CN106987009A - A kind of preparation method of polyacrylic acid PPDO PTMC copolymer of poly lactic acid micella - Google Patents

A kind of preparation method of polyacrylic acid PPDO PTMC copolymer of poly lactic acid micella Download PDF

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CN106987009A
CN106987009A CN201710376634.0A CN201710376634A CN106987009A CN 106987009 A CN106987009 A CN 106987009A CN 201710376634 A CN201710376634 A CN 201710376634A CN 106987009 A CN106987009 A CN 106987009A
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poly
ptmc
copolymer
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朱国全
粟常红
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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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Abstract

The present invention discloses a kind of preparation method of polyacrylic acid PPDO PTMC copolymer of poly lactic acid micella, using following methods：1）Polyacrylic acid, hydroxy-end capped PPDO, hydroxy-end capped PTMC, hydroxy-end capped PLA, 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 Lanthanum Isopropoxide-PTMC-PLA The preparation method of copolymer micelle
Technical field
The present invention relates to a kind of poly acrylic acid-poly Lanthanum Isopropoxide-PTMC-copolymer of poly lactic acid 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.PPDO, PTMC and PLA are that have Excellent biocompatibility and the biomaterial of biodegradability, have preferable hydrophobicity, have extensively in medicine Using.PPDO segment, PTMC segment and polylactic acid chain segment are grafted to polyacrylic acid simultaneously Poly acrylic acid-poly Lanthanum Isopropoxide-PTMC-copolymer of poly lactic acid obtained by strand has amphiphilic Property, micella can be self-assembly of in selective solvent, is a kind of new pharmaceutical carrier, is had extensively in medicine Application prospect.
The content of the invention
It is an object of the invention to provide a kind of preferable poly acrylic acid-poly Lanthanum Isopropoxide of simple to operate and effect- The preparation method of PTMC-copolymer of poly lactic acid micella.Its technical scheme is：
A kind of preparation method of poly acrylic acid-poly Lanthanum Isopropoxide-PTMC-copolymer of poly lactic acid micella, It is characterized in that：The molecular weight of polyacrylic acid segment is 52000~62000 in copolymer, point of PPDO segment Son amount is 2100~2300, and the molecular weight of PTMC segment is 2100~2300, the molecular weight of polylactic acid chain segment For 2100~2300；Its preparation method is as follows：
1）The preparation of poly acrylic acid-poly Lanthanum Isopropoxide-PTMC-copolymer of poly lactic acid：In dry reaction Polyacrylic acid, hydroxy-end capped PPDO list tridecyl ether, hydroxy-end capped polytrimethylene carbon are added in device Under acid esters monododecyl ether, hydroxy-end capped PLA list undecyl ether, solvent and condensing agent, inert atmosphere, in 29~ 32 DEG C of stirring reactions 2~4 days, terminating reaction by filtering, dialysis, is dried, obtains object；
2）The preparation of poly acrylic acid-poly Lanthanum Isopropoxide-PTMC-copolymer of poly lactic acid stoste：In drying Poly acrylic acid-poly Lanthanum Isopropoxide-PTMC-copolymer of poly lactic acid and solvent are added in reactor, in 47 ~51 DEG C of stirring and dissolvings 40~60 minutes, obtain object；
3）The preparation of poly acrylic acid-poly Lanthanum Isopropoxide-PTMC-copolymer of poly lactic acid micella：At room temperature, Stoste is added in bag filter, put it into 500 milliliters of beakers for filling selective solvent, every displacement in 7 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 Lanthanum Isopropoxide-PTMC-copolymer of poly lactic acid micella Preparation method, step 1）In, the mol ratio of PPDO list tridecyl ether and polyacrylic acid is 15~25:1, poly- three The mol ratio of carbonate monododecyl ether and polyacrylic acid is 15~25:1, PLA list undecyl ether is using poly- （D, Pfansteihl）The mol ratio of single undecyl ether, PLA list undecyl ether and polyacrylic acid is 15~25:1.
A kind of described poly acrylic acid-poly Lanthanum Isopropoxide-PTMC-copolymer of poly lactic acid micella 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 1.06~1.9:1, solvent uses two Methyl sulfoxide, reactant solution concentration is 5~15 g:100 ml.
A kind of described poly acrylic acid-poly Lanthanum Isopropoxide-PTMC-copolymer of poly lactic acid micella 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 Lanthanum Isopropoxide-PTMC-copolymer of poly lactic acid micella 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 Lanthanum Isopropoxide-PTMC-copolymer of poly lactic acid micella Preparation 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 Lanthanum Isopropoxide-PTMC-copolymer of poly lactic acid micella is one Plant new pharmaceutical carrier.
Embodiment
Embodiment 1
1）The preparation of poly acrylic acid-poly Lanthanum Isopropoxide-PTMC-copolymer of poly lactic acid
15.2 grams of polyacrylic acid are added in dry reactor（Molecular weight is 52000）, 11.2 grams it is hydroxy-end capped poly- to dioxy Cyclohexanone list tridecyl ether（Molecular weight is 2100）, 11.2 grams of hydroxy-end capped PTMC monododecyl ethers （Molecular weight is 2100）With 11.2 grams of hydroxy-end capped PLA list undecyl ethers（Molecular weight is 2100）, add 451 ml bis- Methyl sulfoxide, adds 0.075 gramN,N’Under-dicyclohexylcarbodiimide, inert atmosphere, in 29 DEG C of stirring reactions 2 days, terminate Reaction, by filtering, dialysis, dries, obtains object；
2）The preparation of poly acrylic acid-poly Lanthanum Isopropoxide-PTMC-copolymer of poly lactic acid stoste
120 milligrams of poly acrylic acid-poly Lanthanum Isopropoxide-PTMC-PLAs are added in dry reactor Copolymer, 100 milliliters of dimethyl sulfoxide (DMSO)s, in 47 DEG C of stirring and dissolvings 40 minutes, obtain object；
3）The preparation of poly acrylic acid-poly Lanthanum Isopropoxide-PTMC-copolymer of poly lactic acid micella
At room temperature, 1 milliliter of poly acrylic acid-poly Lanthanum Isopropoxide-PTMC-copolymer of poly lactic acid stoste is added In the bag filter for entering 6 milliliters of capacity（Molecular cut off is 3500）, put it into 500 milliliters of beakers for filling distilled water, often Every displacement in 7 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 Lanthanum Isopropoxide-PTMC-copolymer of poly lactic acid
15.6 grams of polyacrylic acid are added in dry reactor（Molecular weight is 55000）, 11.5 grams it is hydroxy-end capped poly- to dioxy Cyclohexanone list tridecyl ether（Molecular weight is 2200）, 11.5 grams of hydroxy-end capped PTMC monododecyl ethers （Molecular weight is 2200）With 11.5 grams of hydroxy-end capped PLA list undecyl ethers（Molecular weight is 2200）, add 465 ml bis- Methyl sulfoxide, adds 0.044 gramN,N’Under-DIC, inert atmosphere, in 30 DEG C of stirring reactions 3 days, terminate Reaction, by filtering, dialysis, dries, obtains object；
2）The preparation of poly acrylic acid-poly Lanthanum Isopropoxide-PTMC-copolymer of poly lactic acid stoste
130 milligrams of poly acrylic acid-poly Lanthanum Isopropoxide-PTMC-PLAs are added in dry reactor Copolymer, 100 milliliters of dimethyl sulfoxide (DMSO)s, in 49 DEG C of stirring and dissolvings 50 minutes, obtain object；
3）The preparation of poly acrylic acid-poly Lanthanum Isopropoxide-PTMC-copolymer of poly lactic acid micella
At room temperature, 1 milliliter of poly acrylic acid-poly Lanthanum Isopropoxide-PTMC-copolymer of poly lactic acid stoste is added In the bag filter for entering 7 milliliters of capacity（Molecular cut off is 4000）, put it into 500 milliliters of beakers for filling distilled water, often Every displacement in 7 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 Lanthanum Isopropoxide-PTMC-copolymer of poly lactic acid
16.6 grams of polyacrylic acid are added in dry reactor（Molecular weight is 62000）, 10.9 grams it is hydroxy-end capped poly- to dioxy Cyclohexanone list tridecyl ether（Molecular weight is 2300）, 10.9 grams of hydroxy-end capped PTMC monododecyl ethers （Molecular weight is 2300）With 10.9 grams of hydroxy-end capped PLA list undecyl ethers（Molecular weight is 2300）, add 491 ml bis- Methyl sulfoxide, adds 0.065 gram of 3- ethyls -1-（3- dimethylaminopropyls）It is anti-in 32 DEG C of stirrings under carbodiimide, inert atmosphere Answer 4 days, terminating reaction, by filtering, dialysis, dry, obtain object；
2）The preparation of poly acrylic acid-poly Lanthanum Isopropoxide-PTMC-copolymer of poly lactic acid stoste
140 milligrams of poly acrylic acid-poly Lanthanum Isopropoxide-PTMC-PLAs are added in dry reactor Copolymer, 100 milliliters of dimethyl sulfoxide (DMSO)s, in 51 DEG C of stirring and dissolvings 60 minutes, obtain object；
3）The preparation of poly acrylic acid-poly Lanthanum Isopropoxide-PTMC-copolymer of poly lactic acid micella
At room temperature, 1 milliliter of poly acrylic acid-poly Lanthanum Isopropoxide-PTMC-copolymer of poly lactic acid stoste is added In the bag filter for entering 8 milliliters of capacity（Molecular cut off is 4500）, put it into 500 milliliters of beakers for filling distilled water, often Every displacement in 7 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 side of poly acrylic acid-poly Lanthanum Isopropoxide-PTMC-copolymer of poly lactic acid micella Method, it is characterised in that：The molecular weight of polyacrylic acid segment is 52000~62000 in copolymer, PPDO segment Molecular weight is 2100~2300, and the molecular weight of PTMC segment is 2100~2300, the molecule of polylactic acid chain segment Measure as 2100~2300；Its preparation method is as follows：
1）The preparation of poly acrylic acid-poly Lanthanum Isopropoxide-PTMC-copolymer of poly lactic acid：In dry reaction Polyacrylic acid, hydroxy-end capped PPDO list tridecyl ether, hydroxy-end capped polytrimethylene carbon are added in device Under acid esters monododecyl ether, hydroxy-end capped PLA list undecyl ether, solvent and condensing agent, inert atmosphere, in 29~ 32 DEG C of stirring reactions 2~4 days, terminating reaction by filtering, dialysis, is dried, obtains object；
2）The preparation of poly acrylic acid-poly Lanthanum Isopropoxide-PTMC-copolymer of poly lactic acid stoste：In drying Poly acrylic acid-poly Lanthanum Isopropoxide-PTMC-copolymer of poly lactic acid and solvent are added in reactor, in 47 ~51 DEG C of stirring and dissolvings 40~60 minutes, obtain object；
3）The preparation of poly acrylic acid-poly Lanthanum Isopropoxide-PTMC-copolymer of poly lactic acid micella：At room temperature, Stoste is added in bag filter, put it into 500 milliliters of beakers for filling selective solvent, every displacement in 7 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 Lanthanum Isopropoxide-PTMC-PLA according to claim 1 The preparation method of copolymer micelle, it is characterised in that：Step 1）In, PPDO list tridecyl ether and polyacrylic acid Mol ratio be 15~25:1, the mol ratio of PTMC monododecyl ether and polyacrylic acid is 15~25:1, PLA list undecyl ether is using poly-（D, Pfansteihl）Single undecyl ether, PLA list undecyl ether and polyacrylic acid Mol ratio is 15~25:1.
3. a kind of poly acrylic acid-poly Lanthanum Isopropoxide-PTMC-PLA 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 1.06~1.9:1, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15 g:100 ml.
4. a kind of poly acrylic acid-poly Lanthanum Isopropoxide-PTMC-PLA according to claim 1 The preparation method of copolymer micelle, 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 Lanthanum Isopropoxide-PTMC-PLA according to claim 1 The preparation method of copolymer micelle, it is characterised in that：Step 3）In, bag filter capacity is 5~10 ml, bag filter retention molecule Measure as 3500~4500, selective solvent uses distilled water, solution concentration is 0.1~0.3 mg/ml.
CN201710376634.0A 2017-05-25 2017-05-25 A kind of preparation method of polyacrylic acid PPDO PTMC copolymer of poly lactic acid micella Withdrawn CN106987009A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105622963A (en) * 2016-03-09 2016-06-01 山东理工大学 Preparation method for polyvinyl alcohol-poly (p-dioxanone)-poly lactic acid-glycolic acid double-grafted copolymer micellae
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
CN105622963A (en) * 2016-03-09 2016-06-01 山东理工大学 Preparation method for polyvinyl alcohol-poly (p-dioxanone)-poly lactic acid-glycolic acid double-grafted copolymer micellae
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

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