CN105670004A - Preparation method of POSS (polyhedral oligomeric silsesquioxane)-based nanohybrid micelles - Google Patents
Preparation method of POSS (polyhedral oligomeric silsesquioxane)-based nanohybrid micelles Download PDFInfo
- Publication number
- CN105670004A CN105670004A CN201610031856.4A CN201610031856A CN105670004A CN 105670004 A CN105670004 A CN 105670004A CN 201610031856 A CN201610031856 A CN 201610031856A CN 105670004 A CN105670004 A CN 105670004A
- Authority
- CN
- China
- Prior art keywords
- poss
- preparation
- micella
- glycol monomethyl
- reaction
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/10—Block- or graft-copolymers containing polysiloxane sequences
- C08J2383/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
Abstract
The invention belongs to the field of nano biomedical materials and relates to a preparation method of POSS (polyhedral oligomeric silsesquioxane)-based nanohybrid micelles.The preparation method includes: dissolving octavinyl-POSS in a solvent, adding a mercapto-carboxylate compound and a photoinitiator excessively, performing thiol-vinyl click reaction under the action of ultraviolet light and under the protection of nitrogen, subjecting products to dialysis after the reaction is completed, removing the excessive unreacted mercapto-carboxylate compound and drying precipitate to obtain polycarboxyl POSS; enabling the polycarboxyl POSS and methoxypolyethylene glycols to undergo coupling reaction to obtain polyethylene glycol functionalized POSS easily dispersing in an aqueous medium so as to form the POSS-based nanohybrid micelles with POSS being cores and polyethylene glycol being shells, wherein the POSS-based nanohybrid micelles are small in particle size, narrow in distribution and adjustable in size.The preparation method is simple and raw materials are available, and the prepared POSS-based nanohybrid micelles can be applied to the nano biomedical field hopefully.
Description
Technical field
The present invention relates to nano biological medical field, it is specifically related to the preparation method of a kind of POSS base nano hybridization micella.
Background technology
Polyhedron oligomeric silsesquioxanes (PolyhedralOligomericSilsesquioxane, POSS) is a kind of novel organosilicon/inorganic nano-hybrid material. The structural formula of POSS is (RSiO1.5)n(n >=4), molecular dimension is 1.5nm ~ 3nm, organic R group shell that the inorganic cage type skeleton being made up of Si-O-Si and covalent linkage combine forms, and R can be the inertia groups such as H, alkyl, aryl, it is possible to thinks vinyl, hydroxyl, amino isoreactivity group. POSS has good biocompatibility, the preferably characteristic such as stability and nontoxicity so that it has very big potential use at bio-medical and field of tissue engineering technology. But owing to POSS inorganic cage type skeleton height is hydrophobic, limit its application at nanometer biological field to a certain extent. At present by active R group is carried out the chemical modifications such as surface bond, grafting, copolymerization, introducing hydrophilic polymer, preparation POSS base organic/inorganic polymer hybrid material has become research focus.
In recent years, the research based on the polymer hybrid micella of POSS is more, more existing relevant reports. Chinese patent notification number CN102633953A, the bulletin date is on 08 15th, 2012, name is called the preparation method disclosing a kind of POSS base star hybrid material in ' preparation method of a kind of temperature/pH dual responsiveness star hybrid material taking POSS as core ', the method is taking eight chloropropyl POSS as initiator, cause methacrylic acid-N, the atom transfer radical polymerization of N-dimethylaminoethyl monomer, prepare the star hybrid material that POSS is core and there is temperature/pH stimulating responsive, can self-assembly be stable nanometer micelle in water. Chinese patent notification number CN103030821A, the bulletin date is on 04 10th, 2013, name be called in ' nanometer reverse micelle of a kind of POSS base end-blocking and its preparation method ' to disclose a kind of using have big steric hindrance, super-hydrophobic effect POSS base as hydrophobic side, polyoxyethylene glycol (PEG) macromole is as hydrophilic chain, and the maleic acid ester of band double bond is the tensio-active agent of middle shot. The preparation of above-mentioned POSS base hybrid material needs the POSS of the special construction adopted, utilize atom transfer radical polymerization that polymerizing condition requirement is also harsher, and utilize polyoxyethylene glycol as hydrophilic chain, it is also possible to and obtain the structure that two ends are POSS end-blocking, therefore that structure regulating is unfavorable.
