CN110437568A - A kind of sensitive material and preparation method thereof suitable for selfreparing pressure sensor - Google Patents
A kind of sensitive material and preparation method thereof suitable for selfreparing pressure sensor Download PDFInfo
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- CN110437568A CN110437568A CN201910758651.XA CN201910758651A CN110437568A CN 110437568 A CN110437568 A CN 110437568A CN 201910758651 A CN201910758651 A CN 201910758651A CN 110437568 A CN110437568 A CN 110437568A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L11/00—Measuring steady or quasi-steady pressure of a fluid or a fluent solid material by means not provided for in group G01L7/00 or G01L9/00
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L5/00—Apparatus for, or methods of, measuring force, work, mechanical power, or torque, specially adapted for specific purposes
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Abstract
The present invention provides a kind of sensitive materials in selfreparing pressure sensor, sensitive material includes following component by mass percentage: selfreparing macromolecule 5 ~ 40%, selfreparing conduction plural gel 5 ~ 30%, one-dimensional silver nanowires 1 ~ 40%, solvent 20 ~ 60%, auxiliary agent 3 ~ 15%, wherein, the selfreparing macromolecule includes the following raw material ingredient: polyether polyol, hydroxyl silicon rubber, isophorone diisocyanate, dibutyl tin dilaurate and 3,3,5,5- tetrachloro diphenyl disulfides；The selfreparing conduction plural gel includes the following raw material ingredient: five methene phosphorus of polyacrylic acid, aniline and diethylenetriamine.Sensitive material suitable for selfreparing pressure sensor of the invention, selfreparing conduction plural gel is mixed under solvent condition with conductive metal powder, conductive metal powder is filled into structural void, it is wound with macromolecular chain compound, construct three-dimensional conductive network, it can effectively prevent metal powder sedimentation, further increase sensitive material stability, there is huge market application prospect.
Description
Technical field
Present invention relates particularly to the systems of a kind of sensitive material in selfreparing pressure sensor and the sensitive material
Preparation Method.
Background technique
With the surge of information age information content, in order to more accurately perceive the size of external force, pressure is passed
The requirements such as accuracy, reliability and the sensitivity of sensor are increasingly stringenter.And traditional pressure sensor volume is big, is difficult to meet
Above-mentioned high performance requirement.Therefore, they are replaced various types of high-performance sensors, and wherein pliable pressure senses
Device is increasingly taken seriously.However, sensitive material is the important component of pliable pressure sensor.Currently, for flexible pressure
Sensitive material in force snesor is mainly metal, metal oxide or organic/inorganic semiconductor material etc., this few class material tool
The problems such as flexible is poor, processing cost is high, easy to damage.
To solve the above-mentioned problems, the pliable pressure sensor with Smart self-repairing has become current research hotspot.
Patent disclosure (bulletin) number CN107036741A, CN108548480A, CN109294134A, CN206724883U,
CN106969860A, CN107473208A etc. report selfreparing sensor, conductive paste material employed in these patents
For metal powder, metal oxide, carbon material etc..The single or compound use of these materials, can effectively improve the stress-of sensitive layer
Strain-electrical property.However, these materials easily sink in preparation process, surface resistance is variant up and down for obtained sensitive layer.Cause
How this, prepare the sensitivity that a kind of good, high sensitivity, self-repair function with stability are good and can be used in pressure sensor
Material is the important topic studied at present.
Summary of the invention
In view of this, in order to overcome the drawbacks of the prior art, the object of the present invention is to provide a kind of improved suitable for certainly
The sensitive material in pressure sensor is repaired, stability is good, high sensitivity, service life are long.
In order to achieve the above object, the following technical solution is employed by the present invention:
A kind of sensitive material suitable for selfreparing pressure sensor includes following component by mass percentage:
Wherein, the selfreparing macromolecule includes the following raw material ingredient: polyether polyol, hydroxyl silicon rubber, isophorone
Diisocyanate, dibutyl tin dilaurate and 3,3,5,5- tetrachloro diphenyl disulfide；
The selfreparing conduction plural gel includes the following raw material ingredient: five first of polyacrylic acid, aniline and diethylenetriamine
Pitch phosphoric acid.
Some preferred embodiments according to the present invention, the pure and mild hydroxyl silicon of polyether polyols described in the selfreparing macromolecule
Rubber quality ratio is 1:0.5~1:3；The isophorone diisocyanate and dibutyl tin dilaurate mass ratio be 50:1~
30:4。
Some preferred embodiments according to the present invention, polyacrylic acid, benzene described in the selfreparing conduction plural gel
The mass ratio of five methene phosphoric acid of amine and diethylenetriamine is 300:50:1~800:200:10.In some embodiments preferably poly- third
The mass ratio of five methene phosphoric acid of olefin(e) acid, aniline and diethylenetriamine is 625:100:7.
