CN106257275B - A kind of open celled polymeric gas sensitive and the preparation method and application thereof - Google Patents
A kind of open celled polymeric gas sensitive and the preparation method and application thereof Download PDFInfo
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- CN106257275B CN106257275B CN201610449711.6A CN201610449711A CN106257275B CN 106257275 B CN106257275 B CN 106257275B CN 201610449711 A CN201610449711 A CN 201610449711A CN 106257275 B CN106257275 B CN 106257275B
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- open celled
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/041—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body
Abstract
The present invention relates to a kind of field of compound material, to solve the problems, such as that conductive polymer composite exists as gas sensitive, the invention proposes a kind of open celled polymeric gas sensitive and preparation method thereof, which is the composite material with conductive filler network structure, resistance value 108~ 10 Ω; open celled polymeric gas sensitive is made of following each components; the parts by weight of foam of polymers are 5-99 in each component; the parts by weight of conductive filler are 1-40; the parts by weight of adhesive are 0-84, have and are conducive to the characteristics such as flow at high speed gas passes through, intensity height, responsiveness is sensitive and preparation process is simple, is produced on a large scale.
Description
Technical field
The present invention relates to a kind of field of compound material, a kind of open celled polymeric gas sensitive and its preparation are related in particular to
Method and application.
Background technique
Since conductive filler // conductive polymer gas material resistance occurs significantly with the variation of gaseous surrounding environment
Variation, therefore monitor and " have in terms of electronic nose wide in environmental monitoring, to the leakage of harmful reagent, gas in Chemical Manufacture
Wealthy application prospect.Traditional conductive filler // conductive polymer gas material is using conductor oxidate as conductive filler, pottery
The inorganic compounding gas sensitive as substrate such as porcelain.
At present polymer matrix gas sensitive have the characteristics that cheap, processing temperature is low, flexibility is good, it is easily molded by
Concern.As gas sensitive in use, conductive polymer composite is usually hot pressed or is cast into film, be conducive in this way
The immersion or swelling of gas, to realize high air-sensitive intensity, still, such film there are firmness inadequate, active area
It is small, the disadvantages such as stability is low, such as in monitoring pipeline when flowing gas, as long as there is the air-flow of certain flow rate and pressure to be easy for rushing
Broken film, to limit conducting particles/conductive polymer gas material in the application of similar field.Therefore, it designs a kind of new
There is excellent pressure-resistant performance, can be used for flow at high speed gas by the air-sensitive high molecular material with detection, expanded to further
Its application field is significant.
Summary of the invention
To solve the problems, such as that conductive polymer composite exists as gas sensitive, it is high that the invention proposes a kind of apertures
Molecule gas sensitive and preparation method thereof, with being conducive to, flow at high speed gas passes through the gas sensitive, intensity is high, responsiveness spirit
The characteristics such as quick and preparation process is simple, is produced on a large scale.
The present invention is achieved by the following technical solutions: a kind of open celled polymeric gas sensitive is with conductive filler net
The composite material of network structure, resistance value 108~ 10 Ω, open celled polymeric gas sensitive is made of following each components, in each component
The parts by weight of foam of polymers are 5-99, and the parts by weight of conductive filler are 1-40, and the parts by weight of adhesive are 0-84.
The foam of polymers is selected from polystyrene, polyurethane, polypropylene, polyvinyl chloride, polyethylene, melamine, gathers
One of ester foam,
The conductive filler is selected from stannic oxide/graphene nano piece, stannic oxide/graphene nano band, graphene nanometer sheet, graphite
One of alkene nanobelt, carbon black, carbon fiber, carbon nano-fiber, carbon nanotube.
The adhesive glue is selected from organic silicon adhesive.It preferably is selected from organosilicon silicone resin or organic silicon rubber type gluing
Agent, crosslinking method are add-on type or condensed type.
The open celled polymeric gas sensitive the preparation method comprises the following steps: disperse conductive filler in dispersion liquid, matter is made
The conductive filler mixed liquor that concentration is 0.1-60% is measured, then foam of polymers is dipped in above-mentioned conductive filler mixed liquor, it is rear to locate
Reason obtains open celled polymeric gas sensitive.Dispersion liquid is selected from liquid adhesive, the mixed liquor of adhesive and retarder thinner, You Jirong
It is a kind of in agent, water.Retarder thinner is a kind of or several in n-hexane, petroleum ether, normal heptane, toluene, dimethylbenzene, tetrahydrofuran
Kind, in the mixed liquor of adhesive and retarder thinner, the mass concentration of adhesive is 20-70%, and organic solvent is selected from acetone, ethyl alcohol
One of or both.
Post-processing step are as follows: when dispersion liquid is selected from organic solvent or water, exclude organic solvent or water by the way that drying is dry
Open celled polymeric gas sensitive is obtained, redox graphene band or oxidation after drying exclusion organic solvent or water are either passed through
Graphene modified foam of polymers obtains open celled polymeric gas sensitive；When dispersion liquid when containing adhesive, by adhesive solidification or
Person first excludes retarder thinner, and adhesive solidifies again, obtains open celled polymeric gas sensitive.
Preferably, the technique of the redox graphene band or graphene oxide modified polymer foam is,
80-100 DEG C of steam reduction 3-8h of hydrazine hydrate.
The macromolecule gas sensitive is both conductive filler and open celled polymeric foam or conductive filler, aperture polymerization
The composite material with conductive network structure that object foam and adhesive three are formed, solves film gas-sensitive material firmness not
Enough, the disadvantages such as detection flowing gas is fragile, stability is low, sensitivity, stability and reusability are excellent, can be applicable to detection
Flowing gas, toxic, poisonous gas leakage the open celled polymeric gas sensitive of monitoring of hyperbar high flow rate, or as conductive high
Molecular material uses.
Compared with prior art, the beneficial effects of the present invention are:
(1) with being conducive to, flow at high speed gas passes through the gas sensitive, intensity is high, responsiveness is sensitive, good stability
And reusability；
(2) preparation process is simple, is produced on a large scale.
Detailed description of the invention
Fig. 1 (a) and (b) are that response of the open celled polymeric gas sensitive 1 of the preparation of embodiment 1 in different solvents steam is bent
Line, wherein relative resistance (transient resistance R/ initial resistance R0) characterization material air-sensitive responsiveness；
Fig. 2 (a) and (b) are that response of the open celled polymeric gas sensitive 3 of the preparation of embodiment 3 in different solvents steam is bent
Line, wherein relative resistance (transient resistance R/ initial resistance R0) characterization material air-sensitive responsiveness.
Specific embodiment
Below by embodiment, invention is further described in detail, raw materials used commercially available in embodiment.
Embodiment 1
Stannic oxide/graphene nano piece is added in ethyl alcohol, ultrasonic disperse is made into the oxidation stone that mass percent concentration is 0.1%
The polyurethane open celled foam of 20 × 20 × 10 mm is soaked in wherein, using the side squeezed with vacuum defoamation by black alkene ethanol solution
Method sufficiently infiltrates foam, then takes out and is placed on copper mesh, 100 DEG C of forced air dryings.It repeats above-mentioned immersion-drying 4 times.It takes
Filler modification polyurethane foam is stated, is placed in reaction kettle middle and upper part, beneath dropwise addition hydrazine hydrate is closed to be placed in 3 h in 90 DEG C of baking ovens.
Obtain open celled polymeric gas sensitive 1.
The mass percent of graphene nanometer sheet is 2% in open celled polymeric gas sensitive 1, open celled polymeric gas sensitive 1
Resistance be 44.8K Ω.
Response curve of the open celled polymeric gas sensitive 1 in different solvents steam is as shown in Figure 1, wherein relative resistance
((transient resistance R/ initial resistance R0) characterization material air-sensitive responsiveness；
Embodiment 2
By graphene nanometer sheet adding into acetone, ultrasonic disperse is made into the graphene ethyl alcohol third that mass percent concentration is 1%
The polyethylene open cell foam of 20 × 20 × 10 mm is soaked in wherein, will be steeped using squeezing with the method for vacuum defoamation by ketone solution
Foam sufficiently infiltrates, and then takes out and is placed on copper mesh, 100 DEG C of forced air dryings.Obtain open celled polymeric gas sensitive 2.
The mass percent of graphene nanometer sheet is 3.8% in open celled polymeric gas sensitive 2, open celled polymeric air-sensitive material
The resistance of material 1 is 12.3K Ω.
Embodiment 3
Stannic oxide/graphene nano band is added in ethyl alcohol, ultrasonic disperse is made into the oxidation stone that mass percent concentration is 1.5%
The polyurethane open celled foam of 20 × 20 × 10 mm is soaked in wherein, using extruding and vacuum defoamation by black alkene taking alcohol solution
Method sufficiently infiltrates foam, then takes out and is placed on copper mesh, 100 DEG C of forced air dryings.Take above-mentioned filler modification polyurethane foam
Foam, is placed in reaction kettle middle and upper part, and beneath dropwise addition hydrazine hydrate is closed to be placed in 3 h in 90 DEG C of baking ovens.Obtain open celled polymeric gas
Quick material 3.
The mass percent of graphene nanobelt is 5% in open celled polymeric gas sensitive 3, open celled polymeric gas sensitive 3
Resistance be 147.2K Ω.
Response curve of the open celled polymeric gas sensitive 3 in different solvents steam is as shown in Fig. 2, wherein relative resistance
(transient resistance R/ initial resistance R0) characterization material air-sensitive responsiveness.
Embodiment 4
Graphene oxide band is added in ethyl alcohol, ultrasonic disperse is made into the graphene oxide that mass percent concentration is 2.5%
The melamine open celled foam of 20 × 20 × 10 mm is soaked in wherein, using the side squeezed with vacuum defoamation by taking alcohol solution
Method sufficiently infiltrates foam, then takes out and is placed on copper mesh, forced air drying.Take above-mentioned graphene oxide band modification polyurethane foam
Foam, is placed in reaction kettle middle and upper part, and beneath dropwise addition hydrazine hydrate is closed to be placed in 5 h in 100 DEG C of baking ovens.Obtain open celled polymeric gas
Quick material 5.
The mass percent of graphene ribbon is 10% in open celled polymeric gas sensitive 4, open celled polymeric gas sensitive 4
Resistance is 110.8K Ω.
Embodiment 5
Graphene nanobelt is added in ethyl alcohol, ultrasonic disperse is made into the graphene ribbon second that mass percent concentration is 0.5%
The melamine open celled foam of 20 × 20 × 10 mm is soaked in wherein by alcoholic solution, will with the method for vacuum defoamation using squeezing
Foam sufficiently infiltrates, and then takes out and is placed on copper mesh, forced air drying.Obtain open celled polymeric gas sensitive 5.
The mass percent of graphene nanobelt is 6% in open celled polymeric gas sensitive 5, open celled polymeric gas sensitive 5
Resistance be 1258.6K Ω.
Embodiment 6
The organic siliconresin that crosslinking method is add-on type is dissolved in and is made into the mixing that mass fraction is 70% in n-hexane
Then liquid graphene nanobelt is added in above-mentioned mixed liquor, after ultrasonic 15min, then 20-50min is blended in mechanical stirring, obtains
The dispersion liquid that conductive filler content is 20%.Polyvinyl chloride foam is immersed in the conductive filler mixed liquor prepared, by repeatedly
It squeezes, vacuum row's bubble, the method for centrifugation makes its even application.Then in 70 DEG C of row solvent 30min, it is warming up under the conditions of 80 DEG C,
Solidify 2h, obtains open celled polymeric gas sensitive 6.
The mass percent of graphene nanobelt is 16 % in open celled polymeric gas sensitive 6, and the parts by weight of adhesive are
56 %, the resistance of open celled polymeric gas sensitive 6 are 2.5 K Ω.
Embodiment 7
It is 20% that the organic silicon rubber type adhesive that crosslinking method is add-on type, which is dissolved in toluene, and is made into mass fraction
Then mixed liquor carbon nanotube is added in above-mentioned mixed liquor, after ultrasonic 15min, then 20-50 min is blended in mechanical stirring, obtains
The dispersion liquid for being 1% to conductive filler content.PU foam is immersed in the conductive filler mixed liquor prepared, by repeatedly extruding,
Vacuum row's bubble, the method for centrifugation make its even application.It then in 70 DEG C of row solvent 30min, is warming up under the conditions of 80 DEG C, solidifies
2h obtains open celled polymeric gas sensitive 7.
The mass percent of carbon nanotube is 2.3% in open celled polymeric gas sensitive 7, and the parts by weight of adhesive are 46%,
The resistance of open celled polymeric air-sensitive material 7 is 12.3 K Ω.
Embodiment 8
Carbon nano-fiber is added in the organic silicon rubber type adhesive that crosslinking method is condensed type, after ultrasonic 20min,
20-50 min is blended in mechanical stirring again, obtains the dispersion liquid that conductive filler content is 12%.It is led what the immersion of PU foam prepared
In electric filler mixed liquor, by repeatedly extruding, vacuum row's bubble, the method for centrifugation makes its even application.Then in room temperature curing
72h obtains open celled polymeric gas sensitive 8.
The mass percent of carbon nano-fiber is 9.6% in open celled polymeric gas sensitive 8, and the parts by weight of adhesive are
80%, the resistance of open celled polymeric air-sensitive material 8 is 25.4 K Ω.
Claims (8)
1. a kind of open celled polymeric gas sensitive, which is characterized in that the open celled polymeric gas sensitive is filled out with conduction
Expect the composite material of network structure, resistance value 108~ 10 Ω, open celled polymeric gas sensitive are made of following each components, each group
The parts by weight of open celled polymeric foam are 5-99 in part, and the parts by weight of conductive filler are 1-40, and the parts by weight of adhesive are 46-
84；
The open celled polymeric gas sensitive the preparation method comprises the following steps: disperse conductive filler in dispersion liquid, mass concentration is made
For the conductive filler mixed liquor of 0.1-60%, then foam of polymers is dipped in above-mentioned conductive filler mixed liquor, post-processing obtains
Open celled polymeric gas sensitive；
A kind of in mixed liquor of the dispersion liquid selected from liquid adhesive, adhesive and retarder thinner, the adhesive is selected from organic
Silicon adhesive.
2. a kind of open celled polymeric gas sensitive according to claim 1, which is characterized in that the foam of polymers is selected from
One of polystyrene, polyurethane, polypropylene, polyvinyl chloride, polyethylene, melamine, polyester form.
3. a kind of open celled polymeric gas sensitive according to claim 1, which is characterized in that the conductive filler is selected from
One of graphene nanometer sheet, graphene nanobelt, carbon black, carbon fiber, carbon nano-fiber, carbon nanotube.
4. a kind of preparation method of open celled polymeric gas sensitive as claimed any one in claims 1 to 3, feature exist
In described the preparation method comprises the following steps: dispersing conductive filler in dispersion liquid, the conductive filler that obtained mass concentration is 0.1-60%
Then foam of polymers is dipped in above-mentioned conductive filler mixed liquor by mixed liquor, post-processing obtains open celled polymeric gas sensitive.
5. the preparation method of open celled polymeric gas sensitive according to claim 4, which is characterized in that dispersion liquid is selected from liquid
It is a kind of in the mixed liquor of body adhesive, adhesive and retarder thinner.
6. the preparation method of open celled polymeric gas sensitive according to claim 5, which is characterized in that retarder thinner is selected from
It is n-hexane, petroleum ether, normal heptane, toluene, dimethylbenzene, one or several kinds of in tetrahydrofuran, adhesive and retarder thinner it is mixed
It closes in liquid, the mass concentration of adhesive is 20-70%.
7. the preparation method of open celled polymeric gas sensitive according to claim 4, which is characterized in that post-processing step
Are as follows: adhesive is solidified to or first excluded retarder thinner adhesive solidification again, obtains open celled polymeric gas sensitive.
8. a kind of open celled polymeric gas sensitive as described in claim 1 can be applied to monitor toxic, poisonous gas leakage, inspection
The flowing gas of hyperbar high flow rate is surveyed, or is used as conductive polymer material.
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| CN107474550B (en) * | 2017-07-20 | 2020-08-11 | 杭州师范大学 | Fast-response high-sensitivity polymer-based gas sensitive material and preparation method and application thereof |
| CN107504893B (en) * | 2017-09-06 | 2020-02-14 | 南京理工大学 | High-sensitivity reticular graphene/elastomer strain sensor and preparation method thereof |
| CN108760835A (en) * | 2018-06-26 | 2018-11-06 | 合肥萃励新材料科技有限公司 | A kind of benzene homologues gas detecting element |
| CN109520410B (en) * | 2018-11-19 | 2020-11-24 | 西安电子科技大学 | Three-dimensional graphene foam flexible strain sensor and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1840750A (en) * | 2006-02-09 | 2006-10-04 | 东华大学 | Electrically conductive composite fibre containing carbon nanotube and method for making same |
| CN102361929A (en) * | 2009-03-23 | 2012-02-22 | 阿克马法国公司 | Method for preparing an elastomeric composite material with a high nanotube content |
| CN102557022A (en) * | 2012-03-02 | 2012-07-11 | 杭州电子科技大学 | Preparation method of graphene conductive foam |
| CN104559008A (en) * | 2014-12-30 | 2015-04-29 | 陕西师范大学 | Ternary conductive gas-sensitive sensing material adopting polymers, compatilizer and multiwalled carbon nanotubes as well as preparation method and application of ternary conductive gas-sensitive sensing material |
| CN104559187A (en) * | 2015-02-03 | 2015-04-29 | 国家电网公司 | Preparation method of carbon nanotube modified organic silicon resin based composite material |
| CN105255191A (en) * | 2015-10-21 | 2016-01-20 | 国家电网公司 | Grounding module modified through carbon nano tubes and preparation method of grounding module |
-
2016
- 2016-06-21 CN CN201610449711.6A patent/CN106257275B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1840750A (en) * | 2006-02-09 | 2006-10-04 | 东华大学 | Electrically conductive composite fibre containing carbon nanotube and method for making same |
| CN102361929A (en) * | 2009-03-23 | 2012-02-22 | 阿克马法国公司 | Method for preparing an elastomeric composite material with a high nanotube content |
| CN102557022A (en) * | 2012-03-02 | 2012-07-11 | 杭州电子科技大学 | Preparation method of graphene conductive foam |
| CN104559008A (en) * | 2014-12-30 | 2015-04-29 | 陕西师范大学 | Ternary conductive gas-sensitive sensing material adopting polymers, compatilizer and multiwalled carbon nanotubes as well as preparation method and application of ternary conductive gas-sensitive sensing material |
| CN104559187A (en) * | 2015-02-03 | 2015-04-29 | 国家电网公司 | Preparation method of carbon nanotube modified organic silicon resin based composite material |
| CN105255191A (en) * | 2015-10-21 | 2016-01-20 | 国家电网公司 | Grounding module modified through carbon nano tubes and preparation method of grounding module |
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