CN110437568B - Sensitive material suitable for self-repairing pressure sensor and preparation method thereof - Google Patents
Sensitive material suitable for self-repairing pressure sensor and preparation method thereof Download PDFInfo
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- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
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Abstract
The invention provides a sensitive material for a self-repairing pressure sensor, which comprises the following components in percentage by mass: 5-40% of self-repairing polymer, 5-30% of self-repairing conductive composite gel, 1-40% of one-dimensional silver nanowire, 20-60% of solvent and 3-15% of auxiliary agent, wherein the self-repairing polymer comprises the following raw material components: polyether polyol, hydroxy silicone rubber, isophorone diisocyanate, dibutyltin dilaurate and 3,3,5, 5-tetrachlorodiphenyl disulfide; the self-repairing conductive composite gel comprises the following raw material components: polyacrylic acid, aniline, and diethylenetriamine pentamethylene phosphorus. According to the sensitive material suitable for the self-repairing pressure sensor, the self-repairing conductive composite gel and the conductive metal powder are mixed under the condition of the solvent, the conductive metal powder is filled into the structural gap, the polymer chain is used for winding and compounding, a three-dimensional conductive network is constructed, the metal powder can be effectively prevented from settling, the stability of the sensitive material is further improved, and the sensitive material has a huge market application prospect.
Description
Technical Field
The invention particularly relates to a sensitive material used in a self-repairing pressure sensor and a preparation method of the sensitive material.
Background
With the rapid increase of information quantity in the information age, the requirements on the accuracy, the reliability, the sensitivity and the like of the pressure sensor are more and more strict in order to sense the magnitude of the external force more accurately. The traditional pressure sensor is large in size and difficult to meet the requirement of high performance. They are therefore replaced by various types of high performance sensors, of which flexible pressure sensors are increasingly gaining importance. However, sensitive materials are an important component of flexible pressure sensors. At present, sensitive materials used in a flexible pressure sensor are mainly metals, metal oxides or organic/inorganic semiconductor materials and the like, and the materials have the problems of poor toughness, high processing cost, easy damage and the like.
In order to solve the above problems, a flexible pressure sensor with intelligent self-repair has become a research hotspot. Self-repairing sensors are reported in patent publication (publication) nos. CN107036741A, CN108548480A, CN109294134A, CN206724883U, CN106969860A, CN107473208A, etc., and the conductive phase materials used in these patents are metal powder, metal oxide, carbon material, etc. The single or composite use of the materials can effectively improve the stress-strain-electrical property of the sensitive layer. However, in the preparation process, the materials are easy to sink, and the upper and lower surface resistances of the obtained sensitive layer are different. Therefore, how to prepare a sensitive material which has good stability, high sensitivity and good self-repairing function and can be used in a pressure sensor is an important subject of current research.
Disclosure of Invention
In view of the above, in order to overcome the defects of the prior art, the present invention aims to provide an improved sensitive material suitable for self-repairing pressure sensors, which has good stability, high sensitivity and long lifetime.
In order to achieve the purpose, the invention adopts the following technical scheme:
a sensitive material suitable for a self-repairing pressure sensor comprises the following components in percentage by mass:
the self-repairing polymer comprises the following raw material components: polyether polyol, hydroxy silicone rubber, isophorone diisocyanate, dibutyltin dilaurate and 3,3,5, 5-tetrachlorodiphenyl disulfide;
the self-repairing conductive composite gel comprises the following raw material components: polyacrylic acid, aniline, and diethylenetriamine pentamethylene phosphoric acid.
According to some preferred embodiments of the invention, the mass ratio of the polyether polyol to the hydroxyl silicone rubber in the self-repairing polymer is 1: 0.5-1: 3; the mass ratio of the isophorone diisocyanate to the dibutyltin dilaurate is 50: 1-30: 4.
According to some preferred embodiments of the present invention, the mass ratio of the polyacrylic acid, the aniline and the diethylenetriamine pentamethylene phosphoric acid in the self-repairing conductive composite gel is 300:50:1 to 800:200: 10. In some embodiments, it is preferred that the mass ratio of polyacrylic acid, aniline, and diethylenetriamine pentamethylenephosphoric acid is 625:100: 7.
According to some preferred embodiments of the present invention, the solvent is one or a mixture of ethanol, N-dimethylacetamide and tetrahydrofuran.
According to some preferred embodiments of the present invention, the auxiliary agent includes an antifoaming agent, a leveling agent, and a thickener.