Some preferred embodiments according to the present invention, the solvent are ethyl alcohol, n,N-dimethylacetamide, tetrahydrofuran
One or more of composition mixture.
Some preferred embodiments according to the present invention, the auxiliary agent include defoaming agent, levelling agent and thickener.
The present invention also provides a kind of preparations of sensitive material as described above suitable for selfreparing pressure sensor
Method, the sensitive material include following component by mass percentage:
The preparation method of the sensitive material includes the following steps: in proportion to stir each component substance at 20~50 DEG C
0.5~1.5h obtains uniform mixture；Then, which is moved in mold, at 60~120 DEG C solidify 8~for 24 hours,
The sensitive material being used in selfreparing pressure sensor can be obtained.
Some preferred embodiments according to the present invention, the selfreparing are high molecular the preparation method is as follows: polyethers is more
The pure and mild hydroxyl silicon rubber of member is mixed in proportion, and 2~3h of vacuum dehydration at 110~120 DEG C, and it is mixed to obtain alcohol/silicon rubber
Close object；Isophorone diisocyanate and dibutyl tin dilaurate are successively added drop-wise in alcohol/silastic mixture, 80~
Mechanical stirring 30min at 90 DEG C；Continue to be warming up to 95~100 DEG C, reacts 3.5~5h；Selfreparing performed polymer is obtained, by 3,3,5,
The tetrahydrofuran solution of 5- tetrachloro diphenyl disulfide is added in the selfreparing performed polymer, and selfreparing macromolecule can be obtained.
Wherein, the pure and mild hydroxyl silicon rubber mass ratio 1:0.5~1:3 of the polyether polyols；The isophorone diisocyanate
Ester and dibutyl tin dilaurate mass ratio 50:1~30:4, isophorone diisocyanate and alcohol/silastic mixture quality
Than 1:1~1:6；The tetrahydrofuran solution concentration of described 3,3,5,5- tetrachloro diphenyl disulfides be 0.4~2.8g/mL, 3,3,5,
The tetrahydrofuran solution and selfreparing prepolymer mass ratio of 5- tetrachloro diphenyl disulfide are 1:10~1:40.
Some preferred embodiments according to the present invention, the selfreparing conduction plural gel the preparation method is as follows: pressing
Ratio polypropylene acid, five methene phosphoric acid of aniline and diethylenetriamine, stir 30~360min under the conditions of 0~5 DEG C and obtain
The selfreparing conduction plural gel of five methene phosphatic type of poly propenoic acid aniline/diethylenetriamine.
Wherein, the mass ratio of five methene phosphoric acid of the polyacrylic acid, aniline and diethylenetriamine is 300:50:1~800:
200:10, the mass ratio of five methene phosphoric acid of preferred polyacrylic acid, aniline and diethylenetriamine is 625 in some embodiments:
100:7。
Polyacrylic acid the preparation method is as follows: acrylic acid is dissolved in acetone, Irgacure2959 photoinitiator is added,
15~60min is reacted under ultraviolet light, and product is dried at 50 DEG C, obtains polyacrylic acid；Wherein, the acrylic acid and third
Ketone mass ratio is 1:5~1:20, acrylic acid and photoinitiator mass ratio are 20:1~80:1.In some embodiments, preferred light
Initiator is Irgacure2959 photoinitiator, and acrylic acid and acetone quality ratio are 1:10, acrylic acid and photoinitiator mass ratio
For 64:1.
The preparation method of some preferred embodiments according to the present invention, the one-dimensional silver nanowires is specific as follows:
A) ethylene glycol pre-processes: the ethylene glycol of 50~100mL being added in three-necked flask and is sufficiently added at 180~195 DEG C
35~60min of heat；
B) the NaCl aqueous solution for measuring 5~8mL, which is added in pretreated ethylene glycol, forms mixed solution, and heating 10~
15min；NaCl concentration of aqueous solution is 0.002~0.004mol/L；
C) silver nitrate is dissolved in pretreated ethylene glycol, forms the silver nitrate solution of 0.3~0.5mol/L；By poly- second
Alkene pyrrolones (PVP) is dissolved in pretreated ethylene glycol, forms the PVP solution of 0.4~0.6mol/L；Take 10~15mL nitric acid
Silver-colored solution is added in the mixed solution of step b) formation, while the PVP solution of 30~45mL being taken to be slowly dropped by peristaltic pump,
Time control is instilled in 50~90min, obtains reaction solution；
D) after completion of dropwise addition, the reaction solution that step c) is obtained, which takes out, to be stood to room temperature；Then reaction solution is existed
20min is centrifuged under 12000rpm and with deionized water and washes of absolute alcohol 3 times, finally obtaining powdery product is one-dimensional silver
Nano wire.
Compared with prior art, the invention has the beneficial effects that: it is of the invention suitable for selfreparing pressure sensor
Sensitive material, selfreparing conduction plural gel is mixed under solvent condition with conductive metal powder, by conductive metal powder
Filling is wound compound into structural void with macromolecular chain, constructs three-dimensional conductive network, it is heavy to can effectively prevent metal powder
Drop, further increases sensitive material stability；Meanwhile the metal of the conductive characteristic of selfreparing conduction plural gel itself and conduction
Powder can be effectively formed electronic effect, can effectively solve the problem that current metal powder, metal oxide, carbon material etc. divide in forming process
The disadvantages of uneven, easily settled is dissipated, and there is excellent self-reparing capability after being destroyed, can effectively extend the service life, overcome
The deficiencies in the prior art have huge market application prospect and good economic and social benefits.
Specific embodiment
In order that those skilled in the art will better understand the technical solution of the present invention, below in the embodiment of the present invention
Technical solution be clearly and completely described, it is clear that the described embodiment is only a part of the embodiment of the present invention,
Instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative labor
Every other embodiment obtained under the premise of dynamic, should fall within the scope of the present invention.
Reagent used in following embodiment is commercially available.
Embodiment 1
The sensitive material being used in selfreparing pressure sensor in the present embodiment is grouped by the group of following mass fraction
At:
The preparation method of sensitive material based on said components specifically comprises the following steps:
(1) the high molecular preparation of selfreparing
The pure and mild 12g hydroxyl silicon rubber of 12g polyether polyols is mixed, and the vacuum dehydration 2.5h at 115 DEG C, is obtained
Alcohol/silastic mixture.
8g isophorone diisocyanate and 0.27g dibutyl tin dilaurate are successively added drop-wise to alcohol/silicon rubber to mix
In object, the mechanical stirring 30min at 85 DEG C；Continue to be warming up to 98 DEG C, reacts 3.5h, obtain selfreparing performed polymer.
The tetrahydrofuran solution for the 3,3,5,5- tetrachloro diphenyl disulfide that 1.2g concentration is 0.6g/mL is added to selfreparing
In performed polymer, selfreparing macromolecule can be obtained.
(2) preparation of selfreparing conduction plural gel
10g acrylic acid is dissolved in 100g acetone, Irgacure2959 photoinitiator 0.16 is added, under ultraviolet light instead
15min is answered, and product is dried at 50 DEG C, obtains polyacrylic acid.
The polyacrylic acid, 1g aniline and five methene phosphoric acid of 0.07g diethylenetriamine of 6.25g is taken to be mixed in three-necked flask,
It is compound to obtain five methene phosphatic type selfreparing conduction of poly propenoic acid aniline/diethylenetriamine by stirring 30min under the conditions of 2 DEG C
Gel.
(3) preparation of one-dimensional silver nanowires
A) ethylene glycol pre-processes: the ethylene glycol of 50mL is added in three-necked flask in 180 DEG C of sufficiently heating 35min.
B) the NaCl aqueous solution for measuring 5mL, which is added in pretreated ethylene glycol, forms mixed solution, heats 10min；
NaCl concentration of aqueous solution is 0.002mol/L.
C) 10g silver nitrate is dissolved in ethylene glycol, forms the silver nitrate solution of 0.3mol/L；By 15g polyvinyl pyrrolidone
(PVP) it is dissolved in ethylene glycol, forms the PVP solution of 0.4mol/L；10mL silver nitrate solution is taken to be added to the mixed of step b) formation
It closes in solution, while the PVP solution of 30mL being taken to be slowly dropped by peristaltic pump, instill time control in 50min, reacted
Liquid.
D) after completion of dropwise addition, the reaction solution that step c) is obtained, which takes out, to be stood to room temperature；Then reaction solution is existed
It is centrifuged 20min under 12000rpm and with deionized water and washes of absolute alcohol 3 times, finally obtains powdery product.
(4) preparation of sensitive material
Each component substance and solvent and auxiliary agent that step (1)-(3) are prepared are mixed in proportion, stirred at 20 DEG C
0.5h is mixed, uniform mixture is obtained；Then, mixture is moved in mold, solidifies at 60 DEG C for 24 hours, can be obtained and be used for
Sensitive material in selfreparing pressure sensor.
Embodiment 2
The sensitive material being used in selfreparing pressure sensor in the present embodiment is grouped by the group of following mass fraction
At:
The preparation method of sensitive material based on said components specifically comprises the following steps:
(1) the high molecular preparation of selfreparing
The pure and mild 12g hydroxyl silicon rubber of 12g polyether polyols is mixed, and the vacuum dehydration 2.5h at 115 DEG C, is obtained
Alcohol/silastic mixture.
8g isophorone diisocyanate and 0.27g dibutyl tin dilaurate are successively added drop-wise to alcohol/silicon rubber to mix
In object, the mechanical stirring 30min at 85 DEG C；Continue to be warming up to 98 DEG C, reacts 3.5h, obtain selfreparing performed polymer.
