CN103204970A - Method for preparing polymer sustained-release nanomaterials through free radical polymerization - Google Patents
Method for preparing polymer sustained-release nanomaterials through free radical polymerization Download PDFInfo
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Abstract
The invention discloses a method for preparing polymer sustained-release nanomaterials through free radical polymerization. The method comprises the following steps of: firstly, preparing a hyperbranched polymer with a relatively controllable structure by using a polyethylene glycol azo macromolecular free radical initiator through traditional free radical polymerization, and secondarily, preparing an aqueous-phase dispersion liquid of polymer nanoparticles by using a simple dialysis process. The prepared polymer nanoparticles are very stable and simultaneously have higher guest molecule loading and controlled-release capability which can be up to 20 percent.
Description
One, technical field
The present invention has set forth and has a kind ofly prepared the controlled relatively hyperbranched polymer of structure from traditional radical polymerization, thereby prepares the method for polymer nano-particle, and the application that needs slowly-releasing guest molecule field in daily use chemicals and personal care etc.
Two, background technology
Polymer nano material (comprising colloidal particle, crosslinked colloid and nanometer glue etc.) receives much concern.They can be applied to a lot of fields, such as, the slowly-releasing of medicine (B.G.De Geest, et aL.Chem.Soc.Rev.2007,36,636; A.I.Petrov, et aLMacromolecules2003,36,10079; T.BShutava, et al.Macromolecules2005,38,2850; D.E.Discher, et aL.Prog.Polym.Sci.2007,32,838; S.P.Armes, et aL.Macromol.Rapid Commun.2009,30,267; F.H.Meng, et aL.Biomacromolecules2009,1O, 197; J.M.J.Fr é chet et al.J.Am.Chem.Soc.2004,126,11936), and sensor (C.W.Zhao, et al.Macromol.Rapid.Commun.2008,29,1810; D.Roy, et aL.Chem.Commun.2009,2106).Polymer nano material is generally by letex polymerization, and white package technique is prepared.
Though there is the preparation method of a lot of polymer nano materials to be in the news, but these methods have defective separately, for example, the unstable of nano material (colloid can dissociate along with the variation of environment), relatively more weak loading and releasability (crosslinked colloid and polymer nano rice glue because highly cross-linked structural limitations their stowage capacity), the restriction that these defectives are serious they in the application of association area.Furthermore, assembling prepares polymer nanocomposite length consuming time, is unfavorable for extension production in vain.
In a word, consider them in the application of association area, preparation is stable, the polymer nanocomposite of high stowage capacity and the defective that overcomes white package technique are very big challenges.
Three, summary of the invention
The present invention aims to provide a kind of based on traditional radical polymerization (traditional radical polymerizations, TRP) prepare the method for polymer nanocomposite slow-release material, technical problem to be solved is to improve stability and the stowage capacity of polymer nanocomposite slow-release material, reduces the polymer nanocomposite preparation cost.
Technical solution problem of the present invention adopts following technical scheme:
Radical polymerization of the present invention prepares the method for polymer nanocomposite slow-release material, comprises the preparation of hyperbranched polymer, preparation and each unit process of aftertreatment of nano controlled-release material:
The preparation of described hyperbranched polymer is that monomer, bifunctional crosslinking agent, solvent and methyl-phenoxide is (a small amount of, as marking in the nuclear-magnetism) mix with the macromolecular radical initiator, described solvent is THF, DMF or 1,4-dioxane etc., amount of solvent is 10 times of monomer volume, in 60 ℃ of reactions 22-26 hour, transformation efficiency can reach more than 95% under nitrogen protection, after reaction finishes reaction solution was added in the normal hexane sedimentation and vacuum-drying and obtained hyperbranched polymer; Described macromolecular radical initiator, monomer and bifunctional crosslinking agent's mol ratio is 1:(40-160): 0.9; When bifunctional crosslinking agent's molar ratio greater than 1 the time, whole system can be crosslinked, can not obtain being dissolved in the hyperbranched polymer of solvent.
