CN108034073B - Intelligently-changed particles and preparation method thereof - Google Patents
Intelligently-changed particles and preparation method thereof Download PDFInfo
- Publication number
- CN108034073B CN108034073B CN201711275548.7A CN201711275548A CN108034073B CN 108034073 B CN108034073 B CN 108034073B CN 201711275548 A CN201711275548 A CN 201711275548A CN 108034073 B CN108034073 B CN 108034073B
- Authority
- CN
- China
- Prior art keywords
- particles
- oxide
- acid
- metal
- inorganic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses an intelligent particle with multiple changing functions and a preparation method thereof. The particles comprise two parts, a base polymer particle and an inorganic component, the particle change is responsive to temperature, acid base and light. The preparation method of the particle comprises the following steps: responsive polymer particles are added to a solvent, an inorganic precursor is added, and then a catalyst is added to deposit the inorganic in the particles. The particles provided by the invention can be used for intelligent surfaces, intelligent fibers or clothes, catalytic reaction and the like, have wide application prospects in various fields of catalysis, materials, organic chemistry and the like, and are simple and convenient in preparation method, easy to control, universal and suitable for mass production and application.
Description
Technical Field
The invention relates to an intelligently-changed particle and a preparation method thereof, in particular to a bi-component hybrid particle containing a responsive polymer and an inorganic component and a preparation method thereof.
Background
In the field of material chemistry, the development of smart materials has attracted a great deal of interest, wherein environmentally responsive chemicals have been widely focused, which can change their morphology, structure or properties in response to specific environmental factors, such as poly (N-isopropylacrylamide), which has temperature responsiveness, in aqueous solution, exhibits extended chain configuration, i.e., hydrophilicity, when the temperature is below a critical value (about 32 ℃), and exhibits lipophilicity, i.e., lipophilicity, when the temperature is above a critical value (y. hirokawa et al Chemical Physics1984,81(12), 6379-. If the environment-responsive substance is used as one component of the bi-component particle, the particle has the same environment responsiveness, and the shape of the particle and the volume ratio of the two components can be adjusted according to the environment, so that multiple functions of emulsion conversion, molecular recognition, controlled self-assembly and the like are performed, and the material is prepared from the particlesThe method has wide application prospect and value in various fields of materials, chemical industry, medicine, catalysis and spinning. On this basis, various responsive copolymers have been developed, such as copolymers of acrylic acid with N-isopropylacrylamide which are both temperature-responsive and acid-base responsive (H.Feil et al, Macromolecules 1995,373, 49-52; G.Chen et al, Macromolecules 1995,16,175); in recent years, there have been reports of particles having both photoresponse, such as N-isopropylacrylamide containing organic color-changing groups, and a copolymer (B) of acrylic acid and a color-changing monomer.Et al Soft Matter, 2013, 9, 8754-8760). Research for introducing inorganic substances (gold, silver, ferroferric oxide and the like) into the intelligent particles has also been reported, and some inorganic hybrid responsive materials also show a slight volume shrinkage phenomenon under illumination (J.Yoon et al Angew. chem.2012,124,7258), but the principle is mostly attributed to that the inorganic particles cause shrinkage of poly (N-isopropylacrylamide) polymers after being heated by illumination, so that the volume change of the particles is small, and most of the inorganic hybrid responsive materials only have theoretical research value.
Disclosure of Invention
It is an object of the present invention to provide a intelligently varying particle.
By intelligent change is meant that the volume of the particles changes with temperature, light and/or acid-base, and the resulting property changes, such as hydrophilic-hydrophobic property changes, catalytic property changes.
The intelligent variable particles provided by the invention comprise two parts, namely responsive polymers and inorganic matters.
The mass ratio of the inorganic substance to the responsive polymer may be 100:1 to 100: 1000.
