CN114752209A - Conductive self-repairing polyurethane elastomer based on dynamic coordination bonds and preparation method thereof - Google Patents
Conductive self-repairing polyurethane elastomer based on dynamic coordination bonds and preparation method thereof Download PDFInfo
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- CN114752209A CN114752209A CN202210218382.XA CN202210218382A CN114752209A CN 114752209 A CN114752209 A CN 114752209A CN 202210218382 A CN202210218382 A CN 202210218382A CN 114752209 A CN114752209 A CN 114752209A
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- 229920003225 polyurethane elastomer Polymers 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229920002635 polyurethane Polymers 0.000 claims abstract description 58
- 239000004814 polyurethane Substances 0.000 claims abstract description 58
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 27
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000004132 cross linking Methods 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 10
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 10
- 239000004970 Chain extender Substances 0.000 claims abstract description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000012948 isocyanate Substances 0.000 claims abstract description 8
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 8
- 229920000728 polyester Polymers 0.000 claims abstract description 8
- 229920000570 polyether Polymers 0.000 claims abstract description 8
- 229920005862 polyol Polymers 0.000 claims abstract description 8
- 150000003077 polyols Chemical class 0.000 claims abstract description 8
- 150000002500 ions Chemical class 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- VHNQIURBCCNWDN-UHFFFAOYSA-N pyridine-2,6-diamine Chemical compound NC1=CC=CC(N)=N1 VHNQIURBCCNWDN-UHFFFAOYSA-N 0.000 claims description 16
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 13
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 11
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 11
- -1 polybutylene adipate Polymers 0.000 claims description 11
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000002048 multi walled nanotube Substances 0.000 claims description 7
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002109 single walled nanotube Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000018044 dehydration Effects 0.000 abstract 1
- 238000006297 dehydration reaction Methods 0.000 abstract 1
- 239000008204 material by function Substances 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 10
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 6
- 230000035876 healing Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 229920001940 conductive polymer Polymers 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000013329 compounding Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- SRICROQPOLNYOO-UHFFFAOYSA-N 1h-pyridine-2,2-diamine Chemical compound NC1(N)NC=CC=C1 SRICROQPOLNYOO-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/3844—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing one nitrogen atom in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01D—MEASURING NOT SPECIALLY ADAPTED FOR A SPECIFIC VARIABLE; ARRANGEMENTS FOR MEASURING TWO OR MORE VARIABLES NOT COVERED IN A SINGLE OTHER SUBCLASS; TARIFF METERING APPARATUS; MEASURING OR TESTING NOT OTHERWISE PROVIDED FOR
- G01D5/00—Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable
- G01D5/12—Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable using electric or magnetic means
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
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- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a conductive self-repairing polyurethane elastomer based on dynamic coordination bonds and a preparation method thereof, wherein the preparation method comprises the following steps: (a) taking a certain amount of polyester or polyether polyol or a mixture thereof, carrying out vacuum dehydration, adding a certain amount of isocyanate, adding a chain extender containing a coordination atom after reaction, continuing vacuum reaction, and drying to obtain functional polyurethane; (b) dissolving the functional polyurethane in chloroform, adding the conductive carbon nanotubes, and dispersing uniformly to obtain a stable conductive functional polyurethane solution; (c) and (c) dissolving a compound containing metal coordination ions in methanol, adding the mixture into the polyurethane solution with the conductive function prepared in the step (b), uniformly mixing, and crosslinking to form a film, thereby obtaining the conductive self-repairing polyurethane elastomer. The conductive self-repairing polyurethane disclosed by the invention has the characteristics of high mechanical and conductive self-repairing rates and the like, and is suitable for manufacturing functional materials such as flexible sensors.
Description
Technical Field
The invention belongs to the technical field of conductive polymer composite materials, and relates to a conductive self-repairing polyurethane elastomer based on dynamic coordination bonds and a preparation method thereof.
Background
The conductive polymer composite material is one of important research fields of functional polymer materials. As most polymers are insulators, the conductive polymer composite material prepared by compounding the conductive filler and the polymers has the characteristics of simple and convenient processing, easy conductivity and the like, and has wide application in the fields of automobiles, energy sources, aviation, electronics, electrics, sensing and the like. The conductive polymer composite material commonly used at present is easy to crack when being stretched, so that the service life of the material is influenced. Flexible sensors are required to maintain a certain conductivity even when they are stretchable or bent to a high degree and to be used repeatedly. Because of the adjustable soft and hard chain segments, polyurethane is used as a matrix material of a stretchable sensor in many fields.