The invention also provides a preparation method of the sensitive material suitable for the self-repairing pressure sensor, and the sensitive material comprises the following components in percentage by mass:
the preparation method of the sensitive material comprises the following steps: stirring the components for 0.5-1.5 h at 20-50 ℃ according to the proportion to obtain a uniform mixture; and then, moving the mixture into a mold, and curing for 8-24 hours at 60-120 ℃ to obtain the sensitive material for the self-repairing pressure sensor.
According to some preferred embodiments of the present invention, the self-repairing polymer is prepared by the following steps: mixing polyether polyol and hydroxyl silicone rubber in proportion, and performing vacuum dehydration for 2-3 h at 110-120 ℃ to obtain an alcohol/silicone rubber mixture; sequentially dripping isophorone diisocyanate and dibutyltin dilaurate into an alcohol/silicon rubber mixture, and mechanically stirring for 30min at 80-90 ℃; continuously heating to 95-100 ℃, and reacting for 3.5-5 h; and (3) obtaining a self-repairing prepolymer, and adding a tetrahydrofuran solution of 3,3,5, 5-tetrachlorodiphenyl disulfide into the self-repairing prepolymer to obtain a self-repairing polymer.
Wherein the mass ratio of the polyether polyol to the hydroxyl silicone rubber is 1: 0.5-1: 3; the mass ratio of the isophorone diisocyanate to the dibutyltin dilaurate is 50: 1-30: 4, and the mass ratio of the isophorone diisocyanate to the alcohol/silicon rubber mixture is 1: 1-1: 6; the concentration of the tetrahydrofuran solution of the 3,3,5, 5-tetrachlorodiphenyl disulfide is 0.4-2.8 g/mL, and the mass ratio of the tetrahydrofuran solution of the 3,3,5, 5-tetrachlorodiphenyl disulfide to the self-repairing prepolymer is 1: 10-1: 40.
According to some preferred embodiments of the present invention, the self-repairing conductive composite gel is prepared by the following steps: mixing polyacrylic acid, aniline and diethylenetriamine pentamethylene phosphoric acid in proportion, and stirring for 30-360 min at the temperature of 0-5 ℃ to obtain the polyacrylic acid/polyaniline/diethylenetriamine pentamethylene phosphoric acid type self-repairing conductive composite gel.
Wherein the mass ratio of the polyacrylic acid to the aniline to the diethylenetriamine pentamethylene phosphoric acid is 300:50: 1-800: 200:10, and in some embodiments, the mass ratio of the polyacrylic acid to the aniline to the diethylenetriamine pentamethylene phosphoric acid is 625:100: 7.
The preparation method of polyacrylic acid comprises the following steps: dissolving acrylic acid in acetone, adding an Irgacure2959 photoinitiator, reacting for 15-60 min under ultraviolet light, and drying a product at 50 ℃ to obtain polyacrylic acid; wherein the mass ratio of acrylic acid to acetone is 1: 5-1: 20, the mass ratio of acrylic acid to photoinitiator is 20: 1-80: 1. In some embodiments, it is preferred that the photoinitiator be an Irgacure2959 photoinitiator with a 1:10 acrylic acid to acetone mass ratio and a 64:1 acrylic acid to photoinitiator mass ratio.
According to some preferred embodiments of the present invention, the method for preparing the one-dimensional silver nanowire is as follows:
a) ethylene glycol pretreatment: adding 50-100 mL of ethylene glycol into a three-neck flask, and fully heating at 180-195 ℃ for 35-60 min;
b) measuring 5-8 mL of NaCl aqueous solution, adding the NaCl aqueous solution into the pretreated glycol to form a mixed solution, and heating for 10-15 min; the concentration of the NaCl aqueous solution is 0.002-0.004 mol/L;
c) dissolving silver nitrate in the pretreated glycol to form 0.3-0.5 mol/L silver nitrate solution; dissolving polyvinylpyrrolidone (PVP) in the pretreated glycol to form 0.4-0.6 mol/L PVP solution; adding 10-15 mL of silver nitrate solution into the mixed solution formed in the step b), and slowly dripping 30-45 mL of PVP solution through a peristaltic pump, wherein the dripping time is controlled within 50-90 min, so as to obtain a reaction solution;
d) after the dropwise addition is finished, taking out the reaction liquid obtained in the step c), and standing to room temperature; and then centrifuging the reaction solution at 12000rpm for 20min, and cleaning with deionized water and absolute ethyl alcohol for 3 times to obtain a powdery product, namely the one-dimensional silver nanowire.
