CN116948381A - Self-assembled micro-nano structure Cu 2 O particles and method for preparing same - Google Patents
Self-assembled micro-nano structure Cu 2 O particles and method for preparing same Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 25
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- 239000000412 dendrimer Substances 0.000 claims abstract description 131
- 229920000736 dendritic polymer Polymers 0.000 claims abstract description 131
- 238000003756 stirring Methods 0.000 claims abstract description 82
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 150000001412 amines Chemical class 0.000 claims abstract description 38
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 37
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- 150000001879 copper Chemical class 0.000 claims abstract description 25
- 239000012266 salt solution Substances 0.000 claims abstract description 25
- 238000002360 preparation method Methods 0.000 claims abstract description 17
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- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 40
- 239000007864 aqueous solution Substances 0.000 claims description 37
- 239000008367 deionised water Substances 0.000 claims description 33
- 229910021641 deionized water Inorganic materials 0.000 claims description 33
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- 229910001431 copper ion Inorganic materials 0.000 claims description 9
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
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- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical group OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 claims description 3
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- JVXYHUCXFLBBGA-UHFFFAOYSA-N 16-phosphonohexadecanoic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCP(O)(O)=O JVXYHUCXFLBBGA-UHFFFAOYSA-N 0.000 claims description 2
- JJSYPAGPNHFLML-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;3-sulfanylpropanoic acid Chemical group OC(=O)CCS.OC(=O)CCS.OC(=O)CCS.CCC(CO)(CO)CO JJSYPAGPNHFLML-UHFFFAOYSA-N 0.000 claims description 2
- SYFTUNQVCGSBOV-UHFFFAOYSA-N 6-phosphonohexanoic acid Chemical group OC(=O)CCCCCP(O)(O)=O SYFTUNQVCGSBOV-UHFFFAOYSA-N 0.000 claims description 2
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- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims description 2
- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 claims description 2
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- IGWHDMPTQKSDTL-JXOAFFINSA-N TMP Chemical compound O=C1NC(=O)C(C)=CN1[C@H]1[C@H](O)[C@H](O)[C@@H](COP(O)(O)=O)O1 IGWHDMPTQKSDTL-JXOAFFINSA-N 0.000 claims 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 9
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
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- 238000001338 self-assembly Methods 0.000 description 3
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 2
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
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- MORLYCDUFHDZKO-UHFFFAOYSA-N 3-[hydroxy(phenyl)phosphoryl]propanoic acid Chemical compound OC(=O)CCP(O)(=O)C1=CC=CC=C1 MORLYCDUFHDZKO-UHFFFAOYSA-N 0.000 description 1
- 239000012691 Cu precursor Substances 0.000 description 1
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
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- 125000000539 amino acid group Chemical group 0.000 description 1
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- 235000008429 bread Nutrition 0.000 description 1
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- 239000011247 coating layer Substances 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
- A01N59/20—Copper
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/003—Dendrimers
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2248—Oxides; Hydroxides of metals of copper
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Pest Control & Pesticides (AREA)
- Textile Engineering (AREA)
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- Polymers & Plastics (AREA)
- Agronomy & Crop Science (AREA)
- Zoology (AREA)
- General Chemical & Material Sciences (AREA)
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- Polyethers (AREA)
Abstract
The present application relates toSelf-assembled micro-nano structure Cu 2 O particles and preparation method thereof, and self-assembled micro-nano structure Cu 2 The O particles are made of a plurality of nano-scale Cu 2 The O particles are assembled to form micron-sized spheres, wherein the assembly utilizes physical or chemical forces between dendritic polymers; the preparation method comprises the following steps: first respectively A 2 Monomers and B 3 The monomer adopts A 2 +B 3 Synthesizing dendritic polymer, adding dendritic polymer into polyether amine water solution to form homogeneous transparent reaction system, dropping copper salt solution into the reaction system while stirring, stirring for some time, dropping ascorbic acid water solution into the reaction system while stirring, and stirring to obtain self-assembled micro-nano Cu structure 2 And O particles. The method is simple, and the self-assembled micro-nano structure Cu is prepared 2 The O particles have excellent application performance of nanometer size and good dispersibility of micrometer size, and can keep lasting stability in the use process.
Description
Technical Field
The application belongs to the technical field of self-assembled micro-nano structures, and relates to a self-assembled micro-nano structure Cu 2 O particles and a preparation method thereof, in particular to dendritic polyester coated and induced assembled micro-nano structure Cu 2 O particles and a preparation method thereof.
Background
Cu 2 O is an excellent p-type semiconductor material, cu 2 The O nano-particles have wide application in catalysis, gas sensing, antibiosis and the like.
With the development of nanotechnology, single nano-sized particulate materials have failed to meet the demands of scientific research and practical applications. The agglomeration phenomenon of the nano-scale particles easily occurs in the use process, the specific surface area of the material is reduced, and the use performance of the material is affected. Typically, nano-scale Cu 2 O is very easily oxidized into CuO in moist air or under the condition of long-term heating, so that the problems of poor chemical stability, easy agglomeration and difficult dispersion exist in the use process. Preparation of uniformly dispersed Cu with long-acting and stable chemical property 2 O is always a difficult problem to overcome in academia and industry.
In recent years, researchers have found that constructing micro-nano structures can reduce the degree of agglomeration of nanomaterials,the nanometer material has the advantages of nanometer material, and integrates the characteristics of good stability and easy separation of micron or submicron material. For example, the prior art (j.am.chem.soc., 2014, 136:15781-15786.) uses tyrosine and other polar amino acid residues on fibroin as sites for adsorption of iron ions, generating Fe with micro-nano structure by self-assembly forces of fibroin polypeptide chains 2 O 3 Hybrid materials have good catalytic properties for water oxidation due to extremely high porosity. The construction of the micro-nano structure of the nano material mainly depends on the surfactant used in the preparation process of the material.
Dendrimers are stabilizers and dispersants for synthetic metal nanomaterials or metal semiconductor nanomaterials. In the process of preparing the nano material by a reduction method, the dendritic polymer is dispersed in a solution system, and the dendritic polymer can form a coating layer on the surface of the metal nano particles, so that the nano particles with uniform sizes can be synthesized. There are many reports of this type (petroleum journal, 2017,33 (4): 605-618.), but the nanoparticles formed are smooth and uniform surface nanoparticles, and no self-assembly of the nanoparticles occurs to finally form micro-nano structured nanoparticle aggregates.
Prior art (adv.funct.mate., 2010,20,43-49.) micro-nano structured CuO was prepared with dendrimers as surface modifiers, in which hyperbranched-Cu was formed 2 O intermediate, cuO is prepared after further oxidation, but in hyperbranched-Cu 2 The O intermediate stage does not form a micro-nano structure. Wherein the researchers used a class 2 dendrimer (G 2 Td(COOH) 16 ) As a synthetic template agent of CuO, the polymer is internally composed of benzene rings, and the terminal functional group is-COOH. During the experiment, the researchers performed a test with Cu (NO 3 ) 2 As Cu precursor, at G 2 Td(COOH) 16 Adding NaBH to tetrahydrofuran solution 4 As a reducing agent, cu is first added 2+ Reduction to Cu, G 2 Td(COOH) 16 Has the effect of maintaining stable dispersion of particles, but does not prevent oxidation of Cu, so Cu is oxygen after short Cu atom state under stirring for 2 hrFormation of Cu 2 O, and then the CuO assembled by primary particles is finally obtained under the reaction condition of stirring at 65 ℃ for 2 hours. Preparation of Cu 2 The O micro-nano structure has the difficulty of nano-scale Cu 2 O is very easily oxidized to CuO in humid air or under long-term heating, thus maintaining Cu under general conditions 2 O-persistence stability is very difficult.
Therefore, a Cu having a micro-nano structure and capable of maintaining long-term stability was studied 2 The nanoparticle aggregate in the O state has very important significance.
Disclosure of Invention
The application aims to solve the problems in the prior art and provides a self-assembled micro-nano structure Cu induced by dendritic polyester 2 O particles and method for preparing same, cu synthesized by method 2 The O particles have excellent application performance of nanometer size, have good dispersibility of micrometer size, and can maintain long-term stability in the use process.
In order to achieve the above purpose, the application adopts the following technical scheme:
self-assembled micro-nano structure Cu 2 O particles made of a plurality of nano-sized Cu 2 The O particles are assembled to form micron-sized spheres, wherein the assembly utilizes physical or chemical forces between dendritic polymers;
the structural formula of the dendritic polymer is as follows:
wherein the wavy line represents a dendritic polymer which can be further reacted to form further branching units, R 1 -A-R 2 Raw material A for the Synthesis of dendrimers 2 A monomer, wherein the monomer is a monomer,raw material B for the Synthesis of dendrimers 3 Type monomer, dashed circle represents two radical bonds.
The self-assembled micro-nano structure Cu of the application 2 The O particles not only have excellent application performance of nanometer size, but also have stability of micrometer size and good dispersibility, and the self-assembled micro-nano structure Cu of the application 2 Antibacterial Properties of the O particles and commercially available Cu having a particle size of 100nm 2 As can be seen from comparison of the antibacterial properties of O powder, the self-assembled micro-nano structure Cu of the application 2 O particles are smaller than commercially available Cu having a particle size of 100nm 2 The O powder has higher antibacterial rate; cu of the application 2 The XRD characteristic peaks of the O particles before and after spinning were not significantly increased, decreased or shifted, indicating that good stability was maintained during use.
As a preferable technical scheme:
the self-assembled micro-nano structure Cu 2 O particles, nano-scale Cu 2 The average particle diameter of the O particles is 5-10 nm, and the average particle diameter of the micron-sized spheres is 0.6-1.6 mu m.
The self-assembled micro-nano structure Cu 2 O particles, the branching degree DB of the dendritic polymer is 0.45-0.6, and the number average molecular weight Mn is 30000-60000 g/mol.
The self-assembled micro-nano structure Cu 2 O particles, A 2 End group R of monomer 1 、R 2 Selected from the group consisting of-SH, -COOH, -OH, -PO (OH) 2 AndB 3 end group R of monomer 3 Selected from the group consisting of-SH, -COOH and-OH.
The self-assembled micro-nano structure Cu 2 O particles, A 2 End group R of monomer 1 、R 2 Are all-COOH, or one is-COOH and the other is-PO (OH) 2 Or one of them is-COOH and the other isB 3 End group R of monomer 3 Are both-SH, or are both-OH;
alternatively, A 2 End group R of monomer 1 、R 2 Are all-SH, or are all-OH, B 3 End group R of monomer 3 Are all-COOH.
The self-assembled micro-nano structure Cu 2 O particles, A 2 The monomer being 6-phosphonohexanoic acid11-phosphonoundecanoic acid +.>16-phosphonohexadecanoic acid2, 6-naphthalenedicarboxylic acid +.>Polyethylene glycol dicarboxylic acid->(polymerization degree is 3-10), 1, 11-undecanedicarboxylic acid +.>CEPPA (2-carboxyethylphenyl phosphinic acid)B 3 The monomer is trimethylolpropane tri (3-mercaptopropionate)>Cyanuric acidTMP (trimethylolpropane)/(TMP)>THEIC (tris (2-hydroxyethyl) isocyanurate)>
Alternatively, A 2 The monomer is 1, 2-ethanedithiol HSCH 2 CH 2 SH, 1, 3-propanedithiol, 1, 4-butanedithiol, polyethylene glycol(average molecular weight Mn is 300-8000), B 3 The monomer is trimesic acid +.>
The self-assembled micro-nano structure Cu 2 O particles, self-assembled micro-nano structure Cu 2 The specific surface area of the O particles is 30-80 m 2 ·g -1 The dendritic polymer content is 22.2 to 24.2 wt.%.
The application also provides a method for preparing the self-assembled micro-nano structure Cu 2 The method of O particles is firstly as described in A 2 Monomer and said B 3 The monomer is A as raw material 2 +B 3 Synthesizing dendritic polymer, adding dendritic polymer into polyether amine water solution to form homogeneous transparent reaction system, dropping copper salt solution into the reaction system while stirring, stirring for some time, dropping ascorbic acid water solution into the reaction system while stirring, and stirring to obtain self-assembled micro-nano Cu structure 2 And O particles.
The application adopts dendritic polymers as surface modifying agents, and Cu is prepared by the action of physical or chemical force among the dendritic polymers 2 O nanoparticles assemble into spherical micro-nano structured spheres (the assembly appears to be micron-sized overall, but there are many nano-sized Cu's in it) 2 Assembled from O particles).
The synthetic route for the dendrimer is as follows:
in the method, in the process of the application,the wavy line represents a dendritic polymer which can be further reacted to form further branching units, A during the synthesis reaction 2 R on monomer molecule 1 Radicals and R 2 All radicals being bound to B 3 R on monomer 3 The radicals being chemically reacted and possibly B 3 R on monomer 3 The groups do not undergo any chemical reaction, so that terminal units (T), linear units (L) and dendrimer units (D) in the dendrimer are formed, and the active functional groups exposed outside in the outermost layer of the whole dendrimer are caused to have R 1 、R 2 And R is 3 A group;
the dendrimers used in the present application have a molecular weight of Cu 2 The active functional groups exposed on the outermost layer of the dendrimer during synthesis have R at the binding sites of O action 1 、R 2 And R is 3 The incorporation of the radical, polyetheramine co-stabilizer, also provides-NH 2 All four functional groups being Cu 2 O provides stable nucleation sites, so that many nano-scale primary particles can be formed on the dendritic polymer during synthesis, and physical or chemical interaction between dendritic polyester molecular chains is a driving force for self-assembly, finally promoting Cu 2 The agglomeration of O primary nanoparticles forms micrometer-sized samples, which is just the application of dendrimers with one binding site to finally synthesize Cu 2 Micron Cu assembled by O primary nano particles 2 O particles, also of the pair of binding sites Cu 2 Stable anchoring of O improves Cu 2 Stability of application of O.
FIG. 3 shows the synthesis of micro-nano structure Cu by dendritic polymer 2 O is schematically represented by the mechanism. Dendritic polymers have abundant polar groups and can coordinate with metal ions to form complexes. Polyetheramines play 2 roles in the present application: 1) In the process of dissolving the dendritic polymer into deionized water, the pH of the deionized water is adjusted to be in an alkaline range, so that the solubility of the dendritic polymer in the deionized water is improved; 2) The amine terminal group of the polyether amine is also Cu 2+ Providing a strong polar binding site. Dendritic polymer in aqueous solution of polyetheramineIn a form similar to micelles. When Cu is added 2+ After the solution, cu 2+ Complex is formed by coordinating with abundant polar groups in the dendritic polymer and fixing on the molecular chain of the dendritic polymer, and at the same time, cu 2+ Also coordinates with carboxyl which is originally coordinated with amino, resulting in the falling of part of polyether amine, thus reducing the solubility of the complex in the solution and precipitating, and adding Cu 2+ The complex is gradually assembled to obtain the strip-shaped morphology feature. They are used as Cu 2+ By slow release of Cu 2+ While preventing the reaction rate from being too fast. When ascorbic acid reducing agent is added, cupric ions are reduced into cuprous ions, and the interaction force in the original banded complex is changed, so that the complex is decomposed, and Cu is dissolved + Remain immobilized on the molecular chains of the dendrimer, so that the complex exists in solution in a disordered solid state. In alkaline environment, cu + The CuOH cannot exist stably and can react as shown in the formula 2-1, and CuOH is firstly obtained, and CuOH is unstable and then is hydrolyzed to obtain nano-sized Cu 2 O primary particles (formula 2-2). During the reduction process, the molecular chain of the dendritic polymer is adsorbed to Cu through coordination interaction 2 O primary particles, cu coated by dendritic polymer and polyetheramine is formed 2 O nanospheres. The nanospheres have high specific surface area and instability, and meanwhile polyether amine molecules used for stabilization are adsorbed on the outer layer only through electrostatic interaction, so that the nanospheres are very easy to fall off, and then the free nanospheres are further assembled into larger hybrid microspheres to form a stacked structure so as to further reduce the energy of a system. Finally obtaining micron-sized Cu assembled by nanometer-sized primary particles 2 O microspheres.
Cu + +OH - ＝CuOH (2-1)
2CuOH＝Cu 2 O+H 2 O (2-2)
As a preferable technical scheme:
the method comprises the following specific steps:
(1) Synthesizing a dendritic polymer;
firstly, the A is carried out according to the molar ratio of 3:1-2:5-8 2 Monomer, B 3 After mixing the monomers, heating to 120-190 ℃, and preserving heat for a period of time until more than 80% of H 2 Evaporating O, vacuumizing to 0.098MPa, heating to 145-202 ℃, and reacting at a temperature and pressure maintaining for 2-2.5 h to obtain dendritic polymer (the dendritic polymer is transparent viscous liquid just after the reaction is finished, cooling is needed to obtain transparent solid, and after the transparent solid is completely cooled and shaped, crushing the transparent solid by a stainless steel crusher to obtain a white powdery sample);
(2) Preparing a polyether amine aqueous solution;
adding polyether amine into deionized water, magnetically stirring at 20-30 ℃ and fully dissolving to form polyether amine aqueous solution;
(3) The stirring speed is kept unchanged, the temperature is kept unchanged, and the dendritic polymer is added into the polyether amine aqueous solution to form a uniform and transparent reaction system;
(4) Dropwise adding copper salt solution into the reaction system through a constant pressure dropping funnel under the stirring condition, and continuously stirring for 1h;
(5) Dropping the ascorbic acid water solution into the reaction system through a constant pressure dropping funnel under the stirring condition, and continuing stirring for 2-3 h;
(6) Post-treatment;
suction filtering (using vacuum pump), washing (three times of washing with deionized water and absolute ethyl alcohol respectively), and drying (drying overnight in vacuum oven at 60deg.C) to obtain self-assembled micro-nano structure Cu 2 And O particles.
In the method, in the step (2), the polyetheramine is more than one of polyetheramine D230, polyetheramine M-600 and polyetheramine T-403; the mass ratio of the polyetheramine to the deionized water is 1:2-6; the stirring speed is 300-400 r/min. Increasing the concentration of polyetheramine in deionized water in this step increases the pH of the deionized water, facilitating the formation of smaller nano-sized Cu' s 2 Primary particles of O.
In the method described above, in the step (3), the mass ratio of the dendritic polymer to the polyether amine is 1:10-20.
In the method, in the step (4), the stirring speed is 300-400 r/min; the concentration of the copper salt solution is 0.125-0.175M, and the copper salt solution consists of cupric acetate monohydrate and deionized water; the dropping speed is 3-4 seconds/drop; the mass ratio of the copper salt solution to the dendritic polymer is 1:2-3.
In the method, in the step (5), the stirring speed is 300-400 r/min; the concentration of the ascorbic acid aqueous solution is 0.625-0.875M; the molar ratio of the ascorbic acid to the copper ions in the reaction system is 1:2; the dropping rate is 3-4 seconds/drop. The faster the stirring speed in this step, the higher the ascorbic acid concentration, and the faster the dropping speed, the smaller the size of the produced nano-sized primary particles and the micro-sized assembly particles.
The beneficial effects are that:
(1) The self-assembled micro-nano structure Cu of the application 2 O particles are smaller than commercially available Cu having a particle size of 100nm 2 The O powder has higher antibacterial rate;
(2) The self-assembled micro-nano structure Cu of the application 2 The XRD characteristic peaks of the O particles before and after spinning are not obviously increased, reduced or deviated, which indicates that good stability is maintained in the use process;
(3) The self-assembled micro-nano structure Cu of the application 2 Preparation method of O particles and prepared micro-nano structure Cu 2 The O size is uniform, wherein the sizes of the nano-size primary particles and the micro-size assembly particles can be effectively regulated and controlled;
(4) The self-assembled micro-nano structure Cu of the application 2 The preparation method of the O particles adopts simple raw materials and process flow, is easy to realize and is Cu 2 Mass production of O also provides the possibility.
Drawings
FIG. 1 shows micro-nano structure Cu obtained in example 1 2 SEM images of morphology structures of O particles;
FIG. 2 shows micro-nano structure Cu obtained in example 1 2 Nanoscale Cu in O particles 2 A TEM image of O;
FIG. 3 shows a synthetic micro-nano structure Cu of the present application 2 Schematic of the mechanism of O;
FIG. 4 is a cubic phase Cu 2 O, micro-nano structure Cu prepared in example 4 2 O and micro-nano structure Cu prepared in example 4 2 XRD pattern of O spinning.
Detailed Description
The application is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present application, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
The structural formula of the dendrimer in examples 1 to 7 is as follows:
wherein the wavy line represents a dendritic polymer which can be further reacted to form further branching units, R 1 -A-R 2 Raw material A for the Synthesis of dendrimers 2 A monomer, wherein the monomer is a monomer,raw material B for the Synthesis of dendrimers 3 Type monomer, dashed circle represents two radical bonds.
Raw materials A of examples 1 to 7 2 Monomers and B 3 The type monomers are shown in Table 1:
TABLE 1
Example 1
Self-assembled micro-nano structure Cu 2 The preparation method of the O particles comprises the following specific steps:
(1) Synthesizing a dendritic polymer;
a is firstly added according to the mol ratio of 3:1:5 2 Monomer (B) 3 Monomers and H 2 Mixing O, heating to 120deg.C, and maintaining for a period of time until 80% H 2 Steaming out O, vacuumizing to 0.098MPa, heating to 160 ℃, and reacting for 2 hours under heat and pressure preservation to obtain dendritic polymer (the dendritic polymer is transparent viscous liquid just after the reaction is finished, cooling is needed to obtain transparent solid, and after complete cooling and shaping, crushing the transparent solid by a stainless steel crusher to obtain a white powdery sample);
the branching degree DB of the dendritic polymer obtained was 0.6 and the number average molecular weight Mn was 60000g/mol;
(2) Preparing a polyether amine aqueous solution;
adding polyetheramine (polyetheramine D230) into deionized water according to the mass ratio of 1:2, magnetically stirring at 20 ℃ (stirring speed is 400 r/min), and fully dissolving to form polyetheramine aqueous solution;
(3) The stirring speed is kept unchanged, the temperature is kept unchanged, and the dendritic polymer is added into the polyether amine aqueous solution to form a uniform and transparent reaction system, wherein the mass ratio of the dendritic polymer to the polyether amine is 1:10;
(4) Under the condition of stirring speed of 400r/min, a copper salt solution (composed of cupric acetate monohydrate and deionized water) with the concentration of 0.125M is added dropwise into the reaction system through a constant-pressure dropping funnel (the dropping speed is 3 seconds/drop), and then stirring is continued for 1h; wherein the mass ratio of the copper salt solution to the dendritic polymer in the reaction system is 1:2;
(5) Dropping an ascorbic acid aqueous solution with the concentration of 0.625M into the reaction system through a constant pressure dropping funnel under the condition of the stirring speed of 400r/min (the dropping speed is 3 seconds/drop), and then continuously stirring for 3 hours; wherein the molar ratio of the ascorbic acid to the copper ions in the reaction system is 1:2;
(6) Post-treatment;
suction filtering (using vacuum pump), washing (three times of washing with deionized water and absolute ethyl alcohol respectively), and drying (drying overnight in vacuum oven at 60deg.C) to obtain self-assembled micro-nano structure Cu 2 And O particles.
As shown in figures 1-2, the self-assembled micro-meter is preparedNanostructured Cu 2 O particles (average particle diameter of 0.7 μm, specific surface area of 80m 2 ·g -1 ) Is made of a plurality of nano-scale Cu 2 The O particles (average particle diameter: 5 nm) were assembled into micron-sized spheres by using physical or chemical forces between the dendritic polymers, wherein the content of the dendritic polymer was 24wt%.
Example 2
Self-assembled micro-nano structure Cu 2 The preparation method of the O particles comprises the following specific steps:
(1) Synthesizing a dendritic polymer;
a is firstly added according to the mol ratio of 3:2:6 2 Monomer (B) 3 Monomers and H 2 Mixing O, heating to 190 deg.C, and maintaining for a period of time until 82% H 2 Steaming out O, vacuumizing to 0.098MPa, heating to 201 ℃, and reacting for 2.1h under heat and pressure preservation to obtain dendritic polymer (the dendritic polymer is transparent viscous liquid just after the reaction is finished, the dendritic polymer is required to be cooled to obtain transparent solid, and after the transparent solid is completely cooled and shaped, crushing the transparent solid by a stainless steel crusher to obtain a white powdery sample);
the branching degree DB of the dendritic polymer obtained was 0.5 and the number average molecular weight Mn was 48520g/mol;
(2) Preparing a polyether amine aqueous solution;
adding polyetheramine (polyetheramine M-600) into deionized water according to the mass ratio of 1:3, magnetically stirring at the temperature of 22 ℃ (stirring speed is 390 r/min), and fully dissolving to form polyetheramine aqueous solution;
(3) The stirring speed is kept unchanged, the temperature is kept unchanged, and the dendritic polymer is added into the polyether amine aqueous solution to form a uniform and transparent reaction system, wherein the mass ratio of the dendritic polymer to the polyether amine is 1:12;
(4) Under the condition of the stirring speed of 380r/min, a copper salt solution (composed of cupric acetate monohydrate and deionized water) with the concentration of 0.13M is added into the reaction system through a constant-pressure dropping funnel in a dropwise manner (the dropping speed is 3 seconds/drop), and then stirring is continued for 1h; wherein the mass ratio of the copper salt solution to the dendritic polymer in the reaction system is 1:2;
(5) Dropping an ascorbic acid aqueous solution with the concentration of 0.68M into the reaction system through a constant pressure dropping funnel under the condition of the stirring speed of 380r/min (the dropping speed is 3 seconds/drop), and then continuously stirring for 3 hours; wherein the molar ratio of the ascorbic acid to the copper ions in the reaction system is 1:2;
(6) Post-treatment;
suction filtering (using vacuum pump), washing (three times of washing with deionized water and absolute ethyl alcohol respectively), and drying (drying overnight in vacuum oven at 60deg.C) to obtain self-assembled micro-nano structure Cu 2 And O particles.
The self-assembled micro-nano structure Cu is prepared 2 O particles (average particle diameter of 0.8 μm, specific surface area of 72m 2 ·g -1 ) Is made of a plurality of nano-scale Cu 2 The O particles (average particle diameter: 8 nm) were assembled into micron-sized spheres by physical or chemical forces between the dendritic polymers, wherein the content of the dendritic polymer was 23.2wt%.
Example 3
Self-assembled micro-nano structure Cu 2 The preparation method of the O particles comprises the following specific steps:
(1) Synthesizing a dendritic polymer;
a is firstly added according to the mol ratio of 3:1:7 2 Monomer (B) 3 Monomers and H 2 Mixing O, heating to 172 deg.C, and maintaining for a period of time until 84% H 2 Steaming out O, vacuumizing to 0.098MPa, heating to 202 ℃, and reacting for 2.2 hours under heat and pressure preservation to obtain dendritic polymer (the dendritic polymer is transparent viscous liquid just after the reaction is finished, the dendritic polymer is required to be cooled to obtain transparent solid, and after the transparent solid is completely cooled and shaped, crushing the transparent solid by a stainless steel crusher to obtain a white powdery sample);
the branching degree DB of the dendritic polymer obtained was 0.45 and the number average molecular weight Mn was 30000g/mol;
(2) Preparing a polyether amine aqueous solution;
adding polyetheramine (polyetheramine T-403) into deionized water according to the mass ratio of 1:4, magnetically stirring at 24 ℃ (stirring speed is 380 r/min), and fully dissolving to form polyetheramine aqueous solution;
(3) The stirring speed is kept unchanged, the temperature is kept unchanged, and the dendritic polymer is added into the polyether amine aqueous solution to form a uniform and transparent reaction system, wherein the mass ratio of the dendritic polymer to the polyether amine is 1:14;
(4) Under the condition of stirring speed of 360r/min, copper salt solution (composed of cupric acetate monohydrate and deionized water) with concentration of 0.135M is added dropwise into the reaction system through a constant-pressure dropping funnel (the dropping speed is 3 seconds/drop), and then stirring is continued for 1h; wherein the mass ratio of the copper salt solution to the dendritic polymer in the reaction system is 1:2;
(5) Dropping an ascorbic acid aqueous solution with the concentration of 0.72M into the reaction system through a constant pressure dropping funnel under the condition of the stirring speed of 360r/min (the dropping speed is 3 seconds/drop), and then continuously stirring for 3 hours; wherein the molar ratio of the ascorbic acid to the copper ions in the reaction system is 1:2;
(6) Post-treatment;
suction filtering (using vacuum pump), washing (three times of washing with deionized water and absolute ethyl alcohol respectively), and drying (drying overnight in vacuum oven at 60deg.C) to obtain self-assembled micro-nano structure Cu 2 And O particles.
The self-assembled micro-nano structure Cu is prepared 2 O particles (average particle diameter of 1.2 μm, specific surface area of 65m 2 ·g -1 ) Is made of a plurality of nano-scale Cu 2 The O particles (average particle diameter: 8 nm) were assembled into micron-sized spheres by physical or chemical forces between the dendritic polymers, wherein the content of the dendritic polymer was 22.2wt%.
Example 4
Self-assembled micro-nano structure Cu 2 The preparation method of the O particles comprises the following specific steps:
(1) Synthesizing a dendritic polymer;
a is firstly added according to the mol ratio of 3:1:8 2 Monomer (B) 3 Monomers and H 2 Mixing O, heating to 175 deg.C, and maintaining for a period of time until 86% H 2 O is distilled off, then the vacuum is pumped to 0.098MPa, and the temperature is raised to 200 ℃, the heat preservation and pressure maintaining reaction are carried out for 2.3hObtaining dendritic polymer (the dendritic polymer is transparent viscous liquid after the reaction is just finished, the dendritic polymer needs to be cooled to obtain transparent solid, and after the dendritic polymer is completely cooled and shaped, a stainless steel pulverizer is used for crushing the transparent solid to obtain a white powdery sample);
the branching degree DB of the dendritic polymer obtained was 0.5 and the number average molecular weight Mn was 45000g/mol;
(2) Preparing a polyether amine aqueous solution;
adding polyetheramine (polyetheramine D230) into deionized water according to a mass ratio of 1:5, magnetically stirring at 26 ℃ (stirring speed is 360 r/min), and fully dissolving to form polyetheramine aqueous solution;
(3) The stirring speed is kept unchanged, the temperature is kept unchanged, and the dendritic polymer is added into the polyether amine aqueous solution to form a uniform and transparent reaction system, wherein the mass ratio of the dendritic polymer to the polyether amine is 1:16;
(4) Under the condition of stirring speed of 350r/min, a copper salt solution (composed of cupric acetate monohydrate and deionized water) with the concentration of 0.14M is added dropwise into a reaction system through a constant-pressure dropping funnel (the dropping speed is 3 seconds/drop), and then stirring is continued for 1h; wherein the mass ratio of the copper salt solution to the dendritic polymer in the reaction system is 1:3;
(5) Dropping an ascorbic acid aqueous solution with the concentration of 0.75M into the reaction system through a constant pressure dropping funnel under the condition of the stirring speed of 350r/min (the dropping speed is 3 seconds/drop), and then continuously stirring for 3 hours; wherein the molar ratio of the ascorbic acid to the copper ions in the reaction system is 1:2;
(6) Post-treatment;
suction filtering (using vacuum pump), washing (three times of washing with deionized water and absolute ethyl alcohol respectively), and drying (drying overnight in vacuum oven at 60deg.C) to obtain self-assembled micro-nano structure Cu 2 And O particles.
The self-assembled micro-nano structure Cu is prepared 2 O particles (average particle diameter of 1.35 μm, specific surface area of 30m 2 ·g -1 ) Is made of a plurality of nano-scale Cu 2 O particles (average particle size 10 nm) utilize physical or chemical interactions between dendritic polymersThe resulting microspheres were assembled vigorously, wherein the dendritic polymer content was 23.5wt%.
The prepared micro-nano structure Cu 2 Fully premixing O and polyamide powder, adopting a double-screw extruder to perform melt blending, extruding, granulating and drying to obtain the PA 6/micro-nano structure Cu 2 O composite resin.
The prepared PA 6/micro-nano structure Cu 2 In the O composite resin, cu with micro-nano structure 2 The mass fraction of O is 1wt%.
Adopts a vacuum drum oven to perform Cu treatment on PA 6/micro-nano structure 2 The O composite resin is subjected to water removal treatment twice successively, the first water removal treatment is carried out for 10 hours at 80 ℃, the second water removal treatment is carried out for 24 hours at 130 ℃, and then a double-component composite spinning machine is adopted to carry out the water removal treatment twice on the PA 6/micro-nano structure Cu 2 Spinning the O composite resin serving as a raw material to obtain the PA 6/micro-nano structure Cu 2 O composite fiber yarn.
As can be seen from FIG. 4, the micro-nano structure Cu 2 Diffraction peak position of O powder and cubic Cu 2 The O standard XRD spectrum peak positions are the same, and diffraction peaks appearing at 2θ= 29.554 °, 36.418 °, 42.297 °, 61.344 °, 73.526 ° and 77.763 ° correspond to Cu, respectively 2 The (110), (111), (200), (220), (311) and (322) crystal plane characteristic peaks of O. In micro-nano structure Cu 2 O spinning (i.e. PA 6/micro-nano structure Cu 2 O composite filament) the steamed bread peak occurring between 2θ=20 to 22 ° is the characteristic peak of PA6, and Cu in the spectrogram 2 The characteristic peak of O has no obvious shift and broadening phenomena before and after spinning, which indicates the micro-nano structure Cu 2 Durable stability of O during application.
Example 5
Self-assembled micro-nano structure Cu 2 The preparation method of the O particles comprises the following specific steps:
(1) Synthesizing a dendritic polymer;
a is firstly added according to the mol ratio of 3:2:5 2 Monomer (B) 3 Monomers and H 2 Mixing O, heating to 120deg.C, and maintaining for a period of time until 88% H 2 O is distilled out, and then vacuumized to 0.098MPa,simultaneously heating to 150 ℃, preserving heat and pressure for 2.4 hours to obtain a dendritic polymer (the dendritic polymer is transparent viscous liquid after the reaction is just finished, the dendritic polymer needs to be cooled to obtain transparent solid, and after the transparent solid is completely cooled and shaped, a stainless steel crusher is used for crushing the transparent solid to obtain a white powdery sample);
the branching degree DB of the dendritic polymer obtained was 0.55 and the number average molecular weight Mn was 53830g/mol;
(2) Preparing a polyether amine aqueous solution;
adding polyetheramine (polyetheramine M-600) into deionized water according to a mass ratio of 1:6, magnetically stirring at 28 ℃ (stirring speed is 350 r/min), and fully dissolving to form polyetheramine aqueous solution;
(3) The stirring speed is kept unchanged, the temperature is kept unchanged, and the dendritic polymer is added into the polyether amine aqueous solution to form a uniform and transparent reaction system, wherein the mass ratio of the dendritic polymer to the polyether amine is 1:18;
(4) Under the condition of the stirring speed of 340r/min, a copper salt solution (composed of cupric acetate monohydrate and deionized water) with the concentration of 0.15M is added into the reaction system through a constant-pressure dropping funnel in a dropwise manner (the dropping speed is 4 seconds/drop), and then stirring is continued for 1h; wherein the mass ratio of the copper salt solution to the dendritic polymer in the reaction system is 1:3;
(5) Dropping an ascorbic acid aqueous solution with the concentration of 0.79M into the reaction system through a constant pressure dropping funnel under the condition of the stirring speed of 320r/min (the dropping speed is 4 seconds/drop), and then continuously stirring for 2 hours; wherein the molar ratio of the ascorbic acid to the copper ions in the reaction system is 1:2;
(6) Post-treatment;
suction filtering (using vacuum pump), washing (three times of washing with deionized water and absolute ethyl alcohol respectively), and drying (drying overnight in vacuum oven at 60deg.C) to obtain self-assembled micro-nano structure Cu 2 And O particles.
The self-assembled micro-nano structure Cu is prepared 2 O particles (average particle diameter of 1.4 μm, specific surface area of 38m 2 ·g -1 ) Is made of a plurality of nano-scale Cu 2 O particles (average particle size 10 nm)The resulting microspheres were assembled with physical or chemical forces between the dendrimers, wherein the dendrimer content was 23.8wt%.
Example 6
Self-assembled micro-nano structure Cu 2 The preparation method of the O particles comprises the following specific steps:
(1) Synthesizing a dendritic polymer;
a is firstly added according to the mol ratio of 3:1:6 2 Monomer (B) 3 Monomers and H 2 Mixing O, heating to 130 deg.C, and maintaining for a period of time until 89% H 2 Steaming out O, vacuumizing to 0.098MPa, heating to 150 ℃, and reacting for 2.45 hours under heat and pressure preservation to obtain dendritic polymer (the dendritic polymer is transparent viscous liquid just after the reaction is finished, the dendritic polymer is required to be cooled to obtain transparent solid, and after the transparent solid is completely cooled and shaped, crushing the transparent solid by a stainless steel crusher to obtain a white powdery sample);
the branching degree DB of the dendritic polymer obtained was 0.6 and the number average molecular weight Mn was 58000g/mol;
(2) Preparing a polyether amine aqueous solution;
adding polyetheramine (polyetheramine T-403) into deionized water according to the mass ratio of 1:2, magnetically stirring at 29 ℃ (stirring speed is 320 r/min), and fully dissolving to form polyetheramine aqueous solution;
(3) The stirring speed is kept unchanged, the temperature is kept unchanged, and the dendritic polymer is added into the polyether amine aqueous solution to form a uniform and transparent reaction system, wherein the mass ratio of the dendritic polymer to the polyether amine is 1:19;
(4) Under the condition of a stirring speed of 320r/min, a copper salt solution (composed of cupric acetate monohydrate and deionized water) with a concentration of 0.16M is added dropwise into a reaction system through a constant-pressure dropping funnel (the dropping speed is 4 seconds/drop), and then stirring is continued for 1h; wherein the mass ratio of the copper salt solution to the dendritic polymer in the reaction system is 1:3;
(5) Dropping an ascorbic acid aqueous solution with the concentration of 0.84M into the reaction system through a constant pressure dropping funnel under the condition of the stirring speed of 310r/min (the dropping speed is 4 seconds/drop), and then continuously stirring for 2 hours; wherein the molar ratio of the ascorbic acid to the copper ions in the reaction system is 1:2;
(6) Post-treatment;
suction filtering (using vacuum pump), washing (three times of washing with deionized water and absolute ethyl alcohol respectively), and drying (drying overnight in vacuum oven at 60deg.C) to obtain self-assembled micro-nano structure Cu 2 And O particles.
The self-assembled micro-nano structure Cu is prepared 2 O particles (average particle diameter of 0.9 μm, specific surface area of 54m 2 ·g -1 ) Is made of a plurality of nano-scale Cu 2 The O particles (average particle diameter: 7 nm) were assembled into micron-sized spheres by physical or chemical forces between the dendritic polymers, wherein the content of the dendritic polymer was 22.8wt%.
Example 7
Self-assembled micro-nano structure Cu 2 The preparation method of the O particles comprises the following specific steps:
(1) Synthesizing a dendritic polymer;
a is firstly added according to the mol ratio of 3:1:7 2 Monomer (B) 3 Monomers and H 2 Mixing O, heating to 120deg.C, and maintaining for a period of time until 90% H 2 Steaming out O, vacuumizing to 0.098MPa, heating to 145 ℃, and reacting for 2.5 hours under heat and pressure preservation to obtain dendritic polymer (the dendritic polymer is transparent viscous liquid just after the reaction is finished, the dendritic polymer is required to be cooled to obtain transparent solid, and after the transparent solid is completely cooled and shaped, crushing the transparent solid by a stainless steel crusher to obtain a white powdery sample);
the branching degree DB of the dendritic polymer obtained was 0.48 and the number average molecular weight Mn was 34560g/mol;
(2) Preparing a polyether amine aqueous solution;
adding polyetheramine (a mixture of polyetheramine D230 and polyetheramine M-600 in a mass ratio of 1:1) into deionized water according to a mass ratio of 1:3, magnetically stirring at a temperature of 30 ℃ (stirring speed is 300 r/min), and fully dissolving to form a polyetheramine aqueous solution;
(3) The stirring speed is kept unchanged, the temperature is kept unchanged, and the dendritic polymer is added into the polyether amine aqueous solution to form a uniform and transparent reaction system, wherein the mass ratio of the dendritic polymer to the polyether amine is 1:20;
(4) Under the condition of stirring speed of 300r/min, copper salt solution (composed of cupric acetate monohydrate and deionized water) with concentration of 0.175M is added dropwise into the reaction system through a constant-pressure dropping funnel (the dropping speed is 4 seconds/drop), and then stirring is continued for 1h; wherein the mass ratio of the copper salt solution to the dendritic polymer in the reaction system is 1:3;
(5) Dropping an ascorbic acid aqueous solution with the concentration of 0.875M into the reaction system through a constant pressure dropping funnel under the condition of the stirring speed of 300r/min (the dropping speed is 4 seconds/drop), and then continuing stirring for 2 hours; wherein the molar ratio of the ascorbic acid to the copper ions in the reaction system is 1:2;
(6) Post-treatment;
suction filtering (using vacuum pump), washing (three times of washing with deionized water and absolute ethyl alcohol respectively), and drying (drying overnight in vacuum oven at 60deg.C) to obtain self-assembled micro-nano structure Cu 2 And O particles.
The self-assembled micro-nano structure Cu is prepared 2 O particles (average particle diameter of 1 μm, specific surface area of 45m 2 ·g -1 ) Is made of a plurality of nano-scale Cu 2 The O particles (average particle diameter: 6 nm) were assembled into micron-sized spheres by physical or chemical forces between the dendritic polymers, wherein the content of the dendritic polymer was 24.2wt%.
Claims (10)
1. Self-assembled micro-nano structure Cu 2 O particles, characterized by being made of a plurality of nano-sized Cu 2 The O particles are assembled to form micron-sized spheres, wherein the assembly utilizes physical or chemical forces between dendritic polymers;
the structural formula of the dendritic polymer is as follows:
in the waveThe wavy line represents a dendritic polymer which can be reacted further to form further branching units, R 1 -A-R 2 Raw material A for the Synthesis of dendrimers 2 A monomer, wherein the monomer is a monomer,raw material B for the Synthesis of dendrimers 3 Type monomer, dashed circle represents two radical bonds.
2. A self-assembled micro-nano structure Cu according to claim 1 2 O particles characterized by nano-scale Cu 2 The average particle diameter of the O particles is 5-10 nm, and the average particle diameter of the micron-sized spheres is 0.6-1.6 mu m.
3. A self-assembled micro-nano structure Cu according to claim 1 2 O particles, characterized in that the branching degree DB of the dendritic polymer is 0.45-0.6 and the number average molecular weight Mn is 30000-60000 g/mol.
4. A self-assembled micro-nano structure Cu according to claim 1 2 O particles, characterized in that R 1 、R 2 Selected from the group consisting of-SH, -COOH, -OH, -PO (OH) 2 AndR 3 selected from the group consisting of-SH, -COOH and-OH.
5. A self-assembled micro-nano structure Cu according to claim 4 2 O particles, characterized in that R 1 、R 2 Are all-COOH, or one is-COOH and the other is-PO (OH) 2 Or one of them is-COOH and the other isR 3 Are both-SH, or are both-OH;
alternatively, R 1 、R 2 Are all-SH, or are all-OH，R 3 Are all-COOH.
6. A self-assembled micro-nano structure Cu according to claim 5 2 O particles, characterized in that A 2 The monomer is 6-phosphonohexanoic acid, 11-phosphonoundecanoic acid, 16-phosphonohexadecanoic acid, 2, 6-naphthalene dicarboxylic acid, polyethylene glycol dicarboxylic acid, 1, 11-undecane dicarboxylic acid, CEPPA, B 3 The monomer is trimethylolpropane tri (3-mercaptopropionate), cyanuric acid, TMP, THEIC;
alternatively, A 2 The monomer is 1, 2-ethanedithiol, 1, 3-propanedithiol, 1, 4-butanedithiol, polyethylene glycol, B 3 The type monomer is trimesic acid.
7. A self-assembled micro-nano structure Cu according to claim 1 2 O particles characterized by self-assembled micro-nano structure Cu 2 The specific surface area of the O particles is 30-80 m 2 ·g -1 The dendritic polymer content is 22.2 to 24.2 wt.%.
8. Preparation of a self-assembled micro-nano structure Cu according to any one of claims 1-7 2 A process for preparing O particles, characterized in that firstly the A 2 Monomer and said B 3 The monomer is A as raw material 2 +B 3 Synthesizing dendritic polymer, adding dendritic polymer into polyether amine water solution to form homogeneous transparent reaction system, dropping copper salt solution into the reaction system while stirring, stirring for some time, dropping ascorbic acid water solution into the reaction system while stirring, and stirring to obtain self-assembled micro-nano Cu structure 2 And O particles.
9. The method according to claim 8, characterized by the specific steps of:
(1) Synthesizing a dendritic polymer;
firstly, the A is carried out according to the molar ratio of 3:1-2:5-8 2 Monomer, B 3 Monomer and method for producing the sameH 2 Mixing O, heating to 120-190 deg.C, holding for a period of time until more than 80% of H 2 Evaporating O, vacuumizing to 0.098MPa, heating to 145-202 ℃, and reacting at the temperature and pressure maintaining for 2-2.5 h to obtain dendritic polymer;
(2) Preparing a polyether amine aqueous solution;
adding polyether amine into deionized water, magnetically stirring at 20-30 ℃ and fully dissolving to form polyether amine aqueous solution;
(3) The stirring speed is kept unchanged, the temperature is kept unchanged, and the dendritic polymer is added into the polyether amine aqueous solution to form a uniform and transparent reaction system;
(4) Dropwise adding copper salt solution into the reaction system through a constant pressure dropping funnel under the stirring condition, and continuously stirring for 1h;
(5) Dropping the ascorbic acid water solution into the reaction system through a constant pressure dropping funnel under the stirring condition, and continuing stirring for 2-3 h;
(6) Post-treatment;
suction filtering, washing and drying to obtain the self-assembled micro-nano structure Cu 2 And O particles.
10. The method of claim 9, wherein in step (2), the polyetheramine is one or more of polyetheramine D230, polyetheramine M-600, and polyetheramine T-403; the mass ratio of the polyetheramine to the deionized water is 1:2-6; the stirring speed is 300-400 r/min;
in the step (3), the mass ratio of the dendritic polymer to the polyether amine is 1:10-20;
in the step (4), the stirring speed is 300-400 r/min; the concentration of the copper salt solution is 0.125-0.175M, and the copper salt solution consists of cupric acetate monohydrate and deionized water; the dropping speed is 3-4 seconds/drop; the mass ratio of the copper salt solution to the dendritic polymer is 1:2-3;
in the step (5), the stirring speed is 300-400 r/min; the concentration of the ascorbic acid aqueous solution is 0.625-0.875M; the molar ratio of the ascorbic acid to the copper ions in the reaction system is 1:2; the dropping rate is 3-4 seconds/drop.
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