CN108410016A - A kind of modified barium carbonate nano particle and preparation method thereof and a kind of polymer-modified laminated film and preparation method thereof - Google Patents
A kind of modified barium carbonate nano particle and preparation method thereof and a kind of polymer-modified laminated film and preparation method thereof Download PDFInfo
- Publication number
- CN108410016A CN108410016A CN201810259237.XA CN201810259237A CN108410016A CN 108410016 A CN108410016 A CN 108410016A CN 201810259237 A CN201810259237 A CN 201810259237A CN 108410016 A CN108410016 A CN 108410016A
- Authority
- CN
- China
- Prior art keywords
- nano particle
- barium titanate
- modified
- titanate nano
- preparation
- 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
Classifications
-
- 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
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
-
- 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
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/04—Homopolymers or copolymers of styrene
- C08J2425/06—Polystyrene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention provides a kind of modified barium carbonate nano particles, the particle is core-shell structure, its shell is polydiene, stratum nucleare is barium titanate nano particle, the polydiene shell increases the interfacial area of modified barium carbonate nano particle, further enhances the compatibility of particle and composite matrix.The polydiene shell has excellent mechanical property, ensure that the mechanical property of polymer-modified laminated film.In addition, when polymer-modified laminated film is by certain stretch, a large amount of interface hole is not will produce during inter-modification barium titanate nano particle directional orientation, while ensureing its dielectric properties, the dielectric loss of material is reduced, mechanical property also makes moderate progress.The method that the modified barium carbonate nano particle and polymer-modified laminated film are prepared in the present invention is easy to operate, easy to implement.
Description
Technical field
The present invention relates to dielectric material technical fields more particularly to a kind of modified barium carbonate nano particle and preparation method thereof
With a kind of polymer-modified laminated film and preparation method thereof.
Background technology
With the development of science and technology and the improvement of people's living standards, various multifunction devices, electronic product and light
Just the equipment changed gradually enters into the popular feelings, realizes first evolution, trend, popular.At the same time, the mankind to the utilization of resource,
The requirement of the various aspects such as the recycling of waste and the storage of energy is also higher and higher.It is well known that in electronic device industry, electric energy
Storage and release play very important effect, and important component of the dielectric substance as electrical energy storage unit is sent out
Exhibition is directly related to the development of modern electronics industry.Wherein, high density capacitors have in electron stored energy class industry and lift
The status of sufficient weight, and the key for most directly affecting energy storage efficiency is exactly the high dielectric thin film layer in capacitor.
Currently, in widely used Nano filling/polymeric system, Nano filling is because of its special dimensional effect
With surface-area effects there is a large amount of two-phase interface in laminated film, and the quantity of two-phase interface, interfacial structure and compatible
Degree etc. all largely affects the electrical property and mechanical performance of laminated film.Therefore, two-phase interface problem is also research
The emphasis of Nano filling/polymer composite film, while being also difficulties.
Barium titanate (BaTiO3, BT) and it is a kind of common Nano filling, it is a kind of typical ABO3The pottery of type perovskite structure
Porcelain particle.Under normal temperature condition, barium titanate dielectric constant has good piezoelectricity, ferroelectricity and dielectricity up to 1400, because of tool
There is higher dielectric constant and there is stronger storage charge capability.However, barium titanate directly with compatibility when mixed with polymers
It is universal poor.
Invention content
The purpose of the present invention is to provide a kind of modified barium carbonate nano particles and preparation method thereof and a kind of modified poly
Object laminated film and preparation method thereof has good compatibility between the modified barium carbonate nano particle and polymer, into
And the polymer-modified laminated film that can be had excellent performance.
In order to achieve the above-mentioned object of the invention, the present invention provides following technical scheme：
The present invention provides a kind of preparation methods of modified barium carbonate nano particle, comprise the following steps：
(1) barium titanate nano particle is carried out to hydroxylating in hydrogen peroxide, obtains hydroxylating barium titanate nano particle；
(2) the hydroxylating barium titanate nano particle is scattered in toluene, obtains hydroxylating barium titanate nano particle first
Benzene dispersion liquid；
(3) pH value of the hydroxylating barium titanate nano particle toluene dispersion liquid is adjusted to 3~4, it is then even with silane
Join agent mixing and carry out ammoxidation, obtains amination barium titanate nano particle；
(4) the amination barium titanate nano particle, dichloromethane and triethylamine are mixed, obtains stablizing solution；
(5) ice bath is carried out after mixing the stablizing solution and 2- bromo acids, obtains ice bath solution；
(6) so that the ice bath solution is carried out bromination reaction, obtain bromination barium titanate nano particle；
(7) the bromination barium titanate nano particle and polydiene are dissolved in hexamethylene, then with copper bromide and five
The mixing of methyl diethylenetriamine carries out coating reaction, obtains modified barium carbonate nano particle.
Preferably, the mass concentration of the hydrogen peroxide is 20~40%, the quality and dioxygen of the barium titanate nano particle
The volume ratio of water is (5~15) g:(20~40) mL；
The temperature of the hydroxylating is 100~110 DEG C, and the time of the hydroxylating is 5~15h.
Preferably, in the step (3) mass ratio of hydroxylating barium titanate nano particle and silane coupling agent be (6~
12):1；
The temperature of the ammoxidation is 70~90 DEG C, and the time of the ammoxidation is 20~30h.
Preferably, amination barium titanate nano particle, dichloromethane, triethylamine and 2- in the step (4) and step (5)
The mass ratio of bromo acid is (5~10):(20~40):(0.1~0.3):(0.005~0.01)；
Bromination barium titanate nano particle in the step (7), polydiene, copper bromide and pentamethyl-diethylenetriamine
Mass ratio is (3~7):(2~3):(0.1~1):(0.5~1)；
The quality of bromination barium titanate nano particle and the volume ratio of hexamethylene are (3~7) g in the step (7):(50~
100)mL。
Preferably, the time of the bromination reaction is 10~15h；
The temperature of the coating reaction is 50~70 DEG C, and the time of the coating reaction is 20~30h.
The present invention provides a kind of modified barium carbonate nano particles that the preparation method obtains, and have core-shell structure,
Shell is polydiene, and the thickness of the shell is 2~10nm, and the stratum nucleare is barium titanate nano particle.
The present invention provides a kind of preparation methods of polymer-modified laminated film, comprise the following steps：
Melt blending is carried out after modified barium carbonate nano particle described in claim 6 and polymeric matrix are mixed, is obtained
Blend composition；
Compressing tablet process is carried out to the blend composition, obtains polymer-modified laminated film.
Preferably, the mass ratio of the modified barium carbonate nano particle and polymeric matrix is 1:(3~10)；
The temperature of the melt blending is 190~220 DEG C, and the time of the melt blending is 5~15min, the melting
The rotating speed of blending is 50~70rpm.
Preferably, the temperature of the compressing tablet process is 190~220 DEG C；
The pressure of the compressing tablet process is 10~20MPa；
The time of the compressing tablet process is 20~40min.
The present invention provides a kind of polymer-modified laminated films that the preparation method obtains, including modified barium carbonate is received
The thickness of rice grain and polymeric matrix, the polymer-modified laminated film is 10~200 μm.
The present invention provides a kind of modified barium carbonate nano particle, which is core-shell structure, and shell is dienes
Rubber, stratum nucleare are bromination barium titanate nano particle, and the polydiene shell increases the boundary of modified barium carbonate nano particle
Face area further enhances the compatibility of particle and composite matrix.The polydiene shell has excellent mechanics
Performance ensure that the mechanical property of polymer-modified laminated film.In addition, when polymer-modified laminated film is centainly stretched
When, inter-modification barium titanate nano particle directional orientation not will produce a large amount of interface hole in the process, ensure its dielectricity
While energy, the dielectric loss of material is reduced, mechanical property also makes moderate progress.By embodiment experimental result it is found that the application
The dielectric constant of the laminated film of offer can reach 6.0, and energy storage density can reach 3.25J/cm3。
The method operation provided by the invention for preparing the modified barium carbonate nano particle and polymer-modified laminated film
Simplicity, it is easy to implement.
Description of the drawings
Fig. 1 is the SEM of barium titanate nano particle raw material and the modified barium carbonate nano particle being prepared in embodiment 1
Figure；
Fig. 2 is the TEM figures of modified barium carbonate nano particle in embodiment 1；
Fig. 3 is the SEM figures of EPDM@BT/PP laminated films battens and BT/PP laminated film battens；
Fig. 4 is that stretch ratio is respectively 1:1 and 1:The dielectric constant comparison diagram of 3 EPDM@BT/PP laminated film battens；
Fig. 5 is the disruptive field intensity Weibull distribution curve of the EPDM@BT/PP laminated film battens of different stretch degree；
Fig. 6 is the stress-strain diagram of non-stretched PP, BT/PP, BT/EPDM/PP and EPDM@BT/PP laminated films；
Fig. 7 is that stretch ratio is 1:The energy storage density curve of 3 PP and EPDM@BT/PP laminated films.
Specific implementation mode
The present invention provides a kind of preparation methods of modified barium carbonate nano particle, comprise the following steps：
(1) barium titanate nano particle is carried out to hydroxylating in hydrogen peroxide, obtains hydroxylating barium titanate nano particle；
(2) the hydroxylating barium titanate nano particle is scattered in toluene, obtains hydroxylating barium titanate nano particle first
Benzene dispersion liquid；
(3) pH value of the hydroxylating barium titanate nano particle toluene dispersion liquid is adjusted to 3~4, it is then even with silane
Join agent mixing and carry out ammoxidation, obtains amination barium titanate nano particle；
(4) the amination barium titanate nano particle, dichloromethane and triethylamine are mixed, obtains stablizing solution；
(5) ice bath is carried out after mixing the stablizing solution and 2- bromo acids, obtains ice bath solution；
(6) so that the ice bath solution is carried out bromination reaction, obtain bromination barium titanate nano particle；
(7) the bromination barium titanate nano particle and polydiene are dissolved in hexamethylene, then with copper bromide and five
The mixing of methyl diethylenetriamine carries out coating reaction, obtains modified barium carbonate nano particle.
Barium titanate nano particle is carried out hydroxylating by the present invention in hydrogen peroxide, obtains hydroxylating barium titanate nano
Grain.The present invention does not have particular/special requirement to the source of the barium titanate nano particle and hydrogen peroxide, using those skilled in the art institute
Well known commercially available above-mentioned substance.In the present invention, the grain size of the barium titanate nano particle raw material be preferably 20~
200nm, more preferably 50~150nm, most preferably 100~120nm.In the present invention, the mass concentration of the hydrogen peroxide is excellent
It is selected as 20~40%, more preferably 25~35%.
In the specific embodiment of the invention, preferably barium titanate nano particle is added in hydrogen peroxide by the present invention.The present invention is excellent
Select and ultrasonic disperse carried out to the mixture of the barium titanate nano particle and hydrogen peroxide so that two kinds of material mixings more
It is even.In the present invention, the frequency of the ultrasonic disperse is preferably 150~250W, more preferably 200~220W；The ultrasound point
The scattered time is preferably 30~50min, more preferably 40~45min.The present invention is to all ultrasounds involved in scheme
The embodiment of dispersion is without any particular/special requirement, using ultra-sonic dispersion method well-known to those skilled in the art.
In the present invention, the quality of the barium titanate nano particle and the volume ratio of hydrogen peroxide are preferably (5~15) g:
(20~40) mL, more preferably (10~12) g:(25~30) mL；The temperature of the hydroxylating is preferably 100~110 DEG C,
More preferably 105~108 DEG C；The time of hydroxylating described in the barium titanate nano particle is preferably 5~15h, more preferably
For 9~12h.Hydroxylating of the present invention preferably carries out under the conditions of oil bath.In the present invention, the hydrogen peroxide can
Make barium titanate nano particle hydroxylating.
After the hydroxylating, the present invention preferably centrifuges obtained product system, is dried, with
To the hydroxylating barium titanate nano particle of clean dry.The present invention is without any requirement to the centrifugation, the implementation being dried, and adopts
With centrifugation well-known to those skilled in the art, drying means.
After obtaining hydroxylating barium titanate nano particle, the hydroxylating barium titanate nano particle is scattered in toluene by the present invention
In, obtain hydroxylating barium titanate nano particle toluene dispersion liquid.In the present invention, the toluene uses those skilled in the art institute
Well known commercially available toluene reagent.The hydroxylating barium titanate nano particle is preferably added to laggard in toluene by the present invention
Row ultrasonic disperse, to promote dispersion of the hydroxylating barium titanate nano particle in toluene.In the present invention, the ultrasonic disperse
Frequency is preferably 150~250W, more preferably 200~220W；The time of the ultrasonic disperse is preferably 20~40min, more excellent
It is selected as 30~35min.
In the present invention, the ratio between the quality of the hydroxylating barium titanate nano particle and the volume of toluene be preferably (7~
12)g:(20~30) mL, more preferably (9~10) g:(25~28) mL.
After obtaining hydroxylating barium titanate nano particle toluene dispersion liquid, the present invention is by the hydroxylating barium titanate nano particle
The pH value of toluene dispersion liquid is adjusted to 3~4, is then mixed with silane coupling agent and carries out ammoxidation, obtains amination metatitanic acid
Barium nano particle.The pH of the hydroxylating barium titanate nano particle toluene dispersion liquid is adjusted present invention preferably employs glacial acetic acid
Value.In embodiments of the present invention, the glacial acetic acid uses commercial product well-known to those skilled in the art.The present invention controls institute
It is to ensure being smoothed out for ammoxidation, pH that the pH value for stating hydroxylating barium titanate nano particle toluene dispersion liquid, which is 3~4,
All it is unfavorable for the progress of ammoxidation when being worth higher or relatively low.
In the present invention, the silane coupling agent is preferably commercially available KH550；The hydroxylating barium titanate nano particle and
The mass ratio of silane coupling agent is preferably (6~12):1, more preferably (9~10):1.Present invention preferably employs the modes of dropwise addition
Add the silane coupling agent, the rate of the dropwise addition is preferably 0.3~0.7d/s, more preferably 0.5~0.6d/s.
In the present invention, the temperature of the ammoxidation is preferably 70~90 DEG C, more preferably 80~85 DEG C；It is described
The time of ammoxidation is preferably 20~30h, more preferably 24~26h.During ammoxidation of the present invention, surface
Hydroxylating barium titanate nano particle with hydroxyl is reacted with silane coupling agent generates silicon oxygen bond, and then introduces silane coupling agent table
The amino that face itself carries.
After the ammoxidation, the present invention preferably centrifuges obtained product system, is dried, with
To the amination barium titanate nano particle of clean dry.The present invention is without any requirement to the centrifugation, the implementation being dried, and adopts
With centrifugation well-known to those skilled in the art, drying means.
After obtaining amination barium titanate nano particle, the present invention is by the amination barium titanate nano particle, dichloromethane
It is mixed with triethylamine, obtains stablizing solution.Amination barium titanate nano particle is preferably first added in dichloromethane by the present invention,
Triethylamine is added after ultrasonic disperse processing.In the present invention, the frequency of the ultrasonic disperse is preferably 150~250W, more excellent
It is selected as 200~220W；The time of the ultrasonic disperse is preferably 20~40min, more preferably 30~35min.In the present invention,
The triethylamine is alkalinity, can effectively facilitate the reaction of amino and carboxyl.
In the present invention, the mass ratio of the amination barium titanate nano particle, dichloromethane and triethylamine is preferably
(5~10):(20~40):(0.1~0.3), more preferably (7~8):(25~30):(0.15~0.2).
After obtaining stablizing solution, the present invention carries out ice bath after mixing the stablizing solution and 2- bromo acids, obtains
Ice bath solution.2- bromo acids are preferably added dropwise in stablizing solution by the present invention.In the present invention, the amination barium titanate
The mass ratio of nano particle and 2- bromo acids is preferably (5~10):(0.005~0.01)；, more preferably (6~
10):(0.006~0.009).
In the present invention, the ice bath is carried out using ice bath well-known to those skilled in the art operation, the ice
The time of bath is preferably 2~3h, more preferably 2.5h.In the present invention, the ice bath can prevent postorder bromination reaction mistake
Play can ensure that bromination reaction is stable, adequately carries out.
After obtaining ice bath solution, the present invention makes the ice bath solution carry out bromination reaction, obtains bromination barium titanate nano
Grain.In the present invention, the bromination reaction carries out at room temperature, without carrying out additional heating and cooling；The present invention is excellent
Ice bath system is warming up to room temperature by choosing by the way of heating up naturally；The time of the bromination reaction is preferably 10~15h, more excellent
It is selected as 12~13h.
After obtaining bromination barium titanate nano particle, the present invention is molten by the bromination barium titanate nano particle and polydiene
In hexamethylene, is then mixed with copper bromide and pentamethyl-diethylenetriamine and carry out coating reaction, obtain modified barium carbonate nanometer
Particle.In the present invention, the polydiene is preferably ethylene propylene diene rubber, polyisoprene rubber and polybutadiene rubber
One or more of.Bromination barium titanate nano particle is preferably added to ultrasonic disperse in the hexamethylene of part and obtains bromine by the present invention
Polydiene is added to heating in remaining hexamethylene and obtains polydiene by the cyclohexane solution for changing barium titanate nano particle
Cyclohexane solution, then two kinds of solution are mixed again.In the present invention, the frequency of the ultrasonic disperse be preferably 150~
250W, more preferably 200~220W；The time of the ultrasonic disperse is preferably 20~40min, more preferably 30~35min；Institute
The temperature for stating heating is preferably 40~50 DEG C, more preferably 45~47 DEG C；The heating process is preferably along with stir process, institute
The time of heating is stated so that subject to the dissolving of all polydienes.In the present invention, the part hexamethylene and remainder
The mass ratio of hexamethylene is preferably 2:1.
In the present invention, the bromination barium titanate nano particle, polydiene, copper bromide and pentamethyl-diethylenetriamine
Mass ratio be preferably (3~7):(2~3):(0.1~1):(0.5~1), more preferably 5:2.5:0.5:0.75；The bromine
The volume ratio of the quality and hexamethylene of changing barium titanate nano particle is preferably (3~7) g:(50~100) mL, more preferably 5g:
75mL.The copper bromide and the catalyst that pentamethyl-diethylenetriamine is coating reaction process in the present invention.
Present invention preferably uses oil bath pans to heat the material system of coating reaction.In the present invention, the cladding
The temperature of reaction is preferably 55~70 DEG C, more preferably 60~65 DEG C；The time of the coating reaction is preferably 20~30h, more
Preferably 24~26h.
After the coating reaction, the present invention preferably filters obtained product system, is dried, to obtain
The modified barium carbonate nano particle of clean dry.The present invention is without any requirement to the implementation for filtering, being dried, using this
Centrifugation, drying means known to field technology personnel.
The present invention provides the modified barium carbonate nano particle that preparation method described in a kind of above-mentioned technical proposal obtains, this
Grain is core-shell structure, and shell is polydiene, and the thickness of shell is preferably 2~10nm, more preferably 4~6nm；Its
Stratum nucleare is barium titanate nano particle.
The present invention also provides a kind of preparation methods of polymer-modified laminated film, comprise the following steps：
Melt blending is carried out after modified barium carbonate nano particle described in above-mentioned technical proposal and polymeric matrix are mixed, is obtained
To blend composition；
Compressing tablet process is carried out to the blend composition, obtains polymer-modified laminated film.
The present invention melts after mixing modified barium carbonate nano particle described in above-mentioned technical proposal and polymeric matrix
It is blended, obtains blend composition.In the present invention, the polymeric matrix be preferably polypropylene, polystyrene, makrolon, poly- pair
One kind in ethylene terephthalate, polyphenylene sulfide and the Kynoar either mixture of several substances or several objects
The copolymer of matter；The mass ratio of the modified barium carbonate nano particle and polymeric matrix is preferably 1:(3~10), more preferably
1:(5~6)；The melt blending preferably carries out in Haake device, and the temperature of the melt blending is preferably 190~220 DEG C,
More preferable 200~210；The time of the melt blending is preferably 5~15min, more preferably 8~10min；The melt blending
Rotating speed be preferably 50~70rpm, more preferably 55~60rpm.
After obtaining blend composition, the present invention carries out compressing tablet process to the blend composition, obtains polymer-modified laminated film.
In the present invention, the compressing tablet process carries out preferably in vulcanizing press, and the temperature of the compressing tablet process is preferably 190~220
DEG C, more preferable 200~210；The pressure of the compressing tablet process is preferably 10~20MPa, more preferably 15~18MPa；The pressure
The time of piece processing is preferably 20~40min, more preferably 30~35min.
The present invention also provides the polymer-modified laminated films that preparation method described in a kind of above-mentioned technical proposal obtains, should
Film includes modified barium carbonate nano particle and polymeric matrix, the matter of the modified barium carbonate nano particle and polymeric matrix
Amount is than being 1:(3~10), preferably 1:(5~6)；The thickness of the polymer-modified laminated film is preferably 10~200 μm, more
Preferably 50~100 μm.
With reference to embodiment to modified barium carbonate nano particle provided by the invention and preparation method thereof and a kind of modification
Polymer composite film and preparation method thereof is described in detail, but they cannot be interpreted as to the scope of the present invention
Restriction.
Embodiment 1
10g barium titanate nano particles are placed in the flask for the hydrogen peroxide for filling 30mL 30wt%, with the power of 200W
Flow back after ultrasonic disperse 40min in 105 DEG C of oil bath pans 9h progress hydroxylatings.Centrifugal drying later obtains hydroxylating titanium
Sour barium nano particle.
9g hydroxylating barium titanate nano particles are placed in three-necked flask, 25mL toluene is measured and pours into wherein, with 200W's
Power ultrasonic disperses 30min, is transferred in 80 DEG C of oil bath pans and flows back, and is 3 with glacial acetic acid tune mixed liquor pH value.Measure 1g silane
For coupling agent in dropping funel, it is that 0.5d/s is slowly dropped into flask to adjust drop speed, is reacted for 24 hours in 80 DEG C of oil bath pans.Later
Centrifugal drying obtains amination barium titanate nano particle.
8g amination barium titanate nano particles are taken to be added in 30mL dichloromethane the power ultrasonic dispersion with 200W
30min is added 0.1g triethylamines and stablizes mixed liquor, adds 0.006g 2- bromo acids, ice bath 2.5h.Normal-temperature reaction 12h
Centrifugal drying afterwards obtains bromination barium titanate nano particle.
5g bromination barium titanate nano particles are placed in the three-necked flask for filling 50mL hexamethylenes, with the power ultrasonic of 200W
Disperse 30min, while weighing 2.5g ethylene propylene diene rubbers in the beaker for filling 25mL hexamethylenes, is stirred under the conditions of 45 DEG C molten
Solution.Dissolved ethylene propylene diene rubber is poured slowly into flask later, 0.5g CuBr and 0.75g pentamethyls divinyl three is added
Amine reacts for 24 hours in 60 DEG C of oil bath pans.It filters later, is dry, it is final to obtain modified barium carbonate nano particle, it is denoted as BT@EPDM
Particle.
Pattern inspection is carried out respectively to the modified barium carbonate nano particle that barium titanate nano particle raw material and the present embodiment obtain
It surveys, for SEM shape appearance figures as shown in Figure 1, the SEM that wherein a is barium titanate nano particle raw material schemes, b is modified barium carbonate nanometer
The SEM figures of grain.The modified barium carbonate nano particle that the present embodiment obtains is observed using transmission electron microscope, TEM figure such as Fig. 2
It is shown.By Fig. 1 and Fig. 2 it is found that the obtained modified barium carbonate nano particle of the application is successfully on barium titanate nano particle surface
One layer of rubber components are coated.
Embodiment 2
Under the conditions of 190 DEG C, by BT@EPDM and PP by Haake (rotating speed 60rpm, 10 min of time) melt blending,
The mass ratio of middle BT@EPDM and PP are controlled 1:6, then respectively control filer content be 2wt.%, 5wt.%, 10wt.%,
20wt.%, 30wt.% prepare polymer-modified composite material, are denoted as EPDM@BT/PP composite materials.
EPDM@BT/PP composite materials are compressed to the film of specification needed for test using vulcanizing press, pelletizing temperature is protected
It is 190 DEG C, pressure 15MPa to hold, sample making course totally 30 minutes, wherein exhaust bubble is primary, obtains polymer-modified laminated film,
It is denoted as EPDM@BT/PP laminated films.
Comparative example 1
According to the scheme of embodiment 2 BT/PP laminated films are prepared by raw material of BT.
According to the scheme of embodiment 2 using BT, PP and EPDM as raw material, mixed pressuring plate prepares BT/EPDM/PP laminated films.
Clip specification is the rectangle EPDM@BT/PP laminated films batten and BT/PP laminated film battens of 4cm*2cm,
It is fixed on glass slide with Kapton Tape, is put in pallet and makes somebody a mere figurehead, put it into later in 170 DEG C of baking ovens, constant temperature 5min,
Baking oven is opened, batten is slowly pulled, film in homogeneous thickness after stretch processing is selected and stretch ratio control is 1:1,1:2,1:
3,1:Then 4 batten carries out a series of performance tests.
1 is similarly to stretch ratio:3 EPDM@BT/PP laminated films battens and BT/PP laminated films batten respectively into
Row Shape measure, as shown in figure 3, wherein left side is that the SEM of BT/PP laminated film battens schemes, right side is SEM shape appearance figures
The SEM of EPDM@BT/PP laminated film battens schemes, and arrow direction is draw direction in figure.By Fig. 3 the result shows that EPDM@BT/PP
The defect of laminated film ratio BT/PP laminated films is few.
It is respectively 1 to stretch ratio:1 and 1:3 EPDM@BT/PP laminated film battens carry out the detection of dielectric constant,
Comparison diagram is as shown in Figure 4.As shown in Figure 4, EPDM@BT/PP laminated films provided by the present application have higher dielectric constant,
And stretch the dielectric constant that can improve laminated film.
Breakdown test, disruptive field intensity Weibull point are carried out to the EPDM@BT/PP laminated film battens of different stretch degree
Cloth curve is as shown in Figure 5.As shown in Figure 5, EPDM@BT/PP laminated films provided by the present application have preferable breakdown strength,
And stretch the breakdown strength for being capable of providing laminated film.
Stress test, stress are carried out to non-stretched PP, BT/PP, BT/EPDM/PP and EPDM@BT/PP laminated films
Strain curve is as shown in Figure 6.It will be appreciated from fig. 6 that EPDM@BT/PP laminated films provided by the present application significantly improve the soft of material
Toughness.
It is 1 to stretch ratio:3 PP and EPDM@BT/PP laminated films carry out energy storage density test, and energy storage density is bent
Line is as shown in Figure 7.As shown in Figure 7, EPDM@BT/PP laminated films provided by the present application have preferable energy storage density.
Embodiment 3
10g barium titanate nano particles are placed in the flask for the hydrogen peroxide for filling 30mL 30wt%, with the power of 200W
Flow back after ultrasonic disperse 40min in 105 DEG C of oil bath pans 9h progress hydroxylatings.Centrifugal drying later obtains hydroxylating titanium
Sour barium nano particle.
9g hydroxylating barium titanate nano particles are placed in three-necked flask, 25mL toluene is measured and pours into wherein, with 200W's
Power ultrasonic disperses 30min, is transferred in 80 DEG C of oil bath pans and flows back, and is 3 with glacial acetic acid tune mixed liquor pH value.Measure 1g silane
For coupling agent in dropping funel, it is that 0.5d/s is slowly dropped into flask to adjust drop speed, is reacted for 24 hours in 80 DEG C of oil bath pans.Later
Centrifugal drying obtains amination barium titanate nano particle.
8g amination barium titanate nano particles are taken to be added in 30mL dichloromethane the power ultrasonic dispersion with 200W
30min is added 0.1g triethylamines and stablizes mixed liquor, adds 0.006g 2- bromo acids, ice bath 2.5h.Normal-temperature reaction 12h
Centrifugal drying afterwards obtains bromination barium titanate nano particle.
5g bromination barium titanate nano particles are placed in the three-necked flask for filling 50mL hexamethylenes, it is super with the power of 200W
Sound disperses 30min, while weighing 2.5g polybutadiene rubbers in the beaker for filling 25mL hexamethylenes, is stirred under the conditions of 45 DEG C
Dissolving.Dissolved polybutadiene rubber is poured slowly into flask later, 0.5g CuBr and 0.75g pentamethyl divinyls are added
Triamine reacts for 24 hours in 60 DEG C of oil bath pans.It filters later, is dry, it is final to obtain modified barium carbonate nano particle, it is denoted as BT@PB
Particle.
Under the conditions of 190 DEG C, BT@PB and polycarbonate are melted altogether by Haake (rotating speed 60rpm, time 10min)
Mixed, the mass ratio of wherein BT@PB and PC is controlled 1:6, then respectively control filer content be 2wt.%, 5wt.%,
10wt.%, 20wt.%, 30wt.% prepare polymer-modified composite material, are denoted as PB@BT/PC composite materials.
PB@BT/PC composite materials are compressed to the film of specification needed for test using vulcanizing press, pelletizing temperature is kept
It it is 190 DEG C, pressure 15MPa, sample making course totally 30 minutes obtains polymer-modified laminated film wherein exhaust bubble is primary, remembers
For PB@BT/PC laminated films.
Performance detection is carried out to each product of the present embodiment according to the experimental method of above-described embodiment, testing result shows this Shen
The modified barium carbonate nano particle that please be obtained successfully has coated one layer of rubber components on barium titanate nano particle surface, and obtains
Laminated film defect it is few, there is preferable breakdown strength and flexibility, dielectric constant can reach 6.0, and energy storage density is reachable
To 3.25J/cm3。
Embodiment 4
10g barium titanate nano particles are placed in the flask for the hydrogen peroxide for filling 30mL 30wt%, with the power of 200W
Flow back after ultrasonic disperse 40min in 105 DEG C of oil bath pans 9h progress hydroxylatings.Centrifugal drying later obtains hydroxylating titanium
Sour barium nano particle.
9g hydroxylating barium titanate nano particles are placed in three-necked flask, 25mL toluene is measured and pours into wherein, with 200W's
Power ultrasonic disperses 30min, is transferred in 80 DEG C of oil bath pans and flows back, and is 3 with glacial acetic acid tune mixed liquor pH value.Measure 1g silane
For coupling agent in dropping funel, it is that 0.5d/s is slowly dropped into flask to adjust drop speed, is reacted for 24 hours in 80 DEG C of oil bath pans.Later
Centrifugal drying obtains amination barium titanate nano particle.
8g amination barium titanate nano particles are taken to be added in 30mL dichloromethane the power ultrasonic dispersion with 200W
30min is added 0.1g triethylamines and stablizes mixed liquor, adds 0.006g 2- bromo acids, ice bath 2.5h.Normal-temperature reaction 12h
Centrifugal drying afterwards obtains bromination barium titanate nano particle.
5g bromination barium titanate nano particles are placed in the three-necked flask for filling 50mL hexamethylenes, it is super with the power of 200W
Sound disperses 30min, while weighing 2.5g polyisoprene rubbers in the beaker for filling 25mL hexamethylenes, under the conditions of 45 DEG C
Stirring and dissolving.Dissolved polyisoprene rubber is poured slowly into flask later, 0.5g CuBr and 0.75g pentamethyls are added
Diethylenetriamine reacts for 24 hours in 60 DEG C of oil bath pans.It filters later, is dry, it is final to obtain modified barium carbonate nano particle, note
For BT@PI particles.
Under the conditions of 190 DEG C, BT@PI and polystyrene PS are melted altogether by Haake (rotating speed 60rpm, time 10min)
Mixed, the mass ratio of wherein BT@PI and PS is controlled 1:6, then respectively control filer content be 2wt.%, 5wt.%,
10wt.%, 20wt.%, 30wt.% prepare polymer-modified composite material, are denoted as PI@BT/PS composite materials.
PI@BT/PS composite materials are compressed to the film of specification needed for test using vulcanizing press, pelletizing temperature is kept
It it is 190 DEG C, pressure 15MPa, sample making course totally 30 minutes obtains polymer-modified laminated film wherein exhaust bubble is primary, remembers
For PI@BT/PS laminated films.
Performance detection is carried out to each product of the present embodiment according to the experimental method of above-described embodiment, testing result shows this Shen
The modified barium carbonate nano particle that please be obtained successfully has coated one layer of rubber components on barium titanate nano particle surface, and obtains
Laminated film defect it is few, there is preferable breakdown strength and flexibility, dielectric constant can reach 6.0, and energy storage density is reachable
To 3.25J/cm3。
As seen from the above embodiment, the present invention provides a kind of modified barium carbonate nano particle, which is nucleocapsid shape knot
Structure, shell are polydiene, and stratum nucleare is bromination barium titanate nano particle, and the polydiene shell increases Modified Titanium
The interfacial area of sour barium nano particle, further enhances the compatibility of particle and composite matrix.The polydiene shell
Layer has excellent mechanical property, ensure that the mechanical property of polymer-modified laminated film.In addition, when polymer-modified compound
When film is by certain stretch, a large amount of interface cavity not will produce during inter-modification barium titanate nano particle directional orientation
Gap reduces the dielectric loss of material, mechanical property also makes moderate progress while ensureing its dielectric properties.
The method that the modified barium carbonate nano particle and polymer-modified laminated film are prepared in the present invention is easy to operate,
It is easy to implement.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of modified barium carbonate nano particle, comprises the following steps：
(1) barium titanate nano particle is carried out to hydroxylating in hydrogen peroxide, obtains hydroxylating barium titanate nano particle；
(2) the hydroxylating barium titanate nano particle is scattered in toluene, obtains hydroxylating barium titanate nano particle toluene point
Dispersion liquid；
(3) pH value of the hydroxylating barium titanate nano particle toluene dispersion liquid is adjusted to 3~4, then with silane coupling agent
Mixing carries out ammoxidation, obtains amination barium titanate nano particle；
(4) the amination barium titanate nano particle, dichloromethane and triethylamine are mixed, obtains stablizing solution；
(5) ice bath is carried out after mixing the stablizing solution and 2- bromo acids, obtains ice bath solution；
(6) so that the ice bath solution is carried out bromination reaction, obtain bromination barium titanate nano particle；
(7) the bromination barium titanate nano particle and polydiene are dissolved in hexamethylene, then with copper bromide and pentamethyl
Diethylenetriamine mixing carries out coating reaction, obtains modified barium carbonate nano particle.
2. preparation method according to claim 1, which is characterized in that the mass concentration of the hydrogen peroxide is 20~40%,
The quality of the barium titanate nano particle and the volume ratio of hydrogen peroxide are (5~15) g:(20~40) mL；
The temperature of the hydroxylating is 100~110 DEG C, and the time of the hydroxylating is 5~15h.
3. preparation method according to claim 1, which is characterized in that hydroxylating barium titanate nano in the step (3)
The mass ratio of grain and silane coupling agent is (6~12):1；
The temperature of the ammoxidation is 70~90 DEG C, and the time of the ammoxidation is 20~30h.
4. preparation method according to claim 1, which is characterized in that amination metatitanic acid in the step (4) and step (5)
Barium nano particle, dichloromethane, triethylamine and 2- bromo acids mass ratio be (5~10):(20~40):(0.1~
0.3):(0.005~0.01)；
Bromination barium titanate nano particle, the quality of polydiene, copper bromide and pentamethyl-diethylenetriamine in the step (7)
Than for (3~7):(2~3):(0.1~1):(0.5~1)；
The quality of bromination barium titanate nano particle and the volume ratio of hexamethylene are (3~7) g in the step (7):(50~100)
mL。
5. preparation method according to claim 1 or 4, which is characterized in that the time of the bromination reaction is 10~15h；
The temperature of the coating reaction is 50~70 DEG C, and the time of the coating reaction is 20~30h.
6. the modified barium carbonate nano particle that preparation method described in Claims 1 to 5 any one obtains has nucleocapsid shape knot
Structure, shell are polydiene, and the thickness of the shell is 2~10nm, and the stratum nucleare is barium titanate nano particle.
7. a kind of preparation method of polymer-modified laminated film, comprises the following steps：
Melt blending is carried out after modified barium carbonate nano particle described in claim 6 and polymeric matrix are mixed, is blended
Material；
Compressing tablet process is carried out to the blend composition, obtains polymer-modified laminated film.
8. preparation method according to claim 7, which is characterized in that the modified barium carbonate nano particle and polymer matrix
The mass ratio of body is 1:(3~10)；
The temperature of the melt blending is 190~220 DEG C, and the time of the melt blending is 5~15min, the melt blending
Rotating speed be 50~70rpm.
9. preparation method according to claim 7 or 8, which is characterized in that the temperature of the compressing tablet process is 190~220
℃；
The pressure of the compressing tablet process is 10~20MPa；
The time of the compressing tablet process is 20~40min.
10. the polymer-modified laminated film that preparation method described in claim 7~9 any one obtains, including modified metatitanic acid
The thickness of barium nano particle and polymeric matrix, the polymer-modified laminated film is 10~200 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810259237.XA CN108410016A (en) | 2018-03-27 | 2018-03-27 | A kind of modified barium carbonate nano particle and preparation method thereof and a kind of polymer-modified laminated film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810259237.XA CN108410016A (en) | 2018-03-27 | 2018-03-27 | A kind of modified barium carbonate nano particle and preparation method thereof and a kind of polymer-modified laminated film and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108410016A true CN108410016A (en) | 2018-08-17 |
Family
ID=63133571
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810259237.XA Pending CN108410016A (en) | 2018-03-27 | 2018-03-27 | A kind of modified barium carbonate nano particle and preparation method thereof and a kind of polymer-modified laminated film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108410016A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109166960A (en) * | 2018-08-23 | 2019-01-08 | 浙江理工大学 | A kind of preparation method of fiber base flexible piezoelectric sensors |
| CN109280985A (en) * | 2018-09-25 | 2019-01-29 | 胡小玲 | A kind of modified neodymium-doped titanium acid barium nano particle and the dielectric material being made from it |
| CN113845700A (en) * | 2021-09-28 | 2021-12-28 | 四川大学 | Barium titanate matrix composite material and DIW printing forming method and application thereof |
| CN113956818A (en) * | 2021-10-28 | 2022-01-21 | 东莞市骏青电子科技有限公司 | High-insulativity acrylic adhesive tape and preparation method thereof |
| CN113999461A (en) * | 2021-09-24 | 2022-02-01 | 西安交通大学 | Preparation method of modified composite film based on poly-tetramethyl-pentene-barium titanate nano particles |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101882507A (en) * | 2009-05-08 | 2010-11-10 | 北京化工大学 | Multilayered structural polymer-based dielectric composite material and preparation method thereof |
| CN106496461A (en) * | 2016-10-26 | 2017-03-15 | 章功国 | A kind of impact-resistant polymer cladding dielectric material and preparation method thereof |
| CN106565916A (en) * | 2016-10-26 | 2017-04-19 | 章功国 | Polymer cladding dielectric material and preparing method thereof |
-
2018
- 2018-03-27 CN CN201810259237.XA patent/CN108410016A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101882507A (en) * | 2009-05-08 | 2010-11-10 | 北京化工大学 | Multilayered structural polymer-based dielectric composite material and preparation method thereof |
| CN106496461A (en) * | 2016-10-26 | 2017-03-15 | 章功国 | A kind of impact-resistant polymer cladding dielectric material and preparation method thereof |
| CN106565916A (en) * | 2016-10-26 | 2017-04-19 | 章功国 | Polymer cladding dielectric material and preparing method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109166960A (en) * | 2018-08-23 | 2019-01-08 | 浙江理工大学 | A kind of preparation method of fiber base flexible piezoelectric sensors |
| CN109280985A (en) * | 2018-09-25 | 2019-01-29 | 胡小玲 | A kind of modified neodymium-doped titanium acid barium nano particle and the dielectric material being made from it |
| CN109280985B (en) * | 2018-09-25 | 2019-08-23 | 胡小玲 | A kind of modified neodymium-doped titanium acid barium nano particle and the dielectric material being made from it |
| CN113999461A (en) * | 2021-09-24 | 2022-02-01 | 西安交通大学 | Preparation method of modified composite film based on poly-tetramethyl-pentene-barium titanate nano particles |
| CN113845700A (en) * | 2021-09-28 | 2021-12-28 | 四川大学 | Barium titanate matrix composite material and DIW printing forming method and application thereof |
| CN113956818A (en) * | 2021-10-28 | 2022-01-21 | 东莞市骏青电子科技有限公司 | High-insulativity acrylic adhesive tape and preparation method thereof |
| CN113956818B (en) * | 2021-10-28 | 2023-01-24 | 东莞市骏青电子科技有限公司 | High-insulativity acrylic adhesive tape and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108410016A (en) | A kind of modified barium carbonate nano particle and preparation method thereof and a kind of polymer-modified laminated film and preparation method thereof | |
| CN107163293B (en) | A method of improving dielectric composite breakdown strength and energy storage density | |
| CN100338140C (en) | High dielectric constant polyimide/ceramic complex film and its preparation method | |
| WO2017186127A1 (en) | Method for preparing graphene-modified polymethyl methacrylate composite material having ultra-high conductivity | |
| JP6187795B2 (en) | Composition and molded body | |
| CN103408895A (en) | Preparation method of graphene/epoxy resin composite material | |
| JP2004250620A (en) | Liquid crystalline aromatic polyester for insulating material and resin composition thereof | |
| WO2023241196A1 (en) | Preparation of graphene/natural rubber with simultaneously improved mechanical property, heat conduction and wear resistance | |
| CN104788865A (en) | Composite antistatic agent of nano-metal oxide/polymer antistatic agent, as well as preparation method and application of composite antistatic agent | |
| CN108641559A (en) | A kind of expanding fire retardant and its preparation method and application | |
| CN108299579A (en) | A kind of graphene/nanometer silica/Polystyrene Hybrid Material and its preparation method and application | |
| CN110922787B (en) | Polystyrene-based carbonized microsphere and preparation method and application thereof | |
| WO2024011919A1 (en) | Preparation method for eva material and eva material | |
| Yan et al. | Preparation and characterization of fibrous sepiolite modified silane coupling agent/fluororubber nanocomposite | |
| TWI818179B (en) | Modified carbon black and preparation method thereof, resin composition, and copper-clad plate | |
| CN109294501A (en) | A kind of graphite oxide alkenyl waterproof insulation glue | |
| TW201024350A (en) | Surface modification method of carbon nanotube, liquid crystal display panel and method of manufacturing thereof | |
| CN112410913B (en) | High-strength low-elongation polypropylene fiber containing functionalized silica and preparation method thereof | |
| CN110776695B (en) | Antistatic polypropylene composition and preparation method thereof | |
| CN111019251A (en) | Preparation method of inorganic nanoparticle-doped bio-based composite material | |
| JP2000264974A (en) | Production of resin composition | |
| CN1777639A (en) | Carbon fiber-containing resin dispersion solution and resin composite material | |
| CN115536905B (en) | Composite heat conducting filler and preparation method and application thereof | |
| CN109280176A (en) | The modified method of silica list block graft and its application for improving terylene crystal property | |
| CN116766718A (en) | BOPP composite film with high energy storage density and preparation 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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180817 |
|
| RJ01 | Rejection of invention patent application after publication |