CN107827770A - A kind of hexagonal nanometer boron nitride composite of aliphatic chain grafting and preparation method thereof - Google Patents
A kind of hexagonal nanometer boron nitride composite of aliphatic chain grafting and preparation method thereof Download PDFInfo
- Publication number
- CN107827770A CN107827770A CN201711121039.9A CN201711121039A CN107827770A CN 107827770 A CN107827770 A CN 107827770A CN 201711121039 A CN201711121039 A CN 201711121039A CN 107827770 A CN107827770 A CN 107827770A
- Authority
- CN
- China
- Prior art keywords
- boron nitride
- hexagonal
- aliphatic chain
- preparation
- acid
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
- C07C233/04—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C233/07—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a six-membered aromatic ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/20—Diazonium compounds
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F1/00—Shielding characterised by the composition of the materials
- G21F1/02—Selection of uniform shielding materials
- G21F1/10—Organic substances; Dispersions in organic carriers
- G21F1/103—Dispersions in organic carriers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/11—Compounds covalently bound to a solid support
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Composite Materials (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Lubricants (AREA)
Abstract
The invention discloses hexagonal nanometer boron nitride composite of a kind of aliphatic chain grafting and preparation method thereof, the preparation process is to carry out pre- hydroxylating processing to hexagonal nanometer boron nitride material, then acid solution is added, diazonium reactant salt is acidified with substituted phenylamino, obtain aniline modified hexagonal boron nitride, finally aniline modified hexagonal boron nitride is scattered in the presence of acid binding agent in organic solvent further with acyl chloride reaction.The nano composite material of the aliphatic chain grafting for the different quality containing that the method is prepared and the blending of high density polyethylene (HDPE) experience and moulding process, can prepare nano composite material.The present invention carries out surface modification using gentle, efficient diazol pyroreaction method to hexagonal boron nitride, improves the shortcomings of severe reaction conditions of conventional method, reaction time are long and grafting rate is low.So as to which the hexagonal nanometer boron nitride composite for the short-chain branch aliphatic chain prepared has good dispersiveness in high density polyethylene (HDPE).
Description
Technical field
The present invention relates to a kind of new hexagonal nanometer boron nitride composite of aliphatic chain grafting and preparation method thereof.
Background technology
With the progress that nuclear energy is developed, traditional radiation proof material can not meet that the protection of China's Nuclear Electricity will
Ask, such as traditional radiation proof material --- lead, there is very high toxicity, and concrete poor to neutron shield effectiveness, leaded
Volume is big and the shortcomings of being difficult to move.Therefore, in order to meet the challenge thus brought, research and development are non-toxic, density is small, shield effectiveness
Good, good physical properties Novel radiation-protection materials have turned into the importance of material development.It is presently used for neutron absorber material
In absorbent have a many types, wherein hexagonal boron nitride is because it contains10B isotopes have good absorbability to neutron,
And the surface that nano level hexagonal boron nitride has is with interfacial effect, small-size effect and quantum size effect to improving material
Neutron-absorbing effect and thermodynamic property etc. have good castering action, but because hexagonal boron nitride is nano material, it is solid
The effect that some is easy to reunite makes it in polymeric matrix dispersed very poor, therefore not only influences its neutron absorbent properties,
There is certain limitation to its mechanical property.Therefore need to be modified nitridation boron surface, increase its point in the polymer
Property is dissipated, it is dispersed in polymer, so as to lift its neutron absorption effectiveness.
At present, according to the literature, the surface modifying method of hexagonal boron nitride mainly has plasma method, oxygen radical work(
Method, non-covalent bond absorption and chemical deposition can be changed.Although these methods are to varying degrees all by hexagonal boron nitride table
Face is grafted, it is achieved thereby that the improvement for its difference in functionality, but its grafting rate is low (less than 10%), modified condition
It is harsh that and reaction time is long, it is necessary to 48h, it is necessary to HTHP, the shortcomings of it is received limitation in further application, especially
It is that its dispersiveness does not improve well with polymer compound tense, and the improvement in terms of neutron-absorbing performance raising is not
Substantially.
Therefore, it is necessary to take a kind of high grafting rate, simple, gentle method of modifying to carry out surface to hexagonal boron nitride
It is modified, make hexagonal boron nitride surface that there is special feature, can not only improve its dispersiveness in the polymer, but also
The compatibility of hexagonal boron nitride and polymer after modification can be improved, it is compound so as to prepare high performance inorganic nano-particle
Material.
The content of the invention
In order to solve the above problems, an object of the present invention is to provide a kind of gentle, efficient aliphatic chain grafting
Hexagonal nanometer boron nitride composite preparation method.
The second object of the present invention be to provide a kind of mixed with polymers system for having fine dispersiveness in the polymer and
Its compound method.
The method of modifying that the present invention is taken has efficient, gentle advantage, has hexagonal boron nitride surface special
Feature, its dispersiveness in the polymer can be not only improved, and also improve the hexagonal boron nitride after modification with polymerizeing
The interaction force of thing.
The technical solution adopted by the present invention is as follows：
The present invention provides a kind of hexagonal nanometer boron nitride composite of aliphatic chain grafting, and it possesses as shown in formula (I)
Structure：
Wherein：
A is hexagonal boron nitride；
B is aliphatic chain；Its medium chain length is selected from C1-C50, it is preferably C10-C20。
The present invention " the hexagonal nanometer boron nitride composite of aliphatic chain grafting " has following meanings：The hexagonal boron nitride
By the substituted aliphatic chain of the modified grafting in surface, but the substituted aliphatic chain of each hexagonal boron nitride surface grafting is
It is no to be evenly distributed and uncontrollable, therefore the substituted short-chain branch quantity of the hexagonal boron nitride bonding that is modified of each surface, molecular weight
Deng not fully unifying, therefore composition or mixture can be referred to as.Again because although hexagonal boron nitride surface can not be clear and definite
Illustrate that hexagonal boron nitride surface has been grafted the aliphatic chain of how many substitution on earth, but the present invention is surveyed by thermogravimetry (TGA) method
Weight loss data characterize the quantity of the aliphatic chain for the grafting being grafted on hexagonal boron nitride surface.
