CN116120487A - Alkaline solution decomposable nano-particle, self-healing polyacrylate composite material and preparation method thereof - Google Patents
Alkaline solution decomposable nano-particle, self-healing polyacrylate composite material and preparation method thereof Download PDFInfo
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 80
- 239000002131 composite material Substances 0.000 title claims abstract description 73
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000012670 alkaline solution Substances 0.000 title abstract description 11
- -1 alkaline earth metal salt Chemical class 0.000 claims abstract description 43
- 239000002904 solvent Substances 0.000 claims abstract description 38
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 29
- 239000011859 microparticle Substances 0.000 claims abstract description 27
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 10
- 239000012266 salt solution Substances 0.000 claims abstract description 9
- 239000002244 precipitate Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 229910052751 metal Inorganic materials 0.000 claims description 31
- 239000002184 metal Substances 0.000 claims description 31
- 150000003839 salts Chemical class 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical group [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 14
- 229920002125 Sokalan® Polymers 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 239000004584 polyacrylic acid Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 101000623895 Bos taurus Mucin-15 Proteins 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052749 magnesium Inorganic materials 0.000 claims description 12
- 239000011777 magnesium Substances 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 7
- 239000001110 calcium chloride Substances 0.000 claims description 7
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 7
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 239000012047 saturated solution Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 229910001424 calcium ion Inorganic materials 0.000 claims description 4
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 claims description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 229910001422 barium ion Inorganic materials 0.000 claims description 2
- 229940006460 bromide ion Drugs 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910001427 strontium ion Inorganic materials 0.000 claims description 2
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 230000006378 damage Effects 0.000 abstract description 16
- 239000000126 substance Substances 0.000 abstract description 15
- 239000000463 material Substances 0.000 description 31
- 239000008367 deionised water Substances 0.000 description 17
- 229910021641 deionized water Inorganic materials 0.000 description 17
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 230000008439 repair process Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011258 core-shell material Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000395 magnesium oxide Substances 0.000 description 6
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 208000018380 Chemical injury Diseases 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- DWLAVVBOGOXHNH-UHFFFAOYSA-L magnesium;prop-2-enoate Chemical compound [Mg+2].[O-]C(=O)C=C.[O-]C(=O)C=C DWLAVVBOGOXHNH-UHFFFAOYSA-L 0.000 description 1
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- 238000001291 vacuum drying Methods 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 238000005303 weighing Methods 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/26—Magnesium halides
- C01F5/30—Chlorides
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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
- C08F120/00—Homopolymers 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
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/04—Acids; Metal salts or ammonium salts thereof
- C08F120/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
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- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- 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
- C08K2003/162—Calcium, strontium or barium halides, e.g. calcium, strontium or barium chloride
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- C—CHEMISTRY; METALLURGY
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K2003/166—Magnesium halide, e.g. magnesium chloride
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- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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Abstract
The invention relates to a nanoparticle self-healing polyacrylate composite material and a preparation method thereof. The preparation method of the nanoparticle comprises the following steps: (1) Dissolving alkaline earth metal salt in a first solvent to obtain alkaline earth metal salt solution; (2) Adjusting the concentration, temperature and standing time of the alkaline earth metal salt solution to enable the alkaline earth metal salt to grow into nano microparticles; (3) Adding an ester compound to react with the nano-microparticles, so that the ester compound is coated on the surfaces of the nano-microparticles to form a water-insoluble shell layer so as to control the growth of the nano-microparticles; (4) Centrifuging, and washing the obtained precipitate with a second solvent to obtain the nano particles. The nano particles can be rapidly decomposed in alkaline solution, and have a repairing function, and the polyacrylate composite material prepared by the nano particles has good self-healing repairing performance after mechanical damage or chemical damage, and the mechanical performance and the chemical performance can be recovered to the level before damage.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a self-healing polyacrylate composite material and a preparation method thereof, wherein the nano particles can be decomposed by an alkaline solution.
Background
The polyacrylate is a high molecular polymer with acrylate as monomer, and its main chain is identical to polyacrylic acid, but its side chain is carboxylic acid cation salt. Most of the polyacrylate has the advantages of high modulus, high rigidity, good heat resistance and insulativity and the like, and is widely applied to the fields of electronics, machinery, constructional engineering and the like. In the field of constructional engineering, the water conservancy and hydropower science institute and the Yangtze river academy of sciences in China develop the acrylate chemical grouting material on the basis of the previous work in the middle and later period of 80 years, and the acrylate chemical grouting material has the functions and principles that under a certain initiator, the acrylate is polymerized into an insoluble acrylate gel polymer and the anti-seepage and plugging effects are realized, and the material is also applied to projects such as Yangtze river three gorges and the like.
However, while polyacrylate materials are used in a variety of fields, methods for repairing composite materials have been studied. Taking magnesium acrylate waterproof material used in the field of constructional engineering as an example, the polymer of the material is insoluble in water and has good adhesive force after being sprayed to form a film, but when the material is subjected to environments such as strong acid, strong alkali or high salt content, the polymer material is degraded to a certain extent, the waterproof capacity of the material is seriously affected, and at present, the problem can be overcome only by re-construction or other construction method changes, but the methods all need to spend a great deal of manpower and material resources, and the construction cost is greatly increased.
Accordingly, there is a need to provide a self-healing polyacrylate composite to address the repair problems after experiencing mechanical or chemical damage.
Disclosure of Invention
Based on the above, the invention aims to provide an alkaline solution-decomposable nanoparticle, a self-healable polyacrylate composite material and a preparation method thereof, wherein the polyacrylate composite material prepared from the alkaline solution-decomposable nanoparticle has good self-healing repair performance after mechanical damage or chemical damage, and the mechanical performance and the chemical performance can be restored to the levels before the damage.
In order to achieve the above purpose, the invention comprises the following technical scheme.
In one aspect, the present invention provides a method for preparing alkali solution decomposable nanoparticles, comprising the steps of:
(1) Dissolving alkaline earth metal salt in a first solvent to obtain alkaline earth metal salt solution;
(2) Adjusting the concentration, temperature and standing time of the alkaline earth metal salt solution to enable the alkaline earth metal salt to grow into nano microparticles;
(3) Adding an ester compound to react with the nano-microparticles, so that the ester compound is coated on the surfaces of the nano-microparticles to form a water-insoluble shell layer so as to control the growth of the nano-microparticles;
(4) Centrifuging, and cleaning the obtained precipitate with a second solvent to obtain the nano particles which can be decomposed by the alkaline solution.
On the other hand, the invention also provides alkaline solution-decomposable nano-particles, which are prepared by the preparation method of the alkaline solution-decomposable nano-particles.
In another aspect, the present invention also provides a self-healable polyacrylate composite comprising:
a. a divalent metal salt of polyacrylic acid as a main body of the composite material;
b. nanoparticles as self-healing factors;
the nano-particles are alkaline solution decomposable nano-particles according to the invention.
Furthermore, the self-healing polyacrylate composite material provided by the invention comprises two components a and b, and can also comprise other auxiliary components such as filler, stabilizer, cross-linking agent and the like which do not influence the self-healing property of the self-healing polyacrylate composite material.
On the other hand, the invention also provides a preparation method of the self-healing polyacrylate composite material, which comprises the following steps:
I. uniformly dispersing the nano particles in a third solvent to obtain a component I;
uniformly dispersing the polyacrylic acid divalent metal salt and other auxiliary components in a fourth solvent to obtain a component II;
and III, uniformly mixing the component I and the component II, and drying to obtain the self-healing polyacrylate composite material.
Or the preparation method of the self-healing polyacrylate composite material comprises the following steps:
I. uniformly dispersing the nano particles in a third solvent to obtain a component I;
uniformly dispersing the polymerization monomer of the polyacrylic acid divalent metal salt, an initiator and other auxiliary components in a fourth solvent to obtain a component II;
and III, uniformly mixing the component I and the component II, performing polymerization reaction, and drying to obtain the self-healing polyacrylate composite material.
Compared with the prior art, the nano-particle capable of decomposing by alkaline solution, the self-healing polyacrylate composite material and the preparation method have the following beneficial effects:
the invention utilizes the ester compound to coat the surface of the nanometer microparticles to form a shell layer which is insoluble in water so as to control the growth of the nanometer microparticles, and utilizes the coating of the ester compound to protect the metal salt nanoparticles inside, thereby preventing the agglomeration of the metal salt nanoparticles and the dissolution of the metal salt nanoparticles into water, and further preparing the nanoparticle material with a core-shell structure. The preparation method can well prepare the stable alkaline earth metal salt nanoparticle material with the core-shell structure, and the outer ester compound of the nanoparticle material can be decomposed under the alkaline condition, so that the nanoparticle material can be automatically and rapidly decomposed under the alkaline condition, the defect that the nanoparticle material cannot be decomposed into pollutants which are difficult to clean in the prior art is overcome, and the wider application of the nanoparticle material is realized.
The metal salt nano particles prepared by the method have good compatibility with polyacrylate composite materials, and can be used as nano repair particles and raw materials such as acrylic acid salt to prepare the self-healing polyacrylate composite materials, wherein the metal salt nano particles are uniformly dispersed in the composite materials, and the ester protective shell of the metal salt nano particles can automatically decompose under alkaline conditions and release divalent metal ions in the metal salt nano particles, so that the self-healing polyacrylate composite materials have excellent repair functions on chemical damages such as acid and alkali.
Therefore, after the self-healing polyacrylate composite material prepared by the invention is subjected to certain mechanical damage or chemical damage, the nanoparticle material in the material can release corresponding divalent metal ions, so that the composite material is subjected to complexation crosslinking again, and the mechanical property and the material property are recovered, thereby realizing self-healing repair, enabling the mechanical property and the chemical property to be recovered to the level before damage, and realizing simple and convenient environment-friendly self-healing repair of the acrylate polymer. The self-healing polyacrylate composite material prepared by the invention can be applied to electronic devices, mechanical equipment, building engineering or waterproof engineering, and has wide application prospect.
Drawings
FIG. 1 is an SEM photograph of a composite material prepared according to example 3 of the present invention.
Detailed Description
The technical scheme of the invention is further described by the following specific examples. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The terms "comprising" and "having" and any variations thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, apparatus, article, or device that comprises a list of steps is not limited to the elements or modules listed but may alternatively include additional steps not listed or inherent to such process, method, article, or device.
In the present invention, the term "plurality" means two or more. "and/or", describes an association relationship of an association object, and indicates that there may be three relationships, for example, a and/or B, and may indicate: a exists alone, A and B exist together, and B exists alone. The character "/" generally indicates that the context-dependent object is an "or" relationship.
In the present invention, the term "alkaline earth metal" means a group IIA metal of the periodic Table of elements.
In the present invention, the term "ester compound" means a dehydrated organic compound having a functional group ester group (-COO-) structure, which is formed by reacting an acid (carboxylic acid or inorganic oxy acid) with an alcohol.
In the present invention, the term "core-shell structure" means an ordered assembled structure formed by coating one material with another material by chemical bonds or other forces.
In the present invention, the term "saturated solution" means a solution obtained by adding a certain solute to a certain amount of solvent at a certain temperature, when the solute cannot be dissolved further.
In some embodiments of the present invention, there is provided a method for preparing alkali solution decomposable nanoparticles, comprising the steps of:
(1) Dissolving alkaline earth metal salt in a first solvent to obtain alkaline earth metal salt solution;
(2) Adjusting the concentration, temperature and standing time of the alkaline earth metal salt solution to enable the alkaline earth metal salt to grow into nano microparticles;
(3) Adding an ester compound to react with the nano-microparticles, so that the ester compound is coated on the surfaces of the nano-microparticles to form a water-insoluble shell layer so as to control the growth of the nano-microparticles;
(4) Centrifuging, and cleaning the obtained precipitate with a second solvent to obtain the nano particles which can be decomposed by the alkaline solution.
In some preferred embodiments, the cation of the alkaline earth metal salt is selected from the group consisting of: one or more of magnesium ion, calcium ion, strontium ion, and barium ion, more preferably: one or two of magnesium ions and calcium ions; the corresponding anions are selected from: one or more of chloride, bromide, fluoride, iodide, sulfate, nitrate, and carbonate, more preferably: one or more of chloride ion, bromide ion, fluoride ion, sulfate ion, nitrate ion. For example, the alkaline earth metal salts include, but are not limited to: magnesium chloride, calcium chloride, and the like.
In some preferred embodiments, the ester compound may be selected from: one or more of acetate, butyrate, phosphate, phosphite; the corresponding reaction alcohol is selected from: one or more of ethanol, butanol, ethylene glycol, and glycerol. For example, the ester compounds include, but are not limited to: butyl acetate, tributyl phosphite, and the like.
In some preferred embodiments, the alkaline earth metal salt and the ester compound are added in a mass ratio of 1:0.001 to 1000, more preferably 1:1 to 50, more preferably 1:3-25.
In some preferred embodiments, the concentration in step (2) is from 0.0001mol/L to the saturated solution concentration of the alkaline earth metal salt in the solvent; more preferably a saturated solution concentration.
In some preferred embodiments, the temperature in step (2) is from-50 ℃ to 300 ℃; more preferably 20 to 150 ℃, still more preferably 40 to 130 ℃, still more preferably 60 to 80 ℃.
In some preferred embodiments, the time in step (2) is from 0.5 hours to 3 days, preferably from 1 hour to 10 hours.
In some preferred embodiments, step (2) is specifically: slowly heating the alkaline earth metal salt solution to volatilize the solvent to enable the solution to reach a saturated solution state, so that the alkaline earth metal salt grows into nano microparticles; the slow heating is from room temperature to 60-80 ℃ for 0.5-2 hours.
In some preferred embodiments, the temperature of the reaction in step (3) is from 0 ℃ to the temperature of the solvent reflux, preferably from 60 ℃ to 80 ℃.
In some preferred embodiments, the time of the reaction in step (3) is from 0.5 to 72 hours, more preferably from 8 to 48 hours, more preferably from 16 to 32 hours, more preferably from 20 to 28 hours.
In some preferred embodiments, the first solvent is a polar nonaqueous solvent, which may be selected from: ethanol, butanol, acetone, tetrahydrofuran, pyridine, pyrrole, imidazole.
In some preferred embodiments, the second solvent is water or a water-based mixed solvent.
In some preferred embodiments, the nanoparticle has an average particle size of 1000000 nm to 0.1 nm, more preferably 10000 nm to 1 nm, most preferably 1000 nm to 10 nm.
The invention utilizes the ester compound to coat the surface of the nanometer microparticles to form a shell layer which is insoluble in water so as to control the growth of the nanometer microparticles, and utilizes the coating of the ester compound to protect the metal salt nanoparticles inside, thereby preventing the agglomeration of the metal salt nanoparticles and the dissolution of the metal salt nanoparticles into water, and further preparing the nanoparticle material with a core-shell structure. The preparation method can well prepare the stable alkaline earth metal salt nanoparticle material with the core-shell structure, and the outer ester compound of the nanoparticle material can be decomposed under the alkaline condition, so that the nanoparticle material can be automatically and rapidly decomposed under the alkaline condition, the defect that the nanoparticle material cannot be decomposed into pollutants which are difficult to clean in the prior art is overcome, and the wider application of the nanoparticle material is realized.
And the metal salt nano particles prepared by the method have good compatibility with polyacrylate composite materials, and can be used as nano repair particles and raw materials such as acrylic acid salt to prepare the self-healing polyacrylate composite materials, wherein the metal salt nano particles are uniformly dispersed in the composite materials, and the ester protective shell of the metal salt nano particles can automatically decompose under alkaline conditions and release divalent metal ions in the metal salt nano particles, so that the self-healing polyacrylate composite materials have excellent repair functions on acid-base chemical injury.
Accordingly, in further embodiments of the present invention there is provided a self-healable polyacrylate composite comprising:
a. a divalent metal salt of polyacrylic acid as a main body of the composite material;
b. nanoparticles as self-healing factors;
the nano-particles are alkaline solution decomposable nano-particles according to the invention.
The self-healing polyacrylate composite material provided by the invention comprises two components a and b, and can also comprise other auxiliary components such as filler, stabilizer, cross-linking agent and the like which do not influence the self-healing property of the self-healing polyacrylate composite material.
In some preferred embodiments, the divalent metal may be selected from: mg of 2+ 、Ca 2+ 、Zn 2+ 、Fe 2+ 、Cu 2+ 、Sr 2+ 、Ba 2+ More preferably from: mg of 2+ 、Ca 2+ 、Zn 2+ 、Cu 2+ One or more of the following. For example, the divalent metal salts of polyacrylic acid as the main body of the composite material include, but are not limited to: magnesium polyacrylate, calcium polyacrylate, and the like.
In some of these embodiments, the nanoparticles are present in the self-healable polyacrylate composite in an amount of 0.01% to 10%, more preferably 0.01% to 5%, more preferably 0.05% to 2%, more preferably 0.05% to 0.5%, more preferably 0.1% to 0.3%.
In some embodiments of the present invention, a method for preparing the self-healable polyacrylate composite material is also provided, comprising the steps of:
I. uniformly dispersing the nano particles in a third solvent to obtain a component I;
uniformly dispersing the polyacrylic acid divalent metal salt and other auxiliary components in a fourth solvent to obtain a component II;
and III, uniformly mixing the component I and the component II, and drying to obtain the self-healing polyacrylate composite material.
In some embodiments, the method of preparing the self-healable polyacrylate composite comprises the steps of:
I. uniformly dispersing the nano particles in a third solvent to obtain a component I;
uniformly dispersing the polymerization monomer of the polyacrylic acid divalent metal salt, an initiator and other auxiliary components in a fourth solvent to obtain a component II;
and III, uniformly mixing the component I and the component II, performing polymerization reaction, and drying to obtain the self-healing polyacrylate composite material.
In some preferred embodiments, the polymeric monomer of the divalent metal salt of polyacrylic acid consists of two components: (1) acrylic acid; and, (2) the corresponding divalent metal oxide or hydroxide. For example, the polymeric monomers of the divalent metal salts of polyacrylic acid are acrylic acid and magnesium oxide, or acrylic acid and magnesium hydroxide.
In some preferred embodiments, the initiator is selected from the group consisting of: one or more of azo compound, peroxy compound, persulfate, dichromate, and permanganate, and preferably persulfate.
In some preferred embodiments, the third solvent and the fourth solvent may be the same or different selected from: one or more of water, methanol, ethanol, ethylene glycol, glycerol, propanol, butanol, ethyl acetate, butyl acetate, tetrahydrofuran, furan, pyridine, pyrrole.
In some preferred embodiments, the polymerization reaction temperature is from 0℃to 150 ℃, more preferably from 10℃to 90℃and most preferably from 15℃to 60 ℃.
In some preferred embodiments, the polymerization time is from 0.5 hours to 72 hours, more preferably from 8 hours to 48 hours, more preferably from 16 hours to 32 hours, and more preferably from 20 hours to 28 hours.
In some preferred embodiments, the composite material is dried in a manner selected from the group consisting of: one or more of natural drying, heat drying, vacuum drying, and freeze drying, more preferably: and (5) naturally drying.
After the self-healing polyacrylate composite material prepared by the method is subjected to certain mechanical damage or chemical damage, the nanoparticle material in the material can release corresponding divalent metal ions, so that the composite material is subjected to complexation crosslinking again, and the mechanical property and the material property are recovered, thereby realizing self-healing repair, enabling the mechanical property and the chemical property to be recovered to the level before damage, and realizing simple and convenient environment-friendly self-healing repair of the acrylate polymer. The self-healing polyacrylate composite material prepared by the invention can be applied to electronic devices, mechanical equipment, building engineering or waterproof engineering, and has wide application prospect.
The following are specific examples. Room temperature refers to 25±5 ℃ unless otherwise specified below.
Example 1 preparation of alkaline solution decomposable core-shell structured nanoparticles
Weighing 20g of magnesium chloride, dissolving in 300mL of absolute ethyl alcohol, volatilizing the solvent by slow heating (heating to 70 ℃ from room temperature for 1 hour) to enable the solution to reach a saturated solution state, and enabling the magnesium chloride to grow into nano microparticles; then 70g of butyl acetate is added, and the mixture is stirred and refluxed for 24 hours at 70 ℃ to ensure that the butyl acetate is coated on the surface of the nano-microparticles to form a water-insoluble shell layer so as to control the growth of the nano-microparticles. Cooling after the reaction is finished, centrifuging by using a centrifugal machine, and cleaning the obtained precipitate with 100mL of deionized water for three times to obtain magnesium chloride nano particles with the particle size of 200-300 nanometers.
Example 2 preparation of alkaline solution decomposable core-shell structured nanoparticles
2g of calcium chloride is weighed and dissolved in 300mL of anhydrous tetrahydrofuran, and the solution is saturated by slowly heating (heating to 70 ℃ from room temperature for 1 hour) and volatilizing the solvent, so that the calcium chloride grows into nano microparticles; and adding 50g of tributyl phosphite, stirring and refluxing at 70 ℃ for reaction for 24 hours, so that the tributyl phosphite is coated on the surface of the nano-microparticles to form a water-insoluble shell layer so as to control the growth of the nano-microparticles. And cooling after the reaction is finished, centrifuging by using a centrifugal machine, and cleaning the obtained precipitate with 100mL of deionized water for three times to obtain calcium chloride nano particles with the particle size of 200-300 nanometers.
EXAMPLE 3 preparation of self-healing polyacrylate composite
(1) Uniformly dispersing 0.05g of nanoparticles (magnesium chloride nanoparticles prepared in example 1) in 1mL of water to obtain component 1;
(2) Uniformly stirring 14g of acrylic acid and 22mL of deionized water to obtain a component 2;
(3) Uniformly stirring 4g MgO, 0.014g sodium persulfate and 22mL deionized water to obtain a component 3;
(4) After component 1, component 2 and component 3 were mixed uniformly, poured into a mold and reacted at room temperature for 24 hours.
(5) And (3) taking the gel obtained after the reaction in the step (4) out of the die, soaking in deionized water for 12 hours to remove unreacted raw materials, and finally naturally drying the gel to obtain the self-healing magnesium polyacrylate composite material, wherein an SEM (scanning electron microscope) picture of the self-healing magnesium polyacrylate composite material is shown in figure 1.
EXAMPLE 4 preparation of self-healing polyacrylate composite
(1) Uniformly dispersing 0.05g of nanoparticles (calcium chloride nanoparticles prepared in example 2) in 1mL of water to obtain component 1;
(2) Uniformly stirring 14g of acrylic acid and 22mL of deionized water to obtain a component 2;
(3) Uniformly stirring 4g MgO, 0.014g sodium persulfate and 22mL deionized water to obtain a component 3;
(4) After component 1, component 2 and component 3 were mixed uniformly, poured into a mold and reacted at room temperature for 24 hours.
(5) And (3) taking the gel obtained after the reaction in the step (4) out of the die, soaking the gel in deionized water for 12 hours to remove unreacted raw materials, and finally, naturally drying the gel to obtain the self-healing magnesium polyacrylate composite material.
Comparative example 1
(1) Uniformly stirring 14g of acrylic acid and 22mL of deionized water to obtain a component 2;
(2) Uniformly stirring 4g MgO, 0.014g sodium persulfate and 22mL deionized water to obtain a component 3;
(3) After component 2 and component 3 were mixed uniformly, poured into a mold and reacted at room temperature for 24 hours.
(4) And (3) taking the gel obtained after the reaction in the step (3) out of the die, soaking the gel in deionized water for 12 hours to remove unreacted raw materials, and finally, naturally drying the gel to obtain the magnesium polyacrylate composite material.
Comparative example 2
(1) Uniformly dispersing 0.05g of magnesium chloride in 1mL of water to obtain a component 1;
(2) Uniformly stirring 14g of acrylic acid and 22mL of deionized water to obtain a component 2;
(3) Uniformly stirring 4g MgO, 0.014g sodium persulfate and 22mL deionized water to obtain a component 3;
(4) After component 1, component 2 and component 3 were mixed uniformly, poured into a mold and reacted at room temperature for 24 hours.
(5) And (3) taking the gel obtained after the reaction in the step (4) out of the die, soaking the gel in deionized water for 12 hours to remove unreacted raw materials, and finally, naturally drying the gel to obtain the magnesium polyacrylate composite material.
Comparative example 3
(1) Uniformly dispersing 0.05g of calcium chloride in 1mL of water to obtain a component 1;
(2) Uniformly stirring 14g of acrylic acid and 22mL of deionized water to obtain a component 2;
(3) Uniformly stirring 4g MgO, 0.014g sodium persulfate and 22mL deionized water to obtain a component 3;
(4) After component 1, component 2 and component 3 were mixed uniformly, poured into a mold and reacted at room temperature for 24 hours.
(5) And (3) taking the gel obtained after the reaction in the step (4) out of the die, soaking the gel in deionized water for 12 hours to remove unreacted raw materials, and finally, naturally drying the gel to obtain the magnesium polyacrylate composite material.
Example 5
Cutting the magnesium polyacrylate composite materials prepared in examples 3-4 and comparative examples 1-3 into test pieces with a thickness of 3mm and a length of 2cm×1.5cm, immersing the test pieces in aqueous sodium hydroxide solution (0.1 mol/L) for 2 hours, immersing the test pieces in clear water for 1 hour, and performing performance test on the test pieces, wherein the tensile strength is measured at room temperature by using an electronic universal tester as shown in Table 1, the gauge length of the test pieces is specifically set to 10mm in the experimental test, and the tensile rate of the clamp is specifically set to 5mm·min in the experimental test -1 The test piece traits were obtained by visual inspection. The original test piece was comparative example 1 which was not treated with alkali liquor.
TABLE 1 tensile Strength and shape of test pieces
As can be seen from the table, the self-healable magnesium polyacrylate composite material prepared in the examples 3 to 4 of the present invention has good property recovery and still maintains stronger tensile strength after the material prepared in the examples is self-repaired in clear water for 1 hour after chemical damage compared with the magnesium polyacrylate composite material prepared in the comparative example 1, and the material prepared in the comparative example has great change in property and tensile strength, which indicates that the self-healable magnesium polyacrylate composite material prepared in the present invention has good self-repair function after chemical damage.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (17)
1. A method of preparing nanoparticles comprising the steps of:
(1) Dissolving alkaline earth metal salt in a first solvent to obtain alkaline earth metal salt solution;
(2) Adjusting the concentration, temperature and standing time of the alkaline earth metal salt solution to enable the alkaline earth metal salt to grow into nano microparticles;
(3) Adding an ester compound to react with the nano-microparticles, so that the ester compound is coated on the surfaces of the nano-microparticles to form a water-insoluble shell layer so as to control the growth of the nano-microparticles;
(4) Centrifuging, and washing the obtained precipitate with a second solvent to obtain the nano particles.
2. The method of claim 1, wherein the cation of the alkaline earth metal salt is selected from the group consisting of: one or more of magnesium ion, calcium ion, strontium ion, and barium ion, more preferably: one or two of magnesium ions and calcium ions; the corresponding anions are selected from: one or more of chloride, bromide, fluoride, iodide, sulfate, nitrate, and carbonate, more preferably: one or more of chloride ion, bromide ion, fluoride ion, sulfate ion, nitrate ion.
3. The method of claim 1, wherein the ester compound is selected from the group consisting of: one or more of acetate, butyrate, phosphate, phosphite; the corresponding reaction alcohol is selected from: one or more of ethanol, butanol, ethylene glycol, and glycerol.
4. The method of preparing nanoparticles according to claim 1, wherein the alkaline earth metal salt is magnesium chloride and/or calcium chloride; and/or the number of the groups of groups,
the ester compound is butyl acetate and/or tributyl phosphite.
5. The method for producing a nanoparticle according to any one of claims 1 to 4, wherein the alkaline earth metal salt and the ester compound are fed in a mass ratio of 1:0.001 to 1000, more preferably 1:1 to 50, more preferably 1:3-25.
6. The method for producing nanoparticles according to any one of claims 1 to 4, wherein the concentration in step (2) is from 0.0001mol/L to the saturated solution concentration of the alkaline earth metal salt in the solvent; more preferably a saturated solution concentration.
7. The method of producing nanoparticles according to any one of claims 1 to 4, wherein the temperature in step (2) is from-50 ℃ to 300 ℃; and/or the number of the groups of groups,
the time in the step (2) is 0.5 hour-3 days; and/or the number of the groups of groups,
the temperature of the reaction in step (3) is from 0 ℃ to the temperature of the solvent reflux; and/or the number of the groups of groups,
the reaction time in the step (3) is 0.5 to 72 hours, more preferably 8 to 48 hours; and/or the number of the groups of groups,
the first solvent is a polar nonaqueous solvent selected from the group consisting of: one or more of ethanol, butanol, acetone, tetrahydrofuran, pyridine, pyrrole and imidazole; and/or the number of the groups of groups,
the second solvent is water or a mixed solvent taking water as a main body; and/or the number of the groups of groups,
the average particle diameter of the nanoparticles is 1000000 nm to 0.1 nm, more preferably 10000 nm to 1 nm, most preferably 1000 nm to 10 nm.
8. Nanoparticles prepared by the preparation method according to any one of claims 1 to 7.
9. Use of the nanoparticle of claim 8 as a self-healing factor in the preparation of a self-healable polyacrylate composite.
10. A self-healable polyacrylate composite comprising:
a. a divalent metal salt of polyacrylic acid as a main body of the composite material;
b. nanoparticles as self-healing factors;
the nanoparticle is the nanoparticle of claim 8.
11. The self-healable polyacrylate composite according to claim 10, wherein the self-healable polyacrylate composite further comprises additional auxiliary components that do not affect its self-healing properties; the auxiliary components comprise filler, stabilizer and cross-linking agent.
12. The self-healable polyacrylate composite according to claim 10, wherein the divalent metal is selected from the group consisting of: mg of 2+ 、Ca 2+ 、Zn 2+ 、Fe 2+ 、Cu 2+ 、Sr 2+ 、Ba 2+ More preferably from: mg of 2+ 、Ca 2+ 、Zn 2+ 、Cu 2+ One or more of the following.
13. A self-healing polyacrylate composite according to claim 12, wherein the divalent metal salt of polyacrylic acid that is the main body of the composite is magnesium polyacrylate, calcium polyacrylate.
14. A self-healable polyacrylate composite according to any one of claims 10 to 13, wherein the nanoparticles are present in the self-healable polyacrylate composite in an amount of 0.01% to 10%, more preferably 0.01% to 5%, more preferably 0.05% to 2%.
15. A method of preparing a self-healing polyacrylate composite according to any one of claims 10 to 14, comprising the steps of:
I. uniformly dispersing the nano particles in a third solvent to obtain a component I;
uniformly dispersing the polyacrylic acid divalent metal salt and other auxiliary components in a fourth solvent to obtain a component II;
III, uniformly mixing the component I and the component II, and drying to obtain the self-healable polyacrylate composite material;
or the preparation method of the self-healing polyacrylate composite material comprises the following steps:
I. uniformly dispersing the nano particles in a third solvent to obtain a component I;
uniformly dispersing the polymerization monomer of the polyacrylic acid divalent metal salt, an initiator and other auxiliary components in a fourth solvent to obtain a component II;
and III, uniformly mixing the component I and the component II, performing polymerization reaction, and drying to obtain the self-healing polyacrylate composite material.
16. The method for preparing a self-healing polyacrylate composite according to claim 15, wherein the polymerized monomer of the divalent metal polyacrylate consists of two components: (1) acrylic acid; and, (2) the corresponding divalent metal oxide or hydroxide.
17. The method of preparing a self-healing polyacrylate composite according to claim 15 or 16, wherein the initiator is selected from the group consisting of: one or more of azo compounds, peroxy compounds, persulfates, dichromates, permanganates; and/or the number of the groups of groups,
the third solvent and the fourth solvent may be the same or different selected from: one or more of water, methanol, ethanol, ethylene glycol, glycerol, propanol, butanol, ethyl acetate, butyl acetate, tetrahydrofuran, furan, pyridine, pyrrole; and/or the number of the groups of groups,
the temperature of the polymerization reaction is 0-150 ℃, more preferably 10-90 ℃ and most preferably 15-60 ℃; and/or the number of the groups of groups,
the polymerization time is 0.5 to 72 hours, more preferably 8 to 48 hours.
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