CN106947086A - A kind of preparation method of polyacrylic acid PTMC MPEGPLA copolymer micelles - Google Patents

A kind of preparation method of polyacrylic acid PTMC MPEGPLA copolymer micelles Download PDF

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Publication number
CN106947086A
CN106947086A CN201710362995.XA CN201710362995A CN106947086A CN 106947086 A CN106947086 A CN 106947086A CN 201710362995 A CN201710362995 A CN 201710362995A CN 106947086 A CN106947086 A CN 106947086A
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poly
mpegpla
acrylic acid
trimethylene carbonate
preparation
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高巧春
朱国全
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Shandong University of Technology
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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

Abstract

The present invention discloses a kind of preparation method of polyacrylic acid PTMC MPEGPLA copolymer micelles, 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, hydroxy-end capped MPEGPLA, solvent and condensing agent in reactor, react to obtain polyacrylic acid PTMC MPEGPLA dual graft copolymers；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

A kind of system of poly acrylic acid-poly trimethylene carbonate-MPEGPLA copolymer micelles Preparation Method
Technical field
The present invention relates to a kind of preparation method of poly acrylic acid-poly trimethylene carbonate-MPEGPLA copolymer micelles, 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.PTMC and MPEGPLA are with excellent biocompatibility With the biomaterial of biodegradability, all with good hydrophobicity, had a wide range of applications in medicine.First will be poly- Trimethylene carbonate segment, which is grafted on polyacrylic acid strand, obtains poly acrylic acid-poly trimethylene carbonate graft copolymerization Thing, then MPEGPLA segments are grafted on the polyacrylic acid segment in poly acrylic acid-poly trimethylene carbonate graft copolymer Resulting poly acrylic acid-poly trimethylene carbonate-MPEGPLA dual graft copolymers have it is amphipathic, in selective solvent In can be self-assembly of micella, be a kind of new pharmaceutical carrier, had broad application prospects in medicine.
The content of the invention
Poly acrylic acid-poly trimethylene carbon is preferably prepared it is an object of the invention to provide a kind of simple to operate and effect The method of acid esters-MPEGPLA copolymer micelles.Its technical scheme is：
A kind of preparation method of poly acrylic acid-poly trimethylene carbonate-MPEGPLA copolymer micelles, it is characterised in that：Copolymerization The molecular weight of polyacrylic acid segment is 54000~63000 in thing, the molecular weight of PTMC segment for 2400~ The molecular weight of 2600, MPEGPLA segments is 2200~2400；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 28~34 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 trimethylene carbonate-MPEGPLA dual graft copolymers：Added in dry reactor Poly acrylic acid-poly trimethylene carbonate graft copolymer, hydroxy-end capped MPEGPLA, solvent and condensing agent, inert atmosphere Under, in 29~34 DEG C of stirring reactions 2~4 days, terminating reaction by filtering, dialysis, was dried, obtains object；
3）The preparation of poly acrylic acid-poly trimethylene carbonate-MPEGPLA dual graft copolymer stostes：In dry reactor Poly acrylic acid-poly trimethylene carbonate-MPEGPLA dual grafts copolymer and solvent are added, in 48~53 DEG C of stirring and dissolvings 50 ~60 minutes, obtain object；
4）The preparation of poly acrylic acid-poly trimethylene carbonate-MPEGPLA dual graft copolymer micelles：At room temperature, by stoste plus Enter 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 preparation method of described poly acrylic acid-poly trimethylene carbonate-MPEGPLA copolymer micelles, step 1）In, the mol ratio of PTMC monododecyl ether and polyacrylic acid is 15~25:1.
A kind of preparation method of described poly acrylic acid-poly trimethylene carbonate-MPEGPLA copolymer micelles, 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 1.07~1.8:1, solvent uses dimethyl sulfoxide (DMSO), reaction Thing solution concentration is 5~15 g/100 ml.
A kind of preparation method of described poly acrylic acid-poly trimethylene carbonate-MPEGPLA copolymer micelles, step 2）In, MPEGPLA is poly- using mono methoxy polyethylene glycol（D,L）Lactic acid copolymer（The weight ratio of polyethylene glycol and PLA is 10/90）, MPEGPLA is 15 with the mol ratio of polyacrylic acid segment in poly acrylic acid-poly trimethylene carbonate graft copolymer ~25:1.
A kind of preparation method of described poly acrylic acid-poly trimethylene carbonate-MPEGPLA copolymer micelles, 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 1.07~1.8:1, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15 g/100 ml.
A kind of preparation method of described poly acrylic acid-poly trimethylene carbonate-MPEGPLA copolymer micelles, step 3）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 trimethylene carbonate-MPEGPLA copolymer micelles, 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, the preparation method of described a kind of poly acrylic acid-poly trimethylene carbonate-MPEGPLA copolymer micelles, using two Step esterification and the means that are combined of dialysis, it is simple to operate, be easy to grasp；
2nd, a kind of described poly acrylic acid-poly trimethylene carbonate-MPEGPLA copolymer micelles are that a kind of new medicine is carried Body.
Embodiment
Embodiment 1
1）The preparation of poly acrylic acid-poly trimethylene carbonate graft copolymer
14.3 grams of polyacrylic acid are added in dry reactor（Molecular weight is 54000）, 11.6 grams of hydroxy-end capped poly- three methylenes Base carbonic ester monododecyl ether（Molecular weight is 2400）, 259 milliliters of dimethyl sulfoxide (DMSO)s are added, 0.072 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；
2）The preparation of poly acrylic acid-poly trimethylene carbonate-MPEGPLA dual graft copolymers
Added in dry reactor 10 grams of poly acrylic acid-poly trimethylene carbonate graft copolymers, 7.6 grams it is hydroxy-end capped MPEGPLA（Molecular weight is 2200）, 176 milliliters of dimethyl sulfoxide (DMSO)s are added, 0.048 gram is addedN,N’- dicyclohexyl carbon two is sub- Under amine, inert atmosphere, in 29 DEG C of stirring reactions 2 days, terminating reaction by filtering, dialysis, was dried, obtains object；
3）The preparation of poly acrylic acid-poly trimethylene carbonate-MPEGPLA dual graft copolymer stostes
Added in dry reactor 120 milligrams of poly acrylic acid-poly trimethylene carbonate-MPEGPLA dual grafts copolymers and 100 milliliters of dimethyl sulfoxide (DMSO)s, in 48 DEG C of stirring and dissolvings 50 minutes, obtain object；
4）The preparation of poly acrylic acid-poly trimethylene carbonate-MPEGPLA dual graft copolymer micelles
At room temperature, 1 milliliter of poly acrylic acid-poly trimethylene carbonate-MPEGPLA dual graft copolymers 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
14.2 grams of polyacrylic acid are added in dry reactor（Molecular weight is 55000）, 12.3 grams of hydroxy-end capped poly- three methylenes Base carbonic ester monododecyl ether（Molecular weight is 2500）, 265 milliliters of dimethyl sulfoxide (DMSO)s are added, 0.042 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 trimethylene carbonate-MPEGPLA dual graft copolymers
Added in dry reactor 10.2 grams of poly acrylic acid-poly trimethylene carbonate graft copolymers, 7.8 grams it is hydroxy-end capped MPEGPLA（Molecular weight is 2300）, 179 milliliters of dimethyl sulfoxide (DMSO)s are added, 0.028 gram is addedN,N’- diisopropyl carbon two Under imines, inert atmosphere, in 31 DEG C of stirring reactions 3 days, terminating reaction by filtering, dialysis, was dried, obtains object；
3）The preparation of poly acrylic acid-poly trimethylene carbonate-MPEGPLA dual graft copolymer stostes
Added in dry reactor 130 milligrams of poly acrylic acid-poly trimethylene carbonate-MPEGPLA dual grafts copolymers and 100 milliliters of dimethyl sulfoxide (DMSO)s, in 50 DEG C of stirring and dissolvings 55 minutes, obtain object；
4）The preparation of poly acrylic acid-poly trimethylene carbonate-MPEGPLA dual graft copolymer micelles
At room temperature, 1 milliliter of poly acrylic acid-poly trimethylene carbonate-MPEGPLA dual graft copolymers 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