The tetrahydrofuran solution for the 3,3,5,5- tetrachloro diphenyl disulfide that 1.2g concentration is 0.6g/mL is added to selfreparing
In performed polymer, selfreparing macromolecule can be obtained.
(2) preparation of selfreparing conduction plural gel
10g acrylic acid is dissolved in 100g acetone, Irgacure2959 photoinitiator 0.16 is added, under ultraviolet light instead
15min is answered, and product is dried at 50 DEG C, obtains polyacrylic acid.
The polyacrylic acid, 1g aniline and five methene phosphoric acid of 0.07g diethylenetriamine of 6.25g is taken to be mixed in three-necked flask,
It is compound to obtain five methene phosphatic type selfreparing conduction of poly propenoic acid aniline/diethylenetriamine by stirring 30min under the conditions of 3 DEG C
Gel.
(3) preparation of one-dimensional silver nanowires
A) ethylene glycol pre-processes: the ethylene glycol of 50mL is added in three-necked flask in 180 DEG C of sufficiently heating 35min.
B) the NaCl aqueous solution for measuring 5mL, which is added in pretreated ethylene glycol solution, forms mixed solution, heats
10min；NaCl concentration of aqueous solution is 0.002mol/L.
C) 10g silver nitrate is dissolved in ethylene glycol, forms the silver nitrate solution of 0.3mol/L；By 15g polyvinyl pyrrolidone
(PVP) it is dissolved in ethylene glycol, forms the PVP solution of 0.4mol/L；10mL silver nitrate solution is taken to be added to the mixed of step b) formation
It closes in solution, while the PVP solution of 30mL being taken to be slowly dropped by peristaltic pump, instill time control in 50min, reacted
Liquid.
D) after completion of dropwise addition, the reaction solution that step c) is obtained, which takes out, to be stood to room temperature；Then reaction solution is existed
It is centrifuged 20min under 12000rpm and with deionized water and washes of absolute alcohol 3 times, finally obtains powdery product.
(4) preparation of sensitive material
Each component substance and solvent and auxiliary agent that step (1)-(3) are prepared are mixed in proportion, stirred at 50 DEG C
0.5~1h is mixed, uniform mixture is obtained；Then, mixture is moved in mold, solidifies 8h at 120 DEG C, use can be obtained
Sensitive material in selfreparing pressure sensor.
Embodiment 3
The sensitive material being used in selfreparing pressure sensor in the present embodiment is grouped by the group of following mass fraction
At:
The preparation method of sensitive material based on said components specifically comprises the following steps:
(1) the high molecular preparation of selfreparing
The pure and mild 12g hydroxyl silicon rubber of 12g polyether polyols is mixed, and the vacuum dehydration 3h at 120 DEG C, obtain alcohol/
Silastic mixture.
8g isophorone diisocyanate and 0.27g dibutyl tin dilaurate are successively added drop-wise to alcohol/silicon rubber to mix
In object, the mechanical stirring 30min at 88 DEG C；Continue to be warming up to 100 DEG C, reacts 3.5h, obtain selfreparing performed polymer.
The tetrahydrofuran solution for the 3,3,5,5- tetrachloro diphenyl disulfide that 1.2g concentration is 0.6g/mL is added to selfreparing
In performed polymer, selfreparing macromolecule can be obtained.
(2) preparation of selfreparing conduction plural gel
20g acrylic acid is dissolved in 200g acetone, Irgacure2959 photoinitiator 0.3125g is added, in ultraviolet light
Lower reaction 20min, and product is dried at 50 DEG C, obtain polyacrylic acid.
The polyacrylic acid, 0.5g aniline and five methene phosphoric acid of 0.035g diethylenetriamine of 3.125g is taken to be mixed in three-necked flask
In, it is multiple to obtain five methene phosphatic type selfreparing conduction of poly propenoic acid aniline/diethylenetriamine by stirring 60min under the conditions of 0 DEG C
Close gel.
(3) preparation of one-dimensional silver nanowires
A) ethylene glycol pre-processes: the ethylene glycol of 60mL is added in three-necked flask in 190 DEG C of sufficiently heating 50min.
B) the NaCl aqueous solution for measuring 7mL, which is added in pretreated ethylene glycol, forms mixed solution, heats 10min；
NaCl concentration of aqueous solution is 0.0025mol/L.
C) 15g silver nitrate is dissolved in ethylene glycol, forms the silver nitrate solution of 0.35mol/L；By 14g polyvinyl pyrrolidone
(PVP) it is dissolved in ethylene glycol, forms the PVP solution of 0.48mol/L；13mL silver nitrate solution is taken to be added to the mixed of step b) formation
It closes in solution, while the PVP solution of 35mL being taken to be slowly dropped by peristaltic pump, instill time control in 65min, reacted
Liquid.
D) after completion of dropwise addition, the reaction solution that step c) is obtained, which takes out, to be stood to room temperature；Then reaction solution is existed
It is centrifuged 20min under 12000rpm and with deionized water and washes of absolute alcohol 3 times, finally obtains powdery product.
(4) preparation of sensitive material
Each component substance and solvent and auxiliary agent that step (1)-(3) are prepared are mixed in proportion, stirred at 40 DEG C
1.2h is mixed, uniform mixture is obtained；Then, mixture is moved in mold, solidifies 10h at 100 DEG C, can be obtained and be used for
Sensitive material in selfreparing pressure sensor.
Embodiment 4
The sensitive material being used in selfreparing pressure sensor in the present embodiment is grouped by the group of following mass fraction
At:
The preparation method of sensitive material based on said components specifically comprises the following steps:
(1) the high molecular preparation of selfreparing
The pure and mild 12g hydroxyl silicon rubber of 12g polyether polyols is mixed, and the vacuum dehydration 2.5h at 115 DEG C, is obtained
Alcohol/silastic mixture.
8g isophorone diisocyanate and 0.27g dibutyl tin dilaurate are successively added drop-wise to alcohol/silicon rubber to mix
In object, the mechanical stirring 30min at 86 DEG C；Continue to be warming up to 98 DEG C, reacts 4h, obtain selfreparing performed polymer.
The tetrahydrofuran solution for the 3,3,5,5- tetrachloro diphenyl disulfide that 1.2g concentration is 0.6g/mL is added to selfreparing
In performed polymer, selfreparing macromolecule can be obtained.
(2) preparation of selfreparing conduction plural gel
20g acrylic acid is dissolved in 200g acetone, Irgacure2959 photoinitiator 0.3125g is added, in ultraviolet light
Lower reaction 40min, and product is dried at 50 DEG C, obtain polyacrylic acid.
The polyacrylic acid, 0.5g aniline and five methene phosphoric acid of 0.035g diethylenetriamine of 3.125g is taken to be mixed in three-necked flask
In, 300min is stirred under the conditions of 2 DEG C obtains five methene phosphatic type selfreparing conduction of poly propenoic acid aniline/diethylenetriamine
Plural gel.
(3) preparation of one-dimensional silver nanowires
A) ethylene glycol pre-processes: the ethylene glycol of 70mL is added in three-necked flask in 192 DEG C of sufficiently heating 55min.
B) the NaCl aqueous solution for measuring 7.5mL, which is added in pretreated ethylene glycol solution, forms mixed solution, heats
12min；NaCl concentration of aqueous solution is 0.0035mol/L.
C) 15g silver nitrate is dissolved in ethylene glycol, forms the silver nitrate solution of 0.35mol/L；By 14g polyvinyl pyrrolidone
(PVP) it is dissolved in ethylene glycol, forms the PVP solution of 0.52mol/L；12mL silver nitrate solution is taken to be added to the mixed of step b) formation
It closes in solution, while the PVP solution of 38mL being taken to be slowly dropped by peristaltic pump, instill time control in 70min, reacted
Liquid.
D) after completion of dropwise addition, the reaction solution that step c) is obtained, which takes out, to be stood to room temperature；Then reaction solution is existed
It is centrifuged 20min under 12000rpm and with deionized water and washes of absolute alcohol 3 times, finally obtains powdery product.
(4) preparation of sensitive material
Each component substance and solvent and auxiliary agent that step (1)-(3) are prepared are mixed in proportion, stirred at 45 DEG C
1.5h is mixed, uniform mixture is obtained；Then, mixture is moved in mold, solidifies 9h at 110 DEG C, can be obtained and be used for
Sensitive material in selfreparing pressure sensor.
Embodiment 5
The sensitive material being used in selfreparing pressure sensor in the present embodiment is grouped by the group of following mass fraction
At:
The preparation method of sensitive material based on said components specifically comprises the following steps:
(1) the high molecular preparation of selfreparing
The high molecular preparation of selfreparing is the following steps are included: the pure and mild 12g hydroxyl silicon rubber of 12g polyether polyols is mixed
It closes, and the vacuum dehydration 3h at 120 DEG C, obtains alcohol/silastic mixture.
8g isophorone diisocyanate and 0.27g dibutyl tin dilaurate are successively added drop-wise to alcohol/silicon rubber to mix
In object, the mechanical stirring 30min at 88 DEG C；Continue to be warming up to 100 DEG C, reacts 5h, obtain selfreparing performed polymer.
The tetrahydrofuran solution for the 3,3,5,5- tetrachloro diphenyl disulfide that 1.2g concentration is 0.6g/mL is added to selfreparing
In performed polymer, selfreparing macromolecule can be obtained.
(2) preparation of selfreparing conduction plural gel
20g acrylic acid is dissolved in 200g acetone, Irgacure2959 photoinitiator 0.3125g is added, in ultraviolet light
Lower reaction 20min, and product is dried at 50 DEG C, obtain polyacrylic acid.
The polyacrylic acid, 0.5g aniline and five methene phosphoric acid of 0.035g diethylenetriamine of 3.125g is taken to be mixed in three-necked flask
In, it is multiple to obtain five methene phosphatic type selfreparing conduction of poly propenoic acid aniline/diethylenetriamine by stirring 60min under the conditions of 3 DEG C
Close gel.
(3) preparation of one-dimensional silver nanowires
A) ethylene glycol pre-processes: the ethylene glycol of 60mL is added in three-necked flask in 190 DEG C of sufficiently heating 50min.
B) the NaCl aqueous solution for measuring 7mL, which is added in pretreated ethylene glycol solution, forms mixed solution, heats
10min；NaCl concentration of aqueous solution is 0.0025mol/L.
C) 15g silver nitrate is dissolved in ethylene glycol, forms the silver nitrate solution of 0.35mol/L；By 14g polyvinyl pyrrolidone
(PVP) it is dissolved in ethylene glycol, forms the PVP solution of 0.48mol/L；13mL silver nitrate solution is taken to be added to the mixed of step b) formation
It closes in solution, while the PVP solution of 35mL being taken to be slowly dropped by peristaltic pump, instill time control in 65min, reacted
Liquid.
D) after completion of dropwise addition, the reaction solution that step c) is obtained, which takes out, to be stood to room temperature；Then reaction solution is existed
It is centrifuged 20min under 12000rpm and with deionized water and washes of absolute alcohol 3 times, finally obtains powdery product.
(4) preparation of sensitive material
Each component substance and solvent and auxiliary agent that step (1)-(3) are prepared are mixed in proportion, stirred at 45 DEG C
1.5h is mixed, uniform mixture is obtained；Then, mixture is moved in mold, solidifies 11h at 105 DEG C, can be obtained and be used for
Sensitive material in selfreparing pressure sensor.
Embodiment 6
The sensitive material being used in selfreparing pressure sensor in the present embodiment is grouped by the group of following mass fraction
At:
The preparation method of sensitive material based on said components specifically comprises the following steps:
(1) the high molecular preparation of selfreparing
The pure and mild 12g hydroxyl silicon rubber of 12g polyether polyols is mixed, and the vacuum dehydration 2h at 118 DEG C, obtain alcohol/
Silastic mixture.
8g isophorone diisocyanate and 0.27g dibutyl tin dilaurate are successively added drop-wise to alcohol/silicon rubber to mix
In object, the mechanical stirring 30min at 90 DEG C；Continue to be warming up to 100 DEG C, reacts 3.5h, obtain selfreparing performed polymer.
The tetrahydrofuran solution for the 3,3,5,5- tetrachloro diphenyl disulfide that 1.2g concentration is 0.6g/mL is added to selfreparing
In performed polymer, selfreparing macromolecule can be obtained.
(2) preparation of selfreparing conduction plural gel
25g acrylic acid is dissolved in 250g acetone, Irgacure2959 photoinitiator 0.39g is added, under ultraviolet light
60min is reacted, and product is dried at 50 DEG C, obtains polyacrylic acid.
The polyacrylic acid, 0.5g aniline and five methene phosphoric acid of 0.035g diethylenetriamine of 3.125g is taken to be mixed in three-necked flask
In, it is multiple to obtain five methene phosphatic type selfreparing conduction of poly propenoic acid aniline/diethylenetriamine by stirring 300min under the conditions of 0 °
Close gel.
(3) preparation of one-dimensional silver nanowires
A) ethylene glycol pre-processes: the ethylene glycol of 85mL is added in three-necked flask in 195 DEG C of sufficiently heating 60min.
B) the NaCl aqueous solution for measuring 8mL, which is added in pretreated ethylene glycol, forms mixed solution, heats 13min；
NaCl concentration of aqueous solution is 0.0035mol/L.
C) 6g silver nitrate is dissolved in ethylene glycol, forms the silver nitrate solution of 0.45mol/L；By 20g polyvinyl pyrrolidone
(PVP) it is dissolved in ethylene glycol, forms the PVP solution of 0.55mol/L；15mL silver nitrate solution is taken to be added to the mixed of step b) formation
It closes in solution, while the PVP solution of 40mL being taken to be slowly dropped by peristaltic pump, instill time control in 80min, reacted
Liquid.
D) after completion of dropwise addition, the reaction solution that step c) is obtained, which takes out, to be stood to room temperature；Then reaction solution is existed
It is centrifuged 20min under 12000rpm and with deionized water and washes of absolute alcohol 3 times, finally obtains powdery product.
(4) preparation of sensitive material
Each component substance and solvent and auxiliary agent that step (1)-(3) are prepared are mixed in proportion, stirred at 30 DEG C
0.7h is mixed, uniform mixture is obtained；Then, mixture is moved in mold, solidifies 21h at 90 DEG C, can be obtained and be used for
Sensitive material in selfreparing pressure sensor.
Comparative example 1
Selfreparing macromolecule and selfreparing conduction plural gel are substituted for 184 silicon rubber material of first DOW CORNING by this comparative example
Material, and prepare for the sensitive material in pressure sensor.
Specifically, the sensitive material of this comparative example is grouped as by the group of following mass fraction:
The preparation method of sensitive material based on said components specifically comprises the following steps: each component substance at 30 DEG C
0.7h is stirred, uniform mixture is obtained；Then, mixture is moved in mold, solidifies 21h at 80 DEG C, use can be obtained
Sensitive material in selfreparing pressure sensor.
Wherein, one-dimensional silver nanowires preparation the following steps are included:
A) ethylene glycol pre-processes: the ethylene glycol of 85mL is added in three-necked flask in 195 DEG C of sufficiently heating 60min.
B) the NaCl aqueous solution for measuring 8mL, which is added in pretreated ethylene glycol, forms mixed solution, heats 13min；
NaCl concentration of aqueous solution is 0.0035mol/L.
C) 6g silver nitrate is dissolved in ethylene glycol, forms the silver nitrate solution of 0.45mol/L；By 20g polyvinyl pyrrolidone
(PVP) it is dissolved in ethylene glycol, forms the PVP solution of 0.55mol/L；15mL silver nitrate solution is taken to be added to the mixed of step b) formation
It closes in solution, while the PVP solution of 40mL being taken to be slowly dropped by peristaltic pump, instill time control in 80min, reacted
Liquid.
D) after completion of dropwise addition, the reaction solution that step c) is obtained, which takes out, to be stood to room temperature；Then reaction solution is existed
It is centrifuged 20min under 12000rpm and with deionized water and washes of absolute alcohol 3 times, finally obtains powdery product.
The test of embodiment 7 and interpretation of result
The test of volume resistivity and mechanics repair rate is carried out to embodiment 1-6 and comparative example 1.Wherein, volume resistance
Rate is tested using four probe resistance rate analyzers；Mechanics repair rate is tensile strength of material and the preceding tensile strength of reparation after repairing
Ratio is tested using material stretch test machine, and repairing condition is to stand 2 hours under room temperature environment.Experimental result is shown in Table 1.
1 experimental result of table
Can be seen that from the data in table 1 be prepared in embodiment 1-6 for quick in selfreparing pressure sensor
Material is felt when being destroyed by external force, can effectively restore its function.
Gel is that a kind of macromolecular chain is connected with each other, and forms space net structure, be filled in structural void as point
The substance of dispersion media liquid.The sensitive material in selfreparing pressure sensor of the invention is by selfreparing conduction plural gel
It is mixed under solvent condition with conductive metal powder, conductive metal powder is filled into structural void, is carried out with macromolecular chain
Wind it is compound, construct three-dimensional conductive network, can effectively prevent metal powder sedimentation, further increase sensitive material stability.Meanwhile
The conductive characteristic of selfreparing conduction plural gel itself and conductive metal powder can be effectively formed electronic effect.Obtained by the present invention
Sensitive material, after being destroyed, can not use any renovation agent or regenerative agent, good selfreparing can be reached.And
And self-repair procedure is normal without using high-temperature heating, heating in vacuum, ultraviolet light irradiation, infrared light irradiation, chemical reagent addition etc.
Rule method only needs room temperature condition, autonomous progress, and low energy consumption, does not need inert gas shielding, has actual application effect.This
The method of invention has the advantages that easy to operate, the simple and suitable large-scale industrial production of moulding process.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention, it is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of sensitive material suitable for selfreparing pressure sensor, it is characterised in that: the sensitive material presses quality hundred
Score meter includes following component:
The selfreparing macromolecule includes the following raw material ingredient: polyether polyol, hydroxyl silicon rubber, isophorone diisocyanate
Ester, dibutyl tin dilaurate and 3,3,5,5- tetrachloro diphenyl disulfide；
The selfreparing conduction plural gel includes the following raw material ingredient: five methene phosphorus of polyacrylic acid, aniline and diethylenetriamine
Acid.
2. a kind of sensitive material suitable for selfreparing pressure sensor according to claim 1, it is characterised in that: system
The pure and mild hydroxyl silicon rubber mass ratio of polyether polyols described in the standby high molecular raw material of the selfreparing is 1:0.5~1:3；It is described different
Isophorone diisocyanate and dibutyl tin dilaurate mass ratio are 50:1~30:4.
3. a kind of sensitive material suitable for selfreparing pressure sensor according to claim 1, it is characterised in that: system
The quality of five methene phosphoric acid of polyacrylic acid, aniline and diethylenetriamine described in the raw material of the standby selfreparing conduction plural gel
Than for 300:50:1~800:200:10.
4. a kind of sensitive material suitable for selfreparing pressure sensor according to claim 1, it is characterised in that: institute
State the mixture that solvent is one or more of ethyl alcohol, DMAC N,N' dimethyl acetamide, tetrahydrofuran composition.
5. a kind of sensitive material suitable for selfreparing pressure sensor according to claim 1, it is characterised in that: institute
Stating auxiliary agent is one or more of defoaming agent, levelling agent and thickener.
6. the preparation side of the sensitive material suitable for selfreparing pressure sensor as described in claim 1-5 any one
Method, it is characterised in that: the sensitive material includes following component by mass percentage:
The preparation method of the sensitive material include the following steps: after mixing each component at 20~50 DEG C stirring 0.5~
1.5h obtains uniform mixture；Then, the mixture solidifies to 8 at 60~120 DEG C~for 24 hours, obtain described be used for
Sensitive material in selfreparing pressure sensor.
7. a kind of sensitive material suitable for selfreparing pressure sensor according to claim 6, it is characterised in that: institute
It is high molecular the preparation method is as follows: admixtured polyether polyalcohol and hydroxyl silicon rubber to state selfreparing, and the vacuum at 110~120 DEG C
It is dehydrated 2~3h, obtains alcohol/silastic mixture；Isophorone diisocyanate and dibutyl tin dilaurate are added drop-wise to institute
It states in alcohol/silastic mixture, stirs 30min at 80~90 DEG C；Continue to be warming up to 95~100 DEG C, reacts 3.5~5h, obtain
To selfreparing performed polymer；3,3,5,5- tetrachloro diphenyl disulfide is dissolved in tetrahydrofuran solution and is added to the selfreparing
In performed polymer, selfreparing macromolecule is obtained.
8. a kind of sensitive material suitable for selfreparing pressure sensor according to claim 7, it is characterised in that: institute
State the pure and mild hydroxyl silicon rubber mass ratio 1:0.5~1:3 of polyether polyols；Two isocyanide of isophorone described in the selfreparing performed polymer
Acid esters and alcohol/silastic mixture mass ratio 1:1~1:6；The tetrahydrofuran solution of the 3,3,5,5- tetrachloro diphenyl disulfide
Described in 3,3,5,5- tetrachloro diphenyl disulfides concentration be 0.4~2.8g/mL, described 3,3,5,5- tetrachloro diphenyl disulfides
Tetrahydrofuran solution and selfreparing prepolymer mass ratio are 1:10~1:40.
9. a kind of sensitive material suitable for selfreparing pressure sensor according to claim 6, it is characterised in that: institute
State selfreparing conduction plural gel the preparation method is as follows: polypropylene is sour, five methene phosphoric acid of aniline and diethylenetriamine, In
30~360min is stirred under the conditions of 0~5 DEG C obtains the selfreparing conduction plural gel.
10. a kind of sensitive material suitable for selfreparing pressure sensor according to claim 6, it is characterised in that:
The one-dimensional silver nanowires the preparation method is as follows:
A) ethylene glycol pre-processes: by ethylene glycol in 180~195 DEG C of sufficiently 35~60min of heating；
B) NaCl aqueous solution is added in pretreated ethylene glycol and forms mixed solution, heat 10~15min；
C) silver nitrate is dissolved in pretreated ethylene glycol, forms silver nitrate solution；Polyvinyl pyrrolidone is dissolved in pretreatment
In ethylene glycol afterwards, polyvinyl pyrrolidone solution is formed；Silver nitrate solution is added in the mixed solution of step b) formation, together
When polyvinyl pyrrolidone solution is slowly dropped into, instill the time control in 50~90min, obtain reaction solution；
D) after completion of dropwise addition, the reaction solution that step c) is obtained, which takes out, to be stood to room temperature；Then reaction solution is spent after centrifugation
Ionized water and washes of absolute alcohol finally obtain powdered one-dimensional silver nanowires.
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| CN109974905A (en) * | 2019-04-03 | 2019-07-05 | 南开大学 | A kind of strain gauge and preparation method thereof with self-reparing capability |
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| CN103242656A (en) * | 2013-05-09 | 2013-08-14 | 北京大学 | Multi-component super-molecular hydrogel and preparation method thereof |
| CN105537615A (en) * | 2015-12-24 | 2016-05-04 | 河南大学 | Method of preparing silver nanowires in different diameters with one-pot process |
| CN108548480A (en) * | 2018-05-09 | 2018-09-18 | 电子科技大学 | Three layers of selfreparing flexibility strain transducer of one kind and preparation method thereof |
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