Summary of the invention
The object of the present invention is in order to solve the deficiencies in the prior art part, it provides the preparation method of a kind of POSS base nano hybridization micella. Octavinyl-POSS, mercaptan carboxylic acid's compound and poly glycol monomethyl ether that the present invention adopts are marketable material, preparation method is simple, the polyethyleneglycol modified POSS prepared easily is scattered in water medium, the particle diameter of the POSS base nano hybridization micella formed is little and narrowly distributing, also can regulate and control according to synthetic ratio.
The octavinyl-POSS that the technical scheme realizing the present invention is and mercaptan carboxylic acid's compound, under low strength UV-light and light-initiated dose of condition, through sulfydryl-vinyl click-reaction, obtain many carboxyls POSS; Then many carboxyls POSS and poly glycol monomethyl ether obtain the POSS of polyoxyethylene glycol functionalization under action of coupling agents through linked reaction, again the POSS of polyoxyethylene glycol functionalization is scattered in water medium, the POSS base nano hybridization micella be core, polyoxyethylene glycol being shell can be formed taking POSS.
The preparation method of a kind of POSS base nano hybridization micella; its preparation method comprises following process: first octavinyl-POSS and mercaptan carboxylic acid's compound are dissolved in 1:8.4 ~ 16 N in molar ratio; in dinethylformamide or tetrahydrofuran (THF); add light-initiated dose; its addition is the 0.5 ~ 2.0% of vinyl POSS and mercaptan carboxylic acid's compound total mass; under nitrogen protection, above-mentioned mixed solution is placed in wavelength is 365nm, light intensity is 1 ~ 16mW/cm2UV-light under carry out sulfydryl-vinyl click-reaction, the reaction times is 20 minutes to 1 hour, reaction solution is placed in cellulose ester dialysis tubing in distilled water dialyse 3 days, remove excessive unreacted mercaptan carboxylic acid's compound, take out the throw out in dialysis tubing, dry, namely obtain many carboxyls POSS; Then many carboxyls POSS and poly glycol monomethyl ether are obtained polyethyleneglycol modified POSS through linked reaction, polyethyleneglycol modified POSS is scattered in water medium, namely obtain POSS base nano hybridization micella.
Described mercaptan carboxylic acid's compound is: the one in Thiovanic acid, 3-thiohydracrylic acid, 2 mercaptopropionic acid, 4-mercaptobutyric acid, 3-mercaptobutyric acid or 2-mercaptobutyric acid.
Described light-initiated dose is the one in 2,2-dimethoxy-2-phenyl-methyl phenyl ketone, 2,2-diethoxy-methyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-acetone or 1-hydroxyl-cyclohexyl benzophenone.
The molecular weight of described poly glycol monomethyl ether is 350 ~ 5,000.
Described polyethyleneglycol modified POSS adopts the method for linked reaction as follows, many carboxyls POSS and poly glycol monomethyl ether are dissolved in dry tetrahydrofuran (THF) in 1:1 ~ 8 in molar ratio, add 1 times of 4-methylamino pyridine to poly glycol monomethyl ether mole number and 2 times again to the N of poly glycol monomethyl ether mole number, N '-bicyclohexane carbodiimide or 1 times of N-hydroxy-succinamide to poly glycol monomethyl ether mole number and 2 times are to the N of poly glycol monomethyl ether mole number, N '-bicyclohexane carbodiimide, under nitrogen protection, 25 DEG C of reaction 24h, after having reacted, filter, filtrate is with petroleum ether precipitation, then dissolve with methylene dichloride, again with petroleum ether precipitation, repeat 2-3 time, filter, drying precipitate, namely polyethyleneglycol modified POSS is obtained.
