CN107033362A - A kind of method for preparing polyacrylic acid polycaprolactone PTMC copolymer micelle - Google Patents

A kind of method for preparing polyacrylic acid polycaprolactone PTMC copolymer micelle Download PDF

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CN107033362A
CN107033362A CN201710363018.1A CN201710363018A CN107033362A CN 107033362 A CN107033362 A CN 107033362A CN 201710363018 A CN201710363018 A CN 201710363018A CN 107033362 A CN107033362 A CN 107033362A
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poly
acrylic acid
ptmc
graft copolymer
caprolactone
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高巧春
朱国全
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Shandong University of Technology
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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
    • A—HUMAN NECESSITIES
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2230/00—Compositions for preparing biodegradable polymers
    • C—CHEMISTRY; METALLURGY
    • 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 present invention discloses a kind of method for preparing polyacrylic acid polycaprolactone PTMC copolymer micelle, using following steps：1）Addition polymerization acrylic acid, hydroxy-end capped PTMC monododecyl ether, solvent and condensing agent in reactor, react to obtain polyacrylic acid PTMC graft copolymer；2）Adjunction graft copolymer, amino-terminated polycaprolactone list tridecyl ether, solvent and condensing agent, react to obtain dual graft copolymer in reactor；3）Add dual graft copolymer and solvent in reactor, dissolve to obtain dual graft copolymer stoste；4）Stoste is added into bag filter, the beaker for filling selective solvent is put into, is replaced 3~4 times, is poured into graduated volumetric flask, be adjusted to scale, 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

One kind prepares poly acrylic acid-poly caprolactone-PTMC copolymer micelle Method
Technical field
The present invention relates to a kind of method for preparing poly acrylic acid-poly caprolactone-PTMC copolymer micelle, Belong 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 terms of being widely used in medicine and pharmacology.Polycaprolactone and PTMC are with excellent bio-compatible The biomaterial of property and biodegradability, all with good hydrophobicity, has a wide range of applications in medicine.First will PTMC segment, which is grafted on polyacrylic acid strand, obtains the grafting of poly acrylic acid-poly trimethylene carbonate altogether Polymers, then polycaprolactone segment is grafted to the polyacrylic acid chain in poly acrylic acid-poly trimethylene carbonate graft copolymer In section obtained by poly acrylic acid-poly caprolactone-PTMC dual graft copolymer have it is amphipathic, in selectivity Micella can be self-assembly of in solvent, is a kind of new pharmaceutical carrier, is had broad application prospects in medicine.
The content of the invention
Poly acrylic acid-poly caprolactone-poly- is preferably prepared it is an object of the invention to provide a kind of simple to operate and effect The method of trimethylene carbonate copolymer micelle.Its technical scheme is：
A kind of method for preparing poly acrylic acid-poly caprolactone-PTMC copolymer micelle, it is characterised in that：Altogether The molecular weight of polyacrylic acid segment is 52000~60000 in polymers, the molecular weight of PTMC segment for 2400~ 2500, the molecular weight of polycaprolactone segment is 2200~2300；Its preparation method uses following steps：
1）The preparation of poly acrylic acid-poly trimethylene carbonate graft copolymer：Polyacrylic acid, hydroxyl are added in dry reactor It is anti-in 27~34 DEG C of stirrings under PTMC monododecyl ether, solvent and the condensing agent of base end-blocking, inert atmosphere Answer 2~4 days, terminating reaction, by filtering, dialysis, dry, obtain object；
2）The preparation of poly acrylic acid-poly caprolactone-PTMC dual graft copolymer：Added in dry reactor Poly acrylic acid-poly trimethylene carbonate graft copolymer, amino-terminated polycaprolactone list tridecyl ether, solvent and condensation Under agent, inert atmosphere, in 28~35 DEG C of stirring reactions 2~4 days, terminating reaction by filtering, dialysis, was dried, obtains target Thing；
3）The preparation of poly acrylic acid-poly caprolactone-PTMC dual graft copolymer stoste：In dry reactor Poly acrylic acid-poly caprolactone-PTMC dual graft copolymer and solvent are added, in 46~50 DEG C of stirring and dissolvings 50 ~60 minutes, obtain object；
4）The preparation of poly acrylic acid-poly caprolactone-PTMC dual graft copolymer micelle：At room temperature, by stoste Add in bag filter, put it into 500 milliliters of beakers for filling selective solvent, every displacement in 7 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 described method for preparing poly acrylic acid-poly caprolactone-PTMC copolymer micelle, step 1）In, the mol ratio of PTMC monododecyl ether and polyacrylic acid is 15~25:1.
A kind of described method for preparing poly acrylic acid-poly caprolactone-PTMC copolymer micelle, step 1）In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- DIC or 3- ethyls -1-（3- diformazans Aminopropyl）The mol ratio of carbodiimide, condensing agent and polyacrylic acid is 1.07~1.9:1, solvent uses dimethyl sulfoxide (DMSO), reaction Thing solution concentration is 5~15 g/100 ml.
A kind of described method for preparing poly acrylic acid-poly caprolactone-PTMC copolymer micelle, step 2）In, polycaprolactone list tridecyl ether and polyacrylic acid segment in poly acrylic acid-poly trimethylene carbonate graft copolymer Mol ratio be 15~25:1.
A kind of described method for preparing poly acrylic acid-poly caprolactone-PTMC copolymer micelle, step 2）In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- DIC or 3- ethyls -1-（3- diformazans Aminopropyl）Carbodiimide, condensing agent rubs with polyacrylic acid segment in poly acrylic acid-poly trimethylene carbonate graft copolymer You are than being 1.07~1.9:1, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15 g/100 ml.
A kind of described method for preparing poly acrylic acid-poly caprolactone-PTMC copolymer micelle, step 3）In, solvent uses dimethyl sulfoxide (DMSO), and original liquid concentration is 1~1.5 mg/ml.
A kind of described method for preparing poly acrylic acid-poly caprolactone-PTMC copolymer micelle, step 4）In, bag filter capacity is 5~10 ml, and bag filter molecular cut off is 3500~4000, and selective solvent uses distilled water, Solution concentration is 0.1~0.3 mg/ml.
Compared with prior art, its advantage is the present invention：
1st, a kind of described method for preparing poly acrylic acid-poly caprolactone-PTMC copolymer micelle, using ester Change reaction, the means that are combined of amidation process and dialysis, it is simple to operate, be easy to grasp；
2nd, a kind of described poly acrylic acid-poly caprolactone-PTMC copolymer micelle is a kind of new medicine Carrier.
Embodiment
Embodiment 1
1）The preparation of poly acrylic acid-poly trimethylene carbonate graft copolymer
13.8 grams of polyacrylic acid are added in dry reactor（Molecular weight is 52000）, 11.6 grams of hydroxy-end capped poly- three methylenes Base carbonic ester monododecyl ether（Molecular weight is 2400）, 254 milliliters of dimethyl sulfoxide (DMSO)s are added, 0.071 gram is addedN,N’- Under dicyclohexylcarbodiimide, inert atmosphere, in 27 DEG C of stirring reactions 2 days, terminating reaction by filtering, dialysis, was dried, obtained To object；
2）The preparation of poly acrylic acid-poly caprolactone-PTMC dual graft copolymer
Added in dry reactor 10 grams of poly acrylic acid-poly trimethylene carbonate graft copolymers, 7.5 grams it is amino-terminated Polycaprolactone list tridecyl ether（Molecular weight is 2200）, 175 milliliters of dimethyl sulfoxide (DMSO)s are added, 0.048 gram is addedN,N’- Under dicyclohexylcarbodiimide, inert atmosphere, in 28 DEG C of stirring reactions 2 days, terminating reaction by filtering, dialysis, was dried, obtained To object；
3）The preparation of poly acrylic acid-poly caprolactone-PTMC dual graft copolymer stoste
Added in dry reactor 120 milligrams of poly acrylic acid-poly caprolactone-PTMC dual graft copolymers and 100 milliliters of dimethyl sulfoxide (DMSO)s, in 46 DEG C of stirring and dissolvings 50 minutes, obtain object；
4）The preparation of poly acrylic acid-poly caprolactone-PTMC dual graft copolymer micelle
At room temperature, 1 milliliter of poly acrylic acid-poly caprolactone-PTMC dual graft copolymer stoste is added 5 milliliters In the bag filter of capacity（Molecular cut off is 3500）, put it into 500 milliliters of beakers for filling distilled water, every 7 hours Displacement once, is replaced 3 times, and solution shows blue light in bag filter, is then poured into in graduated 10 milliliters of volumetric flasks, is used Distilled water is adjusted to scale, obtains object.
Embodiment 2
1）The preparation of poly acrylic acid-poly trimethylene carbonate graft copolymer
14.1 grams of polyacrylic acid are added in dry reactor（Molecular weight is 55000）, 11.7 grams of hydroxy-end capped poly- three methylenes Base carbonic ester monododecyl ether（Molecular weight is 2400）, 257 milliliters of dimethyl sulfoxide (DMSO)s are added, 0.041 gram is addedN,N’- Under DIC, inert atmosphere, in 30 DEG C of stirring reactions 3 days, terminating reaction by filtering, dialysis, was dried, obtained To object；
2）The preparation of poly acrylic acid-poly caprolactone-PTMC dual graft copolymer
Added in dry reactor 10.2 grams of poly acrylic acid-poly trimethylene carbonate graft copolymers, 7.4 grams it is amino-terminated Polycaprolactone list tridecyl ether（Molecular weight is 2200）, 176 milliliters of dimethyl sulfoxide (DMSO)s are added, 0.028 gram is addedN, N’Under-DIC, inert atmosphere, in 30 DEG C of stirring reactions 3 days, terminating reaction by filtering, dialysis, was dried, Obtain object；
3）The preparation of poly acrylic acid-poly caprolactone-PTMC dual graft copolymer stoste
Added in dry reactor 130 milligrams of poly acrylic acid-poly caprolactone-PTMC dual graft copolymers and 100 milliliters of dimethyl sulfoxide (DMSO)s, in 48 DEG C of stirring and dissolvings 55 minutes, obtain object；
4）The preparation of poly acrylic acid-poly caprolactone-PTMC dual graft copolymer micelle
At room temperature, 1 milliliter of poly acrylic acid-poly caprolactone-PTMC dual graft copolymer stoste is added 6 milliliters In the bag filter of capacity（Molecular cut off is 3700）, put it into 500 milliliters of beakers for filling distilled water, every 7 hours Displacement once, is replaced 4 times, and solution shows blue light in bag filter, is then poured into in graduated 10 milliliters of volumetric flasks, is used Distilled water is adjusted to scale, obtains object.
Embodiment 3
1）The preparation of poly acrylic acid-poly trimethylene carbonate graft copolymer
14.4 grams of polyacrylic acid are added in dry reactor（Molecular weight is 60000）, 11.1 grams of hydroxy-end capped poly- three methylenes Base carbonic ester monododecyl ether（Molecular weight is 2500）, 255 milliliters of dimethyl sulfoxide (DMSO)s are added, 0.059 gram of 3- second is added Base -1-（3- dimethylaminopropyls）Under carbodiimide, inert atmosphere, in 34 DEG C of stirring reactions 4 days, terminating reaction, by filtering, thoroughly Analyse, dry, obtain object；
2）The preparation of poly acrylic acid-poly caprolactone-PTMC dual graft copolymer
Added in dry reactor 10.3 grams of poly acrylic acid-poly trimethylene carbonate graft copolymers, 7.3 grams it is amino-terminated Polycaprolactone list tridecyl ether（Molecular weight is 2300）, 175 milliliters of dimethyl sulfoxide (DMSO)s are added, 0.039 gram of 3- second is added Base -1-（3- dimethylaminopropyls）Under carbodiimide, inert atmosphere, in 35 DEG C of stirring reactions 4 days, terminating reaction, by filtering, thoroughly Analyse, dry, obtain object；
3）The preparation of poly acrylic acid-poly caprolactone-PTMC dual graft copolymer stoste
Added in dry reactor 140 milligrams of poly acrylic acid-poly caprolactone-PTMC dual graft copolymers and 100 milliliters of dimethyl sulfoxide (DMSO)s, in 50 DEG C of stirring and dissolvings 60 minutes, obtain object；
4）The preparation of poly acrylic acid-poly caprolactone-PTMC dual graft copolymer micelle
At room temperature, 1 milliliter of poly acrylic acid-poly caprolactone-PTMC dual graft copolymer stoste is added 7 milliliters In the bag filter of capacity（Molecular cut off is 4000）, put it into 500 milliliters of beakers for filling distilled water, every 7 hours Displacement once, is replaced 4 times, and solution shows blue light in bag filter, is then poured into in graduated 10 milliliters of volumetric flasks, is used Distilled water is adjusted to scale, obtains object.

Claims (7)

1. a kind of method for preparing poly acrylic acid-poly caprolactone-PTMC copolymer micelle, it is characterised in that： The molecular weight of polyacrylic acid segment is 52000~60000 in copolymer, and the molecular weight of PTMC segment is 2400 ~2500, the molecular weight of polycaprolactone segment is 2200~2300；Its preparation method uses following steps：
1）The preparation of poly acrylic acid-poly trimethylene carbonate graft copolymer：Polyacrylic acid, hydroxyl are added in dry reactor It is anti-in 27~34 DEG C of stirrings under PTMC monododecyl ether, solvent and the condensing agent of base end-blocking, inert atmosphere Answer 2~4 days, terminating reaction, by filtering, dialysis, dry, obtain object；
2）The preparation of poly acrylic acid-poly caprolactone-PTMC dual graft copolymer：Added in dry reactor Poly acrylic acid-poly trimethylene carbonate graft copolymer, amino-terminated polycaprolactone list tridecyl ether, solvent and condensation Under agent, inert atmosphere, in 28~35 DEG C of stirring reactions 2~4 days, terminating reaction by filtering, dialysis, was dried, obtains target Thing；
3）The preparation of poly acrylic acid-poly caprolactone-PTMC dual graft copolymer stoste：In dry reactor Poly acrylic acid-poly caprolactone-PTMC dual graft copolymer and solvent are added, in 46~50 DEG C of stirring and dissolvings 50 ~60 minutes, obtain object；
4）The preparation of poly acrylic acid-poly caprolactone-PTMC dual graft copolymer micelle：At room temperature, by stoste Add in bag filter, put it into 500 milliliters of beakers for filling selective solvent, every displacement in 7 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. one kind according to claim 1 prepares poly acrylic acid-poly caprolactone-PTMC copolymer micelle Method, it is characterised in that：Step 1）In, the mol ratio of PTMC monododecyl ether and polyacrylic acid is 15 ~25:1.
3. one kind according to claim 1 prepares poly acrylic acid-poly caprolactone-PTMC copolymer micelle Method, it is characterised in that：Step 1）In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- diisopropyl carbon two Imines or 3- ethyls -1-（3- dimethylaminopropyls）The mol ratio of carbodiimide, condensing agent and polyacrylic acid is 1.07~1.9:1, Solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15 g/100 ml.
4. one kind according to claim 1 prepares poly acrylic acid-poly caprolactone-PTMC copolymer micelle Method, it is characterised in that：Step 2）In, polycaprolactone list tridecyl ether connects with poly acrylic acid-poly trimethylene carbonate The mol ratio of polyacrylic acid segment is 15~25 in graft copolymer:1.
5. one kind according to claim 1 prepares poly acrylic acid-poly caprolactone-PTMC copolymer micelle Method, it is characterised in that：Step 2）In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- diisopropyl carbon two Imines or 3- ethyls -1-（3- dimethylaminopropyls）Carbodiimide, condensing agent and the grafting of poly acrylic acid-poly trimethylene carbonate are common The mol ratio of polyacrylic acid segment is 1.07~1.9 in polymers:1, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5 ~15 g/100 ml.
6. one kind according to claim 1 prepares poly acrylic acid-poly caprolactone-PTMC copolymer micelle Method, it is characterised in that：Step 3）In, solvent uses dimethyl sulfoxide (DMSO), and original liquid concentration is 1~1.5 mg/ml.
7. one kind according to claim 1 prepares poly acrylic acid-poly caprolactone-PTMC copolymer micelle Method, it is characterised in that：Step 4）In, bag filter capacity is 5~10 ml, and bag filter molecular cut off is 3500~4000, Selective solvent uses distilled water, and solution concentration is 0.1~0.3 mg/ml.
CN201710363018.1A 2017-05-22 2017-05-22 A kind of method for preparing polyacrylic acid polycaprolactone PTMC copolymer micelle Withdrawn CN107033362A (en)

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