CN109265690A - A kind of hollow polymer nanosphere and preparation method thereof - Google Patents
A kind of hollow polymer nanosphere and preparation method thereof Download PDFInfo
- Publication number
- CN109265690A CN109265690A CN201810895527.3A CN201810895527A CN109265690A CN 109265690 A CN109265690 A CN 109265690A CN 201810895527 A CN201810895527 A CN 201810895527A CN 109265690 A CN109265690 A CN 109265690A
- Authority
- CN
- China
- Prior art keywords
- solution
- hollow polymer
- preparation
- organic molecule
- hollow
- 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.)
- Granted
Links
Classifications
-
- 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
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/08—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing boron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
Abstract
The present invention provides a kind of method that hollow polymer nanosphere simply is prepared in situ.Polymer nano-particle is prepared using the method for condensation driving collaboration polymerization first；Then the small organic molecule of the group containing primaquine is added in system, utilize the migration exchange interaction of substance in component inside polymer nano-particle and solution system, and by the competitive reaction of dynamic imine linkage in the organic molecule of group containing primaquine in solution and polymer nano-particle, one-step method, original position prepare hollow polymer nanosphere without template.
Description
Technical field
The invention belongs to field of nanometer material technology, and in particular to a kind of hollow polymer nanosphere and preparation method thereof.
Background technique
Hollow polymer nanosphere is progress nanoparticle morphology control on the basis of macromolecule synthesising technology progress
Product.Hollow polymer nanosphere is a kind of polymer spheres with hollow structure, has ultralight, low close, Gao Bibiao
The features such as face, heat-insulated, sound insulation, extinction.It can be used as catalyst carrier, microreactor, zymoprotein carrier, and applied in special type
The fields such as material, medical and health, resistance damping material, information-recording material show wide application prospect.Currently, hollow polymer
There are mainly three types of the preparation methods of microballoon: microemulsion polymerization method, self-assembly method and template.
Microemulsion polymerization method is to first pass through monomer radical polymerization to generate seed microballoon, and then new reactant is added and passes through
Emulsion polymerization forms shell around " seed ", forms tiny balloon after removing kernel finally by swelling or other modes.It should
The emulsifier of method is big, usually brings that at high cost, post-processing is difficult, is difficult to the problems such as meeting environmental requirements.
Self-assembly method is a kind of important method of polymeric hollow nanosphere.Mainly pass through following three kinds of self assembly approach
Obtain the hollow polymer nanosphere of stable structure.One is obtaining non-covalent bond by molecular self-assembling connects micella, so
It is crosslinked afterwards by shell and karyolysis obtains tiny balloon.The second is first with amphiphilic block or graft polymers shape in the solution
At the micella of core-shell structure, polymer hollow microsphere is then obtained by the chemistry or biodegrade of the crosslinking curing of shell and core.
The third is self assembly directly forms hollow polymer in selective solution using flexible rigid block copolymer.This method preparation
Hollow Nano microballoon stability it is bad.
Template is that polymer shell is formed in template particles well prepared in advance, is then left template removal hollow poly-
It closes object micro-capsule and obtains the microballoon with hollow polymer structure.Common template has solid construction template, such as charges emulsion particle
With inorganic particulate etc.；Imitated vesicle structure soft template, such as natural materials liposome, the soft templates substance such as octadecyl bromination ammonium.The party
The composition that method frequently results in product is not easy uniformly, and particle is easy to reunite etc..
Summary of the invention
It is an object of the invention in place of overcome the deficiencies in the prior art, provide a kind of hollow polymer nanosphere and
Preparation method solves the problems in above-mentioned background technique.
The technical solution adopted by the present invention to solve the technical problems is: provide goal of the invention be to provide it is a kind of hollow
Polymer nano-microspheres and preparation method thereof.
The technical solution adopted by the present invention to solve the technical problems is: providing a kind of hollow polymer nanosphere
Preparation method includes the following steps:
(1) monomer containing catechol group and alcohol are mixed to get solution A with 5~10g:1~100L ratio；
(2) group monomer containing phenyl boric acid and alcohol are mixed to get solution B with 5~10g:1~100L ratio；
(3) under 0~50 DEG C of stirring condition, solution A is added dropwise with the speed of 1mL/min~10mL/min in solution B
In, the volume ratio of the solution A and solution B is 2~4:2~5, drips 4~72h of reaction, obtains solution C；
(4) organic molecule C and alcohol are mixed with 0.5~50mg:1~1000mL ratio, obtains solution D；It is described organic
The general formula of molecule C is, wherein 1≤n≤3；
(5) solution C and solution D are mixed with the ratio of 100:1, reacts 0.5~6h, centrifugation obtains product, the product
For the polymer spheres of hollow structure, diameter is up to 200~500nm, 5~40nm of shell thickness.
In a preferred embodiment of the present invention, the organic molecule C be the group containing primaquine organic molecule, be ethylenediamine,
Any one of propane diamine, propylamine.
In a preferred embodiment of the present invention, the preparation step of monomer containing catechol group are as follows: by polyamino chemical combination
Object and 3,4- 4-dihydroxy benzaldehyde are dissolved in alcohol according to the ratio of molar ratio 1:2~4,10~50 DEG C, be protected from light, stirring rate
It is stirred to react 12~48h under conditions of 200~600rpm, obtains monomer containing catechol group.
In a preferred embodiment of the present invention, the multiamino compound is ethylenediamine, p-phenylenediamine, the bis- [4- (4- of 2,2-
Amino-benzene oxygen) phenyl] hexafluoropropane, three (2- amino-ethyl) amine, three (4- aminophenyl) ammonia, (the 4- ammonia of 5,10,15,20- tetra-
Any one of base phenyl) porphyrin.
In a preferred embodiment of the present invention, the monomer containing catechol group is following structural formula compound represented
One of DEC, DC, DFC, TEC, TC, PC:
In a preferred embodiment of the present invention, the group monomer containing phenyl boric acid is following structural formula compound represented
One of DEB, DB, DFB, TEB, TB, PB:
In a preferred embodiment of the present invention, the alcohol is methanol or ethyl alcohol.
The present invention also provides a kind of hollow polymer nanospheres, are the polymer spheres of hollow structure；The polymerization
The shell of object sphere is polymer of 5~40nm thickness containing B, N element；The general formula of the organic molecule C isWherein 1
≤n≤3。
In a preferred embodiment of the present invention, the organic molecule C be the group containing primaquine organic molecule, be ethylenediamine,
Any one of propane diamine, propylamine.The polymer spheres diameter is 200~500nm.
Preparation method provided by the present invention is different from three kinds of main methods in background technique, provides a kind of simple original
The method that position prepares hollow polymer nanoparticle.Imine linkage is contained using the method preparation of condensation driving collaboration polymerization first
Polymer nano-particle；Then the small organic molecule of the group containing primaquine is added in system, centrifugation obtains hollow after reaction
Polymer nano-microspheres.
The present invention utilizes the migration exchange interaction of component and substance in solution system inside polymer nano-particle, and passes through
In solution in the organic molecule of group containing primaquine and polymer nano-particle dynamic imine linkage competitive reaction, one-step method, original position,
The characteristics of no template prepares hollow polymer nanoparticle, and the particle prepared has monodispersity good, size uniformity.
It is had a characteristic that using hollow polymer nanosphere prepared by the method for the present invention
(1) realize that one-step method is former using the difference (Kinkendal Effect) of component migration rate inside and outside polymer nano-particle
Position prepares hollow polymer nanoparticle.
(2) hollow polymer nanoparticle prepared by the present invention has the characteristics that shell structurre element is controllable, can be according to function
It can need to adulterate the elements such as B, N, F, P.
Detailed description of the invention
Fig. 1 is the infrared spectrum of prepared hollow polymer nanosphere in embodiment 1, and abscissa is to absorb in Fig. 1
Wave number wavenumber (cm-1)。
Fig. 2 is the transmission electron microscope picture (TEM) of prepared hollow polymer nanosphere in embodiment 1, the TEM in Fig. 2
Scale is 200nm.
Fig. 3 is the transmission electron microscope picture (TEM) of prepared hollow polymer nanosphere in embodiment 2, the TEM in Fig. 3
Scale is 500nm.
Specific embodiment
Embodiment 1
(1) 50mg DFC is weighed, DFC is added in 20mL methanol, obtains clear solution A completely by ultrasonic dissolution；
(2) 35mg TB is weighed, TB is added in 20mL ethyl alcohol, obtains clear solution B completely by dissolving by heating；
Under (3) 25 DEG C of stirring conditions, solution B is added in solution A dropwise (drop speed is 5mL/min), drips reaction 12
Hour, obtain solution C；
(4)~(5) after reaction, weigh 50mg ethylenediamine and are dissolved in 50mL methanol, be added in the solution C of step (3),
The ratio of solution C and solution D is 100:1, is reacted 2 hours, and centrifugation obtains product.
Fig. 1~2 are please referred to, a kind of hollow polymer nanosphere prepared using the present embodiment method is hollow structure
Polymer spheres；The diameter of the polymer spheres up to 200~500nm, shell be 5~40nm thickness containing B, N element it is poly-
Close object；The general formula of the organic molecule C is, wherein 1≤n≤3.The organic molecule C is the organic of the group containing primaquine
Molecule is any one of ethylenediamine, propane diamine, propylamine.
Embodiment 2
(1) 60mg DEC is weighed, DEC is added in 40mL methanol, obtains clear solution A completely by ultrasonic dissolution；
(2) 30mg TB is weighed, TB is added in 20mL ethyl alcohol, obtains clear solution B completely by dissolving by heating；
Under (3) 30 DEG C of stirring conditions, solution B is added in solution A dropwise (drop speed is 8mL/min), drips reaction 12
Hour, obtain solution C；
(4)~(5) after reaction, weigh 20mg ethamine and are dissolved in 100mL methanol, be added in the solution C of step (3),
Reaction 2 hours, centrifugation obtain product.
Fig. 3 is please referred to, a kind of hollow polymer nanosphere manufactured in the present embodiment is the polymer drops of hollow structure
Body；
Embodiment 3
(1) 30mg DC is weighed, DC is added in 30mL ethyl alcohol, obtains clear solution A completely by ultrasonic dissolution；
(2) 50mg TEB is weighed, TEB is added in 50mL methanol, obtains clear solution B completely by ultrasonic dissolution；
Under (3) 30 DEG C of stirring conditions, solution B is added in solution A dropwise (drop speed is 4mL/min), drips reaction 12
Hour, obtain solution C；
(4)~(5) after reaction, weigh 30mg propylamine and are dissolved in 200mL methanol, be added in the solution C of step (3),
Reaction 2 hours, centrifugation obtain product.
A kind of hollow polymer nanosphere prepared by the present invention, utilizes component migration rate inside and outside polymer nano-particle
Difference (Kinkendal Effect) realize that one-step method is prepared in situ, product has that monodispersity is good, size uniformity, shell structurre member
The controllable feature of element, can need to adulterate the elements such as B, N, F, P according to function.
The above is only the preferred embodiment of the present invention, the range implemented of the present invention that therefore, it cannot be limited according to, i.e., according to
Equivalent changes and modifications made by the invention patent range and description, should still be within the scope of the present invention.
Claims (11)
1. a kind of preparation method of hollow polymer nanosphere, which comprises the steps of:
(1) monomer containing catechol group and alcohol are mixed to get solution A with 5~10g:1~100L ratio；
(2) group monomer containing phenyl boric acid and alcohol are mixed to get solution B with 5~10g:1~100L ratio；
(3) under 0~50 DEG C of stirring condition, solution B is added dropwise in solution A with the speed of 1mL/min~10mL/min, institute
The volume ratio for stating solution A and solution B is 2~4:2~5, drips 4~72h of reaction, obtains solution C；
(4) organic molecule C and alcohol are mixed with 0.5~50mg:1~1000mL ratio, obtains solution D；The organic molecule C
General formula beWherein 1≤n≤3；
(5) solution C and solution D are mixed with the ratio of 100:1, reacts 0.5~6h, centrifugation obtains product, and the product is sky
The polymer spheres of core structure, diameter is up to 200~500nm, 5~40nm of shell thickness.
2. a kind of preparation method of hollow polymer nanosphere according to claim 1, it is characterised in that: described organic
Molecule C is the organic molecule of the group containing primaquine, is any one of ethylenediamine, propane diamine, propylamine.
3. a kind of preparation method of hollow polymer nanosphere according to claim 1, it is characterised in that: described containing neighbour
Resorcinol groups monomer preparation step are as follows: by multiamino compound and 3,4- 4-dihydroxy benzaldehyde according to the ratio of molar ratio 1:2~4
Example be dissolved in alcohol, 10~50 DEG C, be protected from light, 200~600rpm of stirring rate under conditions of be stirred to react 12~48h, contained
Catechol group monomer.
4. a kind of preparation method of hollow polymer nanosphere according to claim 3, it is characterised in that: more ammonia
Based compound is ethylenediamine, p-phenylenediamine, 2,2- bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane, three (2- amino-ethyls)
Any one of amine, three (4- aminophenyl) ammonia, 5,10,15,20- tetra- (4- aminophenyl) porphyrin.
5. a kind of preparation method of hollow polymer nanosphere according to claim 1 or 3, it is characterised in that: described
Monomer containing catechol group is one of following structural formula compound represented DEC, DC, DFC, TEC, TC, PC:
6. a kind of preparation method of hollow polymer nanosphere according to claim 1, it is characterised in that；It is described to contain benzene
Boric acid base group monomer is one of following structural formula compound represented DEB, DB, DFB, TEB, TB, PB:
7. a kind of preparation method of hollow polymer nanosphere according to claim 1, it is characterised in that；The alcohol is
Methanol or ethyl alcohol.
8. such as a kind of hollow polymer nanosphere of any one of claim 1~7 preparation, it is characterised in that；For hollow structure
Polymer spheres；The shell of the polymer spheres is polymer of 5~40nm thickness containing B, N element；The organic molecule C
General formula beWherein 1≤n≤3.
9. a kind of hollow polymer nanosphere as claimed in claim 8, it is characterised in that；The organic molecule C is containing primary
The organic molecule of amine groups.
10. a kind of hollow polymer nanosphere as claimed in claim 8, it is characterised in that；The organic molecule C is second two
Any one of amine, propane diamine, propylamine.
11. a kind of hollow polymer nanosphere as claimed in claim 8, it is characterised in that；The polymer spheres diameter
For 200~500nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810895527.3A CN109265690B (en) | 2018-08-08 | 2018-08-08 | Hollow polymer nano-microsphere and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810895527.3A CN109265690B (en) | 2018-08-08 | 2018-08-08 | Hollow polymer nano-microsphere and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109265690A true CN109265690A (en) | 2019-01-25 |
| CN109265690B CN109265690B (en) | 2020-10-09 |
Family
ID=65153489
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810895527.3A Active CN109265690B (en) | 2018-08-08 | 2018-08-08 | Hollow polymer nano-microsphere and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109265690B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110534349A (en) * | 2019-08-05 | 2019-12-03 | 厦门大学 | A kind of nitrogen, boron and bimetallic co-doped nano microballoon, preparation method and application |
| CN112480345A (en) * | 2020-10-20 | 2021-03-12 | 厦门大学 | Metal salt @ ammonia aldehyde polymer nanosphere, preparation method and application |
| CN116003806A (en) * | 2022-07-19 | 2023-04-25 | 厦门大学 | Boron-linked borate supermolecule, modified nanoparticle thereof, preparation method and application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001032795A1 (en) * | 1999-10-29 | 2001-05-10 | Closure Medical Corporation | Cyanoacrylate solutions containing preservatives |
| CN106543446A (en) * | 2016-11-18 | 2017-03-29 | 中国工程物理研究院激光聚变研究中心 | A kind of preceramic polymer microsphere and preparation method thereof |
| CN107082411A (en) * | 2017-05-18 | 2017-08-22 | 厦门大学 | A kind of nitrogen, boron codope carbon nanometer micro ball and preparation method thereof |
| CN107096514A (en) * | 2017-06-16 | 2017-08-29 | 江苏科技大学 | Boronate tin oxide trace composite nano-microsphere, its preparation method and its application of a kind of hollow structure |
| CN107180974A (en) * | 2017-05-18 | 2017-09-19 | 厦门大学 | A kind of porous carbon/noble metal nano hybrid material and preparation method thereof |
-
2018
- 2018-08-08 CN CN201810895527.3A patent/CN109265690B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001032795A1 (en) * | 1999-10-29 | 2001-05-10 | Closure Medical Corporation | Cyanoacrylate solutions containing preservatives |
| CN106543446A (en) * | 2016-11-18 | 2017-03-29 | 中国工程物理研究院激光聚变研究中心 | A kind of preceramic polymer microsphere and preparation method thereof |
| CN107082411A (en) * | 2017-05-18 | 2017-08-22 | 厦门大学 | A kind of nitrogen, boron codope carbon nanometer micro ball and preparation method thereof |
| CN107180974A (en) * | 2017-05-18 | 2017-09-19 | 厦门大学 | A kind of porous carbon/noble metal nano hybrid material and preparation method thereof |
| CN107096514A (en) * | 2017-06-16 | 2017-08-29 | 江苏科技大学 | Boronate tin oxide trace composite nano-microsphere, its preparation method and its application of a kind of hollow structure |
Non-Patent Citations (1)
| Title |
|---|
| LI LONGYU，YUAN CONGHUI，DAI, LIZONG: "Thermoresponsive Polymeric Nanoparticles: Nucleation from Cooperative Polymerization Driven byDative Bonds", 《MACROMOLECULES》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110534349A (en) * | 2019-08-05 | 2019-12-03 | 厦门大学 | A kind of nitrogen, boron and bimetallic co-doped nano microballoon, preparation method and application |
| CN112480345A (en) * | 2020-10-20 | 2021-03-12 | 厦门大学 | Metal salt @ ammonia aldehyde polymer nanosphere, preparation method and application |
| CN112480345B (en) * | 2020-10-20 | 2021-09-24 | 厦门大学 | Metal salt @ ammonia aldehyde polymer nanosphere, preparation method and application |
| CN116003806A (en) * | 2022-07-19 | 2023-04-25 | 厦门大学 | Boron-linked borate supermolecule, modified nanoparticle thereof, preparation method and application |
| CN116003806B (en) * | 2022-07-19 | 2024-04-02 | 厦门大学 | Boron-linked borate supermolecule, modified nanoparticle thereof, preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109265690B (en) | 2020-10-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109265690A (en) | A kind of hollow polymer nanosphere and preparation method thereof | |
| Caruso et al. | Robust, double-walled microcapsules for self-healing polymeric materials | |
| Liu et al. | Electrostatic self‐assembly of Au nanoparticles onto thermosensitive magnetic core‐shell microgels for thermally tunable and magnetically recyclable catalysis | |
| Fan et al. | Effect of emulsifier on poly (urea–formaldehyde) microencapsulation of tetrachloroethylene | |
| Chen et al. | A novel one-step approach to core-stabilized nanoparticles at high solid contents | |
| JP4094277B2 (en) | Preparation of metal nanoparticles using shell-crosslinked micelles as templates | |
| Liu et al. | Core functionalization of hollow polymer nanocapsules | |
| Ma et al. | Environmentally-responsive, entirely hydrophilic, shell cross-linked (SCK) nanoparticles | |
| CN105885354A (en) | Preparing method of polyhedral oligomeric silsesquioxane modified carbon nano tubes and application | |
| WO2005033173A1 (en) | Latent hardener | |
| Xiao et al. | Fluorescent nanomaterials combined with molecular imprinting polymer: synthesis, analytical applications, and challenges | |
| KR20160137792A (en) | UV sensitive self-healing polymer nanoparticles and manufacturing method of the same and film with the same | |
| Yang et al. | One-step synthesis of nonspherical organosilica particles with tunable morphology | |
| CN109317068A (en) | A kind of sandwich type hybrid microballoon and preparation method thereof | |
| CN105669967A (en) | Polyether polymer brush hybrid inorganic nano-material and preparation method thereof | |
| Ohnuma et al. | Metal− Polymer Hybrid Colloidal Particles with an Eccentric Structure | |
| JP2011115755A (en) | Core-shell particle, and method for manufacturing the same | |
| CN109010318A (en) | A kind of preparation method of the amido modified 3-d tree-like silica dioxide nano particle carrier for carrying hydrophilic small molecule drugs PH response | |
| Duncan et al. | Hybrid organic–inorganic colloidal composite ‘sponges’ via internal crosslinking | |
| Gargari et al. | Synthesis and characterization of silica–polyvinyl imidazole core–shell nanoparticles via combination of RAFT polymerization and grafting‐to method | |
| CN101983978A (en) | Preparation method of monodisperse conducting polymer microballoon | |
| CN101386671A (en) | Method for preparing environmental responsibility mesoporous silicon sphere | |
| Yang et al. | Fabrication of nano‐sized hybrid Janus particles from strawberry‐like hierarchical composites | |
| Yang et al. | Facile fabrication of lilium pollen-like organosilica particles | |
| Ishihara et al. | Silica/polymer core–shell particles prepared via soap-free emulsion polymerization |
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 |