CN101054442A - Method of preparing amphiphilic superbranched polyether nano-level self-assembly body - Google Patents
Method of preparing amphiphilic superbranched polyether nano-level self-assembly body Download PDFInfo
- Publication number
- CN101054442A CN101054442A CN 200710039628 CN200710039628A CN101054442A CN 101054442 A CN101054442 A CN 101054442A CN 200710039628 CN200710039628 CN 200710039628 CN 200710039628 A CN200710039628 A CN 200710039628A CN 101054442 A CN101054442 A CN 101054442A
- Authority
- CN
- China
- Prior art keywords
- nano
- superbranched
- polyether
- amphiphilic
- assembly body
- 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.)
- Pending
Links
Abstract
The invention relates to a producing method of amphiphilic hyperbranched polyaether nano self-assemblies. The invention includes following steps: (1) preparing monomer 3-eshyl-3-oxacyclobutane carbinol; (2) processing a ring opening polymerization reaction; (3) adding ethylene oxide again for reaction, getting product, depositing by sedimentation agent, drying in vacuum to a constant weight; (4) distributing it in the water solution under the magnetic stirring, then dripping into the water solution or organic solvent for dialysis, obtaining amphiphilic hyperbranched polyaether nano self-assemblies. The inventive self-assemblies has an adjustable size between 10-200nm and stabilize in nano level. The nano micelle has an even size which avoids the PEO phase separation on the micelle surface.
Description
Technical field
That the present invention relates to is a kind of preparation method's of technical field of macromolecules, particularly a kind of amphiphilic superbranched polyether nano-level self-assembly body preparation method.
Background technology
The self-assembly of polymer molecule be exactly its under noncovalent force effects such as hydrogen bond, electrostatic interaction, hydrophilic hydrophobic interaction, Van der Waals force, spontaneously form the process of aggregate with special construction and shape.Because advantages such as the molecular structure designability of synthetic organic polymer molecule are strong, micelle-forming concentration is low, what make it is self-assembled into one of research contents that receives much concern for current nanometer science and technology field.
In decades recently, hyperbranched polymer is because its particular structure and performance and simple preparation method have obtained investigator's extensive concern.Compare with linear macromolecule with same molecular amount, hyperbranched polymer has highly branched three-dimensional spherical molecular structure, thereby makes that it has that molecular chain does not have entanglement, dissolves in multiple organic solvent, characteristic such as higher solubleness, lower fusion and soltion viscosity.Particularly importantly, hyperbranched polymer has a large amount of active end groups, can give the character of the many uniquenesses of material by terminal groups modification, makes it satisfy the different application demand of every field.Hyperbranched polymer has been obtained important application in fields such as coating, polymer processing, biological medicine, makeup.
Contain hydrophilic radical and lipophilic group simultaneously in the molecule of amphipathic nature polyalcohol, thereby make it have not only hydrophilic but also lipophilic amphipathic nature.It is that the nuclear hydrophilic segment is the nanoparticle of the nucleocapsid structure of shell that this amphipathic polymkeric substance can obtain with the hydrophobic part by self-assembly in the aqueous solution.The hydrophobic segment of amphipathic nature polyalcohol is because hydrophobic interaction is gathered into the kernel of nanoparticle, and hydrophilic segment externally forms the shell of nanoparticle.Polyoxyethylene glycol (PEG) has been widely used in food, makeup and the prescription drugs owing to the water-soluble blood compatibility preferably that reaches of its nontoxic, no immunogen, height.In recent years, big quantity research report is to form nano-micelle about PEG is incorporated in the amphipathic nature polyalcohol as hydrophilic component by self-assembly.
Find by prior art documents, Journal of Controlled Release (" sustained release magazine "), the method of the disclosed employing ring-opening polymerization of Micelle-like nanoparticles of star-branchedPEO-PLA copolymers as chemotherapeutic carrier. (" the nanoparticle micella of star-like PEO-PLA multipolymer is as the carrier of chemotherapeutics ") of 110 phases (2005) 20-33 page or leaf has been synthesized the star block copolymer PEO-PLA of polyoxyethylene glycol and poly(lactic acid), by changing the reinforced ratio of EO/LA, can regulate the ratio of hydrophilic section and hydrophobic section in the multipolymer.This based block copolymer can be gathered into micella in aqueous medium.But formed micella is even inadequately, on the micellar surface PEO takes place easily and is separated.And the molecular structure of micellar pattern (as: film, nanoparticle etc.) and multipolymer is bigger to the influence of the degree of being separated.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, a kind of preparation method of amphiphilic superbranched polyether nano-level self-assembly body is provided, the present invention can access the uniform nano-micelle of size, avoids taking place PEO on the micellar surface and is separated.
The present invention is achieved by the following technical solutions, the present invention includes following steps:
A prepares monomer 3-ethyl-3-fourth oxa-ring methyl alcohol: after TriMethylolPropane(TMP) and diethyl carbonate backflow, and pyrolysis, underpressure distillation then, obtaining water white purity is 96.8%-99%3-ethyl-3-fourth oxa-ring methanol liquid;
B carries out ring-opening polymerization: in solvent, monomer 3-ethyl-3-fourth oxa-ring methyl alcohol is carried out cationic ring-opening polymerization with the initiator boron trifluoride diethyl etherate;
C adds oxyethane again and continues reaction, and the amphiphilic superbranched polyether product that obtains having the different degrees of branching is used the sinking agent sedimentation, and vacuum-drying is to constant weight;
D is scattered in the above-mentioned amphiphilic superbranched polyether that makes in the aqueous solution under magnetic agitation, dropwise is added drop-wise in the aqueous solution then and dialyses, and obtains amphiphilic superbranched polyether nano-level self-assembly body; Perhaps with amphiphilic superbranched polyether under magnetic agitation, dropwise be added drop-wise in the organic solvent and dialyse, obtain amphiphilic superbranched polyether nano-level self-assembly body.
Among the step a, described reflux temperature is between 80 ℃～110 ℃, and return time is 0.5 hour～3 hours.The condition of pyrolytic reaction is: temperature is controlled between 180 ℃～220 ℃, and the time is 2 hours～5 hours.
Ring-opening polymerization among the step b, described solvent can be methylene dichloride, trichloromethane, N, dinethylformamide, toluene, dimethylbenzene.
Described ring-opening polymerization, condition is: be that temperature is controlled between 0 ℃～70 ℃, the reaction times is 24 hours～96 hours.
Among the step c, described oxyethane, its charge temperature are-10 ℃～0 ℃.
In the steps d, the described aqueous solution, the concentration range that wherein hydrionic concentration range is 0mol/L～30mol/L or organic solution is 5mg/ml～500mg/ml.
The present invention is by the control degree of branching of amphiphilic superbranched polyether and the environment of self-assembly, and the size of the self-assembly that makes is adjustable at 10nm～200nm, and nano-level self-assembly body that can stable existence.Self-assembly is generally the nano-micelle with nucleocapsid structure that particle diameter is 10～200nm, and the kernel of the nano-micelle of this nucleocapsid structure is to be made of hydrophobic hyperbranched poly 3-ethyl-Ding oxa-ring methyl alcohol, and shell is made of hydrophilic polyoxyethylene glycol.Obtain the uniform nano-micelle of size, be difficult for taking place PEO on the micellar surface and be separated.The hydrophobic parts of amphiphilic superbranched polyether is hyperbranched poly 3-ethyl-3-fourth oxa-ring methyl alcohol, and molecular weight ranges is 2000～8000 variable, and this segment is to be monomer by 3-ethyl-3-fourth oxa-ring methyl alcohol.The hydrophilic parts of amphiphilic superbranched polyether is a polyoxyethylene glycol, and molecular weight ranges is variable from 100～2000.This amphiphilic superbranched polyether is scattered in the aqueous solution of different pH and strength of solution, can self-assembly forms the nano-level self-assembly body of different-grain diameter.
Embodiment
Below embodiments of the invention are elaborated: present embodiment has provided detailed embodiment and process being to implement under the prerequisite with the technical solution of the present invention, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
Present embodiment 1 is implemented under following implementation condition and technical requirements condition:
A joins 268g (2.0mol) TriMethylolPropane(TMP) and 236g (2.0mol) diethyl carbonate in the single port flask of 500ml, after 80 ℃ of following backflows 3 hours.Be warmed up to 180 ℃, pyrolytic reaction 2 hours.It is high purity 3-ethyl-3-fourth oxa-ring methanol liquid liquid of 96.8% that underpressure distillation gets water white concentration.
B is being equipped with magnetic stirrer, thermometer, and in the four-hole boiling flask of nitrogen inlet and feed hopper, the air that earlier logical nitrogen was removed in the reaction system in 30 minutes.7.096g (0.05mol) boron trifluoride diethyl etherate BF3.0Et2 and 80ml methylene dichloride are joined in the flask, hierarchy of control temperature is 10 ℃, in 5 minutes 11.62g (0.1mol) monomer 3-ethyl-3-fourth oxa-ring methyl alcohol slowly is added dropwise in the reaction system, keeps this temperature, reaction 48h.Reaction solution is added drop-wise in the excessive anhydrous diethyl ether slowly, and the adularescent precipitation is produced, filter, and washing, 100 ℃ of vacuum-dryings are to constant weight.The productive rate of the hyperbranched product of gained is 92%, and the degree of branching is 0.41 (degree of branching of the hyperbranched polymer that calculates for the integral area that is characterized the various piece of gained by 13C-NMR).
The c control reaction temperature dropwise adds 20g oxyethane at 0 ℃, reacts 24 hours.Reaction solution is poured out, carried out sedimentation, obtain faint yellow cured shape body with anhydrous diethyl ether.After the filtration, with methylene dichloride with its dissolving after, adding the anhydrous diethyl ether sedimentation, so triplicate.The product vacuum-drying that obtains is to constant weight.The productive rate of products therefrom is 85% (productive rate is a resulting polymers weight and the ratio of the gross weight that feeds intake), and molecular weight Mw is that 3256 (Mw is the molecular weight of being measured by gel permeation chromatography.Following other embodiment together)
D is dissolved in the 5g amphipathy hyperbranched polymer in the 10ml dehydrated alcohol, is made into the solution of 500mg/ml.In the slow-paced 1000ml of the joining deionized water that under magnetic agitation, drips, continue to stir 4h with 10s/.Obtain containing the solution of self-assembly.The gained nano-micelle is evenly distributed, and particle diameter is 30nm (the particle diameter determination of transmission electron microscopy of nano-micelle, following other each embodiment is together).Can stablize and deposit, PEO does not take place and is separated in micellar surface.
Embodiment 2
Present embodiment 2 is implemented under following implementation condition and technical requirements condition:
A, b, the c implementation step is with embodiment 1.
D is dissolved in the 0.5g amphipathy hyperbranched polymer in the 20ml methylene dichloride, is made into the solution of 25mg/ml.This polymers soln is packed into (molecular weight cut-off of dialysis tubing is 1000) in the dialysis tubing, and the 72h that dialyses in deionized water obtains containing the solution of self-assembly.The particle diameter that obtains is the micella of 15nm.Be not separated on the micellar surface.
Embodiment 3
Present embodiment 3 is implemented under following implementation condition and technical requirements condition:
A joins 268g (2.0mol) TriMethylolPropane(TMP) and 236g (2.0mol) diethyl carbonate in the single port flask of 500ml, after 95 ℃ of following backflows 3 hours.Be warmed up to 200 ℃, pyrolytic reaction 3.5 hours.It is high purity 3-ethyl-3-fourth oxa-ring methanol liquid liquid of 97% that underpressure distillation gets water white concentration.
B is being equipped with magnetic stirrer, thermometer, and in the four-hole boiling flask of nitrogen inlet and feed hopper, the air that earlier logical nitrogen was removed in the reaction system in 30 minutes.7.096g (0.05mol) boron trifluoride diethyl etherate BF3.0Et2 and 80ml trichloromethane are joined in the flask, hierarchy of control temperature is 30 ℃, in 5 minutes 11.62g (0.1mol) monomer 3-ethyl-3-fourth oxa-ring methyl alcohol slowly is added dropwise in the reaction system, keeps this temperature, reaction 24h.Reaction solution is added drop-wise in the excessive anhydrous diethyl ether slowly, and the adularescent precipitation is produced, filter, and washing, 100 ℃ of vacuum-dryings are to constant weight.The productive rate of the hyperbranched product of gained is 83.5%, and the degree of branching is 0.47.
The c control reaction temperature dropwise adds 10g oxyethane at-10 ℃, reacts 24 hours.Reaction solution is poured out, carried out sedimentation, obtain faint yellow cured shape body with anhydrous diethyl ether.After the filtration, with methylene dichloride with its dissolving after, adding the anhydrous diethyl ether sedimentation, so triplicate.The product vacuum-drying that obtains is to constant weight.The productive rate of products therefrom is 90%, and molecular weight Mw is 2363.
D is dissolved in the 5g amphipathy hyperbranched polymer in the 10ml dehydrated alcohol, is made into the solution of 500mg/ml.In the slow-paced 1000ml of the joining deionized water that under magnetic agitation, drips, continue to stir 3h with 10s/.Obtain containing the solution of self-assembly.The gained nano-micelle is evenly distributed, and particle diameter is 34nm.Can stablize and deposit, PEO does not take place and is separated in micellar surface.
Embodiment 4
Present embodiment 4 is implemented under following implementation condition and technical requirements condition:
A, b, the c implementation step is with embodiment 3.
D is dissolved in the 0.2g amphipathy hyperbranched polymer in the 20ml dehydrated alcohol, is made into the solution of 10mg/ml.This polymers soln is packed into (molecular weight cut-off of dialysis tubing is 1000) in the dialysis tubing, and the 72h that dialyses in deionized water obtains containing the solution of self-assembly.The particle diameter that obtains is the micella of 20nm.Be not separated on the micellar surface.
Embodiment 5
Present embodiment 5 is implemented under following implementation condition and technical requirements condition:
A joins 268g (2.0mol) TriMethylolPropane(TMP) and 236g (2.0mol) diethyl carbonate in the single port flask of 500ml, and 110 ℃ were refluxed 0.5 hour down.Be warmed up to 220 ℃, pyrolytic reaction 2 hours.It is high purity 3-ethyl-3-fourth oxa-ring methanol liquid liquid of 98% that underpressure distillation gets water white concentration.
B is being equipped with magnetic stirrer, thermometer, and in the four-hole boiling flask of nitrogen inlet and feed hopper, the air that earlier logical nitrogen was removed in the reaction system in 30 minutes.7.096g (0.05mol) boron trifluoride diethyl etherate BF3.0Et2 and 80ml dimethylbenzene are joined in the flask, hierarchy of control temperature is 70 ℃, in 5 minutes 11.62g (0.1mol) monomer 3-ethyl-3-fourth oxa-ring methyl alcohol slowly is added dropwise in the reaction system, keeps this temperature, reaction 96h.Reaction solution is added drop-wise in the excessive anhydrous diethyl ether slowly, and the adularescent precipitation is produced, filter, and washing, 100 ℃ of vacuum-dryings are to constant weight.The productive rate of the hyperbranched product of gained is 94.5%, and the degree of branching is 0.55.
The c control reaction temperature dropwise adds 10g oxyethane at-5 ℃, reacts after 24 hours.Reaction solution is poured out, carried out sedimentation, obtain faint yellow cured shape body with anhydrous diethyl ether.After the filtration, with methylene dichloride with its dissolving after, adding the anhydrous diethyl ether sedimentation, so triplicate.The product vacuum-drying that obtains is to constant weight.The productive rate of products therefrom is 89%, and molecular weight Mw is 2449.
D is dissolved in the 1g amphipathy hyperbranched polymer in the 10ml dehydrated alcohol, is made into the solution of 100mg/ml.The slow-paced 1000ml of the joining pH value that drips with 15s/ under magnetic agitation is in 6.8 the aqueous hydrochloric acid, continues to stir 6h.Obtain containing the solution of self-assembly.The gained nano-micelle is evenly distributed, and particle diameter is 50nm.Can stablize and deposit, PEO does not take place and is separated in micellar surface.
Embodiment 6
Present embodiment 6 is implemented under following implementation condition and technical requirements condition:
A, b, the c implementation step is with embodiment 5.
D is dissolved in the 0.5g amphipathy hyperbranched polymer in the 50ml dehydrated alcohol, is made into the solution of 10mg/ml.This polymers soln is packed into (molecular weight cut-off of dialysis tubing is 1000) in the dialysis tubing, and the 72h that dialyses in deionized water obtains containing the solution of self-assembly.The particle diameter that obtains is the micella of 10nm.Be not separated on the micellar surface.
Embodiment 7
Present embodiment 7 is implemented under following implementation condition and technical requirements condition:
A joins 268g (2.0mol) TriMethylolPropane(TMP) and 236g (2.0mol) diethyl carbonate in the single port flask of 500ml, after 110 ℃ of following backflows 2 hours.Be warmed up to 220 ℃, pyrolytic reaction 5 hours, it is high purity 3-ethyl-3-fourth oxa-ring methanol liquid liquid of 99% that underpressure distillation gets water white concentration.
B is being equipped with magnetic stirrer, thermometer, and in the four-hole boiling flask of nitrogen inlet and feed hopper, the air that earlier logical nitrogen was removed in the reaction system in 30 minutes.7.096g (0.05mol) boron trifluoride diethyl etherate BF3.0Et2 and 80ml toluene are joined in the flask, hierarchy of control temperature is 50 ℃, in 5 minutes 11.62g (0.1mol) monomer 3-ethyl-3-fourth oxa-ring methyl alcohol slowly is added dropwise in the reaction system, keeps this temperature, reaction 96h.Reaction solution is added drop-wise in the excessive anhydrous diethyl ether slowly, and the adularescent precipitation is produced, filter, and washing, 100 ℃ of vacuum-dryings are to constant weight.The productive rate of the hyperbranched product of gained is 91.5%, and the degree of branching is 0.51.
The c control reaction temperature dropwise adds 20g oxyethane at-5 ℃, reacts after 48 hours.Reaction solution is poured out, carried out sedimentation, obtain faint yellow cured shape body with anhydrous diethyl ether.After the filtration, with methylene dichloride with its dissolving after, adding the anhydrous diethyl ether sedimentation, so triplicate.The product vacuum-drying that obtains is to constant weight.The productive rate of products therefrom is 87%, and molecular weight Mw is 2587.
D is dissolved in the 1g amphipathy hyperbranched polymer in the 10ml methylene dichloride, is made into the solution of 100mg/ml.The slow-paced 1000ml of the joining pH value that drips with 10～15s/ under magnetic agitation is in 8.0 the NaOH aqueous solution, continues to stir 6h.Obtain containing the solution of self-assembly.The gained nano-micelle is evenly distributed, and particle diameter is 25nm.Can stablize and deposit, PEO does not take place and is separated in micellar surface.
Embodiment 8
Present embodiment 8 is implemented under following implementation condition and technical requirements condition:
A, b, the c implementation step is with embodiment 7.
D is dissolved in the 1g amphipathy hyperbranched polymer in the 10ml methylene dichloride, is made into the solution of 100mg/ml.This polymers soln is packed into (molecular weight cut-off of dialysis tubing is 1000) in the dialysis tubing, and the 72h that dialyses in deionized water obtains containing the solution of self-assembly.The particle diameter that obtains is the micella of 30nm.Can stablize and deposit, PEO does not take place and is separated in micellar surface.
Claims (8)
1. the preparation method of an amphiphilic superbranched polyether nano-level self-assembly body is characterized in that, comprises the steps:
A prepares monomer 3-ethyl-3-fourth oxa-ring methyl alcohol: after TriMethylolPropane(TMP) and diethyl carbonate backflow, and pyrolysis, underpressure distillation then, obtaining water white purity is 96.8%-99%3-ethyl-3-fourth oxa-ring methanol liquid;
B carries out ring-opening polymerization: in solvent, monomer 3-ethyl-3-fourth oxa-ring methyl alcohol is carried out cationic ring-opening polymerization with the initiator boron trifluoride diethyl etherate;
C adds oxyethane again and continues reaction, and the amphiphilic superbranched polyether product that obtains having the different degrees of branching is used the sinking agent sedimentation, and vacuum-drying is to constant weight;
D is scattered in the above-mentioned amphiphilic superbranched polyether that makes in the aqueous solution under magnetic agitation, dropwise is added drop-wise in the aqueous solution then and dialyses, and obtains amphiphilic superbranched polyether nano-level self-assembly body; Perhaps with amphiphilic superbranched polyether under magnetic agitation, dropwise be added drop-wise in the organic solvent and dialyse, obtain amphiphilic superbranched polyether nano-level self-assembly body.
2. the preparation method of amphiphilic superbranched polyether nano-level self-assembly body as claimed in claim 1 is characterized in that, among the step a, described reflux temperature is between 80 ℃～110 ℃, and return time is 0.5 hour～3 hours.
3. the preparation method of amphiphilic superbranched polyether nano-level self-assembly body as claimed in claim 1 is characterized in that, among the step a, the condition of described pyrolytic reaction is: temperature is controlled between 180 ℃～220 ℃, and the time is 2 hours～5 hours.
4. the preparation method of amphiphilic superbranched polyether nano-level self-assembly body as claimed in claim 1, it is characterized in that, ring-opening polymerization among the step b, described solvent be methylene dichloride, trichloromethane, N, dinethylformamide, toluene, dimethylbenzene any.
5. as the preparation method of claim 1 or 4 described amphiphilic superbranched polyether nano-level self-assembly bodies, it is characterized in that, described ring-opening polymerization, condition is: be that temperature is controlled between 0 ℃～70 ℃, the reaction times is 24 hours～96 hours.
6. the preparation method of amphiphilic superbranched polyether nano-level self-assembly body as claimed in claim 1 is characterized in that, among the step c, described oxyethane, its charge temperature are-10 ℃～0 ℃.
7. the preparation method of amphiphilic superbranched polyether nano-level self-assembly body as claimed in claim 1, it is characterized in that, in the steps d, the described aqueous solution, the concentration range that wherein hydrionic concentration range is 0mol/L～30mol/L or organic solution is 5mg/ml～500mg/ml.
8. the preparation method of amphiphilic superbranched polyether nano-level self-assembly body as claimed in claim 1 is characterized in that, in the steps d, the concentration range of described organic solution is 5mg/ml～500mg/ml.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710039628 CN101054442A (en) | 2007-04-19 | 2007-04-19 | Method of preparing amphiphilic superbranched polyether nano-level self-assembly body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710039628 CN101054442A (en) | 2007-04-19 | 2007-04-19 | Method of preparing amphiphilic superbranched polyether nano-level self-assembly body |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101054442A true CN101054442A (en) | 2007-10-17 |
Family
ID=38794510
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200710039628 Pending CN101054442A (en) | 2007-04-19 | 2007-04-19 | Method of preparing amphiphilic superbranched polyether nano-level self-assembly body |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101054442A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235134B (en) * | 2008-03-06 | 2011-01-19 | 上海交通大学 | Degradable polyglycol modified ultra-branching polyether ester and preparation method thereof |
| CN101450991B (en) * | 2008-11-27 | 2011-02-09 | 上海交通大学 | Method for preparing temperature and pH double responsiveness hyper branched polymer |
| CN102432863A (en) * | 2011-08-09 | 2012-05-02 | 济南大学 | Quaternary ammonium salt type hyperbranched negative-ion exchange resin and preparation method thereof |
| CN102585801A (en) * | 2012-01-29 | 2012-07-18 | 上海交通大学 | Preparation method of quantum dot-hyperbranched polyether nanocomposite-nitrogen oxide fluorescent probe |
| CN102887998A (en) * | 2012-09-24 | 2013-01-23 | 西北工业大学 | Tetrahydrofuran-glycidol random hyperbranched copolyether and preparation method thereof |
| CN105602649A (en) * | 2015-12-21 | 2016-05-25 | 中国科学院兰州化学物理研究所 | Graphene oxide modified nano additive and application thereof to lubricating oil |
| CN105602650A (en) * | 2015-12-18 | 2016-05-25 | 中国科学院兰州化学物理研究所 | Carbon nanotube-modified nano-additive and preparation method and application thereof |
| CN108329809A (en) * | 2018-01-19 | 2018-07-27 | 合肥宸翊商贸有限公司 | The preparation method of window screening coating for air purification |
-
2007
- 2007-04-19 CN CN 200710039628 patent/CN101054442A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235134B (en) * | 2008-03-06 | 2011-01-19 | 上海交通大学 | Degradable polyglycol modified ultra-branching polyether ester and preparation method thereof |
| CN101450991B (en) * | 2008-11-27 | 2011-02-09 | 上海交通大学 | Method for preparing temperature and pH double responsiveness hyper branched polymer |
| CN102432863A (en) * | 2011-08-09 | 2012-05-02 | 济南大学 | Quaternary ammonium salt type hyperbranched negative-ion exchange resin and preparation method thereof |
| CN102432863B (en) * | 2011-08-09 | 2015-09-09 | 济南大学 | A kind of quaternary ammonium salt type hyperbranched negative-ion exchange resin and preparation method thereof |
| CN102585801A (en) * | 2012-01-29 | 2012-07-18 | 上海交通大学 | Preparation method of quantum dot-hyperbranched polyether nanocomposite-nitrogen oxide fluorescent probe |
| CN102887998A (en) * | 2012-09-24 | 2013-01-23 | 西北工业大学 | Tetrahydrofuran-glycidol random hyperbranched copolyether and preparation method thereof |
| CN105602650A (en) * | 2015-12-18 | 2016-05-25 | 中国科学院兰州化学物理研究所 | Carbon nanotube-modified nano-additive and preparation method and application thereof |
| CN105602650B (en) * | 2015-12-18 | 2018-09-25 | 中国科学院兰州化学物理研究所 | It is a kind of based on carbon nano tube modified nanometer additive and its preparation method and application |
| CN105602649A (en) * | 2015-12-21 | 2016-05-25 | 中国科学院兰州化学物理研究所 | Graphene oxide modified nano additive and application thereof to lubricating oil |
| CN105602649B (en) * | 2015-12-21 | 2018-02-27 | 中国科学院兰州化学物理研究所 | A kind of nanometer additive based on graphene oxide modification and its application in lubricating oil |
| CN108329809A (en) * | 2018-01-19 | 2018-07-27 | 合肥宸翊商贸有限公司 | The preparation method of window screening coating for air purification |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101054442A (en) | Method of preparing amphiphilic superbranched polyether nano-level self-assembly body | |
| Ganda et al. | Two-dimensional self-assembled structures of highly ordered bioactive crystalline-based block copolymers | |
| CN107550921B (en) | Nanoparticle-polymer injectable composite hydrogel double-drug-loading system and preparation method thereof | |
| CN1839797A (en) | In situ quick preparation method of injectable supermolecular structure water gel and its uses | |
| CN105348548B (en) | A kind of hydrogel microsphere based on glucan and preparation method thereof | |
| CN1847273A (en) | Nanometer aquogel with both pH and temperature sensitivity and its prepn process | |
| CN101053553A (en) | Biodegradable fluorourcacil polyester medicine-carried nanospheres and its preparation method | |
| CN103087088A (en) | Preparation and applications of novel alkyl cage silsesquioxane nanometer hybrid | |
| CN1718592A (en) | Fluorescence labeling hydrophobic modified chitin polymer, its preparation method and application | |
| CN1698899A (en) | Novel pharmaceutical composition using chitosan or its derivatives as drug carrier | |
| CN101343540B (en) | Method for preparing quantum point with hyperbranched polymer supermolecule nano-reactor | |
| CN101298504B (en) | Supermolecule polymer micelle and preparation thereof | |
| CN111228213A (en) | Preparation method and application of biocompatible nano composite hydrogel | |
| CN101041075A (en) | Biotinylated pulullan polysaccharide nanometer grains and the preparation method | |
| Zhang et al. | Phenylboronic acid-functionalized unimolecular micelles based on a star polyphosphoester random copolymer for tumor-targeted drug delivery | |
| CN106995528B (en) | Refining method of polyethylene glycol monomethyl ether-polylactic acid block copolymer | |
| Salvi et al. | A synthesis, properties and application as a possible drug delivery systems dendrimers–A review | |
| WO2008074154A1 (en) | Polymers comprising zwitterionic endgroups | |
| CN102286155A (en) | Preparation method of sodium alginate-calcium carbonate hybridized micron particles | |
| CN107693505B (en) | Oil-water double-soluble ROS sensitive nanoparticle and preparation method thereof | |
| Islam et al. | Poly (vinyl alcohol)/pullulan blend nanofibres prepared from aqueous solutions using electrospinning method | |
| CN114621417B (en) | Optically active spiral polyfluorene block polyisonitrile copolymer and preparation method and application thereof | |
| Li et al. | Study on the α-cyclodextrin/poly (ethylene glycol) self-assembly supramolecular nanoparticles for drug delivery | |
| CN1626082A (en) | Nano particles of polyglycol-poly(lactide-caprolactone) of carrying camptothecin and preparation method | |
| CN103087277B (en) | POSS/poly lactic acid and poly(n-isopropyl acrylamide) star block copolymer preparation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |