CN103951804A - Polyhedral oligomeric silsesquioxane-based amphiphilic triblock copolymer and preparation method thereof - Google Patents
Polyhedral oligomeric silsesquioxane-based amphiphilic triblock copolymer and preparation method thereof Download PDFInfo
- Publication number
- CN103951804A CN103951804A CN201410189864.2A CN201410189864A CN103951804A CN 103951804 A CN103951804 A CN 103951804A CN 201410189864 A CN201410189864 A CN 201410189864A CN 103951804 A CN103951804 A CN 103951804A
- Authority
- CN
- China
- Prior art keywords
- triblock copolymer
- poss
- reaction
- amphiphilic triblock
- preparation
- 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
Abstract
The invention discloses a polyhedral oligomeric silsesquioxane-based amphiphilic triblock copolymer and a preparation method thereof, relating to a high-molecular copolymer. The polyhedral oligomeric silsesquioxane-based amphiphilic triblock copolymer is polymethyl acrylyloxypropyl POSS-tertiary butyl polyacrylate-polydimethylaminoethyl methacrylate. The polyhedral oligomeric silsesquioxane-based amphiphilic triblock copolymer takes the polymethyl acrylyloxypropyl POSS as the first block, takes the tertiary butyl polyacrylate as the second block and takes the polydimethylaminoethyl methacrylate as the third block, adopts a reversible addition-fragmentation chain transfer radical polymerization method to initiate polymerization in sequence under a cosolvent to finally synthesize the amphiphilic triblock copolymer. By regulating a molar ratio and reaction time of a monomer and a chain transfer agent, block length proportion is effectively regulated to realize controllable design of organic/inorganic hybrid amphiphilic block copolymer; and the polyhedral oligomeric silsesquioxane-based amphiphilic triblock copolymer is gentle in reaction condition, simple and convenient to prepare, high in conversation rate and high in product purity.
Description
Technical field
The present invention relates to a kind of high-molecular copolymer, relate in particular to a kind of RAFT (RAFT) polymerization and using POSS as amphiphilic triblock copolymer of hydrophobic block and preparation method thereof.
Background technology
Over nearly 10 years, polyhedral silsesquioxane (Polyhedral oligomericsilsesquioxane, POSS), as a kind of novel organic-inorganic hybrid nano material, causes increasing concern.The structural formula of POSS classics is (RSiO
1.5)
n(n>=4, R=H, alkyl, aryl or organo-functional group), between silicon-dioxide (SiO
2) and silicone resin (R
2siO)
nbetween.In POSS, silicon, the mutual keyed jointing of Sauerstoffatom, form cage structure, diameter 1.5～3nm, give the performances such as its distinctive nanometer size effect, low density, high heat-resisting, high anti-oxidation, make POSS become the important source material of research and development organic-inorganic nano hybrid composite material.
Amphiphilic block copolymer can self-assembly in selective solvent, forms abundant form, as linear, spherical, cylindricality, vesica shape, stratiform etc., and has good controllability, thereby is the study hotspot of field of polymer technology always.Mainly utilize at present controlled/living polymerisation process to carry out synthesis of amphoteric segmented copolymer, because it has larger controllability in molecular designing.