Compared with the prior art, the invention has the advantages that: according to the sensitive material suitable for the self-repairing pressure sensor, the self-repairing conductive composite gel and the conductive metal powder are mixed under the condition of a solvent, the conductive metal powder is filled into the structural gap, and the polymer chains are wound and compounded to construct a three-dimensional conductive network, so that the metal powder can be effectively prevented from settling, and the stability of the sensitive material is further improved; meanwhile, the self-repairing conductive composite gel has the conductive characteristic and the conductive metal powder can effectively form an electronic effect, can effectively overcome the defects of uneven dispersion, easy sedimentation and the like of the existing metal powder, metal oxide, carbon material and the like in the forming process, has excellent self-repairing capability after being damaged, can effectively prolong the service life, overcomes the defects of the prior art, and has huge market application prospect and good economic and social benefits.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the technical solution in the embodiments of the present invention is clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The reagents used in the following examples are all commercially available.
Example 1
The sensitive material for the self-repairing pressure sensor in the embodiment comprises the following components in parts by mass:
the preparation method of the sensitive material based on the components comprises the following steps:
(1) preparation of self-repairing polymer
12g of polyether polyol and 12g of hydroxy silicone rubber were mixed and dehydrated under vacuum at 115 ℃ for 2.5 hours to give an alcohol/silicone rubber mixture.
8g of isophorone diisocyanate and 0.27g of dibutyltin dilaurate were added dropwise in succession to the alcohol/silicone rubber mixture, and mechanically stirred at 85 ℃ for 30 min; and continuously heating to 98 ℃, and reacting for 3.5 hours to obtain the self-repairing prepolymer.
And adding 1.2g of tetrahydrofuran solution of 3,3,5, 5-tetrachlorodiphenyl disulfide with the concentration of 0.6g/mL into the self-repairing prepolymer to obtain the self-repairing polymer.
(2) Preparation of self-repairing conductive composite gel
Dissolving 10g of acrylic acid in 100g of acetone, adding 0.16 of Irgacure2959 photoinitiator, reacting for 15min under ultraviolet light, and drying the product at 50 ℃ to obtain the polyacrylic acid.
6.25g of polyacrylic acid, 1g of aniline and 0.07g of diethylenetriamine pentamethylene phosphoric acid are mixed in a three-neck flask and stirred for 30min at the temperature of 2 ℃ to obtain the polyacrylic acid/polyaniline/diethylenetriamine pentamethylene phosphoric acid type self-repairing conductive composite gel.
(3) Preparation of one-dimensional silver nanowires
a) Ethylene glycol pretreatment: 50mL of ethylene glycol was added to a three-necked flask and sufficiently heated at 180 ℃ for 35 min.
b) Measuring 5mL of NaCl aqueous solution, adding the NaCl aqueous solution into the pretreated glycol to form a mixed solution, and heating for 10 min; the concentration of the NaCl aqueous solution is 0.002 mol/L.
c) Dissolving 10g of silver nitrate in ethylene glycol to form 0.3mol/L silver nitrate solution; dissolving 15g of polyvinylpyrrolidone (PVP) in ethylene glycol to form a 0.4mol/L PVP solution; adding 10mL of silver nitrate solution into the mixed solution formed in the step b), and slowly dripping 30mL of PVP solution through a peristaltic pump, wherein the dripping time is controlled within 50min, so as to obtain a reaction solution.
d) After the dropwise addition is finished, taking out the reaction liquid obtained in the step c), and standing to room temperature; the reaction solution was then centrifuged at 12000rpm for 20min and washed 3 times with deionized water and absolute ethanol to give a powdered product.
(4) Preparation of sensitive materials
Mixing the component substances prepared in the steps (1) to (3) with the solvent and the auxiliary agent in proportion, and stirring for 0.5h at the temperature of 20 ℃ to obtain a uniform mixture; and then, moving the mixture into a mold, and curing for 24 hours at 60 ℃ to obtain the sensitive material for the self-repairing pressure sensor.
Example 2
The sensitive material for the self-repairing pressure sensor in the embodiment comprises the following components in parts by mass:
the preparation method of the sensitive material based on the components comprises the following steps:
(1) preparation of self-repairing polymer
12g of polyether polyol and 12g of hydroxy silicone rubber were mixed and dehydrated under vacuum at 115 ℃ for 2.5 hours to give an alcohol/silicone rubber mixture.
8g of isophorone diisocyanate and 0.27g of dibutyltin dilaurate were added dropwise in succession to the alcohol/silicone rubber mixture, and mechanically stirred at 85 ℃ for 30 min; and continuously heating to 98 ℃, and reacting for 3.5 hours to obtain the self-repairing prepolymer.
