CN102643442B - Method for preparing polymeric micron/nanometer spherical particle - Google Patents
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- CN102643442B CN102643442B CN201210107974.0A CN201210107974A CN102643442B CN 102643442 B CN102643442 B CN 102643442B CN 201210107974 A CN201210107974 A CN 201210107974A CN 102643442 B CN102643442 B CN 102643442B
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- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000012798 spherical particle Substances 0.000 title abstract 6
- 238000009826 distribution Methods 0.000 claims abstract description 19
- 230000033444 hydroxylation Effects 0.000 claims abstract description 17
- 238000005805 hydroxylation reaction Methods 0.000 claims abstract description 17
- 229920001577 copolymer Polymers 0.000 claims abstract description 13
- 238000001556 precipitation Methods 0.000 claims abstract description 10
- 238000001291 vacuum drying Methods 0.000 claims abstract description 8
- 239000002798 polar solvent Substances 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 229920001400 block copolymer Polymers 0.000 claims description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 7
- 235000019253 formic acid Nutrition 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 229920002319 Poly(methyl acrylate) Polymers 0.000 claims description 2
- 230000001186 cumulative effect Effects 0.000 claims description 2
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims description 2
- 230000000640 hydroxylating effect Effects 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920001195 polyisoprene Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920002102 polyvinyl toluene Polymers 0.000 claims description 2
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 7
- 210000001218 blood-brain barrier Anatomy 0.000 abstract description 2
- 239000003937 drug carrier Substances 0.000 abstract description 2
- 108090000623 proteins and genes Proteins 0.000 abstract description 2
- 230000008499 blood brain barrier function Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000011805 ball Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 210000004087 cornea Anatomy 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000003405 delayed action preparation Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 230000002068 genetic effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012216 imaging agent Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 239000002088 nanocapsule Substances 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 210000000952 spleen Anatomy 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
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- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a method for preparing a polymeric micron/nanometer spherical particle. The micron/nanometer spherical particle prepared by the method is narrow in particle size distribution, and the obtained polymeric micron/nanometer spherical particle can be used in the aspects of a drug carrier, a permeable blood-brain barrier, gene inheritance, a developer carrier and the like. The method for preparing the polymeric micrometer/nanometer spherical particle, which is provided by the invention, comprises the following steps of: 1), dissolving a segmented copolymer into an organic solvent to prepare a segmented copolymer solution; 2), carrying out hydroxylation processing on the prepared segmented copolymer solution; 3), carrying out precipitation processing on an obtained hydroxylated product through a precipitant; 4), carrying out vacuum drying processing on the hydroxylated product obtained through precipitation; and 5), adding the dried hydroxylated product into a polar solvent to be subjected to micellization, so as to obtain the polymeric micrometer/nanometer spherical particle which is narrow in particle size distribution.
Description
Technical field
The present invention relates to a kind of method for preparing micro-nano spherolite, relate in particular to a kind of method for preparing the polymer micro-nanometer spherolite.
Background technology
The polymer micro-nano grain of rice is that a class is the solid-state medicine carrying colloidal particle of carrier with natural or synthesized polymer material, and general particle diameter is 10-1000nm.Nanoparticle is the general name of nanometer ball and nanocapsule.Compare with microballoon, the physical stability of nanoparticle is good, is convenient to heat sterilization and storage; Because it belongs to colloid system, clinically, than the easy administration of suspension type microball preparation; Because its particle diameter is little, surface energy is big, is conducive to locate to be detained at mucous membrane, cornea etc., is conducive to the absorption of medicine and improves bioavailability of medicament; Can be made into skeleton type sustained release preparation; After being ingested, can passive arrival liver, spleen and marrow, have the effect of target administration; Can modify its surface, thereby reach the initiatively purpose of target distribution; Can change medicine to biomembranous perviousness, be conducive to target transmission in drug transdermal absorption and the born of the same parents.
The method of the micro-nano spherolite of existing preparation mainly contains micell polymerization method, emulsion polymerization method, interface polycondensation, coacervation and intra-liquid desiccation method etc.But these methods have the weak point of himself, just have advantage aspect certain or some, can not take into account characteristics such as the adjustable and narrow diameter distribution of particle diameter microcosmic simultaneously.
Summary of the invention
Purpose of the present invention is intended to overcome complex process and the wide defective of micella size distribution of prior art, and a kind of method for preparing the polymer micro-nanometer spherolite is provided.The micro-nano spherolite narrow diameter distribution of this method preparation, resulting polymer micro-nanometer spherolite can be used on pharmaceutical carrier, see through aspects such as hemato encephalic barrier, gene genetic and imaging agent carrier.
The present invention is achieved by the following technical solutions:
The method for preparing the polymer micro-nanometer spherolite of the present invention, it may further comprise the steps:
1) segmented copolymer is dissolved in the organic solvent preparation block copolymer solution;
2) block copolymer solution for preparing being carried out hydroxylation handles;
3) hydroxylation product that obtains is carried out precipitation process by precipitation agent;
4) hydroxylation product that precipitation is obtained carries out vacuum drying treatment;
5) thus the hydroxylation product that drying is crossed adds in the polar solvent and carries out the polymer micro-nanometer spherolite that micellization obtains narrow diameter distribution.
The method for preparing the polymer micro-nanometer spherolite of the present invention, its further technical scheme are that described segmented copolymer is made up of block A and B block, and described block A is polyhutadiene and polyisoprene; B block is polystyrene, polymethylmethacrylate, polymethyl acrylate or polyvinyltoluene, and wherein to account for the per-cent of segmented copolymer cumulative volume be 20-50% to block A.
The method for preparing the polymer micro-nanometer spherolite of the present invention, the mass percentage concentration that its further technical scheme can also be block copolymer solution in the step 1 is 10-30%.
The method for preparing the polymer micro-nanometer spherolite of the present invention, its further technical scheme can also be that the organic solvent described in the step 1 is tetrahydrofuran (THF), toluene, dimethyl formamide or N,N-DIMETHYLACETAMIDE.
The method for preparing the polymer micro-nanometer spherolite of the present invention, its further technical scheme can also be that the hydroxylation processing described in the step 2 is block copolymer solution to be added carry out hydroxylating in hydrogen peroxide, potassium permanganate, potassium perchlorate or the peroxyformic acid.
The method for preparing the polymer micro-nanometer spherolite of the present invention, its further technical scheme can also be that the precipitation agent described in the step 3 is ethanol, methyl alcohol, propyl alcohol or Virahol.
The method for preparing the polymer micro-nanometer spherolite of the present invention, its further technical scheme can also be that the vacuum-drying temperature control described in the step 4 is between 50-80 ℃; Time of drying, control was between 10-24h.
The method for preparing the polymer micro-nanometer spherolite of the present invention, its further technical scheme can also be that the polar solvent described in the step 5 is water, methyl alcohol, ethanol, formic acid or acetic acid.
Compared with prior art the present invention has following beneficial effect:
The present invention is based on the interaction of hydrophilic radical in polar solvent and the segmented copolymer, and forming with hydrophilic block in the segmented copolymer is that shell is the polymer micro-nanometer spherolite of nuclear with the hydrophobic block.Advantage of the present invention is with low cost, and step is simple, and is convenient controlled, and by change the kind of selective solvent, regulate, have good scale operation prospect within the specific limits by temperature and treatment time for the big I of particle diameter.
Description of drawings
Fig. 1, Fig. 2 are the electron scanning micrograph of the polymer micro-nanometer spherolite of embodiment 1 prepared narrow diameter distribution.
Fig. 3 is the size distribution figure of the polymer micro-nanometer spherolite of embodiment 1 prepared narrow diameter distribution.
Fig. 4 is the electron scanning micrograph of the polymer micro-nanometer spherolite of embodiment 2 prepared narrow diameter distributions.
Fig. 5 is the size distribution figure of the polymer micro-nanometer spherolite of embodiment 2 prepared narrow diameter distributions.
Concrete enforcement side executes
Embodiment 1
(1) segmented copolymer (the polyhutadiene volume ratio is 30%) of getting 5g polystyrene and polyhutadiene is dissolved in the 45g toluene, obtains polymer weight ratio and be 10% solution;
(2) in there-necked flask, add formic acid and each 1mol of hydrogen peroxide, under 70 ℃ of conditions, react half an hour, make peroxyformic acid; And to get 12g concentration be that 10% polymers soln adds in the peroxyformic acid and reacts 1h; Treat to add again after this reaction finishes 2mol formic acid and continue reaction 3h;
(3) in the hydroxylation product that obtains, add methyl alcohol and precipitate, refilter repeatable operation 3 times.Take out the polymkeric substance that finally obtains and in 70 ℃ of vacuum drying ovens, carry out dry 12h;
(4) get dry good hydroxylation product 0.05g in hydrothermal reaction kettle, and add 9.95g acetic acid, make that the polymer quality ratio is 0.5%;
(5) with the sample heat treated 15h under 150 ℃ of conditions that obtains, obtain the polymer micro-nanometer spherolite of narrow diameter distribution.The electron scanning micrograph of the spherical micelle of the made narrow diameter distribution that obtains as shown in Figure 1.Carry out particle size analysis by Fig. 1 being got 50 polymer micro-nanometer spherolites, obtaining median size is 450.20nm, and concrete data as shown in Figure 3.
Embodiment 2
(1) segmented copolymer (the polyhutadiene volume ratio is 30%) of getting 5g polystyrene and polyhutadiene is dissolved in the 45g toluene, obtains polymer weight ratio and be 10% solution;
(2) in there-necked flask, add formic acid and each 1mol of hydrogen peroxide, under 70 ℃ of conditions, react half an hour, make peroxyformic acid; And to get 12g concentration be that 10% polymers soln adds in the peroxyformic acid and reacts 1h; Treat to add again after this reaction finishes 2mol formic acid and continue reaction 3h;
(3) in the hydroxylation product that obtains, add methyl alcohol and precipitate, refilter repeatable operation 3 times.Take out the polymkeric substance that finally obtains and in 70 ℃ of vacuum drying ovens, carry out dry 12h;
(4) get dry good hydroxylation product 0.05g in hydrothermal reaction kettle, and add 9.95g acetic acid, make that the polymer quality ratio is 0.5%;
(5) with the sample heat treated 15h under 100 ℃ of conditions that obtains, obtain the polymer micro-nanometer spherolite of narrow diameter distribution.The electron scanning micrograph of the spherical micelle of the made narrow diameter distribution that obtains as shown in Figure 4.Analyze by Fig. 4 being got 50 polymer micro-nanometer spherolites, obtaining median size is 93.46nm, and its concrete data as shown in Figure 5.
(1) gets 5g polystyrene-butadiene-styrene triblock copolymer (the polyhutadiene volume is 35%) and be dissolved in the 25g tetrahydrofuran (THF), obtain polymer weight ratio and be 16.7% solution;
(2) in there-necked flask, add 10g potassium permanganate and 20g polymers soln reaction 4h;
(3) in the hydroxylation product that obtains, add ethanol and precipitate, refilter repeatable operation 3 times.Remove the polymkeric substance dry 15h in 60 ℃ of vacuum drying ovens that finally obtains;
(4) get dry good hydroxylation product 0.1g in hydrothermal reaction kettle, and add 29.9g formic acid, make that polymer weight ratio is 0.33%;
(5) with the sample heat treated 4h under 100 ℃ of conditions that obtains, obtain the polymer micro-nanometer spherolite of narrow diameter distribution.
Claims (6)
1. method for preparing the polymer micro-nanometer spherolite is characterized in that may further comprise the steps:
1) segmented copolymer is dissolved in the organic solvent, the preparation block copolymer solution, wherein said segmented copolymer is made up of block A and B block, and described block A is polyhutadiene and polyisoprene; B block is polystyrene, polymethylmethacrylate, polymethyl acrylate or polyvinyltoluene, and wherein to account for the per-cent of segmented copolymer cumulative volume be 20-50% to block A;
2) block copolymer solution for preparing is carried out hydroxylation and handle, it is block copolymer solution to be added carry out hydroxylating in hydrogen peroxide, potassium permanganate, potassium perchlorate or the peroxyformic acid that wherein said hydroxylation is handled;
3) hydroxylation product that obtains is carried out precipitation process by precipitation agent;
4) hydroxylation product that precipitation is obtained carries out vacuum drying treatment;
5) thus the hydroxylation product that drying is crossed adds in the polar solvent and carries out the polymer micro-nanometer spherolite that micellization obtains narrow diameter distribution.
2. the method for preparing the polymer micro-nanometer spherolite according to claim 1, the mass percentage concentration that it is characterized in that block copolymer solution in the step 1 is 10-30%.
3. the method for preparing the polymer micro-nanometer spherolite according to claim 1 is characterized in that the organic solvent described in the step 1 is tetrahydrofuran (THF), toluene, dimethyl formamide or N,N-DIMETHYLACETAMIDE.
4. the method for preparing the polymer micro-nanometer spherolite according to claim 1 is characterized in that the precipitation agent described in the step 3 is ethanol, methyl alcohol, propyl alcohol or Virahol.
5. the method for preparing the polymer micro-nanometer spherolite according to claim 1 is characterized in that the vacuum-drying temperature control described in the step 4 is between 50-80 ℃; Time of drying, control was between 10-24h.
6. the method for preparing the polymer micro-nanometer spherolite according to claim 1 is characterized in that the polar solvent described in the step 5 is water, methyl alcohol, ethanol, formic acid or acetic acid.
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101260219A (en) * | 2008-04-25 | 2008-09-10 | 华南理工大学 | Method for preparing triblock copolymer micelle system used for realizing reversible fluorescence regulation and control |
CN101481461A (en) * | 2009-02-03 | 2009-07-15 | 厦门大学 | Preparation and use of phenylethylene block copolymer micro-nano microsphere |
CN102391527A (en) * | 2011-07-11 | 2012-03-28 | 南京工业大学 | Preparation method of uniform-dimension polymer nano microspheres |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN101260219A (en) * | 2008-04-25 | 2008-09-10 | 华南理工大学 | Method for preparing triblock copolymer micelle system used for realizing reversible fluorescence regulation and control |
CN101481461A (en) * | 2009-02-03 | 2009-07-15 | 厦门大学 | Preparation and use of phenylethylene block copolymer micro-nano microsphere |
CN102391527A (en) * | 2011-07-11 | 2012-03-28 | 南京工业大学 | Preparation method of uniform-dimension polymer nano microspheres |
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