In polyhedron oligomeric silsesquioxanes (POSS), silica forms cage structure, can pass through molecular designing, modifies multiple functional group, and then POSS can be incorporated in polymkeric substance, preparation POSS based polyalcohol on its drift angle.For utilizing its many excellent specific property, existing many people have done a large amount of research work in synthesizing of POSS group block copolymer.Pyun etc. (1, Pyun, J.; Matyjaszewski, K.; Wu, J.; Kim, G.M.; Chun, S.B.; Mather, P.T.Polymer2003,44,2739.) select difunctionality chain-transfer agent, adopt atom transfer radical polymerization (ATRP) method, synthesized polymethyl acyl-oxygen propyl group POSS-polyacrylic acid positive butyl ester-polymethyl acyl-oxygen propyl group POSS (PMAPOSS-b-PpBA-b-PMAPOSS) triblock polymer, by regulating the content of POSS in multipolymer, under transmission electron microscope, observed and find its formation columnar structure that can be separated.Hirai etc. (2, Hirai, T.; Leolukman, M.; Hayakawa, T.; Kakimoto, M.; Gopalan, P.Macromolecules2008,41,4558.) adopt anionic polymerisation process, polymethylmethacrylate-polymethyl acyl-oxygen propyl group POSS (PMMA-b-PMAPOSS) and two kinds of Synthetic rubber, isoprene-styrene, hydrogenated, block, diblocks of polystyrene-poly methacryloxypropyl POSS (PS-b-PMAPOSS) have been synthesized, under transmission electron microscope, observe and find the two formation nanometer laminated structure that all can be separated, and its formation mechanism is probed into.Ma etc. (3, Ma, L.; Geng, H.; Song, J.; Li, J.; Chen, G.; Li, Q.The Journal of Physical Chemistry B2011,115,10586.) use amino POSS to react preparation with 2-bromine isobutyl acylbromide (BIBB) containing the chain-transfer agent of POSS, and control dimethylaminoethyl methacrylate (DMAEMA) polymerization with it, formation, with the polymkeric substance of POSS end group, find that it can be self-assembled into spherical micelle in water, and micella pattern is affected by pH.Zhang etc. (4, Zhang, W.; Liu, L.; Zhuang, X.; Li, X.; Bai, J.; Chen, Y.Journal of Polymer Science Part A:Polymer Chemistry2008,46,7049; 5, Zhang, W.; Zhuang, X.; Li, X.; Lin, Y.; Bai, J.; Chen, Y.Reactive and Functional Polymers2009,69,124; 6, Zhang, W.; Fang, B.; Walther, A.; Muller, A.H.E.Macromolecules2009,42,2563; ) use amino POSS to synthesize a kind of three thioesters chain-transfer agents with POSS, and use it to control respectively NIPA (NIPAM), vinylbenzene (St), tert-butyl acrylate (tBA) polymerization, form POSS telechelic polymer, and studied the self-assembly behavior of product in water.
Summary of the invention
The present invention aims to provide a kind of POSS of usining as polyhedron oligomeric silsesquioxanes base amphiphilic triblock copolymer of hydrophobic block and preparation method thereof.
Described polyhedron oligomeric silsesquioxanes base amphiphilic triblock copolymer is the polymethyl acyl-oxygen propyl group POSS-polyacrylic acid tert-butyl ester-polymethyl acrylic acid dimethylaminoethyl, and its structural formula is as follows:
Wherein, R is-iBu, isobutyl-; N, m, l is the polymerization degree.
Described polyhedron oligomeric silsesquioxanes base amphiphilic triblock copolymer is usingd polymethyl acyl-oxygen propyl group POSS as the first block, the polyacrylic acid tert-butyl ester is as the second block, polymethyl acrylic acid dimethylaminoethyl is as the 3rd block, adopt RAFT polymerization process, initiated polymerization successively under cosolvent, final synthesis of amphoteric triblock copolymer.
Described polymethyl acyl-oxygen propyl group POSS is the homopolymer of methacryloxypropyl POSS monomer, and structure is as follows:
Wherein, R is-iBu, isobutyl-; N is the polymerization degree.
Described methacryloxypropyl POSS monomer, is called for short MAiBuPOSS, and its structural formula is as follows:
Wherein, R is-iBu, isobutyl-.
The polymethyl acyl-oxygen propyl group POSS-polyacrylic acid tert-butyl ester is the multipolymer of methacrylic acid oxygen propyl group POSS homopolymer and tert-butyl acrylate, and its structural formula is as follows:
Wherein, R is-iBu, isobutyl-; N, m is the polymerization degree.