And adding 1.2g of tetrahydrofuran solution of 3,3,5, 5-tetrachlorodiphenyl disulfide with the concentration of 0.6g/mL into the self-repairing prepolymer to obtain the self-repairing polymer.
(2) Preparation of self-repairing conductive composite gel
Dissolving 10g of acrylic acid in 100g of acetone, adding 0.16 of Irgacure2959 photoinitiator, reacting for 15min under ultraviolet light, and drying the product at 50 ℃ to obtain the polyacrylic acid.
6.25g of polyacrylic acid, 1g of aniline and 0.07g of diethylenetriamine pentamethylene phosphoric acid are mixed in a three-neck flask and stirred for 30min at the temperature of 3 ℃ to obtain the polyacrylic acid/polyaniline/diethylenetriamine pentamethylene phosphoric acid type self-repairing conductive composite gel.
(3) Preparation of one-dimensional silver nanowires
a) Ethylene glycol pretreatment: 50mL of ethylene glycol was added to a three-necked flask and sufficiently heated at 180 ℃ for 35 min.
b) Measuring 5mL of NaCl aqueous solution, adding the NaCl aqueous solution into the pretreated glycol solution to form a mixed solution, and heating for 10 min; the concentration of the NaCl aqueous solution is 0.002 mol/L.
c) Dissolving 10g of silver nitrate in ethylene glycol to form 0.3mol/L silver nitrate solution; dissolving 15g of polyvinylpyrrolidone (PVP) in ethylene glycol to form a 0.4mol/L PVP solution; adding 10mL of silver nitrate solution into the mixed solution formed in the step b), and slowly dripping 30mL of PVP solution through a peristaltic pump, wherein the dripping time is controlled within 50min, so as to obtain a reaction solution.
d) After the dropwise addition is finished, taking out the reaction liquid obtained in the step c), and standing to room temperature; the reaction solution was then centrifuged at 12000rpm for 20min and washed 3 times with deionized water and absolute ethanol to give a powdered product.
(4) Preparation of sensitive materials
Mixing the component substances prepared in the steps (1) to (3) with a solvent and an auxiliary agent in proportion, and stirring at 50 ℃ for 0.5-1 h to obtain a uniform mixture; and then, moving the mixture into a mold, and curing for 8 hours at 120 ℃ to obtain the sensitive material for the self-repairing pressure sensor.
Example 3
The sensitive material for the self-repairing pressure sensor in the embodiment comprises the following components in parts by mass:
the preparation method of the sensitive material based on the components comprises the following steps:
(1) preparation of self-repairing polymer
12g of polyether polyol and 12g of hydroxy silicone rubber were mixed and dehydrated under vacuum at 120 ℃ for 3 hours to give an alcohol/silicone rubber mixture.
8g of isophorone diisocyanate and 0.27g of dibutyltin dilaurate were added dropwise in succession to the alcohol/silicone rubber mixture, and mechanically stirred at 88 ℃ for 30 min; and continuously heating to 100 ℃, and reacting for 3.5 hours to obtain the self-repairing prepolymer.
And adding 1.2g of tetrahydrofuran solution of 3,3,5, 5-tetrachlorodiphenyl disulfide with the concentration of 0.6g/mL into the self-repairing prepolymer to obtain the self-repairing polymer.
(2) Preparation of self-repairing conductive composite gel
Dissolving 20g of acrylic acid in 200g of acetone, adding 0.3125g of Irgacure2959 photoinitiator, reacting for 20min under ultraviolet light, and drying the product at 50 ℃ to obtain polyacrylic acid.
3.125g of polyacrylic acid, 0.5g of aniline and 0.035g of diethylenetriamine pentamethylene phosphoric acid are mixed in a three-neck flask and stirred for 60min at the temperature of 0 ℃ to obtain the polyacrylic acid/polyaniline/diethylenetriamine pentamethylene phosphoric acid type self-repairing conductive composite gel.
(3) Preparation of one-dimensional silver nanowires
a) Ethylene glycol pretreatment: 60mL of ethylene glycol was added to a three-necked flask and sufficiently heated at 190 ℃ for 50 min.
b) Weighing 7mL of NaCl aqueous solution, adding the NaCl aqueous solution into the pretreated glycol to form a mixed solution, and heating for 10 min; the concentration of the NaCl aqueous solution is 0.0025 mol/L.
c) Dissolving 15g of silver nitrate in ethylene glycol to form 0.35mol/L silver nitrate solution; dissolving 14g of polyvinylpyrrolidone (PVP) in ethylene glycol to form a 0.48mol/L PVP solution; adding 13mL of silver nitrate solution into the mixed solution formed in the step b), and slowly dripping 35mL of PVP solution through a peristaltic pump, wherein the dripping time is controlled within 65min, so as to obtain a reaction solution.
d) After the dropwise addition is finished, taking out the reaction liquid obtained in the step c), and standing to room temperature; the reaction solution was then centrifuged at 12000rpm for 20min and washed 3 times with deionized water and absolute ethanol to give a powdered product.
(4) Preparation of sensitive materials
Mixing the component substances prepared in the steps (1) to (3) with the solvent and the auxiliary agent in proportion, and stirring for 1.2 hours at 40 ℃ to obtain a uniform mixture; and then, moving the mixture into a mold, and curing for 10 hours at 100 ℃ to obtain the sensitive material for the self-repairing pressure sensor.
Example 4
The sensitive material for the self-repairing pressure sensor in the embodiment comprises the following components in parts by mass:
the preparation method of the sensitive material based on the components comprises the following steps:
(1) preparation of self-repairing polymer
12g of polyether polyol and 12g of hydroxy silicone rubber were mixed and dehydrated under vacuum at 115 ℃ for 2.5 hours to give an alcohol/silicone rubber mixture.
8g of isophorone diisocyanate and 0.27g of dibutyltin dilaurate were added dropwise in succession to the alcohol/silicone rubber mixture, and mechanically stirred at 86 ℃ for 30 min; and continuously heating to 98 ℃, and reacting for 4 hours to obtain the self-repairing prepolymer.
And adding 1.2g of tetrahydrofuran solution of 3,3,5, 5-tetrachlorodiphenyl disulfide with the concentration of 0.6g/mL into the self-repairing prepolymer to obtain the self-repairing polymer.
(2) Preparation of self-repairing conductive composite gel
Dissolving 20g of acrylic acid in 200g of acetone, adding 0.3125g of Irgacure2959 photoinitiator, reacting for 40min under ultraviolet light, and drying the product at 50 ℃ to obtain polyacrylic acid.
3.125g of polyacrylic acid, 0.5g of aniline and 0.035g of diethylenetriamine pentamethylene phosphoric acid are mixed in a three-neck flask and stirred for 300min at the temperature of 2 ℃ to obtain the polyacrylic acid/polyaniline/diethylenetriamine pentamethylene phosphoric acid type self-repairing conductive composite gel.
(3) Preparation of one-dimensional silver nanowires
a) Ethylene glycol pretreatment: 70mL of ethylene glycol was added to a three-necked flask and heated thoroughly at 192 ℃ for 55 min.
b) Weighing 7.5mL of NaCl aqueous solution, adding the NaCl aqueous solution into the pretreated glycol solution to form a mixed solution, and heating for 12 min; the concentration of the NaCl aqueous solution was 0.0035 mol/L.
c) Dissolving 15g of silver nitrate in ethylene glycol to form 0.35mol/L silver nitrate solution; dissolving 14g of polyvinylpyrrolidone (PVP) in ethylene glycol to form a 0.52mol/L PVP solution; adding 12mL of silver nitrate solution into the mixed solution formed in the step b), and slowly dripping 38mL of PVP solution through a peristaltic pump, wherein the dripping time is controlled within 70min, so as to obtain a reaction solution.
d) After the dropwise addition is finished, taking out the reaction liquid obtained in the step c), and standing to room temperature; the reaction solution was then centrifuged at 12000rpm for 20min and washed 3 times with deionized water and absolute ethanol to give a powdered product.
(4) Preparation of sensitive materials
Mixing the component substances prepared in the steps (1) to (3) with the solvent and the auxiliary agent in proportion, and stirring for 1.5 hours at 45 ℃ to obtain a uniform mixture; and then, moving the mixture into a mold, and curing for 9 hours at 110 ℃ to obtain the sensitive material for the self-repairing pressure sensor.
Example 5
The sensitive material for the self-repairing pressure sensor in the embodiment comprises the following components in parts by mass:
the preparation method of the sensitive material based on the components comprises the following steps:
(1) preparation of self-repairing polymer
The preparation of the self-repairing polymer comprises the following steps: 12g of polyether polyol and 12g of hydroxy silicone rubber were mixed and dehydrated under vacuum at 120 ℃ for 3 hours to give an alcohol/silicone rubber mixture.
8g of isophorone diisocyanate and 0.27g of dibutyltin dilaurate were added dropwise in succession to the alcohol/silicone rubber mixture, and mechanically stirred at 88 ℃ for 30 min; and continuously heating to 100 ℃, and reacting for 5 hours to obtain the self-repairing prepolymer.
