CN109651574A - A kind of star-type polymer compound silver nanometer particle and preparation method thereof controllable with size and dispersibility - Google Patents
A kind of star-type polymer compound silver nanometer particle and preparation method thereof controllable with size and dispersibility Download PDFInfo
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- CN109651574A CN109651574A CN201710938439.2A CN201710938439A CN109651574A CN 109651574 A CN109651574 A CN 109651574A CN 201710938439 A CN201710938439 A CN 201710938439A CN 109651574 A CN109651574 A CN 109651574A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
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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
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
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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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Abstract
The invention discloses a kind of star-type polymer compound silver nanometer particles and preparation method thereof controllable with size and dispersibility.The star-type polymer compound silver nanometer particle includes beta-cyclodextrin, polyacrylic acid, polystyrene and Nano silver grain.The internally positioned center of beta-cyclodextrin, it is described it is polyacrylic acid grafted on the beta-cyclodextrin, outermost end is the polystyrene chain segment, the Nano silver grain is carried on the polyacrylic acid segment.The preparation method includes: so that it is switched to 21Br- β-CD with the hydroxyl in 2- bromine isobutyl acylbromide modification beta-cyclodextrin (β-CD)；Using 21Br- β-CD as macromole evocating agent, respectively cause tert-butyl acrylate monomer (tBA), styrene monomer (St) prepares star-like bi-block copolymer β-CD-g‑[PtBA‑b-PS]；Trifluoroacetic acid is added to be hydrolyzed, obtains unimolecule template β-CD-g‑[PAA‑b-PS]；With the β-CD-g‑[PAA‑b- PS] it is reaction system, oil-soluble Ag nanoparticle is prepared, the PS of outer layer does not give only the lipophilicity of Ag nanoparticle, more greatly improves its monodispersity and stability.
Description
Technical field
The present invention relates to a kind of polymerization of high molecular reactive, functional polymer MOLECULE DESIGN and inorganic crystal growth etc. are multidisciplinary
Crossing domain, and in particular to a kind of the star-type polymer compound silver nanometer particle and its preparation side controllable with size and dispersibility
Method.
Background technique
After in 1984 Germany scientist Gleiter prepares nanocrystalline copper, iron, palladium for the first time, research
Nano material is increasingly becoming a research hotspot field.Having one-dimensional dimensions above in the material of 1 ~ 100nm is generally referred to as nanometer material
Material.Under normal conditions, a large amount of free electron of the inside and surface of the noble metals such as gold, silver, will form free electron air mass.When
When incident light and its surface free electron resonate, surface plasma body resonant vibration can be formed.Shape, size, the surrounding of nano particle
The change of the factors such as environment dielectric constant can cause surface free electron frequency of oscillation to change.Its specificity in structure, silver
Nanoparticle has special physicochemical properties, makes Nano silver grain in biomedicine, sewage treatment, environmental monitoring and catalysis
Agent etc. has broad application prospects.
In different subsciences, such as chemical catalysis, Nano medication, nanoelectronics etc., Nano silver grain and other are expensive
Metal nanocrystal plays an important role.Granule size and granularity point for most of applications, to nano material
The control of cloth is most important.Many aspects in synthesis process can influence the size distribution and granule size of nano material,
Such as the selection of surfactant, pH value, temperature, the concentration of reductant concentration and other metal salts.
There are many kinds of the synthetic methods of Nano silver grain, there are mainly four types of, comprising: photochemistry, crystal seed method, template and electrification
Method etc..Although existing preparation method has successfully prepared Nano silver grain, existing traditional synthetic method has
A series of limitation in preparations mainly includes the following aspects:
(1) it is difficult to realize the accurate control to nanoparticle size；
(2) nanoparticle prepared can not achieve very high monodispersity；
(3) for the application of next step, need to do prepared nano material further surface ligand modification etc.；
(4) preparation process is complicated, it is difficult to be mass produced；
(5) preparation condition is harsh.
Summary of the invention
For the technical problem encountered in Nano silver grain design synthesis above, the present invention propose it is a kind of convenient, can
The preparation method of the star-type polymer compound silver nanometer particle of large scale preparation, not only size is controllable, more greatly improves Yin Na
The monodispersity and stability of rice corpuscles.
First aspect present invention provides a kind of star-type polymer controllable with size and dispersibility that can be prepared on a large scale
Compound silver nanometer particle, including Nano silver grain, beta-cyclodextrin, polyacrylic acid, polystyrene, in which:
The internally positioned center of beta-cyclodextrin, described polyacrylic acid grafted on the beta-cyclodextrin, outermost end is described poly-
Styrene segment, the Nano silver grain are carried on the polyacrylic acid segment；
The chain length of the polyacrylic acid is greater than the chain length of polystyrene.
Second aspect of the present invention provides a kind of preparation method of above-mentioned star-type polymer compound silver nanometer particle,
The described method includes:
Use anhydrous dimethyl formamide (DMF) for diluent and acid absorbent, on 2- bromine isobutyl acylbromide modification beta-cyclodextrin
Hydroxyl, the macromole evocating agent for making it switch to can be used for atom transfer radical polymerization (ATRP)；
Using the Br- beta-cyclodextrin of hub-and-spoke configuration as macromole evocating agent, using the ATRP technology of continuous polymerization, cause third respectively
Enoic acid ter-butyl ester monomer (tBA), styrene monomer (St) prepares a series of star-like bi-block copolymer β-that most outer segments are PS
CD-g-[PtBA-b-PS]；
Take the appropriate star-like bi-block copolymer β-CD-g-[PtBA-b- PS], trifluoroacetic acid is added and is hydrolyzed, obtains list
Molecular template β-CD-g-[PAA-b-PS]；
Based on solution phase synthesis, with a certain number of β-CD-g-[PAA-b- PS] unimolecule template be reactant
System, prepares oil-soluble Ag nanoparticle；
The precursor compound of target material is added first in the unimolecule template reaction system, adds ethyl alcohol as also
Former agent, precursor compound is in polyacrylic acid phase in-situ preparation Nano silver grain；
Presoma used in the precursor compound is AgNO3。
The present invention proposes the preparation side of star-type polymer compound silver nanometer particle that is a kind of convenient, can be prepared on a large scale
Method, size is controllable, and the PS segment of outer layer does not give only the lipophilicity of Ag nanoparticle, more greatly improve its monodispersity and
Stability.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is a kind of star-type polymer compound silver nanometer controllable with size and dispersibility provided in an embodiment of the present invention
The transmission electron microscope picture of particle；
Fig. 2 is a kind of star-type polymer compound silver nanometer particle controllable with size and dispersibility provided in an embodiment of the present invention
X-ray diffractogram；
Fig. 3 is a kind of star-type polymer compound silver nanometer particle controllable with size and dispersibility provided in an embodiment of the present invention
EDS figure；
Fig. 4 is a kind of star-type polymer compound silver nanometer particle controllable with size and dispersibility provided in an embodiment of the present invention
Preparation method flow chart.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Fig. 1 is a kind of star-type polymer compound silver nanometer controllable with size and dispersibility provided in an embodiment of the present invention
The transmission electron microscope picture of particle.As shown in Fig. 1, which includes Nano silver grain, β-ring paste
Essence, polyacrylic acid, polystyrene.
Specifically, the internally positioned center of beta-cyclodextrin, polyacrylic acid grafted on beta-cyclodextrin, outermost end is polystyrene
Segment, Nano silver grain are carried on polyacrylic acid segment.
Fig. 2 is a kind of star-type polymer compound silver nanometer controllable with size and dispersibility provided in an embodiment of the present invention
The X-ray diffractogram of particle.As shown in Fig. 2, different x-ray diffraction maximum respectively corresponds the star-type polymer compound silver nanometer particle
(111), (200), (220) and (222) crystal face.
Fig. 3 is a kind of star-type polymer compound silver nanometer controllable with size and dispersibility provided in an embodiment of the present invention
The EDS of particle schemes.As shown in figure 3, the crystalline state of the star-type polymer compound silver nanometer particle has and only silver element.
Fig. 4 is a kind of star-type polymer compound silver nanometer controllable with size and dispersibility provided in an embodiment of the present invention
The preparation method flow chart of particle.As shown in Figure 1, the preparation method of the star-type polymer compound silver nanometer particle includes following step
It is rapid:
Using beta-cyclodextrin as the star-like macromole evocating agent 21Br- β-CD of precursor synthesis.
Specifically, 6.82 grams of beta-cyclodextrins (6mmol), under vacuum conditions in 80oC is 12 hours dry, then in room temperature
Under the conditions of be dissolved in 60 milliliters of N- crassitude (1-methyl-2-pyrrolidione (NMP)), then make entire anti-
System is answered to be cooled to 0 with ice-water bathoC is slowly added to 58 g (252 mmol) 2- bromine isobutyl under this condition in 2 hours
Acylbromide, finally makes entire reaction system slowly be warming up to room temperature, and the reaction was continued under this condition no less than 24 hours.It is obtained
The solution of brown is evaporated under reduced pressure concentration, is then diluted with 100 milliliters of methylene chloride, closes sodium bicarbonate aqueous solution with full respectively
(100 milliliters) and dilute hydrochloric acid (100 milliliters) are respectively washed three times.Obtained organic phase is dry with anhydrous magnesium sulfate, then with rotation
Evaporimeter concentration, finally precipitates in cold n-hexane, obtains white depositions, 12 hours dry in vacuum drying oven.
Multi-arm star-shaped star-like P is synthesized by macromole evocating agent of 21Br- β-CDtBA。
Specifically, be separately added into a collection of 100mL ampoule bottle CuBr (0.0707 g), PMDETA (0.1707 g),
21Br- β-CD (0.1 g), tert-butyl acrylate monomer (20 mL), butanone (20 mL) reaction system are put in liquid nitrogen and pass through
It freezes-vacuumizes degassing-thaw cycles three times, ampoule bottle is put into 60 after closedoIn C oil bath, it is anti-to open magnetic agitation
It answers.Then ampoule bottle is taken out by certain time interval, and is put into mixture of ice and water, terminate reaction.Crude product is with third
After ketone dilution, crosses neutral alumina pillar and remove catalyst, (methanol and water are then precipitated in the mixture of cold methanol and water
Volume ratio be 1:1).After repeating dissolution/precipitation operation twice, it is dry that gained white powder product is placed at vacuum at 50 DEG C
Dry 12 hours.
Synthesize multiple-arm star block copolymer star-shapedPtBA-b-PS。
Specifically, being separately added into styrene monomer (20 mL), CuBr (0.0707 in a collection of 50 mL ampoule bottles
g), bpy (0.1539 g), star-like PtBA (0.5 g), reaction system are put in liquid nitrogen by freezing-vacuumizing
Ampoule bottle three times, is put into 90 after closed by degassing-thaw cyclesoIn C oil bath, magnetic agitation reaction is opened.Then by certain
Time interval take out ampoule bottle respectively, and put into mixture of ice and water, terminate reaction.Crude product tetrahydrofuran
(THF) it after diluting, crosses neutral alumina pillar and removes catalyst, then precipitated in cold methanol.Repeat dissolution/precipitation operation
After twice, gained white powder product is placed at 50 DEG C and is dried in vacuo 6 hours.
Synthesize multiple-arm star block copolymer star-shaped PAA-b-PS。
Specifically, multiple-arm star block copolymer (star-like PtBA-b- PS) (0.3 g) be dissolved in 30 mL dichloros
In methane, 0oC is vigorously stirred lower addition trifluoroacetic acid (in 5 times of polymertThe amount of the substance of BA unit), 0oC is kept
After 3 hours, continue to be stirred to react 21 hours at room temperature.With the progress of hydrolysis, there are white depositions, reacted
Afterwards, it filters, and is rinsed with methylene chloride, sediment is amphipathic multi-arm star-shaped by the polymer that vacuum freeze drying obtains white
Block copolymer (star-shaped PAA-b- PS).
Synthesize size and dispersed controllable star-type polymer compound silver nanometer particle.
Specifically, based on solution phase synthesis, with star-shaped PAA-b- PS unimolecule template, preparation oil are molten
The nano particle of property.First a certain amount of template molecule star-shaped PAA-b- PS(10 mg) (example is dissolved in good solvent
Such as DMF, 10 mL), unimolecular micelle template solution is made, the precursor compound silver nitrate of target material is next added, it should
Precursor compound is since the ligand complex of core template phase PAA acts on, so that the diffusion aggregation of selectivity is to PAA template phase, when
When reaction condition reaches corresponding mineral crystal formation condition, precursor compound is in the corresponding inorganic nano of template phase in-situ preparation
Crystal, outermost PS phase are used as ligand, are covered in the surface of nano particle in situ, and the nano particle generated can be enable to disperse
In corresponding nonpolar solvent (such as toluene, tetrahydrofuran, acetone etc.), while preventing the nano particle in organic solvent
Reunite.
The star-type polymer compound silver nanometer particle that the embodiment of the invention provides one kind easily, can be prepared on a large scale
Preparation method, not only size is controllable, more greatly improves the monodispersity and stability of Nano silver grain, expands nano grain of silver
Son biomedicine, sewage treatment, environmental monitoring and in terms of application prospect.
The above disclosure is only the preferred embodiments of the present invention, cannot limit the right model of the present invention with this certainly
It encloses, therefore equivalent changes made in accordance with the claims of the present invention, is still within the scope of the present invention.
Claims (5)
1. a kind of star-type polymer compound silver nanometer particle controllable with size and dispersibility, including Nano silver grain, special
Sign is, further includes beta-cyclodextrin, polyacrylic acid, polystyrene, in which:
The internally positioned center of beta-cyclodextrin, described polyacrylic acid grafted on the beta-cyclodextrin, outermost end is described poly-
Styrene segment, the Nano silver grain are carried on the polyacrylic acid segment.
2. star-type polymer compound silver nanometer particle according to claim 1, which is characterized in that the chain of the polyacrylic acid
The long chain length for being greater than polystyrene.
3. a kind of method for preparing star-type polymer compound silver nanometer particle as described in claim 1, which is characterized in that the side
Method includes:
(1) it uses anhydrous dimethyl formamide (DMF) for diluent and acid absorbent, modifies beta-cyclodextrin with 2- bromine isobutyl acylbromide
On hydroxyl, the macromole evocating agent for making it switch to can be used for atom transfer radical polymerization (ATRP)；
(2) using the Br- beta-cyclodextrin of hub-and-spoke configuration as macromole evocating agent, using the ATRP technology of continuous polymerization, cause respectively
Tert-butyl acrylate monomer (tBA), styrene monomer (St) prepares a series of starlike bi-block copolymer that most outer segments are PS
β-CD-g-[PtBA-b-PS]；
(3) the appropriate star-like bi-block copolymer β-CD- is takeng-[PtBA-b- PS], trifluoroacetic acid is added and is hydrolyzed, obtains
Unimolecule template β-CD-g-[PAA-b-PS]；
(4) based on solution phase synthesis, with a certain number of β-CD-g-[PAA-b- PS] unimolecule template be reaction
System prepares oil-soluble Ag nanoparticle.
4. the method according to claim 3(4), which is characterized in that add first in the unimolecule template reaction system
The precursor compound for entering target material adds ethyl alcohol as reducing agent, and precursor compound is mutually in situ raw in polyacrylic acid
At Nano silver grain, outermost polystyrene is mutually used as ligand, is covered in the surface of nanoparticle in situ, forms stable star
Type unimolecular micelle.
5. according to the method described in claim 4, it is characterized in that, the precursor compound is AgNO3。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110903648A (en) * | 2019-11-05 | 2020-03-24 | 武汉华星光电半导体显示技术有限公司 | Polyimide compound and preparation method thereof |
| CN113493568A (en) * | 2020-03-18 | 2021-10-12 | 北京大学深圳研究生院 | High-molecular noble metal nano composite material and preparation method thereof |
| CN113736207A (en) * | 2021-08-17 | 2021-12-03 | 复旦大学 | Multi-component surface organic-inorganic composite nano particle and preparation method and application thereof |
| WO2024020780A1 (en) * | 2022-07-26 | 2024-02-01 | Dic Corporation | Star-shaped polymer, paint, coating, and method for producing star-shaped polymer |
-
2017
- 2017-10-11 CN CN201710938439.2A patent/CN109651574A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110903648A (en) * | 2019-11-05 | 2020-03-24 | 武汉华星光电半导体显示技术有限公司 | Polyimide compound and preparation method thereof |
| CN113493568A (en) * | 2020-03-18 | 2021-10-12 | 北京大学深圳研究生院 | High-molecular noble metal nano composite material and preparation method thereof |
| CN113736207A (en) * | 2021-08-17 | 2021-12-03 | 复旦大学 | Multi-component surface organic-inorganic composite nano particle and preparation method and application thereof |
| WO2024020780A1 (en) * | 2022-07-26 | 2024-02-01 | Dic Corporation | Star-shaped polymer, paint, coating, and method for producing star-shaped polymer |
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Application publication date: 20190419 |