CN110951092A - Preparation method of conductive hydrogel for limiting PNIPAM temperature sensitivity - Google Patents
Preparation method of conductive hydrogel for limiting PNIPAM temperature sensitivity Download PDFInfo
- Publication number
- CN110951092A CN110951092A CN201911263616.7A CN201911263616A CN110951092A CN 110951092 A CN110951092 A CN 110951092A CN 201911263616 A CN201911263616 A CN 201911263616A CN 110951092 A CN110951092 A CN 110951092A
- Authority
- CN
- China
- Prior art keywords
- pnipam
- temperature
- limiting
- monomer
- conductive hydrogel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/19—Quaternary ammonium compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Measurement And Recording Of Electrical Phenomena And Electrical Characteristics Of The Living Body (AREA)
Abstract
The invention provides a preparation method of a conductive hydrogel for limiting PNIPAM temperature sensitivity, which is characterized in that an ionic liquid is prepared by mixing a hydrogen bond acceptor and a hydrogen bond donor at high temperature; dissolving a monomer polymerized by PNIPAM and a cross-linking agent, and deoxidizing the monomer after the monomer and the cross-linking agent are uniformly dissolved; blending the deoxygenated solution with ionic liquids with different contents, and uniformly dispersing the ionic liquids; adding an initiator and an accelerator in an ice bath, uniformly mixing, and reacting at room temperature to obtain the conductive hydrogel for limiting the temperature sensitivity of PNIPAM; the addition of the ionic liquid enables the acrylic acid and NIPAM which are components of the ionic liquid to be copolymerized, so that the choline chloride and the NIPAM are combined, and the combining capability of the ionic liquid is stronger than the interaction between the NIPAM and water, thereby limiting the temperature sensitivity of PNIPAM; the ionic liquid has the advantages of wide raw material source, simple preparation method and good biocompatibility, so that the material is endowed with conductivity and temperature sensing responsiveness.
Description
Technical Field
The invention relates to a preparation method of conductive hydrogel, in particular to a preparation method of conductive hydrogel for limiting PNIPAM temperature sensitivity, and belongs to the field of intelligent materials.
Background
Poly-isopropylacrylamide (PNIPAM) hydrogel, which is a temperature sensitive material, has a low critical solution temperature (LCST ═ 32 ℃). With the rise of temperature, volume collapse and change of gel transparency are generated when the temperature reaches the LCST, so that the method is widely applied to the fields of biomedicine, dynamic switching, moisture collection and the like. However, PNIPAM has poor mechanical properties and single properties (only has temperature sensitivity), and cannot be used as a temperature-stable material due to the limitation of the phase transition point.
The conductive hydrogel as a conductive material of a flexible substrate can be attached to the surface of a human body to monitor the motion, respiration, temperature and the like of the human body in real time, so that the conductive hydrogel is widely concerned.
Therefore, based on a hydrogel system, the strain hydrogel with conductivity and capable of limiting PNIPAM temperature sensitivity is designed, the hydrogel has high mechanical performance and simultaneously gives excellent conductivity to the material, and the material is applied to the aspect of strain sensing.
Disclosure of Invention
The invention aims to provide a preparation method of a conductive hydrogel for limiting the temperature sensitivity of PNIPAM, aiming at solving the problems of the temperature-sensitive volume change and the transparency change of the PNIPAM.
The purpose of the invention is realized as follows:
a preparation method of conductive hydrogel for limiting PNIPAM temperature sensitivity comprises the following steps:
the method comprises the following steps: preparing an ionic liquid by mixing a hydrogen bond acceptor and a hydrogen bond donor at a high temperature;
step two: dissolving a monomer polymerized by PNIPAM and a cross-linking agent, and deoxidizing the monomer after the monomer and the cross-linking agent are uniformly dissolved;
step three: blending the deoxygenated solution with ionic liquids with different contents, and uniformly dispersing the ionic liquids;
step four: adding an initiator and an accelerator in an ice bath, uniformly mixing, and reacting at room temperature to obtain the PNIPAM temperature-sensitive conductive hydrogel.