The preparation method of described polyhedron oligomeric silsesquioxanes base amphiphilic triblock copolymer, comprises the following steps:
(1) selective solvent, preparation monomer solution, adds chain-transfer agent and initiator, the solution of methacryloxypropyl POSS monomer, chain-transfer agent and initiator is placed in to reaction vessel freezing degassed and be filled with the lower reaction of sealing after argon gas, liquid nitrogen freezing after polymerization, stopped reaction;
(2) adopt dissolving precipitated method to remove unreacted methacryloxypropyl POSS, by precipitation agent precipitation, dry after solubilizing agent dilution;
(3) toward the solid of step (2) gained, add tert-butyl acrylate, initiator and solvent, freeze thawing is degassed and be filled with the lower reaction of sealing after argon gas, liquid nitrogen freezing after polymerization, stopped reaction;
(4) adopt dissolving precipitated method to remove unreacted tert-butyl acrylate, add after solvent cut with precipitation agent precipitation, dry;
(5) toward the solid of step (4) gained, add dimethylaminoethyl methacrylate, initiator and solvent, freeze thawing is degassed and be filled with sealed reaction after argon gas, liquid nitrogen freezing after polymerization, stopped reaction;
(6) adopt dissolving precipitated method to remove unreacted dimethylaminoethyl methacrylate, add after solvent cut with precipitation agent precipitation, dry, obtain polyhedron oligomeric silsesquioxanes base amphiphilic triblock copolymer.
In step (1), described solvent can be selected from toluene etc.;
Described initiator is the compound that can add thermogenesis free radical and cause methacryloxypropyl POSS monomer, tert-butyl acrylate and dimethylaminoethyl methacrylate polymerization, preferably Diisopropyl azodicarboxylate (AIBN);
Described chain-transfer agent can adopt two thioesters etc., and preferred dithiobenzoic acid cumyl ester (CDB) (referring to document: Le, T.P.T.; Moad, G.; Rizzardo, E.; Thang, S.H.PCTInt.Pat.Appl.WO9801478A1980115,1998), because of it, can control and form the narrower polymkeric substance of molecular weight distribution at a lower temperature, its structural formula is as follows:
The concentration of described methacryloxypropyl POSS monomer can be 0.3～1.0mol/L; The mol ratio of methacryloxypropyl POSS monomer and chain-transfer agent can be 5～50; The mol ratio of chain-transfer agent and initiator can be 2～20;
The temperature of described reaction can be 40～80 ℃, and the time of reaction can be 48h, and the temperature of preferred reaction is 65 ℃;
The time of described liquid nitrogen freezing can be 2min.
In step (2), described solvent can be selected from toluene etc.; Described precipitation agent can be selected from methyl alcohol etc.
In step (3), described solvent can be selected from tetrahydrofuran (THF) etc.; The mol ratio of tert-butyl acrylate and polymethyl acyl-oxygen propyl group POSS can be 50～200; The mol ratio of methacryloxypropyl POSS monomer and initiator can be 2～20; The temperature of described reaction can be 40～80 ℃, and the time of reaction can be 4～60h, preferably 65 ℃ of the temperature of reaction; The time of described liquid nitrogen freezing can be 2min.
In step (4), described solvent can be selected from tetrahydrofuran (THF) etc.; Described precipitation agent can be selected from methyl alcohol etc.
In step (5), described solvent can be selected from tetrahydrofuran (THF) etc.; The mol ratio of dimethylaminoethyl methacrylate and the polymethyl acyl-oxygen propyl group POSS-polyacrylic acid tert-butyl ester can be 50～200; The mol ratio of the polymethyl acyl-oxygen propyl group POSS-polyacrylic acid tert-butyl ester and initiator can be 2～20; The temperature of described reaction can be 40～80 ℃, and the time of reaction can be 4～48h, preferably 65 ℃ of the temperature of reaction; The time of described liquid nitrogen freezing can be 2min.
In step (6), described solvent can be selected from tetrahydrofuran (THF) etc.; Described precipitation agent can be selected from water etc.
In step (1), (3), (5), described initiator is the compound that can add thermogenesis free radical and cause methacryloxypropyl POSS monomer, tert-butyl acrylate and dimethylaminoethyl methacrylate polymerization, preferably Diisopropyl azodicarboxylate (AIBN).
The synthetic polyhedron oligomeric silsesquioxanes base amphiphilic triblock copolymer of the present invention is the polymethyl acyl-oxygen propyl group POSS-polyacrylic acid tert-butyl ester-polymethyl acrylic acid dimethylaminoethyl, and its structural formula is as follows:
Wherein, R is-iBu, isobutyl-; N, m, l is the polymerization degree.
The present invention using polymethyl acyl-oxygen propyl group POSS as the first block, the polyacrylic acid tert-butyl ester as the second block, polymethyl acrylic acid dimethylaminoethyl as the 3rd block, adopt RAFT polymerization process, initiated polymerization successively under cosolvent, final synthesis of amphoteric triblock copolymer.This polymer architecture is novel, wherein polymethyl acyl-oxygen propyl group POSS block is hydrophobic block, the easy acidolysis of the polyacrylic acid tert-butyl ester forms hydrophilic block, polymethyl acrylic acid dimethylaminoethyl can be protonated, precious metal is had to attraction power, and these performances are achieved the further functionalization of amphiphilic block copolymer.
Compared with the prior art, the present invention has following outstanding advantages:
Polyhedron oligomeric silsesquioxanes base amphiphilic triblock copolymer of the present invention, can be by regulating mole when reaction times of monomer and chain-transfer agent, effectively adjust block length ratio, realize the controlled design of hybrid amphiphilic block copolymer, its reaction conditions is gentle, prepare easyly, transformation efficiency is high, and product purity is high.
Accompanying drawing explanation
Fig. 1 is the polymethyl acyl-oxygen propyl group isobutyl-POSS-polyacrylic acid tert-butyl ester-polymethyl acrylic acid dimethylaminoethyl triblock copolymer
1h NMR spectrogram.In Fig. 1, X-coordinate is chemical shift chemical shift (ppm).
Fig. 2 is the polymethyl acyl-oxygen propyl group isobutyl-POSS-polyacrylic acid tert-butyl ester-polymethyl acrylic acid dimethylaminoethyl triblock copolymer
13c NMR spectrogram.In Fig. 2, X-coordinate is chemical shift chemical shift (ppm).
Embodiment
The present invention is a kind of method of polyhedron oligomeric silsesquioxanes base amphiphilic triblock copolymer.Embodiment is provided in detail by following examples, but the invention is not restricted to following examples; The present invention can explain aspect wider at other, not be subject to the restriction of these embodiment.
Embodiment 1:
By metering than preparation MAiBuPOSS: CDB: AIBN=10: 1: 0.2 toluene solution system, monomer concentration is 0.75mol/L, is placed in bottle sealing 65 ℃ of oil bath 48h after freezing degassed three times repeatedly, freezing stopped reaction.Add after a small amount of dilution with toluene with methanol extraction, filtration drying obtains red solid, i.e. polymethyl acyl-oxygen propyl group POSS (POSS
10).Measure by mol than tert-butyl acrylate (tBA): polymethyl acyl-oxygen propyl group POSS (POSS
10): initiator (AIBN)=60: 1: 0.2, the tBA of metering, POSS and AIBN are joined in reaction soln, after sealing freezing degassed three times repeatedly, 65 ℃ of oil bath 24h, freezing stopped reaction, after adding a small amount of tetrahydrofuran (THF) to dilute, with methanol extraction, filtration drying obtains pink solid, i.e. polymethyl acyl-oxygen propyl group POSS-polyacrylic acid tert-butyl ester (PPOSS
10-b-PtBA
60).
Measure by mol than dimethylaminoethyl methacrylate: polymethyl acyl-oxygen propyl group POSS-polyacrylic acid tert-butyl ester (PPOSS
10-b-PtBA
60): initiator (AIBN)=60: 1: 0.2, by DMAEMA, the PPOSS of metering
10-b-PtBA
60join in tetrahydrofuran (THF) with AIBN, after sealing freezing degassed three times repeatedly, 65 ℃ of oil bath 24h, freezing stopped reaction, add after the dilution of a small amount of tetrahydrofuran (THF) with water precipitation, filtration drying obtains lightpink solid, i.e. the polymethyl acyl-oxygen propyl group POSS-polyacrylic acid tert-butyl ester-polymethyl acrylic acid dimethylaminoethyl (PPOSS
10-b-PtBA
60-b-PDMAEMA
60), its chemical structure is as shown in Figure 1, corresponding
1h NMR,
13c NMR spectrogram as shown in Figure 2.
Embodiment 2
Step 1 preparation MAiBuPOSS: CDB: AIBN=15: 1: 0.2 toluene solution system, all the other are with embodiment 1.
Embodiment 3
The tert-butyl acrylate of step 2 (tBA): polymethyl acyl-oxygen propyl group POSS (PPOSS)=80: 1, all the other are with embodiment 1.
Embodiment 4
Step 2 reaction times is 48h, and all the other are with embodiment 1.
Embodiment 5
Dimethylaminoethyl methacrylate in step 4 (DMAEMA): the polymethyl acyl-oxygen propyl group POSS-polyacrylic acid tert-butyl ester=80: 1, all the other are with embodiment 1.
Embodiment 6
Step 4 reaction times is 36h, and all the other are with embodiment 1.
Claims (10)
1. polyhedron oligomeric silsesquioxanes base amphiphilic triblock copolymer, is characterized in that its structural formula is as follows for the polymethyl acyl-oxygen propyl group POSS-polyacrylic acid tert-butyl ester-polymethyl acrylic acid dimethylaminoethyl:
Wherein, R is-iBu, isobutyl-; N, m, l is the polymerization degree.
2. polyhedron oligomeric silsesquioxanes base amphiphilic triblock copolymer as claimed in claim 1, it is characterized in that described polyhedron oligomeric silsesquioxanes base amphiphilic triblock copolymer usings polymethyl acyl-oxygen propyl group POSS as the first block, the polyacrylic acid tert-butyl ester is as the second block, and polymethyl acrylic acid dimethylaminoethyl is as the 3rd block;
Described polymethyl acyl-oxygen propyl group POSS is the homopolymer of methacryloxypropyl POSS monomer, and structure is as follows:
Wherein, R is-iBu, isobutyl-; N is the polymerization degree;
Described methacryloxypropyl POSS monomer, is called for short MAiBuPOSS, and its structural formula is as follows:
Wherein, R is-iBu, isobutyl-;
The polymethyl acyl-oxygen propyl group POSS-polyacrylic acid tert-butyl ester is the multipolymer of methacrylic acid oxygen propyl group POSS homopolymer and tert-butyl acrylate, and its structural formula is as follows:
Wherein, R is-iBu, isobutyl-; N, m is the polymerization degree.
3. the preparation method of polyhedron oligomeric silsesquioxanes base amphiphilic triblock copolymer as claimed in claim 1, is characterized in that comprising the following steps:
(1) selective solvent, preparation monomer solution, adds chain-transfer agent and initiator, the solution of methacryloxypropyl POSS monomer, chain-transfer agent and initiator is placed in to reaction vessel freezing degassed and be filled with the lower reaction of sealing after argon gas, liquid nitrogen freezing after polymerization, stopped reaction;
(2) adopt dissolving precipitated method to remove unreacted methacryloxypropyl POSS, by precipitation agent precipitation, dry after solubilizing agent dilution;
(3) toward the solid of step (2) gained, add tert-butyl acrylate, initiator and solvent, freeze thawing is degassed and be filled with the lower reaction of sealing after argon gas, liquid nitrogen freezing after polymerization, stopped reaction;
(4) adopt dissolving precipitated method to remove unreacted tert-butyl acrylate, add after solvent cut with precipitation agent precipitation, dry;
(5) toward the solid of step (4) gained, add dimethylaminoethyl methacrylate, initiator and solvent, freeze thawing is degassed and be filled with sealed reaction after argon gas, liquid nitrogen freezing after polymerization, stopped reaction;
(6) adopt dissolving precipitated method to remove unreacted dimethylaminoethyl methacrylate, add after solvent cut with precipitation agent precipitation, dry, obtain polyhedron oligomeric silsesquioxanes base amphiphilic triblock copolymer.
4. the preparation method of polyhedron oligomeric silsesquioxanes base amphiphilic triblock copolymer as claimed in claim 3, is characterized in that, in step (1), described solvent is toluene;
Described chain-transfer agent is two thioesters, preferred dithiobenzoic acid cumyl ester, and its structural formula is as follows:
5. the preparation method of polyhedron oligomeric silsesquioxanes base amphiphilic triblock copolymer as claimed in claim 3, is characterized in that, in step (1), the concentration of described methacryloxypropyl POSS monomer is 0.3～1.0mol/L; The mol ratio of methacryloxypropyl POSS monomer and chain-transfer agent is 5～50; The mol ratio of chain-transfer agent and initiator is 2～20;
The temperature of described reaction can be 40～80 ℃, and the time of reaction can be 48h, and the temperature of preferred reaction is 65 ℃;
The time of described liquid nitrogen freezing can be 2min.
6. the preparation method of polyhedron oligomeric silsesquioxanes base amphiphilic triblock copolymer as claimed in claim 3, is characterized in that, in step (2), described solvent is toluene; Described precipitation agent is methyl alcohol.
7. the preparation method of polyhedron oligomeric silsesquioxanes base amphiphilic triblock copolymer as claimed in claim 3, is characterized in that, in step (3), described solvent is tetrahydrofuran (THF); The mol ratio of tert-butyl acrylate and polymethyl acyl-oxygen propyl group POSS can be 50～200; The mol ratio of methacryloxypropyl POSS monomer and initiator can be 2～20; The temperature of described reaction can be 40～80 ℃, and the time of reaction can be 4～60h, preferably 65 ℃ of the temperature of reaction; The time of described liquid nitrogen freezing can be 2min.
8. the preparation method of polyhedron oligomeric silsesquioxanes base amphiphilic triblock copolymer as claimed in claim 3, is characterized in that, in step (4), described solvent is tetrahydrofuran (THF); Described precipitation agent is methyl alcohol;
In step (6), described solvent is tetrahydrofuran (THF); Described precipitation agent is water.
9. the preparation method of polyhedron oligomeric silsesquioxanes base amphiphilic triblock copolymer as claimed in claim 3, is characterized in that, in step (5), described solvent is tetrahydrofuran (THF); The mol ratio of dimethylaminoethyl methacrylate and the polymethyl acyl-oxygen propyl group POSS-polyacrylic acid tert-butyl ester can be 50～200; The mol ratio of the polymethyl acyl-oxygen propyl group POSS-polyacrylic acid tert-butyl ester and initiator can be 2～20; The temperature of described reaction can be 40～80 ℃, and the time of reaction can be 4～48h, preferably 65 ℃ of the temperature of reaction; The time of described liquid nitrogen freezing can be 2min.
10. the preparation method of polyhedron oligomeric silsesquioxanes base amphiphilic triblock copolymer as claimed in claim 3, it is characterized in that in step (1), (3), (5), described initiator be for adding thermogenesis free radical and cause a kind of in the compound of methacryloxypropyl POSS monomer, tert-butyl acrylate, dimethylaminoethyl methacrylate polymerization, preferably Diisopropyl azodicarboxylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410189864.2A CN103951804B (en) | 2014-05-07 | 2014-05-07 | Polyhedral oligomeric silsesquioxane-basedamphiphilic amphiphilic triblock copolymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410189864.2A CN103951804B (en) | 2014-05-07 | 2014-05-07 | Polyhedral oligomeric silsesquioxane-basedamphiphilic amphiphilic triblock copolymer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103951804A true CN103951804A (en) | 2014-07-30 |
| CN103951804B CN103951804B (en) | 2016-08-10 |
Family
ID=51329173
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410189864.2A Expired - Fee Related CN103951804B (en) | 2014-05-07 | 2014-05-07 | Polyhedral oligomeric silsesquioxane-basedamphiphilic amphiphilic triblock copolymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103951804B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104592464A (en) * | 2015-01-20 | 2015-05-06 | 厦门大学 | Organic and inorganic hybrid block copolymer containing POSS (polyhedral oligomeric silsesquioxane) and zwitter-ion structure and synthesis method of organic and inorganic hybrid block copolymer |
| CN104829793A (en) * | 2015-04-16 | 2015-08-12 | 同济大学 | Preparation method of temperature and pH sensitive organic/inorganic hybrid material POSS/PDMAEMA-b-PNIPAM |
| CN104861098A (en) * | 2015-04-28 | 2015-08-26 | 中科院广州化学有限公司 | Star polymer with pH stimulating responsiveness, preparation method thereof and application |
| CN104892843A (en) * | 2015-06-16 | 2015-09-09 | 厦门大学 | POSS (polyhedral oligomeric silsesquioxane)-group-containing comb polymer with self-repairing function and preparation method of comb polymer |
| CN105670343A (en) * | 2016-01-08 | 2016-06-15 | 厦门大学 | Silicon nitrogen containing flame retardant type polymer dye and preparation method thereof |
| CN105669924A (en) * | 2016-04-21 | 2016-06-15 | 厦门大学 | Organic-inorganic linear-dendritic hybrid copolymer containing POSS structure and synthetic method of organic-inorganic linear-dendritic hybrid copolymer |
| CN112647152A (en) * | 2020-12-17 | 2021-04-13 | 太和县昌达工贸有限公司 | Preparation process of biodegradable antibacterial polyester fiber |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101503497A (en) * | 2009-03-02 | 2009-08-12 | 江南大学 | Preparation of star type block acid sensitive nano micelle |
| CN102206315A (en) * | 2011-04-12 | 2011-10-05 | 厦门大学 | Polyhedron oligomerization sesquialter siloxane-based segmented copolymer and preparation method thereof |
| CN102718933A (en) * | 2012-07-06 | 2012-10-10 | 厦门大学 | Polyhedral oligomeric silsesquioxane-based amphiphilic triblock copolymer and preparation method thereof |
-
2014
- 2014-05-07 CN CN201410189864.2A patent/CN103951804B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101503497A (en) * | 2009-03-02 | 2009-08-12 | 江南大学 | Preparation of star type block acid sensitive nano micelle |
| CN102206315A (en) * | 2011-04-12 | 2011-10-05 | 厦门大学 | Polyhedron oligomerization sesquialter siloxane-based segmented copolymer and preparation method thereof |
| CN102718933A (en) * | 2012-07-06 | 2012-10-10 | 厦门大学 | Polyhedral oligomeric silsesquioxane-based amphiphilic triblock copolymer and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 曾碧榕等: "含POSS聚合物的制备与性能研究进展", 《高分子材料科学与工程》, vol. 28, no. 6, 30 June 2012 (2012-06-30), pages 180 - 183 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104592464A (en) * | 2015-01-20 | 2015-05-06 | 厦门大学 | Organic and inorganic hybrid block copolymer containing POSS (polyhedral oligomeric silsesquioxane) and zwitter-ion structure and synthesis method of organic and inorganic hybrid block copolymer |
| CN104592464B (en) * | 2015-01-20 | 2017-07-25 | 厦门大学 | A kind of organic inorganic hybridization block copolymer and its synthetic method containing POSS and amphion structure |
| CN104829793A (en) * | 2015-04-16 | 2015-08-12 | 同济大学 | Preparation method of temperature and pH sensitive organic/inorganic hybrid material POSS/PDMAEMA-b-PNIPAM |
| CN104829793B (en) * | 2015-04-16 | 2017-02-22 | 同济大学 | Preparation method of temperature and pH sensitive organic/inorganic hybrid material POSS/PDMAEMA-b-PNIPAM |
| CN104861098A (en) * | 2015-04-28 | 2015-08-26 | 中科院广州化学有限公司 | Star polymer with pH stimulating responsiveness, preparation method thereof and application |
| CN104892843A (en) * | 2015-06-16 | 2015-09-09 | 厦门大学 | POSS (polyhedral oligomeric silsesquioxane)-group-containing comb polymer with self-repairing function and preparation method of comb polymer |
| CN105670343A (en) * | 2016-01-08 | 2016-06-15 | 厦门大学 | Silicon nitrogen containing flame retardant type polymer dye and preparation method thereof |
| CN105669924A (en) * | 2016-04-21 | 2016-06-15 | 厦门大学 | Organic-inorganic linear-dendritic hybrid copolymer containing POSS structure and synthetic method of organic-inorganic linear-dendritic hybrid copolymer |
| CN105669924B (en) * | 2016-04-21 | 2018-08-21 | 厦门大学 | The organic inorganic hybridization block copolymer and its synthetic method of the structure containing POSS |
| CN112647152A (en) * | 2020-12-17 | 2021-04-13 | 太和县昌达工贸有限公司 | Preparation process of biodegradable antibacterial polyester fiber |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103951804B (en) | 2016-08-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103951804A (en) | Polyhedral oligomeric silsesquioxane-based amphiphilic triblock copolymer and preparation method thereof | |
| CN102718933B (en) | Polyhedral oligomeric silsesquioxane-based amphiphilic triblock copolymer and preparation method thereof | |
| CN102199262B (en) | Polyhedral oligomeric silsesquioxane amphiphilic block copolymer and preparation method thereof | |
| Li et al. | Bottlebrush polymers: From controlled synthesis, self-assembly, properties to applications | |
| Zhou et al. | Recent advances in RAFT-mediated surfactant-free emulsion polymerization | |
| Mori et al. | New polymeric architectures with (meth) acrylic acid segments | |
| Dai et al. | Polymerization-induced self-assembly via RAFT-mediated emulsion polymerization of methacrylic monomers | |
| JP5260542B2 (en) | polymer | |
| US6627314B2 (en) | Preparation of nanocomposite structures by controlled polymerization | |
| Nakabayashi et al. | Recent progress in controlled radical polymerization of N-vinyl monomers | |
| Moad et al. | Functional polymers for optoelectronic applications by RAFT polymerization | |
| CN102731738B (en) | Polyhedral oligomeric silsesquioxane (POSS) based patterned nano microsphere and preparation method thereof | |
| CN102206315B (en) | Polyhedron oligomerization sesquialter siloxane-based segmented copolymer and preparation method thereof | |
| KR20110115132A (en) | Nanoparticle organic hybrid materials(nohms) | |
| Zamfir et al. | Styrene–vinyl pyridine diblock copolymers: Synthesis by RAFT polymerization and self‐assembly in solution and in the bulk | |
| Kaditi et al. | Amphiphilic block copolymers by a combination of anionic polymerization and selective post-polymerization functionalization | |
| Hussain et al. | Recent developments in nanostructured polyhedral oligomeric silsesquioxane‐based materials via ‘controlled’radical polymerization | |
| CN105085846B (en) | A kind of block copolymer and preparation method thereof | |
| CN102604309B (en) | Hydrophobic and oleophobic polymer film and preparing method thereof | |
| CN104558356A (en) | Method for synthesizing Pickering-type emulsion through semi-continuous polymerization | |
| Xu et al. | Synthesis, characterization and self-assembly of hybrid pH-sensitive block copolymer containing polyhedral oligomeric silsesquioxane (POSS) | |
| CN103146115A (en) | Polyhedral oligomeric silasesquioxane (POSS)-based load metal nanoparticle and preparation method thereof | |
| CN103146146B (en) | Epoxy nanocomposite with controllable phase structure and based on polyhedral oligomeric silsesquioxanes (POSS) | |
| CN103113537A (en) | Segmented copolymer capable of being self-assembled into micelle and preparation method thereof | |
| CN104592464A (en) | Organic and inorganic hybrid block copolymer containing POSS (polyhedral oligomeric silsesquioxane) and zwitter-ion structure and synthesis method of organic and inorganic hybrid block copolymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160810 |