CN111635493A - Preparation method of high-thermal-conductivity modified epoxy resin - Google Patents

Preparation method of high-thermal-conductivity modified epoxy resin Download PDF

Info

Publication number
CN111635493A
CN111635493A CN202010381054.2A CN202010381054A CN111635493A CN 111635493 A CN111635493 A CN 111635493A CN 202010381054 A CN202010381054 A CN 202010381054A CN 111635493 A CN111635493 A CN 111635493A
Authority
CN
China
Prior art keywords
boron nitride
epoxy resin
hexagonal boron
modified epoxy
solvent
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.)
Granted
Application number
CN202010381054.2A
Other languages
Chinese (zh)
Other versions
CN111635493B (en
Inventor
景录如
吴斌
崔益华
张春琪
薛建军
徐晓风
马俊锋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Oubang Science And Technology Suzhou Co ltd
Suzhou Taihu Electric Advanced Material Co ltd
Original Assignee
Oubang Science And Technology Suzhou Co ltd
Suzhou Taihu Electric Advanced Material Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Oubang Science And Technology Suzhou Co ltd, Suzhou Taihu Electric Advanced Material Co ltd filed Critical Oubang Science And Technology Suzhou Co ltd
Priority to CN202010381054.2A priority Critical patent/CN111635493B/en
Publication of CN111635493A publication Critical patent/CN111635493A/en
Application granted granted Critical
Publication of CN111635493B publication Critical patent/CN111635493B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule

Abstract

The invention discloses a preparation method of high-thermal-conductivity modified epoxy resin, which comprises the following raw materials of epoxy resin, an ester group-containing vinyl monomer and a vinyl-containing hydrophobic hexagonal boron nitride nanosheet, and the preparation method comprises the following steps: a) preparing hydrophobic hexagonal boron nitride nanosheets containing vinyl, carrying out freeze-thaw expansion treatment on the hydroxylated hexagonal boron nitride, and then carrying out stripping and esterification modification catalysis on the boron nitride by combining a specific compound of formula (I) with a one-pot method; b) polymerizing epoxy resin, the hydrophobic hexagonal boron nitride nanosheet containing vinyl prepared in the step a) and the rest of the raw materials in a third solvent in the presence of an initiator to generate the epoxy resin; the modified epoxy resin prepared by the method has high conductivityThe advantages of stable product quality during preparation batches and the like are achieved on the basis of thermal coefficient, low dielectric loss, high electric field strength and higher mechanical strength.

