CN114671972A - Heteropoly acid type polyion liquid self-healing material and preparation method and application thereof - Google Patents
Heteropoly acid type polyion liquid self-healing material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 78
- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 40
- 239000007788 liquid Substances 0.000 title claims abstract description 35
- 229920000831 ionic polymer Polymers 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 5
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- 239000000047 product Substances 0.000 claims description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
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- 238000000034 method Methods 0.000 claims description 14
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 12
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- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
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- 229920000774 poly(2-methoxyaniline-5-sulfonic acid) polymer Polymers 0.000 description 7
- XEBWQGVWTUSTLN-UHFFFAOYSA-M phenylmercury acetate Chemical compound CC(=O)O[Hg]C1=CC=CC=C1 XEBWQGVWTUSTLN-UHFFFAOYSA-M 0.000 description 6
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- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
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- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 1
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- 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
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials For Medical Uses (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention belongs to the field of high polymer materials, and discloses a heteropoly acid type polyion liquid self-healing material, and a preparation method and application thereof. Takes heteropoly acid and macromolecule containing sulfonated quaternary ammonium salt group as raw materials, and forms the macromolecule composite material of heteropoly acid type ionic liquid group crosslinking through electrostatic compounding, the general formula is [ -CH2CH(COOCH2CH2N(CH3)2CH2CH2CH2SO3H‑]n‑r‑[CH2CH(COOCH3)‑]m‑@(XM12O4)n/lThe ionic liquid part of the material has microwave responsiveness and can be used for microwave radiationThe material is recombined, and after the room temperature is recovered, the liquefied part can form a solid area again to crosslink the material. Therefore, by utilizing the pyrogenicity effect of the microwave, the heteropoly acid type polyion liquid self-healing material can heal at the fracture part automatically to form self-healing. The self-healing material can heal under the condition of medium and high fire after being radiated by microwave for 30 s.
Description
Technical Field
The invention belongs to the field of high polymer materials, and relates to a heteropolyacid polyion liquid self-healing material as well as a preparation method and application thereof. In particular to a heteropolyacid polyion liquid self-healing material based on microwave irradiation and a preparation method and application thereof.
Background
With the development of society, the application of polymer materials in the building field is wider, and the polymer materials are more and more commonly applied to the industries of aviation, daily use, medical health care and the like. However, in the application process of these materials, the materials themselves are damaged due to the influence of some factors or external factors, and the integrity and the mechanical and optical performance of the materials are further affected, which greatly reduces the service life of the materials. Therefore, it is currently of great importance to be able to detect and repair as early as possible the damages that occur in the material during use. The traditional repairing method is mainly used for repairing the surface of a material by adopting the technologies of welding, bonding, rivet fixing and the like, but the method can only repair macroscopic cracks on the surface of the material and cannot repair internal microcracks.
The self-healing material, as a novel intelligent material, can repair the damage caused by various factors in the using process, recover the function and prolong the service life, thereby receiving wide attention of researchers. Self-healing materials can be classified into external self-healing and intrinsic self-healing. The self-healing materials of the external-aid type are prepared by adding a healing agent to a matrix in advance, and the healing agent can be released when the materials are damaged, so as to fill the defects of the materials, and the healing times of the healing materials are limited. For intrinsic self-healing materials, when the material is broken, the fracture surface is difficult to heal only by self-physical interaction or chemical bond recombination, so that certain external stimuli such as light, electricity, heat or force needs to be applied to promote healing. Generally, it is most common at present to induce the healing of the damaged material by heating, which is used to accelerate the generation of mobile phase and increase the healing rate. Particularly, in the case of a material having a low glass transition temperature (Tg), when the temperature of heating exceeds the Tg, the free volume of the polymer chains at the fracture surface increases, and a sufficient mobile phase is present to promote fusion and entanglement of the polymer segments at the fracture surface. However, the conventional heating method is also interfered by various factors, such as operability of heating, non-uniformity of heating, etc., especially for self-healing materials in biological aspect, the damage to the biological molecules caused by direct heating may be caused.
The Microwave (MV) is an electromagnetic wave having a wavelength of 1nm to 1m and a frequency of 300MHz to 300GHz, and passes through a material made of nonpolar molecules such as glass, plastic, and porcelain almost without being absorbed, and absorbs the microwave and generates heat by itself in a material made of polar molecules. In recent decades, microwave technology has been used for the synthesis of fine organic materials catalyzed by polyoxometallate catalysts. In 2005, MarkJ Gronnow et al promoted heteropoly acid with microwaves to catalyze acetylation of acetyl chloride and acetic anhydride to methyl salicylate, and compared two heating methods, namely conventional heating and microwave heating, found that microwave heating can reduce the generation of reaction byproducts, and only a few minutes is needed for microwave heating, and a few hours is needed for conventional heating. The mechanism of microwave accelerated organic reaction is mainly as follows: the polar medium rotates at high speed with its alternating electric field, and thus a motion similar to "molecular stirring" is generated, and the material can be uniformly heated, which is also called as the heating effect of microwave. Currently, there are more and more fields in which microwave energy is absorbed by microwave responsive materials to perform specific functions, including: chemical reactivity and shape memory materials, but self-healing materials with no microwave response have been developed.
Disclosure of Invention
In order to overcome the defects of response conditions of self-healing materials in the prior art, the invention provides a microwave irradiation-based heteropoly acid type polyion liquid self-healing material and a preparation method and application thereof. The specific principle is that the heteropoly acid group is prepared into polyion liquid, the polyion liquid can be converted between rigid solid and liquid under the condition of microwave radiation, so that molecules between fracture surfaces of the material can flow again to heal, and the functional group is bonded into a polymer chain to serve as a crosslinking group, so that the polymer material has self-healing property under microwave radiation. The healing behavior does not depend on the external temperature, and the self-healing function of the damaged part can be realized under the condition of microwave radiation. Compared with the traditional self-healing property generated by changing the external temperature, the microwave irradiation healing material has the characteristics of high speed, easiness in operation and the like.
The heteropoly acid and the macromolecule containing sulfonated quaternary ammonium salt groups are used as raw materials, the macromolecule composite material crosslinked by heteropoly acid type ionic liquid groups is formed through electrostatic compounding, the ionic liquid part of the material has microwave responsiveness, the material can be liquefied in microwave radiation to realize recombination of the material, and the liquefied part can form a solid area again to crosslink the material after the room temperature is recovered. Therefore, by utilizing the pyrogenicity effect of the microwave, the heteropoly acid type polyion liquid self-healing material can heal at the fracture part automatically to form self-healing. The self-healing material can heal under the condition of medium and high fire after being radiated by microwave for 30 s.
The above purpose of the invention is realized by the following technical scheme:
a heteropolyacid polyion liquid self-healing material based on microwave irradiation has a general formula of- [ -CH2CH(COOCH2CH2N(CH3)2CH2CH2CH2SO3H-]n-r-[CH2CH(COOCH3)-]m-@
(XM12O4)n/l；
Wherein r represents random copolymerization, M is metal element tungsten or molybdenum, X is one of nonmetal elements phosphorus and silicon, n and M are both positive integers more than or equal to 20, and l is 3 or 4.
The cation part of the self-healing material is quaternary ammonium salt polymer with sulfonic acid group, and the anion part is polyoxometallate (heteropoly acid for short).
The heteropoly acid type polyion liquid self-healing material based on microwave irradiationThe preparation method of (1); 2- (dimethylamino) ethyl methacrylate with sulfonic acid group is taken as raw material, Azobisisobutyronitrile (AIBN) is taken as initiator, and chemical reaction is carried out in polar solvent, and finally the chemical formula of- [ -CH is obtained2CH(COOCH2CH2N(CH3)2CH2CH2CH2SO3H-]n-r-[CH2CH(COOCH3)-]mCompounds of formula (I), polymeric materials of this type and heteropoly acid compounds (e.g. [ XM ]12O4]n-(M is one of metal elements tungsten or molybdenum, X is one of nonmetal elements phosphorus and silicon, and n is 3 or 4)) to form [ -CH2CH(COOCH2CH2N(CH3)2CH2CH2CH2SO3H-]n-r-[CH2CH(COOCH3)-]m-@(XM12O4)n/lThe general formula of the heteropolyacid polyion liquid self-healing material is shown in the specification.
A preparation method of a heteropoly acid type polyion liquid self-healing material based on microwave irradiation; the specific reaction equation is as follows:
the method comprises the following specific steps:
s1: preparation of polymers containing tertiary amines: adding Methyl Acrylate (MA), 2- (dimethylamino) ethyl methacrylate (DEAEMA) and 1, 4-dioxane into a round-bottom flask, immersing the round-bottom flask in an oil bath at 80 ℃, stirring and refluxing to be viscous, cooling to room temperature, washing with petroleum ether for three times, and drying in vacuum to form a product A;
s2: preparation of sulfonic acid functionalized quaternary ammonium salt polymer: adding the product A, 1, 3-propane sultone and tetrahydrofuran into a round-bottom flask, immersing the round-bottom flask in an oil bath at 50 ℃, stirring for 24 hours, cooling to room temperature, washing with petroleum ether for three times, and drying in vacuum to obtain a product B;
s3: and mixing the obtained product B and polyoxometallate in N, N-dimethylformamide, reacting for 0.5h at 100 ℃, pouring into a polytetrafluoroethylene plate, and drying for 48h at 80 ℃ in vacuum to obtain a final product compound C.
In the step S1, the weight parts of MA are 10-30 parts, DEAEMA is 2-6 parts, and 1, 4-dioxane is 20-60 parts; in the step S2, the product A is 10-30 parts by weight, the 1, 3-propane sultone is 2-6 parts by weight, and the tetrahydrofuran is 20-60 parts by weight; the DEAEMA of the product B in step S3 is 3 to 6 parts (depending on the charge number of the heteropoly acid anion) and 1 part of polyoxometalate based on parts by mass.
Further, it is preferable that the molar ratio of MA to DEAEMA in the step S1 is 1:0.05 to 0.2.
Further, it is preferable that the molar ratio of the product A and the 1, 3-propane sultone in the step S2 is 1: 1-2.
Further, preferably, the polyoxometallate in the step S3 is H3PW12O40，H3PMo12O40，H4SiMo12O40Or H4SiW12O40Any one of the above.
Further, preferably, the molar ratio of the product B in step S3 to DEAEMA as its constituent components is DEAEMA: the polyoxometallate is mixed in DMF in a ratio of 3:1 or 4:1, depending on the valence of the polyoxometallate anion, i.e. when the anion valence is 3, the ratio is 3: 1.
The application of the heteropoly acid type polyion liquid self-healing material in realizing the self-healing function by utilizing microwave irradiation; the two sections of heteropoly acid type polyion liquid self-healing materials are aligned to prevent the materials from healing into a whole again within 30 seconds under microwave radiation of 2450MHz and 700- & ltSUB & gt 800W. The high-efficiency healing of the self-healing material is completed by utilizing the pyrogenicity effect of the microwave.
Compared with the prior art, the invention has the beneficial effects that:
the sulfonic acid functionalized polyion liquid heteropoly acid anions are repaired by utilizing the pyrogenic effect of microwaves, and the heteropoly acid type polyion liquid self-healing material provided by the invention can heal under the condition of medium and high fire after being radiated by microwaves for 30 seconds.
The heteropolyacid polyion liquid self-healing material provided by the invention has huge potential application in the field of rapid shape recovery and difficult direct heating, such as: flexible filler for human body, electronic components with complicated surrounding conditions, etc.
Drawings
The invention is further illustrated with reference to the following figures and examples:
FIG. 1 is an infrared spectrum of the self-healing material of heteropoly acid type polyion liquid in the invention. Wherein, the diagram a is PMAa synthesis (DMAEMA, MA and PMAa from top to bottom); panel b shows PMAS synthesis (PS, PMAa and PMAS from top to bottom); panel c shows PMAa synthesis (H in sequence from top to bottom)3PW12O40，PMAS@H3PW12O40)。
FIG. 2 is a nuclear magnetic hydrogen spectrum of the heteropoly acid type polyion liquid self-healing material. Wherein, the figure a is a nuclear magnetic hydrogen spectrum of PMAa; and the figure b is a nuclear magnetic hydrogen spectrum of PMAS.
FIG. 3 is a reaction mechanism diagram for microwave irradiation of the heteropolyacid type polyion liquid self-healing material in the invention.
Fig. 4 is a schematic view of the self-healing material prepared in example 1 of the present invention before and after healing. Wherein figure a is a broken two piece of material; figure b is the material after healing by microwave irradiation; fig. c shows the healed material of the load weight.
Detailed Description
The invention is described in more detail below with reference to specific examples, without limiting the scope of the invention. Unless otherwise specified, the experimental methods used in the present invention are conventional methods, and the experimental devices, materials, reagents, etc. used therein are commercially available.
Example 1
To a 50mL dry pear-shaped bottle, methyl acrylate MA (10g, 0.116mol), 2- (dimethylamino) ethyl methacrylate DEAEMA (2.15g, 0.0116mol), 1, 4-dioxane (20mL) and AIBN azobisisobutyronitrile (50mg, 0.3mmol) were added, heated in a water bath at 65 ℃ under stirring and refluxing for 1.0h, 50mg AIBN was added and heated to 80 ℃ under reflux, the solution was further heated under reflux until viscous, and after dilution with Tetrahydrofuran (THF), the mixture was precipitated into an excess amount of petroleum ether, and dissolution and precipitation were repeated three times to purify the solution. The product is dried under vacuum overnight to obtain methyl acrylate-diethylaminoethyl methacrylate copolymer, PMAa for short.
After 10g of PMAa and 1.56g of 1, 3-Propane Sultone (PS) were dissolved in tetrahydrofuran, they were put into a round-bottomed flask, heated and stirred in an oil bath at 50 ℃ to be viscous, and after diluting with tetrahydrofuran THF, the mixture was precipitated into an excess amount of petroleum ether, and the dissolution and precipitation were repeated three times to purify the resulting product. And (3) placing the product in a vacuum oven overnight until the mass is constant, thus obtaining the sulfonated polyion liquid, PMAS for short.
3mL of N, N-dimethylformamide DMF was added to dissolve 0.5g of PMAS in a beaker and dissolved by heating. 3mL of N, N-dimethylformamide was added to dissolve 0.468g of H3PW12O40Heating and dissolving in a small beaker, mixing the two, heating and stirring, then casting the obtained solution into a Polytetrafluoroethylene (PTFE) mould, evaporating the solvent at room temperature, and drying in vacuum at 80 ℃ for 48h to obtain PMAS @ PW12。
Microwave healing test: the prepared self-healing material sample is cut into two parts by a blade, placed in a microwave, and the healing condition is observed under microwave radiation of 2450MHz and 700-800W.
Healing materials typically take half an hour to heal using traditional heating, while microwave-responsive healing materials heal in only 30 seconds to achieve efficient healing.
The pyrogenic effect of microwave is utilized to repair the sulfonic acid functionalized polyion liquid heteropoly acid anion.
The embodiments described above are merely preferred embodiments of the invention, rather than all possible embodiments of the invention. Any obvious modifications to the above would be obvious to those of ordinary skill in the art, but would not bring the invention so modified beyond the spirit and scope of the present invention.
Claims (9)
1. AThe heteropolyacid polyion liquid self-healing material is characterized in that the general formula of the heteropolyacid polyion liquid self-healing material is represented by-CH2CH(COOCH2CH2N(CH3)2CH2CH2CH2SO3H-]n-r-[CH2CH(COOCH3)-]m-@(XM12O4)n/lR represents random copolymerization, M is metal element tungsten or molybdenum, X is one of nonmetal elements phosphorus and silicon, n and M are positive integers more than or equal to 20, and l is 3 or 4.
2. The method for preparing the heteropoly acid type polyion liquid self-healing material according to claim 1, wherein 2- (dimethylamino) ethyl methacrylate with sulfonic acid groups is used as a raw material, azobisisobutyronitrile is used as an initiator, and a chemical reaction is carried out in a polar solvent to finally obtain a compound with a chemical formula of- [ -CH2CH(COOCH2CH2N(CH3)2CH2CH2CH2SO3H-]n-r-[CH2CH(COOCH3)-]mCompounds of the formula, polymeric materials of this type and heteropoly acid compounds (e.g. [ XM ]12O4]n-(M is one of metal elements tungsten or molybdenum, X is one of nonmetal elements phosphorus and silicon, and n is 3 or 4)) to form [ -CH2CH(COOCH2CH2N(CH3)2CH2CH2CH2SO3H-]n-r-[CH2CH(COOCH3)-]m-@(XM12O4)n/lThe general formula of the heteropolyacid polyion liquid self-healing material is shown in the specification.
3. The preparation method of the heteropoly acid type polyion liquid self-healing material according to claim 2, wherein the specific reaction equation is as follows:
the method comprises the following steps:
s1: preparation of polymers containing tertiary amines: adding methyl acrylate, 2- (dimethylamino) ethyl methacrylate and 1, 4-dioxane into a round bottom flask, immersing the round bottom flask in an oil bath at the temperature of 80 ℃, stirring and refluxing to be viscous, cooling to room temperature, washing with petroleum ether for three times, and drying in vacuum to form a product A;
s2: preparation of sulfonic acid functionalized quaternary ammonium salt polymer: adding the product A, 1, 3-propane sultone and tetrahydrofuran into a round-bottom flask, immersing the round-bottom flask in an oil bath at 50 ℃, stirring for 24 hours, cooling to room temperature, washing with petroleum ether for three times, and drying in vacuum to obtain a product B;
s3: and mixing the obtained product B and polyoxometallate in N, N-dimethylformamide, reacting for 0.5h at 100 ℃, pouring into a polytetrafluoroethylene plate, and drying for 48h at 80 ℃ in vacuum to obtain a final product compound C.
4. The method according to claim 3, wherein in step S1, methyl acrylate is 10-30 parts, 2- (dimethylamino) ethyl methacrylate is 2-6 parts, and 1, 4-dioxane is 20-60 parts by weight; in the step S2, the product A is 10-30 parts by weight, the 1, 3-propane sultone is 2-6 parts by weight, and the tetrahydrofuran is 20-60 parts by weight; the product B in the step S3 comprises 3-6 parts of ethyl 2- (dimethylamino) methacrylate and 1 part of polyoxometallate by weight.
5. The method for preparing the heteropoly acid type polyion liquid self-healing material according to claim 4, wherein the molar ratio of methyl acrylate to 2- (dimethylamino) ethyl methacrylate in the step S1 is 1: 0.05-0.2.
6. The method for preparing the self-healing material of heteropolyacid-type polyion liquid according to claim 5, wherein the molar ratio of the product A and the 1, 3-propane sultone in the step S2 is 1: 1-2.
7. The method according to claim 6, wherein the polyoxometalate in step S3 is H3PW12O40，H3PMo12O40，H4SiMo12O40Or H4SiW12O40Any one of the above.
8. The method according to claim 7, wherein the product B in step S3 has a molar ratio of 2- (dimethylamino) ethyl methacrylate to 2- (dimethylamino) ethyl methacrylate: the polyoxometallate is mixed in N, N-dimethylformamide in a ratio of 3:1 or 4:1, depending on the valence of the polyoxometallate anion, i.e. when the anion valence is 3, the ratio is 3: 1.
9. The application of the heteropoly acid type polyion liquid self-healing material in claim 1, wherein two segments of the heteropoly acid type polyion liquid self-healing material are aligned to prevent the two segments of the heteropoly acid type polyion liquid self-healing material from being healed into a whole body again within 30 seconds under microwave radiation of 2450MHz and 700-.
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