CN104558323B - A kind of highly-water-soluble nano-hexagonal boron nitride and the preparation method of polymer composite aquogel thereof - Google Patents
A kind of highly-water-soluble nano-hexagonal boron nitride and the preparation method of polymer composite aquogel thereof Download PDFInfo
- Publication number
- CN104558323B CN104558323B CN201410802063.9A CN201410802063A CN104558323B CN 104558323 B CN104558323 B CN 104558323B CN 201410802063 A CN201410802063 A CN 201410802063A CN 104558323 B CN104558323 B CN 104558323B
- Authority
- CN
- China
- Prior art keywords
- boron nitride
- hexagonal boron
- water
- nano
- highly
- 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.)
- Active
Links
Abstract
The present invention relates to a kind of highly-water-soluble nano-hexagonal boron nitride and the preparation method of polymer composite aquogel thereof, including: 1) use citric acid treatment hexagonal boron nitride, obtain the nano-hexagonal boron nitride of highly-water-soluble；2) the highly-water-soluble nano-hexagonal boron nitride utilizing said method to obtain is mixed homogeneously with deaerated water, polymerisable monomer, initiator and catalyst, has caused free radical in situ polymerization to react, and obtains nano-hexagonal boron nitride/polymer composite aquogel.The inventive method is simple to operation, and its composite aquogel has higher mechanical strength and more excellent swelling behavior and environment-responsive.Additionally, the composite aquogel of the present invention can also water conservation for a long time, lock water superior performance, extend the use cycle of hydrogel, solve hydrogel long storage time can a large amount of dehydrations and can not a wide variety of difficult problem.In fields such as bio-pharmaceuticals, chemical products, mechanical industry and agricultural cultivations, there is good application prospect.
Description
Technical field
The present invention relates to the preparation method of a kind of composite aquogel, particularly to a kind of highly-water-soluble nano-hexagonal boron nitride and
The preparation method of its polymer composite aquogel.
Background technology
Hydrogel is a kind of high molecular polymer with three-dimensional net structure, and it is with water as disperse medium, and three-dimensional network is tied
Structure is cross-linked by the linear polymeric containing hydrophilic radical and constitutes.Hydrophilic radical owing to containing on macromolecular main chain is combined with water,
Can be included in inside network structure by hydrone, hydrogel can absorb substantial amounts of water and keep certain shape, meets water-swellable
Insoluble.
Along with the continuous growth of domestic and international market demand, hydrogel is developed rapidly in recent years.Hydrogel has a variety of
Class, by the difference of its size shape, can be divided into macroscopic hydrogel and microcosmic hydrogel.The difference originated by its macromolecular material,
Synthesis macromolecule hydrogel and natural polymer hydrogel can be divided into.By the difference of its three-dimensional network bonding pattern, thing can be divided into
Reason gel and chemical gel.Physical gel is that the winding by physical force such as hydrogen bond, electrostatic interaction, chain etc. is formed, and is
Impermanency；Chemical gel is then cross-linked to form by chemical bond, is permanent gels.It addition, press its environment sound to external world
Answer the difference of degree, traditional hydrogel and progress in Intelligent Hydrogel can be divided into.The change of traditional hydrogel environment to external world rings
Answering property is slow, even without response；And progress in Intelligent Hydrogel can to the minor variations of external environment condition or stimulation, in physical arrangement or
Making corresponding change in chemical property, this change is the most reversible.