The invention also includes such features:
the hydrogen bond acceptor and the hydrogen bond donor are respectively choline chloride and acrylic acid, the reaction molar ratio is 1:2, and the reaction temperature is 90 ℃.
Compared with the prior art, the invention has the beneficial effects that:
1. the addition of the ion-like liquid enables the component acrylic acid and NIPAM to be copolymerized, so that the choline chloride and the NIPAM are combined, the combination capability of the ion-like liquid is stronger than the interaction between the NIPAM and water, and the temperature sensitivity of the PNIPAM is limited.
2. The ionic liquid-like material has wide raw material source, simple preparation method and good biocompatibility, and has good conductivity similar to the ionic liquid, so that the material is endowed with conductivity and temperature sensing responsiveness.
3. The addition of the acrylic acid enables NIPAM and AA to be copolymerized, so that the mechanical property of the material is improved, and the material can generate different strain responses under different deformations by combining the action of the ionic liquid, so that the material has profound influence on the aspect of strain sensing.
Drawings
FIG. 1 is a temperature sensitive response plot of a synthetic material of the present invention;
FIGS. 2a-b are graphs of the mechanical properties of the material of the present invention;
FIG. 3 is a graph of current at different temperatures for the material of the present invention;
fig. 4 is a strain sensing curve of the sample obtained in inventive example 2.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
The invention relates to a technology for preparing PNIPAM gel by extensive free radical polymerization, and a conductive strain hydrogel is prepared. The invention provides a preparation method of a temperature-sensitive conductive hydrogel capable of limiting PNIPAM, which solves the problems of temperature-sensitive volume change and transparency change of PNIPAM.
The invention can be realized by the following technical scheme:
a preparation method of the conductive hydrogel for limiting the PNIPAM temperature sensitivity comprises the following steps:
the method comprises the following steps: preparing an ionic liquid (DES) by mixing a hydrogen bond acceptor and a hydrogen bond donor at a high temperature;
step two: dissolving a monomer polymerized by PNIPAM and a cross-linking agent, and deoxidizing the monomer after the monomer and the cross-linking agent are uniformly dissolved;
step three: blending the deoxygenated solution with ionic liquids with different contents, and uniformly dispersing the ionic liquids;
step four: adding an initiator and an accelerator in an ice bath, uniformly mixing, and reacting at room temperature.
Four samples were prepared.
The preparation process needs to be deoxygenated and the initiator is processed in ice bath, and the reaction environment is room temperature sealed environment.
Further, the hydrogen bond acceptor and the hydrogen bond donor selected by the prepared ionic liquid are choline chloride and acrylic acid respectively, the reaction molar ratio is 1:2, and transparent liquid is obtained at 90 ℃.
Example 1
The embodiment provides a conductive hydrogel material for limiting PNIPAM temperature sensitivity, and the preparation method comprises the following steps:
1) choline chloride and acrylic acid are placed in a 50mL round-bottom flask according to the molar ratio of 1:2, and oil bath reaction is carried out at 90 ℃ until a uniform and transparent solution is a DES solution.
2) 0.2g of the initiator Ammonium Persulfate (APS) was dissolved in 1mL of deionized water to give an initiator solution, which was placed in an ice bath for precooling.
3) Using a pipette to pipette 4.90mL of deionized water into a 10mL centrifuge tube;
4) 0.35g of monomer N-isopropylacrylamide (NIPAM) and 0.006g of crosslinking agent methylenebisacrylamide (BIS) were weighed out, and the monomer and the initiator were dissolved in the deionized water. Introducing nitrogen for 5-10min to remove oxygen in the system.
5) 0.10mL of DES was removed and dissolved in a centrifuge tube with oxygen removed, 40. mu.L of pre-chilled APS solution was added, mixed well and 40. mu.L of accelerator Tetramethylethylenediamine (TEMED) was added.
6) The reaction was left at room temperature (about 25 ℃) for 24h to obtain a sample PNIPAM-2% DES gel.
