CN106987008A - A kind of preparation method of polyacrylic acid polycaprolactone PPDO dual graft copolymer micelle - Google Patents
A kind of preparation method of polyacrylic acid polycaprolactone PPDO dual graft copolymer micelle Download PDFInfo
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- CN106987008A CN106987008A CN201710376632.1A CN201710376632A CN106987008A CN 106987008 A CN106987008 A CN 106987008A CN 201710376632 A CN201710376632 A CN 201710376632A CN 106987008 A CN106987008 A CN 106987008A
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- 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
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- 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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- A61K9/107—Emulsions ; Emulsion preconcentrates; Micelles
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- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
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Abstract
The present invention discloses a kind of preparation method of polyacrylic acid polycaprolactone PPDO dual graft copolymer micelle, using following methods:1)Polyacrylic acid, hydroxy-end capped polycaprolactone monododecyl ether, hydroxy-end capped PPDO list tridecyl ether, solvent and condensing agent are added in reactor, polyacrylic acid polycaprolactone PPDO dual graft copolymer is reacted to obtain;2)Dual graft copolymer and solvent are added in reactor, copolymer stoste is dissolved to obtain;3)Stoste is added into bag filter, the beaker for filling selective solvent is put into, every displacement in 8 hours once, replaces 3~4 times, is poured into graduated volumetric flask, scale is adjusted to selective solvent, obtain object of the present invention.Preparation technology of the present invention is simple, be easy to grasp, and gained object is a kind of new pharmaceutical carrier.
Description
Technical field
The present invention relates to a kind of preparation of poly acrylic acid-poly caprolactone-PPDO dual graft copolymer micelle
Method, belongs to biodegradated polymer materal preparing technical field.
Background technology
Polyacrylic acid is a kind of biomaterial with good biocompatibility and biodegradability, with excellent
Hydrophily, in medicine extensive application.Polycaprolactone and PPDO are with excellent bio-compatible
The biomaterial of property and biodegradability, has preferable hydrophobicity, is widely used in medicine.By polycaprolactone chain
Section, PPDO segment are grafted to poly acrylic acid-poly caprolactone-poly- pair resulting on polyacrylic acid strand simultaneously
Dioxanone dual graft copolymer has amphipathic, and micella can be self-assembly of in selective solvent, is a kind of new
Pharmaceutical carrier, had broad application prospects in medicine.
The content of the invention
It is an object of the invention to provide a kind of preferable poly acrylic acid-poly caprolactone of simple to operate and effect-poly- to two
The preparation method of oxygen cyclohexanone dual graft copolymer micelle.Its technical scheme is:
A kind of preparation method of poly acrylic acid-poly caprolactone-PPDO dual graft copolymer micelle, its feature exists
In:The molecular weight of polyacrylic acid segment is 51000~61000 in copolymer, the molecular weight of polycaprolactone segment for 2200~
2400, the molecular weight of PPDO segment is 2200~2400;Its preparation method is as follows:
1)The preparation of poly acrylic acid-poly caprolactone-PPDO dual graft copolymer:Added in dry reactor poly-
It is acrylic acid, hydroxy-end capped polycaprolactone monododecyl ether, hydroxy-end capped PPDO list tridecyl ether, molten
Under agent and condensing agent, inert atmosphere, in 26~31 DEG C of stirring reactions 2~3 days, terminating reaction by filtering, dialysis, was dried, obtained
To object;
2)The preparation of poly acrylic acid-poly caprolactone-PPDO dual graft copolymer stoste:Add in dry reactor
Enter poly acrylic acid-poly caprolactone-PPDO dual graft copolymer and solvent, in 47~54 DEG C of stirring and dissolvings 50~60
Minute, obtain object;
3)The preparation of poly acrylic acid-poly caprolactone-PPDO dual graft copolymer micelle:At room temperature, by stoste plus
Enter in bag filter, put it into 500 milliliters of beakers for filling selective solvent, every displacement in 8 hours once, displacement 3~4
Secondary, solution shows blue light in bag filter, is then poured into in graduated volumetric flask, scale is adjusted to selective solvent,
Obtain object.
A kind of preparation method of described poly acrylic acid-poly caprolactone-PPDO dual graft copolymer micelle,
Step 1)In, the mol ratio of polycaprolactone monododecyl ether and polyacrylic acid is 15~25:1, PPDO list ten
The mol ratio of trialkyl ether and polyacrylic acid is 15~25:1.
A kind of preparation method of described poly acrylic acid-poly caprolactone-PPDO dual graft copolymer micelle,
Step 1)In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- DIC or 3- ethyls -1-(3-
Dimethylaminopropyl)The mol ratio of carbodiimide, condensing agent and polyacrylic acid is 1.08~1.9:1, solvent uses dimethyl sulfoxide (DMSO),
Reactant solution concentration is 5~15 g/100 ml.
A kind of preparation method of described poly acrylic acid-poly caprolactone-PPDO dual graft copolymer micelle,
Step 2)In, solvent uses dimethyl sulfoxide (DMSO), and original liquid concentration is 1~1.5 mg/ml.
A kind of preparation method of described poly acrylic acid-poly caprolactone-PPDO dual graft copolymer micelle,
Step 3)In, bag filter capacity is 5~10 ml, and bag filter molecular cut off is 3500~4500, and selective solvent is using distillation
Water, solution concentration is 0.1~0.3 mg/ml.
Compared with prior art, its advantage is the present invention:
1st, a kind of preparation method of described poly acrylic acid-poly caprolactone-PPDO dual graft copolymer micelle, is adopted
The means being combined with a kind of polymer with the esterification and dialysis that two kinds of different polymeric monomers are carried out simultaneously, simple to operate,
It is easy to grasp;
2nd, a kind of described poly acrylic acid-poly caprolactone-PPDO dual graft copolymer micelle is a kind of new
Pharmaceutical carrier.
Embodiment
Embodiment 1
1)The preparation of poly acrylic acid-poly caprolactone-PPDO dual graft copolymer
14.6 grams of polyacrylic acid are added in dry reactor(Molecular weight is 51000), 11.2 grams of hydroxy-end capped polycaprolactones
Monododecyl ether(Molecular weight is 2200)With 11.2 grams of hydroxy-end capped PPDO list tridecyl ethers(Molecular weight
For 2200), 371 ml dimethyl sulfoxide (DMSO)s are added, 0.076 gram is addedN,N’Under-dicyclohexylcarbodiimide, inert atmosphere, in
26 DEG C of stirring reactions 2 days, terminating reaction by filtering, dialysis, is dried, obtains object;
2)The preparation of poly acrylic acid-poly caprolactone-PPDO dual graft copolymer stoste
120 milligrams of poly acrylic acid-poly caprolactone-PPDO dual graft copolymers, 100 are added in dry reactor
Milliliter dimethyl sulfoxide (DMSO), in 47 DEG C of stirring and dissolvings 50 minutes, obtains object;
3)The preparation of poly acrylic acid-poly caprolactone-PPDO dual graft copolymer micelle
At room temperature, 1 milliliter of poly acrylic acid-poly caprolactone-PPDO dual graft copolymer stoste is added into 5 milliliters of appearances
In the bag filter of amount(Molecular cut off is 3500), put it into 500 milliliters of beakers for filling distilled water, put every 8 hours
Change once, replace 3 times, solution shows blue light in bag filter, is then poured into in graduated 10 milliliters of volumetric flasks, with steaming
Distilled water is adjusted to scale, obtains object.
Embodiment 2
1)The preparation of poly acrylic acid-poly caprolactone-PPDO dual graft copolymer
15.3 grams of polyacrylic acid are added in dry reactor(Molecular weight is 55000), 11.1 grams of hydroxy-end capped polycaprolactones
Monododecyl ether(Molecular weight is 2300)With 11.1 grams of hydroxy-end capped PPDO list tridecyl ethers(Molecular weight
For 2300), 375 ml dimethyl sulfoxide (DMSO)s are added, 0.043 gram is addedN,N’Under-DIC, inert atmosphere, in
29 DEG C of stirring reactions 2 days, terminating reaction by filtering, dialysis, is dried, obtains object;
2)The preparation of poly acrylic acid-poly caprolactone-PPDO dual graft copolymer stoste
130 milligrams of poly acrylic acid-poly caprolactone-PPDO dual graft copolymers, 100 are added in dry reactor
Milliliter dimethyl sulfoxide (DMSO), in 50 DEG C of stirring and dissolvings 55 minutes, obtains object;
3)The preparation of poly acrylic acid-poly caprolactone-PPDO dual graft copolymer micelle
At room temperature, 1 milliliter of poly acrylic acid-poly caprolactone-PPDO dual graft copolymer stoste is added into 6 milliliters of appearances
In the bag filter of amount(Molecular cut off is 4000), put it into 500 milliliters of beakers for filling distilled water, put every 8 hours
Change once, replace 4 times, solution shows blue light in bag filter, is then poured into in graduated 10 milliliters of volumetric flasks, with steaming
Distilled water is adjusted to scale, obtains object.
Embodiment 3
1)The preparation of poly acrylic acid-poly caprolactone-PPDO dual graft copolymer
16.8 grams of polyacrylic acid are added in dry reactor(Molecular weight is 61000), 11.6 grams of hydroxy-end capped polycaprolactones
Monododecyl ether(Molecular weight is 2400)With 11.6 grams of hydroxy-end capped PPDO list tridecyl ethers(Molecular weight
For 2400), 398 ml dimethyl sulfoxide (DMSO)s are added, 0.067 gram of 3- ethyls -1- is added(3- dimethylaminopropyls)Carbodiimide, it is lazy
Property atmosphere under, in 31 DEG C of stirring reactions 3 days, terminating reaction by filtering, dialysis, was dried, and obtains object;
2)The preparation of poly acrylic acid-poly caprolactone-PPDO dual graft copolymer stoste
140 milligrams of poly acrylic acid-poly caprolactone-PPDO dual graft copolymers, 100 are added in dry reactor
Milliliter dimethyl sulfoxide (DMSO), in 54 DEG C of stirring and dissolvings 60 minutes, obtains object;
3)The preparation of poly acrylic acid-poly caprolactone-PPDO dual graft copolymer micelle
At room temperature, 1 milliliter of poly acrylic acid-poly caprolactone-PPDO dual graft copolymer stoste is added into 7 milliliters of appearances
In the bag filter of amount(Molecular cut off is 4500), put it into 500 milliliters of beakers for filling distilled water, put every 8 hours
Change once, replace 3 times, solution shows blue light in bag filter, is then poured into in graduated 10 milliliters of volumetric flasks, with steaming
Distilled water is adjusted to scale, obtains object.
Claims (5)
1. a kind of preparation method of poly acrylic acid-poly caprolactone-PPDO dual graft copolymer micelle, its feature exists
In:The molecular weight of polyacrylic acid segment is 51000~61000 in copolymer, the molecular weight of polycaprolactone segment for 2200~
2400, the molecular weight of PPDO segment is 2200~2400;Its preparation method is as follows:
1)The preparation of poly acrylic acid-poly caprolactone-PPDO dual graft copolymer:Added in dry reactor poly-
It is acrylic acid, hydroxy-end capped polycaprolactone monododecyl ether, hydroxy-end capped PPDO list tridecyl ether, molten
Under agent and condensing agent, inert atmosphere, in 26~31 DEG C of stirring reactions 2~3 days, terminating reaction by filtering, dialysis, was dried, obtained
To object;
2)The preparation of poly acrylic acid-poly caprolactone-PPDO dual graft copolymer stoste:Add in dry reactor
Enter poly acrylic acid-poly caprolactone-PPDO dual graft copolymer and solvent, in 47~54 DEG C of stirring and dissolvings 50~60
Minute, obtain object;
3)The preparation of poly acrylic acid-poly caprolactone-PPDO dual graft copolymer micelle:At room temperature, by stoste plus
Enter in bag filter, put it into 500 milliliters of beakers for filling selective solvent, every displacement in 8 hours once, displacement 3~4
Secondary, solution shows blue light in bag filter, is then poured into in graduated volumetric flask, scale is adjusted to selective solvent,
Obtain object.
2. a kind of poly acrylic acid-poly caprolactone-PPDO dual graft copolymer micelle according to claim 1
Preparation method, it is characterised in that:Step 1)In, the mol ratio of polycaprolactone monododecyl ether and polyacrylic acid for 15~
25:1, the mol ratio of PPDO list tridecyl ether and polyacrylic acid is 15~25:1.
3. a kind of poly acrylic acid-poly caprolactone according to claim 1-PPDO dual graft copolymer glue
The preparation method of beam, it is characterised in that:Step 1)In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- diisopropyl
Base carbodiimide or 3- ethyls -1-(3- dimethylaminopropyls)The mol ratio of carbodiimide, condensing agent and polyacrylic acid be 1.08~
1.9:1, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15 g/100 ml.
4. a kind of poly acrylic acid-poly caprolactone-PPDO dual graft copolymer micelle according to claim 1
Preparation method, it is characterised in that:Step 2)In, solvent uses dimethyl sulfoxide (DMSO), and original liquid concentration is 1~1.5 mg/ml.
5. a kind of poly acrylic acid-poly caprolactone-PPDO dual graft copolymer micelle according to claim 1
Preparation method, it is characterised in that:Step 3)In, bag filter capacity be 5~10 ml, bag filter molecular cut off be 3500~
4500, selective solvent uses distilled water, and solution concentration is 0.1~0.3 mg/ml.
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN105542185A (en) * | 2016-03-14 | 2016-05-04 | 山东理工大学 | Method for preparing polyvinyl alcohol-polycaprolactone-poly(p-dioxanone) dual-grafted copolymer micelle |
CN105754109A (en) * | 2016-03-09 | 2016-07-13 | 山东理工大学 | Preparation method of polyvinyl alcohol-polycaprolactone-poly-p-dioxanone dual-grafted copolymer micelle |
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- 2017-05-25 CN CN201710376632.1A patent/CN106987008A/en not_active Withdrawn
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN105754109A (en) * | 2016-03-09 | 2016-07-13 | 山东理工大学 | Preparation method of polyvinyl alcohol-polycaprolactone-poly-p-dioxanone dual-grafted copolymer micelle |
CN105542185A (en) * | 2016-03-14 | 2016-05-04 | 山东理工大学 | Method for preparing polyvinyl alcohol-polycaprolactone-poly(p-dioxanone) dual-grafted copolymer micelle |
Non-Patent Citations (1)
Title |
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YANHUI MA等: ""Polymer Micelles from Poly(acrylic acid)-graft-polystyrene"", 《MACROMOLECULES》 * |
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