Description

Preparation method of high-thermal-conductivity modified epoxy resin
The invention is a divisional application of Chinese invention patent application with application date of 26.6.2019, application number of 2019105590099 and name of 'a high thermal conductive modified epoxy resin and a preparation method thereof'.
Technical Field
The invention belongs to the technical field of polymer composite materials and electricians, and particularly relates to a preparation method of a high-thermal-conductivity modified epoxy resin.
Background
The heat conduction material is widely applied to the national defense industry and the national economy industry as an important functional material. For example, with the rapid development of microelectronic integration technology and assembly technology, the volumes of electronic components and logic circuits are smaller and smaller, the operating frequency is increased rapidly, the thermal environment of semiconductors changes rapidly towards high temperature, and at the moment, the heat generated by electronic equipment is accumulated and increased rapidly. If the temperature is not timely derived, the working efficiency of the motor is directly influenced, the service life of the motor is shortened, and the reliability of the motor is reduced. Therefore, for the above reasons, there is a strong need for an insulating material having high thermal conductivity to solve the above problems.
At present, the filled high-thermal-conductivity insulating polymer composite can solve the problems to a certain extent and is widely applied and researched, and the filled high-thermal-conductivity insulating polymer composite is mainly prepared by filling a heat-conducting component into a polymer, and the heat-conducting filler is a high-thermal-conductivity inorganic material, has a high heat conductivity coefficient, is low in price, simple in process and easy for industrial production, and is the main direction of research on the high-thermal-conductivity insulating polymer composite at present. Among them, epoxy resin has excellent insulating properties, and thus is widely used as an important insulating medium in electrical insulating devices, and miniaturization and high power of electrical devices generate more and more heat, which poses new challenges to conventional insulating materials. Meanwhile, the construction of the smart power grid also urgently needs an insulating material with high heat conduction capability. However, the epoxy resin has poor heat conductivity, the heat conductivity is only 0.17-0.21w/mk, and in order to improve the heat conductivity of the epoxy resin, the filled composite material is prepared by filling the epoxy resin with the inorganic filler with high heat conductivity, which is the most economical and efficient method for obtaining the heat-conducting epoxy resin. However, when the ratio of the thermal conductivity of the thermal conductive filler to the thermal conductivity of the resin matrix is too high, the defects of air holes and the like exist at the joint of the interface of the thermal conductive filler and the resin matrix, which causes the interface to have larger thermal resistance and serious phonon scattering, and influences the heat transfer of the material, thereby greatly reducing the contribution of the thermal conductive filler to the thermal conductivity of the epoxy resin composite material.
Boron Nitride (BN) is a very promising dielectric composite due to its high thermal conductivity, excellent mechanical properties, and its electrical insulating properties. The surface treatment is carried out on the heat-conducting filler, the interface combination of the epoxy resin matrix and the heat-conducting filler is improved, the interface thermal resistance is reduced, and the method is an important research approach for further improving the heat-conducting property of the epoxy resin matrix composite material.
For example, in the existing method for preparing the high-thermal-conductivity epoxy resin, Wattanakul and other researches find that the surface wettability of BN and the interface adhesive force between the filler and a resin matrix can be effectively increased by treating the inorganic filler BN with a surfactant. Compared with untreated BN filler, the thermal conductivity of the BN/EP (epoxy resin) composite material is improved from 1.5W/(m.K) to 2.69W/(m.K).
Also, like Liang et al (IEEE 59th Electronic components and technology reference [ C ],2009: 437-440.), BN without any surface treatment is directly filled into epoxy resin, and studies have found that when the volume filling amount is 80 wt%, the thermal conductivity of the resin-based composite is only 3.35W/(m.K); chung et al (compositions PartA,2001,32(12): 1749-1757.) found that the heat-conducting property of the resin-based composite material is greatly improved after the silane coupling agent performs surface functionalization treatment on the filler BN. When the volume filling amount of BN is 57%, the thermal conductivity of the resin-based composite material is increased from 5.27W/(m.K) to 10W/(m.K), which is twice that of the untreated composite material.
For example, Yung et al (Journal of Applied Polymer Science,2007, 3587-3591.) have two types of hexagonal boron nitride and cubic boron nitride with different particle diameter ratios and surface modification added into epoxy resin, and the influence of filler surface modification on the thermal conductivity of the composite material is observed. The composite material was found to have the highest thermal conductivity of 19.0W/(m.K) when the volume fraction of BN loading reached 25.7%. Compared with the method of directly doping single hexagonal boron nitride, the heat conduction performance of the composite material is improved by 2.17 times.
However, although the prior art also realizes great improvement of the thermal conductivity of the epoxy resin composite material by the thermal conductive filler boron nitride, the prior prepared high thermal conductive epoxy resin has the following problems:
(1) in the prior art, the amount of the heat-conducting particle filled modified epoxy resin is large, generally more than 50 percent, and at least 25 percent, so that the application range is greatly limited;
(2) in the prior art, when the modified epoxy resin is filled with the heat-conducting particles, the filler is subjected to surface activation treatment and then added into an epoxy matrix, but the dispersion is uneven and the sedimentation phenomenon occurs in practical application with great probability, so that the heat-conducting efficiency and the electromechanical performance of the product are influenced, and the quality of the product is unstable among batches.
Accordingly, there is a need in the art for a way to address the above-mentioned problems.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a modified epoxy resin with high heat conductivity.
In order to solve the technical problems, the invention adopts the following technical scheme:
a raw material of the modified epoxy resin comprises epoxy resin, an ester group-containing vinyl monomer and a vinyl-containing hydrophobic hexagonal boron nitride nanosheet, wherein the modified epoxy resin is prepared by carrying out polymerization reaction on the epoxy resin and the rest of raw materials; the hydrophobic hexagonal boron nitride nanosheet containing the vinyl group is prepared by the following method:
(1) carrying out surface hydroxylation modification on the hexagonal boron nitride to prepare hydroxylated hexagonal boron nitride;
(2) carrying out freeze-thaw expansion treatment on the hydroxylated hexagonal boron nitride prepared in the step (1) to prepare expanded hydroxylated hexagonal boron nitride;
(3) mixing and stirring the expanded hydroxylated hexagonal boron nitride prepared in the step (2) and a compound shown in a formula (I) in a first solvent to obtain a first mixed solution, adding an unsaturated acid and/or unsaturated anhydride and a second solvent into the obtained first mixed solution, and reacting to prepare the hydrophobic hexagonal boron nitride nanosheet containing the vinyl group;
Figure BDA0002482086850000031
wherein R is0Is C1-6Alkyl group of (1).
According to some preferred aspects of the present invention, the ester group-containing vinyl monomer is a compound represented by formula (II):
Figure BDA0002482086850000032
in the formula, R1Is C1-10Alkyl of R2、R3Are each independently hydrogen or C1-10Alkyl group of (1). C1-10The alkyl group of (a) includes methyl, ethyl, propyl, isopropyl, butyl, pentyl, isopentyl, neopentyl, hexyl and the like.
According to some particular aspects of the invention, in formula (II), R2And R3At least one of which is hydrogen.
According to some preferred and specific aspects of the present invention, the ester group-containing vinyl monomer is at least two selected from the group consisting of compounds represented by formula (ii). According to a particular aspect of the invention, the vinyl monomer containing an ester group is a combination of methyl Methacrylate (MAA) and Butyl Acrylate (BA).
According to some preferred aspects of the present invention, the epoxy resin is a bisphenol type epoxy resin.
According to some preferred and specific aspects of the present invention, the epoxy resin is a combination of one or more selected from the group consisting of compounds represented by formula (iii):
Figure BDA0002482086850000041
Figure BDA0002482086850000042
in the formula: r4is-C (CH)3)2-、-CH2-or-S (O)2N is an integer selected from 0 to 10, i.e. n can be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. According to a particular aspect of the invention, the epoxy resin is epoxy E-51 and/or epoxy E-44.
According to some preferred aspects of the present invention, the feeding mass ratio of the epoxy resin, the hydrophobic hexagonal boron nitride nanosheets containing vinyl groups, and the vinyl monomer containing ester groups is 1: 0.05-0.1: 0.15-0.4. More preferably, the feeding mass ratio of the epoxy resin, the hydrophobic hexagonal boron nitride nanosheets containing vinyl groups and the vinyl monomer containing ester groups is 1: 0.05-0.085: 0.18-0.32.
According to some preferred aspects of the present invention, the polymerization reaction is conducted at a temperature of 100 ℃ and 120 ℃. More preferably, the polymerization reaction is carried out at a temperature of 105 ℃ and 115 ℃.
According to some specific aspects of the present invention, in step (1), the hydroxylated hexagonal boron nitride is prepared by: mixing hexagonal boron nitride with a sodium hydroxide aqueous solution, and stirring and reacting at the temperature of 90-150 ℃ to prepare the boron nitride-based catalyst.
According to some specific aspects of the present invention, in the step (1), the hexagonal boron nitride is a commercially available product with a purity of 99% or more and a particle size of about 2 to 5 μm.
According to some specific and preferred aspects of the present invention, in the step (1), the temperature is achieved by means of heating by an oil bath.
According to some specific aspects of the invention, in the step (1), after the stirring reaction, a step of washing with distilled water is further included until the washing is neutral, and drying is performed to obtain the hydroxylated hexagonal boron nitride.
According to some preferred aspects of the present invention, in step (2), the freeze-thaw expansion process is operated in the following manner: preparing the hydroxylated hexagonal boron nitride prepared in the step (1) into an aqueous solution, freezing the obtained aqueous solution at a first set temperature, then unfreezing the aqueous solution to a second set temperature, and circularly freezing and unfreezing the aqueous solution for multiple times to prepare the expanded hydroxylated hexagonal boron nitride; wherein the first set temperature is-50 to-5 ℃, and the second set temperature is 10 to 30 ℃. More preferably, the first set temperature is-45 to-15 ℃, and the second set temperature is 18 to 28 ℃.
According to some specific aspects of the invention, in the step (2), the mass fraction of the aqueous solution is 5-20%.
According to some specific aspects of the invention, in the step (2), the freezing time is 1-8 h.
According to some specific aspects of the present invention, in the step (2), the number of the cycles is 4 to 12.
According to some specific and preferred aspects of the present invention, in the step (3), R is0And may be methyl, ethyl, propyl, butyl or pentyl.
According to some preferred aspects of the present invention, in the step (3), the mixing and stirring are performed at a temperature of 60 to 78 ℃. More preferably, in the step (3), the mixing and stirring are carried out at a temperature of 65 to 75 ℃. In some embodiments of the present invention, the mixing and stirring may be performed by using ultrasonic waves, and the mixing and stirring may be performed under water bath heating to control the temperature.
According to some preferred aspects of the present invention, in the step (3), the reaction occurring in the second solvent is performed at a temperature of 80 to 120 ℃ in the presence of an inert gas. More preferably, in the step (3), the reaction in the second solvent is performed at a temperature of 85 to 115 ℃. Wherein the inert gas comprises nitrogen, argon and the like.
According to some preferred aspects of the present invention, in the step (3), the mixing and stirring are controlled to be performed in an anhydrous environment. In some embodiments of the present invention, the raw materials and the moisture in the environment can be separated by refluxing and water separation, so that the mixing and stirring can be carried out in a water-free environment.
According to some preferred aspects of the invention, in the step (3), the feeding mass ratio of the compound shown in the formula (I) to the expanded hydroxylated hexagonal boron nitride is 6-12: 1.
According to some preferred aspects of the invention, the feeding mass ratio of the unsaturated acid and/or unsaturated anhydride to the expanded hydroxylated hexagonal boron nitride is 0.05-0.5: 1.
According to some preferred aspects of the present invention, in the step (3), the first solvent is cyclohexane and the second solvent is ethyl acetate.
According to some preferred aspects of the invention, the unsaturated acid is linoleic acid and/or methacrylic acid and the unsaturated anhydride is itaconic anhydride and/or maleic anhydride.
The method for preparing the hydrophobic hexagonal boron nitride nanosheet containing the vinyl is different from the prior art, the stripping and hydrophobic modification of the boron nitride nanosheet can be carried out in one pot without separating an intermediate, the compound shown in the formula (I) can be reused, the high yield of the hydrophobic hexagonal boron nitride nanosheet containing the vinyl is realized, the modification is thorough, almost no unmodified boron nitride nanosheet exists, and further the industrial batch production can be realized.
The invention provides another technical scheme that: the preparation method of the modified epoxy resin comprises the following steps:
(a) preparing hydrophobic hexagonal boron nitride nanosheets containing vinyl;
(b) and (b) carrying out a polymerization reaction of an epoxy resin, the vinyl group-containing hydrophobic hexagonal boron nitride nanosheet prepared in step (a) and the remaining raw materials in a third solvent in the presence of an initiator to produce the modified epoxy resin.
According to some specific aspects of the invention, in process step (b), the initiator is dibenzoyl peroxide (BPO).
According to some specific aspects of the invention, in step (b), the third solvent is n-butanol.
According to some specific aspects of the present invention, specific embodiments for preparing the modified epoxy resin are: (i) uniformly mixing epoxy resin, a third solvent and an initiator of 1/4, placing the mixture into a four-neck flask connected with a condensate pipe and nitrogen, adding the hydrophobic hexagonal boron nitride nanosheet containing the vinyl prepared in the step (a), and heating the mixture in an oil bath to 85-95 ℃ for 10-60min at constant temperature;
(ii) heating to about 100 ℃ and 120 ℃, simultaneously dropwise adding the ester group-containing vinyl monomer solution in which the 3/4 initiator is dissolved by using a constant-pressure dropping funnel, slowly dropwise adding, reacting for 3-4h under the condition of heat preservation after dropwise adding, and then distilling under reduced pressure to remove the third solvent (which can be recycled) to obtain the product.
Due to the implementation of the technical scheme, compared with the prior art, the invention has the following advantages:
according to the invention, the vinyl monomer containing ester groups and the hydrophobic hexagonal boron nitride nanosheets containing vinyl groups are innovatively adopted to carry out polymerization modification on the epoxy resin, so that covalent bond connection between the boron nitride nanosheets and the epoxy resin is realized, the addition amount of the hydrophobic hexagonal boron nitride nanosheets containing vinyl groups is very small (about 5%), the problems of difficult uniform dispersion and sedimentation of physical filling are effectively solved, and the modified epoxy resin after polymerization modification has stable product quality in batches during preparation on the basis of high heat conductivity coefficient, low dielectric loss, high electric field strength and high mechanical strength;
meanwhile, as the crude product of the modified boron nitride nanosheet obtained by modifying the boron nitride nanosheet in the prior art contains the unmodified boron nitride nanosheet and is difficult to realize effective separation, the modified boron nitride nanosheet directly obtained in the prior art is not ideal in performance in all aspects after epoxy resin is modified, the hydrophobic hexagonal boron nitride nanosheet containing the vinyl is prepared by adopting a specific method, specifically, surface hydroxyl modification and freeze-thaw expansion treatment are adopted, and then the catalysis of boron nitride stripping and esterification modification is carried out by combining a specific compound shown in the formula (I), so that on one hand, the stripping and hydrophobic modification by a one-pot method are realized, an intermediate is not required to be separated, on the other hand, the compound shown in the formula (I) can be repeatedly used, the yield is high, the cost is greatly saved, on the other hand, the purity of the crude product of the hydrophobic hexagonal boron nitride nanosheet containing the vinyl is high, almost no unmodified boron nitride or boron nitride nanosheets exist, so that the modified epoxy resin can be directly used in the process of modifying the epoxy resin, and the properties of the modified epoxy resin in all aspects are not influenced.
Drawings
FIG. 1 is a Transmission Electron Micrograph (TEM) of vinyl-containing hydrophobic hexagonal boron nitride nanosheets prepared in example 3, with the left and right being at different magnifications;
FIG. 2 is an Atomic Force Microscope (AFM) image of hydrophobic hexagonal boron nitride nanoplates containing vinyl groups prepared in example 3;
fig. 3 is an XRD spectrum of the hydrophobic hexagonal boron nitride nanosheet containing vinyl group prepared in example 3.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is to be understood that these examples are for the purpose of illustrating the general principles, essential features and advantages of the present invention, and the present invention is not limited by the following examples. The implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not indicated are generally the conditions in routine experiments. The raw materials used in the examples are all commercially available commercial products. In the following examples, all starting materials are essentially obtained commercially or prepared by conventional methods in the art, unless otherwise specified.
Example 1
A compound of formula (Ia) (i.e. R in formula (I))0Propyl) preparation: 15.8g (0.073mo1) of N-butylpyridinium bromide ([ bpy ] was weighed out]Br) and 8g (0.073mo1) (sodium tetrafluoroborate) NaBF4Adding 100mL of acetone as a solvent into a plastic washing bottle, magnetically stirring, condensing and refluxing at room temperature, reacting for 12h, standing, performing vacuum filtration, discarding a white solid NaBr to obtain a pale yellow clear filtrate, adding 100mL of dichloromethane into the pale yellow clear filtrate, precipitating a white precipitate, performing vacuum filtration, performing rotary evaporation and concentration on the filtrate to remove acetone and dichloromethane in the filtrate, and performing vacuum drying on the obtained yellow oily liquid at 60 ℃ for 8h to obtain a product, namely a compound [ bpy ] shown in the formula (Ia)]BF413.8g, yield 85.2%;
Figure BDA0002482086850000071
example 2
A compound of formula (Ib) (i.e. R in formula (I))0Methyl group): 28.2g (0.15mol) of bromo-N-ethylpyridine were added to a Erlenmeyer flask containing 50mL of acetone, and 16.5g (0.15mol) of NaBF was added4Magnetically stirring at room temperature for 10h, filtering, rotary evaporating to remove volatile acetone, and vacuum drying to obtain white solid compound represented by formula (Ib) 25.16g with yield of 86.5% and m.p.53.2-53%.6℃；
Figure BDA0002482086850000072
Example 3
The embodiment provides a preparation method of modified epoxy resin and the modified epoxy resin prepared by the method, wherein the modified epoxy resin comprises the following raw materials: epoxy resin E-5180 g, hydrophobic hexagonal boron nitride nanosheet (M-BNNSs) containing vinyl, methyl Methacrylate (MAA)13g and Butyl Acrylate (BA)7 g. The solvent adopted in the preparation process is 25g of third solvent, namely n-butanol, and the initiator is 4g of dibenzoyl peroxide (BPO).
The preparation method specifically comprises the following steps:
(a) preparing a hydrophobic hexagonal boron nitride nanosheet containing vinyl:
(1) the method for preparing the hydroxylated hexagonal boron nitride by carrying out surface hydroxylation modification on the hexagonal boron nitride comprises the following specific implementation modes: adding 50g of hexagonal boron nitride (hBN with the purity of more than or equal to 99 percent and the particle size of 2-5 microns) into a 1000ml three-mouth reaction bottle, then adding the hexagonal boron nitride into a prepared 5mol/L sodium hydroxide aqueous solution, mechanically stirring for 10 hours under the oil bath heating condition at about 100 ℃, washing the obtained mixture with distilled water for multiple times until the filtrate is neutral, and drying to obtain 49.5g of hydroxylated hexagonal boron nitride (hBN-OH);
(2) performing freeze-thaw expansion treatment on the hydroxylated hexagonal boron nitride prepared in the step (1) to prepare expanded hydroxylated hexagonal boron nitride, wherein the specific implementation mode is as follows: preparing a 10% distilled water solution from the hydroxylated hexagonal boron nitride (hBN-OH) product prepared in the step (1), freezing the distilled water solution in a freezer at the temperature of about-25 ℃ for 5 hours, then unfreezing the distilled water solution to room temperature, and performing freeze-thaw cycle for 6 times to obtain 49.1g of expanded hydroxylated hexagonal boron nitride (P-hBN-OH), wherein the surface hydroxyl number of the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) is determined to be 0.0209 mmol/g;
(3) taking 25g of expanded hydroxylated hexagonal boron nitride (P-hBN-OH) prepared in the step (2) and 250mL of cyclohexane, putting the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) and the cyclohexane into 1000mL of three-neck flask with a stirrer and a reflux water separator, heating the three-neck flask to reflux, gradually removing water in a system by a refluxing solvent, cooling the temperature to 80 ℃ when no water is evaporated in the reflux water separator, adding 237g of the prepared compound shown in the formula (Ia), putting the reactor into an ultrasonic cleaner, controlling the water temperature to be about 70 ℃, carrying out ultrasonic stirring reaction for 24 hours, then adding 12g of linoleic acid and 50mL of ethyl acetate, introducing nitrogen, heating the mixture to 100 ℃ for 4 hours, cooling the mixture to 65 ℃, carrying out vacuum filtration, cleaning a filter cake twice by using a toluene/acetone (1:1 volume ratio) mixed solution, then carrying out filtration, adding the mixture into 500mL of a toluene/isopropanol mixed solution to form a micro-nano dispersion solution, centrifuging at a rotating speed of 8000r/min, taking the upper suspension, filtering, and drying (140 ℃) to obtain 14.4g of the hydrophobic hexagonal boron nitride nanosheet M-BNNSs (formula (IV-1)) containing vinyl, wherein the yield is 57.3%;
the yield is calculated as follows:
Figure BDA0002482086850000081
：mM-BNNSsthe obtained hydrophobic hexagonal boron nitride nanosheet (M-BNNSs) containing vinyl has the mass g; : wP-BNOHIs the mass g of expanded hydroxylated hexagonal boron nitride (P-hBN-OH); n isP-BNOH: the surface hydroxyl content of the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) is mmol/g; mma: molecular weight of modifier (unsaturated acid or unsaturated anhydride), in this case linoleic acid: 280.44g/mol, calculated in the same manner as in the examples below.
TEM images of the measured products As shown in FIGS. 1(a) (b) (c), TEM images of single exfoliated M-BNNSs were visible on the porous carbon mesh, exhibiting the transparent effect of single layer M-BNNSs, and showing the lateral dimension of 2-3 μ M, and superimposed images of crimp of few-layer M-BNNSs at the side, which was caused by the test environment at 200KV electron microscope and the number of clearly visible crimp of BNNS was 7, were measured using HRTEM (high definition Transmission Electron microscope) FIG. 1(d), demonstrating that single-layer or few-layer M-BNNSs were obtained by the present invention. As shown in fig. 2: a typical Atomic Force Microscope (AFM) image of M-BNNSs deposited on a mica substrate from an ethanol/water dispersion is shown, showing a flake height of 3nm, which also reveals the nature of the exfoliated M-BNNSs. The XRD patterns of the original hexagonal boron nitride and the hydrophobic hexagonal boron nitride nanosheets M-BNNSs containing the vinyl are measured, diffraction peaks (002), (100), (101), (102), (004), (104), (110) and (112) shown in the XRD contrast patterns are consistent with the standard peaks of the hexagonal boron nitride XRD, and the hydrophobic hexagonal boron nitride nanosheets containing the vinyl and obtained by stripping are also proved to be free of other impurities. In addition, we can see from the figure that the (002) peak is shifted to a small angle direction and the peak is relatively enhanced, which all indicate that the modified hexagonal boron nitride (002) face after exfoliation is more exposed and the face spacing becomes larger, indicating that boron nitride has been well exfoliated.
Cooling the filtrate subjected to vacuum filtration to below 25 ℃, standing and layering for 4h, and performing simple rotary evaporation treatment on the lower layer liquid (namely the compound shown in the formula (Ia)), so that the lower layer liquid can be used as a stripping agent and a catalyst for the next cycle again, thereby being repeatedly used; the upper layer after standing and layering is a mixed solvent and can be recycled after vacuum distillation treatment;
the structural formula of the formula (IV-1) is shown as follows, and only shows a schematic structure of covalent connection after one hydroxyl group on the boron nitride nanosheet reacts with linoleic acid, and other hydroxyl groups on the boron nitride nanosheet can also react with linoleic acid and then be covalently connected:
Figure BDA0002482086850000091
(b) preparation of modified epoxy resin
(b-1) uniformly mixing epoxy resin E-51, n-butanol and 1/4 BPO, placing the mixture in a four-neck flask connected with a condensate pipe and nitrogen, adding the hydrophobic hexagonal boron nitride nanosheet (M-BNNSs) containing vinyl and shown in the formula (IV-1) and prepared, and heating the mixture in an oil bath to 90 ℃ for constant temperature for 30 min;
(b-2) heating to about 110 ℃, simultaneously dropwise adding a mixed monomer (MAA and BA) solution dissolved with 3/4BPO initiator by using a constant pressure dropping funnel, slowly dropwise adding for about 30min, reacting for 3-4h under heat preservation after dropwise adding, and then distilling under reduced pressure to remove n-butyl alcohol (which can be recycled) to obtain 108g of modified epoxy resin (formula V-1), wherein the synthetic route is shown as follows:
Figure BDA0002482086850000101
x, y and z are independently integers between 1 and 25, and n is an integer selected from 0 to 10; specifically, the epoxy value of the above-mentioned E51 epoxy resin used is 0.51, and then the average molecular weight of this epoxy resin should be 200/0.51 ═ 392.16;
Figure BDA0002482086850000102
Figure BDA0002482086850000103
Figure BDA0002482086850000104
represents the average number of n, which is the same in the examples below when E51 epoxy resin is used;
Figure BDA0002482086850000105
the monomers MAA and BA and the hydrophobic hexagonal boron nitride nanosheet (M-BNNSs) containing vinyl and shown in the formula (IV-1) prepared by the method can be copolymerized and polymerized, and the active site is grafted and copolymerized at one position only by way of example, so that the method can graft the hydrophobic hexagonal boron nitride nanosheet (M-BNNSs) containing vinyl and shown in the formula (IV-1) onto an epoxy resin molecule in a copolymerization way, and hybrid toughening modification of epoxy by inorganic boron nitride is realized; meanwhile, three vinyl-containing hydrophobic hexagonal boron nitride nanosheets, MAA and BA, shown in formula (IV-1) in the modified epoxy resin shown in formula V-1 are copolymerized and grafted onto an epoxy resin matrix, wherein the three copolymerization modes are not in sequence, only one grafting mode is exemplarily provided in formula V-1, and likewise, the schematic structures of the vinyl-containing hydrophobic hexagonal boron nitride nanosheets and the modified epoxy resin are exemplarily given in the following embodiments.
Example 4
The embodiment provides a preparation method of modified epoxy resin and the modified epoxy resin prepared by the method, wherein the epoxy resin comprises the following raw materials: epoxy resin E-5180 g, hydrophobic hexagonal boron nitride nanosheet (M-BNNSs) containing vinyl, methyl Methacrylate (MAA)13g and Butyl Acrylate (BA)7 g. In the preparation process, 25g of n-butanol serving as a third solvent is adopted, and 4g of dibenzoyl peroxide (BPO) serving as an initiator is adopted.
The preparation method specifically comprises the following steps:
(a) preparing a hydrophobic hexagonal boron nitride nanosheet containing vinyl:
(1) the method for preparing the hydroxylated hexagonal boron nitride by carrying out surface hydroxylation modification on the hexagonal boron nitride comprises the following specific implementation modes: adding 50g of hexagonal boron nitride (hBN with the purity of more than or equal to 99 percent and the particle size of 2-5 microns) into a 1000ml three-mouth reaction bottle, then adding the hexagonal boron nitride into a prepared 5mol/L sodium hydroxide aqueous solution, mechanically stirring for 10 hours under the oil bath heating condition at about 100 ℃, washing the obtained mixture with distilled water for multiple times until the filtrate is neutral, and drying to obtain 49.5g of hydroxylated hexagonal boron nitride (hBN-OH);
(2) performing freeze-thaw expansion treatment on the hydroxylated hexagonal boron nitride prepared in the step (1) to prepare expanded hydroxylated hexagonal boron nitride, wherein the specific implementation mode is as follows: preparing a 10% distilled water solution from the hydroxylated hexagonal boron nitride (hBN-OH) product prepared in the step (1), freezing the distilled water solution in a freezer at the temperature of about-25 ℃ for 5 hours, then unfreezing the distilled water solution to room temperature, and performing freeze-thaw cycle for 6 times to obtain 49.1g of expanded hydroxylated hexagonal boron nitride (P-hBN-OH), wherein the surface hydroxyl number of the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) is determined to be 0.0209 mmol/g;
(3) taking 25g of expanded hydroxylated hexagonal boron nitride (P-hBN-OH) prepared in the step (2) and 250mL of cyclohexane, putting the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) and the cyclohexane into 1000mL of three-neck flask with a stirrer and a reflux water separator, heating the three-neck flask to reflux, gradually removing water in a system by a refluxing solvent, cooling the temperature to 80 ℃ when no water is evaporated in the reflux water separator, adding 218g of the prepared compound shown in the formula (Ib), putting the reactor into an ultrasonic cleaner, controlling the water temperature to be about 70 ℃, carrying out ultrasonic stirring reaction for 24 hours, then adding 12g of linoleic acid and 50mL of ethyl acetate, introducing nitrogen, heating the mixture to 100 ℃ and carrying out reflux reaction for 4 hours, cooling the mixture to 65 ℃, carrying out vacuum filtration, cleaning a filter cake twice by using a toluene/acetone (1:1 volume ratio) mixed solution, then carrying out filtration, adding the mixture into 500mL of a toluene/isopropanol mixed solution to form a micro-nano dispersion solution, centrifuging at a rotating speed of 8000r/min, taking the upper suspension, filtering and drying (140 ℃) to obtain 14.5g of the hydrophobic hexagonal boron nitride nanosheet M-BNNSs formula (IV-1) containing vinyl, wherein the yield is 57.7%;
Figure BDA0002482086850000111
the structure only shows a schematic structure of covalent connection after one hydroxyl on the boron nitride nanosheet reacts with linoleic acid, and other hydroxyl on the boron nitride nanosheet can also react with linoleic acid and then be covalently connected;
(b) preparation of modified epoxy resin:
(b-1) uniformly mixing epoxy resin E-51, n-butanol and 1/4 BPO, placing the mixture in a four-neck flask connected with a condensate pipe and nitrogen, adding the hydrophobic hexagonal boron nitride nanosheet (M-BNNSs) containing vinyl and shown in the formula (IV-1) and prepared, and heating the mixture in an oil bath to 90 ℃ for constant temperature for 30 min;
(b-2) heating to about 110 ℃, simultaneously dropwise adding a mixed monomer (MAA and BA) solution dissolved with 3/4BPO initiator by using a constant pressure dropping funnel, slowly dropwise adding for about 30min, reacting for 3-4h under the condition of heat preservation after dropwise adding, and then distilling under reduced pressure to remove n-butyl alcohol (which can be recycled) to obtain 108.1g of the modified epoxy resin.
Example 5
The embodiment provides a preparation method of modified epoxy resin and the modified epoxy resin prepared by the method, wherein the modified epoxy resin comprises the following raw materials: epoxy resin E-4485g, hydrophobic hexagonal boron nitride nanosheet (M-BNNSs) containing vinyl, methyl Methacrylate (MAA)13g and Butyl Acrylate (BA)7 g. The solvent adopted in the preparation process is 25g of third solvent, namely n-butanol, and the initiator is 4g of dibenzoyl peroxide (BPO).
The preparation method specifically comprises the following steps:
(a) preparing a hydrophobic hexagonal boron nitride nanosheet containing vinyl:
(1) the method for preparing the hydroxylated hexagonal boron nitride by carrying out surface hydroxylation modification on the hexagonal boron nitride comprises the following specific implementation modes: adding 50g of hexagonal boron nitride (hBN with the purity of more than or equal to 99 percent and the particle size of 2-5 microns) into a 1000ml three-mouth reaction bottle, then adding the hexagonal boron nitride into a prepared 5mol/L sodium hydroxide aqueous solution, mechanically stirring for 10 hours under the oil bath heating condition at about 100 ℃, washing the obtained mixture with distilled water for multiple times until the filtrate is neutral, and drying to obtain 49.5g of hydroxylated hexagonal boron nitride (hBN-OH);
(2) performing freeze-thaw expansion treatment on the hydroxylated hexagonal boron nitride prepared in the step (1) to prepare expanded hydroxylated hexagonal boron nitride, wherein the specific implementation mode is as follows: preparing a 10% distilled water solution from the hydroxylated hexagonal boron nitride (hBN-OH) product prepared in the step (1), freezing the distilled water solution in a freezer at the temperature of about-25 ℃ for 5 hours, then unfreezing the distilled water solution to room temperature, and performing freeze-thaw cycle for 6 times to obtain 49.1g of expanded hydroxylated hexagonal boron nitride (P-hBN-OH), wherein the surface hydroxyl number of the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) is determined to be 0.0209 mmol/g;
(3) taking 25g of expanded hydroxylated hexagonal boron nitride (P-hBN-OH) prepared in the step (2) and 250mL of cyclohexane, putting the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) into 1000mL of three-neck flask with a stirrer and a reflux water separator, heating the three-neck flask to reflux, gradually removing water in a system by a refluxing solvent, cooling the temperature to 80 ℃ when no water is evaporated in the reflux water separator, adding 237g of the prepared compound shown in the formula (Ia), putting the reactor into an ultrasonic cleaner, controlling the water temperature to be about 70 ℃, carrying out ultrasonic stirring reaction for 24 hours, then adding 4g of methacrylic acid and 50mL of ethyl acetate, introducing nitrogen, heating the mixture to 100 ℃ for 4 hours, cooling the mixture to 65 ℃, carrying out vacuum filtration, cleaning a filter cake twice by using a toluene/acetone (1:1 volume ratio) mixed solution, then filtering the mixture, adding the mixture into 500mL of toluene/isopropanol mixed solution to form a micro-nano dispersion solution, centrifuging at a rotating speed of 8000r/min, taking the upper suspension, filtering, and drying (140 ℃) to obtain 14.3g of the hydrophobic hexagonal boron nitride nanosheet M-BNNSs (formula (IV-2)) containing vinyl, wherein the yield is 57.1%;
the structural formula of the formula (IV-2) is shown as follows, and only shows a schematic structure of covalent connection after one hydroxyl group on the boron nitride nanosheet reacts with methacrylic acid, and other hydroxyl groups on the boron nitride nanosheet can also react with methacrylic acid and then be covalently connected:
Figure BDA0002482086850000131
(b) preparing modified epoxy resin:
(b-1) uniformly mixing epoxy resin E-44, n-butanol and 1/4 BPO, placing the mixture in a four-neck flask connected with a condensate pipe and nitrogen, adding the hydrophobic hexagonal boron nitride nanosheet (M-BNNSs) containing vinyl and shown in the formula (IV-2) and prepared, and heating the mixture in an oil bath to 90 ℃ for constant temperature for 30 min;
(b-2) heating to about 110 ℃, simultaneously dropwise adding a mixed monomer (MAA and BA) solution dissolved with 3/4BPO initiator by using a constant pressure dropping funnel, slowly dropwise adding for about 30min, reacting for 3-4h under heat preservation after dropwise adding, and then distilling under reduced pressure to remove n-butyl alcohol (which can be recycled) to obtain 113.5g of the modified epoxy resin (formula V-2), wherein the synthetic route is shown as follows:
Figure BDA0002482086850000132
x, y and z are independently numbers between 1 and 25, and n is an integer selected from 0 to 10; the epoxy value of the E44 epoxy resin used above is 0.44, and the average molecular weight of the epoxy resin should be 200/0.44-454.55;
Figure BDA0002482086850000133
Figure BDA0002482086850000141
Figure BDA0002482086850000142
represents the average number of n, which is the same when E44 epoxy is used in the examples described below.
Example 6
The embodiment provides a preparation method of modified epoxy resin and the modified epoxy resin prepared by the method, wherein the modified epoxy resin comprises the following raw materials: epoxy resin E-4485g, hydrophobic hexagonal boron nitride nanosheet (M-BNNSs) containing vinyl, methyl Methacrylate (MAA)13g and Butyl Acrylate (BA)7 g. The solvent adopted in the preparation process is 25g of third solvent, namely n-butanol, and the initiator is 4g of dibenzoyl peroxide (BPO).
The preparation method specifically comprises the following steps:
(a) preparing a hydrophobic hexagonal boron nitride nanosheet containing vinyl:
(1) the method for preparing the hydroxylated hexagonal boron nitride by carrying out surface hydroxylation modification on the hexagonal boron nitride comprises the following specific implementation modes: adding 50g of hexagonal boron nitride (hBN with the purity of more than or equal to 99 percent and the particle size of 2-5 microns) into a 1000ml three-mouth reaction bottle, then adding the hexagonal boron nitride into a prepared 5mol/L sodium hydroxide aqueous solution, mechanically stirring for 10 hours under the oil bath heating condition at about 100 ℃, washing the obtained mixture with distilled water for multiple times until the filtrate is neutral, and drying to obtain 49.5g of hydroxylated hexagonal boron nitride (hBN-OH);
(2) performing freeze-thaw expansion treatment on the hydroxylated hexagonal boron nitride prepared in the step (1) to prepare expanded hydroxylated hexagonal boron nitride, wherein the specific implementation mode is as follows: preparing a 10% distilled water solution from the hydroxylated hexagonal boron nitride (hBN-OH) product prepared in the step (1), freezing the distilled water solution in a freezer at the temperature of about-25 ℃ for 5 hours, then unfreezing the distilled water solution to room temperature, and performing freeze-thaw cycle for 6 times to obtain 49.1g of expanded hydroxylated hexagonal boron nitride (P-hBN-OH), wherein the surface hydroxyl number of the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) is determined to be 0.0209 mmol/g;
(3) taking 25g of expanded hydroxylated hexagonal boron nitride (P-hBN-OH) prepared in the step (2) and 250mL of cyclohexane, putting the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) and the cyclohexane into 1000mL of three-neck flask with a stirrer and a reflux water separator, heating the three-neck flask to reflux, gradually removing water in a system by a refluxing solvent, cooling the temperature to 80 ℃ when no water is evaporated in the reflux water separator, adding 218g of the prepared compound shown in the formula (Ib), putting the reactor into an ultrasonic cleaner, controlling the water temperature to be about 70 ℃, carrying out ultrasonic stirring reaction for 24 hours, then adding 4g of methacrylic acid and 50mL of ethyl acetate, introducing nitrogen, heating the mixture to 100 ℃ for 4 hours, cooling the mixture to 65 ℃, carrying out vacuum filtration, cleaning a filter cake twice by using a toluene/acetone (1:1 volume ratio) mixed solution, then filtering the mixture, adding the mixture into 500mL of toluene/isopropanol mixed solution to form a micro-nano dispersion solution, centrifuging at a rotating speed of 8000r/min, taking the upper suspension, filtering, and drying (140 ℃) to obtain 14.5g of the hydrophobic hexagonal boron nitride nanosheet M-BNNSs (formula (IV-2)) containing vinyl, wherein the yield is 57.9%;
the structural formula of the formula (IV-2) is shown as follows, and only shows a schematic structure of covalent connection after one hydroxyl group on the boron nitride nanosheet reacts with methacrylic acid, and other hydroxyl groups on the boron nitride nanosheet can also react with methacrylic acid and then be covalently connected:
Figure BDA0002482086850000151
(b) preparing modified epoxy resin:
(b-1) uniformly mixing epoxy resin E-44, n-butanol and 1/4 BPO, placing the mixture in a four-neck flask connected with a condensate pipe and nitrogen, adding the hydrophobic hexagonal boron nitride nanosheet (M-BNNSs) containing vinyl and shown in the formula (IV-2) and prepared, and heating the mixture in an oil bath to 90 ℃ for constant temperature for 30 min;
(b-2) heating to about 110 ℃, simultaneously dropwise adding a mixed monomer (MAA and BA) solution dissolved with 3/4BPO initiator by using a constant pressure dropping funnel, slowly dropwise adding for about 30min, reacting for 3-4h under the condition of heat preservation after dropwise adding, and then distilling under reduced pressure to remove n-butyl alcohol (which can be recycled) to obtain 113.7g of the modified epoxy resin.
Example 7
The embodiment provides a preparation method of modified epoxy resin and the modified epoxy resin prepared by the method, wherein the modified epoxy resin comprises the following raw materials: epoxy resin E-5180 g, hydrophobic hexagonal boron nitride nanosheet (M-BNNSs) containing vinyl, methyl Methacrylate (MAA)13g and Butyl Acrylate (BA)7 g. The solvent adopted in the preparation process is 25g of third solvent, namely n-butanol, and the initiator is 4g of dibenzoyl peroxide (BPO).
The preparation method specifically comprises the following steps:
(a) preparing a hydrophobic hexagonal boron nitride nanosheet containing vinyl:
(1) the method for preparing the hydroxylated hexagonal boron nitride by carrying out surface hydroxylation modification on the hexagonal boron nitride comprises the following specific implementation modes: adding 50g of hexagonal boron nitride (hBN with the purity of more than or equal to 99 percent and the particle size of 2-5 microns) into a 1000ml three-mouth reaction bottle, then adding the hexagonal boron nitride into a prepared 5mol/L sodium hydroxide aqueous solution, mechanically stirring for 10 hours under the oil bath heating condition at about 100 ℃, washing the obtained mixture with distilled water for multiple times until the filtrate is neutral, and drying to obtain 49.5g of hydroxylated hexagonal boron nitride (hBN-OH);
(2) performing freeze-thaw expansion treatment on the hydroxylated hexagonal boron nitride prepared in the step (1) to prepare expanded hydroxylated hexagonal boron nitride, wherein the specific implementation mode is as follows: preparing a 10% distilled water solution from the hydroxylated hexagonal boron nitride (hBN-OH) product prepared in the step (1), freezing the distilled water solution in a freezer at the temperature of about-25 ℃ for 5 hours, then unfreezing the distilled water solution to room temperature, and performing freeze-thaw cycle for 6 times to obtain 49.1g of expanded hydroxylated hexagonal boron nitride (P-hBN-OH), wherein the surface hydroxyl number of the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) is determined to be 0.0209 mmol/g;
(3) taking 25g of expanded hydroxylated hexagonal boron nitride (P-hBN-OH) prepared in the step (2) and 250mL of cyclohexane, putting the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) and the cyclohexane into 1000mL of three-neck flask with a stirrer and a reflux water separator, heating the three-neck flask to reflux, gradually removing water in a system by a refluxing solvent, cooling the temperature to 80 ℃ when no water is evaporated in the reflux water separator, adding 237g of the prepared compound shown in the formula (Ia), putting the reactor into an ultrasonic cleaner, controlling the water temperature to be about 70 ℃, carrying out ultrasonic stirring reaction for 24 hours, then adding 5g of itaconic anhydride and 50mL of ethyl acetate, introducing nitrogen, heating the mixture to 100 ℃ for 4 hours, cooling the mixture to 65 ℃, carrying out vacuum filtration, cleaning a filter cake twice by using a toluene/acetone (1:1 volume ratio) mixed solution, then filtering the mixture, adding the mixture into 500mL of toluene/isopropanol mixed solution to form a micro-nano dispersion solution, centrifuging at a rotating speed of 8000r/min, taking the upper suspension, filtering, and drying (140 ℃) to obtain 14.8g of the hydrophobic hexagonal boron nitride nanosheet M-BNNSs (formula (IV-3)) containing vinyl, wherein the yield is 59.1%; the structural formula of the formula (IV-3) is shown as follows, and only shows a schematic structure of covalent connection after one hydroxyl group on the boron nitride nanosheet reacts with itaconic anhydride, and other hydroxyl groups on the boron nitride nanosheet can also react with itaconic anhydride and then be covalently connected:
Figure BDA0002482086850000161
(b) preparing modified epoxy resin:
(b-1) uniformly mixing epoxy resin (E-51), n-butanol and 1/4 BPO, placing the mixture into a four-neck flask connected with a condensate pipe and nitrogen, adding the prepared hydrophobic hexagonal boron nitride nanosheet (M-BNNSs) containing vinyl shown in the formula (IV-3), and heating in an oil bath to 90 ℃ for constant temperature for 30 min;
(b-2) heating to about 110 ℃, simultaneously dropwise adding a mixed monomer (MAA and BA) solution dissolved with 3/4BPO initiator by using a constant pressure dropping funnel, slowly dropwise adding for about 30min, reacting for 3-4h under heat preservation after dropwise adding, and then distilling under reduced pressure to remove n-butyl alcohol (which can be recycled) to obtain 108.9g of the modified epoxy resin (formula V-3), wherein the synthetic route is shown as follows:
Figure BDA0002482086850000171
x, y and z are independently numbers between 0 and 25 and are not 0, and n is an integer selected from 0 to 10;
example 8
The embodiment provides a preparation method of modified epoxy resin and the modified epoxy resin prepared by the method, wherein the modified epoxy resin comprises the following raw materials: epoxy resin E-5180 g, hydrophobic hexagonal boron nitride nanosheet (M-BNNSs) containing vinyl, methyl Methacrylate (MAA)13g and Butyl Acrylate (BA)7 g. The solvent adopted in the preparation process is 25g of third solvent, namely n-butanol, and the initiator is 4g of dibenzoyl peroxide (BPO).
The preparation method specifically comprises the following steps:
(a) preparing a hydrophobic hexagonal boron nitride nanosheet containing vinyl:
(1) the method for preparing the hydroxylated hexagonal boron nitride by carrying out surface hydroxylation modification on the hexagonal boron nitride comprises the following specific implementation modes: adding 50g of hexagonal boron nitride (hBN with the purity of more than or equal to 99 percent and the particle size of 2-5 microns) into a 1000ml three-mouth reaction bottle, then adding the hexagonal boron nitride into a prepared 5mol/L sodium hydroxide aqueous solution, mechanically stirring for 10 hours under the oil bath heating condition at about 100 ℃, washing the obtained mixture with distilled water for multiple times until the filtrate is neutral, and drying to obtain 49.5g of hydroxylated hexagonal boron nitride (hBN-OH);
(2) performing freeze-thaw expansion treatment on the hydroxylated hexagonal boron nitride prepared in the step (1) to prepare expanded hydroxylated hexagonal boron nitride, wherein the specific implementation mode is as follows: preparing a 10% distilled water solution from the hydroxylated hexagonal boron nitride (hBN-OH) product prepared in the step (1), freezing the distilled water solution in a freezer at the temperature of about-25 ℃ for 5 hours, then unfreezing the distilled water solution to room temperature, and performing freeze-thaw cycle for 6 times to obtain 49.1g of expanded hydroxylated hexagonal boron nitride (P-hBN-OH), wherein the surface hydroxyl number of the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) is determined to be 0.0209 mmol/g;
(3) taking 25g of expanded hydroxylated hexagonal boron nitride (P-hBN-OH) prepared in the step (2) and 250mL of cyclohexane, putting the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) and the cyclohexane into 1000mL of three-neck flask with a stirrer and a reflux water separator, heating the three-neck flask to reflux, gradually removing water in a system by a refluxing solvent, cooling the temperature to 80 ℃ when no water is evaporated in the reflux water separator, adding 218g of the prepared compound shown in the formula (Ib), putting the reactor into an ultrasonic cleaner, controlling the water temperature to be about 70 ℃, carrying out ultrasonic stirring reaction for 24 hours, then adding 5g of itaconic anhydride and 50mL of ethyl acetate, introducing nitrogen, heating the mixture to 100 ℃ for 4 hours, cooling the mixture to 65 ℃, carrying out vacuum filtration, cleaning a filter cake twice by using a toluene/acetone (1:1 volume ratio) mixed solution, then filtering the mixture, adding the mixture into 500mL of toluene/isopropanol mixed solution to form a micro-nano dispersion solution, centrifuging at a rotating speed of 8000r/min, taking the upper suspension, filtering and drying (140 ℃) to obtain 14.7g of the hydrophobic hexagonal boron nitride nanosheet M-BNNSs (formula (IV-3)) containing vinyl, wherein the yield is 58.7%; the structural formula of the formula (IV-3) is shown as follows, and only shows a schematic structure of covalent connection after one hydroxyl group on the boron nitride nanosheet reacts with itaconic anhydride, and other hydroxyl groups on the boron nitride nanosheet can also react with itaconic anhydride and then be covalently connected:
Figure BDA0002482086850000181
(b) preparing modified epoxy resin:
(b-1) uniformly mixing epoxy resin (E-51), n-butanol and 1/4 BPO, placing the mixture into a four-neck flask connected with a condensate pipe and nitrogen, adding the prepared hydrophobic hexagonal boron nitride nanosheet (M-BNNSs) containing vinyl shown in the formula (IV-3), and heating in an oil bath to 90 ℃ for constant temperature for 30 min;
and (b-2) heating to about 110 ℃, simultaneously dropwise adding a mixed monomer (MAA and BA) solution dissolved with 3/4BPO initiator by using a constant-pressure dropping funnel, slowly dropwise adding for about 30min, reacting for 3-4h under the condition of heat preservation after dropwise adding, and then distilling under reduced pressure to remove n-butyl alcohol (which can be recycled) to obtain 108.8g of the modified epoxy resin.
Example 9
The embodiment provides a preparation method of modified epoxy resin and the modified epoxy resin prepared by the method, wherein the modified epoxy resin comprises the following raw materials: epoxy resin E-4485g, hydrophobic hexagonal boron nitride nanosheet (M-BNNSs) containing vinyl, methyl Methacrylate (MAA)13g and Butyl Acrylate (BA)7 g. The solvent adopted in the preparation process is 25g of third solvent, namely n-butanol, and the initiator is 4g of dibenzoyl peroxide (BPO).
The preparation method specifically comprises the following steps:
(a) preparing a hydrophobic hexagonal boron nitride nanosheet containing vinyl:
(1) the method for preparing the hydroxylated hexagonal boron nitride by carrying out surface hydroxylation modification on the hexagonal boron nitride comprises the following specific implementation modes: adding 50g of hexagonal boron nitride (hBN with the purity of more than or equal to 99 percent and the particle size of 2-5 microns) into a 1000ml three-mouth reaction bottle, then adding the hexagonal boron nitride into a prepared 5mol/L sodium hydroxide aqueous solution, mechanically stirring for 10 hours under the oil bath heating condition at about 100 ℃, washing the obtained mixture with distilled water for multiple times until the filtrate is neutral, and drying to obtain 49.5g of hydroxylated hexagonal boron nitride (hBN-OH);
(2) performing freeze-thaw expansion treatment on the hydroxylated hexagonal boron nitride prepared in the step (1) to prepare expanded hydroxylated hexagonal boron nitride, wherein the specific implementation mode is as follows: preparing a 10% distilled water solution from the hydroxylated hexagonal boron nitride (hBN-OH) product prepared in the step (1), freezing the distilled water solution in a freezer at the temperature of about-25 ℃ for 5 hours, then unfreezing the distilled water solution to room temperature, and performing freeze-thaw cycle for 6 times to obtain 49.1g of expanded hydroxylated hexagonal boron nitride (P-hBN-OH), wherein the surface hydroxyl number of the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) is determined to be 0.0209 mmol/g;
(3) taking 25g of expanded hydroxylated hexagonal boron nitride (P-hBN-OH) prepared in the step (2) and 250mL of cyclohexane, putting the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) and the cyclohexane into 1000mL of three-neck flask with a stirrer and a reflux water separator, heating the three-neck flask to reflux, gradually removing water in a system by a refluxing solvent, cooling the temperature to 80 ℃ when no water is evaporated in the reflux water separator, adding 237g of the prepared compound shown in the formula (Ia), putting the reactor into an ultrasonic cleaner, controlling the water temperature to be about 70 ℃, carrying out ultrasonic stirring reaction for 24 hours, then adding 4.5g of maleic anhydride and 50mL of ethyl acetate, introducing nitrogen, heating the mixture to about 100 ℃, carrying out reflux reaction for 4 hours, cooling the mixture to 65 ℃, carrying out vacuum filtration, cleaning a filter cake twice by using a toluene/acetone (1:1 volume ratio) mixed solution, then filtering the mixture, adding the mixture into 500mL of toluene/isopropanol mixed solution to form a micro-nano dispersion solution, centrifuging at a rotating speed of 8000r/min, taking the upper suspension, filtering, and drying (140 ℃) to obtain 14.8g of the hydrophobic hexagonal boron nitride nanosheet M-BNNSs (formula (IV-4)) containing vinyl, wherein the yield is 59.1%;
the structural formula of the formula (IV-4) is shown as follows, only a schematic structure of covalent connection after one hydroxyl group on the boron nitride nanosheet is reacted with maleic anhydride is shown, and other hydroxyl groups on the boron nitride nanosheet can also be covalently connected after the other hydroxyl groups are reacted with maleic anhydride:
Figure BDA0002482086850000191
(b) preparation of modified epoxy resin:
(b-1) uniformly mixing epoxy resin E-44, n-butanol and 1/4 BPO, placing the mixture in a four-neck flask connected with a condensate pipe and nitrogen, adding the prepared hydrophobic hexagonal boron nitride nanosheet (M-BNNSs) containing vinyl shown in the formula (IV-4), and heating in an oil bath to 90 ℃ for constant temperature for 30 min;
(b-2) heating to about 110 ℃, simultaneously dropwise adding a mixed monomer (MAA and BA) solution dissolved with 3/4BPO initiator by using a constant pressure dropping funnel, slowly dropwise adding for about 30min, reacting for 3-4h under heat preservation after dropwise adding, and then distilling under reduced pressure to remove n-butyl alcohol (which can be recycled) to obtain 113.9g of the modified epoxy resin (formula V-4), wherein the synthetic route is as follows:
Figure BDA0002482086850000201
x, y and z are independently numbers between 1 and 25, and n is an integer selected from 0 to 10.
Example 10
The embodiment provides a preparation method of modified epoxy resin and the modified epoxy resin prepared by the method, wherein the modified epoxy resin comprises the following raw materials: epoxy resin E-4485g, hydrophobic hexagonal boron nitride nanosheet (M-BNNSs) containing vinyl, methyl Methacrylate (MAA)13g and Butyl Acrylate (BA)7 g. The solvent adopted in the preparation process is 25g of third solvent, namely n-butanol, and the initiator is 4g of dibenzoyl peroxide (BPO).
The preparation method specifically comprises the following steps:
(a) preparing a hydrophobic hexagonal boron nitride nanosheet containing vinyl:
(1) the method for preparing the hydroxylated hexagonal boron nitride by carrying out surface hydroxylation modification on the hexagonal boron nitride comprises the following specific implementation modes: adding 50g of hexagonal boron nitride (hBN with the purity of more than or equal to 99 percent and the particle size of 2-5 microns) into a 1000ml three-mouth reaction bottle, then adding the hexagonal boron nitride into a prepared 5mol/L sodium hydroxide aqueous solution, mechanically stirring for 10 hours under the oil bath heating condition at about 100 ℃, washing the obtained mixture with distilled water for multiple times until the filtrate is neutral, and drying to obtain 49.5g of hydroxylated hexagonal boron nitride (hBN-OH);
(2) performing freeze-thaw expansion treatment on the hydroxylated hexagonal boron nitride prepared in the step (1) to prepare expanded hydroxylated hexagonal boron nitride, wherein the specific implementation mode is as follows: preparing a 10% distilled water solution from the hydroxylated hexagonal boron nitride (hBN-OH) product prepared in the step (1), freezing the distilled water solution in a freezer at the temperature of about-25 ℃ for 5 hours, then unfreezing the distilled water solution to room temperature, and performing freeze-thaw cycle for 6 times to obtain 49.1g of expanded hydroxylated hexagonal boron nitride (P-hBN-OH), wherein the surface hydroxyl number of the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) is determined to be 0.0209 mmol/g;
(3) taking 25g of expanded hydroxylated hexagonal boron nitride (P-hBN-OH) prepared in the step (2) and 250mL of cyclohexane, putting the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) and the cyclohexane into 1000mL of three-neck flask with a stirrer and a reflux water separator, heating the three-neck flask to reflux, gradually removing water in a system by a refluxing solvent, cooling the temperature to 80 ℃ when no water is evaporated in the reflux water separator, adding 218g of the prepared compound shown in the formula (Ib), putting the reactor into an ultrasonic cleaner, controlling the water temperature to be about 70 ℃, carrying out ultrasonic stirring reaction for 24 hours, then adding 4.5g of maleic anhydride and 50mL of ethyl acetate, introducing nitrogen, heating the mixture to 100 ℃ for 4 hours, cooling the mixture to 65 ℃, carrying out vacuum filtration, cleaning a filter cake twice by using a toluene/acetone (1:1 volume ratio) mixed solution, then filtering the mixture, adding the mixture into 500mL of toluene/isopropanol mixed solution to form a micro-nano dispersion solution, centrifuging at a rotating speed of 8000r/min, taking the upper suspension, filtering and drying (140 ℃) to obtain 14.7g of the hydrophobic hexagonal boron nitride nanosheet M-BNNSs (formula (IV-4)) containing vinyl, wherein the yield is 58.7%;
the structural formula of the formula (IV-4) is shown as follows, only a schematic structure of covalent connection after one hydroxyl group on the boron nitride nanosheet is reacted with maleic anhydride is shown, and other hydroxyl groups on the boron nitride nanosheet can also be covalently connected after the other hydroxyl groups are reacted with maleic anhydride:
Figure BDA0002482086850000211
(b) preparation of modified epoxy resin:
(b-1) uniformly mixing epoxy resin (E-44), n-butanol and 1/4 BPO, placing the mixture into a four-neck flask connected with a condensate pipe and nitrogen, adding the prepared hydrophobic hexagonal boron nitride nanosheet (M-BNNSs) containing vinyl shown in the formula (IV-4), and heating in an oil bath to 90 ℃ for constant temperature for 30 min;
(b-2) heating to about 110 ℃, simultaneously dropwise adding a mixed monomer (MAA and BA) solution dissolved with 3/4BPO initiator by using a constant pressure dropping funnel, slowly dropwise adding for about 30min, reacting for 3-4h under the condition of heat preservation after dropwise adding, and then distilling under reduced pressure to remove n-butyl alcohol (which can be recycled) to obtain 113.8g of the modified epoxy resin.
Comparative example 1
The embodiment provides a modified epoxy resin, which comprises the following raw materials: epoxy resin E-4485g, hydrophobic hexagonal boron nitride nanosheet (M-BNNSs)6g, methyl Methacrylate (MAA)13g and Butyl Acrylate (BA)7 g. The solvent adopted in the preparation process is 25g of third solvent, namely n-butanol, and the initiator is 4g of dibenzoyl peroxide (BPO).
The preparation method comprises the following steps:
preparing a hydrophobic hexagonal boron nitride nanosheet:
(1) preparing hydroxylated hexagonal boron nitride, and specifically implementing the following steps: adding 50g of hexagonal boron nitride (hBN with the purity of more than or equal to 99 percent and the particle size of 2-5 microns) into a 1000ml three-mouth reaction bottle, then adding the hexagonal boron nitride into a prepared 5mol/L sodium hydroxide aqueous solution, mechanically stirring for 10 hours under the oil bath heating condition at about 100 ℃, washing the obtained mixture with distilled water for multiple times until the filtrate is neutral, and drying to obtain 49.5g of hydroxylated hexagonal boron nitride (hBN-OH);
(2) the preparation method of the expanded hydroxylated hexagonal boron nitride comprises the following specific steps: preparing a 10% distilled water solution from the hydroxylated hexagonal boron nitride (hBN-OH) product prepared in the step (1), freezing the distilled water solution in a freezer at the temperature of about-25 ℃ for 5 hours, then unfreezing the distilled water solution to room temperature, and performing freeze-thaw cycle for 6 times to obtain 49.1g of expanded hydroxylated hexagonal boron nitride (P-hBN-OH), wherein the surface hydroxyl number of the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) is determined to be 0.0209 mmol/g;
(3) taking 25g of expanded hydroxylated hexagonal boron nitride (P-hBN-OH) prepared in the step (2), adding 250mL of mixed solvent (toluene/cyclohexane is 1:1), putting the mixed solvent into 1000mL of three-neck flask with a stirrer, heating to reflux, gradually removing water in the system from the refluxing solvent, cooling to 80 ℃ after no water is evaporated from a reflux water separator, adding polyethylene glycol
Figure BDA0002482086850000221
86g, putting the reactor into an ultrasonic cleaner, controlling the water temperature to be about 70 ℃, carrying out ultrasonic stirring reaction for 24 hours, then cooling to 65 ℃, precipitating for 30min, and removing the solvent under reduced pressure;
(4) then adding 12g of linoleic acid into the obtained precipitate, adding 100mL of mixed solvent (toluene/cyclohexane is 1:1), introducing nitrogen, heating to about 120 ℃, carrying out reflux reaction for 8h, cooling to 65 ℃, carrying out vacuum filtration, washing a filter cake twice by using toluene/acetone (1:1 volume ratio) mixed solution, then filtering, adding the filter cake into 500mL of toluene/isopropanol mixed solution to form micro-nano dispersion, carrying out centrifugal treatment at a rotating speed of 8000r/min, taking upper-layer suspension, filtering and drying (140 ℃) to obtain 9.0g of hydrophobic hexagonal boron nitride nanosheets (M-BNNSs), wherein the yield is 35.8%;
(II) preparing modified epoxy resin:
(1) uniformly mixing epoxy resin E-44, n-butanol and BPO (bisphenol A) of 1/4, placing the mixture in a four-neck flask connected with a condensate pipe and nitrogen, adding the prepared hydrophobic hexagonal boron nitride nanosheet, and heating in an oil bath to 90 ℃ for 30min at constant temperature;
(2) heating to about 110 ℃, simultaneously dropwise adding a mixed monomer (MAA and BA) solution dissolved with 3/4BPO initiator by using a constant-pressure dropping funnel, slowly dropwise adding for about 30min, reacting for 3-4h under the condition of heat preservation after dropwise adding, and then distilling under reduced pressure to remove n-butyl alcohol (which can be recycled) to obtain 113.6g of modified epoxy resin.
Comparative example 1 is different from the present invention in that the compound represented by formula (I) of the present invention is not used for exfoliation and esterification, resulting in the need for two steps to carry out the reaction and doubling of the synthesis time. The obtained hydrophobic hexagonal boron nitride nanosheet product contains unmodified hexagonal boron nitride nanosheets and is not easy to separate. Therefore, the prepared modified epoxy resin contains independent unmodified hexagonal boron nitride nanosheets, and the performance of the product is influenced.
Comparative example 2
Directly using a commercially available hexagonal boron nitride nanosheet, wherein the raw materials of the modified epoxy resin comprise: epoxy resin E-4485g, commercially available hexagonal boron nitride nanosheets (M-BNNSs)6g, methyl Methacrylate (MAA)13g and Butyl Acrylate (BA)7 g. The solvent adopted in the preparation process is 25g of third solvent, namely n-butanol, and the initiator is 4g of dibenzoyl peroxide (BPO).
The preparation method specifically comprises the following steps:
(1) uniformly mixing epoxy resin E-44, n-butanol and BPO (bisphenol A) of 1/4, placing the mixture in a four-neck flask connected with a condensate pipe and nitrogen, adding a commercially available hexagonal boron nitride nanosheet (M-BNNSs), and heating the mixture in an oil bath to 90 ℃ for 30min at constant temperature;
(2) heating to about 110 ℃, simultaneously dropwise adding a mixed monomer (MAA and BA) solution dissolved with 3/4BPO initiator by using a constant-pressure dropping funnel, slowly dropwise adding for about 30min, reacting for 3-4h under the condition of heat preservation after dropwise adding, and then distilling under reduced pressure to remove n-butyl alcohol (which can be recycled) to obtain 113.8g of modified epoxy resin.
The difference between the comparative example 2 and the invention is that the commercial boron nitride nanosheet is directly doped into the acrylate grafted epoxy resin system, although the brittleness of the epoxy resin can be improved and the impact strength is improved, the unmodified boron nitride nanosheet has poor compatibility with the epoxy resin, so that the thermal conductivity and the electrical property of a cured product are far lower than those of the invention.
Performance testing
The modified epoxy resins obtained in examples 3 to 10 and comparative examples 1 to 2 were subjected to the following performance tests, specifically, see Table 1.
TABLE 1
Figure BDA0002482086850000231
Figure BDA0002482086850000241
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.

Claims (10)

1. The preparation method of the modified epoxy resin is characterized in that raw materials of the modified epoxy resin comprise epoxy resin, a vinyl monomer containing an ester group and a hydrophobic hexagonal boron nitride nanosheet containing vinyl;
the preparation method of the modified epoxy resin comprises the following steps:
(a) preparing a hydrophobic hexagonal boron nitride nanosheet containing vinyl:
carrying out freeze-thaw expansion treatment on the hydroxylated hexagonal boron nitride to prepare expanded hydroxylated hexagonal boron nitride;
mixing and stirring the expanded hydroxylated hexagonal boron nitride and a compound shown in a formula (I) in a first solvent to obtain a first mixed solution, adding unsaturated acid and/or unsaturated anhydride and a second solvent into the obtained first mixed solution, and reacting to prepare the hydrophobic hexagonal boron nitride nanosheet containing the vinyl group;
Figure FDA0002482086840000011
wherein R is0Is C1-6Alkyl groups of (a);
(b) subjecting an epoxy resin, the vinyl group-containing hydrophobic hexagonal boron nitride nanosheets prepared in step (a), and the remaining raw materials to a polymerization reaction in a third solvent in the presence of an initiator to produce the modified epoxy resin;
wherein the vinyl monomer containing the ester group is a composition of methyl methacrylate and butyl acrylate.
2. The method for producing a modified epoxy resin according to claim 1, wherein the epoxy resin is a bisphenol type epoxy resin.
3. The method for preparing a modified epoxy resin according to claim 2, wherein the epoxy resin is one or a combination of more selected from the compounds represented by the formula (III):
Figure FDA0002482086840000012
Figure FDA0002482086840000013
in the formula: r4is-C (CH)3)2-、-CH2-or-S (O)2N is 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.
4. The method for preparing the modified epoxy resin according to claim 1, wherein the feeding mass ratio of the epoxy resin, the hydrophobic hexagonal boron nitride nanosheets containing vinyl groups, and the vinyl monomer containing ester groups is 1: 0.05-0.1: 0.15-0.4.
5. The method for producing a modified epoxy resin according to claim 1, wherein the freeze-thaw-expansion treatment is performed in the following manner: preparing hydroxylated hexagonal boron nitride into an aqueous solution, freezing the obtained aqueous solution at a first set temperature, then unfreezing the aqueous solution to a second set temperature, and circularly freezing and unfreezing the aqueous solution for multiple times to prepare the expanded hydroxylated hexagonal boron nitride; wherein the first set temperature is-50 to-5 ℃, and the second set temperature is 10 to 30 ℃.
6. The method for producing a modified epoxy resin according to claim 1, characterized in that: in the step (a), the mixing and stirring are carried out at a temperature of 60-78 ℃ in an anhydrous environment; and the reaction in the second solvent is carried out at a temperature of 80 to 120 ℃ in the presence of an inert gas.
7. The process according to claim 1, wherein in the step (a), the mass ratio of the compound represented by the formula (I) to the expanded hydroxylated hexagonal boron nitride is 6 to 12: 1, and the mass ratio of the unsaturated acid and/or unsaturated acid anhydride to the expanded hydroxylated hexagonal boron nitride is 0.05 to 0.5: 1; the first solvent is cyclohexane, the second solvent is ethyl acetate, the unsaturated acid is linoleic acid and/or methacrylic acid, and the unsaturated anhydride is itaconic anhydride and/or maleic anhydride.
8. The method of claim 1, wherein in the step (b), the initiator is dibenzoyl peroxide, and the third solvent is n-butanol.
9. The method for preparing a modified epoxy resin according to claim 1 or 8, wherein the polymerization reaction is carried out at a temperature of 100 ℃ and 120 ℃ in the step (b) under a nitrogen atmosphere.
10. The method for preparing a modified epoxy resin according to claim 9, wherein the polymerization reaction is carried out at a temperature of 105 ℃ to 115 ℃ in the step (b).
CN202010381054.2A 2019-06-26 2019-06-26 Preparation method of high-thermal-conductivity modified epoxy resin Active CN111635493B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010381054.2A CN111635493B (en) 2019-06-26 2019-06-26 Preparation method of high-thermal-conductivity modified epoxy resin

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202010381054.2A CN111635493B (en) 2019-06-26 2019-06-26 Preparation method of high-thermal-conductivity modified epoxy resin
CN201910559009.9A CN110283284B (en) 2019-06-26 2019-06-26 High-thermal-conductivity modified epoxy resin and preparation method thereof

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CN201910559009.9A Division CN110283284B (en) 2019-06-26 2019-06-26 High-thermal-conductivity modified epoxy resin and preparation method thereof

Publications (2)

Publication Number Publication Date
CN111635493A true CN111635493A (en) 2020-09-08
CN111635493B CN111635493B (en) 2022-09-20

Family

ID=68005865

Family Applications (2)

Application Number Title Priority Date Filing Date
CN201910559009.9A Active CN110283284B (en) 2019-06-26 2019-06-26 High-thermal-conductivity modified epoxy resin and preparation method thereof
CN202010381054.2A Active CN111635493B (en) 2019-06-26 2019-06-26 Preparation method of high-thermal-conductivity modified epoxy resin

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CN201910559009.9A Active CN110283284B (en) 2019-06-26 2019-06-26 High-thermal-conductivity modified epoxy resin and preparation method thereof

Country Status (2)

Country Link
CN (2) CN110283284B (en)
WO (1) WO2020258621A1 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111484627A (en) * 2020-04-26 2020-08-04 赵汉波 Functional boron nitride in-situ modified epoxy resin insulating material and preparation method thereof
CN111423684B (en) * 2020-04-30 2022-01-04 珠海三臻新材料科技有限公司 Boron nitride graft modified epoxy acrylic resin insulating material and preparation method thereof
CN113185805A (en) * 2021-04-14 2021-07-30 许新姿 Degradable plastic film with super-strong toughness and preparation method thereof
CN115028892A (en) * 2022-06-10 2022-09-09 安徽建筑大学 Three-dimensional structure modified boron nitride and preparation method and application thereof
CN115926181B (en) * 2022-12-05 2023-11-17 苏州太湖电工新材料股份有限公司 Polyimide modified epoxy resin and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001192500A (en) * 2000-01-12 2001-07-17 Edison Polymer Innovation Corp Surface-treated boron nitride for forming high thermal conductive polymer based boron nitride composition having low viscosity and method for forming the same composition
CN102786815A (en) * 2012-08-15 2012-11-21 中国科学院上海硅酸盐研究所 Method for modifying surface of BN (boron nitride) powder, modified BN and polymer composite material
CN109280332A (en) * 2018-08-03 2019-01-29 吉林大学 A kind of preparation method of boron nitride/epoxy resin heat conductive insulating composite material

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6911109B2 (en) * 2000-12-11 2005-06-28 Henkel Corporation Two-part, room temperature curable epoxy resin/ (meth)acrylate compositions and process for using same to bond substrates
EP1694769A4 (en) * 2003-11-21 2007-08-29 Lord Corp Dual-stage wafer applied underfills
CN106752673B (en) * 2016-11-17 2018-12-11 中国科学院宁波材料技术与工程研究所 Hexagonal boron nitride epoxy composite anticorrosive paint, preparation method and application
CN106751477A (en) * 2016-11-29 2017-05-31 太湖县金辉煌电子科技有限公司 A kind of high-molecular-weight epoxy Heat Conduction Material and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001192500A (en) * 2000-01-12 2001-07-17 Edison Polymer Innovation Corp Surface-treated boron nitride for forming high thermal conductive polymer based boron nitride composition having low viscosity and method for forming the same composition
CN102786815A (en) * 2012-08-15 2012-11-21 中国科学院上海硅酸盐研究所 Method for modifying surface of BN (boron nitride) powder, modified BN and polymer composite material
CN109280332A (en) * 2018-08-03 2019-01-29 吉林大学 A kind of preparation method of boron nitride/epoxy resin heat conductive insulating composite material

Also Published As

Publication number Publication date
CN111635493B (en) 2022-09-20
CN110283284B (en) 2020-06-02
WO2020258621A1 (en) 2020-12-30
CN110283284A (en) 2019-09-27

Similar Documents

Publication Publication Date Title
CN110283284B (en) High-thermal-conductivity modified epoxy resin and preparation method thereof
Chen et al. Significantly improved energy density of BaTiO 3 nanocomposites by accurate interfacial tailoring using a novel rigid-fluoro-polymer
CN110194918B (en) Modified epoxy organic silicon high-thermal-conductivity insulating impregnating varnish and preparation method thereof
CN108264735B (en) Preparation method of toughened, heat-conducting and insulating epoxy resin-based composite material
CN109206853B (en) High-thermal-conductivity epoxy resin-based composite material, and preparation method and application thereof
CN102492173A (en) Halloysite with modified surface and preparation method for halloysite
CN112940257B (en) Eugenol epoxy group double-splint type cage-like silsesquioxane as well as preparation method and application thereof
CN109929093B (en) Microcapsule type epoxy resin latent curing accelerator and preparation and application methods thereof
CN113969040B (en) Modified boron nitride/epoxy resin heat conduction composite material and preparation method thereof
CN112194822B (en) Phosphorus-containing flame retardant, preparation method and modified epoxy resin
CN1256372C (en) Stripped polystyrene-clay nano-composite material containing star polymer
JP5742219B2 (en) (Meth) acrylate polymer, resin composition and molded article
CN108264765B (en) Preparation method of toughened heat-conducting insulating cyanate resin-based composite material
CN112694856B (en) Two-component epoxy pouring sealant
CN107663278B (en) A kind of epoxy resin highly effective flame-retardant agent dispersing liquid and preparation method thereof
CN109897227B (en) Polyether amine modified graphene oxide and epoxy nanocomposite thereof
Mansoori et al. Polymer–clay nanocomposites via chemical grafting of polyacrylonitrile onto cloisite 20A
CN116426090A (en) Preparation method of graphene-based epoxy resin composite material
JP5384923B2 (en) Method for producing polymer-based nanocomposite and flame-retardant polymer-based nanocomposite formed by the method
CN108727782B (en) Phosphorus-nitrogen nanometer flame-retardant epoxy resin composite material and preparation method thereof
CN113121882A (en) Functionalized graphene oxide-aluminum hypophosphite flame retardant and preparation method and application thereof
CN115838496B (en) Preparation method and application of polyphosphazene modified titanium carbide nanosheet organic-inorganic hybrid carbonizing agent
CN116355133B (en) Modified silicon dioxide-bismaleimide composite material and synthesis process thereof
Goktas et al. Poly (methyl methacrylate) nanocomposites involving aromatic diboronic acid
CN116120520A (en) Epoxy resin monomer and preparation method and application 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
GR01 Patent grant
GR01 Patent grant