Example 2
The embodiment provides a conductive hydrogel material for limiting PNIPAM temperature sensitivity, and the preparation method comprises the following steps:
1) choline chloride and acrylic acid are placed in a 50mL round-bottom flask according to the molar ratio of 1:2, and oil bath reaction is carried out at 90 ℃ until a uniform and transparent solution is a DES solution.
2) 0.2g of initiator Ammonium Persulfate (APS) was dissolved in 1mL of deionized water to give an initiator solution, which was placed in an ice bath for precooling.
3) Using a pipette to pipette 4.75mL of deionized water into a 10mL centrifuge tube;
4) 0.35g of monomer N-isopropylacrylamide (NIPAM) and 0.006g of crosslinking agent methylenebisacrylamide (BIS) were weighed out, and the monomer and the initiator were dissolved in the deionized water. Introducing nitrogen for 5-10min to remove oxygen in the system.
5) 0.25mL of DES was removed and dissolved in a centrifuge tube with oxygen removed, 40. mu.L of pre-chilled APS solution was added, mixed well and 40. mu.L of accelerator Tetramethylethylenediamine (TEMED) was added.
6) The reaction was left at room temperature (about 25 ℃) for 24h to obtain a sample PNIPAM-5% DES gel.
Example 3
The embodiment provides a conductive hydrogel material for limiting PNIPAM temperature sensitivity, and the preparation method comprises the following steps:
1) choline chloride and acrylic acid are placed in a 50mL round-bottom flask according to the molar ratio of 1:2, and oil bath reaction is carried out at 90 ℃ until a uniform and transparent solution is a DES solution.
2) 0.2g of initiator Ammonium Persulfate (APS) was dissolved in 1mL of deionized water to give an initiator solution, which was placed in an ice bath for precooling.
3) Using a pipette to pipette 4.50mL of deionized water into a 10mL centrifuge tube;
4) 0.35g of monomer N-isopropylacrylamide (NIPAM) and 0.006g of crosslinking agent methylenebisacrylamide (BIS) were weighed out, and the monomer and the initiator were dissolved in the deionized water. Introducing nitrogen for 5-10min to remove oxygen in the system.
5) 0.50mL of DES was removed and dissolved in a centrifuge tube with oxygen removed, 40. mu.L of pre-chilled APS solution was added, mixed well and 40. mu.L of accelerator Tetramethylethylenediamine (TEMED) was added.
6) The reaction was left at room temperature (about 25 ℃) for 24h to obtain a sample PNIPAM-10% DES gel.
Comparative example
The comparative example provides a PNIPAM hydrogel with temperature responsiveness, and the preparation method thereof is as follows:
1) 0.2g of initiator Ammonium Persulfate (APS) was dissolved in 1mL of deionized water to give an initiator solution, which was placed in an ice bath for precooling.
2) Using a pipette to pipette 5.0mL of deionized water into a 10mL centrifuge tube;
3) 0.35g of monomer N-isopropylacrylamide (NIPAM) and 0.006g of crosslinking agent methylenebisacrylamide (BIS) were weighed out, and the monomer and the initiator were dissolved in the deionized water. Introducing nitrogen for 5-10min to remove oxygen in the system.
4) Add 40. mu.L of pre-chilled APS solution to the centrifuge tube, mix well, and add 40. mu.L of accelerator Tetramethylethylenediamine (TEMED).
5) The reaction was left at room temperature (about 25 ℃) for 24h to obtain a sample PNIPAM gel.
In order to verify the temperature-responsive phase transition point of the material of the present invention, we performed DSC measurements on gels in different states, and the results are shown in fig. 1.
In order to verify the mechanical strength of the material of the present invention, we performed compressive stress-strain measurements on gels in different states, and the results are shown in fig. 2a-2 b.
In order to verify the response of the current of the material of the present invention to temperature, we tested the current of different state gels at different temperatures, and the specific results are shown in fig. 3.
To verify the strain sensing performance of the material of the present invention, we performed the detection of the current change under different compression deformation on the gel of example 2, and the specific results are shown in fig. 4.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, but rather as the subject matter of any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention.
Claims (2)
1. A preparation method of conductive hydrogel for limiting PNIPAM temperature sensitivity is characterized by comprising the following steps:
the method comprises the following steps: preparing an ionic liquid by mixing a hydrogen bond acceptor and a hydrogen bond donor at a high temperature;
step two: dissolving a monomer polymerized by PNIPAM and a cross-linking agent, and deoxidizing the monomer after the monomer and the cross-linking agent are uniformly dissolved;
step three: blending the deoxygenated solution with ionic liquids with different contents, and uniformly dispersing the ionic liquids;
step four: adding an initiator and an accelerator in an ice bath, uniformly mixing, and reacting at room temperature to obtain the PNIPAM temperature-sensitive conductive hydrogel.
2. The method for preparing the conductive hydrogel for limiting PNIPAM temperature sensitivity according to claim 1, wherein the hydrogen bond acceptor and the hydrogen bond donor are choline chloride and acrylic acid respectively, the reaction molar ratio is 1:2, and the reaction temperature is 90 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911263616.7A CN110951092B (en) | 2019-12-11 | 2019-12-11 | Preparation method of conductive hydrogel for limiting PNIPAM temperature sensitivity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911263616.7A CN110951092B (en) | 2019-12-11 | 2019-12-11 | Preparation method of conductive hydrogel for limiting PNIPAM temperature sensitivity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110951092A true CN110951092A (en) | 2020-04-03 |
| CN110951092B CN110951092B (en) | 2022-06-17 |
Family
ID=69980750
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911263616.7A Active CN110951092B (en) | 2019-12-11 | 2019-12-11 | Preparation method of conductive hydrogel for limiting PNIPAM temperature sensitivity |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110951092B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112212779A (en) * | 2020-09-04 | 2021-01-12 | 厦门大学 | Preparation method of hydrogel flexible strain sensor |
| CN113201098A (en) * | 2021-06-03 | 2021-08-03 | 哈尔滨工程大学 | Preparation method of high-transparency conductive polyurethane based on ionic liquid |
| CN113308226A (en) * | 2021-06-07 | 2021-08-27 | 绍兴徐越环境服务有限公司 | Pavement humectant and preparation method thereof |
| CN114539487A (en) * | 2022-03-25 | 2022-05-27 | 深圳市华星光电半导体显示技术有限公司 | Conductive material, electronic device and manufacturing method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824123A (en) * | 2009-12-23 | 2010-09-08 | 天津大学 | High-strength temperature-sensitive hydrogel as well as preparation method and application thereof |
| CN108948413A (en) * | 2018-06-11 | 2018-12-07 | 天津医科大学 | The method that wave polymerization prepares thymopeptide-5 molecule imprinting hydrogel |
| CN110054721A (en) * | 2019-05-10 | 2019-07-26 | 华南理工大学 | Application and ionic gel and preparation method of the eutectic solvent in ionic gel |
| US20190258093A1 (en) * | 2016-11-02 | 2019-08-22 | Nanyang Technological University | Non-volatile thermotropic optical switches based on ionic liquid(s) and polymer blends |
| CN110218338A (en) * | 2019-05-21 | 2019-09-10 | 江汉大学 | A kind of conduction gelatin method for producing elastomers |
-
2019
- 2019-12-11 CN CN201911263616.7A patent/CN110951092B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824123A (en) * | 2009-12-23 | 2010-09-08 | 天津大学 | High-strength temperature-sensitive hydrogel as well as preparation method and application thereof |
| US20190258093A1 (en) * | 2016-11-02 | 2019-08-22 | Nanyang Technological University | Non-volatile thermotropic optical switches based on ionic liquid(s) and polymer blends |
| CN108948413A (en) * | 2018-06-11 | 2018-12-07 | 天津医科大学 | The method that wave polymerization prepares thymopeptide-5 molecule imprinting hydrogel |
| CN110054721A (en) * | 2019-05-10 | 2019-07-26 | 华南理工大学 | Application and ionic gel and preparation method of the eutectic solvent in ionic gel |
| CN110218338A (en) * | 2019-05-21 | 2019-09-10 | 江汉大学 | A kind of conduction gelatin method for producing elastomers |
Non-Patent Citations (2)
| Title |
|---|
| 杨忠连等: "低共熔离子液体改性木质素基吸附剂性能研究", 《安徽理工大学学报(自然科学版)》 * |
| 陈亚鹏等: "基于低共熔溶剂前端聚合制备大孔水凝胶及其溶胀和吸附性能", 《高分子材料科学与工程》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112212779A (en) * | 2020-09-04 | 2021-01-12 | 厦门大学 | Preparation method of hydrogel flexible strain sensor |
| CN112212779B (en) * | 2020-09-04 | 2022-05-17 | 厦门大学 | Preparation method of hydrogel flexible strain sensor |
| CN113201098A (en) * | 2021-06-03 | 2021-08-03 | 哈尔滨工程大学 | Preparation method of high-transparency conductive polyurethane based on ionic liquid |
| CN113308226A (en) * | 2021-06-07 | 2021-08-27 | 绍兴徐越环境服务有限公司 | Pavement humectant and preparation method thereof |
| CN114539487A (en) * | 2022-03-25 | 2022-05-27 | 深圳市华星光电半导体显示技术有限公司 | Conductive material, electronic device and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110951092B (en) | 2022-06-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110951092B (en) | Preparation method of conductive hydrogel for limiting PNIPAM temperature sensitivity | |
| Zeng et al. | Anti-freezing dual-network hydrogels with high-strength, self-adhesive and strain-sensitive for flexible sensors | |
| CN105175755B (en) | High stretching dual network physical cross-linking hydrogel of a kind of high intensity and preparation method thereof | |
| CN111040194A (en) | Conductive hydrogel and preparation method and application thereof | |
| CN108440772A (en) | A kind of selfreparing conduction dual network structure hydrogel and preparation method thereof | |
| CN109180962A (en) | A kind of preparation method of PAA class pectin self-healing hydrogel and its capacitance type sensor | |
| CN105295077A (en) | Temperature sensitive type polyion liquid gel and preparation method thereof | |
| Rathjen et al. | The effect of preparation temperature on some properties of a temperature-sensitive hydrogel | |
| CN110013808A (en) | The preparation method of polyalcohol stephanoporate microballoons with triple responsiveness | |
| Xia et al. | Itaconic acid-enhanced robust ionic conductive elastomers for strain/pressure sensors | |
| Zhang et al. | A high strain, adhesive, self-healable poly (acrylic acid) hydrogel with temperature sensitivity as an epidermal sensor | |
| He et al. | PSS-dispersed dopamine triggered formation of PAA adhesive hydrogel as flexible wearable sensors | |
| CN113372492A (en) | High-performance polyion liquid gel, multi-mode flexible sensor and preparation method thereof | |
| CN110229269A (en) | A kind of freeze proof intelligent aqueous gel | |
| CN116358743A (en) | Preparation method of hydrophobic swelling-resistant ionic gel pressure sensing device | |
| CN116375939A (en) | Full-hydrophobic eutectic gel and preparation method and application thereof | |
| CN115141384A (en) | Preparation method of high-toughness, high-sensitivity and self-adhesive conductive hydrogel | |
| Sun et al. | Dual Ion Regulated Eutectogels with High Elasticity and Adhesive Strength for Accurate Strain Sensors | |
| He et al. | Self‐Repairable Ionic Skin Based on Multiple Dynamic Bonds with Self‐Adhesive, Anti‐Freezing, and Antimicrobial Capabilities for Monitoring Human Motions | |
| CN114213673A (en) | Preparation method of polypyrrole-modified bovine serum albumin, protein conductive hydrogel and preparation method and application thereof | |
| Chen et al. | Modified lignin‐induced composite hydrogels with good mechanical properties, adhesion, and UV resistance for strain sensors | |
| CN114672042A (en) | Preparation method and application of metal-coordinated conductive hydrogel | |
| CN107619452B (en) | A kind of preparation method of the chitosan-based hydrogel of physical crosslinking with efficient pH sensibility and high mechanical strength | |
| CN117866270B (en) | Self-healing hydrogel and preparation method and application thereof | |
| CN110776707A (en) | Adhesive hydrogel and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |