CN104558323A - High-water-solubility nanometer hexagonal boron nitride and preparation method of polymer composite hydrogel of high-water-solubility nanometer hexagonal boron nitride - Google Patents
High-water-solubility nanometer hexagonal boron nitride and preparation method of polymer composite hydrogel of high-water-solubility nanometer hexagonal boron nitride Download PDFInfo
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Abstract
The invention relates to a preparation method of high-water-solubility nanometer hexagonal boron nitride and polymer composite hydrogel of the high-water-solubility nanometer bexagonal boron nitride. The preparation method comprises the following steps: (1) treating hexagonal boron nitride by using citric acid to obtain high-water-solubility nanometer hexagonal boron nitride; (2) uniformly mixing the high-water-solubility nanometer hexagonal boron nitride obtained by the method with oxygen-removed water, a polymerizable monomer, a triggering agent and a catalyst; triggering and implementing a free radical in-situ polymerization reaction to obtain nanometer hexagonal boron nitride/polymer composite hydrogel. The method disclosed by the invention is simple and easy to operate; the composite hydrogel of the high-water-solubility nanometer hexagonal boron nitride is higher in mechanical strength and better in swelling property and environmental responsiveness. Besides, the composite hydrogel disclosed by the invention is water-retained for a long time and excellent in water retention property; the service period of the hydrogel is prolonged; the problem that the hydrogel cannot be widely applied because water is greatly lost after the hydrogel is stored for a long time can be solved. The polymer composite hydrogel disclosed by the invention has quite good application prospect in fields such as bio-pharmaceuticals, chemical products, mechanical industry and agricultural cultivation.
Description
Technical field
The present invention relates to a kind of preparation method of composite aquogel, particularly the preparation method of a kind of highly water-soluble nano-hexagonal boron nitride and polymkeric substance composite aquogel thereof.
Background technology
Hydrogel is a kind of high molecular polymer with three-dimensional net structure, and it take water as dispersion medium, and three-dimensional net structure is cross-linked by the linear polymeric containing hydrophilic radical and forms.Because the hydrophilic radical that macromolecular main chain contains is combined with water, water molecules can be included in reticulated structure inside, hydrogel can absorb a large amount of water and keep certain shape, meets water-soluble swollenly not dissolve.
Along with the continuous growth of domestic and international market demand, hydrogel is developed rapidly in recent years.Hydrogel has many types, by the difference of its size shape, can be divided into macroscopic hydrogel and microcosmic hydrogel.By the difference that its macromolecular material is originated, synthesis macromolecule hydrogel and natural polymer hydrogel can be divided into.By the difference of its three-dimensional network bonding pattern, physical gel and chemical gel can be divided into.Physical gel is by physical force as formation such as the windings of hydrogen bond, electrostatic interaction, chain, is volatile; Chemical gel is then cross-linked to form by chemical bond, is permanent gels.In addition, by the difference of its environmental response degree to external world, traditional hydrogel and progress in Intelligent Hydrogel can be divided into.The change responsiveness of traditional hydrogel environment is to external world slow, even without responding; And progress in Intelligent Hydrogel to the subtle change of outside atmosphere or stimulation, physical structure or chemical property can be made corresponding change, this change is often still reversible.
Traditional hydrogel due to the polymkeric substance between the random distribution of cross-linking set, cross-linking set extensively chain length distribution, and highdensity cross-linking set limit polymer chain cause its not for another example linear polymer chain tool is flexible just like that, inevitably have that mechanicalness is weak, property is crisp, deformability is poor and a series of shortcomings such as environment-responsive difference, thus greatly limit its widespread use in field.In addition, existing hydrogel is ubiquitous can not the phenomenon of water conservation very well, and this point also limit the application of hydrogel.In recent years, novel hydrogels such as topological type hydrogel, dual network type hydrogel and the Nanometer composite hydrogel of better mechanical property receive all the more the concern of people.At present, existing increasing scholar begins one's study how to improve the mechanical property of hydrogel both at home and abroad.In 2002, the first time such as Haraguchi reported using inorganics clay as linking agent, and the Nanometer composite hydrogel obtained by in-situ polymerization is (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.).The mechanical property of this novel hydrogels is greatly improved, and the performance such as swelling, environmental response is also all significantly improved.Recently, Shi etc. prepare 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.), prepare graphene oxide-polymkeric substance composite aquogel (see Huai-Ping Cong from bosom duckweed etc.; Ping Wang; Shu-Hong Yu. Highly elastic and superstretchable graphene oxide/polyacrylamide hydrogels [J]. Small. 2013; 1-6.), Chen Guangming etc. prepare double-hydroxide/polymkeric substance composite aquogel etc. (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 Nanometer composite hydrogel and compare traditional hydrogel and have more excellent performance, and then have widened the Application Areas of hydrogel.
As the analog of Graphene, nano-hexagonal boron nitride itself has much excellent character, such as good mechanical property and thermal conductivity etc., but the solubility property of its difference limits its application.Therefore, hexagonal boron nitride solvability is improved particularly important and crucial.From current result of study, Br nsted acid and protonic acid all can modification hexagonal boron nitride to improve solvability, but also there is no organic acid to the study on the modification of hexagonal boron nitride.Itself there is the hexagonal boron nitride of excellent mechanical properties, be expected to, with the form of inorganics/polymkeric substance composite aquogel, become one of inorganic substance improving conventional hydrogels performance.In addition, existing hydrogel is ubiquitous can not the phenomenon of water conservation very well, also improves.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of highly water-soluble nano-hexagonal boron nitride and polymkeric substance composite aquogel thereof, solve the problem of conventional hydrogels bad mechanical property, bad response and poor water retention property.
In order to realize above-mentioned object, the present invention provide firstly a kind of preparation method of highly water-soluble nano-hexagonal boron nitride, specifically comprises the steps:
Hexagonal boron nitride raw material mixes with citric acid by S1;
The citric acid mixed in S1-hexagonal boron nitride system is transferred in reaction flask by S2, is warming up to the complete melting of citric acid, reacts under agitation condition;
S3, by gained reaction product in S2, washs respectively through water and ethanol, refilters, dry, obtains a kind of highly water-soluble nano-hexagonal boron nitride.
Citric acid, as organic acid, has stronger acidity, can ionize multiple H simultaneously
+, be expected to as acid hexagonal boron nitride modification.Based on this, in step S1, use citric acid treatment hexagonal boron nitride.
As preferably, the mass ratio of the hexagonal boron nitride raw material described in step S1 and citric acid is 1:5 ~ 1:70.In the present invention, the consumption of citric acid has certain influence to modified effect.Very little, modification is incomplete, causes modified effect not obvious for the consumption of citric acid; Consumption is too many, causes the waste of citric acid, is unfavorable for saving technical costs.
As preferably, the temperature of reaction described in step S2 is 120 ~ 200 DEG C, and the reaction times is 1 ~ 10 day.In the present invention, the temperature and time of citric acid treatment hexagonal boron nitride has impact to modified effect.Temperature is too low, and citric acid does not have melting, mixes uneven, thus affect modified effect with hexagonal boron nitride; Temperature is too high, and citric acid decomposes, and loses modification power.Time is too short, reactant partial reaction, causes modification incomplete; Time is oversize, and the technical process cycle is oversize.
As preferably, the drying temperature described in step S3 is 55 ~ 70 DEG C, and time of drying is 8 ~ 24 h.
The present invention also mainly provides the preparation method of a kind of high-performance nano hexagonal boron nitride/polymkeric substance composite aquogel, and the highly water-soluble nano-hexagonal boron nitride mainly utilizing aforesaid method to prepare, as raw material, specifically comprises the steps:
C1, by joining in deaerated water with the highly water-soluble nano-hexagonal boron nitride prepared by any one of claim 1 ~ 3, obtains system A;
System A is placed in ultrasonic disperse in Ultrasonic Cleaners by C2;
C3 adds polymerisable monomer, initiator and catalyzer successively in the system A after dispersion, is uniformly mixed to evenly, obtains system B;
System B is transferred in mould by C4, causes free radical in situ polymerization reaction, obtains a kind of nano-hexagonal boron nitride/polymkeric substance composite aquogel.
As preferably, the consumption of the highly water-soluble nano-hexagonal boron nitride described in step C1 is 1 ~ 10 wt% of polymerisable monomer consumption, described deaerated water before use, first through nitrogen bubble deoxygenation 0.5 ~ 5 hour.In the present invention, highly water-soluble nano-hexagonal boron nitride is both as the linking agent of free radical in situ polymerization reaction, serves again the effect improving hydrogel performance.Its consumption has certain influence to formation hydrogel.Consumption is too low, and namely dosage of crosslinking agent very little, is not enough to be cross-linked to form hydrogel; Consumption is too high, and cross-linking set is too intensive, and the motion of meeting limit polymerization thing chain and flexibility, make the machinery of hydrogel and swelling behavior be deteriorated.Water is formed with impact through time of nitrogen bubble deoxygenation to hydrogel.The deoxygenation time is too short, and deoxygenation is incomplete, and oxygen is free radical capture body, and this free radical in situ polymerization can be caused to react can not carry out, thus can not form hydrogel; The deoxygenation time is oversize, waste nitrogen and time.
As preferably, the ultrasonic power described in step C2 is 90 ~ 300 W, and the time is 15 ~ 45 min.
As preferably, the concentration of the polymerisable monomer described in step C3 in water is 0.05 ~ 1 g/ml, and described polymerisable monomer is acrylamide or vinylformic acid.The concentration of monomer has impact to the hydrogel formed.Concentration is too low, and polymeric matrix molecular weight is too little, and sample strength is little, and hydrogel is easy-formation not; Concentration is too high, can produce a large amount of heat in original position radical polymerization process, and again because now system viscosity is comparatively large, a large amount of heat can not distribute in time, makes the hydrogel inside formed occur a large amount of bubble, has a strong impact on the mechanical property of hydrogel.
As preferably, in step C3, initiator amount is 0.1 ~ 5 wt% of polymerisable monomer consumption, and catalyst levels is 1 ~ 50 μ l.Initiator amount has impact to formation hydrogel.Initiator amount very little, can not cause the carrying out of free radical in situ polymerization reaction; Consumption is too many, polymeric matrix molecular weight can be caused too little, cannot form hydrogel.Catalyst levels has impact to formation hydrogel.Very little, initiation free radical in situ polymerization reaction time consumption is oversize even cannot react catalyst levels; Consumption is too many, and it is too fast that free radical in situ polymerization reaction is carried out, and easily occurs sudden and violent poly-phenomenon, affects gained hydrogel performance.
As preferably, the initiator described in step C3 and catalyzer are ammonium persulphate common in Raolical polymerizable and the combination of N, N, N', N'-Tetramethyl Ethylene Diamine.
As preferably, in step C4, the temperature of initiated polymerization is 5 ~ 50 DEG C, and the reaction times is 0.5 ~ 48 h.The temperature of initiated polymerization has impact to formation hydrogel.The temperature of initiated polymerization is too low, can not reach the effect of initiation reaction; Temperature is too high, easily causes the appearance of implode phenomenon, thus produces bubble, and then affects the mechanical property of hydrogel.
Compared with prior art, preparation method of the present invention is simple, easy to operate, and the composite aquogel obtained has higher physical strength and more excellent swelling behavior and environment-responsive, and water retention property is outstanding.In the structure of the composite aquogel being linking agent with highly water-soluble nano-hexagonal boron nitride, nano-hexagonal boron nitride is no longer just present in hydrogel with the form of simple physics compound, especially as a polyfunctional crosslinking agent by crosslinked together for linear organic polymer long-chain, by the initiation of Raolical polymerizable, formed have very long polymer chain, special inorganic/organic network structure.Pliable and tough due to the polymkeric substance chain length that obtains, when drawn gel, polymer chain does not rupture easily.In addition, the hexagonal boron nitride of high-mechanical property, also substantially increases the physical strength of hydrogel.Finally, physical strength and the ductility of nano-hexagonal boron nitride/polymkeric substance composite aquogel all obtain remarkable improvement.Meanwhile, also solving hydrogel long storage time can a large amount of dehydration and can not the difficult problem of widespread use, extends the life cycle of hydrogel.Be expected to, in fields such as bio-pharmaceuticals, chemical products, mechanical industry and agricultural cultivations, to 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/polymkeric substance composite aquogel;
Fig. 3 is the contrast photo of nano-hexagonal boron nitride/polyacrylamide composite aquogel finished product of preparing of the present invention and polyacrylamide conventional hydrogels finished product.
Embodiment
For a better understanding of the present invention, set forth the solution of the present invention further below in conjunction with embodiment, but content of the present invention comprises and is not only confined to the following examples.
embodiment 1
500 mg hexagonal boron nitride powder raw materials are mixed with 2.5 g citric acids, is warmed up to 200 DEG C, stirring reaction 1 day, be cooled to room temperature, show neutral by ethanol and water washing to washing lotion, filter, collect filter cake, at 55 DEG C, vacuum-drying 24 h, obtains highly water-soluble nano-hexagonal boron nitride.
embodiment 2
500 mg hexagonal boron nitride powder raw materials are mixed with 15 g citric acids, is warmed up to 160 DEG C, stirring reaction 5 days, be cooled to room temperature, show neutral by ethanol and water washing to washing lotion, filter, collect filter cake, vacuum-drying 8h at 70 DEG C, obtains highly water-soluble nano-hexagonal boron nitride.
embodiment 3
500 mg hexagonal boron nitride powder raw materials are mixed with 35 g citric acids, is warmed up to 120 DEG C, stirring reaction 10 days, be cooled to room temperature, show neutral by ethanol and water washing to washing lotion, filter, collect filter cake, at 65 DEG C, vacuum-drying 16 h, obtains highly water-soluble nano-hexagonal boron nitride.
embodiment 4
10 mg highly water-soluble nano-hexagonal boron nitrides are dissolved in 1 ml in the water of nitrogen deoxygenation 0.5 h, ultrasonic 15 ~ 45 min under 90 ~ 300 W power, obtain uniform hexagonal boron nitride aqueous dispersions, again under condition of ice bath, add acrylamide monomer 1 g successively, initiator ammonium persulfate 1 mg and catalyst n, N, N', N'-Tetramethyl Ethylene Diamine 1 μ l, stir, being transferred to diameter is respectively in the cylindrical die of 2.6 cm and 0.7 cm, cause at 5 DEG C and complete polyreaction, 48 hours reaction times, namely nano-hexagonal boron nitride/polyacrylamide composite aquogel is obtained.
Utilize the mechanical property of universal tensile testing machine test compound hydrogel, result shows that its tensile elongation is more than 8000 %, and compressive strength reaches 2.5 MPa; Study its water retention property, find that ambient temperatare puts 1 year, the substantially non-dehydration of hydrogel, water retention property is remarkable.
embodiment 5
50 mg highly water-soluble nano-hexagonal boron nitrides are dissolved in 10 ml in the water of nitrogen deoxygenation 5 h, ultrasonic 15 ~ 45 min under 90 ~ 300 W power, obtain uniform hexagonal boron nitride aqueous dispersions, again under condition of ice bath, add acrylamide monomer 0.5 g successively, initiator ammonium persulfate 25 mg and catalyst n, N, N', N'-Tetramethyl Ethylene Diamine 25 μ l, stir, being transferred to diameter is respectively in the cylindrical die of 2.6 cm and 0.7 cm, cause at 50 DEG C and complete polyreaction, 0.5 hour reaction times, namely nano-hexagonal boron nitride/polyacrylamide composite aquogel is obtained.
Utilize the mechanical property of universal tensile testing machine test compound hydrogel, result shows that its tensile elongation is more than 10000 %, and compressive strength reaches 3 MPa; Study its water retention property, find that ambient temperatare puts 1 year, the substantially non-dehydration of hydrogel, water retention property is remarkable.
embodiment 6
50 mg highly water-soluble nano-hexagonal boron nitrides are dissolved in 5 ml in the water of nitrogen deoxygenation 3 h, ultrasonic 15 ~ 45 min under 90 ~ 300 W power, obtain uniform hexagonal boron nitride aqueous dispersions, again under condition of ice bath, add acrylamide monomer 1 g successively, initiator ammonium persulfate 20 mg and catalyst n, N, N', N'-Tetramethyl Ethylene Diamine 50 μ l, stir, being transferred to diameter is respectively in the cylindrical die of 2.6 cm and 0.7 cm, cause at 30 DEG C and complete polyreaction, 30 hours reaction times, namely nano-hexagonal boron nitride/polyacrylamide composite aquogel is obtained.
Utilize the mechanical property of universal tensile testing machine test compound hydrogel, result shows that its tensile elongation is more than 6000 %, and compressive strength reaches 3 MPa; Study its water retention property, find that ambient temperatare puts 1 year, the substantially non-dehydration of hydrogel, water retention property is remarkable.
embodiment 7
10 mg highly water-soluble nano-hexagonal boron nitrides are dissolved in 1 ml in the water of nitrogen deoxygenation 0.5 h, ultrasonic 15 ~ 45 min under 90 ~ 300 W power, obtain uniform hexagonal boron nitride aqueous dispersions, again under condition of ice bath, add Acrylic Acid Monomer 1 g successively, initiator ammonium persulfate 1 mg and catalyst n, N, N', N'-Tetramethyl Ethylene Diamine 1 μ l, stir, being transferred to diameter is respectively in the cylindrical die of 2.6 cm and 0.7 cm, cause at 5 DEG C and complete polyreaction, reaction times is 40 hours, namely nano-hexagonal boron nitride/polyacrylic acid composite aquogel is obtained.
embodiment 8
50 mg highly water-soluble nano-hexagonal boron nitrides are dissolved in 10 ml in the water of nitrogen deoxygenation 5 h, ultrasonic 15 ~ 45 min under 90 ~ 300 W power, obtain uniform hexagonal boron nitride aqueous dispersions, again under condition of ice bath, add Acrylic Acid Monomer 0.5 g successively, initiator ammonium persulfate 25 mg and catalyst n, N, N', N'-Tetramethyl Ethylene Diamine 25 μ l, stir, being transferred to diameter is respectively in the cylindrical die of 2.6 cm and 0.7 cm, cause at 50 DEG C and complete polyreaction, 1 hour reaction times, namely nano-hexagonal boron nitride/polyacrylic acid composite aquogel is obtained.
embodiment 9
50 mg highly water-soluble nano-hexagonal boron nitrides are dissolved in 5 ml in the water of nitrogen deoxygenation 3 h, ultrasonic 15 ~ 45 min under 90 ~ 300 W power, obtain uniform hexagonal boron nitride aqueous dispersions, again under condition of ice bath, add Acrylic Acid Monomer 1 g successively, initiator ammonium persulfate 20 mg and catalyst n, N, N', N'-Tetramethyl Ethylene Diamine 50 μ l, stir, being transferred to diameter is respectively in the cylindrical die of 2.6 cm and 0.7 cm, cause at 30 DEG C and complete polyreaction, 10 hours reaction times, namely nano-hexagonal boron nitride/polyacrylic acid composite aquogel is obtained.
comparative example
50 mg methylene diacrylamides (conventional hydrogels commonly uses linking agent) are dissolved in 10 ml in the distilled water of nitrogen deoxygenation 5 h, ultrasonic dissolution obtains the methylene diacrylamide aqueous solution, again under condition of ice bath, add acrylamide monomer 2 g successively, initiator ammonium persulfate 20 mg and catalyst n, N, N', N'-Tetramethyl Ethylene Diamine 20 μ l, be stirred to each material to dissolve completely, be transferred to diameter to be respectively in the columniform mould of 2.6 cm and 0.7 cm, cause at 20 DEG C and complete polyreaction, namely obtaining traditional polyacrylamide hydrophilic gel.
Utilize universal tensile testing machine to test the mechanical property of conventional hydrogels, result shows its compressive strength only 40 kPa, and property is crisp cannot stretch; Its water retention property is studied, finds that its water retention property can not show a candle to composite aquogel of the present invention.
Claims (10)
1. a preparation method for highly water-soluble nano-hexagonal boron nitride, is characterized in that, comprises the steps:
Hexagonal boron nitride raw material mixes with citric acid by S1;
The citric acid mixed in S1-hexagonal boron nitride system is transferred in reaction flask by S2, is warming up to citric acid melting, with the citric acid of melting for solvent, reacts under agitation condition;
S3, by gained reaction product in S2, washs respectively through water and ethanol, refilters, dry, obtains a kind of highly water-soluble nano-hexagonal boron nitride.
2. the preparation method of highly water-soluble nano-hexagonal boron nitride according to claim 1, is characterized in that, the mass ratio that in step S1, hexagonal boron nitride raw material mixes with citric acid is 1:5 ~ 1:70.
3. the preparation method of highly water-soluble nano-hexagonal boron nitride according to claim 1, is characterized in that, in step S2, temperature of reaction is 120 ~ 200 DEG C, and the reaction times is 1 ~ 10 day.
4. a preparation method for nano-hexagonal boron nitride/polymkeric substance composite aquogel, is characterized 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 claim 1 ~ 3, obtains system A;
System A is placed in ultrasonic disperse in Ultrasonic Cleaners by C2;
C3 adds polymerisable monomer, initiator and catalyzer successively in the system A after dispersion, is uniformly mixed to evenly, obtains system B;
System B is transferred in mould by C4, causes free radical in situ polymerization reaction, obtains a kind of nano-hexagonal boron nitride/polymkeric substance composite aquogel.
5. the preparation method of nano-hexagonal boron nitride according to claim 4/polymkeric substance composite aquogel, is characterized in that, the linking agent that the highly water-soluble nano-hexagonal boron nitride described in step C1 reacts as this free radical in situ polymerization.
6. the preparation method of nano-hexagonal boron nitride according to claim 4/polymkeric substance composite aquogel, it is characterized in that, the consumption of the highly water-soluble nano-hexagonal boron nitride described in step C1 is 1 ~ 10 wt% of polymerisable monomer consumption, and described deaerated water is through nitrogen bubble deoxygenation 0.5 ~ 5 hour gained.
7. the preparation method of nano-hexagonal boron nitride according to claim 4/polymkeric substance composite aquogel, it is characterized in that, the concentration of polymerisable monomer described in step C3 in water is 0.05 ~ 1 g/ml, and described polymerisable monomer is acrylamide or vinylformic acid.
8. the preparation method of nano-hexagonal boron nitride according to claim 4/polymkeric substance composite aquogel, is characterized in that, the initiator amount described in step C3 is 0.1 ~ 5 wt% of polymerisable monomer consumption, and catalyst levels is 1 ~ 50 μ l.
9. the preparation method of nano-hexagonal boron nitride according to claim 4/polymkeric substance composite aquogel, is characterized in that, the initiator described in step C3 and catalyzer are ammonium persulphate and the combination of N, N, N', N'-Tetramethyl Ethylene Diamine.
10. the preparation method of nano-hexagonal boron nitride according to claim 4/polymkeric substance composite aquogel, is characterized in that, the temperature causing free radical in situ polymerization reaction in step C4 is 5 ~ 50 DEG C, and the reaction times is 0.5 ~ 48 hour.
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