Described POSS base nano hybridization micella, being be scattered in the polyethyleneglycol modified POSS prepared in water medium to obtain, water medium can be water, D/W, injectable salt brine solution, it is also possible to be the aqueous solution containing various buffer reagent and/or sanitas.
Owing to adopting above technical scheme, the POSS base nano hybridization micella obtained by preparation method of the present invention, has the following advantages:
(1) raw material of preparing involved by is easy to get, and is marketable material;
(2) under low strength UV-light and light-initiated dose exist, octavinyl-POSS and mercaptan carboxylic acid's compound carry out ethene-sulfydryl click-reaction, and the time is short, react more abundant;
(3) by the molecular weight of the feed ratio and poly glycol monomethyl ether that regulate many carboxyls POSS and poly glycol monomethyl ether, the size and distribution of the POSS base nano hybridization micella formed is regulated and controled;
(4) prepare the polyethyleneglycol modified POSS obtained easily to be scattered in water medium, form the POSS base nano hybridization micella take POSS as core, polyoxyethylene glycol being shell, and good stability.
Accompanying drawing explanation
(a) in Fig. 1, (b) and (c) are respectively the size distribution figure of the preparation-obtained POSS base nano hybridization micella of embodiment 1,3,6 utilizing dynamic light scattering (DLS) to record.
Embodiment
Below in conjunction with embodiment, the technical scheme of the present invention is further described.
Embodiment 1
Being dissolved in 30mL tetrahydrofuran (THF) by 2g octavinyl-POSS, then add 2.83g3-thiohydracrylic acid and 0.03g2,2-dimethoxy-2-phenyl-methyl phenyl ketone, under nitrogen protection, it be 365nm, light intensity is 16mW/cm that mixed solution is placed in wavelength2UV-light under reaction 0.5 hour, product is placed in cellulose ester dialysis tubing and dialyses 3 days in distilled water, every day changes once new distilled water, removes excessive unreacted 3-thiohydracrylic acid, by the drying precipitate in dialysis tubing, namely obtains many carboxyls POSS.
Then above-mentioned many carboxyls POSS and 0.47g poly glycol monomethyl ether (M prepared of 2g is gotn=350) it is dissolved in dry tetrahydrofuran (THF); add 0.15g4-methylamino pyridine and 0.56gN again; N '-bicyclohexane carbodiimide; under nitrogen protection; 25 DEG C of reaction 24h; with petroleum ether precipitation after product filtration; then dissolve with methylene dichloride; with petroleum ether precipitation; repeat 2-3 time, finally it is placed in vacuum drying oven 60 DEG C oven dry to constant weight, obtained polyethyleneglycol modified POSS by filtering the product obtained; polyethyleneglycol modified POSS is scattered in water medium, obtains POSS base nano hybridization micella.
Embodiment 2
Being dissolved in 30mL tetrahydrofuran (THF) by 2g octavinyl-POSS, then add 2.83g4-mercaptobutyric acid and 0.06g2,2-diethoxy-methyl phenyl ketone, under nitrogen protection, it be 365nm, light intensity is 1mW/cm that mixed solution is placed in wavelength2UV-light under reaction 20 minutes, product is placed in cellulose ester dialysis tubing and dialyses 3 days in distilled water, every day changes once new distilled water, removes excessive unreacted 4-mercaptobutyric acid, by the drying precipitate in dialysis tubing, namely obtains many carboxyls POSS.
Then above-mentioned many carboxyls POSS and 12.56g poly glycol monomethyl ether (M prepared of 2g is gotn=5; 000) it is dissolved in dry tetrahydrofuran (THF); add 0.27g4-methylamino pyridine and 1.04gN again; N '-bicyclohexane carbodiimide; under nitrogen protection; 25 DEG C of reaction 24h; with petroleum ether precipitation after product filtration; then dissolve with methylene dichloride, with petroleum ether precipitation, repeat 2-3 time; finally it is placed in vacuum drying oven 60 DEG C oven dry to constant weight by filtering the product obtained; obtained polyethyleneglycol modified POSS, it is in 25% D/W that polyethyleneglycol modified POSS is scattered in massfraction, obtains POSS base nano hybridization micella.
