CN110204776A - A kind of polyvinylidene fluoride nanometer fiber aerogel material and preparation method thereof - Google Patents
A kind of polyvinylidene fluoride nanometer fiber aerogel material and preparation method thereof Download PDFInfo
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- CN110204776A CN110204776A CN201910484667.6A CN201910484667A CN110204776A CN 110204776 A CN110204776 A CN 110204776A CN 201910484667 A CN201910484667 A CN 201910484667A CN 110204776 A CN110204776 A CN 110204776A
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- polyvinylidene fluoride
- fluoride nanometer
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- aerogel material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/048—Elimination of a frozen liquid phase
- C08J2201/0484—Elimination of a frozen liquid phase the liquid phase being aqueous
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
- C08J2205/026—Aerogel, i.e. a supercritically dried gel
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
- C08K5/357—Six-membered rings
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Abstract
The invention discloses a kind of preparation methods of polyvinylidene fluoride nanometer fiber aerogel material, which comprises the following steps: step 1: Kynoar spinning solution progress electrostatic spinning is obtained polyvinylidene fluoride nanometer tunica fibrosa；Step 2: the obtained polyvinylidene fluoride nanometer tunica fibrosa of step 1 being add to deionized water with crosslinking agent, ultrasonic disperse obtains uniform dispersion liquid；Step 3: the obtained dispersion liquid of step 2 being poured into mold, is freezed under liquid nitrogen atmosphere；Step 4: the sample after step 3 freezing is freeze-dried；Step 5: the dry complete sample of step 4 being heat-treated, polyvinylidene fluoride nanometer fiber aeroge is obtained.Polyvinylidene fluoride nanometer fiber aeroge density is light prepared by the present invention, thermal conductivity is low, hydrophobic and high temperature resistant, is a kind of excellent heat preserving and insulating material that can be used in wet condition.
Description
Technical field
The present invention relates to heat preserving and insulating material fields, are specifically related to a kind of polyvinylidene fluoride nanometer fiber aerogel material
And preparation method thereof.
Background technique
Aeroge is a kind of using gas as decentralized medium, the new material with continuous three-D nano-porous network structure,
Porosity is up to 99.8%, since its excellent performance includes big specific surface area, low-density, low heat conductivity and high porosity
Deng having broad application prospects in fields such as biological support, energy storage device, sensor, pollutant process and heat-barrier materials.
Kynoar, appearance are translucent or white powder or particle, and the arrangement of molecule interchain is close, and has stronger hydrogen
Key, oxygen index (OI) 46% are non-ignitable.Kynoar is removed with good chemical corrosion resistance, heat-resisting quantity, oxidative resistance, resistance to
Outside Hou Xing, resistance to ray radiation performance, also there are the properties such as piezoelectricity, dielectricity, pyroelectricity.Fluorination in Kynoar
Segment shields the polarity effect of polar group such as methyl, carbonyl etc., and surface is made to have hydrophobic effect.
Performance can decline when existing insulation aerogel material uses in wet condition, limit aeroge heat preservation
The application of material.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation process simple, low in cost, insulation and hydrophobic performance is excellent
Polyvinylidene fluoride nanometer fiber aeroge and preparation method thereof.
In order to achieve the above object, the present invention provides a kind of preparation sides of polyvinylidene fluoride nanometer fiber aerogel material
Method, which comprises the following steps:
Step 1: Kynoar spinning solution progress electrostatic spinning is obtained into polyvinylidene fluoride nanometer tunica fibrosa；
Step 2: the obtained polyvinylidene fluoride nanometer tunica fibrosa of step 1 being add to deionized water with crosslinking agent, is surpassed
Sound dispersion, obtains uniform dispersion liquid；
Step 3: the obtained dispersion liquid of step 2 being poured into mold, is freezed under liquid nitrogen atmosphere；
Step 4: the sample after step 3 freezing is freeze-dried；
Step 5: the dry complete sample of step 4 being heat-treated, polyvinylidene fluoride nanometer fiber aeroge is obtained.
Preferably, in the step 1 Kynoar spinning solution by Kynoar and polar solvent preparation gained.
It is highly preferred that the polar solvent is N, N-dimethyl acetamide, N-methyl pyrrolidone and N, N-dimethyl methyl
Any one in amide.
Preferably, Kynoar solid content is 0.1~0.2g/mL in Kynoar spinning solution in the step 1.
Preferably, the voltage of electrostatic spinning is 15~20kv in the step 1, and injecting speed is 0.05~0.10mm/
Min, reception speed are 65~100r/min.
Preferably, crosslinking agent is any one of benzoxazine, Dopamine hydrochloride and polyvinylpyrrolidone in the step 2
Kind.
Preferably, crosslinking agent is benzoxazine, the matter of polyvinylidene fluoride nanometer tunica fibrosa and benzoxazine in the step 2
Amount is than being 2:1~5:1.
Preferably, in step 2 dispersion liquid total solid content of polyvinylidene fluoride nanometer tunica fibrosa and crosslinking agent be 10~
20mg/mL。
Preferably, it is heat-treated in the step 5 specifically: from room temperature to 175~250 DEG C, keep the temperature 1~2h, heating
Rate is 1~3 DEG C/min.
During heat treatment, crosslinking agent makes polyvinylidene fluoride nanometer fibre matting be bonded together to obtain Kynoar
Nanofiber aeroge.
The present invention also provides the polyvinylidene fluoride nanometer fiber aerogel materials of above method preparation.
The present invention has the advantages that
(1) preparation process of the present invention is simple, easily operated, is a kind of preparation method of convenient and efficient.
(2) present invention is bonded together polyvinylidene fluoride nanometer fibre matting using suitable crosslinking agent, to obtain
Polyvinylidene fluoride nanometer fiber aerogel material.
(3) the polyvinylidene fluoride nanometer fiber aeroge in the present invention can have hydrophobic and incubation and thermal insulation function.
Detailed description of the invention
Fig. 1 is the SEM figure that fiber is crosslinked in 2 polyvinylidene fluoride nanometer fiber aeroge of embodiment；
Fig. 2 is the water contact angle figure of embodiment 1-4 polyvinylidene fluoride nanometer fiber aeroge.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
A kind of polyvinylidene fluoride nanometer fiber aeroge is present embodiments provided, preparation method is specific as follows:
Step 1: weighing 1.5g Kynoar, 10mLN is added, N-dimethylformamide is stirred at room temperature 2h, obtains
The Kynoar spinning solution that solid content is 15% receives speed then voltage is 18kv, to inject speed be 0.08mm/min
To carry out electrostatic spinning under the conditions of 90r/min, polyvinylidene fluoride nanometer tunica fibrosa is obtained；
Step 2: weighing 200mg polyvinylidene fluoride nanometer tunica fibrosa and 100mg benzoxazine in beaker, 30mL is added and goes
Ionized water, ultrasonic disperse 2000w, 30min obtain uniform dispersion liquid；
Step 3: the obtained dispersion liquid of step 2 being poured into mold, is freezed under liquid nitrogen atmosphere；
Step 4: the sample after step 3 freezing is put into freeze drying box in -48 DEG C of dry 72h until sample drying is complete
Entirely；
Step 5: the dry complete sample of step 4 being heat-treated, setting condition is to protect from room temperature to 200 DEG C
Warm 2h, heating rate are 2 DEG C/min, obtain polyvinylidene fluoride nanometer fiber and benzoxazine mass ratio as the polyvinylidene fluoride of 2:1
Alkene nanofiber aeroge, is denoted as PVDF-NA-2-1.
Embodiment 2
The present embodiment the difference from embodiment 1 is that: polyvinylidene fluoride nanometer fiber and benzoxazine mass ratio are changed to 3:
1, that is, 300mg polyvinylidene fluoride nanometer tunica fibrosa and 100mg benzoxazine are weighed in beaker, 30mL deionized water is added, and are surpassed
Sound disperses to obtain uniform dispersion liquid, remaining is the same as implementation 1.Obtaining polyvinylidene fluoride nanometer fiber and benzoxazine mass ratio is 3:
1 polyvinylidene fluoride nanometer fiber aeroge, is denoted as PVDF-NA-3-1.
Embodiment 3
The present embodiment the difference from embodiment 1 is that: polyvinylidene fluoride nanometer fiber and benzoxazine mass ratio are changed to 4:
1, that is, 400mg polyvinylidene fluoride nanometer tunica fibrosa and 100mg benzoxazine are weighed in beaker, 30mL deionized water is added, and are surpassed
Sound disperses to obtain uniform dispersion liquid, remaining is the same as implementation 1.Obtaining polyvinylidene fluoride nanometer fiber and benzoxazine mass ratio is 4:
1 polyvinylidene fluoride nanometer fiber aeroge, is denoted as PVDF-NA-4-1.
Embodiment 4
The present embodiment the difference from embodiment 1 is that: polyvinylidene fluoride nanometer fiber and benzoxazine mass ratio are changed to 5:
1, that is, 500mg polyvinylidene fluoride nanometer tunica fibrosa and 100mg benzoxazine are weighed in beaker, 30mL deionized water is added, and are surpassed
Sound disperses to obtain uniform dispersion liquid, remaining is the same as implementation 1.Obtaining polyvinylidene fluoride nanometer fiber and benzoxazine mass ratio is 5:
1 polyvinylidene fluoride nanometer fiber aeroge, is denoted as PVDF-NA-5-1.
Embodiment 5
The present embodiment is control group: benzoxazine is not added during preparation.Weigh 300mg polyvinylidene fluoride nanometer
30mL deionized water is added in beaker in tunica fibrosa, and ultrasonic disperse obtains uniform dispersion liquid, remaining is final made with implementation 1
Standby polyvinylidene fluoride nanometer fiber aeroge, is denoted as PVDF.
Fig. 1 is the SEM figure that fiber is crosslinked in 1 polyvinylidene fluoride nanometer fiber aeroge of embodiment, it may be clearly seen that
Fiber, which is interweaved, to be entangled to together.
Fig. 2 is the water contact angle figure of embodiment 1-4 polyvinylidene fluoride nanometer fiber aeroge, and contact angle is 152 °, is said
The bright aeroge is a kind of excellent hydrophobic material.
Claims (10)
1. a kind of preparation method of polyvinylidene fluoride nanometer fiber aerogel material, which comprises the following steps:
Step 1: Kynoar spinning solution progress electrostatic spinning is obtained into polyvinylidene fluoride nanometer tunica fibrosa；
Step 2: the obtained polyvinylidene fluoride nanometer tunica fibrosa of step 1 being add to deionized water with crosslinking agent, ultrasound point
It dissipates, obtains uniform dispersion liquid；
Step 3: the obtained dispersion liquid of step 2 being poured into mold, is freezed under liquid nitrogen atmosphere；
Step 4: the sample after step 3 freezing is freeze-dried；
Step 5: the dry complete sample of step 4 being heat-treated, polyvinylidene fluoride nanometer fiber aeroge is obtained.
2. the preparation method of polyvinylidene fluoride nanometer fiber aerogel material as described in claim 1, which is characterized in that the step
Kynoar spinning solution is by Kynoar and polar solvent preparation gained in rapid 1.
3. the preparation method of polyvinylidene fluoride nanometer fiber aerogel material as claimed in claim 2, which is characterized in that the pole
Property solvent be N, N-dimethyl acetamide, N-methyl pyrrolidone and N, any one in N-dimethylformamide.
4. the preparation method of polyvinylidene fluoride nanometer fiber aerogel material as described in claim 1, which is characterized in that the step
Kynoar solid content is 0.1~0.2g/mL in Kynoar spinning solution in rapid 1.
5. the preparation method of polyvinylidene fluoride nanometer fiber aerogel material as described in claim 1, which is characterized in that the step
The voltage of electrostatic spinning is 15~20kv in rapid 1, and injecting speed is 0.05~0.10mm/min, and reception speed is 65~100r/
min。
6. the preparation method of polyvinylidene fluoride nanometer fiber aerogel material as described in claim 1, which is characterized in that the step
Crosslinking agent is any one of benzoxazine, Dopamine hydrochloride and polyvinylpyrrolidone in rapid 2.
7. the preparation method of polyvinylidene fluoride nanometer fiber aerogel material as described in claim 1, which is characterized in that the step
Crosslinking agent is benzoxazine in rapid 2, and the mass ratio of polyvinylidene fluoride nanometer tunica fibrosa and benzoxazine is 2:1~5:1.
8. the preparation method of polyvinylidene fluoride nanometer fiber aerogel material as described in claim 1, which is characterized in that the step
The total solid content of polyvinylidene fluoride nanometer tunica fibrosa and crosslinking agent is 10~20mg/mL in dispersion liquid in rapid 2.
9. the preparation method of polyvinylidene fluoride nanometer fiber aerogel material as described in claim 1, which is characterized in that the step
It is heat-treated in rapid 5 specifically: from room temperature to 175~250 DEG C, keep the temperature 1~2h, heating rate is 1~3 DEG C/min.
10. the polyvinylidene fluoride nanometer fiber aerogel material of any one of claim 1~9 the method preparation.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111135771A (en) * | 2020-02-24 | 2020-05-12 | 浙江工业大学之江学院 | Preparation method of efficient oil-absorbing nanofiber aerogel |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103285789A (en) * | 2013-05-27 | 2013-09-11 | 东华大学 | Preparation method of three-dimensional fiber-based aerogel material and product thereof |
| CN103285920A (en) * | 2013-05-27 | 2013-09-11 | 东华大学 | Three-dimensional fiber-based aerogel catalyst carrier and preparation method thereof |
| CN104674383A (en) * | 2015-02-12 | 2015-06-03 | 中国科学院城市环境研究所 | Carbon nano fiber aerogel electrostatic spinning construction method |
| CN105622767A (en) * | 2016-04-04 | 2016-06-01 | 刘云晖 | Preparation method of hydrophobic nano cellulose aerogel |
| CN106178599A (en) * | 2015-05-06 | 2016-12-07 | 华东理工大学 | A kind of automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic fiber web material and preparation thereof and application in oil-water separation |
-
2019
- 2019-06-05 CN CN201910484667.6A patent/CN110204776A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103285789A (en) * | 2013-05-27 | 2013-09-11 | 东华大学 | Preparation method of three-dimensional fiber-based aerogel material and product thereof |
| CN103285920A (en) * | 2013-05-27 | 2013-09-11 | 东华大学 | Three-dimensional fiber-based aerogel catalyst carrier and preparation method thereof |
| CN104674383A (en) * | 2015-02-12 | 2015-06-03 | 中国科学院城市环境研究所 | Carbon nano fiber aerogel electrostatic spinning construction method |
| CN106178599A (en) * | 2015-05-06 | 2016-12-07 | 华东理工大学 | A kind of automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic fiber web material and preparation thereof and application in oil-water separation |
| CN105622767A (en) * | 2016-04-04 | 2016-06-01 | 刘云晖 | Preparation method of hydrophobic nano cellulose aerogel |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111135771A (en) * | 2020-02-24 | 2020-05-12 | 浙江工业大学之江学院 | Preparation method of efficient oil-absorbing nanofiber aerogel |
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