CN105670006A - Preparation method of polyvinyl alcohol-poly(lactide-glycolide) graft copolymer micelle - Google Patents
Preparation method of polyvinyl alcohol-poly(lactide-glycolide) graft copolymer micelle Download PDFInfo
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- CN105670006A CN105670006A CN201610131729.1A CN201610131729A CN105670006A CN 105670006 A CN105670006 A CN 105670006A CN 201610131729 A CN201610131729 A CN 201610131729A CN 105670006 A CN105670006 A CN 105670006A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
- C08J3/097—Sulfur containing compounds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/34—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyesters, polyamino acids, polysiloxanes, polyphosphazines, copolymers of polyalkylene glycol or poloxamers
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/10—Dispersions; Emulsions
- A61K9/107—Emulsions ; Emulsion preconcentrates; Micelles
- A61K9/1075—Microemulsions or submicron emulsions; Preconcentrates or solids thereof; Micelles, e.g. made of phospholipids or block copolymers
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
- C08G81/027—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyester or polycarbonate sequences
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2387/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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Abstract
The invention discloses a preparation method of a polyvinyl alcohol-poly(lactide-glycolide) graft copolymer micelle. The preparation method comprises the following steps: 1) adding polyvinyl alcohol, carboxy-terminated poly(lactide-glycolide) monododecyl ether, a solvent and a condensing agent into a dry reactor, and reacting to obtain a polyvinyl alcohol-poly(lactide-glycolide) graft copolymer; 2) adding the polyvinyl alcohol-poly(lactide-glycolide) graft copolymer and a solvent into a dry reactor, and dissolving to obtain a polyvinyl alcohol-poly(lactide-glycolide) graft copolymer raw solution; and 3) adding the raw solution into a dialysis bag, putting the dialysis bag into a selective-solvent-containing beaker, replacing 3-4 times every other 8 hours until the solution in the dialysis bag appears blue light, pouring the solution into a calibrated volumetric flask, and adjusting to the calibration with a selective solvent, thereby obtaining the target substance. The preparation technique is simple and easy to master. The obtained target substance is a novel drug carrier.
Description
Technical field
The preparation method that the present invention relates to a kind of polyvinyl alcohol-poly-(lactide coglycolide) graft copolymer micelle, belongs to biodegradated polymer materal preparing technical field.
Background technology
Polyvinyl alcohol is a kind of biomaterial with good biocompatibility and biodegradability, has excellent hydrophilic, in medicine extensive application. Poly-(lactide coglycolide) (weight ratio of lactide and Acetic acid, hydroxy-, bimol. cyclic ester is 90/10) is the biomaterial with excellent biocompatibility and biodegradability, has good hydrophobicity, is widely used at medicine. Poly-(lactide coglycolide) segment is grafted to polyvinyl alcohol-poly-(lactide coglycolide) graft copolymer obtained on polyvinyl alcohol molecule chain and has amphipathic, selective solvent can be self-assembly of micelle, it is a kind of novel pharmaceutical carrier, has broad application prospects in the difficult miscellaneous diseases such as treatment cancer.
Summary of the invention
It is an object of the invention to provide a kind of simple to operate and the good polyvinyl alcohol of effect-poly-(lactide coglycolide) graft copolymer micelle preparation method. Its technical scheme is:
A kind of preparation method of polyvinyl alcohol-poly-(lactide coglycolide) graft copolymer micelle, it is characterised in that: in copolymer, the molecular weight of polyvinyl alcohol segments is 42000～50000, and the molecular weight of poly-(lactide coglycolide) segment is 2000～2300; Its preparation method adopts following steps:
1) preparation of polyvinyl alcohol-poly-(lactide coglycolide) graft copolymer: add polyvinyl alcohol, poly-(lactide coglycolide) monododecyl ether of carboxy blocking, solvent and condensing agent in dry reactor, under inert atmosphere, in 27～35 DEG C of stirring reactions 2～3 days, terminate reaction, by filtering, dialyse, drying, obtain object;
2) preparation of polyvinyl alcohol-poly-(lactide coglycolide) graft copolymer stock solution: add polyvinyl alcohol-poly-(lactide coglycolide) graft copolymer and solvent in dry reactor, in 46～51 DEG C of stirring and dissolving 40～60 minutes, obtains object;
3) preparation of polyvinyl alcohol-poly-(lactide coglycolide) graft copolymer micelle: under room temperature, stock solution is added in bag filter, put it in 500 ml beakers filling selective solvent, every displacement in 8 hours once, replace 3～4 times, solution display blue light in bag filter, be then poured in the graduated volumetric flask of band, it is adjusted to scale with selective solvent, obtains object.
The preparation method of described a kind of polyvinyl alcohol-poly-(lactide coglycolide) graft copolymer micelle, in step 1), poly-(lactide coglycolide) monododecyl ether adopts poly-(D, L-lactide coglycolide) monododecyl ether, and the weight ratio of lactide and Acetic acid, hydroxy-, bimol. cyclic ester is 90/10, the mol ratio of poly-(lactide coglycolide) monododecyl ether and polyvinyl alcohol is 15～25:1.
The preparation method of described a kind of polyvinyl alcohol-poly-(lactide coglycolide) graft copolymer micelle, in step 1), condensing agent adoptsN,N’-dicyclohexylcarbodiimide,N,N’-DIC or 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, the mol ratio of condensing agent and polyvinyl alcohol is 1.08～1.8:1, and solvent adopts dimethyl sulfoxide, and reactant solution concentration is 5～15g/100ml.
The preparation method of described a kind of polyvinyl alcohol-poly-(lactide coglycolide) graft copolymer micelle, step 2) in, solvent adopts dimethyl sulfoxide, and original liquid concentration is 1～1.5mg/ml.
The preparation method of described a kind of polyvinyl alcohol-poly-(lactide coglycolide) graft copolymer micelle, in step 3), bag filter capacity is 5～10ml, and bag filter molecular cut off is 3500～4500, selective solvent adopts distilled water, and solution concentration is 0.1～0.3mg/ml.
Compared with prior art, its advantage is the present invention:
1, the preparation method of described a kind of polyvinyl alcohol-poly-(lactide coglycolide) graft copolymer micelle, adopts the means that esterification and dialysis combine, simple to operate, be prone to grasp;
2, described a kind of polyvinyl alcohol-poly-(lactide coglycolide) graft copolymer micelle is a kind of novel pharmaceutical carrier.
Detailed description of the invention
Embodiment 1
1) preparation of polyvinyl alcohol-poly-(lactide coglycolide) graft copolymer
Add poly-(lactide coglycolide) monododecyl ether (molecular weight is 2000) of 12 grams of polyvinyl alcohol (molecular weight is 42000), 10.5 grams of carboxy blockings at dry reactor, add 224 milliliters of dimethyl sulfoxide, add 0.076 gramN,N’-dicyclohexylcarbodiimide, under inert atmosphere, in 27 DEG C of stirring reactions 2 days, terminates reaction, by filtering, dialysis, dry, obtains object;
2) preparation of polyvinyl alcohol-poly-(lactide coglycolide) graft copolymer stock solution
In dry reactor, add 120 milligrams of polyvinyl alcohol-poly-(lactide coglycolide) graft copolymer, 100 milliliters of dimethyl sulfoxide, in 46 DEG C of stirring and dissolving 40 minutes, obtain object;
3) preparation of polyvinyl alcohol-poly-(lactide coglycolide) graft copolymer micelle
Under room temperature, 1 milliliter of polyvinyl alcohol-poly-(lactide coglycolide) graft copolymer stock solution is added in the bag filter of 5 milliliters of capacity (molecular cut off is 3500), put it in 500 ml beakers filling distilled water, every displacement in 8 hours once, replace 3 times, solution display blue light in bag filter, be then poured in the graduated 10 milliliters of volumetric flasks of band, it is adjusted to scale with distilled water, obtains object.
Embodiment 2
1) preparation of polyvinyl alcohol-poly-(lactide coglycolide) graft copolymer
Add poly-(lactide coglycolide) monododecyl ether (molecular weight is 2100) of 13.1 grams of polyvinyl alcohol (molecular weight is 46000), 11.1 grams of carboxy blockings at dry reactor, add 232 milliliters of dimethyl sulfoxide, add 0.046 gramN,N’-DIC, under inert atmosphere, in 30 DEG C of stirring reactions 2 days, terminates reaction, by filtering, dialysis, dry, obtains object;
2) preparation of polyvinyl alcohol-poly-(lactide coglycolide) graft copolymer stock solution
In dry reactor, add 130 milligrams of polyvinyl alcohol-poly-(lactide coglycolide) graft copolymer, 100 milliliters of dimethyl sulfoxide, in 48 DEG C of stirring and dissolving 50 minutes, obtain object;
3) preparation of polyvinyl alcohol-poly-(lactide coglycolide) graft copolymer micelle
Under room temperature, 1 milliliter of polyvinyl alcohol-poly-(lactide coglycolide) graft copolymer stock solution is added in the bag filter of 6 milliliters of capacity (molecular cut off is 4000), put it in 500 ml beakers filling distilled water, every displacement in 8 hours once, replace 4 times, solution display blue light in bag filter, be then poured in the graduated 10 milliliters of volumetric flasks of band, it is adjusted to scale with distilled water, obtains object.
Embodiment 3
1) preparation of polyvinyl alcohol-poly-(lactide coglycolide) graft copolymer
Poly-(lactide coglycolide) monododecyl ether (molecular weight is 2300) of 14 grams of polyvinyl alcohol (molecular weight is 50000), 12.1 grams of carboxy blockings is added at dry reactor, add 240ml dimethyl sulfoxide, add 0.066 gram of 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, under inert atmosphere, in 35 DEG C of stirring reactions 3 days, terminate reaction, by filtering, dialyse, drying, obtain object;
2) preparation of polyvinyl alcohol-poly-(lactide coglycolide) graft copolymer stock solution
In dry reactor, add 140 milligrams of polyvinyl alcohol-poly-(lactide coglycolide) graft copolymer, 100 milliliters of dimethyl sulfoxide, in 51 DEG C of stirring and dissolving 60 minutes, obtain object;
3) preparation of polyvinyl alcohol-poly-(lactide coglycolide) graft copolymer micelle
Under room temperature, 1.2 milliliters of polyvinyl alcohol-poly-(lactide coglycolide) graft copolymer stock solution is added in the bag filter of 8 milliliters of capacity (molecular cut off is 4500), put it in 500 ml beakers filling distilled water, every displacement in 8 hours once, replace 3 times, solution display blue light in bag filter, be then poured in the graduated 12 milliliters of volumetric flasks of band, it is adjusted to scale with distilled water, obtains object.
Claims (5)
1. the preparation method of polyvinyl alcohol-poly-(lactide coglycolide) graft copolymer micelle, it is characterised in that: in copolymer, the molecular weight of polyvinyl alcohol segments is 42000～50000, and the molecular weight of poly-(lactide coglycolide) segment is 2000～2300; Its preparation method adopts following steps:
1) preparation of polyvinyl alcohol-poly-(lactide coglycolide) graft copolymer: add polyvinyl alcohol, poly-(lactide coglycolide) monododecyl ether of carboxy blocking, solvent and condensing agent in dry reactor, under inert atmosphere, in 27～35 DEG C of stirring reactions 2～3 days, terminate reaction, by filtering, dialyse, drying, obtain object;
2) preparation of polyvinyl alcohol-poly-(lactide coglycolide) graft copolymer stock solution: add polyvinyl alcohol-poly-(lactide coglycolide) graft copolymer and solvent in dry reactor, in 46～51 DEG C of stirring and dissolving 40～60 minutes, obtains object;
3) preparation of polyvinyl alcohol-poly-(lactide coglycolide) graft copolymer micelle: under room temperature, stock solution is added in bag filter, put it in 500 ml beakers filling selective solvent, every displacement in 8 hours once, replace 3～4 times, solution display blue light in bag filter, be then poured in the graduated volumetric flask of band, it is adjusted to scale with selective solvent, obtains object.
2. the preparation method of a kind of polyvinyl alcohol according to claim 1-poly-(lactide coglycolide) graft copolymer micelle, it is characterized in that: in step 1), poly-(lactide coglycolide) monododecyl ether adopts poly-(D, L-lactide coglycolide) monododecyl ether, and the weight ratio of lactide and Acetic acid, hydroxy-, bimol. cyclic ester is 90/10, the mol ratio of poly-(lactide coglycolide) monododecyl ether and polyvinyl alcohol is 15～25:1.
3. the preparation method of a kind of polyvinyl alcohol according to claim 1-poly-(lactide coglycolide) graft copolymer micelle, it is characterised in that: in step 1), condensing agent adoptsN,N’-dicyclohexylcarbodiimide,N,N’-DIC or 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, the mol ratio of condensing agent and polyvinyl alcohol is 1.08～1.8:1, and solvent adopts dimethyl sulfoxide, and reactant solution concentration is 5～15g/100ml.
4. the preparation method of a kind of polyvinyl alcohol according to claim 1-poly-(lactide coglycolide) graft copolymer micelle, it is characterised in that: step 2) in, solvent adopts dimethyl sulfoxide, and original liquid concentration is 1～1.5mg/ml.
5. the preparation method of a kind of polyvinyl alcohol according to claim 1-poly-(lactide coglycolide) graft copolymer micelle, it is characterized in that: in step 3), bag filter capacity is 5～10ml, bag filter molecular cut off is 3500～4500, selective solvent adopts distilled water, and solution concentration is 0.1～0.3mg/ml.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610131729.1A CN105670006A (en) | 2016-03-09 | 2016-03-09 | Preparation method of polyvinyl alcohol-poly(lactide-glycolide) graft copolymer micelle |
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| CN201610131729.1A CN105670006A (en) | 2016-03-09 | 2016-03-09 | Preparation method of polyvinyl alcohol-poly(lactide-glycolide) graft copolymer micelle |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106987139A (en) * | 2017-05-25 | 2017-07-28 | 山东理工大学 | A kind of method that MPEGPLA lifts polypropylene sorrel water resistance and compliance with polylactide |
| CN106986996A (en) * | 2017-05-22 | 2017-07-28 | 山东理工大学 | A kind of polyacrylic acid polycaprolactone gathers（Lactide glycolide）The preparation method of copolymer micelle |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106986996A (en) * | 2017-05-22 | 2017-07-28 | 山东理工大学 | A kind of polyacrylic acid polycaprolactone gathers（Lactide glycolide）The preparation method of copolymer micelle |
| CN106987139A (en) * | 2017-05-25 | 2017-07-28 | 山东理工大学 | A kind of method that MPEGPLA lifts polypropylene sorrel water resistance and compliance with polylactide |
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