CN113088064A - Bionic nano composite material for realizing enhancement of electrical conductivity and mechanical property through supermolecule effect and preparation method thereof - Google Patents
Bionic nano composite material for realizing enhancement of electrical conductivity and mechanical property through supermolecule effect and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a bionic nano composite material for enhancing electrical conductivity and mechanical property through supermolecule effect and a preparation method thereof, wherein a series of waterborne polyurethane with different multistage hydrogen bond unit quantities is synthesized by introducing quadruple hydrogen bond unit UPy groups into a polyurethane side chain, and a two-dimensional conductive nano sheet is added to obtain waterborne polyurethane macromolecules which are fully and uniformly adsorbed on the nano sheet; the nano composite material film is prepared by a vacuum filtration method, a solvent volatilization method or a coating method. The prepared nano composite material film has a 'brick-wall' structure with ordered shell-like layers on a micro-nano scale, and weak one-hydrogen bonds and strong two-hydrogen bonds and four-hydrogen bonds are introduced between layers of the nano composite material film. On the premise of not increasing the conductive filler, the conductivity and the mechanical property of the material are enhanced by changing polyurethane containing different quadruple hydrogen bond units, and the material has good flexibility, good conductivity, high strength and various preparation methods, and can be widely applied to various fields such as electromagnetic shielding and electric heating fields.
Description
Technical Field
The invention belongs to the field of composite materials, relates to a bionic nano composite material for enhancing electrical conductivity and mechanical property through supermolecule effect and a preparation method thereof, and relates to a composite material with a bionic shell layer-shaped ordered structure on a micro-nano scale and a preparation method thereof.
Background
The nature provides a lot of inspiration in the construction of high performance synthetic materials with both good mechanical properties and functionality. Among these natural materials, nacre has received great attention from researchers due to its excellent mechanical properties and unique layered "brick-and-mud" structure. Especially, the abundant interaction among the layers brings important reference value to material design. In recent years, researchers have developed a large number of biomimetic shell materials through a number of methods. However, most of these studies only focus on using commercial polymers to obtain high-strength composite materials with seashell-like structures, but these commercial polymer materials lack designability and are difficult to impart functionality to the materials from the perspective of polymer structure design. MXene (Ti) on the other hand3C2Tx，Ti2CTxOr Ti3CNTx) And graphene and other novel two-dimensional nano materials, and the graphene and other novel two-dimensional nano materials are widely applied to polymer-based functional bionic shell materials due to excellent conductivity. The introduction of polymers does improve the mechanical properties of the material, but the electrical conductivity of the composite material is impaired without exception in comparison with these two-dimensional nanomaterials. Therefore, it is necessary to synthesize a novel polymer from the viewpoint of molecular design.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a bionic nano composite material for enhancing the electrical conductivity and the mechanical property through the supermolecule effect and a preparation method thereof, and solves the defect that the mechanical property and the functionality of the existing bionic nano composite material cannot be synergistically improved.
Technical scheme
A bionic nano composite material for realizing the enhancement of electric conductivity and mechanical property through supermolecule action is characterized in that: the nano-scale polyurethane composite material has a shell-like layered ordered brick-wall structure, an inorganic phase of the nano-scale composite material is a two-dimensional nanosheet MXene or graphene oxide, an organic polymer phase of the nano-scale composite material is waterborne polyurethane with side groups containing different UPy (2-ureido-4 (1H) pyrimidinone) group amounts, and a molecular structure of the nano-scale composite material contains a carbamate group capable of forming a double hydrogen bond, a ureido group capable of forming a double hydrogen bond and a UPy group capable of forming a quadruple hydrogen bond;
the UPy content is 15%, and the nano-sheet layer spacing determined by XRD test is
The layers have weak one-hydrogen bonds and strong two-and four-hydrogen bonds between them.
The MXene is Ti3C2Tx、Ti2CTxOr Ti3CNTxOne or two of them are mixed in any proportion.