And adding 1.2g of tetrahydrofuran solution of 3,3,5, 5-tetrachlorodiphenyl disulfide with the concentration of 0.6g/mL into the self-repairing prepolymer to obtain the self-repairing polymer.
(2) Preparation of self-repairing conductive composite gel
Dissolving 20g of acrylic acid in 200g of acetone, adding 0.3125g of Irgacure2959 photoinitiator, reacting for 20min under ultraviolet light, and drying the product at 50 ℃ to obtain polyacrylic acid.
3.125g of polyacrylic acid, 0.5g of aniline and 0.035g of diethylenetriamine pentamethylene phosphoric acid are mixed in a three-neck flask and stirred for 60min at the temperature of 3 ℃ to obtain the polyacrylic acid/polyaniline/diethylenetriamine pentamethylene phosphoric acid type self-repairing conductive composite gel.
(3) Preparation of one-dimensional silver nanowires
a) Ethylene glycol pretreatment: 60mL of ethylene glycol was added to a three-necked flask and sufficiently heated at 190 ℃ for 50 min.
b) Weighing 7mL of NaCl aqueous solution, adding the NaCl aqueous solution into the pretreated glycol solution to form a mixed solution, and heating for 10 min; the concentration of the NaCl aqueous solution is 0.0025 mol/L.
c) Dissolving 15g of silver nitrate in ethylene glycol to form 0.35mol/L silver nitrate solution; dissolving 14g of polyvinylpyrrolidone (PVP) in ethylene glycol to form a 0.48mol/L PVP solution; adding 13mL of silver nitrate solution into the mixed solution formed in the step b), and slowly dripping 35mL of PVP solution through a peristaltic pump, wherein the dripping time is controlled within 65min, so as to obtain a reaction solution.
d) After the dropwise addition is finished, taking out the reaction liquid obtained in the step c), and standing to room temperature; the reaction solution was then centrifuged at 12000rpm for 20min and washed 3 times with deionized water and absolute ethanol to give a powdered product.
(4) Preparation of sensitive materials
Mixing the component substances prepared in the steps (1) to (3) with the solvent and the auxiliary agent in proportion, and stirring for 1.5 hours at 45 ℃ to obtain a uniform mixture; and then, moving the mixture into a mold, and curing at 105 ℃ for 11h to obtain the sensitive material for the self-repairing pressure sensor.
Example 6
The sensitive material for the self-repairing pressure sensor in the embodiment comprises the following components in parts by mass:
the preparation method of the sensitive material based on the components comprises the following steps:
(1) preparation of self-repairing polymer
12g of polyether polyol and 12g of hydroxy silicone rubber were mixed and dehydrated under vacuum at 118 ℃ for 2h to give an alcohol/silicone rubber mixture.
8g of isophorone diisocyanate and 0.27g of dibutyltin dilaurate were added dropwise in succession to the alcohol/silicone rubber mixture, and mechanically stirred at 90 ℃ for 30 min; and continuously heating to 100 ℃, and reacting for 3.5 hours to obtain the self-repairing prepolymer.
And adding 1.2g of tetrahydrofuran solution of 3,3,5, 5-tetrachlorodiphenyl disulfide with the concentration of 0.6g/mL into the self-repairing prepolymer to obtain the self-repairing polymer.
(2) Preparation of self-repairing conductive composite gel
Dissolving 25g of acrylic acid in 250g of acetone, adding 0.39g of Irgacure2959 photoinitiator, reacting for 60min under ultraviolet light, and drying the product at 50 ℃ to obtain polyacrylic acid.
3.125g of polyacrylic acid, 0.5g of aniline and 0.035g of diethylenetriamine pentamethylene phosphoric acid are mixed in a three-neck flask and stirred for 300min under the condition of 0 ℃ to obtain the polyacrylic acid/polyaniline/diethylenetriamine pentamethylene phosphoric acid type self-repairing conductive composite gel.
(3) Preparation of one-dimensional silver nanowires
a) Ethylene glycol pretreatment: 85mL of ethylene glycol was added to a three-necked flask and sufficiently heated at 195 ℃ for 60 min.
b) Measuring 8mL of NaCl aqueous solution, adding the NaCl aqueous solution into the pretreated glycol to form a mixed solution, and heating for 13 min; the concentration of the NaCl aqueous solution was 0.0035 mol/L.
c) Dissolving 6g of silver nitrate in ethylene glycol to form 0.45mol/L silver nitrate solution; dissolving 20g of polyvinylpyrrolidone (PVP) in ethylene glycol to form a 0.55mol/L PVP solution; adding 15mL of silver nitrate solution into the mixed solution formed in the step b), and slowly dripping 40mL of PVP solution through a peristaltic pump, wherein the dripping time is controlled within 80min, so as to obtain a reaction solution.
d) After the dropwise addition is finished, taking out the reaction liquid obtained in the step c), and standing to room temperature; the reaction solution was then centrifuged at 12000rpm for 20min and washed 3 times with deionized water and absolute ethanol to give a powdered product.