15.1 grams of polyacrylic acid are added in dry reactor（Molecular weight is 63000）, 11.6 grams of hydroxy-end capped poly- three methylenes Base carbonic ester monododecyl ether（Molecular weight is 2600）, 267 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 trimethylene carbonate-MPEGPLA dual graft copolymers
Added in dry reactor 10.3 grams of poly acrylic acid-poly trimethylene carbonate graft copolymers, 7.6 grams it is hydroxy-end capped MPEGPLA（Molecular weight is 2400）, 179 milliliters of dimethyl sulfoxide (DMSO)s are added, 0.039 gram of 3- ethyls -1- is added（3- diformazans Aminopropyl）Under carbodiimide, inert atmosphere, in 34 DEG C of stirring reactions 4 days, terminating reaction by filtering, dialysis, was dried, obtained Object；
3）The preparation of poly acrylic acid-poly trimethylene carbonate-MPEGPLA dual graft copolymer stostes
Added in dry reactor 140 milligrams of poly acrylic acid-poly trimethylene carbonate-MPEGPLA dual grafts copolymers and 100 milliliters of dimethyl sulfoxide (DMSO)s, in 53 DEG C of stirring and dissolvings 60 minutes, obtain object；
4）The preparation of poly acrylic acid-poly trimethylene carbonate-MPEGPLA dual graft copolymer micelles
At room temperature, 1 milliliter of poly acrylic acid-poly trimethylene carbonate-MPEGPLA dual graft copolymers 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 preparation method of poly acrylic acid-poly trimethylene carbonate-MPEGPLA copolymer micelles, it is characterised in that：Altogether The molecular weight of polyacrylic acid segment is 54000~63000 in polymers, the molecular weight of PTMC segment for 2400~ The molecular weight of 2600, MPEGPLA segments is 2200~2400；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 28~34 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 trimethylene carbonate-MPEGPLA dual graft copolymers：Added in dry reactor Poly acrylic acid-poly trimethylene carbonate graft copolymer, hydroxy-end capped MPEGPLA, solvent and condensing agent, inert atmosphere Under, in 29~34 DEG C of stirring reactions 2~4 days, terminating reaction by filtering, dialysis, was dried, obtains object；
3）The preparation of poly acrylic acid-poly trimethylene carbonate-MPEGPLA dual graft copolymer stostes：In dry reactor Poly acrylic acid-poly trimethylene carbonate-MPEGPLA dual grafts copolymer and solvent are added, in 48~53 DEG C of stirring and dissolvings 50 ~60 minutes, obtain object；
4）The preparation of poly acrylic acid-poly trimethylene carbonate-MPEGPLA dual graft copolymer micelles：At room temperature, by stoste plus Enter 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. a kind of system of poly acrylic acid-poly trimethylene carbonate-MPEGPLA copolymer micelles according to claim 1 Preparation Method, it is characterised in that：Step 1）In, the mol ratio of PTMC monododecyl ether and polyacrylic acid is 15 ~25:1.
3. a kind of system of poly acrylic acid-poly trimethylene carbonate-MPEGPLA copolymer micelles according to claim 1 Preparation 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 1.07~1.8:1, Solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15 g/100 ml.
4. a kind of system of poly acrylic acid-poly trimethylene carbonate-MPEGPLA copolymer micelles according to claim 1 Preparation Method, it is characterised in that：Step 2）In, MPEGPLA is poly- using mono methoxy polyethylene glycol（D,L）Lactic acid copolymer（Poly- second The weight ratio of glycol and PLA is 10/90）, MPEGPLA in poly acrylic acid-poly trimethylene carbonate graft copolymer with gathering The mol ratio of acrylate is 15~25:1.
5. a kind of system of poly acrylic acid-poly trimethylene carbonate-MPEGPLA copolymer micelles according to claim 1 Preparation 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 1.07~1.8 in polymers:1, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5 ~15 g/100 ml.
6. a kind of system of poly acrylic acid-poly trimethylene carbonate-MPEGPLA copolymer micelles according to claim 1 Preparation 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. a kind of system of poly acrylic acid-poly trimethylene carbonate-MPEGPLA copolymer micelles according to claim 1 Preparation 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.
CN201710362995.XA 2017-05-22 2017-05-22 A kind of preparation method of polyacrylic acid PTMC MPEGPLA copolymer micelles Withdrawn CN106947086A (en)

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