Described monomer selects white methyl acrylic ester monomer, acrylic ester monomer or styrene monomer;
Described methyl acrylic ester monomer is tert-butyl methacrylate, n-BMA, methyl methacrylate, Jia Jibingxisuanyizhi or propyl methacrylate;
Described acrylic ester monomer is the special butyl ester of vinylformic acid, n-butyl acrylate, methyl acrylate, ethyl propenoate or propyl acrylate;
Described styrene monomer is vinylbenzene or vinyl toluene.
Described bifunctional crosslinking agent selects Baiyi glycol dimethacrylate, polyethylene glycol dimethacrylate, glycol diacrylate, polyethyleneglycol diacrylate or to Vinylstyrene; The number-average molecular weight of described polyethylene glycol dimethacrylate≤1000, the number-average molecular weight of described polyethyleneglycol diacrylate≤1000.
Described macromolecular radical initiator is polyoxyethylene glycol azo class macromolecular radical initiator fmacro-azo PEG Initiator, MAI), and the number-average molecular weight of described macromolecular radical initiator≤8000;
The model of described polyoxyethylene glycol azo class macromolecular radical initiator is VPE-0201, VPE-0401 or VPE-0601, is produced by Japan and light Pure pharmaceutical worker industry Co., Ltd..
The preparation of described nano controlled-release material is that described hyperbranched polymer is dissolved among the THF of 200-2000 times of volume, and water dialysis back (3000-10000g/mol Mw cut-off dialysis membrane) obtains the aqueous dispersion liquid of transparent polymer nanocomposite slow-release material.
The aqueous dispersion liquid of the polymer nanocomposite slow-release material that obtains is directly used in existence and the size that nano particle was analyzed and confirmed to dynamic light scattering (DLS) and transmission electron microscope (TEM).
The present invention adopts polyoxyethylene glycol azo class macromolecular radical (MAI) initiator, tert-butyl methacrylate (tBMA) is monomer, ethylene glycol dimethacrylate (EGDMA) is linking agent, (TRP) at first prepares hyperbranched polymer by traditional radical polymerization, obtains the aqueous dispersion liquid of polymer nano granules (being the polymer nanocomposite slow-release material) then by the water dialysis.Wherein the used in amounts of EGDMA is controlled to the macromole unit of synthesizing soluble, avoids the crosslinked caking of whole system.TRP is more suitable for industrial production, and the use of MAI initiator can be controlled the structure of hyperbranched polymer relatively.The polymer nano granules that the present invention makes is highly stable, and higher guest molecule stowage capacity is arranged simultaneously, can be used for the slowly-releasing of different guest molecules.As representative, the contriver loads and has realized the slowly-releasing of rose oil.
The loading of rose oil and slowly-releasing:
Hyperbranched polymer and rose oil are dissolved among the 10ml THF jointly, and the quality of rose oil is the 10-20% of hyperbranched polymer quality.Under agitation slow Dropwise 5 mL distilled water is followed THF and is evaporated fully, and remaining clear liquid is placed in the dialysis tubing (7000g/mol Mw cut-off), then dialysis tubing is put into 1000ml water, to measure the release of rose oil.In test process, adopt the chloroform extraction water, concentrate and be used for gas chromatographic analysis, to detect burst size.The result shows 90% rose oil through 80 talentes come out by slowly-releasing (Fig. 4), and sustained release rate is even.
In the loading and slowly-releasing process of rose oil; because of dialysis procedure longer; and having the part rose oil in the dialysis procedure just is released in the process of preparation polymer nano granules; for making test result accurate; so adopt the method for steaming except THF to prepare aqueous dispersion liquid, accurate to guarantee the slowly-releasing data.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, the present invention prepares the polymer nanocomposite slow-release material by simple dialysis process, does not need white assembling, saves time and the production of can magnifying.
2, with respect to the radical polymerization of adopting small molecules initiators such as AIBN, the present invention adopts polyoxyethylene glycol azo class macromolecular radical initiator to guarantee controlled relatively hyperbranched polymer.
3, the present invention adopts traditional radical polymerization to prepare hyperbranched polymer, and is simply inexpensive, is suitable for industrial production.
4, polymer nanocomposite slow-release material of the present invention is highly stable, does not have in 1 year to change.
5, with respect to highly cross-linked micron and nanometer glue, polymer nanocomposite slow-release material of the present invention has higher stowage capacity, and maximum payload can reach 20%.
6, polymer nanocomposite slow-release material of the present invention can be good at realizing reprinting and the slowly-releasing of guest molecule; comprise daily use chemicals and personal care field (as the slowly-releasing of spices, biological activity guest molecule), biomedicine field (slowly-releasing of medicine), soil treatment and environment protection (release of active substance or objectionable impurities and absorption are as water treatment).
Four, description of drawings
Fig. 1 is the preparation flow figure of polymer nanocomposite slow-release material of the present invention.The present invention adopts polyoxyethylene glycol azo class macromolecular radical initiator, be monomer with tert-butyl methacrylate (tBMA), ethylene glycol dimethacrylate (EGDMA) is linking agent, (TRP) at first prepares hyperbranched polymer by traditional radical polymerization, obtains polymer nano granules by simple dialysis then.
Fig. 2 is the DLS curve of the present invention BCPl, the BCP2, BCP3 and the BCP4 polymer nano granules that prepare.Prepared polymer nano granules is more even as can be seen from Figure 2, and distribution of sizes is narrower, and wherein the prepared nano particle of BCPl and BCP4 has small peak near 10 nanometers, is likely due to the homopolymer that produces in the polymerization process.
Fig. 3 is the TEM photo of BCPl of the present invention, and the scale among Fig. 3 is 500nm.Prepared polymer nano granules is more even as can be seen from Figure 3, is of a size of 120 nanometer to 180 nanometers.
Fig. 4 is that polymer nanocomposite slow-release material of the present invention is to the water elution profiles of rose oil.Rose oil can be well come out by slowly-releasing in the polymer nanocomposite from then on as can be seen from Figure 4, and sustained release rate is even, and 90% rose oil can be come out by slowly-releasing through 80 talentes.
Five, embodiment
Material and sign:
All raw materials of the present invention are commercial, and process neutral alumina post was to remove stopper earlier before wherein tert-butyl methacrylate and ethylene glycol dimethacrylate used, and other raw material can directly use.
Nuclear-magnetism uses the BrukerAC400 instrument, and GPC uses Waters company product.The DLS instrument is Malvern Nano-S DLS.TEM is Tecnai Spirit transmission electron microscope (TecnaiG2 12) (acceleration voltage 110kv).
Because being close to identical polymer chain by some, hyperbranched polymer that the present invention synthesized links up by the bifunctional crosslinking agent, and the molecular weight behind the formation hyperbranched polymer is (present domestic this test set that do not possess) that can't measure, so for showing the immanent structure of hyperbranched polymer of the present invention, be the representative name with the structure of a polymer chain wherein, brief note is P (PEG x/tBMA y), wherein x represents the number-average molecular weight of each bar polyoxyethylene glycol that polymer chain contains (PEG) in the hyperbranched polymer, and y represents the polymerization degree of each bar tBMA that polymer chain contains in the hyperbranched polymer.
Embodiment 1:P (PEG
4000/ tBMA
20)
1, the preparation of hyperbranched polymer
Polyoxyethylene glycol azo macromolecular radical initiator VPE-0401 (polyoxyethylene glycol number-average molecular weight 4000) 0.67g (O.0833mmol) is placed in the Schlenk flask of a drying, vacuumizes-Tong nitrogen three times repeatedly.In another Schlenk flask, add tert-butyl methacrylate 0.47g (3.33mmol), ethylene glycol dimethacrylate 14.5mg (0.075mmol), solvent 1 successively, 4 one dioxane 4.5ml and methyl-phenoxide are (a small amount of, as marking in the nuclear-magnetism), by argon gas bubbling 60min to eliminate oxygen.Next the mixture in second flask is gone in first flask, place 60 ℃ oil bath to react 24h, the transformation efficiency of tert-butyl methacrylate reaches 95%, and transformation efficiency is recorded by nuclear-magnetism.Reaction solution obtains hyperbranched polymer through precipitation and the vacuum-drying in normal hexane, notes by abridging to be BCPl.
