000rpm，10s。
(8) The film was then transferred to an 80 ℃ oven for solvent removal in vacuo for 1h.
(9) Finally, hot-pressing the film for 15min at 280 ℃ and 15 MPa.
Example 4
The embodiment provides a high-heat-conductivity low-dielectric film based on a sandwich structure and a preparation method thereof, and the method comprises the following steps:
(1) h-BN and (NH) 3 PO 4 ·3H 2 And stripping and functionalizing the h-BN by using a physical ball milling method. The method comprises the following specific steps:
1) Weighing the following components in percentage by mass: 25 h-BN & lt (NH) 3 PO 4 ·3H 2 O is added into a ball milling tank, and ball milling is carried out for 20 hours at the rotating speed of 640 r/min;
2) Dispersing ball-milled BNSs in deionized water, and washing with deionized water for multiple times to remove residual (NH) in the solution 3 PO 4 ·3H 2 O, until the pH value is 7;
3) Crushing the obtained uniformly dispersed solution for 1 hour under the power of 500W by using a point-to-point cytoclasis instrument;
4) Centrifuging at 2000rpm for 10min, collecting supernatant, and removing non-stripped h-BN;
5) Centrifugation was performed at 8000rpm for 10min and the pellet was removed, repeated 3 times, and the dispersion was solvent-exchanged for DCM.
(2) Weighing 1g of MWCNTs-COOH,0.5g of EDC and 0.3g of NHS, mixing and dispersing in DCM solvent, stirring the mixed solution in a three-neck flask for 30min, and then adding 2g of BNSS-NH in the step (1) 2 And (3) reacting for 12 hours in a nitrogen environment, and obtaining the covalently linked BNSs@MWCNTs after the reaction.
(3) 4.2g PEI powder was weighed into 42mL DCM solution and sonicated to dissolve completely.
(4) Weighing 0.8g of BNSs@MWCNTs obtained in the step (2), mixing with the solution obtained in the step (3), and carrying out ultrasonic dispersion and uniform mixing to obtain a first mixed solution.
(5) 3.4g PEI powder was weighed into 34mL DCM solution and sonicated to dissolve completely.
(6) Weigh 1.6g step (1) BNSs-NH obtained in (a) a process for preparing BNSs-NH 2 Mixing with the solution in the step (5), and uniformly dispersing and mixing by ultrasonic to obtain a second mixed solution.
(7) 1mL of the first mixed solution is dripped on a glass sheet of a coating machine at one time, spin coating is carried out to form a film, then 1mL of the second mixed solution is continuously spin coated, a sandwich-like sandwich structure is alternately and repeatedly formed, the total spin coating is carried out for 5 times, and the spin coating conditions are as follows:
1)1000rpm，20s；
2)3000rpm，20s；
3)7000rpm，10s。
(8) The film was then transferred to an 80 ℃ oven for solvent removal in vacuo for 1h.
(9) Finally, hot-pressing the film for 15min at 250 ℃ and 15 MPa.
Comparative example 1
The embodiment provides a high-heat-conductivity low-dielectric film based on a sandwich structure and a preparation method thereof, and the method comprises the following steps:
(1) 5g PEI powder was weighed into 50mL DCM solution and sonicated to dissolve completely.
(2) 1mL of the mixed solution is dripped on a glass sheet of an applicator at one time, spin-coated to form a film, and the process is repeated for 5 times. Spin coating conditions were as follows:
1)1000rpm，20s；
2)3000rpm，20s；
3)7000rpm，10s。
(3) The film was then transferred to an 80 ℃ oven for solvent removal in vacuo for 1h.
(4) Finally, hot-pressing the film for 15min at 280 ℃ and 15 MPa.
Comparative example 2
The comparative example provides a composite material and a preparation method thereof, comprising the following steps:
(1) h-BN and (NH) 3 PO 4 ·3H 2 And stripping and functionalizing the h-BN by using a physical ball milling method. The method comprises the following specific steps:
1) Weighing the following components in percentage by mass: 25 h-BN & lt (NH) 3 PO 4 ·3H 2 O is added into a ball milling tank at 640r/minBall milling for 20 hours at the rotating speed;
2) Dispersing ball-milled BNSs in deionized water, and washing with deionized water for multiple times to remove residual (NH) in the solution 3 PO 4 ·3H 2 O, until the pH value is 7;
3) Crushing the obtained uniformly dispersed solution for 1 hour under the power of 500W by using a point-to-point cytoclasis instrument;
4) Centrifuging at 2000rpm for 10min, collecting supernatant, and removing non-stripped h-BN;
5) Centrifugation was performed at 8000rpm for 10min and the pellet was removed, repeated 3 times, and the dispersion was solvent-exchanged for DCM.
(2) 7.6g PEI powder was weighed into 76mL DCM solution and sonicated to dissolve completely.
(3) Weighing 2g of BNSs-NH obtained in the step (1) 2 And (3) mixing 0.4g of MWCNTs-COOH with the solution in the step (2), and uniformly dispersing and mixing by ultrasonic.
(4) 1mL of the mixed solution is dripped on a glass sheet of an applicator at one time, spin-coated to form a film, spin-coated for 5 times in total, and spin-coating conditions are as follows:
1)1000rpm，20s；
2)3000rpm，20s；
3)7000rpm，10s。
(5) The film was then transferred to an 80 ℃ oven for solvent removal in vacuo for 1h.
(6) Finally, hot-pressing the film for 15min at 280 ℃ and 15 MPa.
Comparative example 3
The composite material and the preparation method thereof provided by the comparative example comprise the following steps:
(1) h-BN and (NH) 3 PO 4 ·3H 2 And stripping and functionalizing the h-BN by using a physical ball milling method. The method comprises the following specific steps:
1) Weighing the following components in percentage by mass: 25 h-BN & lt (NH) 3 PO 4 ·3H 2 O is added into a ball milling tank, and ball milling is carried out for 20 hours at the rotating speed of 640 r/min;
2) Dispersing ball-milled BNSs in deionized water, and using the deionized waterMultiple washes to remove residual (NH) from the solution 3 PO 4 ·3H 2 O, until the pH value is 7;
3) Crushing the obtained uniformly dispersed solution for 1 hour under the power of 500W by using a point-to-point cytoclasis instrument;
4) Centrifuging at 2000rpm for 10min, collecting supernatant, and removing non-stripped h-BN;
5) Centrifugation was performed at 8000rpm for 10min and the pellet was removed, repeated 3 times, and the dispersion was solvent-exchanged for DCM.
(2) 7.6g PEI powder was weighed into 76mL DCM solution and sonicated to dissolve completely.
(3) Weighing 2g of BNSs-NH obtained in the step (1) 2 And (3) mixing 0.4g of MWCNTs-COOH with the solution in the step (2), and uniformly dispersing and mixing by ultrasonic.
(4) And (5) forming a film by a casting method.
(5) The film was then transferred to an 80 ℃ oven for solvent removal in vacuo for 1h.
The centrifugal times, the centrifugal rotating speed, the ultrasonic power and the ball milling rotating speed have small influence on the final experimental result, and although only the optimal conditions are shown in the embodiment, the high-heat-conductivity low-dielectric film with obvious effect and based on the sandwich structure can be obtained in the protection scope of the invention, so that the description of the values of the condition scope of the invention is included in the protection scope of the invention.
Analysis of experimental results:
the thermal conductivities of the composite films of examples 1, 2, 3, and 4 and comparative examples 1, 2, and 3 were 3.36W/mK,6.88W/mK,2.86W/mK,2.54W/mK,0.17W/mK,1.08W/mK, and 1.17W/mK, respectively. By comparing examples 1 and 2, when the reaction ratio of MWCNTs to BNSs is controlled at 1:2, the thermal conductivity of the composite material is the highest, and the ratio of the two is 1:2, the reaction is optimized, and a more effective phonon transmission channel can be provided. By comparing examples 2 and 3, when the ball milling ratio is 1:25 h-BN & lt (NH) 3 PO 4 ·3H 2 In the case of O, the BNSS has better stripping effect and is more uniformly dispersed in the matrix. At the same time, example 2 shows excellent mechanical properties, E' reaches 2502MPa, T g Up to 229 ℃. Comparative examples 2 and 4 show that the composite material has the highest heat conductivity coefficient at the hot pressing temperature of 280 ℃, and the higher temperature can fully improve the orientation degree of the matrix and the filler, form a heat conduction path in the in-plane direction and increase the heat conduction performance.
Figure 1 is the XRD pattern of comparative example 3 and example 2. Wherein in example 2I 002 /I 100 =152, comparative example 3I 002 /I 100 =10, by comparing the two sets of data, the spin coating method achieves an oriented structure of the thermally conductive filler in the in-plane direction.
FIG. 2 is an infrared thermal image of BNSs@MWCNTs/PEI composite films of comparative example 1 and example 2 and the film surface temperature versus time. It can be intuitively observed that the surface temperature reaches 82 ℃ at 6.9s in example 2, and the heat transfer rate is the fastest.
Fig. 3 and 4 are dielectric properties of the composite films of comparative examples 1, 2 and example 2. The heat conduction film material with the sandwich structure constructed by the invention has low dielectric constant and low dielectric loss, and meets the insulation performance requirement of the thermal interface material.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.

Claims (10)

1. The preparation method of the high-heat-conductivity low-dielectric film based on the sandwich structure is characterized by comprising the following steps of:
(1) Weighing and weighinghBN and (NH) 3 PO 4 ·3H 2 O, pair ofhStripping and functionalizing BN to obtain BNSs-NH 2； wherein ,hBN and (NH) 3 PO 4 ·3H 2 The mass ratio of O is 1:25-100;
(2) Dispersing MWCNTs-COOH, EDC and NHS in DCM, stirring and adding BNSS-NH obtained in step (1) 2 Obtaining BNSs@MWCNTs after reacting in a nitrogen environment; wherein MWCNTs-COOH and BNSs-NH 2 The mass ratio is 1:1-2;
(3) Weighing PEI powder and dissolving in DCM to obtain PEI solution;
(4) Weighing BNSs@MWCNTs obtained in the step (2), and uniformly mixing the PEI solution and the BNSs@MWCNTs to obtain a first mixed solution;
(5) Weighing BNSs-NH obtained in the step (1) 2 Mixing PEI solution with BNSs-NH 2 Uniformly mixing to obtain a second mixed solution;
(6) Dripping the first mixed solution on a glass sheet of a coater, and spin-coating to form a film; then the second mixed solution is taken for continuous spin coating, and films similar to a sandwich structure are alternately and repeatedly formed;
(7) Carrying out hot pressing treatment on the film;
wherein in the step (1), the following steps are performedhThe specific steps of stripping and functionalization of BN are:
(11) Weighing and weighinghBN and (NH) 3 PO 4 ·3H 2 O is added into a ball milling tank for ball milling;
(12) Washing the ball milled BNSs to remove (NH) 3 PO 4 ·3H 2 O；
(13) Crushing the solution obtained in the step (12);
(14) Centrifuging to obtain supernatant, removing unpeeledh-BN；
(15) The lower precipitate was again centrifuged and repeated 3-5 times, and finally the dispersion solvent was changed to DCM.
2. The method for preparing a high thermal conductivity low dielectric film based on a sandwich structure according to claim 1, wherein in the step (14), the rotation speed is 2000-4000 rpm during centrifugation;
in the step (15), the rotating speed is 6000-8000 rpm when the centrifugal separation is performed.
3. The method for preparing a high thermal conductivity low dielectric film based on a sandwich structure according to claim 1, wherein in the step (1),hBN and (NH) 3 PO 4 ·3H 2 O mass ratio 1:25.
4. the method for preparing a high thermal conductivity low dielectric film based on a sandwich structure according to claim 1, wherein in the step (2), MWCNTs-COOH and BNSS-NH are as follows 2 The mass ratio is 1:2.
5. the preparation method of the high-heat-conductivity low-dielectric film based on the sandwich structure according to claim 1, wherein in the step (3), the mass ratio of PEI to DCM is 1:10.
6. the method for preparing the high-heat-conductivity low-dielectric film based on the sandwich structure according to claim 1, wherein in the step (6), spin coating conditions are as follows:
1）1000 rpm ，20 s；
2）3000 rpm ，20 s；
3）7000 rpm ，10 s。
7. the method for preparing a high thermal conductivity low dielectric film based on a sandwich structure according to claim 1, wherein in the step (6), the number of the interlayers is 5; after obtaining a film with a sandwich-like structure, the film was transferred to an oven for vacuum solvent removal.
8. The method for preparing the high-heat-conductivity low-dielectric film based on the sandwich structure according to claim 1, wherein in the step (7), the hot pressing condition is 250-280 ℃, 10-20MPa and 10-30 min.
9. The preparation method of the high-heat-conductivity low-dielectric film based on the sandwich structure according to claim 8, wherein the hot-pressing condition is 280 ℃,15MPa and 15min.
10. The sandwich structure-based high-heat-conductivity low-dielectric film prepared by the preparation method of any one of claims 1 to 9 is characterized by having a highly oriented heat-conductivity channel structure of BNSs@MWCNTs in-plane direction formed by spin coating and hot pressing processes.
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