Embodiment 3
2g octavinyl-POSS being dissolved in 30mlN, in dinethylformamide, then adds 2.92g Thiovanic acid and 0.05g2,2-diethoxy-methyl phenyl ketone, under nitrogen protection, to be placed in wavelength be 365nm, light intensity is 10mW/cm2UV-light under reaction 30 minutes, product is placed in cellulose ester dialysis tubing and dialyses 3 days in distilled water, every day changes once new distilled water, removes excessive unreacted Thiovanic acid, by the drying precipitate in dialysis tubing, namely obtains many carboxyls POSS;
Then above-mentioned many carboxyls POSS and 7.3g poly glycol monomethyl ether (M prepared of 2g is gotn=1; 000) it is dissolved in dry tetrahydrofuran (THF); add 0.84gN-N-Hydroxysuccinimide and 3.01gN again; N '-bicyclohexane carbodiimide; under nitrogen protection; 25 DEG C of reaction 24h; with petroleum ether precipitation after product filtration; then dissolve with methylene dichloride, then add petroleum ether precipitation, repeat 2-3 time; finally it is placed in vacuum drying oven 60 DEG C oven dry to constant weight by filtering the product obtained; obtained polyethyleneglycol modified POSS, is scattered in polyethyleneglycol modified POSS in water medium (containing sodium succinate and xitix potassium), obtains POSS base nano hybridization micella.
Embodiment 4
Being dissolved in 30ml tetrahydrofuran (THF) by 2g octavinyl-POSS, then add 3.8g3-mercaptobutyric acid and 0.06g1-hydroxyl-cyclohexyl benzophenone, under nitrogen protection, to be placed in wavelength be 365nm, light intensity is 3mW/cm2UV-light under reaction 50 minutes, product is placed in cellulose ester dialysis tubing and dialyses 3 days in distilled water, every day changes once new distilled water, removes excessive unreacted 3-mercaptobutyric acid, by the drying precipitate in dialysis tubing, namely obtains many carboxyls POSS;
Then above-mentioned many carboxyls POSS and 7.3g poly glycol monomethyl ether (M prepared of 2g is gotn=1; 000) it is dissolved in dry tetrahydrofuran (THF); add 0.54g4-methylamino pyridine and 2.08gN again; N '-bicyclohexane carbodiimide; under nitrogen protection; 25 DEG C of reaction 24h; with petroleum ether precipitation after product filtration; then dissolve with methylene dichloride, then add petroleum ether precipitation, repeat 2-3 time; finally it is placed in vacuum drying oven 60 DEG C oven dry to constant weight by filtering the product obtained; obtained polyethyleneglycol modified POSS, is scattered in the phosphate buffer solution of pH7.4 by polyethyleneglycol modified POSS, obtains POSS base nano hybridization micella.
Embodiment 5
Being dissolved in 30ml tetrahydrofuran (THF) by 2g octavinyl-POSS, then add 3.8g2-mercaptobutyric acid and 0.06g2-hydroxy-2-methyl-1-phenyl-1-acetone, under nitrogen protection, to be placed in wavelength be 365nm, light intensity is 14mW/cm2UV-light under reaction 1 hour, product is placed in cellulose ester dialysis tubing and dialyses 3 days in distilled water, every day changes once new distilled water, removes excessive unreacted 2-mercaptobutyric acid, by the drying precipitate in dialysis tubing, namely obtains many carboxyls POSS;
Then above-mentioned many carboxyls POSS and 6.03g poly glycol monomethyl ether (M prepared of 2g is gotn=600) it is dissolved in dry tetrahydrofuran (THF); add 1.08g4-methylamino pyridine and 4.16gN again; N '-bicyclohexane carbodiimide; under nitrogen protection; 25 DEG C of reaction 24h; with petroleum ether precipitation after product filtration; then dissolve with methylene dichloride; add petroleum ether precipitation again; repeat 2-3 time, finally it is placed in vacuum drying oven 60 DEG C oven dry to constant weight, obtained polyethyleneglycol modified POSS by filtering the product obtained; polyethyleneglycol modified POSS is scattered in the sodium chloride aqueous solution of 0.9%, obtains POSS base nano hybridization micella.
Embodiment 6
2g octavinyl-POSS being dissolved in 30mlN, in dinethylformamide, then adds 5.37g2-thiohydracrylic acid and 0.1g2,2-diethoxy-methyl phenyl ketone, under nitrogen protection, to be placed in wavelength be 365nm, light intensity is 8mW/cm2UV-light under reaction 40 minutes, product is placed in cellulose ester dialysis tubing and dialyses 3 days in distilled water, every day changes once new distilled water, removes excessive unreacted 2 mercaptopropionic acid, by the drying precipitate in dialysis tubing, namely obtains many carboxyls POSS;
Then above-mentioned many carboxyls POSS and 10.81g poly glycol monomethyl ether (M prepared of 2g is gotn=1, 000) it is dissolved in dry tetrahydrofuran (THF), add 1.24gN-N-Hydroxysuccinimide and 4.46gN again, N '-bicyclohexane carbodiimide, under nitrogen protection, 25 DEG C of reaction 24h, with petroleum ether precipitation after product filtration, then dissolve with methylene dichloride, add petroleum ether precipitation again, repeat 2-3 time, finally it is placed in vacuum drying oven 60 DEG C oven dry to constant weight by filtering the product obtained, obtained polyethyleneglycol modified POSS, polyethyleneglycol modified POSS is scattered in water medium (containing Trisodium Citrate and sodium bisulfite), obtain POSS base nano hybridization micella.
From the particles size and distribution (see figure 1) of the POSS base nano hybridization micella prepared by the different embodiments measured by dynamic light scattering (DLS), the particle diameter of the POSS base nano hybridization micella prepared according to the technical scheme of the present invention is less, and narrow distribution, and all the size of POSS base nano hybridization micella can be regulated and controled by the feed ratio selected the poly glycol monomethyl ether of different molecular weight and adjust many carboxyls POSS and poly glycol monomethyl ether.
Claims (6)
1. the preparation method of a POSS base nano hybridization micella; its preparation method comprises following process: first octavinyl-POSS and mercaptan carboxylic acid's compound are dissolved in 1:8.4 ~ 16 N in molar ratio; in dinethylformamide or tetrahydrofuran (THF); add light-initiated dose; its addition is the 0.5 ~ 2.0% of vinyl POSS and mercaptan carboxylic acid's compound total mass; under nitrogen protection, above-mentioned mixed solution is placed in wavelength is 365nm, light intensity is 1 ~ 16mW/cm2UV-light under carry out sulfydryl-vinyl click-reaction, the reaction times is 20 minutes to 1 hour, reaction solution is placed in cellulose ester dialysis tubing in distilled water dialyse 3 days, remove excessive unreacted mercaptan carboxylic acid's compound, take out the throw out in dialysis tubing, dry, namely obtain many carboxyls POSS; Then many carboxyls POSS and poly glycol monomethyl ether are obtained polyethyleneglycol modified POSS through linked reaction, polyethyleneglycol modified POSS is scattered in water medium, namely obtain POSS base nano hybridization micella.
2. the preparation method of a kind of POSS base nano hybridization micella according to claim 1, it is characterised in that: described mercaptan carboxylic acid's compound is: the one in Thiovanic acid, 3-thiohydracrylic acid, 2 mercaptopropionic acid, 4-mercaptobutyric acid, 3-mercaptobutyric acid or 2-mercaptobutyric acid.
3. the preparation method of a kind of POSS base nano hybridization micella according to claim 1, it is characterized in that: described light-initiated dose is 2, one in 2-dimethoxy-2-phenyl-methyl phenyl ketone, 2,2-diethoxy-methyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-acetone or 1-hydroxyl-cyclohexyl benzophenone.
4. the preparation method of a kind of POSS base nano hybridization micella according to claim 1, it is characterised in that: the molecular weight of described poly glycol monomethyl ether is 350 ~ 5,000.
5. the preparation method of a kind of POSS base nano hybridization micella according to claim 1, it is characterized in that: described polyethyleneglycol modified POSS adopts the method for linked reaction as follows, many carboxyls POSS and poly glycol monomethyl ether are dissolved in dry tetrahydrofuran (THF) in 1:1 ~ 8 in molar ratio, add 1 times of 4-methylamino pyridine to poly glycol monomethyl ether mole number and 2 times again to the N of poly glycol monomethyl ether mole number, N '-bicyclohexane carbodiimide or 1 times of N-hydroxy-succinamide to poly glycol monomethyl ether mole number and 2 times are to the N of poly glycol monomethyl ether mole number, N '-bicyclohexane carbodiimide, under nitrogen protection, 25 DEG C of reaction 24h, after having reacted, filter, filtrate is with petroleum ether precipitation, then dissolve with methylene dichloride, again with petroleum ether precipitation, repeat 2-3 time, filter, drying precipitate, namely polyethyleneglycol modified POSS is obtained.
6. the preparation method of a kind of POSS base nano hybridization micella according to claim 1, it is characterized in that: described POSS base nano hybridization micella, it is be scattered in the polyethyleneglycol modified POSS prepared in water medium to obtain, water medium can be water, D/W, injectable salt brine solution, it is also possible to be the aqueous solution containing various buffer reagent and/or sanitas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610031856.4A CN105670004B (en) | 2016-01-19 | 2016-01-19 | A kind of preparation method of POSS bases nano hybridization micella |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610031856.4A CN105670004B (en) | 2016-01-19 | 2016-01-19 | A kind of preparation method of POSS bases nano hybridization micella |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105670004A true CN105670004A (en) | 2016-06-15 |
| CN105670004B CN105670004B (en) | 2017-12-22 |
Family
ID=56301287
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610031856.4A Expired - Fee Related CN105670004B (en) | 2016-01-19 | 2016-01-19 | A kind of preparation method of POSS bases nano hybridization micella |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105670004B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106478953A (en) * | 2016-09-26 | 2017-03-08 | 华南理工大学 | A kind of metal hybrid POSS complex and its preparation method and application |
| CN110215903A (en) * | 2019-06-13 | 2019-09-10 | 湖南工业大学 | A kind of POSS base weight metal ion adsorbent and mercapto alkene clicking chemistry preparation method |
| CN112011267A (en) * | 2020-09-07 | 2020-12-01 | 胡承跃 | Heat-preservation and heat-insulation coating and preparation method thereof |
| CN112174611A (en) * | 2020-10-09 | 2021-01-05 | 康亚男 | Regenerated building material and preparation method thereof |
| CN112920787A (en) * | 2021-02-05 | 2021-06-08 | 西华师范大学 | Cage-shaped amphiphilic nano-particle and preparation method and application thereof |
| CN114015051A (en) * | 2021-11-12 | 2022-02-08 | 东莞理工学院 | Preparation method and application of DOPO-POSS flame retardant |
| CN114122617A (en) * | 2021-11-24 | 2022-03-01 | 惠州亿纬锂能股份有限公司 | Thermal closed-pore composite diaphragm and preparation method and application thereof |
| CN114292404A (en) * | 2021-12-30 | 2022-04-08 | 广东盈骅新材料科技有限公司 | POSS (polyhedral oligomeric silsesquioxane) modified oxazoline derivative, preparation method thereof and epoxy resin composition |
| CN114561019A (en) * | 2022-03-21 | 2022-05-31 | 国科广化精细化工孵化器(南雄)有限公司 | Amphiphilic polymer taking cage-shaped silsesquioxane as core and modified LMHs |
| CN115819777A (en) * | 2022-11-09 | 2023-03-21 | 金湖金凌新材料科技有限公司 | Preparation method of POSS-based giant surfactant |
| CN116695194A (en) * | 2023-05-25 | 2023-09-05 | 舒城燎原表面处理有限公司 | Production process for chromium plating |
| CN117209887A (en) * | 2023-09-06 | 2023-12-12 | 广东科净塑料制品有限公司 | High-toughness durable polypropylene material and preparation process thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102603786A (en) * | 2012-01-17 | 2012-07-25 | 浙江大学 | Water-soluble multifunctional group oligomeric silsesquioxane and synthetic method of water-soluble multifunctional group oligomeric silsesquioxane |
| CN103030821A (en) * | 2012-12-21 | 2013-04-10 | 厦门大学 | POSS-terminated nano reverse micelle and preparation method thereof |
| CN103642050A (en) * | 2013-11-04 | 2014-03-19 | 中国科学院化学研究所 | Dendritic polymer with POSS group and preparation method thereof |
| CN104744650A (en) * | 2015-04-07 | 2015-07-01 | 华东理工大学 | Preparation and application of hybrid copolymer containing POSS (polyhedral oligomeric silsesquioxane) base |
-
2016
- 2016-01-19 CN CN201610031856.4A patent/CN105670004B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102603786A (en) * | 2012-01-17 | 2012-07-25 | 浙江大学 | Water-soluble multifunctional group oligomeric silsesquioxane and synthetic method of water-soluble multifunctional group oligomeric silsesquioxane |
| CN103030821A (en) * | 2012-12-21 | 2013-04-10 | 厦门大学 | POSS-terminated nano reverse micelle and preparation method thereof |
| CN103642050A (en) * | 2013-11-04 | 2014-03-19 | 中国科学院化学研究所 | Dendritic polymer with POSS group and preparation method thereof |
| CN104744650A (en) * | 2015-04-07 | 2015-07-01 | 华东理工大学 | Preparation and application of hybrid copolymer containing POSS (polyhedral oligomeric silsesquioxane) base |
Non-Patent Citations (1)
| Title |
|---|
| 薛磊: "经巯基-双键点击反应设计合成含硅聚合物及性能研究", 《中国博士学位论文全文数据库 工程科技I辑》 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106478953A (en) * | 2016-09-26 | 2017-03-08 | 华南理工大学 | A kind of metal hybrid POSS complex and its preparation method and application |
| CN110215903A (en) * | 2019-06-13 | 2019-09-10 | 湖南工业大学 | A kind of POSS base weight metal ion adsorbent and mercapto alkene clicking chemistry preparation method |
| CN112011267A (en) * | 2020-09-07 | 2020-12-01 | 胡承跃 | Heat-preservation and heat-insulation coating and preparation method thereof |
| CN112011267B (en) * | 2020-09-07 | 2021-12-28 | 江苏瑞复达高温新材料股份有限公司 | Heat-preservation and heat-insulation coating and preparation method thereof |
| CN112174611A (en) * | 2020-10-09 | 2021-01-05 | 康亚男 | Regenerated building material and preparation method thereof |
| CN112920787A (en) * | 2021-02-05 | 2021-06-08 | 西华师范大学 | Cage-shaped amphiphilic nano-particle and preparation method and application thereof |
| CN112920787B (en) * | 2021-02-05 | 2021-09-21 | 西华师范大学 | Cage-shaped amphiphilic nano-particle and preparation method and application thereof |
| CN114015051A (en) * | 2021-11-12 | 2022-02-08 | 东莞理工学院 | Preparation method and application of DOPO-POSS flame retardant |
| CN114122617A (en) * | 2021-11-24 | 2022-03-01 | 惠州亿纬锂能股份有限公司 | Thermal closed-pore composite diaphragm and preparation method and application thereof |
| CN114122617B (en) * | 2021-11-24 | 2024-01-02 | 惠州亿纬锂能股份有限公司 | Thermal closed cell composite diaphragm and preparation method and application thereof |
| CN114292404A (en) * | 2021-12-30 | 2022-04-08 | 广东盈骅新材料科技有限公司 | POSS (polyhedral oligomeric silsesquioxane) modified oxazoline derivative, preparation method thereof and epoxy resin composition |
| CN114561019A (en) * | 2022-03-21 | 2022-05-31 | 国科广化精细化工孵化器(南雄)有限公司 | Amphiphilic polymer taking cage-shaped silsesquioxane as core and modified LMHs |
| CN115819777A (en) * | 2022-11-09 | 2023-03-21 | 金湖金凌新材料科技有限公司 | Preparation method of POSS-based giant surfactant |
| CN116695194A (en) * | 2023-05-25 | 2023-09-05 | 舒城燎原表面处理有限公司 | Production process for chromium plating |
| CN117209887A (en) * | 2023-09-06 | 2023-12-12 | 广东科净塑料制品有限公司 | High-toughness durable polypropylene material and preparation process thereof |
| CN117209887B (en) * | 2023-09-06 | 2024-04-16 | 珠海市金塑塑料有限公司 | High-toughness durable polypropylene material and preparation process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105670004B (en) | 2017-12-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105670004A (en) | Preparation method of POSS (polyhedral oligomeric silsesquioxane)-based nanohybrid micelles | |
| Zhao et al. | Carboxymethyl chitosan grafted trisiloxane surfactant nanoparticles with pH sensitivity for sustained release of pesticide | |
| JP6709780B2 (en) | Functional zwitterionic and mixed charge polymers, related hydrogels and methods of use thereof | |
| Kumar et al. | A review on the modification of polysaccharide through graft copolymerization for various potential applications | |
| CN107652452B (en) | A kind of Subjective and Objective supramolecular hydrogel and the preparation method and application thereof | |
| Salinas et al. | Mixed mode thiol− acrylate photopolymerizations for the synthesis of PEG− peptide hydrogels | |
| TWI308570B (en) | Water absorbent and producing method of same | |
| Li et al. | An environment-friendly fertilizer prepared by layer-by-layer self-assembly for pH-responsive nutrient release | |
| Ashmore et al. | Flocculation of model latex particles by chitosans of varying degrees of acetylation | |
| Vega-Hernández et al. | A review on the synthesis, characterization, and modeling of polymer grafting | |
| JP2020513461A (en) | Polymers with a certain level of bio-based carbon | |
| CN101696272A (en) | Degradable material having multiple sensitive properties, manufacturing method thereof and use thereof | |
| CN110267996A (en) | Polymer comprising certain horizontal biology base carbon | |
| CN103347899A (en) | Glucan gels | |
| CN103193989A (en) | Preparation method of light/pH-sensitive amphiphilic azobenzene polymer micelles | |
| CN108348404A (en) | Utilize the polymerizable dental composition of the redox of photo-labile transition metal complex | |
| CN103624268B (en) | The preparation method of the sugary ag nano-cluster of anticancer fluorescence | |
| CN104906073B (en) | A kind of preparation method for the chitosan quaternary ammonium salt hyaluronic acid nanometer gel containing basic fibroblast growth factor | |
| Tebong Mbah et al. | A sacrificial PLA block mediated route to injectable and degradable PNIPAAm-based hydrogels | |
| CN110452704A (en) | Preparation method with temperature, the dual intelligent response microcapsules soil conditioner of pH | |
| CN107286349B (en) | Polyethylene glycol-polycaprolactone diblock copolymer and preparation method and application thereof | |
| CN107530279A (en) | The poly ion complexes of block copolymer and polyanion polymer containing poly- (L arginine) segment | |
| CN106065039A (en) | Preparation method of water-soluble antibacterial acrylic polymer silver salt | |
| CN111167374A (en) | Hydrogels as rheology modifiers and methods of making the same | |
| CN101230139B (en) | Polycaprolactone/amylose amphiphilic block polymer as well as preparation method and use thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171222 Termination date: 20190119 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |