CN106987003A - A kind of preparation method of polyacrylic acid PTMC PPDO dual graft copolymer micelle - Google Patents

A kind of preparation method of polyacrylic acid PTMC PPDO dual graft copolymer micelle Download PDF

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CN106987003A
CN106987003A CN201710376565.3A CN201710376565A CN106987003A CN 106987003 A CN106987003 A CN 106987003A CN 201710376565 A CN201710376565 A CN 201710376565A CN 106987003 A CN106987003 A CN 106987003A
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poly
preparation
ppdo
dual graft
acrylic acid
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朱国全
董抒华
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Shandong University of Technology
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    • 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
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Polymers & Plastics (AREA)
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  • Proteomics, Peptides & Aminoacids (AREA)
  • Inorganic Chemistry (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Graft Or Block Polymers (AREA)
  • Medicinal Preparation (AREA)

Abstract

The present invention discloses a kind of preparation method of polyacrylic acid PTMC PPDO dual graft copolymer micelle, using following methods：1）Polyacrylic acid, hydroxy-end capped PTMC monododecyl ether, hydroxy-end capped PPDO list tridecyl ether, solvent and condensing agent are added in reactor, polyacrylic acid PTMC 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

A kind of poly acrylic acid-poly trimethylene carbonate-PPDO dual graft is total to The preparation method of polymers micella
Technical field
The present invention relates to a kind of poly acrylic acid-poly trimethylene carbonate-PPDO dual graft copolymer glue The preparation method of beam, 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 and PPDO are with excellent The biomaterial of biocompatibility and biodegradability, has preferable hydrophobicity, is widely used in medicine.Will be poly- Trimethylene carbonate segment, PPDO segment are grafted to polypropylene resulting on polyacrylic acid strand simultaneously Acid-PTMC-PPDO dual graft copolymer have it is amphipathic, in selective solvent can from Assembling forms micella, is a kind of new pharmaceutical carrier, is 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 trimethylene carbonic acid of simple to operate and effect The preparation method of ester-PPDO dual graft copolymer micelle.Its technical scheme is：
A kind of preparation method of poly acrylic acid-poly trimethylene carbonate-PPDO dual graft copolymer micelle, its It is characterised by：The molecular weight of polyacrylic acid segment is 51000~63000 in copolymer, point of PTMC segment Son amount is 2200~2500, and the molecular weight of PPDO segment is 2200~2500；Its preparation method is as follows：
1）The preparation of poly acrylic acid-poly trimethylene carbonate-PPDO dual graft copolymer：In dry reactor It is interior add polyacrylic acid, it is hydroxy-end capped PTMC monododecyl ether, hydroxy-end capped poly- to dioxocyclohex Under ketone list tridecyl ether, solvent and condensing agent, inert atmosphere, in 26~33 DEG C of stirring reactions 2~4 days, terminating reaction passed through Filter, dialyse, dry, obtain object；
2）The preparation of poly acrylic acid-poly trimethylene carbonate-PPDO dual graft copolymer stoste：It is anti-drying Answer and poly acrylic acid-poly trimethylene carbonate-PPDO dual graft copolymer and solvent are added in device, in 47~52 DEG C stirring and dissolving 50~60 minutes, obtains object；
3）The preparation of poly acrylic acid-poly trimethylene carbonate-PPDO dual graft copolymer micelle：At room temperature, Stoste is added in bag filter, put it into 500 milliliters of beakers for filling selective solvent, every displacement in 8 hours once, is put Change 3~4 times, solution shows blue light in bag filter, is then poured into in graduated volumetric flask, is adjusted to selective solvent Scale, obtains object.
A kind of described poly acrylic acid-poly trimethylene carbonate-PPDO dual graft copolymer micelle Preparation method, step 1）In, the mol ratio of PTMC monododecyl ether and polyacrylic acid is 15~25:1, gather The mol ratio of Lanthanum Isopropoxide list tridecyl ether and polyacrylic acid is 15~25:1.
A kind of described poly acrylic acid-poly trimethylene carbonate-PPDO dual graft copolymer micelle Preparation method, step 1）In, condensing agent is usedN,N’- dicyclohexylcarbodiimide,N,N’- DIC or 3- second Base -1-（3- dimethylaminopropyls）The mol ratio of carbodiimide, condensing agent and polyacrylic acid is 1.08~1.9:1, solvent uses two Methyl sulfoxide, reactant solution concentration is 5~15 g/100 ml.
A kind of described poly acrylic acid-poly trimethylene carbonate-PPDO dual graft copolymer micelle Preparation method, step 2）In, solvent uses dimethyl sulfoxide (DMSO), and original liquid concentration is 1~1.5 mg/ml.
A kind of described poly acrylic acid-poly trimethylene carbonate-PPDO dual graft copolymer micelle Preparation method, step 3）In, bag filter capacity is 5~10 ml, and bag filter molecular cut off is 3500~4500, and selectivity is molten Agent uses distilled water, and solution concentration is 0.1~0.3 mg/ml.
Compared with prior art, its advantage is the present invention：
1st, the system of described a kind of poly acrylic acid-poly trimethylene carbonate-PPDO dual graft copolymer micelle Preparation Method, the means being combined using a kind of polymer with the esterification and dialysis that two kinds of different polymeric monomers are carried out simultaneously, It is simple to operate, be easy to grasp；
2nd, a kind of described poly acrylic acid-poly trimethylene carbonate-PPDO dual graft copolymer micelle is one Plant new pharmaceutical carrier.
Embodiment
Embodiment 1
1）The preparation of poly acrylic acid-poly trimethylene carbonate-PPDO dual graft copolymer
14.7 grams of polyacrylic acid are added in dry reactor（Molecular weight is 51000）, 11.2 grams of hydroxy-end capped poly- three methylenes Base carbonic ester monododecyl ether（Molecular weight is 2200）With 11.2 grams of hydroxy-end capped PPDO list tridecyls Ether（Molecular weight is 2200）, 372 ml dimethyl sulfoxide (DMSO)s are added, 0.076 gram is addedN,N’- dicyclohexylcarbodiimide, inertia Under atmosphere, in 26 DEG C of stirring reactions 2 days, terminating reaction by filtering, dialysis, was dried, obtains object；
2）The preparation of poly acrylic acid-poly trimethylene carbonate-PPDO dual graft copolymer stoste
120 milligrams of poly acrylic acid-poly trimethylene carbonate-PPDO dual grafts are added in dry reactor to be total to Polymers, 100 milliliters of dimethyl sulfoxide (DMSO)s, in 47 DEG C of stirring and dissolvings 50 minutes, obtain object；
3）The preparation of poly acrylic acid-poly trimethylene carbonate-PPDO dual graft copolymer micelle
At room temperature, 1 milliliter of poly acrylic acid-poly trimethylene carbonate-PPDO dual graft copolymer stoste is added In the bag filter for entering 5 milliliters of capacity（Molecular cut off is 3500）, put it into 500 milliliters of beakers for filling distilled water, often Every displacement in 8 hours once, replace 3 times, solution shows blue light in bag filter, is then poured into graduated 10 milliliters of capacity In bottle, scale is adjusted to distilled water, object is obtained.
Embodiment 2
1）The preparation of poly acrylic acid-poly trimethylene carbonate-PPDO dual graft copolymer
15.4 grams of polyacrylic acid are added in dry reactor（Molecular weight is 55000）, 11.1 grams of hydroxy-end capped poly- three methylenes Base carbonic ester monododecyl ether（Molecular weight is 2300）With 11.1 grams of hydroxy-end capped PPDO list tridecyls Ether（Molecular weight is 2300）, 377 ml dimethyl sulfoxide (DMSO)s are added, 0.043 gram is addedN,N’- DIC, inertia Under atmosphere, in 30 DEG C of stirring reactions 3 days, terminating reaction by filtering, dialysis, was dried, obtains object；
2）The preparation of poly acrylic acid-poly trimethylene carbonate-PPDO dual graft copolymer stoste
140 milligrams of poly acrylic acid-poly trimethylene carbonate-PPDO dual grafts are added in dry reactor to be total to Polymers, 100 milliliters of dimethyl sulfoxide (DMSO)s, in 50 DEG C of stirring and dissolvings 55 minutes, obtain object；
3）The preparation of poly acrylic acid-poly trimethylene carbonate-PPDO dual graft copolymer micelle
At room temperature, 1 milliliter of poly acrylic acid-poly trimethylene carbonate-PPDO dual graft copolymer stoste is added In the bag filter for entering 6 milliliters of capacity（Molecular cut off is 4000）, put it into 500 milliliters of beakers for filling distilled water, often Every displacement in 8 hours once, replace 4 times, solution shows blue light in bag filter, is then poured into graduated 10 milliliters of capacity In bottle, scale is adjusted to distilled water, object is obtained.
Embodiment 3
1）The preparation of poly acrylic acid-poly trimethylene carbonate-PPDO dual graft copolymer
17.3 grams of polyacrylic acid are added in dry reactor（Molecular weight is 63000）, 12.1 grams of hydroxy-end capped poly- three methylenes Base carbonic ester monododecyl ether（Molecular weight is 2500）With 12.1 grams of hydroxy-end capped PPDO list tridecyls Ether（Molecular weight is 2500）, 413 ml dimethyl sulfoxide (DMSO)s are added, 0.067 gram of 3- ethyls -1- is added（3- dimethylaminopropyls）Carbon Under diimine, inert atmosphere, in 33 DEG C of stirring reactions 4 days, terminating reaction by filtering, dialysis, was dried, obtains object；
2）The preparation of poly acrylic acid-poly trimethylene carbonate-PPDO dual graft copolymer stoste
145 milligrams of poly acrylic acid-poly trimethylene carbonate-PPDO dual grafts are added in dry reactor to be total to Polymers, 100 milliliters of dimethyl sulfoxide (DMSO)s, in 52 DEG C of stirring and dissolvings 60 minutes, obtain object；
3）The preparation of poly acrylic acid-poly trimethylene carbonate-PPDO dual graft copolymer micelle
At room temperature, 1 milliliter of poly acrylic acid-poly trimethylene carbonate-PPDO dual graft copolymer stoste is added In the bag filter for entering 7 milliliters of capacity（Molecular cut off is 4500）, put it into 500 milliliters of beakers for filling distilled water, often Every displacement in 8 hours once, replace 3 times, solution shows blue light in bag filter, is then poured into graduated 10 milliliters of capacity In bottle, scale is adjusted to distilled water, object is obtained.

Claims (5)

1. a kind of preparation method of poly acrylic acid-poly trimethylene carbonate-PPDO dual graft copolymer micelle, It is characterized in that：The molecular weight of polyacrylic acid segment is 51000~63000 in copolymer, PTMC segment Molecular weight is 2200~2500, and the molecular weight of PPDO segment is 2200~2500；Its preparation method is as follows：
1）The preparation of poly acrylic acid-poly trimethylene carbonate-PPDO dual graft copolymer：In dry reactor It is interior add polyacrylic acid, it is hydroxy-end capped PTMC monododecyl ether, hydroxy-end capped poly- to dioxocyclohex Under ketone list tridecyl ether, solvent and condensing agent, inert atmosphere, in 26~33 DEG C of stirring reactions 2~4 days, terminating reaction passed through Filter, dialyse, dry, obtain object；
2）The preparation of poly acrylic acid-poly trimethylene carbonate-PPDO dual graft copolymer stoste：It is anti-drying Answer and poly acrylic acid-poly trimethylene carbonate-PPDO dual graft copolymer and solvent are added in device, in 47~52 DEG C stirring and dissolving 50~60 minutes, obtains object；
3）The preparation of poly acrylic acid-poly trimethylene carbonate-PPDO dual graft copolymer micelle：At room temperature, Stoste is added in bag filter, put it into 500 milliliters of beakers for filling selective solvent, every displacement in 8 hours once, is put Change 3~4 times, solution shows blue light in bag filter, is then poured into in graduated volumetric flask, is adjusted to selective solvent Scale, obtains object.
2. a kind of poly acrylic acid-poly trimethylene carbonate-PPDO dual graft according to claim 1 is total to The preparation method of polymers micella, it is characterised in that：Step 1）In, PTMC monododecyl ether and polyacrylic acid Mol ratio be 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 trimethylene carbonate-PPDO dual graft according to claim 1 The preparation method of copolymer micelle, it is characterised in that：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 For 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 trimethylene carbonate-PPDO dual graft according to claim 1 is total to The preparation method of polymers 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-PPDO dual graft according to claim 1 is total to The preparation method of polymers micella, it is characterised in that：Step 3）In, bag filter capacity is 5~10 ml, bag filter molecular cut off For 3500~4500, selective solvent uses distilled water, and solution concentration is 0.1~0.3 mg/ml.
CN201710376565.3A 2017-05-25 2017-05-25 A kind of preparation method of polyacrylic acid PTMC PPDO dual graft copolymer micelle Withdrawn CN106987003A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105646909A (en) * 2016-03-14 2016-06-08 山东理工大学 Method for preparing polyvinyl alcohol-poly(trimethylene carbonate)-poly(p-dioxanone) double-grafted copolymer glairin
CN105646908A (en) * 2016-03-09 2016-06-08 山东理工大学 Preparation method of polyvinyl alcohol-poly trimethylene carbonate-poly (p-dioxanone) double-grafted copolymer micelle

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105646908A (en) * 2016-03-09 2016-06-08 山东理工大学 Preparation method of polyvinyl alcohol-poly trimethylene carbonate-poly (p-dioxanone) double-grafted copolymer micelle
CN105646909A (en) * 2016-03-14 2016-06-08 山东理工大学 Method for preparing polyvinyl alcohol-poly(trimethylene carbonate)-poly(p-dioxanone) double-grafted copolymer glairin

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YANHUI MA等: ""Polymer Micelles from Poly(acrylic acid)-graft-polystyrene"", 《MACROMOLECULES》 *

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Application publication date: 20170728