2, the preparation of nano controlled-release material
The hyperbranched polymer of preparation is dissolved among the THF, and mass volume ratio 2.0mg/ml obtains the aqueous dispersion liquid of transparent polymer nano granules behind the water dialysis 20h (7000g/mol Mw cut-off dialysis membrane).
The aqueous dispersion liquid of polymer nano granules can be directly used in DLS and tem analysis.The nano-scale that DLS records is 174nm, and the nano-scale that TEM records is 120nm to 180nm.The polymer nano granules of the present invention's preparation is to be nuclear with PtBMA, and PEG is the polymer nano granules of shell.
Embodiment 2:P (PEG
4000/ tBMA
40)
1, the preparation of hyperbranched polymer
Polyoxyethylene glycol azo macromolecular radical initiator VPE-0401 (polyoxyethylene glycol number-average molecular weight 4000) 0.67g (0.0833mmol) is placed in the Schlenk flask of a drying, vacuumizes a logical nitrogen three times repeatedly.In another Schlenk flask, add tBMA0.94g (6.62mmol), EGDMA14.5mg (0.075mmol), solvent 1,4 one dioxane 4.5ml and methyl-phenoxide (a small amount of, as marking in the nuclear-magnetism) successively, by argon gas bubbling 60min to eliminate oxygen.Next the mixture in second flask is gone in first flask, place 60 ℃ oil bath to react 24h, the transformation efficiency of tBMA reaches 95%, and transformation efficiency is recorded by nuclear-magnetism.Reaction solution obtains hyperbranched polymer through precipitation and the vacuum-drying in normal hexane, notes by abridging to be BCP2.
2, the preparation of nano controlled-release material
The hyperbranched polymer of preparation is dissolved among the THF, and mass volume ratio 2.0mg/ml obtains the aqueous dispersion liquid of transparent polymer nano granules behind the water dialysis 20h (7000g/mol Mw cut-off dialysis membrane).
The aqueous dispersion liquid of polymer nano granules can be directly used in DLS and tem analysis.The nano-scale that DLS records is 192nm.The polymer nano granules of the present invention's preparation is to be nuclear with PtBMA, and PEG is the polymer nano granules of shell.The loading of rose oil and slowly-releasing:
Hyperbranched polymer BCP2 (0.5g) and rose oil are dissolved among the 10ml THF jointly, and the quality of rose oil is the 10-20% of hyperbranched polymer quality.Under agitation slow Dropwise 5 mL distilled water is followed THF and is evaporated fully, and remaining clear liquid is placed in the dialysis tubing (7000g/mol Mw cut-off), then dialysis tubing is put into 1000ml water, to measure the release of rose oil.In test process, adopt the chloroform extraction water, concentrate and be used for gas chromatographic analysis, to detect burst size.The result shows 90% rose oil through 80 talentes come out by slowly-releasing (Fig. 4), and sustained release rate is even.
Embodiment 3:P (PEG
4000/ tBMA
60)
1, the preparation of hyperbranched polymer
Polyoxyethylene glycol azo macromolecular radical initiator VPE-0401 (polyoxyethylene glycol number-average molecular weight 4000) 0.67g (0.0833mmol) is placed in the Schlenk flask of a drying, vacuumizes a logical nitrogen three times repeatedly.In another Schlenk flask, add tBMA1.42g (9.996mmol), EGDMA14.5mg (0.075mmol), solvent 1,4 one dioxane 4.5ml and methyl-phenoxide (a small amount of, as marking in the nuclear-magnetism) successively, by argon gas bubbling 60min to eliminate oxygen.Next the mixture in second flask is gone in first flask, place 60 ℃ oil bath to react 24h, the transformation efficiency of tBMA reaches 95%, and transformation efficiency is recorded by nuclear-magnetism.Reaction solution obtains hyperbranched polymer through precipitation and the vacuum-drying in normal hexane, notes by abridging to be BCP3.
2, the preparation of nano controlled-release material
The hyperbranched polymer of preparation is dissolved among the THF, and mass volume ratio 2.0mg/ml obtains the aqueous dispersion liquid of transparent polymer nano granules behind the water dialysis 20h (7000g/mol Mw cut-off dialysis membrane).
The aqueous dispersion liquid of polymer nano granules can be directly used in DLS and tem analysis.The nano-scale that DLS records is 210nm.The polymer nano granules of the present invention's preparation is to be nuclear with PtBMA, and PEG is the polymer nano granules of shell.
Embodiment 4:P (PEG
4000/ tBMA
80)
1, the preparation of hyperbranched polymer
Polyoxyethylene glycol azo macromolecular radical initiator VPE-0401 (polyoxyethylene glycol number-average molecular weight 4000) 0.67g (0.0833mmol) is placed in the Schlenk flask of a drying, vacuumizes a logical nitrogen three times repeatedly.In another Schlenk flask, add tBMA1.89g (13.34mmol), EGDMA14.5mg (0.075mmol), solvent 1 successively, 4-dioxane 4.5ml and methyl-phenoxide (a small amount of, as marking in the nuclear-magnetism), by argon gas bubbling 60min to eliminate oxygen.Next the mixture in second flask is gone in first flask, place 60 ℃ oil bath to react 24h, the transformation efficiency of tBMA reaches 95%, and transformation efficiency is recorded by nuclear-magnetism.Reaction solution obtains hyperbranched polymer through precipitation and the vacuum-drying in normal hexane, notes by abridging to be BCP4.
2, the preparation of nano controlled-release material
The hyperbranched polymer of preparation is dissolved among the THF, and mass volume ratio 2.0mg/ml obtains the aqueous dispersion liquid of transparent polymer nano granules behind the water dialysis 20h (7000g/molMw cut-off dialysis membrane).
The aqueous dispersion liquid of polymer nano granules can be directly used in DLS and tem analysis.The nano-scale that DLS records is 231nm.The polymer nano granules of the present invention's preparation is to be nuclear with PtBMA, and PEG is the polymer nano granules of shell.
Among the embodiment 1-4, can obtain with PtBMA through simple dialysis is nuclear, and PEG is the polymer nano granules of shell.Can synthesize the nanoparticle of different size by this preparation method, only need to change the molecular weight of PtBMA.DLS data instance with the nanoparticle for preparing among the embodiment 1-4, the nano-scale of P (PEG4000/tBMA20) nano controlled-release material is 174nm, the nano-scale of P (PEG4000/tBMA40) nano controlled-release material is 192nm, the nano-scale of P (PEG4000/tBMA60) nano controlled-release material is 210nm, and the nano-scale of P (PEG4000/tBMA80) nano controlled-release material is 231nm.Above data show that the polymerization degree of tBMA in the hyperbranched polymer is more big, and the nano-scale of the nano controlled-release material that makes is also just more big, and are also just more big for the loading capacity of guest molecule.We just can meet the nano controlled-release material of certain nano-scale of this loading capacity requirement according to the needed loading capacity preparation of guest molecule conversely.
Comparative Examples 1:
Polyoxyethylene glycol azo macromolecular radical initiator VPE-0201 (polyoxyethylene glycol number-average molecular weight 2000) 0.335g (0.0833mmol) is placed in the Schlenk flask of a drying, vacuumizes-Tong nitrogen three times repeatedly.In another Schlenk flask, add tBMA0.47g (3.33mmol), EGDMA14.5mg (0.075mmol), solvent 1,4 one dioxane 4.5ml and methyl-phenoxide (a small amount of, as marking in the nuclear-magnetism) successively, by argon gas bubbling 60min to eliminate oxygen.Next the mixture in second flask is gone in first flask, place 60 ℃ oil bath to react 24h, the transformation efficiency of tBMA reaches 95%, and transformation efficiency is recorded by nuclear-magnetism.Reaction solution obtains hyperbranched polymer through precipitation and the vacuum-drying in normal hexane, notes by abridging to be BCP5.
The hyperbranched polymer of preparation is dissolved among the THF, and mass volume ratio 2.0mg/ml carries out water dialysis (7000g/mol Mw cut-off dialysis membrane) subsequently, has sedimentation to take place in the process of water dialysis, and this shows does not have nanoparticle to generate.This is because relatively short outer PEG chain can not guarantee the stable of the whole nanoparticle of aqueous phase.
Claims (3)
1. a radical polymerization prepares the method for polymer nanocomposite slow-release material, comprises the preparation of hyperbranched polymer, preparation and each unit process of aftertreatment of nano controlled-release material, it is characterized in that:
The preparation of described hyperbranched polymer is that monomer, bifunctional crosslinking agent, solvent are mixed with the macromolecular radical initiator, under nitrogen protection, in 60 ℃ of reactions 22-26 hour, after reaction finishes reaction solution added in the normal hexane sedimentation and vacuum-drying and obtain hyperbranched polymer; Described macromolecular radical initiator, monomer and bifunctional crosslinking agent's mol ratio is 1:(40-160): 0.9;
Described monomer selects white methyl acrylic ester monomer, acrylic ester monomer or styrene monomer;
Described bifunctional crosslinking agent selects Baiyi glycol dimethacrylate, polyethylene glycol dimethacrylate, glycol diacrylate, polyethyleneglycol diacrylate or to Vinylstyrene;
Described macromolecular radical initiator is polyoxyethylene glycol azo class macromolecular radical initiator, the number-average molecular weight of described macromolecular radical initiator≤8000;
The preparation of described nano controlled-release material is that described hyperbranched polymer is dissolved among the THF of 200-2000 times of volume, obtains the aqueous dispersion liquid of transparent polymer nanocomposite slow-release material after the water dialysis.
2. preparation method according to claim 1 is characterized in that:
Described methyl acrylic ester monomer is tert-butyl methacrylate, n-BMA, methyl methacrylate, Jia Jibingxisuanyizhi or propyl methacrylate;
Described acrylic ester monomer is the special butyl ester of vinylformic acid, n-butyl acrylate, methyl acrylate, ethyl propenoate or propyl acrylate;
Described styrene monomer is vinylbenzene or vinyl toluene.
3. preparation method according to claim 1 is characterized in that:
The model of described polyoxyethylene glycol azo class macromolecular radical initiator is VPE-0201, VPE-0401 or VPE-0601.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015053716A1 (en) * | 2013-10-11 | 2015-04-16 | Agency For Science, Technology And Research | Direct synthesis of ph-responsive polymer particles and application in control release of hydrophobic therapeutic compounds |
| CN105153354A (en) * | 2015-10-18 | 2015-12-16 | 长春工业大学 | Preparation method of highly-branched polymer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009018215A (en) * | 2007-07-10 | 2009-01-29 | Osaka Prefecture | Method of immobilizing core-shell polymer gel particle, and separation agent |
| CN101575402A (en) * | 2009-05-31 | 2009-11-11 | 中国科学院化学研究所 | Multi-arm star-type polymer and preparation method thereof |
| CN101850121A (en) * | 2010-01-26 | 2010-10-06 | 北京科技大学 | Hyperbranched polyurethane hydrogel for controlled release of medicament and preparation method thereof |
-
2013
- 2013-04-23 CN CN2013101430661A patent/CN103204970A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009018215A (en) * | 2007-07-10 | 2009-01-29 | Osaka Prefecture | Method of immobilizing core-shell polymer gel particle, and separation agent |
| CN101575402A (en) * | 2009-05-31 | 2009-11-11 | 中国科学院化学研究所 | Multi-arm star-type polymer and preparation method thereof |
| CN101850121A (en) * | 2010-01-26 | 2010-10-06 | 北京科技大学 | Hyperbranched polyurethane hydrogel for controlled release of medicament and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 储鸿等: "VPE引发的苯乙烯无皂乳液聚合研究", 《化工新型材料》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015053716A1 (en) * | 2013-10-11 | 2015-04-16 | Agency For Science, Technology And Research | Direct synthesis of ph-responsive polymer particles and application in control release of hydrophobic therapeutic compounds |
| CN105153354A (en) * | 2015-10-18 | 2015-12-16 | 长春工业大学 | Preparation method of highly-branched polymer |
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Application publication date: 20130717 |