At present, in the process of using the conductive polyurethane material, micro cracks are inevitably generated on the surface and inside of the material, and the mechanical property and the conductivity of the material are influenced. The common self-repairing polyurethane has the advantages of self-repairing, long service life and the like, but has no conductivity as common high polymer materials, so that the use of the polyurethane in flexible sensors is limited.
Disclosure of Invention
The purpose is as follows: in order to overcome the defects in the prior art, the invention provides a conductive self-repairing polyurethane elastomer based on dynamic coordination bonds and a preparation method thereof, so as to be suitable for manufacturing a flexible sensor.
The technical scheme is as follows: the technical scheme adopted by the invention is as follows:
according to a first aspect of the present invention, there is provided a method for preparing an electrically conductive self-repairing polyurethane elastomer, comprising:
step (a), taking a certain amount of polyester or polyether polyol or a mixture thereof, dehydrating in vacuum, adding a certain amount of isocyanate, adding a chain extender containing coordination atoms after reaction, continuing the vacuum reaction, and drying to obtain functional polyurethane;
dissolving functional polyurethane in chloroform, adding a conductive carbon nanotube, and uniformly dispersing to obtain a stable conductive functional polyurethane solution;
and (c) dissolving a compound containing metal coordination ions in methanol, adding the solution into the polyurethane solution with the conductive function prepared in the step (b), uniformly mixing, volatilizing the solvent, and crosslinking to form a film to obtain the conductive self-repairing polyurethane elastomer.
In some embodiments, in step (a), the polyester or polyether polyol or the mixture thereof is one or more of polybutylene adipate glycol, polytetrahydrofuran and polypropylene glycol;
preferably, the polytetrahydrofuran is polytetrahydrofuran with a molecular weight of 1000, and the polypropylene glycol is polypropylene glycol with a molecular weight of 1000;
and/or the isocyanate is one or more of hexamethylene diisocyanate or isophorone diisocyanate, preferably hexamethylene diisocyanate;
and/or the chain extender containing the coordinating atom is preferably 2, 6-diaminopyridine, 2, 6-diaminopyridine being chosen because it can react with Fe3+、Cu2+And Zn2+And various metal ions are coordinated.
The 2, 2-diaminopyridine is recrystallized at a temperature of 60-70 ℃.
In some embodiments, in step (a), the polyester or polyether polyol or mixture thereof, the isocyanate and the chain extender are in a molar ratio of 1 (1.2-2.4): 1.
In some embodiments, in step (a), a catalyst is also added, preferably dibutyltin dilaurate.
In some embodiments, in step (b), the conductive carbon nanotubes are single-walled carbon nanotubes or multi-walled carbon nanotubes.
In some embodiments, in step (b), the amount of the conductive carbon nanotubes added is 0.5 to 7% by mass, preferably 1 to 3% by mass, of the functional polyurethane.
In some embodiments, in step (c), the metal complex ion is Fe3+、Cu2+Or Zn2+Preferably, the compound containing a metal complex ion is Fe3+Compounds, e.g. iron trichloride hexahydrate, Fe3+The molar ratio to polyurethane is 2:1, so Fe is selected3+The compound is due to Fe3+Two weak bonds and one strong bond exist in coordination with 2, 6-diaminopyridine, which is beneficial to fracture repair, and Cu2+And Zn2+The coordination with 2, 6-diaminopyridine is only strong bond, which is not beneficial to repair.
In some embodiments, the temperature of the crosslinking reaction in step (c) is 60 to 80 ℃.
According to the second aspect of the invention, the conductive self-repairing polyurethane elastomer is provided, and is prepared by the preparation method.
According to a third aspect of the invention, the application of the conductive self-repairing polyurethane elastomer in a flexible sensor is provided.
Has the advantages that: the invention relates to a conductive self-repairing polyurethane elastomer based on dynamic coordination bonds and a preparation method thereof, wherein polyester or polyether polyol or a mixture thereof, isocyanate and a chain extender containing coordination atoms are adopted to prepare functional polyurethane, conductive carbon nanotubes are added for compounding, and metal ions are used for crosslinking to obtain the conductive self-repairing polyurethane.