The responsive polymer may be: a polymer of a monomer such as N-ethylacrylamide, N-ethyl-2-methylacrylamide, N-diethylacrylamide, N-dimethylacrylamide, N-isopropylacrylamide, N-isopropylmethacrylamide, acrylic acid, methacrylic acid, ethacrylic acid, propylacrylic acid, N-dimethylaminoethyl methacrylate, cyclopropylmethacrylamide, N-dimethylaminoethyl methacrylate, or a copolymer thereof with a crosslinking agent, or a copolymer thereof in any combination with another monomer, and a polymer mainly composed of poly N-isopropylacrylamide may be preferable.
The other monomers in the copolymer with other monomers may be: olefin monomers containing carboxyl groups (such as acrylic acid, methacrylic acid, ethacrylic acid), acrylic esters (such as methyl methacrylate, ethyl methacrylate, butyl methacrylate), N-methylolacrylamide (NMA), N-hydroxyethyl acrylamide, diacetone acrylamide (DAAM), Glycidyl Methacrylate (GMA), hydroxyethyl methacrylate (HEMA), acetoacetic acid ethyl methacrylate, acrylamide, N' -methylenebisacrylamide, styrene or vinylpyridine;
the polymer also includes derived polymers obtained by further reaction on the above polymers, such as sulfonated products of poly (N-isopropylacrylamide-styrene) and hydrolyzed products of poly (N-isopropylacrylamide-methyl methacrylate).
The crosslinking agent is an olefin monomer containing at least two double bonds, such as 1, 5-hexadiene, triallyl isocyanurate, ethylene glycol dimethacrylate, divinylbenzene, NN' -methylenebisacrylamide and the like.
The inorganic substance may be at least one of an oxide, a hydroxide, a metal oxo acid or a salt thereof (e.g., sodium molybdate, potassium molybdate, sodium tungstate, potassium tungstate or tungstic acid, molybdic acid, etc.), a metal carbonate, and a metal oxalate of a metal.
Wherein the metal at least comprises a metal with valence variation characteristics, and the metal with valence variation characteristics can be: at least one metal selected from tungsten, molybdenum, scandium, and rhodium.
The inorganic substance may specifically be: tungsten oxide (e.g., tungsten trioxide, tungsten dioxide), molybdenum oxide (e.g., molybdenum trioxide, molybdenum dioxide), rhodium oxide, rhodium hydroxide, sodium molybdate, sodium tungstate, potassium tungstate, or tungstic acid, molybdic acid, scandium hydroxide, scandium oxide, etc., and may also be an oxalate or carbonate, such as scandium oxalate, rhodium oxalate, tungsten carbonate, tungsten oxalate, scandium carbonate, etc.; other inorganic components such as iron oxide, ferroferric oxide, titanium dioxide, silicon dioxide, sodium oxide, potassium oxide, magnesium oxide, antimony trioxide, barium sulfate, etc. may also be included.
The intelligently variable particles are prepared according to a method comprising the following steps:
dispersing the particles of the responsive polymer in a solvent, adding the metal salt or soluble compound, and separating the particles after full contact to obtain intelligently-changed particles; or
Dispersing the particles of the responsive polymer in a solvent, adding a salt or a soluble compound of the metal, adding a precipitating agent, reacting, and separating out the particles to obtain the intelligently-changed particles.
In the above method, the solvent may be: water, ethanol, propanol, butanol, isopropanol, tetrahydrofuran, N-dimethylformamide, or a mixed solution thereof, preferably water or a mixed solution of water and alcohol.
The salt or soluble compound of the metal may be: tungstate, molybdate, rhodium oxide, scandium trichloride, rhodium trichloride and hydrates thereof, K [ Rh (H)2O)Cl3]、K2[Rh(H2O)Cl5]And rhodium oxide.
The mass ratio of the salt or soluble compound of the metal to the particles of the responsive polymer may be 0.01 to 100, and specifically may be 0.1 to 10.
The precipitating agent may be: at least one of hydrochloric acid, oxalic acid, sulfuric acid, phosphoric acid, nitric acid, formic acid, acetic acid, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate.
The application of the intelligent change particles in catalysis, water treatment and intelligent surface of materials also belongs to the protection scope of the invention.
The inventor finds out in the research that: hybrid particles prepared by incorporating certain oxides or metal salts into polymers show significant shrinkage under light. The particles not only have obvious shrinkage phenomena under the conditions of temperature and acid-base response, but also under the illumination of visible light or ultraviolet light; in addition, some particles also exhibit discoloration under light.
For example: the tungsten oxide/poly (N-isopropylacrylamide) smart particles become smaller with increasing temperature; the particle size of the tungsten oxide/poly (N-isopropylacrylamide-acrylic acid) intelligent particles becomes smaller after illumination.
These properties make it useful in a wide range of applications in the field of smart materials; and the introduction of the inorganic metal compound can bring new catalytic performance. And the preparation method is suitable for mass production.
The invention has the advantages that:
the intelligent particles provided by the invention effectively combine the intelligent color change of inorganic matters with the volume change of polymers, thereby realizing the light-operated volume change; the volume change of the particles has multiple responsibilities of temperature, light, acid and alkali and the like;
in addition, the catalytic performance of the inorganic matter is combined with the environmental response performance of the particles, so that on-off catalysis can be realized; a creative breakthrough is made for developing novel intelligent materials;
the preparation method of the intelligent particles provided by the invention is easy to control the process, is suitable for preparing the particles with different scales, and is particularly suitable for mass production and preparation.
Drawings
FIG. 1 is a graph showing the particle size distribution of the tungsten oxide/poly (N-isopropylacrylamide) smart particles prepared in example 2 as a function of temperature.
FIG. 2 is a photograph of tungsten oxide/poly (N-isopropylacrylamide-acrylic acid) smart particles prepared in example 3 taken before and after exposure to light.
FIG. 3 is a graph showing the change of the hydrophilic and hydrophobic properties of the surface of the tungsten oxide/poly (N, N-diethylacrylamide) smart particles prepared in example 8 after being used in combination with a polyester cloth.
Detailed Description
The present invention will be described below with reference to specific examples, but the present invention is not limited thereto.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
According to the present invention there is provided a smart hybrid particle comprising two components, a responsive polymer and an inorganic, characterised in that a functionalised metal salt is supported on one responsive polymer particle.
The intelligent change particle is characterized in that the particle at least comprises two components of a responsive polymer and an inorganic substance containing tungsten, molybdenum, scandium, rhodium and the like;
the responsive polymer is a polymer of monomers such as N-ethyl acrylamide, N-ethyl-2-methacrylamide, N-diethylacrylamide, N-dimethylacrylamide, N-isopropylacrylamide, N-isopropyl methacrylamide, cyclopropyl methacrylamide, N-dimethylaminoethyl acrylate, methacrylic acid, ethacrylic acid, propylacrylic acid, N-dimethylaminoethyl methacrylate and the like, or a polymer formed by the monomers and a crosslinking agent, or a copolymer formed by the monomers and other monomers in any combination. The polymer is preferably a poly (N-isopropylacrylamide) -based polymer.
Other monomers of the above-mentioned copolymer include olefin monomers having a carboxyl group (e.g., acrylic acid, methacrylic acid, ethacrylic acid), acrylic esters (e.g., methyl methacrylate, ethyl methacrylate, butyl methacrylate), N-methylolacrylamide (NMA), N-hydroxyethyl acrylamide, diacetone acrylamide (DAAM), Glycidyl Methacrylate (GMA), hydroxyethyl methacrylate (HEMA), acetoacetic acid ethyl methacrylate, acrylamide, NN' -methylenebisacrylamide, styrene, or vinylpyridine;
the crosslinking agent is an olefin monomer containing at least two double bonds, such as 1, 5-hexadiene, triallyl isocyanurate, ethylene glycol dimethacrylate, divinylbenzene, NN' -methylenebisacrylamide and the like.
The above-mentioned polymer also includes a derivative polymer obtained by further reacting the above-mentioned polymer, such as a sulfonated product of poly (N-isopropylacrylamide-styrene), a hydrolyzed product of poly (N-isopropylacrylamide-methyl methacrylate).
The inorganic substance is mainly an oxide, a hydroxide, a carbonate or an oxalate, preferably tungsten oxide (such as tungsten trioxide and tungsten dioxide), molybdenum oxide (such as molybdenum trioxide and molybdenum dioxide), rhodium oxide, rhodium hydroxide, sodium molybdate, sodium tungstate, potassium tungstate or tungstic acid, molybdic acid, scandium hydroxide, scandium oxide and the like, and also can be an oxalate or a carbonate, such as scandium oxalate, rhodium oxalate, tungsten carbonate, tungsten oxalate, scandium carbonate and the like; other inorganic components such as iron oxide, ferroferric oxide, titanium dioxide, silicon dioxide, sodium oxide, potassium oxide, magnesium oxide, antimony trioxide, barium sulfate, etc. may also be included.
The preparation method of the intelligent particles comprises the following specific steps:
1) the above responsive polymer particles synthesized by any method are dispersed in a solvent; adding a certain amount of metal salt solution or mixed solution of more than two metal salts or soluble metal compound solution according to the proportion; separating the particles after a certain time to obtain intelligent change particles;
2) the above responsive polymer particles synthesized by any method are dispersed in a solvent; adding a certain amount of metal salt solution or soluble metal compound solution or mixed solution of more than two metal salts according to the proportion; then a certain amount of precipitant solution is added, after full reaction, particles are separated and washed to obtain intelligently changed particles.
The solvent is water, ethanol, propanol, butanol, isopropanol, tetrahydrofuran, N-dimethylformamide or a mixed solution thereof, and is preferably water or a mixed solution of water and alcohol.
The metal salt or soluble metal compound is tungstate, molybdate, rhodium oxide, scandium trichloride, rhodium trichloride or its hydrate, K [ Rh (H)2O)Cl3]、K2[Rh(H2O)Cl5]Rhodium oxide, or any of the above mixed metal salt solutions in a ratio of 0.01 to 100, preferably 0.1 to 10, to the polymer particles.
The precipitant is selected from hydrochloric acid, oxalic acid, sulfuric acid, phosphoric acid, nitric acid, formic acid, acetic acid, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate or their aqueous solution.
The other metal salts may also contain titanates, aluminates, silicates, and the like.
EXAMPLE 1 preparation of sodium molybdate/poly (N-isopropylacrylamide) particles
20mL of 0.1g of poly (N-isopropylacrylamide) particles are added into a 50mL flask, 5mL of 1M sodium molybdate solution is added, and after stirring for 30min, centrifugal separation is carried out to obtain the intelligent particles loaded with sodium molybdate.
EXAMPLE 2 preparation of tungsten oxide/Poly (N-isopropylacrylamide) Smart particles
Adding 10g of poly (N-isopropylacrylamide) into a 250mL flask, adding 150mL of water, adding 10g of potassium tungstate after fully dispersing, stirring for 10 minutes, adding 10mL of 10M hydrochloric acid, reacting for 1 hour, performing centrifugal separation, and fully washing with water to obtain the intelligent particles.
FIG. 1 is a graph showing the particle size distribution of the prepared tungsten oxide/poly (N-isopropylacrylamide) smart particles as a function of temperature.
As can be seen from fig. 1: the particles become smaller at high temperatures.
EXAMPLE 3 preparation of tungsten oxide/Poly (N-isopropylacrylamide-acrylic acid) Smart particles
Adding 10g of poly (N-isopropylacrylamide-acrylic acid) into a 250mL flask, adding 100mL of water, adding 2g of potassium tungstate after fully dispersing, stirring for 1 hour, adding 10mL of 1M hydrochloric acid, reacting for 10 hours, performing centrifugal separation, and fully washing with water to obtain the intelligent particles.