Traditional hydrogel is chain length distribution extensively due to the polymer between the random distribution of crosslinking points, crosslinking points, and high
The crosslinking points of density limit polymer chain cause its most for another example linear polymer chain have flexibility just like that, be inevitably present machine
A series of shortcomings such as tool is weak, property is crisp, deformability is poor and environment-responsive is poor, thus greatly limit its wide in field
General application.Additionally, existing hydrogel generally exist can not the phenomenon of water conservation very well, what this point also limit hydrogel should
With.In recent years, the novel hydrogels of better mechanical property such as topological type hydrogel, dual network type hydrogel and nano combined water
Gel is paid close attention to by people all the more.At present, the most existing increasing scholar begins one's study how to improve hydrogel
Mechanical performance.In 2002, Haraguchi etc. reported using inorganic matter clay as cross-linking agent for the first time, by the most poly-
Close the Nanometer composite hydrogel prepared (see Kazutoshi Haraguchi；Toru Takehisa.Nanocomposite hydrogels:a
unique organic-inorganic network structure with extraordinary mechanical,optical,and
swelling/de-swelling properties[J].Advanced Materials.2002,14,1120-1124.).This novel water-setting
The mechanical performance of glue is greatly improved, and the performance such as swelling, environmental response is the most all significantly improved.Recently, the system such as Shi
For going out carbon nano-tube/polymer hydrogel (see Jiahua Shi；Zhi-Xin Guo；Bohan Zhan；Hongxia Luo；Yongfang
Li；Daoben Zhu.Actuator based on MWNT/PVA hydrogels[J].Journal of Physical Chemistry B.
2005,109,14789-14791.), graphene oxide-polymer composite aquogel is prepared (see Huai-Ping from bosom duckweed etc.
Cong；Ping Wang；Shu-Hong Yu.Highly elastic and superstretchable graphene
Oxide/polyacrylamide hydrogels [J] .Small.2013,1-6.), Chen Guangming etc. prepares double-hydroxide/polymer
Composite aquogels etc. are (see Ziqiao Hu；Guangming Chen.Novel nanocomposite hydrogels consisting of
layered double hydroxide with ultrahigh tensibility and hierarchical porous structure at low
Inorganic content [J] .Advanced Materials.2014,26,5950-5956.), these results of study all show that nanometer is multiple
Heshui gel phase has more excellent performance than traditional hydrogel, and then has widened the application of hydrogel.
As the analog of Graphene, nano-hexagonal boron nitride itself has the most excellent character, the best machine
Tool performance and thermal conductivity etc., but the solubility property of its difference limits its application.Therefore, hexagonal boron nitride dissolubility is improved outstanding
For important and crucial.Knowable to current result of study,Acid and Bronsted acid all can modified hexagonal boron nitride to improve
Dissolubility, but without the organic acid study on the modification to hexagonal boron nitride.Itself there is the hexagonal boron nitride of excellent mechanical properties,
It is expected to the form of inorganic matter/polymer composite aquogel, becomes one of inorganic substances of improving conventional hydrogels performance.Additionally,
Existing hydrogel generally exist can not the phenomenon of water conservation very well, also improved.
Summary of the invention
It is an object of the invention to provide a kind of highly-water-soluble nano-hexagonal boron nitride and the preparation of polymer composite aquogel thereof
Method, the problem solving conventional hydrogels bad mechanical property, bad response and poor water retention property.
In order to realize above-mentioned purpose, present invention firstly provides the preparation method of a kind of highly-water-soluble nano-hexagonal boron nitride,
Specifically include following steps:
Hexagonal boron nitride raw material is mixed homogeneously by S1 with citric acid；
The citric acid of mix homogeneously-hexagonal boron nitride system in S1 is transferred in reaction bulb by S2, is warming up to citric acid the most melted,
React under stirring condition；
S3, by gained product in S2, washs respectively through water and ethanol, refilters, is dried, obtains a kind of highly-water-soluble nanometer six
Side's boron nitride.
Citric acid, as organic acid, has stronger acidity, can ionize multiple H simultaneously+, it is expected to as acid six side's nitrogen
Change boron modification.Based on this, step S1 is used citric acid treatment hexagonal boron nitride.
As preferably, the hexagonal boron nitride raw material described in step S1 is 1:5～1:70 with the mass ratio of citric acid.The present invention
The consumption of middle citric acid has certain impact to modified effect.The consumption of citric acid is very little, modified incomplete, causes modified effect
Inconspicuous；Consumption is too many, causes the waste of citric acid, is unfavorable for saving technical costs.
As preferably, the reaction temperature described in step S2 is 120～200 DEG C, and the response time is 1～10 day.The present invention
Modified effect is had an impact by the temperature and time of middle citric acid treatment hexagonal boron nitride.Temperature is the lowest, and citric acid does not melt,
Mix with hexagonal boron nitride uneven, thus affect modified effect；Temperature is the highest, and citric acid decomposes, and loses modification power.