A method for preparing the bionic nano composite material for realizing the enhancement of electric conductivity and mechanical property by the supermolecule action is characterized by comprising the following steps:
step 1, synthesizing waterborne polyurethane WPU-UPy-x with multistage supramolecular units:
a. drying the macromolecular dihydric alcohol in a vacuum oven at 90-110 ℃ for 2-24 h; then adding the mixture into a drying reactor with a mechanical stirring device, and dropwise adding diisocyanate; the molar ratio of the diisocyanate to the macromolecular dihydric alcohol is 1.2: 1-3: 1, and then the temperature is raised to 75-85 ℃ for reaction for 2-4 h;
b. respectively dissolving a hydrophilic chain extender and a UPy chain extender in the dehydrated strong polar aprotic solvent, then adding a chain extender solution into the reaction system in the step a, and controlling the temperature to be 75-85 ℃ to react for 2-4 h;
the using amount of the UPy chain extender accounts for 1-30 mol percent of the hydrophilic chain extender, and the total using amount is 0.8-1.2 times of the theoretical residual molar mass of the isocyanate group after the reaction in the step a;
c. cooling the system in the step b to below 50 ℃, adding a neutralizing agent, and reacting for 10-30 min, wherein the using amount of the neutralizing agent is 0.9-1.1 times of the molar mass of the hydrophilic chain extender;
d. adjusting the stirring speed to 2000-5000rpm, adding deionized water for emulsification and dispersion for 15-45 min to obtain WPU-UPy-x emulsion;
step 2, WPU-UPy-x/two-dimensional nanosheet composite material preparation:
a. diluting WPU-UPy-x with water to obtain emulsion with mass fraction of 0.1-20%;
b. preparing the two-dimensional nanosheets into an aqueous dispersion with the mass fraction of 0.01-5%;
c. adding the two-dimensional nanosheet dispersion into the WPU-UPy-x emulsion, and continuously stirring for 2-8 hours to enable the WPU-UPy-x to be fully adsorbed on the two-dimensional nanosheets, so as to prepare a composite dispersion with the mass ratio of the WPU-UPy-x to the two-dimensional nanosheets being 7: 3-0.5: 9.5;
d. preparing a nano composite material film with the thickness of 2 um-2 mm from the composite dispersion liquid by a vacuum filtration method, a solvent volatilization method or a coating method;
e. after drying the nano composite material film, soaking the nano composite material film in HI to reduce the nano composite material film for 8 hours at 60 ℃, and then washing and drying the nano composite material film.
The neutralizing agent can be one or a mixture of more of ammonia water, triethylamine or triethanolamine in any ratio.
The mass fraction of the chain extender solution is 10-50%.
The strong polar aprotic solvent is one or a mixture of N, N-dimethylformamide DMF and N-methylpyrrolidone NMP in any proportion.
The hydrophilic chain extender is one or the mixture of dimethylolpropionic acid DMPA or dimethylolbutyric acid DMBA in any proportion.
The diisocyanate is one or a mixture of more of isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), dicyclohexylmethane-4, 4' -diisocyanate (HMDI) and Toluene Diisocyanate (TDI) in any ratio.
The dihydric alcohol is one or a mixture of more of polytetrahydrofuran ether glycol PTMEG, polyester dihydric alcohol and polyethylene glycol PEG in any ratio.
The number average molecular weight of the dihydric alcohol is 500-3000.
Advantageous effects
The invention provides a bionic nano composite material for realizing electrical conductivity and mechanical property enhancement through supermolecule effect and a preparation method thereof, wherein a series of waterborne polyurethane with different multistage hydrogen bond unit quantities is synthesized by introducing quadruple hydrogen bond unit UPy groups into a polyurethane side chain, and a two-dimensional conductive nano sheet is added into the waterborne polyurethane under the stirring action to obtain waterborne polyurethane macromolecules which are fully and uniformly adsorbed on the nano sheet; taking a certain amount of the composite dispersion liquid, and preparing the nano composite material film by a vacuum filtration method, a solvent volatilization method or a coating method. The prepared nano composite material film has a 'brick-wall' structure with ordered shell-like layers on a micro-nano scale, and weak hydrogen bonds and strong double and quadruple hydrogen bonds are introduced between the layers of the nano composite material film. On the premise of not increasing the conductive filler, the conductivity and the mechanical property of the material can be enhanced by changing polyurethane containing different quadruple hydrogen bond units, and the material has good flexibility, good conductivity, high strength and various preparation methods, and can be widely applied to various fields such as electromagnetic shielding and electric heating fields.
A bionic nano composite material with a shell-like layered structure on a micro-nano scale is prepared through a bionic strategy. By using the combination of the waterborne polyurethane with different UPy (2-ureido-4 (1H) pyrimidone) group amounts in the molecular structure and the two-dimensional nano-sheet, the bionic nano-composite material is successfully introduced into the multi-stage supermolecular unit, and the close degree of the stacking of the nano-sheet in the nano-composite material can be effectively improved by introducing the multi-stage hydrogen bond supermolecular group (the UPy content is increased from 0 to 15 percent, and the interlayer distance is increased from 0 to 15 percent)
Is reduced to
). On the premise of not increasing the nano filler, the conductivity of the composite material can be improved and the mechanical property can be enhanced only by increasing the content of UPy in a polyurethane molecular chain. For example, with waterborne polyurethanes and Ti which do not contain UPy groups3C2TxCompared with the composite material constructed by assembly, the waterborne polyurethane containing 15 percent of UPy groups and Ti are used3C2TxThe conductivity of the composite material constructed by assembly can be improved by 1.3 times (from 3214.0S/cm to 4136.1S/cm), and the tensile strength can be improved by 1.6 times (from 87.9MPa to 137.0 MPa). The composite material is light in weight, the preparation method of the composite material is diversified, different preparation methods can be selected according to different requirements, the thickness of the film can be adjusted at will, the composite material can be widely applied to various fields such as electromagnetic shielding and electric heating fields, and the used polymer is an aqueous substrate, and is environment-friendly and pollution-free.
Drawings
FIG. 1: FIG. 1 chemical Structure of UPy chain extender
FIG. 2: WPU-UPy-x/Ti prepared by vacuum filtration method3C2TxConductivity results of MXene (mass ratio 2:8) composite film.
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
the invention synthesizes a series of waterborne polyurethane with different UPy (2-ureido-4 (1H) pyrimidone) group contents in side groups, so that the molecular structure of the waterborne polyurethane contains a carbamate group capable of forming a double hydrogen bond, an ureido group capable of forming a double hydrogen bond and an UPy group capable of forming a quadruple hydrogen bond. And then by a shell bionic construction strategy, utilizing the synthesized waterborne polyurethane with hierarchical hydrogen bond molecular action and MXene (Ti)3C2Tx，Ti2CTxOr Ti3CNTx) Or the GO nano-sheets are combined and assembled through supermolecule interaction, so that the bionic nano-composite material with multi-stage supermolecule units between layers is constructed, and the stacking tightness degree of the nano-sheets in the nano-composite material can be effectively improved by introducing multi-stage hydrogen bond supermolecule groups. On the premise of not increasing the nano filler, the improvement of the electrical conductivity and the enhancement of the mechanical property of the composite material can be realized by increasing the content of UPy in a polyurethane molecular chain.
Example 1:
step 1, WPU-UPy-30 synthesis: drying dihydric alcohol in a vacuum oven at 100 ℃ for 10h, taking out 0.023mol of the dihydric alcohol, adding the dihydric alcohol into a dry three-necked bottle provided with a mechanical stirring device, setting the rotating speed of a stirrer to be 100rpm, then adding 0.046mol of diisocyanate, heating to 80 ℃ and reacting for 3.5 h; 0.0161mol of hydrophilic chain extender and 0.0069mol of UPy chain extender are put into 5mL of anhydrous DMF, and then added into a reaction system to react for 2.5h at 80 ℃; and (3) cooling the system to 40 ℃, adding 0.0234mol of neutralizer, reacting for 15min, adjusting the stirring speed to 3000rpm, adding 75mL of deionized water, emulsifying and dispersing for 20min to obtain the WPU-UPy-30 emulsion.
Step 2, preparing the composite material: diluting WPU-UPy-30 with deionized water to obtain 0.3% emulsion; then adding Ti3C2TxMXene is prepared into water dispersion with the mass fraction of 0.6 percent; mixing WPU-UPy-30 with Ti3C2TxMXene mass ratio was set to 3: 7, then Ti of corresponding mass3C2TxAdding MXene dispersion into WPU-UPy-30 emulsion, and stirring for 2 hr to make WPU-UPy-30 be fully adsorbed on Ti3C2TxMXene nano-sheet, finally preparing WPU-UPy-30 and Ti3C2TxComposite dispersions of MXene. 30g of the composite dispersion was filtered through a 5cm diameter glass frit funnel using a 5cm diameter filter membrane with a 0.2um pore size to yield a nanocomposite membrane of approximately 6um thickness.
Example 2:
step 1, WPU-UPy-20 synthesis: drying dihydric alcohol in a vacuum oven at 100 ℃ for 10h, taking out 0.023mol of the dihydric alcohol, adding the dihydric alcohol into a dry three-necked bottle provided with a mechanical stirring device, setting the rotating speed of a stirrer to be 100rpm, then adding 0.046mol of diisocyanate, heating to 80 ℃ and reacting for 3.5 h; 0.0184mol of hydrophilic chain extender and 0.0046mol of UPy chain extender are put into 5mL of anhydrous DMF, and then added into a reaction system to react for 2.5h at 80 ℃; and (3) cooling the system to 40 ℃, adding 0.0234mol of neutralizer, reacting for 15min, adjusting the stirring speed to 3000rpm, adding 75mL of deionized water, emulsifying and dispersing for 20min to obtain the WPU-UPy-20 emulsion.
And 2, replacing WPU-UPy-30 in the example 1 with WPU-UPy-20.
Example 3:
step 1, WPU-UPy-10 synthesis: drying dihydric alcohol in a vacuum oven at 100 ℃ for 10h, taking out 0.023mol of the dihydric alcohol, adding the dihydric alcohol into a dry three-necked bottle provided with a mechanical stirring device, setting the rotating speed of a stirrer to be 100rpm, then adding 0.046mol of diisocyanate, heating to 80 ℃ and reacting for 3.5 h; adding 0.0207mol of hydrophilic chain extender and 0.0023mol of UPy chain extender into 5mL of anhydrous DMF, then adding into a reaction system, and reacting for 2.5h at 80 ℃; and (3) cooling the system to 40 ℃, adding 0.0234mol of neutralizer, reacting for 15min, adjusting the stirring speed to 3000rpm, adding 75mL of deionized water, emulsifying and dispersing for 20min to obtain the WPU-UPy-10 emulsion.
Step 2, preparing the composite material: diluting WPU-UPy-10 with deionized water to obtain 0.3% emulsion; then preparing GO into a water dispersion with the mass fraction of 0.8%; setting the mass ratio of WPU-UPy-10 to GO as 4: and 6, adding GO dispersion liquid with corresponding mass into the WPU-UPy-10 emulsion, continuously stirring for 6 hours to enable the WPU-UPy-10 to be fully adsorbed on GO nano-sheets, and finally preparing the WPU-UPy-10 and GO composite dispersion liquid. And (3) pouring 20g of the composite dispersion liquid into a polytetrafluoroethylene culture dish with the diameter of 6cm, placing the culture dish in a drying oven at 40 ℃ for drying, soaking the composite film into HI, reducing the composite film at 60 ℃ for 8 hours, washing with water, and drying at 60 ℃ to obtain the composite film.
Example 4:
step 1, WPU-UPy-5 synthesis: drying dihydric alcohol in a vacuum oven at 100 ℃ for 10h, taking out 0.023mol of the dihydric alcohol, adding the dihydric alcohol into a dry three-necked bottle provided with a mechanical stirring device, setting the rotating speed of a stirrer to be 100rpm, then dripping 0.046mol of diisocyanate, heating to 80 ℃ and reacting for 3.5 h; adding 0.0219mol of hydrophilic chain extender and 0.0011mol of UPy chain extender into 5mL of anhydrous DMF, then adding into a reaction system, and reacting for 2.5h at 80 ℃; and (3) cooling the system to 40 ℃, adding 0.0234mol of neutralizer, reacting for 15min, adjusting the stirring speed to 3000rpm, adding 75mL of deionized water, emulsifying and dispersing for 20min to obtain the WPU-UPy-5 emulsion.
Step 2, preparing the composite material: diluting WPU-UPy-5 with deionized water to obtain 0.3% emulsion; then adding Ti3C2TxMXene and GO are respectively prepared into water dispersion liquid with the mass fraction of 0.8 percent and 0.8 percent; setting the mass ratio of WPU-UPy-5 to GO as 4: 6, mixing Ti3C2TxMixing MXene and GO dispersion liquid in a mass ratio of 5: 5; followed by respective masses of GO and Ti3C2TxAdding MXene dispersion into WPU-UPy-5 emulsion, and stirring for 6 hr to make WPU-UPy-5 be fully adsorbed on GO and Ti3C2TxMXene nano-sheet, finally preparing WPU-UPy-5 and Ti3C2TxComposite dispersions of MXene. And (3) taking 20g of the composite dispersion, using a filter membrane with the diameter of 5cm and the aperture of 0.2um, performing suction filtration on a glass sand core funnel with the diameter of 5cm to obtain a film, placing the film in a drying oven at 40 ℃ for drying, then soaking the film in HI to reduce the film for 8 hours at 60 ℃, washing the film with water, and drying the film at 60 ℃ to obtain the composite film.
Example 5:
step 1, WPU-UPy-20 synthesis: drying dihydric alcohol in a vacuum oven at 100 ℃ for 10h, taking out 0.023mol of the dihydric alcohol, adding the dihydric alcohol into a dry three-mouth bottle provided with a mechanical stirring device, setting the rotating speed of a stirrer to be 100rpm, then dropwise adding 0.046mol of diisocyanate, heating to 80 ℃ and reacting for 3.5 h; adding 0.023mol of hydrophilic chain extender into 5mL of anhydrous DMF, then adding the obtained product into a reaction system, and reacting for 2.5h at 80 ℃; and (3) cooling the system to 40 ℃, adding 0.0234mol of neutralizer, reacting for 15min, adjusting the stirring speed to 3000rpm, adding 75mL of deionized water, emulsifying and dispersing for 20min to obtain the WPU-UPy-20 emulsion.
And 2, replacing WPU-UPy-30 in the example 1 with WPU-UPy-0.
Example 6:
step 1, WPU-UPy-30 in example 1 was synthesized.
Step 2, mixing Ti in example 13C2TxReplacement of MXene by Ti3CNTx MXene。
Claims (10)
1. A bionic nano composite material for realizing the enhancement of electric conductivity and mechanical property through supermolecule action is characterized in that: the nano-scale polyurethane composite material has a shell-like layered ordered brick-wall structure, an inorganic phase of the nano-scale composite material is a two-dimensional nanosheet MXene or graphene oxide, an organic polymer phase of the nano-scale composite material is waterborne polyurethane with side groups containing different UPy (2-ureido-4 (1H) pyrimidinone) group amounts, and a molecular structure of the nano-scale composite material contains a carbamate group capable of forming a double hydrogen bond, a ureido group capable of forming a double hydrogen bond and a UPy group capable of forming a quadruple hydrogen bond;
the UPy content is 15%, and the nano-sheet layer spacing determined by XRD test is
The layers have weak one-hydrogen bonds and strong two-and four-hydrogen bonds between them.
2. The biomimetic nanocomposite material according to claim 1, which achieves electrical conductivity and mechanical property enhancement through supramolecular action, characterized in that: the MXene is Ti3C2Tx、Ti2CTxOr Ti3CNTxOne or two of them are mixed in any proportion.
3. A process for the preparation of biomimetic nanocomposites according to claim 1 or 2 with enhanced electrical conductivity and mechanical properties through supramolecular interactions, characterized by the following steps:
step 1, synthesizing waterborne polyurethane WPU-UPy-x with multistage supramolecular units:
a. drying the macromolecular dihydric alcohol in a vacuum oven at 90-110 ℃ for 2-24 h; then adding the mixture into a drying reactor with a mechanical stirring device, and dropwise adding diisocyanate; the molar ratio of the diisocyanate to the macromolecular dihydric alcohol is 1.2: 1-3: 1, and then the temperature is raised to 75-85 ℃ for reaction for 2-4 h;
b. respectively dissolving a hydrophilic chain extender and a UPy chain extender in the dehydrated strong polar aprotic solvent, then adding a chain extender solution into the reaction system in the step a, and controlling the temperature to be 75-85 ℃ to react for 2-4 h;
the using amount of the UPy chain extender accounts for 1-30 mol percent of the hydrophilic chain extender, and the total using amount is 0.8-1.2 times of the theoretical residual molar mass of the isocyanate group after the reaction in the step a;
c. cooling the system in the step b to below 50 ℃, adding a neutralizing agent, and reacting for 10-30 min, wherein the using amount of the neutralizing agent is 0.9-1.1 times of the molar mass of the hydrophilic chain extender;
d. adjusting the stirring speed to 2000-5000rpm, adding deionized water for emulsification and dispersion for 15-45 min to obtain WPU-UPy-x emulsion;
step 2, WPU-UPy-x/two-dimensional nanosheet composite material preparation:
a. diluting WPU-UPy-x with water to obtain emulsion with mass fraction of 0.1-20%;
b. preparing the two-dimensional nanosheets into an aqueous dispersion with the mass fraction of 0.01-5%;
c. adding the two-dimensional nanosheet dispersion into the WPU-UPy-x emulsion, and continuously stirring for 2-8 hours to enable the WPU-UPy-x to be fully adsorbed on the two-dimensional nanosheets, so as to prepare a composite dispersion with the mass ratio of the WPU-UPy-x to the two-dimensional nanosheets being 7: 3-0.5: 9.5;
d. preparing a nano composite material film with the thickness of 2 um-2 mm from the composite dispersion liquid by a vacuum filtration method, a solvent volatilization method or a coating method;
e. after drying the nano composite material film, soaking the nano composite material film in HI to reduce the nano composite material film for 8 hours at 60 ℃, and then washing and drying the nano composite material film.
4. The method of claim 3, wherein: the neutralizing agent can be one or a mixture of more of ammonia water, triethylamine or triethanolamine in any ratio.
5. The method of claim 3, wherein: the mass fraction of the chain extender solution is 10-50%.
6. The method of claim 3, wherein: the strong polar aprotic solvent is one or a mixture of N, N-dimethylformamide DMF and N-methylpyrrolidone NMP in any proportion.
7. The method of claim 3, wherein: the hydrophilic chain extender is one or the mixture of dimethylolpropionic acid DMPA or dimethylolbutyric acid DMBA in any proportion.
8. The method of claim 3, wherein: the diisocyanate is one or a mixture of more of isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), dicyclohexylmethane-4, 4' -diisocyanate (HMDI) and Toluene Diisocyanate (TDI) in any ratio.
9. The method of claim 3, wherein: the dihydric alcohol is one or a mixture of more of polytetrahydrofuran ether glycol PTMEG, polyester dihydric alcohol and polyethylene glycol PEG in any ratio.
10. The method of claim 9, wherein: the number average molecular weight of the dihydric alcohol is 500-3000.
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| CN114724775A (en) * | 2022-05-24 | 2022-07-08 | 西北工业大学 | Preparation method of low-temperature polyester polyurethane-based conductive slurry |
| CN114724775B (en) * | 2022-05-24 | 2022-09-13 | 西北工业大学 | Preparation method of low-temperature polyester polyurethane-based conductive slurry |
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| CN113088064B (en) | 2022-12-27 |
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