According to the present invention, the hexagonal boron nitride is nano-hexagonal boron nitride.
Wherein, the technical parameter of nano-hexagonal boron nitride is as shown in table 1：
The present invention also provides the preparation method of the nano composite material of above-mentioned aliphatic chain grafting, and methods described includes following step
Suddenly：
Step 1, pre- hydroxylating processing is carried out to hexagonal nanometer boron nitride material：Nano material and strong alkali compound are carried out
Reaction, and remove unreacted strong alkali compound；
Step 2, pre- hydroxylated nano material is added into acid solution, is acidified diazonium reactant salt with substituted phenylamino, obtains
To aniline modified hexagonal boron nitride, the substituted anilino- sulphation diazol is by following representation：
Wherein R1For hydrogen, alkyl or alkoxy.It is preferred that abovementioned alkyl or alkoxy are C1-C16, C1-C8Or C1-C4Alkyl
Or alkoxy, X-For the acid ion of the acid solution, preferably HSO4 -。
Step 3, aniline modified hexagonal boron nitride is scattered in the presence of acid binding agent in organic solvent further with
Acyl chloride reaction, obtain the nano composite material of the aliphatic chain grafting of the structure as shown in formula (I).
The nano composite material and high-density polyethylene of the aliphatic chain grafting for the different quality containing that the above method is prepared
The blending of alkene experience and moulding process, can prepare nano composite material.
According to the present invention, in step 1, the method for carrying out pre- hydroxylating processing to the hexagonal boron nitride has：Six sides nitrogenize
Boron carries out solid phase reaction with highly basic；Or hexagonal boron nitride carries out liquid phase reactor in the solution with highly basic.The solid phase reaction or
Person's liquid phase reactor, which can be administered alone, or both, all to be applied.In the case that both of which is applied, regardless of front and rear implementation order.
Preferably, the pre- hydroxylating processing method is that the hexagonal boron nitride carries out solid phase reaction with highly basic.
Preferably, the reaction temperature is 100~350 DEG C, preferably 150-250 DEG C, more preferably 170~190 DEG C.
According to the present invention, in step (1), it is preferable that the strong alkali compound is selected from the hydrogen of group i and group ii alkali metal
Oxide.
Preferably, one or more of the strong alkali compound in sodium hydroxide, potassium hydroxide, rubidium hydroxide.
Preferably, the strong alkali compound is the mixture of sodium hydroxide and potassium hydroxide.
Preferably, the mass ratio of the sodium hydroxide and potassium hydroxide is 1:1~3:1.
Preferably, the method for the pre- hydroxylating processing carries out high temperature solid state reaction for the hexagonal boron nitride and highly basic,
The mixed system of reaction includes：
(i) sodium hydroxide (ii) potassium hydroxide (iii) hexagonal boron nitride nanosheet.
According to the present invention, in above-mentioned reaction mixture, the mass ratio of (i) sodium hydroxide and (ii) potassium hydroxide is 1:1
~3:1, preferably 1.5~2.5；And the mass ratio of the highly basic mixture and hexagonal boron nitride is 1:1~8:1, preferably 2:1
~5:1.
According to the present invention, after the reaction of step (2), aniline modified hexagonal boron nitride contains to be taken with surface bond
The phenylamino substituted described in the phenylamino in generation is by following representation：
Wherein R1For hydrogen, alkyl or alkoxy, the alkyl or alkoxy are defined as above.Preferably, wherein R1For hydrogen.
According to the present invention, be bonded to the substituted phenylamino of hexagonal boron nitride with it is aniline modified after hexagonal boron nitride
Mass ratio be 5~95%.Preferably 5%, 10%, 20%, 30%, 50%, 70%, 80%, 95%.
According to the present invention, in step 2, the synthetic method of the diazol is：Under cryogenic conditions, p-phenylenediamine and excessive Asia
Sodium nitrate is reacted.
According to the present invention, in step 2, the one kind or more of the acid solution in hydrochloric acid, sulfuric acid, nitric acid and permanganic acid
Kind；Preferably, the concentrated acid is sulfuric acid.
According to the present invention, in step 2, the acid solution has at least 20% acid concentration, is preferably, 20-80%；
According to the present invention, in step 2, the reaction temperature is more than 100 DEG C, preferably 100-300 DEG C, more preferably
100-200℃。
According to the present invention, the mass ratio of the substituted phenyl acidifying diazol and raw material hexagonal boron nitride is 1:1~20:
1.Preferably, mass ratio 5:1~15:1.
According to the present invention, in step 3, the acyl chlorides is selected from stearyl chloride, palmitoyl chloride, n-amyl chloride, lauroyl chloride, meat
One or more combinations in the acyl chlorides of the aliphatic chains such as cardamom acyl chlorides, oenanthyl chloro, caprylyl chloride, caproyl chloride, n-butyryl chloride；It is preferred that
Ground, the acyl chlorides are stearyl chloride.
According to the present invention, in step 3, the acid binding agent is selected from triethylamine, pyridine, diisopropylethylamine, sodium acetate, carbonic acid
One or more kinds of combinations in sodium, potassium carbonate.Preferably, the acid binding agent is pyridine.
According to the present invention, in step 3, the organic solvent includes DMF, dichloromethane, four chlorinations
One or more combinations in carbon, thionyl chloride, toluene.Preferably, the organic solvent is dichloromethane.
According to the present invention, in step 3, the reaction temperature is more than 0 DEG C, preferably 0-100 DEG C, more preferably 0-80
℃。
According to the present invention, in step 3, the reaction time is more than 12h, preferably 24~48h.
According to the present invention, in step 3, the mol ratio of the substituted phenylamino hexagonal boron nitride and acyl chlorides is 1:1~1:
20.Preferably, mol ratio 1:1~10:1.
According to the present invention, in step 3, the mol ratio of the acyl chlorides and acid binding agent is 1:1~1:20.Preferably, mol ratio
For 1:2~1:10.
According to the present invention, in step 3, reaction whole process is carried out under water-less environment.
According to the present invention, in step (4), blend method is total to including melt blending, emulsion blending, solution blending and powder
It is mixed, it is preferably melt blending.
According to the present invention, in step (4), the temperature of melt blending is 150~250 DEG C, preferably 180~220 DEG C.
According to the present invention, in step (4), the time of melt blending is more than 5min, preferably 10~30min.
According to the present invention, in step (4), forming method includes injection molding, extrusion molding, foaming and is blow molded into
Type, preferably injection molding.
Gather in the nano composite material that the aliphatic chain for the different quality containing for preparing the above method is grafted with high density
In the blending of ethene experience and molding process, forming temperature is 180~300 DEG C, preferably 200~250 DEG C；Chilling temperature is
20~60 DEG C, preferably 40~50 DEG C；Briquetting pressure is 2~20MPa, preferably 5~10MPa.
In the present invention, to hexagonal boron nitride surface using a kind of gentle, efficient method of modifying in step 2.Specifically,
Under strong alkali environment, the pre- hydroxylating of hexagonal boron nitride is handled the boron nitrogen key on hexagonal boron nitride surface is disconnected so as to introduce largely
Boron hydroxyl and amino.Hydrogen-oxygen key and hydrogen bound to nitrogen on boron hydroxyl slough hydrogen at high temperature, form oxygen radical and nitrogen free radical.
Also, pre- hydroxylated hexagonal boron nitride and the phenyl sulphation diazol of substitution are carried out instead in hot sulfuric acid solution
At once, substituted phenyl sulphation diazol, which decomposes, loses nitrogen and generates as lively as a cricket aminophenyl cation, aminophenyl just from
The sub further boron hydroxyl reaction with pre- hydroxylated hexagonal boron nitride surface, discharges hydrogen.Meanwhile the sulfuric acid of highly acid is molten
Liquid can not only improve the temperature of above-mentioned decomposition reaction, can also reduce the generation of side reaction.
A large amount of aniline groups of hexagonal boron nitride surface grafting, wherein amino activity very it is high can further from different fat
The acyl chloride reaction of fat chain length, there is the hexagonal nanometer boron nitride composite of a large amount of short-chain branch aliphatic chains so as to produce surface.
According to the present invention, method of modifying is to carry out different length aliphatic chain to hexagonal boron nitride surface in the step 2
Grafting.
According to the present invention, method of modifying can be that new chemicals are produced on hexagonal boron nitride surface in the step 2
Matter.
The present invention also provides a kind of mixed with polymers system as neutron shielding material, it is characterised in that the mixing
It is prepared by the hexagonal nanometer boron nitride composite and polyethylene that system is modified by surface proposed by the invention.
The beneficial effects of the invention are as follows：Hexagonal boron nitride is entered using gentle, efficient diazol pyroreaction method
Row surface is modified, and improves the shortcomings of severe reaction conditions of conventional method, reaction time are long and grafting rate is low.So as to system
Hexagonal nanometer boron nitride composite for the short-chain branch aliphatic chain gone out has good dispersiveness in high density polyethylene (HDPE).
Brief description of the drawings
Fig. 1 a are the hexagonal boron nitride nanosheet stereoscan photograph (SEM) of reset condition；B is to be made according to embodiment 1
Hexagonal nanometer boron nitride composite SEM.
The hexagonal nanometer boron nitride composite wood that the original hexagonal boron nitrides of Fig. 2 are prepared with the method for modifying in embodiment 1
The infrared spectrum of material.
The SEM of the hexagonal boron nitride of Fig. 3 different contents and the HDPE composites prepared.
The SEM of the hexagonal nanometer boron nitride composite of Fig. 4 different contents and the HDPE composites prepared.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limit the scope of the invention.Furthermore, it is to be understood that after content disclosed in this invention has been read, ability
Field technique personnel can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the protection that the present invention is limited
Within the scope of.
Thermogravimetry：Tested under conditions of air atmosphere, the 10 DEG C/min rates of heat addition, thermogravimetric analysis shows, is based on
Weight loss between 250 DEG C to 600 DEG C, so obtained sample are included based on the hexagonal boron nitride weight that the acyl chlorides is modified
The acyl chlorides of certain percentage composition.
Infrared analysis：Phenetic analysis is carried out by the infrared acyl chlorides side chain to modified hexagonal boron nitride surface.If
There is aliphatic alkane, the characteristic absorption peak of amide groups, then illustrate that acyl chlorides is successfully grafted to hexagonal boron nitride surface.
Electronic microscope photos：Surface observation by Electronic Speculum to modified hexagonal boron nitride, if surface or edge occur
With the different pattern of hexagonal boron nitride matrix, then illustrate the influence for partly belonging to acyl chlorides.And nitrogenized with six original sides
Boron surface pattern is contrasted, and checking modified effect can be further supplemented from pattern.
Embodiment 1
(1) 2.8g sodium hydroxides and 2.2g potassium hydroxide are weighed, 1g hexagonal boron nitride nanosheets is added and is ground in mortar
To fine powder, and it is well mixed.The powder of mixing at 180 DEG C is reacted into 3h in crucible, is cooled to room temperature.At solid phase method
Mixed-powder after reason is scattered in a certain amount of water, is handled mixed liquor 2h using Ultrasonic cell smash, is then centrifuged for
Remove supernatant liquor.It is neutral in pH to solution with water washing is distilled 3 times, obtain pre- hydroxylated hexagonal boron nitride.
(2) in ice bath, 5.4g p-phenylenediamine is dissolved in the concentrated sulfuric acids of 4mL 98% and 32mL deionized waters, stirred to right
Phenylenediamine is completely dissolved.Under liquid level be added dropwise 30% sodium nitrite solution in above-mentioned solution be made corresponding sulphation weight
Nitrogen salt solution.
(3) step (1) completed to pre- hydroxylated hexagonal boron nitride is scattered in 100mL deionized waters and 50mL98% is dense
In sulfuric acid, 130 DEG C are warming up to.Under fast stirring, obtained diazonium salt solution in step (2) is added drop-wise to above-mentioned acidic dispersion
In body.Diazonium salt solution is added dropwise in 30min.Continue after stirring 3h, reaction solution naturally cooled into room temperature, filter,
And washed successively with water, ammonia solution, absolute methanol.
(4) 1000mL three-necked flasks are subjected to vacuum pump drainage three times, manufacture anhydrous and oxygen-free environment.Under ice bath, by step
(3) phenylamino hexagonal boron nitride is made to be dispersed in anhydrous DMF solvent, then adds 10mL pyridines and make
For acid binding agent, lasting stirring.10g stearyl chlorides are dissolved in the anhydrous dichloromethane of 100mL again, are added dropwise in being dispersed with phenylamino
In the solvent of base hexagonal boron nitride.Allow reaction system to return to and persistently stir 18h at room temperature, reaction terminates, and is washed with absolute ether
Wash at least three times, the product after washing is dried into 24h so that dry hexagonal nanometer boron nitride is made in 60 DEG C of vacuum drying chambers
Composite.Fig. 1 a represent the SEM of the hexagonal boron nitride nanosheet of reset condition；The hexagonal boron nitride that embodiment 1 is prepared
The SEM of nano composite material is as shown in Figure 1 b.
Embodiment 2
(1) 2.8g sodium hydroxides and 2.2g potassium hydroxide are weighed, 1g hexagonal boron nitride nanosheets is added and is ground in mortar
To fine powder, and it is well mixed.The powder of mixing is moved into 100mL hydrothermal reaction kettle, 70mL pure water is added, 180
After reacting 6h at DEG C, room temperature is cooled to, mixed liquor 2h is handled using Ultrasonic cell smash, it is clear to be then centrifuged for removing upper strata
Liquid, lower floor obtain pre- hydroxylated hexagonal boron nitride with water washing is distilled 3 times to pH value of solution in neutrality.
(2) in ice bath, 5.4g p-phenylenediamine is dissolved in the concentrated sulfuric acids of 4mL 98% and 32mL deionized waters, stirred to right
Phenylenediamine is completely dissolved.Under liquid level be added dropwise 30% sodium nitrite solution in above-mentioned solution be made corresponding sulphation weight
Nitrogen salt solution.
(3) pre- hydroxylated hexagonal boron nitride will have been completed in step (1) and has been scattered in 100mL deionized waters and 50mL98%
In the concentrated sulfuric acid, 130 DEG C are warming up to.Under fast stirring, obtained diazonium salt solution in step (2) is added drop-wise to above-mentioned acid point
In granular media.Diazonium salt solution is added dropwise in 30min.Continue after stirring 3h, reaction solution is naturally cooled into room temperature, mistake
Filter, and washed successively with water, ammonia solution, absolute methanol.
(4) 1000mL three-necked flasks are subjected to vacuum pump drainage three times, manufacture anhydrous and oxygen-free environment.Under ice bath, by step
(3) phenylamino hexagonal boron nitride is made to be dispersed in anhydrous DMF solvent, then adds 10mL pyridines and make
For acid binding agent, lasting stirring.10g stearyl chlorides are dissolved in the anhydrous dichloromethane of 100mL again, are added dropwise in being dispersed with phenylamino
In the solvent of base hexagonal boron nitride.Allow reaction system to return to and persistently stir 18h at room temperature, reaction terminates, and is washed with absolute ether
Wash at least three times, the product after washing is dried into 24h so that dry hexagonal nanometer boron nitride is made in 60 DEG C of vacuum drying chambers
Composite.
Embodiment 3
(1) 2.8g sodium hydroxides and 2.2g potassium hydroxide are weighed, 1g hexagonal boron nitride nanosheets is added and is ground in mortar
To fine powder, and it is well mixed.The powder of mixing at 180 DEG C is first reacted into 3h in crucible, after the powder of mixing is moved into
In 100mL hydrothermal reaction kettle, 70mL pure water is added, reacts 6h at 180 DEG C.It is thin using ultrasonic wave after being cooled to room temperature
Born of the same parents' crusher handles mixed liquor 2h, is then centrifuged for removing supernatant liquor, and lower floor is with distilling during water washing is in for 3 times to pH value of solution
Property, obtain pre- hydroxylated hexagonal boron nitride.
(2) in ice bath, 5.4g p-phenylenediamine is dissolved in the concentrated sulfuric acids of 4mL 98% and 32mL deionized waters, stirred to right
Phenylenediamine is completely dissolved.Under liquid level be added dropwise 30% sodium nitrite solution in above-mentioned solution be made corresponding sulphation weight
Nitrogen salt solution.
(3) in step (1), will complete pre- hydroxylated hexagonal boron nitride be scattered in 100mL deionized waters and
In the 50mL98% concentrated sulfuric acids, 130 DEG C are warming up to.Under fast stirring, obtained diazonium salt solution in step (2) is added drop-wise to
State in acid dispersion.Diazonium salt solution is added dropwise in 30min.Continue after stirring 3h, reaction solution is naturally cooled to
Room temperature, filtering, and washed successively with water, ammonia solution, absolute methanol.
(4) 1000mL three-necked flasks are subjected to vacuum pump drainage three times, manufacture anhydrous and oxygen-free environment.Under ice bath, by step
(3) phenylamino hexagonal boron nitride is made to be dispersed in anhydrous DMF solvent, then adds 10mL pyridines and make
For acid binding agent, lasting stirring.10g stearyl chlorides are dissolved in the anhydrous dichloromethane of 100mL again, are added dropwise in being dispersed with phenylamino
In the solvent of base hexagonal boron nitride.Allow reaction system to return to and persistently stir 18h at room temperature, reaction terminates, and is washed with absolute ether
Wash at least three times, the product after washing is dried into 24h so that dry hexagonal nanometer boron nitride is made in 60 DEG C of vacuum drying chambers
Composite.
Embodiment 4
(1) 2.8g sodium hydroxides and 2.2g potassium hydroxide are weighed, adds 1g hexagonal boron nitride nanosheets in three-necked flask,
Add 150mL deionized water dissolvings to disperse, the mechanical agitation under 150 DEG C of high temperature, after reacting 8h, be cooled to room temperature, be centrifuged off
Supernatant liquor, lower floor obtain pre- hydroxylated hexagonal boron nitride with water washing is distilled 3 times to pH value of solution in neutrality.
(2) in ice bath, 5.4g p-phenylenediamine is dissolved in the concentrated sulfuric acids of 4mL 98% and 32mL deionized waters, stirred to right
Phenylenediamine is completely dissolved.Under liquid level be added dropwise 30% sodium nitrite solution in above-mentioned solution be made corresponding sulphation weight
Nitrogen salt solution.
(3) pre- hydroxylated hexagonal boron nitride will have been completed in step (1) and has been scattered in 100mL deionized waters and 50mL98%
In the concentrated sulfuric acid, 130 DEG C are warming up to.Under fast stirring, obtained diazonium salt solution in step (2) is added drop-wise to above-mentioned acid point
In granular media.Diazonium salt solution is added dropwise in 30min.Continue after stirring 3h, reaction solution is naturally cooled into room temperature, mistake
Filter, and washed successively with water, ammonia solution (20cc ammonia solutions are in one liter of water), absolute methanol.
(4) 1000mL three-necked flasks are subjected to vacuum pump drainage three times, manufacture anhydrous and oxygen-free environment.Under ice bath, by step
(3) phenylamino hexagonal boron nitride is made to be dispersed in anhydrous DMF solvent, then adds 10mL pyridines and make
For acid binding agent, lasting stirring.10g stearyl chlorides are dissolved in the anhydrous dichloromethane of 100mL again, are added dropwise in being dispersed with phenylamino
In the solvent of base hexagonal boron nitride.Allow reaction system to return to and persistently stir 18h at room temperature, reaction terminates, and is washed with absolute ether
Wash at least three times, the product after washing is dried into 24h so that dry hexagonal nanometer boron nitride is made in 60 DEG C of vacuum drying chambers
Composite.
The Weight loss data that the thermogravimetry of embodiment 1~4 (TGA) measures (between 250~600 DEG C) is used as and connect
Aliphatic short-chain branch of the branch on hexagonal boron nitride nanosheet surface accounts for relative to the weight of hexagonal nanometer boron nitride composite
Than.As a result it is shown in Table 2.
Embodiment 5
Weigh hexagonal nanometer boron nitride composite and 44.75g prepared by the embodiment 1 of 0.5% mass fraction
High density polyethylene (HDPE) (HDPE), add the antioxidant of quality accounting 3/1000ths, melt blending 10 minutes at 200 DEG C.Then
The material of mixing is subjected to injection molding and breaks into batten, batten is freezed into 5h under liquid nitrogen, then low-temperature brittle fracture prepares ESEM
Sample.
Embodiment 6
Weigh the hexagonal nanometer boron nitride composite of the preparation of the embodiment 1 and 44.55g height of 1% mass fraction
Density polyethylene (HDPE), add the antioxidant of quality accounting 3/1000ths, melt blending 10 minutes at 200 DEG C.Then will
The material of mixing carries out injection molding and breaks into batten, batten is freezed into 5h under liquid nitrogen, then low-temperature brittle fracture prepares ESEM sample
Product.
Embodiment 7
Weigh the hexagonal nanometer boron nitride composite of the preparation of the embodiment 1 and 43.65g height of 3% mass fraction
Density polyethylene (HDPE), add the antioxidant of quality accounting 3/1000ths, melt blending 10 minutes at 200 DEG C.Then will
The material of mixing carries out injection molding and breaks into batten, batten is freezed into 5h under liquid nitrogen, then low-temperature brittle fracture prepares ESEM sample
Product.
Embodiment 8
Weigh the hexagonal nanometer boron nitride composite of the preparation of the embodiment 1 and 42.75g height of 5% mass fraction
Density polyethylene (HDPE), add the antioxidant of quality accounting 3/1000ths, melt blending 10 minutes at 200 DEG C.Then will
The material of mixing carries out injection molding and breaks into batten, batten is freezed into 5h under liquid nitrogen, then low-temperature brittle fracture prepares ESEM sample
Product.
Embodiment 9
Weigh the hexagonal nanometer boron nitride composite of the preparation of the embodiment 1 and 40.5g height of 10% mass fraction
Density polyethylene (HDPE), add the antioxidant of quality accounting 3/1000ths, melt blending 10 minutes at 200 DEG C.Then will
The material of mixing carries out injection molding and breaks into batten, batten is freezed into 5h under liquid nitrogen, then low-temperature brittle fracture prepares ESEM sample
Product.
Fig. 4 is that the hexagonal nanometer boron nitride composite of different addition mass fractions in embodiment 5-9 is prepared with HDPE
The SEM figures of composite.
Schemed by SEM of the hexagonal nanometer boron nitride composite of different addition mass fractions in HDP, can be intuitively
Go out with the gradual increase of hexagonal nanometer boron nitride composite addition, it shows good dispersion effect in HDPE.
From the figure, it can be seen that even if the hexagonal nanometer boron nitride composite of 10% addition still has well in HDPE matrixes
Dispersiveness, this illustrates that the aliphatic short-chain branch on modified hexagonal boron nitride surface and HDPE compatibility are good, so as to modified
Hexagonal nanometer boron nitride composite have good dispersiveness in HDPE.
It is analyzed as a comparison case below by way of not hydroxylated hexagonal boron nitride.
Comparative example 1
In ice bath, 5.4g p-phenylenediamine is dissolved in the concentrated sulfuric acids of 4mL 98% and 32mL deionized waters, stirred to benzene
Diamines is completely dissolved.Under liquid level be added dropwise 30% sodium nitrite solution in above-mentioned solution be made corresponding sulphation diazonium
Salt.
Not hydroxylated original h-BN is scattered in 100mL deionized waters and the 50mL98% concentrated sulfuric acids, is warming up to 130
℃.Under fast stirring, the above-mentioned diazonium salt solution being prepared is added drop-wise in above-mentioned acid dispersion.Diazonium salt solution exists
It is added dropwise in 30min.Continue stir 3h after, reaction solution is naturally cooled into room temperature, filter, and successively with water, ammonia solution,
Absolute methanol washs.1000mL three-necked flasks are subjected to vacuum pump drainage three times, manufacture anhydrous and oxygen-free environment., will be upper under ice bath
State the obtained phenylamino hexagonal boron nitride of step to be dispersed in anhydrous DMF solvent, then add 10mL pyridines
As acid binding agent, lasting stirring.10g stearyl chlorides are dissolved in the anhydrous dichloromethane of 100mL again, are added dropwise in being dispersed with benzene
In the solvent of amino hexagonal boron nitride.Allow reaction system to return to and persistently stir 18h at room temperature, reaction terminates, and uses absolute ether
Washing is dried 24h in 60 DEG C of vacuum drying chambers at least three times, by the product after washing and received so that dry hexagonal boron nitride is made
Nano composite material.Thermogravimetric, IR Characterization are carried out to product.The weight loss that will be measured from TGA (between 250~600 DEG C)
Data are as the aliphatic short-chain branch being grafted on hexagonal boron nitride nanosheet surface relative to hexagonal nanometer boron nitride composite wood
The weight accounting of material.As a result it is shown in Table 3.
Fig. 2 is that original hexagonal boron nitride and the hexagonal nanometer boron nitride of the method for modifying preparation in embodiment 1 are compound
The infrared spectrum of material.
Comparative example 2
Weigh the original hexagonal boron nitride of non-hydroxylating and 44.75g mono- as prepared by comparative example 1 of 0.5% mass fraction
Quantitative high density polyethylene (HDPE) (HDPE), the antioxidant of quality accounting 3/1000ths is added, melt blending 10 divides at 200 DEG C
Clock.Then the material of mixing is subjected to injection molding and breaks into batten, batten is freezed into 5h under liquid nitrogen, then low-temperature brittle fracture is prepared and swept
Retouch electron microscopic sample.
Comparative example 3
Weigh 1% mass fraction the original hexagonal boron nitride of non-hydroxylating as prepared by comparative example 1 and 44.5g it is highly dense
Polyethylene (HDPE) is spent, adds the antioxidant of quality accounting 3/1000ths, melt blending 10 minutes at 200 DEG C.Then will be mixed
Even material carries out injection molding and breaks into batten, batten is freezed into 5h under liquid nitrogen, then low-temperature brittle fracture prepares scanning electron microscope example.
Comparative example 4
Weigh the original hexagonal boron nitride of non-hydroxylating as prepared by comparative example 1 of 3% mass fraction and 43.65g height
Density polyethylene (HDPE), add the antioxidant of quality accounting 3/1000ths, melt blending 10 minutes at 200 DEG C.Then will
The material of mixing carries out injection molding and breaks into batten, batten is freezed into 5h under liquid nitrogen, then low-temperature brittle fracture prepares ESEM sample
Product.
Comparative example 5
Weigh the original hexagonal boron nitride of non-hydroxylating as prepared by comparative example 1 of 5% mass fraction and 42.75g height
Density polyethylene (HDPE), add the antioxidant of quality accounting 3/1000ths, melt blending 10 minutes at 200 DEG C.Then will
The material of mixing carries out injection molding and breaks into batten, batten is freezed into 5h under liquid nitrogen, then low-temperature brittle fracture prepares ESEM sample
Product.
Comparative example 6
Weigh the original hexagonal boron nitride of non-hydroxylating as prepared by comparative example 1 of 10% mass fraction and 40.5g height
Density polyethylene (HDPE), add the antioxidant of quality accounting 3/1000ths, melt blending 10 minutes at 200 DEG C.Then will
The material of mixing carries out injection molding and breaks into batten, batten is freezed into 5h under liquid nitrogen, then low-temperature brittle fracture prepares ESEM sample
Product.
Comparative example 7
45g high density polyethylene (HDPE) (HDPE) is weighed, adds the antioxidant of quality accounting 3/1000ths, is melted at 200 DEG C
Melt blending 10 minutes.Then the material of mixing is subjected to injection molding and breaks into batten, batten is freezed into 5h under liquid nitrogen, then low temperature
Brittle failure prepares scanning electron microscope example.
Fig. 3 is the composite that the original hexagonal boron nitride of different addition mass fractions in comparative example 2-7 is prepared with HDPE
SEM figure.
Schemed by SEM of the original hexagonal boron nitride of different addition mass fractions in HDP, can visually see with six
Side's nitridation Boron addition gradually increases, and agglomeration is increasingly severe, and obvious group is especially occurred as soon as since 3% addition
Poly- phenomenon.This illustrates the poor compatibility of unmodified original hexagonal boron nitride and HDPE, so as to which original hexagonal boron nitride is in HDPE
In poor dispersion.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to above-mentioned embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution and improvements done etc., it should be included in the guarantor of the present invention
Within the scope of shield.
Claims (11)
1. a kind of hexagonal nanometer boron nitride composite of aliphatic chain grafting, it is characterised in that possess the knot as shown in formula (I)
Structure：
Wherein：
A is hexagonal boron nitride；
B is aliphatic chain；Its medium chain length is selected from C1-C50, it is preferably C10-C20。
2. a kind of preparation method of the hexagonal nanometer boron nitride composite of aliphatic chain grafting as claimed in claim 1, it is special
Sign is, comprises the following steps：
Step 1, pre- hydroxylating processing is carried out to hexagonal nanometer boron nitride material：Nano material and strong alkali compound are carried out anti-
Should, and remove unreacted strong alkali compound；
Step 2, pre- hydroxylated nano material is added into acid solution, is acidified diazonium reactant salt with substituted phenylamino, obtains benzene
The hexagonal boron nitride that amine is modified, the substituted anilino- sulphation diazol is by following representation：
Wherein R1For hydrogen, alkyl or alkoxy.It is preferred that abovementioned alkyl or alkoxy are C1-C16, C1-C8Or C1-C4Alkyl or alkane
Epoxide, X-For the acid ion of the acid solution, preferably HSO4 -。
Step 3, aniline modified hexagonal boron nitride is scattered in the presence of acid binding agent in organic solvent further with acyl chlorides
Reaction, obtain the nano composite material of the aliphatic chain grafting of the structure as shown in formula (I).
3. a kind of preparation method of the hexagonal nanometer boron nitride composite of aliphatic chain grafting as claimed in claim 2, it is special
Sign is, in the step 1, the method for carrying out pre- hydroxylating processing to the hexagonal boron nitride has：Hexagonal boron nitride and highly basic
Carry out solid phase reaction；Or hexagonal boron nitride carries out liquid phase reactor in the solution with highly basic；The solid phase reaction or liquid phase are anti-
It should can be administered alone, or both and all to apply.
4. a kind of preparation method of the hexagonal nanometer boron nitride composite of aliphatic chain grafting as claimed in claim 2, it is special
Sign is, in the step 2, it is preferable that the strong alkali compound is selected from the hydroxide of group i and group ii alkali metal.
5. a kind of preparation method of the hexagonal nanometer boron nitride composite of aliphatic chain grafting as claimed in claim 2, it is special
Sign is that the method for pre- hydroxylating processing carries out high temperature solid state reaction for the hexagonal boron nitride and highly basic in the step 2, instead
The mixed system answered includes：
(i) sodium hydroxide (ii) potassium hydroxide (iii) hexagonal boron nitride nanosheet.
6. a kind of preparation method of the hexagonal nanometer boron nitride composite of aliphatic chain grafting as claimed in claim 2, it is special
Sign is, in the step 2, one or more of the acid solution in hydrochloric acid, sulfuric acid, nitric acid and permanganic acid；Preferably,
The concentrated acid is sulfuric acid, and the acid solution has at least 20% acid concentration.
7. a kind of preparation method of the hexagonal nanometer boron nitride composite of aliphatic chain grafting as claimed in claim 2, it is special
Sign is, in the step 3, the acyl chlorides is selected from stearyl chloride, palmitoyl chloride, n-amyl chloride, lauroyl chloride, myristoyl
One or more combinations in the acyl chlorides of the aliphatic chains such as chlorine, oenanthyl chloro, caprylyl chloride, caproyl chloride, n-butyryl chloride.
8. a kind of preparation method of the hexagonal nanometer boron nitride composite of aliphatic chain grafting as claimed in claim 2, it is special
Sign is, in the step 3, the acid binding agent is selected from triethylamine, pyridine, diisopropylethylamine, sodium acetate, sodium carbonate, carbonic acid
One or more kinds of combinations in potassium.
9. a kind of preparation method of the hexagonal nanometer boron nitride composite of aliphatic chain grafting as claimed in claim 2, it is special
Sign is, in the step 3, it is sub- that the organic solvent includes DMF, dichloromethane, carbon tetrachloride, dichloro
One or more combinations in sulfone, toluene.
10. a kind of preparation method of the hexagonal nanometer boron nitride composite of aliphatic chain grafting as claimed in claim 2, it is special
Sign is, in the step 3, reaction whole process is carried out under water-less environment.
11. a kind of mixed with polymers system as neutron shielding material, it is characterised in that the mixed system will by such as right
Seek the hexagonal nanometer boron nitride composite and polyethylene preparation that the aliphatic chain described in 1 is grafted.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711121039.9A CN107827770A (en) | 2017-11-14 | 2017-11-14 | A kind of hexagonal nanometer boron nitride composite of aliphatic chain grafting and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711121039.9A CN107827770A (en) | 2017-11-14 | 2017-11-14 | A kind of hexagonal nanometer boron nitride composite of aliphatic chain grafting and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107827770A true CN107827770A (en) | 2018-03-23 |
Family
ID=61654394
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711121039.9A Pending CN107827770A (en) | 2017-11-14 | 2017-11-14 | A kind of hexagonal nanometer boron nitride composite of aliphatic chain grafting and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107827770A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109762436A (en) * | 2018-12-12 | 2019-05-17 | 苏州太湖电工新材料股份有限公司 | A kind of low temperature resistant heat conductive insulating lacquer type organic coating and its preparation method and application suitable for superconducting insulation material |
| CN110182770A (en) * | 2019-06-26 | 2019-08-30 | 苏州太湖电工新材料股份有限公司 | A kind of preparation method of hydrophobic type hexagonal boron nitride nanosheet |
| RU2737188C1 (en) * | 2019-09-20 | 2020-11-25 | Российская Федерация, от имени которой выступает Государственная корпорация по атомной энергии "Росатом" (Госкорпорация "Росатом") | Method of producing polymer-based neutron-protective material |
| CN112759796A (en) * | 2020-12-29 | 2021-05-07 | 江苏集萃智能液晶科技有限公司 | Esterification method for improving dispersibility of hydroxyl-containing nano material |
| RU2762731C1 (en) * | 2021-05-21 | 2021-12-22 | Российская Федерация, от имени которой выступает Государственная корпорация по атомной энергии "Росатом" (Госкорпорация "Росатом") | Method of producing polymer-based neutron-protective material |
| CN113956539A (en) * | 2021-12-14 | 2022-01-21 | 广东思泉新材料股份有限公司 | Production process and application of modified hexagonal boron nitride powder |
| CN114561139A (en) * | 2022-02-25 | 2022-05-31 | 华南理工大学 | Heat-conducting coating utilizing synergistic effect of three fillers and preparation method and application thereof |
| CN117126565A (en) * | 2023-09-01 | 2023-11-28 | 鹤山市炎墨科技有限公司 | Anti-welding ink based on DCPD phenolic epoxy resin and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102421701A (en) * | 2009-05-13 | 2012-04-18 | 纳幕尔杜邦公司 | Surface modified hexagonal boron nitride particles |
-
2017
- 2017-11-14 CN CN201711121039.9A patent/CN107827770A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102421701A (en) * | 2009-05-13 | 2012-04-18 | 纳幕尔杜邦公司 | Surface modified hexagonal boron nitride particles |
Non-Patent Citations (2)
| Title |
|---|
| CHUNYI ZHI等: "Covalent Functionalization: Towards Soluble Multiwalled Boron Nitride Nanotubes", 《ANGEW. CHEM. INT. ED.》 * |
| KIHO KIM, JOOHEON KIM: "Vertical filler alignment of boron nitride/epoxy composite for thermal conductivity enhancement via external magnetic field", 《INTERNATIONAL JOURNAL OF THERMAL SCIENCES》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109762436A (en) * | 2018-12-12 | 2019-05-17 | 苏州太湖电工新材料股份有限公司 | A kind of low temperature resistant heat conductive insulating lacquer type organic coating and its preparation method and application suitable for superconducting insulation material |
| CN109762436B (en) * | 2018-12-12 | 2021-04-13 | 苏州太湖电工新材料股份有限公司 | Low-temperature-resistant heat-conducting insulating resin paint suitable for superconducting insulating material and preparation method and application thereof |
| CN110182770A (en) * | 2019-06-26 | 2019-08-30 | 苏州太湖电工新材料股份有限公司 | A kind of preparation method of hydrophobic type hexagonal boron nitride nanosheet |
| RU2737188C1 (en) * | 2019-09-20 | 2020-11-25 | Российская Федерация, от имени которой выступает Государственная корпорация по атомной энергии "Росатом" (Госкорпорация "Росатом") | Method of producing polymer-based neutron-protective material |
| CN112759796A (en) * | 2020-12-29 | 2021-05-07 | 江苏集萃智能液晶科技有限公司 | Esterification method for improving dispersibility of hydroxyl-containing nano material |
| WO2022142658A1 (en) * | 2020-12-29 | 2022-07-07 | 江苏集萃智能液晶科技有限公司 | Esterification method for improving dispersibility of hydroxyl-containing nano-material |
| RU2762731C1 (en) * | 2021-05-21 | 2021-12-22 | Российская Федерация, от имени которой выступает Государственная корпорация по атомной энергии "Росатом" (Госкорпорация "Росатом") | Method of producing polymer-based neutron-protective material |
| CN113956539A (en) * | 2021-12-14 | 2022-01-21 | 广东思泉新材料股份有限公司 | Production process and application of modified hexagonal boron nitride powder |
| CN113956539B (en) * | 2021-12-14 | 2023-08-25 | 广东思泉新材料股份有限公司 | Production process and application of modified hexagonal boron nitride powder |
| CN114561139A (en) * | 2022-02-25 | 2022-05-31 | 华南理工大学 | Heat-conducting coating utilizing synergistic effect of three fillers and preparation method and application thereof |
| CN117126565A (en) * | 2023-09-01 | 2023-11-28 | 鹤山市炎墨科技有限公司 | Anti-welding ink based on DCPD phenolic epoxy resin and preparation method thereof |
| CN117126565B (en) * | 2023-09-01 | 2024-02-20 | 鹤山市炎墨科技有限公司 | Anti-welding ink based on DCPD phenolic epoxy resin and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107827770A (en) | A kind of hexagonal nanometer boron nitride composite of aliphatic chain grafting and preparation method thereof | |
| CN106046683B (en) | Low-smoke and flame retardant polymer composite and preparation method thereof | |
| CN109134271A (en) | A kind of pair of hexagonal boron nitride carries out the modified method in surface | |
| CN104893248B (en) | Preparation method and application of inorganic hybrid smoke-suppression flame retardant | |
| CN104448299A (en) | In-situ-polymerized halogen-free flame-retardant nylon 6/attapulgite nano composite material and preparation method thereof | |
| CN103241735A (en) | Hybrid nanomaterial of melamine chemically-modified graphene oxide and preparation method of hybrid nanomaterial | |
| CN103980636B (en) | A kind of Wood-plastic foam composite and preparation method thereof | |
| CN102963898A (en) | Preparation method of dual-functional group organically modified montmorillonite | |
| CN105017565B (en) | A kind of preparation method of graphene oxide shell material cladding sulfur microcapsule | |
| CN104893102B (en) | Acrylic resin based nano composite material and preparation method thereof | |
| CN104448830B (en) | A kind of phosphorus silicon composite flame-retardant agent and its preparation method and application | |
| CN108299653A (en) | Phosphorus-nitrogen flame retardant functionalization graphene and preparation method thereof | |
| CN100391846C (en) | Method for prepring and modifying high heat-resistant aluminium hydroxide | |
| CN109534306A (en) | The method for preparing spherical hexagonal boron nitride powder based on urea nitrogen source | |
| CN103059567A (en) | Fire-retarding hexagonal boron nitride/thermosetting resin composite material and preparation method thereof | |
| CN109880295A (en) | A kind of graphene oxide and its epoxy nano composite material of amino-terminated modification | |
| CN104861201A (en) | Method for preparing core-shell synergistic magnesium zinc composite flame retardants | |
| CN1830788A (en) | Technology of transforming common magnesium hydrexide into hexagonal sheel shaped magnesium hydroxide by hydrothermal method | |
| CN107986313A (en) | A kind of preparation method of spherical calcium carbonate | |
| CN103806088B (en) | Method for preparing calcium carbonate whisker by taking triethanolamine as aid | |
| CN101967275A (en) | Nano magnesium carbonate modified fire protection engineering plastic and preparation method thereof | |
| CN108409513A (en) | A kind of method of ammonium salt induction crystallization | |
| CN100398441C (en) | Method of preparing nano-zinc borate | |
| CN102220144A (en) | Preparation method of flame retardant additive | |
| CN107353448A (en) | A kind of natural rubber/modified white carbon black composite 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 | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180323 |
|
| WD01 | Invention patent application deemed withdrawn after publication |