Time is the shortest, reactant partial reaction, causes modified incomplete；Time is oversize, and the technological process cycle is oversize.
As preferably, the baking temperature described in step S3 is 55～70 DEG C, and drying time is 8～24h.
The present invention mainly provides the preparation method of a kind of high-performance nano hexagonal boron nitride/polymer composite aquogel, main
Highly-water-soluble nano-hexagonal boron nitride prepared by said method to be utilized, as raw material, specifically includes following steps:
C1, by joining in deaerated water with the highly-water-soluble nano-hexagonal boron nitride prepared by any one of claims 1 to 3, obtains body
It is A；
System A is placed in ultrasonic disperse in ultrasonic washing unit by C2；
C3 is sequentially added into polymerisable monomer, initiator and catalyst in system A after dispersion, and stirring mixing, to uniformly, obtains body
It is B；
System B is transferred in mould by C4, causes free radical in situ polymerization reaction, obtains a kind of nano-hexagonal boron nitride/polymer multiple
Heshui gel.
As preferably, the consumption of the highly-water-soluble nano-hexagonal boron nitride described in step C1 is polymerisable monomer consumption
1～10wt%, described deaerated water before use, first through nitrogen bubble deoxygenation 0.5～5 hours.In the present invention, highly-water-soluble is received
Rice hexagonal boron nitride, both as the cross-linking agent of free radical in situ polymerization reaction, serves again the effect improving hydrogel performance.Its
Consumption has certain impact to forming hydrogel.Consumption is the lowest, and i.e. dosage of crosslinking agent is very little, is not enough to be cross-linked to form hydrogel；
Consumption is the highest, and crosslinking points is the most intensive, can limit motion and the flexibility of polymer chain so that the machinery of hydrogel and swelling behavior
It is deteriorated.Water is formed with impact through time of nitrogen bubble deoxygenation to hydrogel.The deoxygenation time is the shortest, and deoxygenation is incomplete, and
Oxygen is free radical capture body, the reaction of this free radical in situ polymerization can be caused not carry out, thus can not form hydrogel；Deoxygenation
Time is oversize, waste nitrogen and time.
As preferably, the ultrasonic power described in step C2 is 90～300W, and the time is 15～45min.
As preferably, the concentration in water of the polymerisable monomer described in step C3 is 0.05～1g/ml, and described gathers
Closing monomer is acrylamide or acrylic acid.The hydrogel formed is had an impact by the concentration of monomer.Concentration is the lowest, polymeric matrix
Molecular weight is the least, and sample strength is little, hydrogel not easy-formation；Concentration is the highest, can produce big in situ in radical polymerization process
The heat of amount, relatively big due to now system viscosity again, substantial amounts of heat can not distribute in time so that inside the hydrogel of formation
A large amount of bubble occurs, has a strong impact on the mechanical performance of hydrogel.
In step C3, initiator amount and catalyst amount have an impact forming hydrogel.Initiator amount is very little, it is impossible to draw
From the carrying out by base home position polymerization reaction；Consumption is too many, and polymeric matrix molecular weight can be caused the least, it is impossible to form water-setting
Glue.Catalyst amount very little, causes that free radical in situ polymerization reaction time consumption is oversize even cannot react；Consumption is too many, freely
It is too fast that base home position polymerization reaction is carried out, and sudden and violent poly-phenomenon easily occurs, affects gained hydrogel performance.
As preferably, the initiator described in step C3 and catalyst be Ammonium persulfate. common in Raolical polymerizable and
N, N, N', N'-tetramethylethylenediamine combines.
As preferably, in step C4, the temperature of initiated polymerization is 5～50 DEG C, and the response time is 0.5～48h.Cause
The temperature of polyreaction has an impact forming hydrogel.The temperature of initiated polymerization is the lowest, it is impossible to reach the effect of initiation reaction
Really；Temperature is the highest, is easily caused the appearance of implode phenomenon, thus produces bubble, and then affects the mechanical performance of hydrogel.
Compared with prior art, preparation method of the present invention is simple, easily operates, and the composite aquogel obtained has higher machine
Tool intensity and more excellent swelling behavior and environment-responsive, and water retention property highlights.With highly-water-soluble nano-hexagonal boron nitride
For in the structure of the composite aquogel of cross-linking agent, nano-hexagonal boron nitride is no longer simply presented in simple physics is compound
In hydrogel, especially as polyfunctional crosslinking agent by crosslinked together for linear organic polymer long-chain, pass through radical polymerization
The initiation of reaction, is formed and has inorganic/organic network structure the longest polymer chain, special.Due to the polymer chain obtained
Long and pliable and tough, when drawn gel, polymer chain ruptures the most easily.Additionally, the hexagonal boron nitride of high-mechanical property, the most significantly
Improve the mechanical strength of hydrogel.Finally, the mechanical strength of nano-hexagonal boron nitride/polymer composite aquogel and ductility
All significantly improved.Meanwhile, also solve hydrogel long storage time can a large amount of dehydrations and can not a wide variety of difficult problem,
Extend the use cycle of hydrogel.It is expected to be used in fields such as bio-pharmaceuticals, chemical products, mechanical industry and agricultural cultivations,
There is good application prospect.
Accompanying drawing explanation
Fig. 1 is the schematic diagram preparing highly-water-soluble nano-hexagonal boron nitride；
Fig. 2 is the schematic diagram preparing nano-hexagonal boron nitride/polymer composite aquogel；
Fig. 3 is nano-hexagonal boron nitride/polyacrylamide composite aquogel finished product of preparing of the present invention and polyacrylamide conventional hydrogels
The contrast photo of finished product.
Detailed description of the invention
In order to be better understood from the present invention, the solution of the present invention is expanded on further below in conjunction with embodiment, but the present invention's is interior
Hold and include but being not limited solely to the following examples.
Embodiment 1
500mg hexagonal boron nitride powder raw material is mixed homogeneously with 2.5g citric acid, is warmed up to 200 DEG C, stirring reaction 1 day,
It is cooled to room temperature, washs to the aobvious neutrality of washing liquid with ethanol and water, filter, collect filter cake, at 55 DEG C, be vacuum dried 24h,
Obtain highly-water-soluble nano-hexagonal boron nitride.
Embodiment 2
500mg hexagonal boron nitride powder raw material is mixed homogeneously with 15g citric acid, is warmed up to 160 DEG C, stirring reaction 5 days,
It is cooled to room temperature, washs to the aobvious neutrality of washing liquid with ethanol and water, filter, collect filter cake, at 70 DEG C, be vacuum dried 8h,
Obtain highly-water-soluble nano-hexagonal boron nitride.
Embodiment 3
500mg hexagonal boron nitride powder raw material is mixed homogeneously with 35g citric acid, is warmed up to 120 DEG C, stirring reaction 10 days,
It is cooled to room temperature, washs to the aobvious neutrality of washing liquid with ethanol and water, filter, collect filter cake, at 65 DEG C, be vacuum dried 16h,
Obtain highly-water-soluble nano-hexagonal boron nitride.
Embodiment 4
10mg highly-water-soluble nano-hexagonal boron nitride is dissolved in 1ml in the water of nitrogen deoxygenation 0.5h, under 90～300W power
Ultrasonic 15～45min, obtain uniform hexagonal boron nitride aqueous dispersions, then under condition of ice bath, be sequentially added into acrylamide list
Body 1g, initiator ammonium persulfate 1mg and catalyst n, N, N', N'-tetramethylethylenediamine 1 μ l, stir, be transferred to
Diameter is respectively in the cylindrical die of 2.6cm and 0.7cm, causes and completes polyreaction, response time at 5 DEG C
48 hours, i.e. obtain nano-hexagonal boron nitride/polyacrylamide composite aquogel.
Utilizing the mechanical property of universal tensile testing machine test compound hydrogel, result shows that its tensile elongation exceedes
8000%, compressive strength reaches 2.5MPa；Its water retention property is studied, finds that ambient temperatare is put 1 year, water-setting gum base
This non-dehydration, water retention property is notable.
Embodiment 5
50mg highly-water-soluble nano-hexagonal boron nitride is dissolved in 10ml in the water of nitrogen deoxygenation 5h, under 90～300W power
Ultrasonic 15～45min, obtain uniform hexagonal boron nitride aqueous dispersions, then under condition of ice bath, be sequentially added into acrylamide list
Body 0.5g, initiator ammonium persulfate 25mg and catalyst n, N, N', N'-tetramethylethylenediamine 25 μ l, stir, turn
Move to diameter be respectively in the cylindrical die of 2.6cm and 0.7cm, at 50 DEG C, cause and complete polyreaction, reaction
0.5 hour time, i.e. obtain nano-hexagonal boron nitride/polyacrylamide composite aquogel.
Utilizing the mechanical property of universal tensile testing machine test compound hydrogel, result shows that its tensile elongation exceedes
10000%, compressive strength reaches 3MPa；Its water retention property is studied, finds that ambient temperatare is put 1 year, water-setting gum base
This non-dehydration, water retention property is notable.
Embodiment 6
50mg highly-water-soluble nano-hexagonal boron nitride is dissolved in 5ml in the water of nitrogen deoxygenation 3h, super under 90～300W power
Sound 15～45min, obtains uniform hexagonal boron nitride aqueous dispersions, then under condition of ice bath, is sequentially added into acrylamide monomer
1g, initiator ammonium persulfate 20mg and catalyst n, N, N', N'-tetramethylethylenediamine 50 μ l, stir, be transferred to
Diameter is respectively in the cylindrical die of 2.6cm and 0.7cm, causes and completes polyreaction, response time at 30 DEG C
30 hours, i.e. obtain nano-hexagonal boron nitride/polyacrylamide composite aquogel.
Utilizing the mechanical property of universal tensile testing machine test compound hydrogel, result shows that its tensile elongation exceedes
6000%, compressive strength reaches 3MPa；Its water retention property is studied, finds that ambient temperatare is put 1 year, water-setting gum base
This non-dehydration, water retention property is notable.
Embodiment 7
10mg highly-water-soluble nano-hexagonal boron nitride is dissolved in 1ml in the water of nitrogen deoxygenation 0.5h, under 90～300W power
Ultrasonic 15～45min, obtain uniform hexagonal boron nitride aqueous dispersions, then under condition of ice bath, be sequentially added into acrylic monomers
1g, initiator ammonium persulfate 1mg and catalyst n, N, N', N'-tetramethylethylenediamine 1 μ l, stir, be transferred to straight
Footpath is respectively in the cylindrical die of 2.6cm and 0.7cm, causes and complete polyreaction at 5 DEG C, and the response time is
40 hours, i.e. obtain nano-hexagonal boron nitride/polyacrylic acid composite aquogel.
Embodiment 8
50mg highly-water-soluble nano-hexagonal boron nitride is dissolved in 10ml in the water of nitrogen deoxygenation 5h, under 90～300W power
Ultrasonic 15～45min, obtain uniform hexagonal boron nitride aqueous dispersions, then under condition of ice bath, be sequentially added into acrylic monomers
0.5g, initiator ammonium persulfate 25mg and catalyst n, N, N', N'-tetramethylethylenediamine 25 μ l, stir, transfer
It is respectively in the cylindrical die of 2.6cm and 0.7cm to diameter, at 50 DEG C, causes and complete polyreaction, during reaction
Between 1 hour, i.e. obtain nano-hexagonal boron nitride/polyacrylic acid composite aquogel.
Embodiment 9
50mg highly-water-soluble nano-hexagonal boron nitride is dissolved in 5ml in the water of nitrogen deoxygenation 3h, super under 90～300W power
Sound 15～45min, obtains uniform hexagonal boron nitride aqueous dispersions, then under condition of ice bath, is sequentially added into acrylic monomers 1g,
Initiator ammonium persulfate 20mg and catalyst n, N, N', N'-tetramethylethylenediamine 50 μ l, stir, be transferred to diameter
Being respectively in the cylindrical die of 2.6cm and 0.7cm, cause and complete polyreaction at 30 DEG C, the response time 10 is little
Time, i.e. obtain nano-hexagonal boron nitride/polyacrylic acid composite aquogel.
Comparative example
50mg methylene diacrylamide (conventional hydrogels commonly uses cross-linking agent) is dissolved in 10ml in the distilled water of nitrogen deoxygenation 5h,
Ultrasonic dissolution obtains methylene diacrylamide aqueous solution, then under condition of ice bath, is sequentially added into acrylamide monomer 2g, initiator
Ammonium persulfate. 20mg and catalyst n, N, N', N'-tetramethylethylenediamine 20 μ l, stirs and is completely dissolved to each material, shift
It is respectively in the cylindrical mould of 2.6cm and 0.7cm to diameter, causes at 20 DEG C and complete polyreaction, to obtain final product
To traditional polyacrylamide hydrophilic gel.
Utilizing the mechanical property of universal tensile testing machine test conventional hydrogels, result shows its compressive strength only 40kPa,
And property is crisp cannot stretch；Its water retention property is studied, finds that its water retention property can not show a candle to the composite aquogel of the present invention.
Claims (9)
1. the preparation method of a highly-water-soluble nano-hexagonal boron nitride, it is characterised in that comprise the steps:
Hexagonal boron nitride raw material is mixed by S1 with citric acid；
The citric acid of mix homogeneously-hexagonal boron nitride system in S1 is transferred in reaction bulb by S2, is warming up to citric acid and melts, with molten
The citric acid melted is to react under solvent, stirring condition；
S3, by gained product in S2, washs respectively through water and ethanol, refilters, is dried, obtains a kind of highly-water-soluble nanometer six
Side's boron nitride.
The preparation method of highly-water-soluble nano-hexagonal boron nitride the most according to claim 1, it is characterised in that in step S1 six
The mass ratio that side's boron nitride raw mixes with citric acid is 1:5～1:70.
The preparation method of highly-water-soluble nano-hexagonal boron nitride the most according to claim 1, it is characterised in that anti-in step S2
Answering temperature is 120～200 DEG C, and the response time is 1～10 day.
4. the preparation method of nano-hexagonal boron nitride/polymer composite aquogel, it is characterised in that comprise the steps:
C1, by joining in deaerated water with the highly-water-soluble nano-hexagonal boron nitride prepared by any one of claims 1 to 3, obtains system
A；
System A is placed in ultrasonic disperse in ultrasonic washing unit by C2；
C3 is sequentially added into polymerisable monomer, initiator and catalyst in system A after dispersion, and stirring mixing, to uniformly, obtains body
It is B；
System B is transferred in mould by C4, causes free radical in situ polymerization reaction, obtains a kind of nano-hexagonal boron nitride/polymer multiple
Heshui gel.
The preparation method of nano-hexagonal boron nitride the most according to claim 4/polymer composite aquogel, it is characterised in that step
The cross-linking agent that highly-water-soluble nano-hexagonal boron nitride described in rapid C1 reacts as this free radical in situ polymerization.
The preparation method of nano-hexagonal boron nitride the most according to claim 4/polymer composite aquogel, it is characterised in that step
The consumption of the highly-water-soluble nano-hexagonal boron nitride described in rapid C1 is the 1～10wt% of polymerisable monomer consumption, and described removes
Oxygen water is through nitrogen bubble deoxygenation 0.5～5 hours gained.
The preparation method of nano-hexagonal boron nitride the most according to claim 4/polymer composite aquogel, it is characterised in that step
The polymerisable monomer described in rapid C3 concentration in water is 0.05～1g/ml, and described polymerisable monomer is acrylamide or third
Olefin(e) acid.
The preparation method of nano-hexagonal boron nitride the most according to claim 4/polymer composite aquogel, it is characterised in that step
Initiator described in rapid C3 and catalyst are Ammonium persulfate. and N, and N, N', N'-tetramethylethylenediamine combines.
The preparation method of nano-hexagonal boron nitride the most according to claim 4/polymer composite aquogel, it is characterised in that step
The temperature causing free radical in situ polymerization reaction in rapid C4 is 5～50 DEG C, and the response time is 0.5～48 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410802063.9A CN104558323B (en) | 2014-12-22 | 2014-12-22 | A kind of highly-water-soluble nano-hexagonal boron nitride and the preparation method of polymer composite aquogel thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410802063.9A CN104558323B (en) | 2014-12-22 | 2014-12-22 | A kind of highly-water-soluble nano-hexagonal boron nitride and the preparation method of polymer composite aquogel thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104558323A CN104558323A (en) | 2015-04-29 |
| CN104558323B true CN104558323B (en) | 2016-08-24 |
Family
ID=53075468
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410802063.9A Active CN104558323B (en) | 2014-12-22 | 2014-12-22 | A kind of highly-water-soluble nano-hexagonal boron nitride and the preparation method of polymer composite aquogel thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104558323B (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107573446B (en) * | 2016-07-04 | 2019-09-24 | 香港城市大学深圳研究院 | Boron nitride nanosheet and carbopol gel composite heat interfacial material and preparation method |
| KR101850244B1 (en) * | 2017-04-05 | 2018-06-07 | 한국과학기술원 | Nanocomposite with bnnp and fabrication process thereof |
| CN107163290B (en) * | 2017-05-18 | 2019-08-23 | 清华-伯克利深圳学院筹备办公室 | A kind of functionalization hexagonal boron nitride nanosheet, dispersion liquid and its preparation method and application |
| US10774211B2 (en) * | 2017-10-12 | 2020-09-15 | Saudi Arabian Oil Company | Polymer gel with nanocomposite crosslinker |
| CN107674112B (en) * | 2017-10-31 | 2020-12-08 | 苏州博进生物技术有限公司 | Affinity chromatography medium using heparin as ligand |
| CN108485158B (en) * | 2018-03-27 | 2020-07-10 | 华中科技大学 | H-BN and PAAm double-network hydrogel and preparation method thereof |
| CN109134888A (en) * | 2018-08-30 | 2019-01-04 | 成都华点知享知识产权运营有限公司 | A kind of composite hydrogel and preparation method thereof of boron nitride filling |
| CN110999595A (en) * | 2019-12-31 | 2020-04-14 | 赵梓权 | Hydrogel seed and preparation method thereof |
| CN111234429A (en) * | 2020-03-18 | 2020-06-05 | 衢州市中通化工有限公司 | PTFE/boron nitride composite material and preparation method thereof |
| US11421141B2 (en) * | 2020-04-21 | 2022-08-23 | Saudi Arabian Oil Company | Nanosheet polymer composite for water shutoff |
| US11306159B2 (en) | 2020-04-21 | 2022-04-19 | Saudi Arabian Oil Company | Nanosheet polymer composite for water shutoff |
| US11261367B2 (en) | 2020-04-21 | 2022-03-01 | Saudi Arabian Oil Company | Polymer-sand nanocomposite for water shutoff |
| US11578543B2 (en) | 2020-10-09 | 2023-02-14 | Saudi Arabian Oil Company | Polymer-sand nanocomposite lost circulation material |
| CN112979869B (en) * | 2021-03-01 | 2023-03-17 | 武汉科技大学 | Hexagonal boron nitride nanosheet hydrogel composite material, and preparation method and application thereof |
| CN117603506B (en) * | 2024-01-22 | 2024-04-23 | 汕头大学 | Boron nitride heat conduction material with three-dimensional network structure and preparation and application thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102015913B (en) * | 2008-04-25 | 2013-09-25 | 3M创新有限公司 | Process for the surface modification of particles |
| CN102229683B (en) * | 2010-12-13 | 2013-10-16 | 北京理工大学 | Preparation method of graphene based nano composite hydrogel |
| CN102604302B (en) * | 2012-03-02 | 2014-06-11 | 北京航空航天大学 | Preparing method of biomimetic laminated high-strength composite hydrogel film |
| CN103172924A (en) * | 2013-04-17 | 2013-06-26 | 天津大学 | High-thermal conductivity polymer composite material and preparation method thereof |
| CN105246983B (en) * | 2013-05-30 | 2017-10-24 | 住友电木株式会社 | Hydrophobic inorganic particle, thermal component resin combination and electronic part apparatus |
-
2014
- 2014-12-22 CN CN201410802063.9A patent/CN104558323B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104558323A (en) | 2015-04-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104558323B (en) | A kind of highly-water-soluble nano-hexagonal boron nitride and the preparation method of polymer composite aquogel thereof | |
| Qi et al. | Fabrication of a new polysaccharide-based adsorbent for water purification | |
| Dai et al. | Synthesis and response of pineapple peel carboxymethyl cellulose-g-poly (acrylic acid-co-acrylamide)/graphene oxide hydrogels | |
| Bahrami et al. | Double network hydrogel of sodium alginate/polyacrylamide cross-linked with POSS: Swelling, dye removal and mechanical properties | |
| Chen et al. | Fabrication of starch-based high-performance adsorptive hydrogels using a novel effective pretreatment and adsorption for cationic methylene blue dye: Behavior and mechanism | |
| Cheng et al. | Preparation and properties of pH-responsive reversible-wettability biomass cellulose-based material for controllable oil/water separation | |
| Nasseri et al. | Cellulose nanocrystals in smart and stimuli-responsive materials: a review | |
| Dragan et al. | Enhanced sorption of methylene blue from aqueous solutions by semi-IPN composite cryogels with anionically modified potato starch entrapped in PAAm matrix | |
| Bhattacharyya et al. | Removal of congo red and methyl violet from water using nano clay filled composite hydrogels of poly acrylic acid and polyethylene glycol | |
| Li et al. | Double network hydrogels for energy/environmental applications: challenges and opportunities | |
| Wang et al. | Synthesis, swelling and responsive properties of a new composite hydrogel based on hydroxyethyl cellulose and medicinal stone | |
| Rashidzadeh et al. | On the preparation and swelling properties of hydrogel nanocomposite based on sodium alginate-g-poly (acrylic acid-co-acrylamide)/clinoptilolite and its application as slow release fertilizer | |
| Feng et al. | Synthesis and swelling behaviors of yeast-g-poly (acrylic acid) superabsorbent co-polymer | |
| Li et al. | Preparation and characterization of pH-and temperature-responsive hydrogels with surface-functionalized graphene oxide as the crosslinker | |
| Adair et al. | Superabsorbent materials derived from hydroxyethyl cellulose and bentonite: Preparation, characterization and swelling capacities | |
| Guo et al. | High-strength and pH-responsive self-healing polyvinyl alcohol/poly 6-acrylamidohexanoic acid hydrogel based on dual physically cross-linked network | |
| Nie et al. | Preparation of amphoteric nanocomposite hydrogels based on exfoliation of montmorillonite via in-situ intercalative polymerization of hydrophilic cationic and anionic monomers | |
| CN104710584A (en) | Polymer hydrogel and preparation method thereof | |
| Yu et al. | Facile fabrication of functional chitosan microspheres and study on their effective cationic/anionic dyes removal from aqueous solution | |
| Soliman et al. | Preparation of carboxymethyl cellulose-g-poly (acrylic acid-2-acrylamido-2-methylpropane sulfonic acid)/attapulgite superabsorbent composite | |
| Zhang et al. | Multi-responsive, tough and reversible hydrogels with tunable swelling property | |
| Wen et al. | Characterization of p (AA‐co‐AM)/bent/urea and its swelling and slow release behavior in a simulative soil environment | |
| Gao et al. | Structure and mechanical properties of superabsorbent poly (acrylamide)-montmorillonite composite hydrogels | |
| Qi et al. | Honeycomb-like hydrogel adsorbents derived from salecan polysaccharide for wastewater treatment | |
| Wang et al. | Poly (acrylic acid)/palygorskite microgel via radical polymerization in aqueous phase for reinforcing poly (vinyl alcohol) hydrogel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |