CN107011518A - A kind of preparation method of polyacrylic acid PTMC polylactic acid poly propylene glycol copolymers micella - Google Patents

A kind of preparation method of polyacrylic acid PTMC polylactic acid poly propylene glycol copolymers micella Download PDF

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Publication number
CN107011518A
CN107011518A CN201710376591.6A CN201710376591A CN107011518A CN 107011518 A CN107011518 A CN 107011518A CN 201710376591 A CN201710376591 A CN 201710376591A CN 107011518 A CN107011518 A CN 107011518A
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pla
poly
polypropylene glycol
preparation
acrylic acid
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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
    • 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
    • C08G81/025—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyether sequences
    • 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
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Proteomics, Peptides & Aminoacids (AREA)
  • General Chemical & Material Sciences (AREA)
  • Pharmacology & Pharmacy (AREA)
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  • General Health & Medical Sciences (AREA)
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  • External Artificial Organs (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

The present invention discloses a kind of preparation method of polyacrylic acid PTMC polylactic acid poly propylene glycol copolymers micella, using following methods：1）Polyacrylic acid, hydroxy-end capped PTMC, hydroxy-end capped PLA, hydroxy-end capped polypropylene glycol, solvent and condensing agent are added in dry reactor, reacts 2~4 days, obtains three graft copolymers；2）Three graft copolymers and solvent are added in dry reactor, dissolves 40~60 minutes, obtains three graft copolymer stostes；3）At room temperature, stoste is added in bag filter, put it into the beaker for filling selective solvent, replaced 3~4 times, solution shows blue light in bag filter, is poured into in 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

A kind of poly acrylic acid-poly trimethylene carbonate-PLA-polypropylene glycol copolymers The preparation method of micella
Technical field
The present invention relates to a kind of system of poly acrylic acid-poly trimethylene carbonate-PLA-polypropylene glycol copolymers micella Preparation 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.PTMC, PLA and polypropylene glycol（Molecular weight 2000 More than）It is the biomaterial with excellent biocompatibility and biodegradability, with hydrophobicity, has in medicine Extensive use.PTMC segment, polylactic acid chain segment and polypropylene glycol segment are grafted to polyacrylic acid point simultaneously In subchain obtained by poly acrylic acid-poly trimethylene carbonate-PLA-polypropylene glycol copolymers have it is amphipathic, choosing Micella can be self-assembly of in selecting property solvent, is a kind of new pharmaceutical carrier, is had a wide range of applications in medicine Prospect.
The content of the invention
It is an object of the invention to provide a kind of preferable poly acrylic acid-poly trimethylene carbonic acid of simple to operate and effect The preparation method of ester-PLA-polypropylene glycol copolymers micella.Its technical scheme is：
A kind of preparation method of poly acrylic acid-poly trimethylene carbonate-PLA-polypropylene glycol copolymers micella, its feature It is：The molecular weight of polyacrylic acid segment is 51000~64000, the molecular weight of PTMC segment in copolymer For 2200~2500, the molecular weight of polylactic acid chain segment is 2200~2500, and the molecular weight of polypropylene glycol segment is 2200~2500； Its preparation method is as follows：
1）The preparation of poly acrylic acid-poly trimethylene carbonate-PLA-polypropylene glycol copolymers：Add in dry reactor Enter polyacrylic acid, hydroxy-end capped PTMC list tridecyl ether, hydroxy-end capped PLA list dodecyl Under ether, hydroxy-end capped polypropylene glycol monobutyl ether, solvent and condensing agent, inert atmosphere, in 27~32 DEG C of stirring reactions 2~4 days, Terminating reaction, by filtering, dialysis, dries, obtains object；
2）The preparation of poly acrylic acid-poly trimethylene carbonate-PLA-polypropylene glycol copolymers stoste：In dry reactor Interior addition poly acrylic acid-poly trimethylene carbonate-PLA-polypropylene glycol copolymers and solvent, it is molten in 49~53 DEG C of stirrings Solution 40~60 minutes, obtains object；
3）The preparation of poly acrylic acid-poly trimethylene carbonate-PLA-polypropylene glycol copolymers micella：At room temperature, by stoste Add in bag filter, put it into 500 milliliters of beakers for filling selective solvent, every displacement in 6 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 side of described poly acrylic acid-poly trimethylene carbonate-PLA-polypropylene glycol copolymers micella Method, step 1）In, the mol ratio of PTMC list tridecyl ether and polyacrylic acid is 15~25:1, PLA list Lauryl ether is using poly-（D, Pfansteihl）The mol ratio of monododecyl ether, PLA monododecyl ether and polyacrylic acid is 15~25:1, the mol ratio of polypropylene glycol monobutyl ether and polyacrylic acid is 15~25:1.
A kind of preparation side of described poly acrylic acid-poly trimethylene carbonate-PLA-polypropylene glycol copolymers micella Method, step 1）In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- DIC or 3- ethyls -1- （3- dimethylaminopropyls）The mol ratio of carbodiimide, condensing agent and polyacrylic acid is 1.06~1.8:1, solvent is sub- using dimethyl Sulfone, reactant solution concentration is 5~15 g:100 ml.
A kind of preparation side of described poly acrylic acid-poly trimethylene carbonate-PLA-polypropylene glycol copolymers micella Method, step 2）In, solvent uses dimethyl sulfoxide (DMSO), and original liquid concentration is 1~1.5 mg/ml.
A kind of preparation side of described poly acrylic acid-poly trimethylene carbonate-PLA-polypropylene glycol copolymers micella Method, step 3）In, bag filter capacity is 5~10 ml, and bag filter molecular cut off is 3500~4500, and selective solvent is used Distilled water, solution concentration is 0.1~0.3 mg/ml.
Compared with prior art, its advantage is the present invention：
1st, the preparation side of described a kind of poly acrylic acid-poly trimethylene carbonate-PLA-polypropylene glycol copolymers micella Method, the means being combined using esterification and dialysis, it is simple to operate, be easy to grasp；
2nd, a kind of described poly acrylic acid-poly trimethylene carbonate-PLA-polypropylene glycol copolymers micella is a kind of new Pharmaceutical carrier.
Embodiment
Embodiment 1
1）The preparation of poly acrylic acid-poly trimethylene carbonate-PLA-polypropylene glycol copolymers
14.9 grams of polyacrylic acid are added in dry reactor（Molecular weight is 51000）, 11.5 grams of hydroxy-end capped poly- three methylenes Base carbonic ester list tridecyl ether（Molecular weight is 2200）, 11.5 grams of hydroxy-end capped PLA monododecyl ethers（Molecular weight For 2200）With 11.5 grams of hydroxy-end capped polypropylene glycol monobutyl ethers（Molecular weight is 2200）, 475 ml dimethyl sulfoxide (DMSO)s are added, then Add 0.075 gramN,N’Under-dicyclohexylcarbodiimide, inert atmosphere, in 27 DEG C of stirring reactions 2 days, terminating reaction passed through mistake Filter, dialyse, dry, obtain object；
2）The preparation of poly acrylic acid-poly trimethylene carbonate-PLA-polypropylene glycol copolymers stoste
Added in dry reactor 120 milligrams of poly acrylic acid-poly trimethylene carbonate-PLA-polypropylene glycol copolymers, 100 milliliters of dimethyl sulfoxide (DMSO)s, in 49 DEG C of stirring and dissolvings 40 minutes, obtain object；
3）The preparation of poly acrylic acid-poly trimethylene carbonate-PLA-polypropylene glycol copolymers micella
At room temperature, 1 milliliter of poly acrylic acid-poly trimethylene carbonate-PLA-polypropylene glycol copolymers stoste is added into 6 millis In the bag filter for rising capacity（Molecular cut off is 3500）, put it into 500 milliliters of beakers for filling distilled water, it is small every 6 When displacement once, replace 3 times, solution shows blue light in bag filter, be then poured into in graduated 10 milliliters of volumetric flasks, Scale is adjusted to distilled water, object is obtained.
Embodiment 2
1）The preparation of poly acrylic acid-poly trimethylene carbonate-PLA-polypropylene glycol copolymers
15.6 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 list tridecyl ether（Molecular weight is 2300）, 11.7 grams of hydroxy-end capped PLA monododecyl ethers（Molecular weight For 2300）With 11.7 grams of hydroxy-end capped polypropylene glycol monobutyl ethers（Molecular weight is 2300）, 488 ml dimethyl sulfoxide (DMSO)s are added, then Add 0.044 gramN,N’Under-DIC, inert atmosphere, in 30 DEG C of stirring reactions 3 days, terminating reaction passed through mistake Filter, dialyse, dry, obtain object；
2）The preparation of poly acrylic acid-poly trimethylene carbonate-PLA-polypropylene glycol copolymers stoste
Added in dry reactor 130 milligrams of poly acrylic acid-poly trimethylene carbonate-PLA-polypropylene glycol copolymers, 100 milliliters of dimethyl sulfoxide (DMSO)s, in 51 DEG C of stirring and dissolvings 50 minutes, obtain object；
3）The preparation of poly acrylic acid-poly trimethylene carbonate-PLA-polypropylene glycol copolymers micella
At room temperature, 1 milliliter of poly acrylic acid-poly trimethylene carbonate-PLA-polypropylene glycol copolymers stoste is added into 7 millis In the bag filter for rising capacity（Molecular cut off is 4000）, put it into 500 milliliters of beakers for filling distilled water, it is small every 6 When displacement once, replace 4 times, solution shows blue light in bag filter, be then poured into in graduated 10 milliliters of volumetric flasks, Scale is adjusted to distilled water, object is obtained.
Embodiment 3
1）The preparation of poly acrylic acid-poly trimethylene carbonate-PLA-polypropylene glycol copolymers
16.8 grams of polyacrylic acid are added in dry reactor（Molecular weight is 64000）, 11.8 grams of hydroxy-end capped poly- three methylenes Base carbonic ester list tridecyl ether（Molecular weight is 2500）, 11.8 grams of hydroxy-end capped PLA monododecyl ethers（Molecular weight For 2500）With 11.8 grams of hydroxy-end capped polypropylene glycol monobutyl ethers（Molecular weight is 2500）, 511 ml dimethyl sulfoxide (DMSO)s are added, then Add 0.065 gram of 3- ethyls -1-（3- dimethylaminopropyls）Under carbodiimide, inert atmosphere, in 32 DEG C of stirring reactions 4 days, terminate Reaction, by filtering, dialysis, dries, obtains object；
2）The preparation of poly acrylic acid-poly trimethylene carbonate-PLA-polypropylene glycol copolymers stoste
Added in dry reactor 140 milligrams of poly acrylic acid-poly trimethylene carbonate-PLA-polypropylene glycol copolymers, 100 milliliters of dimethyl sulfoxide (DMSO)s, in 53 DEG C of stirring and dissolvings 60 minutes, obtain object；
3）The preparation of poly acrylic acid-poly trimethylene carbonate-PLA-polypropylene glycol copolymers micella
At room temperature, 1 milliliter of poly acrylic acid-poly trimethylene carbonate-PLA-polypropylene glycol copolymers stoste is added into 8 millis In the bag filter for rising capacity（Molecular cut off is 4500）, put it into 500 milliliters of beakers for filling distilled water, it is small every 6 When displacement once, replace 3 times, solution shows blue light in bag filter, be then poured into in graduated 10 milliliters of volumetric flasks, Scale is adjusted to distilled water, object is obtained.

Claims (5)

1. a kind of preparation method of poly acrylic acid-poly trimethylene carbonate-PLA-polypropylene glycol copolymers micella, it is special Levy and be：The molecular weight of polyacrylic acid segment is 51000~64000, the molecule of PTMC segment in copolymer Measure as 2200~2500, the molecular weight of polylactic acid chain segment is 2200~2500, the molecular weight of polypropylene glycol segment for 2200~ 2500；Its preparation method is as follows：
1）The preparation of poly acrylic acid-poly trimethylene carbonate-PLA-polypropylene glycol copolymers：Add in dry reactor Enter polyacrylic acid, hydroxy-end capped PTMC list tridecyl ether, hydroxy-end capped PLA list dodecyl Under ether, hydroxy-end capped polypropylene glycol monobutyl ether, solvent and condensing agent, inert atmosphere, in 27~32 DEG C of stirring reactions 2~4 days, Terminating reaction, by filtering, dialysis, dries, obtains object；
2）The preparation of poly acrylic acid-poly trimethylene carbonate-PLA-polypropylene glycol copolymers stoste：In dry reactor Interior addition poly acrylic acid-poly trimethylene carbonate-PLA-polypropylene glycol copolymers and solvent, it is molten in 49~53 DEG C of stirrings Solution 40~60 minutes, obtains object；
3）The preparation of poly acrylic acid-poly trimethylene carbonate-PLA-polypropylene glycol copolymers micella：At room temperature, by stoste Add in bag filter, put it into 500 milliliters of beakers for filling selective solvent, every displacement in 6 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 trimethylene carbonate-PLA-polypropylene glycol copolymers according to claim 1 The preparation method of micella, it is characterised in that：Step 1）In, PTMC list tridecyl ether and polyacrylic acid rub You are than being 15~25:1, PLA monododecyl ether is using poly-（D, Pfansteihl）Monododecyl ether, PLA list dodecane The mol ratio of base ether and polyacrylic acid is 15~25:1, the mol ratio of polypropylene glycol monobutyl ether and polyacrylic acid is 15~25:1.
3. a kind of poly acrylic acid-poly trimethylene carbonate-PLA-polypropylene glycol copolymers according to claim 1 The preparation method of micella, it is characterised in that：Step 1）In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- two is different Propyl group carbodiimide or 3- ethyls -1-（3- dimethylaminopropyls）The mol ratio of carbodiimide, condensing agent and polyacrylic acid is 1.06 ~1.8:1, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15 g:100 ml.
4. a kind of poly acrylic acid-poly trimethylene carbonate-PLA-polypropylene glycol copolymers according to claim 1 The preparation method of micella, 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 trimethylene carbonate-PLA-polypropylene glycol copolymers according to claim 1 The preparation method of micella, it is characterised in that：Step 3）In, bag filter capacity is 5~10 ml, and bag filter molecular cut off is 3500~4500, selective solvent uses distilled water, and solution concentration is 0.1~0.3 mg/ml.
CN201710376591.6A 2017-05-25 2017-05-25 A kind of preparation method of polyacrylic acid PTMC polylactic acid poly propylene glycol copolymers micella Withdrawn CN107011518A (en)

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Application publication date: 20170804