Preferably, polytetrahydrofuran and hexamethylene diisocyanate are used as base materials, and 2, 6-diaminopyridine is used as a functional chain extender to prepare the polyurethane elastomer. Using metal ions (Fe)3+) Crosslinking, adding conductive carbon nanotubes (multi-walled carbon nanotubes) for compounding to obtain the conductive self-repairing polyurethane, which has the characteristics of high mechanical and conductive self-repairing rate and the like, and overcomes the characteristic of short service life of common flexible conductive materials.
Detailed Description
The present invention will be further described with reference to the following examples.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
For the purposes of the present specification and appended claims, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values used in the specification and appended claims, are to be understood as being modified in all instances by the term "about". Moreover, all ranges disclosed herein are inclusive of the endpoints and independently combinable.
Example 1 (comparative conductive function)
Firstly, polytetrahydrofuran and hexamethylene with molecular weight of 1000 are weighed according to the molar ratio of 1:2:1Isocyanate and 2, 6-diaminopyridine, polytetrahydrofuran is dehydrated at 120 ℃ and in vacuo. Then, adding hexamethylene diisocyanate and dibutyltin dilaurate as catalysts, heating to 85 ℃ after the system is stable, reacting for 2 hours, adding 2, 6-diaminopyridine dissolved in N, N-dimethylformamide, reacting for 5 minutes, putting into a vacuum oven for further reaction to be complete, and drying to obtain the functional polyurethane. The resulting functional polyurethane was dissolved in chloroform (solute as 10% w/v of the solvent) and iron trichloride hexahydrate was dissolved in methanol (solute as 1% w/v of the solvent). Then will contain Fe3+Is added to the solution of polyurethane, Fe3+The molar ratio of the polyurethane to the polyurethane is 2:1, the mixture is poured into a polytetrafluoroethylene mold to form a film at room temperature, and the self-repairing polyurethane elastomer film is obtained by crosslinking at 60 ℃.
And vertically cutting the sample from the middle part, attaching the sections, and putting the sections into an oven for healing. The conductivity of the material obtained by testing is 0S/cm, and the restoration efficiency of the mechanical property is more than 99%.
In example 1, no conductive carbon nanotubes were added, and thus the self-repairing polyurethane elastomer film obtained did not have a conductive function.
Example 2
First, polytetrahydrofuran having a molecular weight of 1000, hexamethylene diisocyanate and 2, 6-diaminopyridine were weighed in a molar ratio of 1:2:1, and the polytetrahydrofuran was dehydrated at 120 ℃ in vacuo. And then, adding hexamethylene diisocyanate and dibutyltin dilaurate as catalysts, heating to 85 ℃ after the system is stable, reacting for 2 hours, adding 2, 6-diaminopyridine dissolved in N, N-dimethylformamide, reacting for 5 minutes, putting into a vacuum oven for further reaction to be complete, and drying to obtain the functional polyurethane. Dissolving the obtained functional polyurethane in chloroform (solute is 10% w/v of solvent), adding multi-walled carbon nanotubes with the mass of 1% of that of the polyurethane into the chloroform solution of the polyurethane, magnetically stirring at room temperature, and ultrasonically dispersing to obtain the polyurethane solution with the conductive function. Dissolving ferric trichloride hexahydrate in methanol solvent (solute is 1% w/v of solvent), and then adding Fe3+Adding the solution into a polyurethane solution with a conductive function, and adding Fe3+Molar ratio to polyurethaneThe ratio of the monomer to the monomer is 2:1, the monomer is poured into a polytetrafluoroethylene mold to form a film at room temperature, and the self-repairing polyurethane elastomer film is obtained by crosslinking at 60 ℃.
And vertically cutting the sample from the middle part, attaching the sections, and putting the sections into an oven for healing. The material tested had an electrical conductivity of 1.35 x 10-4S/cm, the repairing efficiency of the mechanical property is 98%, and the repairing efficiency of the electrical property is 100%.
Example 3
First, polytetrahydrofuran having a molecular weight of 1000, hexamethylene diisocyanate and 2, 6-diaminopyridine were weighed in a molar ratio of 1:2:1, and the polytetrahydrofuran was dehydrated at 120 ℃ in vacuo. Then, adding hexamethylene diisocyanate and dibutyltin dilaurate as catalysts, heating to 85 ℃ after the system is stable, reacting for 2 hours, adding 2, 6-diaminopyridine dissolved in N, N-dimethylformamide, reacting for 5 minutes, putting into a vacuum oven for further reaction to be complete, and drying to obtain the functional polyurethane. Dissolving the obtained functional polyurethane in chloroform (solute is 10% w/v of solvent), adding multi-walled carbon nanotubes with the mass of 3% of that of the polyurethane into the chloroform solution of the polyurethane, magnetically stirring at room temperature, and ultrasonically dispersing to obtain the polyurethane solution with the conductive function. Dissolving ferric trichloride hexahydrate in methanol solvent (solute is 1% w/v of solvent), and then adding Fe3+Adding the solution into a polyurethane solution with a conductive function, and adding Fe3+The molar ratio of the polyurethane to the polyurethane is 2:1, the mixture is poured into a polytetrafluoroethylene mold to form a film at room temperature, and the self-repairing polyurethane elastomer film is obtained by crosslinking at 60 ℃.
And vertically cutting the sample from the middle part, attaching the sections, and putting the sections into an oven for healing. The material tested had a conductivity of 7.79 x 10-3S/cm, the repairing efficiency of the mechanical property is 96%, and the repairing efficiency of the electrical property is 100%.
Example 4
First, polytetrahydrofuran having a molecular weight of 1000, isophorone diisocyanate and 2, 6-diaminopyridine were weighed in a molar ratio of 1:2.2:1, and the polytetrahydrofuran was dehydrated at 120 ℃ in vacuo. Then adding isophorone diisocyanate and dibutyltin dilaurate as catalysts, heating to 85 ℃ after the system is stable, and reacting for 2 hoursAdding 2, 6-diaminopyridine dissolved in N, N-dimethylformamide, reacting for 5min, putting into a vacuum oven for further reaction to be complete, and drying to obtain the functional polyurethane. Dissolving the obtained functional polyurethane in chloroform (solute is 10% w/v of solvent), adding multi-walled carbon nanotubes with the mass of 1% of that of the polyurethane into the chloroform solution of the polyurethane, magnetically stirring at room temperature, and ultrasonically dispersing to obtain the polyurethane solution with the conductive function. Dissolving ferric chloride hexahydrate in methanol solvent (solute is 1% w/v of the solvent), and then adding Fe3+Adding the solution into a conductive functional polyurethane solution, Fe3+The molar ratio of the polyurethane to the polyurethane is 2:1, the mixture is poured into a polytetrafluoroethylene mold to form a film at room temperature, and the self-repairing polyurethane elastomer film is obtained by crosslinking at 60 ℃.
And vertically cutting the sample from the middle part, attaching the sections, and putting the sections into an oven for healing. The material tested had a conductivity of 1.48 x 10-4S/cm, the restoration efficiency of the mechanical property is 97%, and the restoration efficiency of the electrical property is 100%.
Example 5
First, polypropylene glycol having a molecular weight of 1000, hexamethylene diisocyanate and 2, 6-diaminopyridine were weighed in a molar ratio of 1:2.2:1, and the polypropylene glycol was dehydrated at 120 ℃ in vacuum. And then adding hexamethylene diisocyanate and dibutyltin dilaurate as catalysts, heating to 85 ℃ after the system is stable, reacting for 2 hours, adding 2, 6-diaminopyridine dissolved in N, N-dimethylformamide, reacting for 5 minutes, putting into a vacuum oven for further reaction to be complete, and drying to obtain the functional polyurethane. Dissolving the obtained functional polyurethane in chloroform (solute is 10% w/v of solvent), adding multi-walled carbon nanotubes with the mass of 1% of that of the polyurethane into the chloroform solution of the polyurethane, magnetically stirring at room temperature, and ultrasonically dispersing to obtain the polyurethane solution with the conductive function. Dissolving ferric trichloride hexahydrate in methanol solvent (solute is 1% w/v of solvent), and then adding Fe3+Adding the solution into a conductive functional polyurethane solution, Fe3+The molar ratio of the polyurethane to the polyurethane is 2:1, the mixture is poured into a polytetrafluoroethylene mold to form a film at room temperature, and the self-repairing polyurethane elastomer film is obtained by crosslinking at 60 ℃.
Subjecting the sample toAfter the middle part is vertically cut off, the sections are jointed and put into an oven for healing. The material tested had an electrical conductivity of 1.32 x 10-4S/cm, the repairing efficiency of the mechanical property is 99%, and the repairing efficiency of the electrical property is 100%.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a conductive self-repairing polyurethane elastomer is characterized by comprising the following steps:
step (a), taking a certain amount of polyester or polyether polyol or a mixture thereof, dehydrating in vacuum, adding a certain amount of isocyanate, adding a chain extender containing coordination atoms after reaction, continuing the vacuum reaction, and drying to obtain functional polyurethane;
dissolving functional polyurethane in chloroform, adding a conductive carbon nanotube, and uniformly dispersing to obtain a stable conductive functional polyurethane solution;
and (c) dissolving a compound containing metal coordination ions in methanol, adding the methanol into the polyurethane solution with the conductive function prepared in the step (b), uniformly mixing, and crosslinking to form a film, thereby obtaining the conductive self-repairing polyurethane elastomer.
2. The preparation method according to claim 1, wherein in the step (a), the polyester or polyether polyol or the mixture thereof is one or a mixture of polybutylene adipate glycol, polytetrahydrofuran and polypropylene glycol;
and/or the isocyanate is one or more of hexamethylene diisocyanate or isophorone diisocyanate;
and/or the chain extender containing the coordination atom is preferably 2, 6-diaminopyridine.
3. The preparation method of claim 1 or 2, wherein in the step (a), the molar ratio of the polyester or polyether polyol or the mixture thereof, the isocyanate and the chain extender is 1 (1.2-2.4) to 1.
4. The method of claim 1, wherein in step (a), a catalyst is also added, preferably dibutyltin dilaurate.
5. The method according to claim 1, wherein in the step (b), the conductive carbon nanotubes are one or more of single-walled carbon nanotubes or multi-walled carbon nanotubes.
6. The method according to claim 1, wherein the amount of the carbon nanotubes added in step (b) is 0.5 to 7% by mass of the functional polyurethane.
7. The method according to claim 1, wherein in the step (c), the metal complex ion is Fe3+、Cu2+Or Zn2+Preferably, the compound containing a metal complex ion is Fe3+A compound is provided.
8. The method according to claim 1, wherein the temperature of the crosslinking reaction in the step (c) is 60 to 80 ℃.
9. A conductive self-repairing polyurethane elastomer prepared by the preparation method of any one of claims 1 to 8.
10. Use of the electrically conductive self-healing polyurethane elastomer of claim 9 in a flexible sensor.
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| CN106750145A (en) * | 2016-12-16 | 2017-05-31 | 四川大学 | Review one's lessons by oneself polyurethane material of redoubling force-responsive and preparation method thereof |
| CN107216643A (en) * | 2017-08-03 | 2017-09-29 | 四川大学 | A kind of selfreparing polyurethane nano composite material and its production and use |
| US20200332053A1 (en) * | 2017-08-22 | 2020-10-22 | Electric Power Research Institute Of Guangdong Power Grid Co., Ltd. | Polyurethane polymer, method for preparing the same and use thereof |
| CN113831493A (en) * | 2021-09-27 | 2021-12-24 | 中国科学院宁波材料技术与工程研究所 | Self-repairing polyurethane elastomer containing six-fold intermolecular hydrogen bonds and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106750145A (en) * | 2016-12-16 | 2017-05-31 | 四川大学 | Review one's lessons by oneself polyurethane material of redoubling force-responsive and preparation method thereof |
| CN107216643A (en) * | 2017-08-03 | 2017-09-29 | 四川大学 | A kind of selfreparing polyurethane nano composite material and its production and use |
| US20200332053A1 (en) * | 2017-08-22 | 2020-10-22 | Electric Power Research Institute Of Guangdong Power Grid Co., Ltd. | Polyurethane polymer, method for preparing the same and use thereof |
| CN113831493A (en) * | 2021-09-27 | 2021-12-24 | 中国科学院宁波材料技术与工程研究所 | Self-repairing polyurethane elastomer containing six-fold intermolecular hydrogen bonds and preparation method thereof |
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