CN1990516A - Process for preparing polymer nano container - Google Patents
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- CN1990516A CN1990516A CN 200610167504 CN200610167504A CN1990516A CN 1990516 A CN1990516 A CN 1990516A CN 200610167504 CN200610167504 CN 200610167504 CN 200610167504 A CN200610167504 A CN 200610167504A CN 1990516 A CN1990516 A CN 1990516A
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Abstract
The invention discloses a method for preparing nanometer container, comprising following steps: (A) dissolving chitosan in organic acid solution containing polyradical group; (B) purging with nitrogen gas to remove oxygen, adding initiator to initiating grafting polymerization; (C) reacting under nitrogen gas protection. The invention avoides the multiple steps in normal methods (such as amphiphilic bock polymers sely- assembly method and step- by- step self- assembly method mentioned above) is charactetrized by one- step process, cheap raw material and temperate reaction condition.
Description
Technical field
The present invention relates to a kind of preparation method of nano container.Belong to chemical technology field.
Background technology
Over nearly 20 years, nano material has been subjected to the extensive concern of Chinese scholars.Nanometer system, this is different from what is called Jie's sight field of both macro and micro, because three-dimensional dimension is little, many unusual brand-new physicalies occurred.The organic materials of nano-scale has demonstrated wide application prospect owing to have controlled composition, structure, performance and function.
Nano container (nanocontainer) is polymer microcapsule with cavity structure or the hollow microsphere on nanometer or submicron-scale.Research to polymer nano container has in recent years caused numerous concerns especially; this be because nano container biochemical and separate aspect have many potential purposes, for example: be used as the protecting sheathing of restricted reaction vessel, pharmaceutical carrier, enzyme or catalyzer and artificial cell etc.The conventional method for preparing nano container needs trivial step, can not be used for mass production, and need to use a large amount of organic solvents in preparation process, and environment is easily polluted; Simultaneously early stage nano container is that effect by non covalent bond forms, and mechanical stability is relatively poor, thereby has limited its application in many aspects.
The method that is used to prepare nano container at present mainly contains self-assembly method, template and microemulsion method.
Self-assembly method at first will prepare parents' molecule of polymerizable functional group, parents' molecular dispersion that will have the polymerizable functional group then forms micella in water or organic solvent or water/ORGANIC SOLVENT MIXTURES, add the initiator initiated polymerization again, just can obtain nano container.The step of preparation parents molecule relates to the multistep organic synthesis in this method, and process is loaded down with trivial details, needs very high cost and a lot of time.
Template at first prepares a kind of Nano microsphere (as nanometer gold, nano silicon etc.), successively adsorb polyelectrolyte on its surface then, again the nuclear decomposition of inside is fallen, perhaps earlier in Nano microsphere template surface chemical bonding polymerizable or crosslinkable unimolecular layer, initiated polymerization or crosslinked just can obtain nano container with the nano-form dissolving again.This method still needs multistep to carry out, especially microsphere surface successively adsorb or when bonding polymerizable or crosslinkable unimolecular layer condition wayward.And some solvents (as potassium cyanide solution, hydrofluoric acid solution etc.) that need use in the dissolving nano-form are very unfriendly to environment.
Microemulsion method at first needs to prepare the polymer emulsion that contains carboxyl, forms the rigid polymer shell on its surface again, again under near the shell glass transition temperature of polymer with alkaline solution in and the carboxyl in the polymer emulsion nuclear make it dissolving, the acquisition nano container.This method still needs the branch multistep to carry out, and technology is more complicated also, complex operation.
The other method is short of such as the preparation technologies such as preparation of branch-shape polymer nano container, and with high costs.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of nano container, present method is dissolved in certain amount of chitosan in the certain density organic acid soln, the vesica structure of utilizing its self-assembly to form, add the organic acid graft polymerization that contains polymerizable groups in the initiator initiator system, make the constitutionally stable nano container of uniform particle diameter by single step reaction.
One of advantage of the present invention is the loaded down with trivial details step that has overcome ordinary method (as amphiphilic block copolymer self-assembly method, method as described in the leading portion such as self-assembly method layer by layer), adopt single stage method, utilize cheap raw material under mild conditions, directly simple synthesis of nano container.
Two of advantage of the present invention is that the described process of present method is all carried out in the aqueous solution, avoided with an organic solvent with other to the disagreeableness solution of environment, compare environmental protection more with additive method and save cost.
Three of advantage of the present invention is that the material of preparation nano container in present method is mainly chitosan, makes the prepared nano container of present method have part biological degradability and certain biocompatibility, is convenient to use at bioengineering field.
Four of advantage of the present invention is to take the method for graft polymerization to prepare nano container in present method, has replaced non-covalent bonding action in the early stage nano container with covalent linkage, makes the nano container of preparation that satisfactory stability be arranged.
Five of advantage of the present invention is that the nano container of present method preparation has homogeneous particle diameter, is convenient to use at drug release, microreactor chemical field.
For reaching above-mentioned target, the invention provides a kind of method for preparing nano container, this method comprises that (A) is dissolved in chitosan in the organic acid aqueous solution that contains polymerizable groups; (B) the logical nitrogen of above-mentioned solution is removed oxygen, add initiator; (C) under nitrogen protection, react.
The organic acid that contains polymerizable groups of the present invention is methacrylic acid, vinylformic acid or maleic acid.The concentration that contains the aqueous solutions of organic acids of polymerizable groups is preferably 0.01～1 mol, and is more preferably 0.025～0.25 mol.
Chitosan molecule amount of the present invention is 10,000～800,000, and deacetylation is greater than 50%.The consumption of chitosan is preferably and adds 2～200 grams in every liter of organic acid aqueous solution that contains polymerizable groups, adds 5～50 grams and be more preferably in every liter of organic acid aqueous solution that contains polymerizable groups.
Initiator of the present invention be a kind of can with the oxygenant of chitosan reaction production free radical polymerization.It can be (a) cerium salt; (b) high cuprate; (c) permanganate; (d) persulphate; (e) chromic salt; (f) vanadate.
Wherein cerium salt is meant and contains positive quadrivalent cerium ionic compound, as ceric ammonium nitrate (NH
4)
2[Ce (NO
3)
6]; High mantoquita is meant the compound of the high-copper acid group that contains positive means of trivalent copper, closes the sour potassium K of copper (III) as two positive Periodic acid
5[Cu (HIO
6)
2]; Permanganate is meant the compound of the MnO4 that contains positive septivalency manganese, as potassium permanganate KMnO
4Persulphate refers to contain the compound of persulfate, as Potassium Persulphate K
2S
2O
8, ammonium persulphate (NH
4)
2S
2O
8Vanadate is meant the compound of the vanadic acid root that contains positive pentavalent vanadium, as vanadic acid sodium Na
3VO
4Chromic salt is meant the compound that contains just chromic chromate, dichromate ion, as potassium bichromate K
2Cr
2O
7, strontium yellow SrCrO
4
Initiator amount of the present invention is 0.01～1 mol, preferred 0.01～0.5 mol.
Entire reaction is all carried out under nitrogen protection among the preparation method of the present invention, and the reaction times is 0.5～12 hour, preferred 0.5～5 hour.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1
Take by weighing chitosan (molecular weight 800,000, deacetylation 55%) 10 grams, render in the acrylic acid aqueous solution of 5 liter of 0.01 mol, stir and make it dissolving.Dissolving finishes, and feeds nitrogen 30 minutes, constantly stirs.Under nitrogen protection, add 10 gram ceric ammonium nitrates, constantly stirred stopped reaction 0.5 hour.
Gained nano container particle diameter 263nm, dispersion coefficient 0.086
Embodiment 2
Take by weighing chitosan (molecular weight 300,000, deacetylation 75%) 50 grams, render in the methacrylic aqueous acid of 5 liter of 1 mol, stir and make it dissolving.Dissolving finishes, and feeds nitrogen 15 minutes, constantly stirs.Under nitrogen protection, add 40 gram potassium permanganate, constantly stirred stopped reaction 6 hours.
Gained nano container particle diameter 210nm, dispersion coefficient 0.021
Embodiment 3
Take by weighing chitosan (molecular weight 10,000, deacetylation 96%) 1000 grams, render in the maleic acid aqueous solution of 5 liter of 0.5 mol, stir and make it dissolving.Dissolving finishes, and feeds nitrogen 60 minutes, constantly stirs.Under nitrogen protection, add 125 gram vanadic acid sodiums, constantly stirred stopped reaction 12 hours.
Gained nano container particle diameter 321nm, dispersion coefficient 0.115
Claims (9)
1. the preparation method of a nano container, it is characterized in that: this method comprises the steps:
(A) chitosan is dissolved in the organic acid aqueous solution that contains polymerizable groups;
(B) the logical nitrogen of above-mentioned solution is removed oxygen, add initiator, the initiation grafting polymerization;
(C) under nitrogen protection, react.
2. the preparation method of a kind of nano container according to claim 1, it is characterized in that: the wherein said organic acid that contains polymerizable groups is selected from the organic acid that has polymerizable double bond, wherein preferable methyl vinylformic acid, vinylformic acid, maleic acid, furoate clothing.
3. by the method for claim 1, it is characterized in that: the wherein said aqueous solutions of organic acids concentration that contains polymerizable groups is 0.01～1 mol.
4. the preparation method of a kind of nano container according to claim 1, it is characterized in that: wherein said chitosan molecule amount is 10,000～800,000.
5. the preparation method of a kind of nano container according to claim 1, it is characterized in that: wherein said deacetylating degree of chitosan is greater than 50%.
6. the preparation method of a kind of nano container according to claim 1 is characterized in that: wherein said chitosan dosage is to add 2～200 grams in every liter of organic acid aqueous solution that contains polymerizable groups.
7. the preparation method of a kind of nano container according to claim 1, it is characterized in that: wherein initiator is selected from:
(a) cerium salt
(b) high cuprate
(c) permanganate
(d) persulphate
(e) chromic salt
(f) vanadate
8. the preparation method of a kind of nano container according to claim 1, it is characterized in that: the amount of wherein said adding initiator is 0.01～1 mol.
9. the preparation method of a kind of nano container according to claim 1 is characterized in that: wherein said be reflected at room temperature and under nitrogen protection, constantly stir under carried out 0.5～12 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610167504 CN1990516A (en) | 2005-12-26 | 2006-12-25 | Process for preparing polymer nano container |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200510022397 | 2005-12-26 | ||
| CN200510022397.5 | 2005-12-26 | ||
| CN 200610167504 CN1990516A (en) | 2005-12-26 | 2006-12-25 | Process for preparing polymer nano container |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1990516A true CN1990516A (en) | 2007-07-04 |
Family
ID=38213070
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200610167504 Pending CN1990516A (en) | 2005-12-26 | 2006-12-25 | Process for preparing polymer nano container |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977271A (en) * | 2012-12-14 | 2013-03-20 | 西北师范大学 | Method for preparing chitosan/crylic acid composite through initiating polymerization by using glow discharge electrolysis plasma |
| CN104764876A (en) * | 2014-07-11 | 2015-07-08 | 青岛科技大学 | Preparation and application of biological nanometer container to treatment of cancer |
| CN104927418A (en) * | 2015-07-06 | 2015-09-23 | 江苏固格澜栅防护设施有限公司 | Acid-alkali dual response intelligent nano container based anti-corrosion coating preparation method and application |
| CN105727299A (en) * | 2014-12-12 | 2016-07-06 | 南京理工大学 | PH-stimulation responsive intelligent nano container and preparation method thereof |
-
2006
- 2006-12-25 CN CN 200610167504 patent/CN1990516A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977271A (en) * | 2012-12-14 | 2013-03-20 | 西北师范大学 | Method for preparing chitosan/crylic acid composite through initiating polymerization by using glow discharge electrolysis plasma |
| CN102977271B (en) * | 2012-12-14 | 2015-03-04 | 西北师范大学 | Method for preparing chitosan/crylic acid composite through initiating polymerization by using glow discharge electrolysis plasma |
| CN104764876A (en) * | 2014-07-11 | 2015-07-08 | 青岛科技大学 | Preparation and application of biological nanometer container to treatment of cancer |
| CN105727299A (en) * | 2014-12-12 | 2016-07-06 | 南京理工大学 | PH-stimulation responsive intelligent nano container and preparation method thereof |
| CN104927418A (en) * | 2015-07-06 | 2015-09-23 | 江苏固格澜栅防护设施有限公司 | Acid-alkali dual response intelligent nano container based anti-corrosion coating preparation method and application |
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