(4) Preparation of sensitive materials
Mixing the component substances prepared in the steps (1) to (3) with the solvent and the auxiliary agent in proportion, and stirring for 0.7h at the temperature of 30 ℃ to obtain a uniform mixture; and then, moving the mixture into a mold, and curing at 90 ℃ for 21h to obtain the sensitive material for the self-repairing pressure sensor.
Comparative example 1
The comparative example replaces the self-repairing polymer and the self-repairing conductive composite gel with the Atlantic kangning 184 silicon rubber material, and prepares the sensitive material used in the pressure sensor.
Specifically, the sensitive material of the comparative example consists of the following components in parts by mass:
the preparation method of the sensitive material based on the components comprises the following steps: stirring the components at 30 ℃ for 0.7h to obtain a uniform mixture; and then, moving the mixture into a mold, and curing at 80 ℃ for 21h to obtain the sensitive material for the self-repairing pressure sensor.
The preparation method of the one-dimensional silver nanowire comprises the following steps:
a) ethylene glycol pretreatment: 85mL of ethylene glycol was added to a three-necked flask and sufficiently heated at 195 ℃ for 60 min.
b) Measuring 8mL of NaCl aqueous solution, adding the NaCl aqueous solution into the pretreated glycol to form a mixed solution, and heating for 13 min; the concentration of the NaCl aqueous solution was 0.0035 mol/L.
c) Dissolving 6g of silver nitrate in ethylene glycol to form 0.45mol/L silver nitrate solution; dissolving 20g of polyvinylpyrrolidone (PVP) in ethylene glycol to form a 0.55mol/L PVP solution; adding 15mL of silver nitrate solution into the mixed solution formed in the step b), and slowly dripping 40mL of PVP solution through a peristaltic pump, wherein the dripping time is controlled within 80min, so as to obtain a reaction solution.
d) After the dropwise addition is finished, taking out the reaction liquid obtained in the step c), and standing to room temperature; the reaction solution was then centrifuged at 12000rpm for 20min and washed 3 times with deionized water and absolute ethanol to give a powdered product.
Example 7 test and results analysis
The volume resistivity and the mechanical repair rate were measured for examples 1 to 6 and comparative example 1. Wherein, the volume resistivity is tested by a four-probe resistivity tester; the mechanical repair rate is the ratio of the tensile strength of the repaired material to the tensile strength before repair, and the material tensile testing machine is adopted for testing, and the repair condition is that the material is kept stand for 2 hours in a room temperature environment. The results are shown in Table 1.
TABLE 1 results of the experiment
As can be seen from the data in Table 1, the sensitive materials prepared in examples 1-6 for use in self-repairing pressure sensors can effectively recover their functions when damaged by an external force.
The gel is a substance in which polymer chains are connected with each other to form a space network structure, and the voids of the structure are filled with a liquid as a dispersion medium. According to the sensitive material for the self-repairing pressure sensor, the self-repairing conductive composite gel and the conductive metal powder are mixed under the condition of a solvent, the conductive metal powder is filled into the structural gap, and the polymer chains are wound and compounded to construct the three-dimensional conductive network, so that the metal powder can be effectively prevented from settling, and the stability of the sensitive material is further improved. Meanwhile, the self-repairing conductive composite gel has the conductive characteristic and the conductive metal powder can effectively form an electronic effect. After the sensitive material prepared by the invention is damaged, good self-repairing can be achieved without using any repairing agent or regenerating agent. And the self-repairing process does not need to use conventional methods such as high-temperature heating, vacuum heating, ultraviolet light irradiation, infrared light irradiation, chemical reagent addition and the like, only needs to be carried out at room temperature and independently, has low energy consumption, does not need inert gas protection, and has practical application effects. The method has the advantages of convenient operation, simple forming process and suitability for large-scale industrial production.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (9)
1. A sensitive material suitable for self-repairing pressure sensors is characterized in that: the sensitive material comprises the following components in percentage by mass:
the self-repairing polymer comprises the following raw material components: polyether polyol, hydroxy silicone rubber, isophorone diisocyanate, dibutyltin dilaurate and 3,3,5, 5-tetrachlorodiphenyl disulfide;
the self-repairing conductive composite gel comprises the following raw material components: polyacrylic acid, aniline, and diethylenetriamine pentamethylenephosphoric acid; the mass ratio of the polyacrylic acid to the aniline to the diethylenetriamine pentamethylene phosphoric acid is 300:50: 1-800: 200: 10.
2. The sensitive material suitable for use in a self-healing pressure sensor according to claim 1, wherein: the mass ratio of the polyether polyol to the hydroxyl silicone rubber in the raw materials for preparing the self-repairing polymer is 1: 0.5-1: 3; the mass ratio of the isophorone diisocyanate to the dibutyltin dilaurate is 50: 1-30: 4.
3. The sensitive material suitable for use in a self-healing pressure sensor according to claim 1, wherein: the solvent is one or a mixture of ethanol, N-dimethylacetamide and tetrahydrofuran.
4. The sensitive material suitable for use in a self-healing pressure sensor according to claim 1, wherein: the auxiliary agent is one or more of a defoaming agent, a flatting agent and a thickening agent.
5. The method for preparing the sensitive material suitable for being used in the self-repairing pressure sensor according to any one of claims 1 to 4, wherein: the sensitive material comprises the following components in percentage by mass:
the preparation method of the sensitive material comprises the following steps: mixing the components, and stirring at 20-50 ℃ for 0.5-1.5 h to obtain a uniform mixture; and then, curing the mixture at 60-120 ℃ for 8-24 h to obtain the sensitive material for the self-repairing pressure sensor.
6. The method for preparing the sensitive material suitable for the self-repairing pressure sensor according to claim 5, wherein the method comprises the following steps: the preparation method of the self-repairing polymer comprises the following steps: mixing polyether polyol and hydroxyl silicone rubber, and performing vacuum dehydration for 2-3 h at 110-120 ℃ to obtain an alcohol/silicone rubber mixture; dropwise adding isophorone diisocyanate and dibutyltin dilaurate into the alcohol/silicon rubber mixture, and stirring for 30min at 80-90 ℃; continuously heating to 95-100 ℃, and reacting for 3.5-5 h to obtain a self-repairing prepolymer; and dissolving 3,3,5, 5-tetrachlorodiphenyl disulfide in tetrahydrofuran solution and adding the tetrahydrofuran solution into the self-repairing prepolymer to obtain the self-repairing polymer.
7. The method for preparing the sensitive material suitable for the self-repairing pressure sensor as claimed in claim 6, wherein: the mass ratio of the polyether polyol to the hydroxyl silicone rubber is 1: 0.5-1: 3; the mass ratio of the isophorone diisocyanate to the alcohol/silicone rubber mixture in the self-repairing prepolymer is 1: 1-1: 6; the concentration of the 3,3,5, 5-tetrachlorodiphenyl disulfide in the tetrahydrofuran solution of the 3,3,5, 5-tetrachlorodiphenyl disulfide is 0.4-2.8 g/mL, and the mass ratio of the tetrahydrofuran solution of the 3,3,5, 5-tetrachlorodiphenyl disulfide to the self-repairing prepolymer is 1: 10-1: 40.
8. The method for preparing the sensitive material suitable for the self-repairing pressure sensor according to claim 5, wherein the method comprises the following steps: the preparation method of the self-repairing conductive composite gel comprises the following steps: mixing polyacrylic acid, aniline and diethylenetriamine pentamethylene phosphoric acid, and stirring for 30-360 min at the temperature of 0-5 ℃ to obtain the self-repairing conductive composite gel.
9. The method for preparing the sensitive material suitable for the self-repairing pressure sensor according to claim 5, wherein the method comprises the following steps: the preparation method of the one-dimensional silver nanowire comprises the following steps:
a) ethylene glycol pretreatment: fully heating ethylene glycol at 180-195 ℃ for 35-60 min;
b) adding a NaCl aqueous solution into the pretreated ethylene glycol to form a mixed solution, and heating for 10-15 min;
c) dissolving silver nitrate in the pretreated glycol to form a silver nitrate solution; dissolving polyvinylpyrrolidone in the pretreated glycol to form polyvinylpyrrolidone solution; adding a silver nitrate solution into the mixed solution formed in the step b), and slowly dripping a polyvinylpyrrolidone solution for 50-90 min to obtain a reaction solution;
d) after the dropwise addition is finished, taking out the reaction liquid obtained in the step c), and standing to room temperature; and then centrifuging the reaction solution, and cleaning with deionized water and absolute ethyl alcohol to obtain the powdery one-dimensional silver nanowire.
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