Fig. 2 is a volume shrinkage diagram of the prepared tungsten oxide/poly (N-isopropylacrylamide-acrylic acid) smart particles in water before and after illumination, and the diagram shows that: the particle size of the tungsten oxide/poly (N-isopropylacrylamide-acrylic acid) smart particles becomes smaller after illumination.
EXAMPLE 4 preparation of rhodium hydroxide/Poly (N-isopropylacrylamide-styrene)
Adding 0.1g of poly (N, N-isopropylacrylamide-styrene) copolymer particles (the ratio of the two is 1:1) into concentrated sulfuric acid, heating to 50 ℃ for reacting for 2 hours, fully washing with water, and dispersing the particles in 20mL of water; then adding 0.1g of rhodium chloride, stirring, adding 2mL of 1M potassium hydroxide, reacting for 24 hours, separating and washing to obtain the intelligent particles containing styrene.
EXAMPLE 5 preparation of scandia/poly (N-methylethylacrylamide-methacrylic acid-styrene)
Dispersing 0.1g of poly (N, N-isopropylacrylamide-methacrylic acid-styrene) copolymer particles (the ratio of the three is 5: 5: 1) in 50mL of water; then 0.5g of scandium trichloride is added, 1mL of 2M hydrochloric acid is added after stirring, and separation and washing are carried out after 48 hours of reaction, so as to obtain intelligent particles containing styrene.
EXAMPLE 6 preparation of molybdenum oxide/Poly (N, N-dimethylaminoethyl methacrylate-styrene)
Adding 10g of poly (N, N-dimethylaminoethyl methacrylate-styrene) copolymer particles (the proportion of the two is 2: 1) into concentrated sulfuric acid, heating to 40 ℃ for reaction for 4 hours, fully washing with water, and dispersing the particles in 200mL of water; then 0.1g of sodium molybdate is added, 10mL of 1M hydrochloric acid is added after stirring, and the intelligent particles containing styrene are obtained after reaction for 1 hour and separation and washing.
EXAMPLE 7 preparation of sodium tungstate/Poly (N, N-isopropylacrylamide-methyl methacrylate)
Adding 10g of poly (N, N-dimethylaminoethyl methacrylate-styrene) copolymer particles (the proportion of the two is 2: 1) into concentrated sulfuric acid, heating to 40 ℃ for reaction for 4 hours, fully washing with water, and dispersing the particles in 200mL of water; then adding 0.1g of sodium tungstate, stirring, adding 10mL of 1M hydrochloric acid, reacting for 1 hour, separating and washing to obtain intelligent particles containing styrene.
Example 8 preparation of tungsten oxide/Poly (N, N-diethylacrylamide) Smart particles
Adding 10g of poly (N, N-diethylacrylamide) into a 250mL flask, adding 150mL of water, adding 10g of potassium tungstate after fully dispersing, stirring for 10 minutes, adding 10mL of 10M hydrochloric acid, reacting for 1 hour, performing centrifugal separation, and fully washing with water to obtain the intelligent particles.
The change of the hydrophilic and hydrophobic properties of the surface of the prepared tungsten oxide/poly (N, N-diethylacrylamide) intelligent particle after being combined on polyester cloth for use is shown in FIG. 3.
As can be seen from fig. 3: the contact angle of a water drop on polyester cloth with tungsten oxide/poly (N, N-diethylacrylamide) smart particles bonded thereto changed from 80 degrees to 11 degrees when the temperature was from 40 ℃ to room temperature. This change in wettability will facilitate moisture transport, leading to the use of fabric garments for moisture control, which is beneficial for enhancing the comfort of the textile.
Claims (9)
1. The intelligently-variable particles comprise two parts, namely responsive polymers and inorganic matters, wherein the mass ratio of the inorganic matters to the responsive polymers is 100:1-100: 1000; the inorganic matter is at least one of metal oxide and hydroxide;
the metal includes at least a metal having a valence-altering characteristic,
the metal with valence-change characteristics is as follows: at least one metal selected from tungsten, molybdenum, scandium, and rhodium;
the responsive polymer is: polymers of N-ethylacrylamide, N-ethyl-2-methylacrylamide, N-diethylacrylamide, N-dimethylacrylamide, N-isopropylacrylamide, N-isopropylmethacrylamide, cyclopropylmethacrylamide, N-dimethylaminoethyl ester monomers, acrylic acid, methacrylic acid, N-dimethylaminoethyl methacrylate, ethacrylic acid, propylacrylic acid, or any combination thereof, or copolymers thereof with other monomers;
the other monomers in the copolymer with other monomers are: a carboxyl group-containing olefin monomer, acrylate, N-methylolacrylamide, N-hydroxyethylacrylamide, diacetoneacrylamide, glycidyl methacrylate, hydroxyethyl methacrylate, ethyl acetoacetate methacrylate, acrylamide, N' -methylenebisacrylamide, styrene, or vinylpyridine;
the polymer also comprises a derivative polymer obtained by further reacting on the basis of the polymer;
the intelligent change particles are prepared by the following method:
dispersing the particles of the responsive polymer in a solvent, adding the salt or soluble compound of the metal, adding a precipitator, reacting, and separating out the particles to obtain the intelligently-changed particles.
2. The intelligently varied particle of claim 1, wherein: the inorganic substances are: tungsten oxide, molybdenum oxide, rhodium hydroxide, scandium hydroxide, or scandium oxide.
3. The intelligently varied particle of claim 2, wherein: the inorganic substance also contains other inorganic components;
the other inorganic components are: iron oxide, ferroferric oxide, titanium dioxide, silicon dioxide, sodium oxide, potassium oxide, magnesium oxide, antimony trioxide or barium sulfate.
4. A method of making the intelligently varied particle of any one of claims 1-3, comprising:
dispersing the particles of the responsive polymer in a solvent, adding the salt or soluble compound of the metal, adding a precipitator, reacting, and separating out the particles to obtain the intelligently-changed particles.
5. The method of claim 4, wherein: the solvent is as follows: water, ethanol, propanol, butanol, isopropanol, tetrahydrofuran, N-dimethylformamide, or a mixed solution thereof.
6. The method according to claim 4 or 5, characterized in that: the salts or soluble compounds of the metals are: tungstate, molybdate, rhodium oxide, scandium trichloride, rhodium trichloride, hydrates thereof, and K [ Rh (H)2O)Cl3]、K2[Rh(H2O)Cl5]And rhodium oxide.
7. The method according to claim 4 or 5, characterized in that: the mass ratio of the salt or soluble compound of the metal to the particles of the responsive polymer is 0.01 to 100.
8. The method according to claim 4 or 5, characterized in that: the precipitating agent is: at least one of hydrochloric acid, oxalic acid, sulfuric acid, phosphoric acid, nitric acid, formic acid, acetic acid, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate.
9. Use of the smart change particles of any one of claims 1 to 3 or prepared by the method of any one of claims 4 to 8 in catalysis, water treatment, smart surfaces of materials.
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 CN108034073A (en) | 2018-05-15 |
CN108034073B true CN108034073B (en) | 2021-04-06 |
Family
ID=62095381
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201711275548.7A Active CN108034073B (en) | 2017-12-06 | 2017-12-06 | Intelligently-changed particles and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108034073B (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
CN116813823A (en) * | 2022-03-11 | 2023-09-29 | 北京服装学院 | Supported catalyst, preparation method thereof and application thereof in photocatalytic polymerization |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4519930A (en) * | 1982-01-11 | 1985-05-28 | Kabushiki Kaisha Daini Seikosha | Electrochromic display device |
CN105884969A (en) * | 2016-06-13 | 2016-08-24 | 复旦大学 | Intelligent aerogel with dual responses and adjustable response behaviors and preparation method thereof |
CN105949368A (en) * | 2016-05-31 | 2016-09-21 | 西北师范大学 | Multi-responsiveness amphiphilic polymer microparticle and preparation method thereof |
CN106916248A (en) * | 2017-04-24 | 2017-07-04 | 新疆大学 | A kind of preparation method of temperature and pH double-responses polymer/sodium tungstate composite aquogel |
-
2017
- 2017-12-06 CN CN201711275548.7A patent/CN108034073B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4519930A (en) * | 1982-01-11 | 1985-05-28 | Kabushiki Kaisha Daini Seikosha | Electrochromic display device |
CN105949368A (en) * | 2016-05-31 | 2016-09-21 | 西北师范大学 | Multi-responsiveness amphiphilic polymer microparticle and preparation method thereof |
CN105884969A (en) * | 2016-06-13 | 2016-08-24 | 复旦大学 | Intelligent aerogel with dual responses and adjustable response behaviors and preparation method thereof |
CN106916248A (en) * | 2017-04-24 | 2017-07-04 | 新疆大学 | A kind of preparation method of temperature and pH double-responses polymer/sodium tungstate composite aquogel |
Non-Patent Citations (1)
Title |
---|
聚合物/三氧化钨电致变色复合材料的制备;王晓鹏;《硕士学位论文》;20071111 * |
Also Published As
Publication number | Publication date |
---|---|
CN108034073A (en) | 2018-05-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108034073B (en) | Intelligently-changed particles and preparation method thereof | |
CN101293936B (en) | Preparation method of monodisperse polystyrene microsphere with controllable particle size | |
Gao et al. | Research progress of poly (methyl methacrylate) microspheres: preparation, functionalization and application | |
CN103554376B (en) | The preparation method of monodisperse cross-linked poly (methyl methacrylate) micro-sphere | |
CN103709341A (en) | Preparation method of magnetic zinc ion surface-imprinted polymer | |
CN106916260B (en) | A kind of preparation method of hud typed porous high water absorption microballoon | |
CN101220128B (en) | Polymethyl methacrylate composite microsphere, preparation method and application thereof | |
JP5439691B2 (en) | High valent metal ion scavenger | |
CN102977266A (en) | Preparation method of temperature and pH value dual responsive microgel | |
CN110713609A (en) | Method for preparing self-repairing hydrogel based on Janus nano material | |
CN101544723A (en) | Method for preparing fluorinated acrylate copolymer | |
CN105601831B (en) | A kind of preparation method of amino modified acrylic resin complex microsphere | |
CN101066772A (en) | One-step process of preparing nanometer magnesium hydroxide fire retardant in alcohol water system | |
CN106582492A (en) | ZrO2 for heavy metal wastewater treatment and preparation method and application thereof | |
KR860001409B1 (en) | Method of producing for bead-like polymer production | |
CN105440196B (en) | A kind of polystyrene-acrylate copolymer microballoon and preparation method thereof | |
CN107236078B (en) | Preparation method of flexible soft monomer colloid photonic crystal emulsion | |
CN112831147A (en) | Color-changing particle and preparation method thereof | |
CN104592532A (en) | Amphiphilic copolymer network and preparation method thereof | |
CN111533917A (en) | High-critical-dissolution-temperature-type temperature-sensitive zirconium-based metal organic framework material and preparation method thereof | |
CN106977639B (en) | A kind of pair of lead ion has porous microsphere shape absorption resin of selective absorption and preparation method thereof | |
CN103643338B (en) | A kind of method utilizing superabsorbent water micro-nano ball to prepare antistatic fibre | |
CN108822238A (en) | A kind of preparation method for the polymethylacrylic acid trifluoro ethyl ester colloid emulsion that monodisperse is hydrophobic | |
CN104628975A (en) | Pharmaceutical amphiphilic copolymer network and preparation method thereof | |
JP2009227883A (en) | Complex fine particles, and its dispersion liquid and molding |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |