CN108485514B - Polymer-based composite material for capacitor and preparation method thereof - Google Patents
Polymer-based composite material for capacitor and preparation method thereof Download PDFInfo
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C09D181/00—Coating compositions based on 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; Coating compositions based on polysulfones; Coating compositions based on derivatives of such polymers
- C09D181/06—Polysulfones; Polyethersulfones
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
Abstract
The invention provides a polymer matrix composite material for a capacitor and a preparation method thereof, wherein the composite material comprises the following components in parts by weight: 60-70 parts of polymer matrix; 20-30 parts of dopamine-coated tin-titanium oxide nano-fiber; 5-10 parts of an auxiliary agent; wherein the auxiliary agent is a mixture of aminopropyl silanetriol and vinyl trimethoxy silane, and the mass ratio of the aminopropyl silanetriol to the vinyl trimethoxy silane is (3-8) to 1. According to the polymer-based composite material, the auxiliary agent is added and the nano fiber with the core-shell structure is matched, so that the polymer-based composite material has high thermal conductivity, high dielectric constant and low dielectric loss and simultaneously has good coating uniformity.
Description
Technical Field
The invention belongs to the technical field of electronic components, and relates to a polymer-based composite material for a capacitor and a preparation method thereof.
Background
The embedded Capacitor printed circuit board is one of the integrated circuit boards, first proposed by Zycon, a PCB company, 1992 (distributed Capacitor). However, at that time, due to the price, performance, etc. of SMT capacitors being able to accommodate the development of integrated circuit processes, embedded capacitors have not received particular attention from the PCB industry for a long time. The progress of electronic technology, the rapid development of high density of PCB, and the embedded capacitor can preferentially increase the interconnection density and improve the performance of the PCB, which has become an important aspect of the development of the next generation of HDI board. For a dielectric material for fabricating an embedded capacitor, it is required to have a low processing temperature to match the fabrication process of a PCB board, and at the same time, to have a high dielectric constant (to reduce a used area, to facilitate miniaturization of equipment), a low dielectric loss (to reduce energy loss and to reduce heat generation), and a high thermal conductivity (to dissipate heat).
The current common method for preparing dielectric materials of embedded capacitors is to use a material compounding method to prepare high dielectric constant polymer matrix composite materials. Ceramic/polymer composites (such as barium titanate/epoxy resin) and conductive filler/polymer (such as silver/polyimide) composites are two major types of high dielectric constant polymer-based composites which have been studied most recently, but they often have difficulty in combining three properties of high dielectric constant, high thermal conductivity and low loss.
CN 104893187A discloses a polymer composite film with high energy storage density and efficiency and a preparation method thereof, wherein the composite film is composed of a polyvinylidene fluoride matrix and nano-fibers with a core-shell structure dispersed in the polyvinylidene fluoride matrix; the core layer of the nano fiber with the core-shell structure is ceramic fiber, and the shell layer is a silicon dioxide coating layer. However, since the ceramic fiber has a high dielectric constant but a low thermal conductivity, the thermal conductivity of the polymer-based composite film prepared therefrom is also low.
For conductive filler/polymer (e.g., silver/polyimide) composites, metal fillers such as copper, silver, and nickel powders typically have high thermal conductivities that increase the thermal conductivity of the polymer matrix, and metal/polymer composites also exhibit high dielectric constants at metal contents close to but not above the percolation threshold due to the percolation effect, but the high electrical conductivity of the metal results in large dielectric losses for the metal/polymer composite. In addition, some insulating high thermal conductivity fillers such as aluminum nitride and alumina powders, although high in thermal conductivity and low in dielectric loss, have low dielectric constants, resulting in low dielectric constants for aluminum nitride/polymer and alumina/polymer composites. Meanwhile, the coating film uniformity of aluminum nitride/polymer and alumina/polymer composites and the like is also to be improved.
Therefore, there is a need for the development of a polymer base having high thermal conductivity, high dielectric constant and low dielectric loss, and good coating film uniformity.
Disclosure of Invention
The invention provides a polymer-based composite material for a capacitor and a preparation method thereof, aiming at the problems that the existing polymer-based composite material for the capacitor cannot have high thermal conductivity, high dielectric constant and low dielectric loss, and the coating film uniformity is poor. According to the polymer-based composite material, the auxiliary agent is added and the nano fiber with the core-shell structure is matched, so that the polymer-based composite material has high thermal conductivity, high dielectric constant and low dielectric loss and simultaneously has good coating uniformity.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a polymer matrix composite for a capacitor, the composite consisting of, by weight:
60-70 parts of polymer matrix;
20-30 parts of dopamine-coated tin-titanium oxide nano-fiber;
5-10 parts of an auxiliary agent;
wherein the auxiliary agent is a mixture of aminopropylsilanetriol and vinyl trimethoxy silane, the mass ratio of the aminopropylsilanetriol to the vinyl trimethoxy silane is (3-8): 1, for example, 3:1, 4:1, 5:1, 6:1 or 8:1, and the like, but the auxiliary agent is not limited to the numerical values listed, and other numerical values not listed in the numerical value range are also applicable.
The polymer matrix may be present in amounts of 60 parts, 62 parts, 64 parts, 66 parts, 68 parts, 70 parts, etc., but is not limited to the recited amounts, and other unrecited amounts within the recited range are equally applicable; the dopamine-coated tin-titanium oxide nanofiber can be 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, 30 parts, and the like by weight, but is not limited to the recited values, and other values in the range of the recited values are also applicable; the amount of the auxiliary may be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts by weight, but is not limited to the above-mentioned amounts, and other values not shown in the above-mentioned range are also applicable.
According to the invention, the auxiliary agent has a good effect achieved by the mass ratio of the mixture of aminopropyl silanetriol and vinyl trimethoxy silane being (3-8): 1, and the effect is optimal when the mass ratio of the mixture of aminopropyl silanetriol and vinyl trimethoxy silane being (3-5): 1. The auxiliary agent interacts with the dopamine-coated tin-titanium oxide nanofiber, so that the compatibility of the tin-titanium oxide nanofiber and a polymer matrix is improved, and the tin-titanium oxide nanofiber contributes to further improvement of the comprehensive performance of the material.
The following technical solutions are preferred technical solutions of the present invention, but not limited to the technical solutions provided by the present invention, and technical objects and advantageous effects of the present invention can be better achieved and achieved by the following technical solutions.
As a preferable technical scheme of the invention, the composite material comprises the following components in parts by weight:
63-66 parts of a polymer matrix;
25-28 parts of dopamine-coated tin-titanium oxide nano-fiber;
6-8 parts of an auxiliary agent.
Preferably, the composite material consists of the following components in parts by weight:
65 parts of a polymer matrix;
27 parts of dopamine-coated tin-titanium oxide nanofiber;
and 8 parts of an auxiliary agent.
According to a preferable technical scheme of the invention, the mass ratio of aminopropyl silanetriol to vinyl trimethoxy silane in the auxiliary agent is (3-5): 1.
Preferably, the composite material consists of the following components in parts by weight:
65 parts of a polymer matrix;
27 parts of dopamine-coated tin-titanium oxide nanofiber;
8 parts of an auxiliary agent;
wherein the mass ratio of aminopropyl silanetriol to vinyl trimethoxy silane in the auxiliary agent is (3-5): 1.
As a preferred technical scheme of the invention, the polymer matrix is polyimide and/or polyether sulfone.
As a preferred technical scheme of the invention, the method comprises the following steps:
(1) placing the dopamine-coated tin-titanium oxide nano-fiber and the auxiliary agent in a formula amount in an organic solvent, and performing ultrasonic dispersion to form a stable suspension;
(2) adding a polymer matrix with a formula amount into the suspension liquid in the step (1) and stirring until the polymer matrix is completely dissolved to obtain a mixed solution;
(3) and (3) casting the mixed solution obtained in the step (2) on a substrate, naturally leveling, evaporating the solvent, performing heat treatment and cooling to obtain the polymer matrix composite.
As a preferable technical solution of the present invention, the preparation method of the dopamine-coated tin titanium oxide nanofiber in step (1) includes the steps of:
(a) uniformly mixing a polymer precursor, a precursor solution of tin and a precursor solution of titanium to obtain an electrostatic spinning solution;
(b) performing electrostatic spinning on the electrostatic spinning solution obtained in the step (a) to obtain a polymer nanofiber membrane;
(c) carrying out heat treatment on the polymer nanofiber membrane obtained in the step (b) to obtain tin-titanium oxide nanofibers;
(d) dispersing the tin titanium oxide nano fiber obtained in the step (c) in a Tris-HCl buffer solution, adding dopamine after ultrasonic dispersion, stirring for 10-12 h at 30-40 ℃, and filtering, washing and drying to obtain the dopamine-coated tin titanium oxide nano fiber, wherein the stirring temperature can be 30 ℃, 32 ℃, 34 ℃, 36 ℃, 38 ℃ or 40 ℃, and the like, but is not limited to the enumerated values, and other unrecited values in the numerical range are also applicable; the stirring time may be 10 hours, 10.5 hours, 11 hours, 11.5 hours, 12 hours, etc., but is not limited to the recited values, and other values not recited within the range of the values are also applicable.
In the invention, the electrostatic spinning method is a conventional method in the field, and the operation parameters and the like are not described again.
In a preferred embodiment of the present invention, the polymer precursor in step (a) is polyimide.
Preferably, the precursor of tin in step (a) is tin tetrachloride and/or stannous chloride.
Preferably, the solvent in the precursor solution of tin in step (a) is absolute ethyl alcohol.
Preferably, the precursor of titanium of step (a) is tetrabutyl titanate.
Preferably, the solvent in the precursor solution of titanium in step (a) is absolute ethyl alcohol.
Preferably, the polymer concentration in the electrospinning solution of step (a) is 0.5g/mL to 0.8g/L, such as 0.5g/mL, 0.6g/mL, 0.7g/mL, or 0.8g/mL, but not limited to the recited values, and other non-recited values within the range are equally applicable; the concentration of the tin precursor is 1mol/mL to 1.5mol/mL, for example, 1mol/mL, 1.1mol/mL, 1.2mol/mL, 1.3mol/mL, 1.4mol/mL, or 1.5mol/mL, but is not limited to the values listed, and other values not listed in the numerical range are also applicable; the concentration of the precursor of titanium is 0.5mol/mL to 1mol/mL, for example, 0.5mol/mL, 0.6mol/mL, 0.7mol/mL, 0.8mol/mL, 0.9mol/mL, or 1mol/mL, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
As a preferred embodiment of the present invention, the heat treatment in the step (c) is carried out in an air atmosphere.
Preferably, the temperature of the heat treatment in step (c) is 300 ℃ to 400 ℃, such as 300 ℃, 320 ℃, 340 ℃, 360 ℃, 380 ℃ or 400 ℃, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the heat treatment time in step (c) is 2h to 4h, such as 2h, 2.5h, 3h, 3.5h or 4h, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the concentration of the tin-titanium oxide nanofibers in the Tris-HCl buffer solution in step (d) is 4mg/mL to 5mg/mL, such as 4mg/mL, 4.2mg/mL, 4.4mg/mL, 4.6mg/mL, 4.8mg/mL, or 5mg/mL, but is not limited to the values listed, and other values not listed in this range are equally applicable; the concentration of dopamine is 6mg/mL to 8mg/mL, for example, 6mg/mL, 6.5mg/mL, 7mg/mL, 7.5mg/mL, or 8mg/mL, but the concentration is not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the drying temperature in step (d) is from 60 ℃ to 80 ℃, such as 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃ and the like, but is not limited to the recited values, and other values not recited within this range are equally applicable.
As a preferable technical scheme of the invention, the organic solvent in the step (1) is N, N-dimethylformamide.
Preferably, the ultrasonic dispersion time in step (1) is 30min to 50min, such as 30min, 35min, 40min, 45min or 50min, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferred technical solution of the present invention, the evaporation solvent is: vacuum drying at 60-70 deg.C for 3-4 hr, wherein the drying temperature can be 60 deg.C, 62 deg.C, 64 deg.C, 66 deg.C, 68 deg.C or 70 deg.C, but is not limited to the recited values, and other values in the range are also applicable; the drying time may be 3 hours, 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours, 4 hours, etc., but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the heat treatment is: heating at 80-100 deg.C for 1-2 hr, wherein the heating temperature can be 80 deg.C, 83 deg.C, 85 deg.C, 87 deg.C, 90 deg.C, 93 deg.C, 95 deg.C, 97 deg.C or 100 deg.C, but is not limited to the recited values, and other values not recited in the range of the recited values are also applicable; the heating time may be 1 hour, 1.3 hours, 1.5 hours, 1.7 hours, 2 hours, etc., but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
In the invention, the temperature of the heat treatment is not required to be too high so as to prevent the dopamine-coated tin-titanium oxide nano-fiber from carbonizing.
Compared with the prior art, the invention has the following beneficial effects:
according to the polymer matrix composite material, the additive and the dopamine-coated tin-titanium oxide nanofiber are added, the interaction of the additive and the dopamine-coated tin-titanium oxide nanofiber is utilized, the compatibility of the tin-titanium oxide nanofiber and a polymer matrix is improved, the tin-titanium oxide nanofiber contributes to further improvement of the comprehensive performance of the material, the thermal conductivity of the polymer matrix composite material at room temperature can reach 2.2W/m.K, the dielectric constant at room temperature of 1kHz can reach about 50, the dielectric loss is only 0.005, and the polymer matrix composite material has good coating uniformity.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
The invention provides a polymer matrix composite material for a capacitor and a preparation method thereof, wherein the composite material comprises the following components in parts by weight:
60-70 parts of polymer matrix;
20-30 parts of dopamine-coated tin-titanium oxide nano-fiber;
5-10 parts of an auxiliary agent;
wherein the auxiliary agent is a mixture of aminopropyl silanetriol and vinyl trimethoxy silane, and the mass ratio of the aminopropyl silanetriol to the vinyl trimethoxy silane is (3-8) to 1.
The preparation method of the polymer matrix composite material comprises the following steps:
(1) placing the dopamine-coated tin-titanium oxide nano-fiber and the auxiliary agent in a formula amount in an organic solvent, and performing ultrasonic dispersion to form a stable suspension;
(2) adding a polymer matrix with a formula amount into the suspension liquid in the step (1) and stirring until the polymer matrix is completely dissolved to obtain a mixed solution;
(3) and (3) casting the mixed solution obtained in the step (2) on a substrate, naturally leveling, evaporating the solvent, performing heat treatment and cooling to obtain the polymer matrix composite.
The preparation method of the dopamine-coated tin-titanium oxide nanofiber comprises the following steps:
(a) uniformly mixing a polymer precursor, a precursor solution of tin and a precursor solution of titanium to obtain an electrostatic spinning solution;
(b) performing electrostatic spinning on the electrostatic spinning solution obtained in the step (a) to obtain a polymer nanofiber membrane;
(c) carrying out heat treatment on the polymer nanofiber membrane obtained in the step (b) to obtain tin-titanium oxide nanofibers;
(d) and (c) dispersing the tin-titanium oxide nano-fibers obtained in the step (c) in a Tris-HCl buffer solution, adding dopamine after ultrasonic dispersion, stirring for 10-12 h at 30-40 ℃, filtering, washing and drying to obtain the dopamine-coated tin-titanium oxide nano-fibers.
The following are typical but non-limiting examples of the invention:
example 1:
the embodiment provides a preparation method of a dopamine-coated tin titanium oxide nanofiber, which comprises the following steps:
(a) uniformly mixing a polymer precursor polyimide, an absolute ethyl alcohol solution of tin tetrachloride and an absolute ethyl alcohol solution of tetrabutyl titanate to obtain an electrostatic spinning solution, wherein the concentration of a polymer in the solution is 0.6g/mL, the concentration of tin tetrachloride is 1.3mol/mL, and the concentration of tetrabutyl titanate is 0.7 mol/mL;
(b) performing electrostatic spinning on the electrostatic spinning solution obtained in the step (a) to obtain a polymer nanofiber membrane;
(c) carrying out heat treatment on the polymer nanofiber membrane obtained in the step (b) at 340-360 ℃ for 3h to obtain tin-titanium oxide nanofibers;
(d) and (c) dispersing the tin-titanium oxide nano fibers obtained in the step (c) in a Tris-HCl buffer solution, adding dopamine after ultrasonic dispersion to enable the concentration of the tin-titanium oxide nano fibers in the solution to be 4.6mg/mL and the concentration of the dopamine to be 7mg/mL, stirring for 10-12 h at the temperature of 30-40 ℃, filtering, washing and drying to obtain the dopamine-coated tin-titanium oxide nano fibers.
Example 2:
this example provides a method for preparing dopamine coated tin titanium oxide nanofibers, with reference to the steps of example 1, except that:
the concentration of the polymer in the solution in the step (a) is 0.52g/mL, the concentration of tin tetrachloride is 1.1mol/mL, and the concentration of tetrabutyl titanate is 0.53 mol/mL;
the heat treatment temperature of the step (c) is 300-320 ℃, and the time is 4 hours;
the concentration of the tin-titanium oxide nano-fiber in the solution in the step (d) is 4.1mg/mL, and the concentration of the dopamine is 6.2 mg/mL.
Example 3:
this example provides a method for preparing dopamine coated tin titanium oxide nanofibers, with reference to the steps of example 1, except that:
the concentration of the polymer in the solution in the step (a) is 0.78g/mL, the concentration of tin tetrachloride is 1.5mol/mL, and the concentration of tetrabutyl titanate is 0.98 mol/mL;
the heat treatment temperature of the step (c) is 380-400 ℃, and the time is 2 h;
the concentration of the tin-titanium oxide nano-fiber in the solution in the step (d) is 5mg/mL, and the concentration of the dopamine is 7.9 mg/mL.
Example 4:
the embodiment provides a polymer matrix composite material for a capacitor and a preparation method thereof, wherein the composite material comprises the following components in parts by weight:
65 parts of a polymer matrix;
27 parts of dopamine-coated tin-titanium oxide nanofiber;
8 parts of an auxiliary agent;
wherein the mass ratio of aminopropyl silanetriol to vinyl trimethoxy silane in the auxiliary agent is 4: 1.
The preparation method of the polymer matrix composite material comprises the following steps:
(1) placing the dopamine-coated tin titanium oxide nano-fiber prepared in the embodiment 1 and the auxiliary agent in the formula amount into N, N-dimethylformamide, and performing ultrasonic dispersion for 40min to form a stable suspension;
(2) adding a polymer matrix with a formula amount into the suspension liquid in the step (1) and stirring until the polymer matrix is completely dissolved to obtain a mixed solution;
(3) and (3) casting the mixed solution obtained in the step (2) on a substrate, naturally leveling, vacuum-drying at 60-70 ℃ for 3-4 h, heating at 90 ℃ for 1-2 h, and cooling to obtain the polymer-based composite material.
Example 5:
the embodiment provides a polymer matrix composite material for a capacitor and a preparation method thereof, wherein the composite material comprises the following components in parts by weight:
63 parts of a polymer matrix;
25 parts of dopamine-coated tin-titanium oxide nanofiber;
6 parts of an auxiliary agent;
wherein the mass ratio of aminopropyl silanetriol to vinyl trimethoxy silane in the auxiliary agent is 3: 1.
The preparation of the polymer matrix composite was made with reference to the preparation in example 4, with the only difference that:
the dopamine-coated tin-titanium oxide nanofiber prepared in the step (1) is prepared in example 2, and is subjected to ultrasonic dispersion for 30 min; the heat treatment temperature in the step (3) is 80 ℃.
Example 6:
the embodiment provides a polymer matrix composite material for a capacitor and a preparation method thereof, wherein the composite material comprises the following components in parts by weight:
66 parts of a polymer matrix;
28 parts of dopamine-coated tin-titanium oxide nano-fibers;
7 parts of an auxiliary agent;
wherein the mass ratio of aminopropyl silanetriol to vinyl trimethoxy silane in the auxiliary agent is 5: 1.
The preparation of the polymer matrix composite was made with reference to the preparation in example 4, with the only difference that:
the dopamine-coated tin-titanium oxide nanofiber prepared in the step (1) is prepared in example 2, and is subjected to ultrasonic dispersion for 50 min; the heat treatment temperature in the step (3) is 100 ℃.
Example 7:
the embodiment provides a polymer matrix composite material for a capacitor and a preparation method thereof, wherein the composite material comprises the following components in parts by weight:
61 parts of a polymer matrix;
22 parts of dopamine-coated tin-titanium oxide nano-fiber;
5 parts of an auxiliary agent;
wherein the mass ratio of aminopropyl silanetriol to vinyl trimethoxy silane in the auxiliary agent is 7: 1.
The preparation method of the polymer matrix composite material refers to the preparation method in example 4.
Example 8:
the embodiment provides a polymer matrix composite material for a capacitor and a preparation method thereof, wherein the composite material comprises the following components in parts by weight:
70 parts of a polymer matrix;
29 parts of dopamine-coated tin-titanium oxide nanofiber;
9 parts of an auxiliary agent;
wherein the mass ratio of aminopropyl silanetriol to vinyl trimethoxy silane in the auxiliary agent is 8: 1.
The preparation method of the polymer matrix composite material refers to the preparation method in example 4.
Comparative example 1:
this comparative example provides a polymer-based composite material for capacitors having the same composition and amount ratio as those of example 4 except that no additive was added, and a method for preparing the same.
The preparation method refers to the method in example 4.
Comparative example 2:
this comparative example provides a polymer matrix composite for capacitors having the same composition and amount ratios as in example 4, except that aminopropylsilanetriol and vinyltrimethoxysilane were used in a mass ratio of 1:1 as an adjuvant, and a method for preparing the same.
The preparation method refers to the method in example 4.
Comparative example 3:
this comparative example provides a polymer matrix composite for capacitors having the same composition and amount ratios as in example 4, except that aminopropylsilanetriol and vinyltrimethoxysilane were present in the adjuvant at a mass ratio of 10:1, and a method for preparing the same.
The preparation method refers to the method in example 4.
Comparative example 4:
the present comparative example provides a polymer-based composite material for capacitors having the same composition and dosage ratio as those of example 4, except that the tin-titanium oxide nanofibers in the dopamine-coated tin-titanium oxide nanofibers were replaced with ceramic fibers, and a method for preparing the same.
The preparation method of the ceramic fiber in the dopamine-coated ceramic fiber refers to the preparation method in CN 104893187A, and the dopamine is coated by adopting the method disclosed by the application after the ceramic fiber is prepared.
The preparation method of the polymer matrix composite material refers to the method in example 4.
Comparative example 5:
this comparative example provides a polymer-based composite material for capacitors having the same composition and amount ratio as those of example 4, and a method for preparing the same.
The preparation is as in example 4, with the only difference that: the heat treatment temperature in the step (3) is higher and is 300 ℃.
The polymer-based composites prepared in examples 4 to 8 and comparative examples 1 to 5 were subjected to the performance test, and the test results are shown in table 1.
Table 1: performance test tables of examples 4 to 8 and comparative examples 1 to 5
It can be seen from the above examples and comparative examples that the polymer-based composite material of the present invention, by adding the additive and the dopamine-coated tin-titanium oxide nanofiber, improves the compatibility of the tin-titanium oxide nanofiber with the polymer matrix by utilizing the interaction between the additive and the dopamine-coated tin-titanium oxide nanofiber, and the tin-titanium oxide nanofiber contributes to further improvement of the comprehensive properties of the material, so that the thermal conductivity of the polymer-based composite material at room temperature can reach 2.2W/m.k, the dielectric constant at room temperature of 1kHz can reach about 50, the dielectric loss is only 0.005, and the polymer-based composite material has good coating uniformity.
The applicant indicates that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed application, that is, the present invention is not meant to be necessarily dependent on the above detailed method. It will be apparent to those skilled in the art that any modifications to the invention, equivalent alterations to the starting materials for the products of the invention, and additions of auxiliary components, specific operating conditions and modes of choice, etc., are deemed to be within the scope and disclosure of the invention.
Claims (22)
1. A polymer matrix composite material for a capacitor, characterized in that the composite material consists of the following components in parts by weight:
60-70 parts of polymer matrix;
20-30 parts of dopamine-coated tin-titanium oxide nano-fiber;
5-10 parts of an auxiliary agent;
wherein the auxiliary agent is a mixture of aminopropyl silanetriol and vinyl trimethoxy silane, and the mass ratio of the aminopropyl silanetriol to the vinyl trimethoxy silane is (3-8) to 1.
2. The polymer-matrix composite according to claim 1, wherein the composite consists of, in parts by weight:
63-66 parts of a polymer matrix;
25-28 parts of dopamine-coated tin-titanium oxide nano-fiber;
6-8 parts of an auxiliary agent.
3. The polymer-matrix composite according to claim 1, wherein the composite consists of, in parts by weight:
65 parts of a polymer matrix;
27 parts of dopamine-coated tin-titanium oxide nanofiber;
and 8 parts of an auxiliary agent.
4. The polymer-based composite material according to claim 1 or 2, wherein the mass ratio of aminopropylsilanetriol to vinyltrimethoxysilane in the auxiliary is (3-5): 1.
5. The polymer-matrix composite according to claim 1, wherein the composite consists of, in parts by weight:
65 parts of a polymer matrix;
27 parts of dopamine-coated tin-titanium oxide nanofiber;
8 parts of an auxiliary agent;
wherein the mass ratio of aminopropyl silanetriol to vinyl trimethoxy silane in the auxiliary agent is (3-5): 1.
6. The polymer-matrix composite according to claim 1, wherein the polymer matrix is a polyimide and/or polyethersulfone.
7. A method for preparing a polymer matrix composite according to any one of claims 1 to 6, characterized in that it comprises the following steps:
(1) placing the dopamine-coated tin-titanium oxide nano-fiber and the auxiliary agent in a formula amount in an organic solvent, and performing ultrasonic dispersion to form a stable suspension;
(2) adding a polymer matrix with a formula amount into the suspension liquid in the step (1) and stirring until the polymer matrix is completely dissolved to obtain a mixed solution;
(3) casting the mixed solution obtained in the step (2) on a substrate, naturally leveling, evaporating a solvent, performing heat treatment and cooling to obtain a polymer matrix composite;
the heat treatment in the step (3) is as follows: heating for 1-2 h at 80-100 ℃.
8. The method according to claim 7, wherein the dopamine-coated tin-titanium oxide nanofiber prepared in step (1) is prepared by a method comprising the following steps:
(a) uniformly mixing a polymer precursor, a precursor solution of tin and a precursor solution of titanium to obtain an electrostatic spinning solution;
(b) performing electrostatic spinning on the electrostatic spinning solution obtained in the step (a) to obtain a polymer nanofiber membrane;
(c) carrying out heat treatment on the polymer nanofiber membrane obtained in the step (b) to obtain tin-titanium oxide nanofibers;
(d) and (c) dispersing the tin-titanium oxide nano-fibers obtained in the step (c) in a Tris-HCl buffer solution, adding dopamine after ultrasonic dispersion, stirring for 10-12 h at 30-40 ℃, filtering, washing and drying to obtain the dopamine-coated tin-titanium oxide nano-fibers.
9. The method of claim 8, wherein the polymer precursor of step (a) is a polyimide.
10. The method according to claim 8, wherein the precursor of tin in step (a) is tin tetrachloride and/or stannous chloride.
11. The method according to claim 8, wherein the solvent in the precursor solution of tin in step (a) is absolute ethanol.
12. The method according to claim 8, wherein the precursor of titanium in the step (a) is tetrabutyl titanate.
13. The method according to claim 8, wherein the solvent in the precursor solution of titanium in step (a) is absolute ethanol.
14. The method according to claim 8, wherein the polymer concentration in the electrospinning solution of step (a) is 0.5 to 0.8g/mL, the tin precursor concentration is 1 to 1.5mol/mL, and the titanium precursor concentration is 0.5 to 1 mol/mL.
15. The method according to claim 8, wherein the heat treatment in the step (c) is performed in an air atmosphere.
16. The method of claim 8, wherein the temperature of the heat treatment in the step (c) is 300 to 400 ℃.
17. The method of claim 8, wherein the heat treatment time in step (c) is 2 to 4 hours.
18. The method according to claim 8, wherein the concentration of the tin-titanium oxide nanofibers in the Tris-HCl buffer solution in step (d) is 4mg/mL to 5mg/mL, and the concentration of the dopamine is 6mg/mL to 8 mg/mL.
19. The method according to claim 8, wherein the drying temperature in the step (d) is 60 to 80 ℃.
20. The method according to claim 7, wherein the organic solvent used in the step (1) is N, N-dimethylformamide.
21. The method according to claim 7, wherein the time for the ultrasonic dispersion in the step (1) is 30 to 50 min.
22. The method of claim 7, wherein the evaporative solvent is: vacuum drying at 60-70 deg.c for 3-4 hr.
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| CN104194020A (en) * | 2014-08-03 | 2014-12-10 | 北京化工大学 | Method for preparing flexible inorganic/polymer composite film with high dielectric property |
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