CN108034073A - A kind of particle intelligently changed and preparation method thereof - Google Patents
A kind of particle intelligently changed and preparation method thereof Download PDFInfo
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- CN108034073A CN108034073A CN201711275548.7A CN201711275548A CN108034073A CN 108034073 A CN108034073 A CN 108034073A CN 201711275548 A CN201711275548 A CN 201711275548A CN 108034073 A CN108034073 A CN 108034073A
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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
- C08K3/24—Acids; Salts thereof
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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
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/48—Oxides or hydroxides of chromium, molybdenum or tungsten; Chromates; Dichromates; Molybdates; Tungstates
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
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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
- C08K2003/2255—Oxides; Hydroxides of metals of molybdenum
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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
- C08K2003/2258—Oxides; Hydroxides of metals of tungsten
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
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Abstract
The invention discloses a kind of intelligent particle with multiple change and preparation method thereof.The particle includes substrate polymer particle and the part of inorganic component two, and particle change has response to temperature, soda acid and light.The preparation method of the particle includes：Responsive polymer particle is added in solvent, inorganic precursor is added, then adding catalyst makes inorganic deposition in the grain.Particle provided by the invention can be used for intelligent surface, intelligent fiber or clothes and catalytic reaction etc., there is wide application prospect in multiple fields such as catalysis, material, organic chemistry, its preparation method is easy, easy to control, with universality, suitable for producing in enormous quantities and applying.
Description
Technical field
The present invention relates to a kind of particle intelligently changed and preparation method thereof, and in particular to one kind polymerize containing response
Bi-component hybrid particulates of thing and inorganic component and preparation method thereof.
Background technology
In technical field of material chemistry, the development of intellectual material causes the broad interest of people, wherein with environment-responsive
Chemical substance it is wide always concerned, it can change its own shape, structure or property with the change of specific factor in environment,
As poly(N-isopropylacrylamide) has temperature-responsive, its in aqueous when temperature is less than critical value (about 32 DEG C),
For the chain configuration of stretching, extension, hydrophily is shown as, when the temperature is greater than a threshold value, chain shrinks aggregation, shows as lipophile
(Chemical such as Y.Hirokawa Physics1984,81 (12), 6379-6380).If using environment-responsive material as
One component of bicomponent non-woven fabric, then the particle also there is identical environment-responsive, the shape of itself can be adjusted according to environment
The volume ratio of state and two components, so as to perform lotion transformation, molecular recognition, the control multiple functions such as self assembly, material,
Chemical industry, medicine, catalysis, weaving multiple fields have wide application prospect and value.On this basis, various response copolymerization
Thing also grows up, and is both rung such as acrylic acid and the copolymer of n-isopropyl acrylamide with temperature-responsive or with soda acid
Answering property (H.Feil etc., Macromolecules 1995,373,49-52；G.Chen etc.
Macromol.RapidCommun.1995,16,175.)；In recent years, while have the particle of photoresponse also it has been reported that such as
Copolymer (the B. of n-isopropyl acrylamide, acrylic acid and photochromic monomer containing organic photochromic groupsDeng
Soft Matter, 2013,9,8754-8760).Inorganic matter (gold, silver and ferroso-ferric oxide etc.) is introduced these intelligent
The research of grain also has been reported that the response material of some inorganic hybridizations also shows that volume contraction phenomenon slight under illumination
(Angew.Chem.2012 such as J.Yoon, 124,7258), but its principle causes after being attributed to inorganic particle illumination heating mostly
The contraction of poly(N-isopropylacrylamide) polymer, causes the volume change of particle smaller, only has theoretical research valency mostly
Value.
The content of the invention
The object of the present invention is to provide a kind of particle intelligently changed.
So-called intelligence change refers to that the volume of particle changes with temperature, light and/or soda acid, and the property thus brought
Change, as variation of hydrophilic-hydrophobic property, catalytic performance change.
The particle provided by the present invention intelligently changed includes responsive polymer and inorganic matter two parts.
The mass ratio of the inorganic matter and responsive polymer can be 100:1-100:1000.
The responsive polymer can be：N- ethyl acrylamides, N- Ethyl-2-Methyls acrylamide, N, N- diethyl
Acrylamide, N, N-dimethacrylamide, n-isopropyl acrylamide, N- isopropyl acrylamides, acrylic acid, first
Base acrylic acid, ethylacrylic acid, propylacrylate, methacrylic acid N, N- dimethylaminoethyl, Cvclopropvlmethvl acryloyl
The polymer of monomer such as amine, N- dimethylaminoethyls or its copolymer with crosslinking agent, or the copolymer of their any combination,
Or its copolymer with other monomers, preferably it is the polymer based on poly-N-isopropyl acrylamide.
Other monomers with the copolymer of other monomers can be：Containing carboxyl olefinic monomer (such as acrylic acid,
Methacrylic acid, ethylacrylic acid), acrylate (such as methyl methacrylate, ethyl methacrylate, methacrylic acid fourth
Ester), N hydroxymethyl acrylamide (NMA), N- hydroxyethyl acrylamides, Diacetone Acrylamide (DAAM), methacrylic acid contracting
Water glyceride (GMA), hydroxyethyl methacrylate (HEMA), methacrylic acid ethyl acetoacetate, acrylamide, N, N '-Asia
Bisacrylamide, styrene or vinylpyridine；
The polymer is additionally included in the derived polymer that the enterprising single step reaction of above-mentioned polymer base obtains, such as poly- (N-
N-isopropylacrylamide-styrene) sulfonated products, poly- (n-isopropyl acrylamide-methyl methacrylate) hydrolysis production
Thing.
The crosslinking agent is the olefinic monomer at least containing two double bonds, such as 1,5- hexadienes, triallyl isocyanide urea
Acid esters, ethylene glycol dimethacrylate, divinylbenzene, NN '-methylene-bisacrylamide etc..
The inorganic matter can be oxide, hydroxide, the metal oxygen-containing acid or its salt (such as sodium molybdate, molybdic acid of metal
Potassium, sodium tungstate, potassium tungstate or wolframic acid, molybdic acid etc.), at least one of metal carbonate and metal oxalate.
Wherein, the metal includes at least the metal with feature of appraising at the current rate, and the metal with feature of appraising at the current rate can be：
At least one of tungsten, molybdenum, scandium, rhodium metal.
The inorganic matter is concretely：Tungsten oxide (such as tungstic acid, tungsten dioxide), molybdenum oxide (such as molybdenum trioxide, two
Molybdenum oxide), rhodium oxide, rhodium hydroxide, sodium molybdate, sodium tungstate, potassium tungstate or wolframic acid, molybdic acid, scandium hydroxide, scandium oxide
Deng, or oxalates or carbonate, such as oxalic acid scandium, oxalic acid rhodium, carbonic acid tungsten, oxalic acid tungsten, scandium carbonate；It can also be contained
Its inorganic component, such as iron oxide, ferroso-ferric oxide, titanium dioxide, silica, sodium oxide molybdena, potassium oxide, magnesia, three oxygen
Change two antimony, barium sulfate etc..
The above-mentioned particle intelligently changed is prepared by the method comprising the following steps：
The salt or soluble compounds that the particle of the responsive polymer is disperseed in a solvent, to add the metal, fill
Tap isolates particle after touch, the particle intelligently changed；Or
The salt or soluble compounds that the particle of the responsive polymer is disperseed in a solvent, to add the metal, add
Enter precipitating reagent, react, isolate particle, the particle intelligently changed.
In the above method, the solvent can be：Water, ethanol, propyl alcohol, butanol, isopropanol, tetrahydrofuran, N, N- dimethyl
Formamide or its mixed solution, are preferably the mixed solution of water or water and alcohol.
The salt or soluble compounds of the metal can be：Tungstates, molybdate, rhodium oxide, tri-chlorination scandium, rhodium chloride
And its hydrate, K [Rh (H2O)Cl3]、K2[Rh(H2O)Cl5At least one of] and rhodium oxide.
The salt or soluble compounds of the metal and the mass ratio of the particle of the responsive polymer can be 0.01-
100, concretely 0.1-10.
The precipitating reagent can be：Hydrochloric acid, oxalic acid, sulfuric acid, phosphoric acid, nitric acid, formic acid, acetic acid, sodium hydroxide, potassium hydroxide,
At least one of sodium carbonate, potassium carbonate, sodium acid carbonate and saleratus.
Application of the above-mentioned particle intelligently changed in catalysis, water process, material intelligent surface falls within the guarantor of the present invention
Protect scope.
The present inventor has found under study for action：The hydridization prepared by introducing some oxides or metal salt in the polymer
Particle shows obvious contraction under light illumination.This particle not only responds temperature, soda acid, but also in visible ray or ultraviolet
Obvious shrinkage phenomenon is respectively provided with illumination；In addition, some particles also show the metachromatism under illumination.
Such as：Tungsten oxide/poly(N-isopropylacrylamide) intelligence particle is tapered into the rise particle of temperature；
The particle diameter of particle diminishes after tungsten oxide/poly- (n-isopropyl acrylamide-acrylic acid) intelligence particle illumination.
These performances make it have been widely used in intellectual material field tool；And the introducing of inorganic metal compound is also
New catalytic performance can be brought.And the preparation method of the present invention is suitable for producing in enormous quantities.
Beneficial effect includes possessed by the present invention：
Intelligence particle provided by the invention effectively combines the volume change of the intelligent color-changing of inorganic matter and polymer
Come, so as to fulfill light-operated volume change；Make the volume change of particle there is the multiple responses such as temperature, light and/or soda acid；
In addition, the catalytic performance of inorganic matter is combined with the environmental response performance of particle, so as to realize switch
Catalysis；Creative breakthrough is made that for exploitation novel intelligent material；
The preparation method process of intelligence particle provided by the invention is easy to control, suitable for the particle of different scales
Prepare, be particularly suitable for producing preparation in enormous quantities.
Brief description of the drawings
Fig. 1 is that tungsten oxide/poly(N-isopropylacrylamide) intelligence particle prepared by embodiment 2 varies with temperature its grain
Footpath distribution map.
Before and after tungsten oxide/poly- (n-isopropyl acrylamide-acrylic acid) the intelligence particle illumination that Fig. 2 is prepared for embodiment 3
Optical photograph figure.
Fig. 3 is that the intelligent particle of tungsten oxide/poly- (N, N- acrylamide) prepared by embodiment 8 is incorporated in mylar
The change of its surface hydrophobe property after upper use.
Embodiment
Below by specific embodiment, the present invention will be described, but the present invention is not limited thereto.
Experimental method used in following embodiments is conventional method unless otherwise specified；Institute in following embodiments
Reagent, material etc., are commercially available unless otherwise specified.
According to the present invention, there is provided a kind of intelligence hybrid particulates, the particle include two kinds of groups of responsive polymer and inorganic matter
Point, it is characterised in that the metal salt of functionalization is supported on a responsive polymer particle.
Intelligence change particle of the present invention, it is characterised in that the particle at least has responsive polymer and contains
Two kinds of components of inorganic matter of the elements such as tungsten, molybdenum, scandium, rhodium；
The responsive polymer is N- ethyl acrylamides, N- Ethyl-2-Methyls acrylamide, N, N- diethyl
Acrylamide, N, N-dimethacrylamide, n-isopropyl acrylamide, N- isopropyl acrylamides, cyclopropyl first
Base acrylamide, N- dimethylaminoethyls, acrylic acid, methacrylic acid, ethylacrylic acid, propylacrylate, methacrylic acid
The polymer of the monomers such as N, N- dimethylaminoethyl or its polymer formed with crosslinking agent, or the copolymerization of their any combination
Thing, or its copolymer with other monomers.Polymer preferably based on poly-N-isopropyl acrylamide.
Other monomers of copolymer described above include olefinic monomer (such as acrylic acid, metering system containing carboxyl
Acid, ethylacrylic acid), acrylate (such as methyl methacrylate, ethyl methacrylate, butyl methacrylate), N- hydroxyls
Methacrylamide (NMA), N- hydroxyethyl acrylamides, Diacetone Acrylamide (DAAM), glycidyl methacrylate
(GMA), hydroxyethyl methacrylate (HEMA), methacrylic acid ethyl acetoacetate, acrylamide, NN '-di-2-ethylhexylphosphine oxide third
Acrylamide, styrene or vinylpyridine；
The crosslinking agent is the olefinic monomer at least containing two double bonds, such as 1,5- hexadienes, triallyl isocyanide urea
Acid esters, ethylene glycol dimethacrylate, divinylbenzene, NN '-methylene-bisacrylamide etc..
Above-mentioned polymer is additionally included in the derived polymer that the enterprising single step reaction of above-mentioned polymer base obtains, such as poly- (N-
N-isopropylacrylamide-styrene) sulfonated products, poly- (n-isopropyl acrylamide-methyl methacrylate) hydrolysis production
Thing.
The inorganic matter is preferably aoxidized based on the inorganic matters such as oxide, hydroxide, carbonate or oxalates
Tungsten (such as tungstic acid, tungsten dioxide), molybdenum oxide (such as molybdenum trioxide, molybdenum dioxide), rhodium oxide, rhodium hydroxide, sodium molybdate,
Sodium tungstate, potassium tungstate or wolframic acid, molybdic acid, scandium hydroxide, scandium oxide etc. or oxalates or carbonate, such as oxalic acid
Scandium, oxalic acid rhodium, carbonic acid tungsten, oxalic acid tungsten, scandium carbonate etc.；Other inorganic components can also be contained, as iron oxide, ferroso-ferric oxide,
Titanium dioxide, silica, sodium oxide molybdena, potassium oxide, magnesia, antimony oxide, barium sulfate etc..
The preparation method of a kind of above-mentioned intelligent particle, its detailed process are as follows：
1) the above-mentioned responsive polymer particle synthesized by any method disperses in a solvent；Proportionally add one
The mixed solution or soluble metal compound solution of quantitative metal salt solution or two or more metal salts；Separate after a certain period of time
Particle, obtains intelligence change particle；
2) the above-mentioned responsive polymer particle synthesized by any method disperses in a solvent；Proportionally add one
Quantitative metal salt solution or soluble metal compound solution, or the mixed solution of two or more metal salts；Then adjust and add one
After quantitative precipitant solution, fully reaction, particle is separated, washs the particle intelligently changed.
Above-mentioned solvent for water, ethanol, propyl alcohol, butanol, isopropanol, tetrahydrofuran, N,N-dimethylformamide or its
Mixed solution, is preferably the mixed solution of water or water and alcohol.
Above-mentioned metal salt or soluble metal compound are tungstates, molybdate, rhodium oxide, tri-chlorination scandium, rhodium chloride
And its hydrate, K [Rh (H2O)Cl3]、K2[Rh(H2O)Cl5], rhodium oxide, or the two any of the above mixed salt solution
It is preferably 0.1-10. with the 0.01-100 of polymer beads ratio
The precipitating reagent is optionally hydrochloric acid, oxalic acid, sulfuric acid, phosphoric acid, nitric acid, formic acid, acetic acid, sodium hydroxide, hydroxide
Potassium, sodium carbonate, potassium carbonate, sodium acid carbonate, saleratus or their aqueous solution.
Other metal salts can also contain titanate, aluminate and silicate etc..
The preparation of embodiment 1, sodium molybdate/poly(N-isopropylacrylamide) particle
20mL 0.1g poly(N-isopropylacrylamide) particles are added in the flask of 50mL, the sodium molybdate for adding 1M is molten
Liquid 5ml, after stirring 30min, centrifuges, obtains being loaded with the intelligent particle of sodium molybdate.
The preparation of experimental example 2, tungsten oxide/poly(N-isopropylacrylamide) intelligence particle
10g poly(N-isopropylacrylamide) is added in 250mL flasks, 150mL water is added, is added after fully dispersed
10g potassium tungstates, stirring after ten minutes add 10M hydrochloric acid 10mL, reaction 1 it is small when after, centrifuge, fully washed with water
To intelligent particle.
Fig. 1 is that the tungsten oxide/poly(N-isopropylacrylamide) intelligence particle being prepared varies with temperature its particle diameter point
Butut.
As shown in Figure 1：Particle tapers at high temperature.
The preparation of experimental example 3, tungsten oxide/poly- (n-isopropyl acrylamide-acrylic acid) intelligence particle
It is poly- (n-isopropyl acrylamide-acrylic acid) that 10g is added in 250mL flasks, adds 100mL water, it is fully dispersed
Afterwards add 2g potassium tungstates, stirring 1 it is small when after add 1M hydrochloric acid 10mL, reaction 10 it is small when after, centrifuge, fully washed with water
Wash to obtain intelligent particle.
Fig. 2 is front and rear of the intelligent particle illumination of tungsten oxide/poly- (n-isopropyl acrylamide-acrylic acid) being prepared
Grain volume contraction figure in water, as seen from the figure：Illumination rear oxidation tungsten/poly- (n-isopropyl acrylamide-acrylic acid) intelligence particle
Particle diameter diminish.
The preparation of experimental example 4, rhodium hydroxide/poly- (n-isopropyl acrylamide-styrene)
By poly- (N, the n-isopropyl acrylamide-styrene) copolymer pellets of 0.1g, (the two ratio is 1:1) dense sulphur is added
In acid, when 50 degree of reactions 2 of heating are small, fully washed with water, particle is dispersed in 20mL water；Then 0.1g radium chlorides are added,
After stirring add 1M potassium hydroxide 2mL, reaction 24 it is small when after separating, washing, obtain the intelligent particle containing styrene.
The preparation of experimental example 5, scandium oxide/poly- (N- Methylethyls acrylamide-methacrylic acid-styrene)
By poly- (N, the n-isopropyl acrylamide-methacrylic acid-styrene) copolymer pellets of 0.1g, (proportions are
5:5：1) particle is dispersed in 50mL water；Then 0.5g tri-chlorination scandiums are added, the hydrochloric acid 1mL of 2M is added after stirring, reaction 48 is small
When after separating, washing, obtain the intelligent particle containing styrene.
The preparation of experimental example 6, molybdenum oxide/poly- (methacrylic acid N, N- dimethylaminoethyl-styrene)
By poly- (methacrylic acid N, the N- dimethylaminoethyl-styrene) copolymer pellets of 10g, (the two ratio is 2：1)
Particle is added in the concentrated sulfuric acid, when 40 degree of reactions 4 of heating are small, fully washed with water, particle is dispersed in 200mL water；Then plus
Enter 0.1g sodium molybdates, after stirring add 1M hydrochloric acid 10mL, reaction 1 it is small when after separating, washing, obtain the intelligence containing styrene
Particle.
The preparation of experimental example 7, sodium tungstate/poly- (N, n-isopropyl acrylamide-methyl methacrylate)
By poly- (methacrylic acid N, the N- dimethylaminoethyl-styrene) copolymer pellets of 10g, (the two ratio is 2：1)
Particle is added in the concentrated sulfuric acid, when 40 degree of reactions 4 of heating are small, fully washed with water, particle is dispersed in 200mL water；Then plus
Enter 0.1g sodium tungstates, after stirring add 1M hydrochloric acid 10mL, reaction 1 it is small when after separating, washing, obtain the intelligence containing styrene
Particle.
The preparation of embodiment 8, tungsten oxide/poly- (N, N- acrylamide) intelligence particle
It is poly- (N, N- acrylamide) that 10g is added in 250mL flasks, 150mL water is added, adds after fully dispersed
Enter 10g potassium tungstates, stirring adds the hydrochloric acid 10mL of 10M after ten minutes, when reaction 1 is small after, centrifuge, fully washed with water
Obtain intelligent particle.
The intelligent particle of the tungsten oxide being prepared/poly- (N, N- acrylamide) is incorporated on mylar and is used
The change of its surface hydrophobe property is as shown in Figure 3 afterwards.
As shown in Figure 3：When temperature by 40 DEG C to room temperature when, water droplet is being combined with tungsten oxide/poly- (N, N- diethyl propylene
Acid amides) contact angle of mylar of intelligent particle changes to 11 degree from 80 degree.The change of this wetability is beneficial to the biography of moisture
Lead, cause fabric clothes controlling the application on wet, be conducive to improve the comfort level of textile.
Claims (9)
1. a kind of particle intelligently changed, including responsive polymer and inorganic matter two parts, the inorganic matter is the oxygen of metal
Compound, hydroxide, metal oxygen-containing acid or at least one of its salt, metal carbonate and metal oxalate；
The metal includes at least the metal with feature of appraising at the current rate,
It is described that there is the metal of feature of appraising at the current rate to be：At least one of tungsten, molybdenum, scandium, rhodium metal.
2. the particle according to claim 1 intelligently changed, it is characterised in that：The responsive polymer is：N- ethyls
Acrylamide, N- Ethyl-2-Methyls acrylamide, N, N- acrylamides, N, N-dimethacrylamide, N- isopropyls
Base acrylamide, N- isopropyl acrylamides, Cvclopropvlmethvl acrylamide, N- dimethylaminoethyls monomer, acrylic acid,
Methacrylic acid, methacrylic acid N, N- dimethylaminoethyl, ethylacrylic acid, the polymer of propylacrylate or itself and crosslinking
The copolymer of agent, or the copolymer of their any combination, or its copolymer with other monomers；
Other monomers with the copolymer of other monomers are：Olefinic monomer, acrylate, N- methylols containing carboxyl
Acrylamide, N- hydroxyethyl acrylamides, Diacetone Acrylamide, glycidyl methacrylate, hydroxyethyl methacrylate second
Ester, methacrylic acid ethyl acetoacetate, acrylamide, N, N '-methylene-bisacrylamide, styrene or vinylpyridine；
The crosslinking agent is the olefinic monomer containing at least two double bonds, such as 1,5- hexadienes, Triallyl isocyanurate,
Ethylene glycol dimethacrylate, N N '-methylene-bisacrylamide, divinylbenzene etc..
The polymer is additionally included in the derived polymer that the enterprising single step reaction of above-mentioned polymer base obtains.
3. the particle according to claim 1 or 2 intelligently changed, it is characterised in that：The inorganic matter is：Tungsten oxide, oxygen
Change molybdenum, rhodium oxide, rhodium hydroxide, sodium molybdate, sodium tungstate, potassium tungstate or wolframic acid, molybdic acid, scandium hydroxide, scandium oxide, oxalic acid
Scandium, oxalic acid rhodium, carbonic acid tungsten, oxalic acid tungsten, scandium carbonate；
Other inorganic components can also be contained；
Other inorganic components are：Iron oxide, ferroso-ferric oxide, titanium dioxide, silica, sodium oxide molybdena, potassium oxide, oxidation
Magnesium, antimony oxide, barium sulfate.
4. preparing the method for the particle intelligently changed any one of claim 1-3, it is：
The salt or soluble compounds that the particle of the responsive polymer is disperseed in a solvent, to add the metal, fully connect
Particle is isolated after touch, the particle intelligently changed；Or
The salt or soluble compounds that the particle of the responsive polymer is disperseed in a solvent, to add the metal, it is heavy to add
Shallow lake agent, reaction, isolates particle, the particle intelligently changed.
5. according to the method described in claim 4, it is characterized in that：The solvent is：Water, ethanol, propyl alcohol, butanol, isopropanol,
Tetrahydrofuran, N,N-dimethylformamide or its mixed solution.
6. method according to claim 4 or 5, it is characterised in that：The salt or soluble compounds of the metal is：Wolframic acid
Salt, molybdate, rhodium oxide, tri-chlorination scandium, rhodium chloride and its hydrate, K [Rh (H2O)Cl3]、K2[Rh(H2O)Cl5] and oxidation
At least one of rhodium.
7. according to the method any one of claim 4-6, it is characterised in that：The salt or soluble compounds of the metal with
The mass ratio of the particle of the responsive polymer is 0.01-100.
8. according to the method any one of claim 4-7, it is characterised in that：The precipitating reagent is：Hydrochloric acid, oxalic acid, sulphur
In acid, phosphoric acid, nitric acid, formic acid, acetic acid, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium acid carbonate and saleratus
It is at least one.
9. the answering in catalysis, water process, material intelligent surface of the particle intelligently changed any one of claim 1-3
With.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711275548.7A CN108034073B (en) | 2017-12-06 | 2017-12-06 | Intelligently-changed particles and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711275548.7A CN108034073B (en) | 2017-12-06 | 2017-12-06 | Intelligently-changed particles and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108034073A true CN108034073A (en) | 2018-05-15 |
| CN108034073B CN108034073B (en) | 2021-04-06 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109467628A (en) * | 2018-10-26 | 2019-03-15 | 上海交通大学 | A kind of preparation method of composite nano-polymers particle |
| CN112831147A (en) * | 2019-11-22 | 2021-05-25 | 北京服装学院 | Color-changing particle and preparation method thereof |
| WO2023169566A1 (en) * | 2022-03-11 | 2023-09-14 | 北京服装学院 | Catalyst for photocatalytic polymerization reaction, and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109467628B (en) * | 2018-10-26 | 2020-06-12 | 上海交通大学 | Preparation method of polymer composite nanoparticles |
| CN112831147A (en) * | 2019-11-22 | 2021-05-25 | 北京服装学院 | Color-changing particle and preparation method thereof |
| WO2023169566A1 (en) * | 2022-03-11 | 2023-09-14 | 北京服装学院 | Catalyst for photocatalytic polymerization reaction, and application thereof |
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| CN108034073B (en) | 2021-04-06 |
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