CN116041978A - LCP material with high dielectric constant and low dielectric loss and preparation method thereof - Google Patents
LCP material with high dielectric constant and low dielectric loss and preparation method thereof Download PDFInfo
- Publication number
- CN116041978A CN116041978A CN202211713501.5A CN202211713501A CN116041978A CN 116041978 A CN116041978 A CN 116041978A CN 202211713501 A CN202211713501 A CN 202211713501A CN 116041978 A CN116041978 A CN 116041978A
- Authority
- CN
- China
- Prior art keywords
- barium titanate
- modified
- modified barium
- nanofiber
- dielectric constant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 10
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims abstract description 147
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 87
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 83
- 229920000106 Liquid crystal polymer Polymers 0.000 claims abstract description 73
- 239000002121 nanofiber Substances 0.000 claims abstract description 65
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 31
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 26
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 18
- 230000004048 modification Effects 0.000 claims abstract description 18
- 238000012986 modification Methods 0.000 claims abstract description 18
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 13
- 239000004976 Lyotropic liquid crystal Substances 0.000 claims abstract description 11
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical class [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 39
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 12
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000002861 polymer material Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- 239000000945 filler Substances 0.000 description 21
- 239000000203 mixture Substances 0.000 description 20
- 238000001035 drying Methods 0.000 description 19
- 238000001914 filtration Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 238000010992 reflux Methods 0.000 description 10
- 239000011521 glass Substances 0.000 description 8
- 238000005266 casting Methods 0.000 description 7
- 230000002535 lyotropic effect Effects 0.000 description 7
- 125000003277 amino group Chemical group 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical class [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/08—Oxygen-containing compounds
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- 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
-
- 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
- C08K2201/016—Additives defined by their aspect ratio
Abstract
The application relates to a LCP material with high dielectric constant and low dielectric loss and a preparation method thereof, belonging to the technical field of high polymer materials; the method comprises the following steps: carrying out surface hydroxyl modification on the barium titanate nanofiber to obtain first modified barium titanate; amino modification is carried out on the first modified barium titanate to obtain second modified barium carbonate; mixing the first modified barium titanate and the second modified barium titanate in methylene dichloride to obtain a mixed solution; mixing the mixed solution, a silane coupling agent and a lyotropic liquid crystal polymer to obtain an LCP material; through carrying out hydroxyl and amino modification on the barium titanate nanofiber and finally mixing the barium titanate nanofiber with the liquid crystal polymer, the effect of improving the combination property of the barium titanate nanofiber and the liquid crystal polymer is achieved while the polar group is introduced, and the purpose of improving the dielectric constant of the liquid crystal polymer is achieved by utilizing the advantage that the barium titanate nanofiber has a higher dielectric constant.
Description
Technical Field
The application relates to the technical field of high polymer materials, in particular to a LCP material with high dielectric constant and low dielectric loss and a preparation method thereof.
Background
LCP is an intermediate state polymer between solid crystals and liquid, and its molecular arrangement is not three-dimensionally ordered as in the solid crystals, but is not disordered as in the liquid, but has a certain order. It is a novel polymer material, and generally exhibits liquid crystallinity in a molten state. Because of its excellent dielectric properties, heat resistance and molding processability, it is widely used in the fields of electronics, electricity, optical fibers, automobiles, aerospace and the like.
The dielectric constant of LCP is lower, generally 3-5, and can not meet the application requirements of energy storage electronic devices such as high-power high-temperature capacitors. There are two ways to increase the dielectric constant of the polymer, one is to modify the material structure during the polymer synthesis process, and introduce a strong polar group, where the polar group has hydroxyl, carboxyl, amino, nitrile, etc.; the method for improving the dielectric constant of the polymer material by introducing the polar groups into the polymer structure has the advantages of complex implementation process, difficult process, higher cost and longer period, and the prepared modified polymer has limited space for improving the dielectric constant. Another is to add a high dielectric constant filler comprising a metal or metal oxide and a conductive graphene filler. The addition of the filler with high dielectric constant into the polymer can effectively improve the dielectric constant of the polymer material, but with the increase of the filler content with high dielectric constant, the dielectric loss is improved on one hand, and the molding processability of the material is affected on the other hand.
Disclosure of Invention
The application provides an LCP material with high dielectric constant and low dielectric loss and a preparation method thereof, so as to solve the problem of lower dielectric constant of the existing LCP.
In a first aspect, the present application provides a method of preparing a high dielectric constant low dielectric loss LCP material, the method comprising:
carrying out surface hydroxyl modification on the barium titanate nanofiber to obtain first modified barium titanate;
amino modification is carried out on the first modified barium titanate to obtain second modified barium carbonate;
mixing the first modified barium titanate and the second modified barium titanate in methylene dichloride to obtain a mixed solution;
and mixing the mixed solution, the silane coupling agent and the lyotropic liquid crystal polymer to obtain the LCP material.
As an alternative embodiment, the surface hydroxyl modification of the barium titanate nanofiber to obtain the first modified barium titanate specifically includes:
and reacting the barium titanate nanofiber with hydrogen peroxide to modify the surface hydroxyl of the barium titanate nanofiber, so as to obtain the first modified barium titanate.
As an alternative embodiment, the diameter of the barium titanate nanofiber is 50-200nm; and/or
The length-diameter ratio of the barium titanate nanofiber is 5-50.
As an alternative embodiment, the mass concentration of the hydrogen peroxide is 20% -50%.
As an optional implementation manner, the usage relation of the barium titanate nanofiber and the hydrogen peroxide is as follows: 3-6g of barium titanate nanofiber is added into every 100ml of hydrogen peroxide solution.
As an alternative embodiment, the amino modification of the first modified barium titanate to obtain a second modified barium carbonate specifically includes:
dispersing the first modified barium titanate in toluene, then reacting with 3-aminopropyl trimethoxy silane, and performing amino modification on the first modified barium titanate to obtain second modified barium carbonate.
As an alternative embodiment, the usage relation of the first modified barium titanate and toluene satisfies: adding 4-10g of first modified barium titanate to 100ml of toluene; and/or
The mass ratio of the first modified barium titanate to the 3-aminopropyl trimethoxysilane is (1-2): 1.
as an alternative embodiment, in the mixed solution, the mass ratio of the first modified barium titanate to the second modified barium titanate is (1-5): 1.
as an alternative embodiment, the usage relation of the dichloromethane and the lyotropic liquid crystal polymer is as follows: adding 10-15g of the lyotropic liquid crystal polymer into every 100ml of dichloromethane; and/or
The modified barium titanate nanofiber comprises first modified barium titanate and second barium titanate, and the dosage relation of the methylene dichloride and the modified barium titanate nanofiber satisfies the following conditions: adding 3-9g of modified barium titanate nanofiber into every 100ml of dichloromethane; and/or
The dosage relation of the dichloromethane and the silane coupling agent is as follows: 0.1-1.5g of silane coupling agent is added per 100ml of dichloromethane.
In a second aspect, the present application provides a high dielectric constant low dielectric loss LCP material made using the method of making a high dielectric constant low dielectric loss LCP material of the first aspect.
Compared with the prior art, the technical scheme provided by the embodiment of the application has the following advantages:
according to the method provided by the embodiment of the application, through modifying the hydroxyl and amino groups of the barium titanate nanofiber and finally mixing the barium titanate nanofiber with the liquid crystal polymer, the effect of improving the combination property of the barium titanate nanofiber and the liquid crystal polymer is achieved while the polar group is introduced, and the purpose of improving the dielectric constant of the liquid crystal polymer is achieved by utilizing the advantage that the barium titanate nanofiber has a higher dielectric constant.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the application and together with the description, serve to explain the principles of the application.
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required to be used in the description of the embodiments or the prior art will be briefly described below, and it will be obvious to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
Fig. 1 is a flowchart of a method provided in an embodiment of the present application.
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present application based on the embodiments herein.
Unless specifically indicated otherwise, the various raw materials, reagents, instruments, equipment, and the like used in this application are commercially available or may be prepared by existing methods.
As shown in fig. 1, an embodiment of the present application provides a method for preparing an LCP material with high dielectric constant and low dielectric loss, the method including:
s1, carrying out surface hydroxyl modification on barium titanate nanofiber to obtain first modified barium titanate;
in some embodiments, the surface hydroxyl modification of the barium titanate nanofiber to obtain the first modified barium titanate specifically includes:
and reacting the barium titanate nanofiber with hydrogen peroxide to modify the surface hydroxyl of the barium titanate nanofiber, so as to obtain the first modified barium titanate.
In some embodiments, the barium titanate nanofibers have a diameter of 50-200nm; the length-diameter ratio of the barium titanate nanofiber is 5-50. The mass concentration of the hydrogen peroxide is 20% -50%. The dosage relation of the barium titanate nanofiber and the hydrogen peroxide satisfies the following conditions: 3-6g of barium titanate nanofiber is added into every 100ml of hydrogen peroxide solution.
Specifically, in this embodiment, a certain amount of barium titanate nanofibers with different diameters and length-diameter ratios are added into a certain mass portion of hydrogen peroxide aqueous solution, and reflux is performed for 5 hours at 110 ℃. And then the barium titanate hydrogen peroxide solution after 5 hours of reflux is centrifuged at a high speed by a centrifuge, and is filtered after being centrifuged for 5-20min at the rotating speed of 10000-20000 rpm/min. And then drying the barium titanate modified filler obtained by filtering in an oven at 80 ℃ for 12 hours to obtain the first modified barium titanate.
S2, performing amino modification on the first modified barium titanate to obtain second modified barium carbonate;
in some embodiments, the first modified barium titanate is amino-modified to obtain a second modified barium carbonate, specifically including:
dispersing the first modified barium titanate in toluene, then reacting with 3-aminopropyl trimethoxy silane, and performing amino modification on the first modified barium titanate to obtain second modified barium carbonate.
In some embodiments, the usage relationship of the first modified barium titanate and toluene satisfies: adding 4-10g of first modified barium titanate to 100ml of toluene; the mass ratio of the first modified barium titanate to the 3-aminopropyl trimethoxysilane is (1-2): 1.
specifically, in this embodiment, a certain amount of barium titanate nanofiber with modified surface hydroxyl (namely first modified barium titanate) is added into a proper amount of toluene and dispersed for 20min by ultrasound, then a proper amount of 3-aminopropyl trimethoxysilane is added for continuing to carry out ultrasound for 10min, and the mixture is heated to 90 ℃ in nitrogen atmosphere and then stirred for 12h under heat preservation. Cooling to room temperature after the reaction is finished, centrifuging the mixed solution, centrifuging for 5-20min at the rotating speed of 10000-20000rpm/min, and filtering. And then drying the barium titanate modified filler obtained by filtering in an oven at 80 ℃ for 12 hours to obtain second modified barium carbonate.
S3, mixing the first modified barium titanate and the second modified barium titanate in methylene dichloride to obtain a mixed solution;
in some embodiments, the mass ratio of the first modified barium titanate to the second modified barium titanate in the mixed solution is (1-5): 1.
specifically, in this example, a certain amount of fibrous nano barium titanate with surface hydroxyl/amino modified is added into a dichloromethane solution, and dispersed for 15min by ultrasonic to obtain a mixed solution.
S4, mixing the mixed solution, the silane coupling agent and the lyotropic liquid crystal polymer to obtain the LCP material.
In some embodiments, the amount of dichloromethane and the lyotropic liquid crystal polymer is in the relationship: adding 10-15g of the lyotropic liquid crystal polymer into every 100ml of dichloromethane; the modified barium titanate nanofiber comprises first modified barium titanate and second barium titanate, and the dosage relation of the methylene dichloride and the modified barium titanate nanofiber satisfies the following conditions: adding 3-9g of modified barium titanate nanofiber into every 100ml of dichloromethane; the dosage relation of the dichloromethane and the silane coupling agent is as follows: 0.1-1.5g of silane coupling agent is added per 100ml of dichloromethane.
Specifically, in this example, the mixed solution was transferred to a beaker and placed on a heating table, and an appropriate amount of silane coupling agent KH550 and Lyotropic Liquid Crystal Polymer (LLCP) was added to the beaker and magnetically stirred at 30 ℃ for 2 hours. Finally, the mixture was cast on a clean glass plate and dried in an oven at 60 ℃ for 6h.
Based on one general inventive concept, embodiments of the present application also provide a high dielectric constant low dielectric loss LCP material manufactured by the method for manufacturing a high dielectric constant low dielectric loss LCP material of the first aspect.
The LCP material is prepared based on the above-mentioned method for preparing the LCP material with high dielectric constant and low dielectric loss, and specific steps of the method for preparing the LCP material with high dielectric constant and low dielectric loss can refer to the above-mentioned embodiments, and since the LCP material adopts some or all of the technical solutions of the above-mentioned embodiments, at least the LCP material has all the beneficial effects brought by the technical solutions of the above-mentioned embodiments, and will not be described in detail herein.
The present application is further illustrated below in conjunction with specific examples. It should be understood that these examples are illustrative only of the present application and are not intended to limit the scope of the present application. The experimental procedures, which are not specified in the following examples, are generally determined according to national standards. If the corresponding national standard does not exist, the method is carried out according to the general international standard, the conventional condition or the condition recommended by the manufacturer.
Example 1
A preparation method of a LCP material with high dielectric constant and low dielectric loss comprises the following steps:
1. firstly, 5g of barium titanate nanofiber with the diameter of 200nm and the length-diameter ratio of 10 is added into 100ml of 30% hydrogen peroxide aqueous solution in parts by mass, and the mixture is refluxed for 5 hours at 110 ℃. And then the barium titanate hydrogen peroxide solution after 5 hours of reflux is centrifuged at a high speed by a centrifuge, and is filtered after being centrifuged for 15 minutes at 10000 rpm/min. And then drying the barium titanate modified filler obtained by filtering in an oven at 80 ℃ for 12 hours to obtain the barium titanate nanofiber with the surface modified by hydroxyl.
2. Adding 4g of barium titanate nanofiber with surface hydroxyl modified into 100ml of toluene, performing ultrasonic dispersion for 20min, adding 2g of 3-aminopropyl trimethoxysilane, continuing ultrasonic treatment for 10min, heating to 90 ℃ in nitrogen atmosphere, and performing heat preservation and stirring reaction for 12h. After the reaction, cooling to room temperature, centrifuging the mixed solution, centrifuging at 10000rpm/min for 10min, and filtering. And then drying the barium titanate modified filler obtained by filtering in an oven at 80 ℃ for 12 hours to obtain the barium titanate nanofiber with the modified surface amino group.
3. 4g of surface-modified fibrous nano barium titanate (hydroxyl-modified 0.8g, amino-modified 3.2 g) was added to 100ml of methylene chloride solution and dispersed ultrasonically for 15min. Then, it was transferred to a beaker and placed on a heating table, and 0.3g of a silane coupling agent KH550 and 10g of a Lyotropic Liquid Crystalline Polymer (LLCP) were added to the beaker and magnetically stirred at 30℃for 2 hours. Finally, casting the mixture on a clean glass plate, and drying the mixture in a 60 ℃ oven for 6 hours to obtain the LCP material.
Example 2
A preparation method of a LCP material with high dielectric constant and low dielectric loss comprises the following steps:
1. firstly, adding 9g of barium titanate nanofiber with the diameter of 50nm and the length-diameter ratio of 30 into 200ml of 35% hydrogen peroxide aqueous solution in parts by mass, and refluxing for 5 hours at 110 ℃. And then the barium titanate hydrogen peroxide solution after 5 hours of reflux is centrifuged at a high speed by a centrifuge, and is filtered after being centrifuged for 15 minutes at a rotating speed of 15000 rpm/min. And then drying the barium titanate modified filler obtained by filtering in an oven at 80 ℃ for 12 hours to obtain the barium titanate nanofiber with the surface modified by hydroxyl.
2. 7g of barium titanate nanofiber with surface hydroxyl modified is added into 100ml of toluene and dispersed for 20min by ultrasonic, 4g of 3-aminopropyl trimethoxysilane is added for continuous ultrasonic treatment for 10min, and the mixture is heated to 90 ℃ in nitrogen atmosphere and then stirred for reaction for 12h under heat preservation. After the reaction, cooling to room temperature, centrifuging the mixed solution at 15000rpm/min for 10min, and filtering. And then drying the barium titanate modified filler obtained by filtering in an oven at 80 ℃ for 12 hours to obtain the barium titanate nanofiber with the modified surface amino group.
3. 8g of surface-modified fibrous nano barium titanate (hydroxyl-modified 1.6g, amino-modified 6.4 g) was added to 200ml of methylene chloride solution and dispersed ultrasonically for 15min. Then, it was transferred to a beaker and placed on a heating table, and 0.5g of a silane coupling agent KH550 and 20g of a Lyotropic Liquid Crystalline Polymer (LLCP) were added to the beaker and magnetically stirred at 30℃for 2 hours. Finally, casting the mixture on a clean glass plate, and drying the mixture in a 60 ℃ oven for 6 hours to obtain the LCP material.
Example 3
A preparation method of a LCP material with high dielectric constant and low dielectric loss comprises the following steps:
1. firstly, adding 9g of barium titanate nanofiber with the diameter of 50nm and the length-diameter ratio of 40 into 200ml of 45% hydrogen peroxide aqueous solution in parts by mass, and refluxing for 5 hours at 110 ℃. And then the barium titanate hydrogen peroxide solution after 5 hours of reflux is centrifuged at a high speed by a centrifuge, and is filtered after being centrifuged for 20 minutes at a rotating speed of 15000 rpm/min. And then drying the barium titanate modified filler obtained by filtering in an oven at 80 ℃ for 12 hours to obtain the barium titanate nanofiber with the surface modified by hydroxyl.
2. 7g of barium titanate nanofiber with surface hydroxyl modified is added into 200ml of toluene and dispersed for 20min by ultrasonic, 6g of 3-aminopropyl trimethoxy silane is added for continuous ultrasonic treatment for 10min, and the mixture is heated to 90 ℃ in nitrogen atmosphere and then stirred for reaction for 12h under heat preservation. After the reaction, cooling to room temperature, centrifuging the mixed solution at 15000rpm/min for 20min, and filtering. And then drying the barium titanate modified filler obtained by filtering in an oven at 80 ℃ for 12 hours to obtain the barium titanate nanofiber with the modified surface amino group.
3. 8g of surface-modified fibrous nano barium titanate (hydroxyl-modified 1.6g, amino-modified 6.4 g) was added to 200ml of methylene chloride solution and dispersed ultrasonically for 15min. Then, it was transferred to a beaker and placed on a heating table, and 0.5g of a silane coupling agent KH550 and 20g of a Lyotropic Liquid Crystalline Polymer (LLCP) were added to the beaker and magnetically stirred at 30℃for 2 hours. Finally, casting the mixture on a clean glass plate, and drying the mixture in a 60 ℃ oven for 6 hours to obtain the LCP material.
Example 4
A preparation method of a LCP material with high dielectric constant and low dielectric loss comprises the following steps:
1. firstly, adding 8g of barium titanate nanofiber with the diameter of 50nm and the length-diameter ratio of 40 into 200ml of 45% hydrogen peroxide aqueous solution in parts by mass, and refluxing for 5 hours at 110 ℃. And then the barium titanate hydrogen peroxide solution after 5 hours of reflux is centrifuged at a high speed by a centrifuge, and is filtered after being centrifuged for 20 minutes at a rotating speed of 15000 rpm/min. And then drying the barium titanate modified filler obtained by filtering in an oven at 80 ℃ for 12 hours to obtain the barium titanate nanofiber with the surface modified by hydroxyl.
2. Adding 4g of barium titanate nanofiber with surface hydroxyl modified into 100ml of toluene, performing ultrasonic dispersion for 20min, adding 3g of 3-aminopropyl trimethoxysilane, continuing ultrasonic treatment for 10min, heating to 90 ℃ in nitrogen atmosphere, and performing heat preservation and stirring reaction for 12h. After the reaction, cooling to room temperature, centrifuging the mixed solution at 15000rpm/min for 20min, and filtering. And then drying the barium titanate modified filler obtained by filtering in an oven at 80 ℃ for 12 hours to obtain the barium titanate nanofiber with the modified surface amino group.
3. 8g of surface-modified fibrous nano barium titanate (hydroxyl-modified 4g, amino-modified 4 g) was added to 200ml of methylene chloride solution and dispersed ultrasonically for 15min. Then, it was transferred to a beaker and placed on a heating table, and 0.8g of a silane coupling agent KH550 and 25g of a Lyotropic Liquid Crystalline Polymer (LLCP) were added to the beaker and magnetically stirred at 30℃for 2 hours. Finally, casting the mixture on a clean glass plate, and drying the mixture in a 60 ℃ oven for 6 hours to obtain the LCP material.
Example 5
A preparation method of a LCP material with high dielectric constant and low dielectric loss comprises the following steps:
1. 15g of barium titanate nanofiber with the diameter of 50nm and the length-diameter ratio of 40 is added into 300ml of 45% hydrogen peroxide aqueous solution in parts by mass, and the mixture is refluxed for 5 hours at 110 ℃. And then the barium titanate hydrogen peroxide solution after 5 hours of reflux is centrifuged at a high speed by a centrifuge, and is filtered after being centrifuged for 20 minutes at a rotating speed of 15000 rpm/min. And then drying the barium titanate modified filler obtained by filtering in an oven at 80 ℃ for 12 hours to obtain the barium titanate nanofiber with the surface modified by hydroxyl.
2. Adding 6g of barium titanate nanofiber with surface hydroxyl modified into 100ml of toluene, performing ultrasonic dispersion for 20min, adding 4g of 3-aminopropyl trimethoxysilane, continuing ultrasonic treatment for 10min, heating to 90 ℃ in nitrogen atmosphere, and performing heat preservation and stirring reaction for 12h. After the reaction, cooling to room temperature, centrifuging the mixed solution at 15000rpm/min for 20min, and filtering. And then drying the barium titanate modified filler obtained by filtering in an oven at 80 ℃ for 12 hours to obtain the barium titanate nanofiber with the modified surface amino group.
3. 12g of surface-modified fibrous nano barium titanate (hydroxyl-modified 8g, amino-modified 4 g) was added to 200ml of dichloromethane solution and dispersed ultrasonically for 15min. Then, it was transferred to a beaker and placed on a heating table, and 1.5g of a silane coupling agent KH550 and 25g of a Lyotropic Liquid Crystalline Polymer (LLCP) were added to the beaker and magnetically stirred at 30℃for 2 hours. Finally, casting the mixture on a clean glass plate, and drying the mixture in a 60 ℃ oven for 6 hours to obtain the LCP material.
Comparative example 1
A method of preparing an LCP material, the method comprising:
15g of a commercial barium titanate particulate filler was added to 200ml of a methylene chloride solution and dispersed ultrasonically for 15min. Then, it was transferred to a beaker and placed on a heating table, and 1g of a silane coupling agent KH550 and 20g of a Lyotropic Liquid Crystalline Polymer (LLCP) were added to the beaker and magnetically stirred at 30℃for 2 hours. Finally, casting the mixture on a clean glass plate, and drying the mixture in a 60 ℃ oven for 6 hours to obtain the LCP material.
Comparative example 2
A method of preparing an LCP material, the method comprising:
1g of a commercially available barium titanate particulate filler was added to a 200ml dichloromethane solution and dispersed ultrasonically for 15min. Then, it was transferred to a beaker and placed on a heating table, and 0.5g of a silane coupling agent KH550 and 20g of a Lyotropic Liquid Crystalline Polymer (LLCP) were added to the beaker and magnetically stirred at 30℃for 2 hours. Finally, casting the mixture on a clean glass plate, and drying the mixture in a 60 ℃ oven for 6 hours to obtain the LCP material.
The LCP materials provided in examples 1-5 and comparative examples 1-2 were tested for dielectric constant and dielectric loss properties and the results are shown in the following table:
from the table, by introducing barium titanate nanofiber fillers with different surface hydroxyl groups and amino modified high length-diameter ratio, the LCP material can reduce the addition amount of the barium titanate fillers and reduce the dielectric loss of the LCP film material while ensuring high dielectric constant. As is clear from the data of examples 4 and 5 and comparative example 1, the dielectric constants were all substantially 120 to 130, and the addition amount of the filler was reduced from 15g to 12g and then to 8g, by reducing 7g, and the dielectric loss was reduced from 0.17 to 0.7 and by reducing 0.1 by selecting an appropriate fibrous barium titanate and modifying.
Various embodiments of the present application may exist in a range format; it should be understood that the description in a range format is merely for convenience and brevity and should not be interpreted as a rigid limitation on the scope of the application. It is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
In this application, unless otherwise indicated, terms of orientation such as "upper" and "lower" are used specifically to refer to the orientation of the drawing in the figures. In addition, in the description of the present application, the terms "include", "comprise", "comprising" and the like mean "including but not limited to". Relational terms such as "first" and "second", and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Herein, "and/or" describing an association relationship of an association object means that there may be three relationships, for example, a and/or B, may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. Herein, "at least one" means one or more, and "a plurality" means two or more. "at least one", "at least one" or the like refer to any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
The foregoing is merely a specific embodiment of the application to enable one skilled in the art to understand or practice the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A method for preparing a high dielectric constant, low dielectric loss LCP material, the method comprising:
carrying out surface hydroxyl modification on the barium titanate nanofiber to obtain first modified barium titanate;
amino modification is carried out on the first modified barium titanate to obtain second modified barium carbonate;
mixing the first modified barium titanate and the second modified barium titanate in methylene dichloride to obtain a mixed solution;
and mixing the mixed solution, the silane coupling agent and the lyotropic liquid crystal polymer to obtain the LCP material.
2. The method for preparing the LCP material with high dielectric constant and low dielectric loss according to claim 1, wherein the surface hydroxyl modification of the barium titanate nanofiber is performed to obtain the first modified barium titanate, specifically comprising:
and reacting the barium titanate nanofiber with hydrogen peroxide to modify the surface hydroxyl of the barium titanate nanofiber, so as to obtain the first modified barium titanate.
3. The method for preparing a high dielectric constant low dielectric loss LCP material according to claim 1 or 2, wherein the diameter of the barium titanate nanofiber is 50-200nm; and/or
The length-diameter ratio of the barium titanate nanofiber is 5-50.
4. The method for preparing the high-dielectric-constant low-dielectric-loss LCP material according to claim 2, wherein the mass concentration of hydrogen peroxide is 20% -50%.
5. The method for preparing the LCP material with high dielectric constant and low dielectric loss according to claim 2, wherein the usage amount relationship of the barium titanate nanofiber and the hydrogen peroxide is as follows: 3-6g of barium titanate nanofiber is added into every 100ml of hydrogen peroxide solution.
6. The method for preparing the LCP material with high dielectric constant and low dielectric loss according to claim 1, wherein the amino modification of the first modified barium titanate to obtain the second modified barium carbonate specifically comprises:
dispersing the first modified barium titanate in toluene, then reacting with 3-aminopropyl trimethoxy silane, and performing amino modification on the first modified barium titanate to obtain second modified barium carbonate.
7. The method for preparing a high dielectric constant low dielectric loss LCP material of claim 6, wherein the amount of the first modified barium titanate and toluene is: adding 4-10g of first modified barium titanate to 100ml of toluene; and/or
The mass ratio of the first modified barium titanate to the 3-aminopropyl trimethoxysilane is (1-2): 1.
8. the method for preparing a high dielectric constant low dielectric loss LCP material according to claim 1, wherein the mass ratio of the first modified barium titanate to the second modified barium titanate in the mixed solution is (1-5): 1.
9. the method for preparing a high dielectric constant low dielectric loss LCP material of claim 1, wherein the usage amount relationship of the dichloromethane and the lyotropic liquid crystal polymer is as follows: adding 10-15g of the lyotropic liquid crystal polymer into every 100ml of dichloromethane; and/or
The modified barium titanate nanofiber comprises first modified barium titanate and second barium titanate, and the dosage relation of the methylene dichloride and the modified barium titanate nanofiber satisfies the following conditions: adding 3-9g of modified barium titanate nanofiber into every 100ml of dichloromethane; and/or
The dosage relation of the dichloromethane and the silane coupling agent is as follows: 0.1-1.5g of silane coupling agent is added per 100ml of dichloromethane.
10. A high dielectric constant low dielectric loss LCP material prepared by the method of any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211713501.5A CN116041978A (en) | 2022-12-29 | 2022-12-29 | LCP material with high dielectric constant and low dielectric loss and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211713501.5A CN116041978A (en) | 2022-12-29 | 2022-12-29 | LCP material with high dielectric constant and low dielectric loss and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116041978A true CN116041978A (en) | 2023-05-02 |
Family
ID=86119296
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211713501.5A Pending CN116041978A (en) | 2022-12-29 | 2022-12-29 | LCP material with high dielectric constant and low dielectric loss and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116041978A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008074699A (en) * | 2006-09-19 | 2008-04-03 | Korea Res Inst Of Chem Technol | Method for manufacturing high dielectric-constant inorganic/organic hybrid film containing crystalline barium titanate nanoparticle |
| US20100314581A1 (en) * | 2009-06-15 | 2010-12-16 | Ueno Fine Chemicals Industry, Ltd. | Liquid-crystalline polyester blend compositions |
| CN110698859A (en) * | 2018-07-09 | 2020-01-17 | 中国海洋大学 | Silicon dioxide coated modified barium titanate/polysulfone dielectric composite material and preparation method thereof |
| CN111117169A (en) * | 2019-12-26 | 2020-05-08 | 江苏沃特特种材料制造有限公司 | High-dielectric-constant liquid crystal polymer and preparation method thereof |
-
2022
- 2022-12-29 CN CN202211713501.5A patent/CN116041978A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008074699A (en) * | 2006-09-19 | 2008-04-03 | Korea Res Inst Of Chem Technol | Method for manufacturing high dielectric-constant inorganic/organic hybrid film containing crystalline barium titanate nanoparticle |
| US20100314581A1 (en) * | 2009-06-15 | 2010-12-16 | Ueno Fine Chemicals Industry, Ltd. | Liquid-crystalline polyester blend compositions |
| CN110698859A (en) * | 2018-07-09 | 2020-01-17 | 中国海洋大学 | Silicon dioxide coated modified barium titanate/polysulfone dielectric composite material and preparation method thereof |
| CN111117169A (en) * | 2019-12-26 | 2020-05-08 | 江苏沃特特种材料制造有限公司 | High-dielectric-constant liquid crystal polymer and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109913968B (en) | Antibacterial polypropylene fiber and preparation method thereof | |
| CN109778335B (en) | Modified polypropylene fiber and preparation method thereof | |
| CN110093680B (en) | Graphene/cage type polysilsesquioxane modified polyester fiber and preparation method thereof | |
| CN109943902B (en) | Modified polyester fiber and preparation method thereof | |
| CN101880361B (en) | Composition for forming substrate, and prepreg and substrate using the same | |
| CN104672502B (en) | Cyanoethyl cellulose based high-dielectric flexible nano-composite film and preparation method thereof | |
| CN105646944B (en) | A kind of preparation method of organically-modified molybdenum disulfide nano sheet | |
| CN105002595A (en) | Polymer composite function fibers containing partial graphene, and preparation method thereof | |
| CN107418204B (en) | Preparation method of graphene @ calcium copper titanate-polybenzoxazole three-phase composite film | |
| JP5595629B2 (en) | Dielectric resin composition and molded product obtained therefrom | |
| CN111087690B (en) | Flame-retardant polypropylene composite material with electromagnetic shielding effect and scratch resistance and preparation method thereof | |
| CN102040837B (en) | Method for preparing nanocomposite materials comprising surface-modified nanofiller for substrates | |
| CN116041978A (en) | LCP material with high dielectric constant and low dielectric loss and preparation method thereof | |
| Li et al. | CuxS/PAN 3D Nanofiber Mats as Ultra‐Lightweight and Flexible Electromagnetic Interference Shielding Materials | |
| Zhang et al. | Superior comprehensive performance of a rigid-rod poly (hydroxy-p-phenylenebenzobisoxazole) fiber | |
| CN109593358A (en) | Modified boron nitride doped composite material and preparation method thereof | |
| CN104532390B (en) | A kind of conductive fabric and preparation method thereof | |
| Gao et al. | Improved dielectric properties of poly (arylene ether nitrile) with sulfonated poly (arylene ether nitrile) modified CaCu3Ti4O12 | |
| CN112898760A (en) | Wave-absorbing polycarbonate composition and preparation method thereof | |
| CN111778575A (en) | Conductive fiber and preparation method and application thereof | |
| Chu et al. | Preparation and properties comparison of ZIF-67/PVDF and SiCNWs/PVDF composites for energy storage | |
| LU501683B1 (en) | Cyanoethyl cellulose-based high-dielectric nano composite film and preparation method thereof | |
| CN110982232A (en) | Antistatic PET/nano carbon fiber composite material and preparation method thereof | |
| CN109097857A (en) | A kind of preparation method of rare earth cladded type conducting PET fiber | |
| TW201912864A (en) | The compressing molding body using complex-fiber and manufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |