CN109134789A - A kind of synthesis of fluorine-containing block copolymer and its preparation method of micella - Google Patents
A kind of synthesis of fluorine-containing block copolymer and its preparation method of micella Download PDFInfo
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- CN109134789A CN109134789A CN201810839295.XA CN201810839295A CN109134789A CN 109134789 A CN109134789 A CN 109134789A CN 201810839295 A CN201810839295 A CN 201810839295A CN 109134789 A CN109134789 A CN 109134789A
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- Prior art keywords
- micella
- block copolymer
- fluorine
- preparation
- glycol monomethyl
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
- C08F220/24—Esters containing halogen containing perhaloalkyl radicals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
Abstract
The invention discloses a kind of poly glycol monomethyl ethers-bThe synthesis of fluorine-containing ester block copolymer and its preparation method of micella, poly glycol monomethyl ether-bFluorine-containing ester block copolymer is polymerize by RAFT to be prepared, and can be obtained that a series of chain lengths are controllable, the relatively narrow fluorine-containing block copolymer of molecular weight distribution;The poly glycol monomethyl ether-of different chain lengthsbFluorine-containing ester block copolymer is self-assembly of different shape micella in weak solution.The di-block copolymer that the present invention is formed using the fluorinated ester and hydrophilic poly glycol monomethyl ether of hydrophobic oleophobic, the normal-temperature reaction in its good solvent, products obtained therefrom is self-assembly of sheet micella in weak solution, dandelion shape micella, bulbus cordis micella in midair has application value in fields such as medicament slow release, biological detections.
Description
Technical field
The present invention relates to a kind of synthesis of fluorine-containing block copolymer and its preparation methods of micella, belong to high molecular material skill
Art field.
Background technique
Polymer self assembles micellization is one and is related to perhaps various complex processes, can be formed in the solution a series of
In addition to this form, is answered always by the concern of academia and industry in the potential of fields such as medicine, biology and electronics
With also always in R and D.The common selective solvent-induced method of the method for preparing polymer micelle, emulsification are molten
Agent volatility process.Thermodynamic differences of the block copolymer between blocks different in selective solvent and solvent will lead to microfacies point
From to form a variety of ordered structures, such as spherical shape, column, vermiform, vesica, lameller micelles.
Fluorine-containing block copolymer is structurally similar with common not fluorine-containing hydrocarbon hydro carbons block copolymer, is all by hydrophilic
Segment and hydrophobic segment composition.But the fluorine-containing groups in fluorine-containing block copolymer reduce surface tension, have particularity
Energy.And with the growth of polymer fluorine-containing groups, hydrophobicity is gradually increased, and the water solubility and critical micell of polymer are dense
Some important performances such as degree all show certain rule.Currently, generally good in one section of hydrophilic another section of hydrophobic block copolymer
The poor solvent of a block is added in solvent, two blocks generate microphase-separated and obtain micella in this self assembling process, such to obtain
The micellar conformation arrived is relatively simple, to influence its application range.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of synthesis of fluorine-containing block copolymer and its micellas
Preparation method, the synthesising method reacting condition is relatively mild, and preparation method is simple, obtained poly glycol monomethyl ether-bIt is fluorine-containing
Ester block copolymer narrow molecular weight distribution, can be self-assembly of sheet micella in weak solution, dandelion shape micella and in midair
Heart globular micelle.
The present invention selects RAFT reagent and poly glycol monomethyl ether to carry out esterification, forms Macromolecular chain transfer agent, with
This is transfer agent, carries out RAFT with fluorochemical monomer and polymerize to obtain poly glycol monomethyl ether-bFluorine-containing ester block copolymer, will be fluorine-containing
Block copolymer, which is dissolved into good solvent, forms weak solution, is self-assembly of sheet glue by the way that poor solvent is added in weak solution
Beam, dandelion shape micella and in midair bulbus cordis micella.
Specific technical solution of the present invention is as follows:
A kind of synthesis of fluorine-containing block copolymer and its preparation method of micella, it is characterized in that the following steps are included:
(1) RAFT reagent and poly glycol monomethyl ether carry out esterification and obtain Macromolecular chain transfer agent, as chain tra nsfer
Agent carries out RAFT with fluorochemical monomer and polymerize, obtains that a series of chain lengths are controllable, the relatively narrow fluorine-containing block copolymer of molecular weight distribution;
(2) fluorine-containing block copolymer that step (1) obtains is dissolved in good solvent, formed weak solution, then under stiring to
The poor solvent of fluorine-containing block is added in weak solution, carries out self assembly;
(3) after the completion of self assembly, good solvent is removed, fluorine-containing block copolymer micella is obtained.
Further, micella obtained by the method for the present invention is sheet micella, dandelion shape micella, semi-hollow globular micelle.
Further, in step (1), RAFT reagent is S- dodecyl-S '-two (α, α '-methyl-α "-acetic acid) trithio
For carbonic ester, S, S '-dipropionic acid trithiocarbonate, S- propionic acid-S '-(Alpha-Methyl-α '-acetic acid) trithiocarbonate or S- third
One of acid-S '-(α, α '-methyl-α "-acetic acid) trithiocarbonate is a variety of, preferably S- dodecyl-S '-two (α,
α '-methyl-α "-acetic acid) trithiocarbonate;It is to urge that esterification, which is with dicyclohexylcarbodiimide/4-dimethylaminopyridine,
Change system, esterification occurs for the hydroxyl in carboxyl and poly glycol monomethyl ether in RAFT reagent, to obtain bis- containing C=S
The Macromolecular chain transfer agent of key;The fluorochemical monomer is dodecafluoroheptyl methacrylate, Hexafluorobutyl mathacrylate or first
One of base acrylic acid trifluoro ethyl ester is a variety of;The fluorine-containing block copolymer is prepared with RAFT polymerization, is obtained
To a series of block copolymer of different fluorine-containing groups.
Further, in step (1), esterification carries out at normal temperature, and the solvent is methylene chloride, reaction time
For 24-96 h;RAFT polymerization is carried out under room temperature, inert gas shielding, and solvent is tetrahydrofuran, reaction time 20-50
h;Solid content is 10%-50%, preferably 25%-35%.
It further, is 5%-60%, preferably 10%-30% to system plus the volume ratio of poor solvent in step (2).
Further, in step (2), self assembly carries out at room temperature;The good solvent is tetrahydrofuran.It is described fluorine-containing embedding
Concentration of the section copolymer in good solvent is 0.01%-0.1%, preferably 0.02%-0.06%.
In above-mentioned preparation method, the self assembly in weak solution of gained fluorine-containing block copolymer can form sheet micella, Pu
Public English shape micella and semi-hollow globular micelle have a good application prospect in fields such as medicine, biology and electronics.
RAFT reagent and poly glycol monomethyl ether are carried out esterification first by the method for the present invention, obtain macromolecular chain transfer
Then agent carries out RAFT with fluorochemical monomer as chain-transferring agent and polymerize, obtains fluorine-containing block copolymer poly glycol monomethyl ether-bFluorinated ester.Poly glycol monomethyl ether-bFluorinated ester is in weak solution by adding poor solvent to be self-assembly of sheet micella, Pu
Public English shape micella and semi-hollow globular micelle.The present invention polymerize synthesizing polyethylene glycol monomethyl ether-with RAFTbFluorinated ester.Poly- second two
Alcohol monomethyl ether-bIn fluorine-containing ester block copolymer, fluorine-containing groups have the property of hydrophobic oleophobic, and poor solvent self assembly is added
Microphase-separated can occur for poly glycol monomethyl ether and fluorinated ester block in journey, form sheet micella, dandelion shape micella and in midair
Heart globular micelle has application value in fields such as medicine, biological detection and intelligent devices.
Detailed description of the invention
Poly glycol monomethyl ether-prepared by Fig. 1 embodiment 1bThe transmission of fluorinated ester Self-Assembling of Block Copolymer micella
Electron micrograph.
Poly glycol monomethyl ether-prepared by Fig. 2 embodiment 2bThe transmission electricity of fluorinated ester Self-Assembling of Block Copolymer micella
Sub- microscope photo.
Poly glycol monomethyl ether-prepared by Fig. 3 embodiment 3bThe awkward silence at a meeting of fluorinated ester Self-Assembling of Block Copolymer micella is sent out
Penetrate electron scanning micrograph.
Specific embodiment
The present invention is further described in detail combined with specific embodiments below.In following embodiments, poly- second used
Glycol monomethyl ether, fluorochemical monomer, catalyst are the commodity from market purchasing.
Embodiment 1
(1) poly glycol monomethyl ether-bTen difluoro heptyl ester preparation step of polymethylacrylic acid:
By poly glycol monomethyl ether 5 g, S- dodecyl-S '-two (α, α '-methyl-α "-acetic acid) trithiocarbonate 2.275
G, 0.075 g of 4-dimethylaminopyridine, 40 ml methylene chloride are uniformly mixed, and dicyclohexylcarbodiimide is added dropwise under ice-water bath
The mixed solution of 1.29 g and 15 ml methylene chloride are added dropwise to complete, are added dropwise to complete recession and go ice-water bath, magnetic agitation for about 1 hour
48 h of lower reaction are filtered, revolving, are then slowly poured into the beaker equipped with a large amount of cold ethers and precipitated, wash, drying 24
H obtains mPEG-DDMAT Macromolecular chain transfer agent;By 20 g of dodecafluoroheptyl methacrylate monomer, Macromolecular chain transfer agent
(mPEG-DDMAT) 2.2 g, 0.054 g of initiator, 43 g THF mixing, low temperature vacuumize, and drum nitrogen 3-5 times except deoxidation
Gas under nitrogen protection, reacts 24 h in 70 DEG C of water-baths, is then precipitated in the beaker equipped with a large amount of n-hexanes, first
Alcohol washing, 24 h of drying at room temperature, obtains mPEG- in vacuum drying ovenb- PDFMA fluorine-containing block copolymer, according to infrared spectroscopy,
NMR spectrum, GPC data determine degree of polymerization DP=50.
(2) poly glycol monomethyl ether-bTen difluoro heptyl ester block copolymer self assembly in weak solution of polymethylacrylic acid:
Fluorine-containing block copolymer is dissolved in tetrahydrofuran, 0.05% weak solution is formed, under agitation into weak solution
It is added ultrapure water (volume ratio of ultrapure water and THF are 0.2:1), is fitted into bag filter after 6 h, is removed at room temperature with ultrapure water
THF is removed, product is obtained.
Fig. 1 is product transmission electron microscope photo, can be seen that in figure and has obtained sheet micella, and pattern is single, average
Micella is having a size of 4 μm.
Embodiment 2
Poly glycol monomethyl ether-is prepared according to the method for embodiment 1bTen difluoro heptyl ester block copolymer of polymethylacrylic acid is certainly
Micella is assembled, unlike: in step (1), the volume ratio of ultrapure water and THF are increased into 0.3:1.The photo of products therefrom is such as
Shown in Fig. 2, it can be seen from the figure that gained micella is dandelion shape micella, pattern is single, and micella average-size is 2.5 μm.
Embodiment 3
Poly glycol monomethyl ether-is prepared according to the method for embodiment 1bTen difluoro heptyl ester block copolymer of polymethylacrylic acid is certainly
Micella is assembled, unlike: in step (2), the volume ratio of ultrapure water and THF is reduced to 0.1:1.The photo of products therefrom is such as
Shown in Fig. 3, it can be seen from the figure that gained micella is semi-hollow globular micelle, pattern is single, and micella average-size is 1.7 μ
m。
Embodiment 4
Poly glycol monomethyl ether-is prepared according to the method for embodiment 3bTen difluoro heptyl ester block copolymer of polymethylacrylic acid is certainly
Micella is assembled, unlike: 12 g dodecafluoroheptyl methacrylates are added to system, 28 g THF obtain degree of polymerization DP=30
Fluorine-containing block copolymer.It is detected through SEM, gained micella is that bulbus cordis micella and a small amount of precipitating, micella average-size are 800 in midair
nm。
Embodiment 5
Poly glycol monomethyl ether-is prepared according to the method for embodiment 3bTen difluoro heptyl ester block copolymer of polymethylacrylic acid is certainly
Micella is assembled, unlike: 28 g dodecafluoroheptyl methacrylates are added to system, 48 g THF obtain degree of polymerization DP=70
Fluorine-containing block copolymer.It is detected through SEM, gained micella is semi-hollow globular micelle and partly precipitated, and micella average-size is
2.3 μm。
Embodiment 6
Poly glycol monomethyl ether-is prepared according to the method for embodiment 3bTen difluoro heptyl ester block copolymer of polymethylacrylic acid is certainly
Micella is assembled, unlike: in step (2), fluorine-containing block copolymer/THF solution mass concentration is increased to 0.1%, warp
SEM detection, products therefrom are semi-hollow globular micelle and partly precipitated, and micella average-size is 2.5 μm.
Embodiment 7
Poly glycol monomethyl ether-is prepared according to the method for embodiment 3bTen difluoro heptyl ester block copolymer of polymethylacrylic acid is certainly
Micella is assembled, unlike: in step (2), fluorine-containing block copolymer/THF solution mass concentration is diluted to 0.02%, warp
SEM detection, products therefrom are semi-hollow globular micelle, and pattern is single, and micella average-size is 1.2 μm.
Embodiment 8
Poly glycol monomethyl ether-is prepared according to the method for embodiment 3bTen difluoro heptyl ester block copolymer of polymethylacrylic acid is certainly
Micella is assembled, unlike: in step (2), fluorine-containing block copolymer/THF solution mass concentration is increased to 0.08%, warp
SEM detection, products therefrom are semi-hollow globular micelle and microprecipitation, and micella average-size is 2 μm.
Embodiment 9
Poly glycol monomethyl ether-is prepared according to the method for embodiment 1bPolymethylacrylic acid hexafluoro butyl ester block copolymer is from group
Micella is filled, unlike: in step (1), dodecafluoroheptyl methacrylate is replaced with into Hexafluorobutyl mathacrylate, is passed through
SEM detection, products therefrom are semi-hollow globular micelle and microprecipitation, and micella average-size is 1.3 μm.
Embodiment 10
Poly glycol monomethyl ether-is prepared according to the method for embodiment 1bPolymethylacrylic acid trifluoro ethyl ester block copolymer is from group
Micella is filled, unlike: in step (1), dodecafluoroheptyl methacrylate is replaced with into trifluoroethyl methacrylate, is passed through
SEM detection, products therefrom are common globular micelle, and micella average-size is 800 nm.
Comparative example 1
Poly glycol monomethyl ether-is prepared according to the method for embodiment 1bTen difluoro heptyl ester block copolymer of polymethylacrylic acid is certainly
Micella is assembled, unlike: in step (2), fluorine-containing block copolymer/THF solution mass concentration is increased to 0.2%, adds water
After obtain floccule, micella cannot be obtained.
Comparative example 2
Poly glycol monomethyl ether-is prepared according to the method for embodiment 1bTen difluoro heptyl ester block copolymer of polymethylacrylic acid is certainly
Assemble micella, unlike: in step (2), the volume ratio of ultrapure water and THF are increased into 0.8:1, add obtain after water it is cotton-shaped
Object cannot obtain micella.
Claims (8)
1. a kind of synthesis of fluorine-containing block copolymer and its preparation method of micella, it is characterized in that the following steps are included:
(1) RAFT reagent and poly glycol monomethyl ether carry out esterification and obtain Macromolecular chain transfer agent, as chain-transferring agent,
RAFT is carried out with fluorochemical monomer to polymerize, and obtains that a series of chain lengths are controllable, the relatively narrow fluorine-containing block copolymer of molecular weight distribution;
(2) fluorine-containing block copolymer that step (1) obtains is dissolved in good solvent, formed weak solution, then under stiring to
The poor solvent of fluorine-containing groups is added in weak solution, carries out self assembly;
(3) after the completion of self assembly, good solvent is removed, fluorine-containing block copolymer micella is obtained.
2. preparation method according to claim 1, it is characterized in that: the fluorochemical monomer is ten difluoro heptan of methacrylic acid
Ester, Hexafluorobutyl mathacrylate, one of trifluoroethyl methacrylate or a variety of, preferably ten difluoro of methacrylic acid
Heptyl ester.
3. preparation method according to claim 1, it is characterized in that: the micella is sheet micella, dandelion shape micella,
Semi-hollow globular micelle.
4. preparation method according to claim 1, it is characterized in that: esterification is with dicyclohexyl carbon two in step (1)
Imines/4-dimethylaminopyridine is catalyst system;RAFT reagent is S- dodecyl-S '-two (α, α "-methyl-α "-acetic acid) three
Sulfocarbonate, S, S '-dipropionic acid trithiocarbonate, S- propionic acid-S '-(Alpha-Methyl-α '-acetic acid) trithiocarbonate or S-
One of propionic acid-S '-(α, α '-methyl-α "-acetic acid) trithiocarbonate or a variety of, preferably S- dodecyl-S '-two
(α, α '-methyl-α "-acetic acid) trithiocarbonate.
5. preparation method according to claim 1, it is characterized in that: esterification carries out at normal temperature in step (1), institute
The solvent stated is methylene chloride;RAFT polymerization is at normal temperature, to carry out under inert gas shielding, and solvent is tetrahydrofuran.
6. preparation method according to claim 1, it is characterized in that: the fluorine-containing block copolymer is good molten in step (2)
Concentration in agent is 0.01%-0.1%, preferably 0.02%-0.06%.
7. preparation method according to claim 1, it is characterized in that: in step (2), to system plus the volume ratio of poor solvent
For 5%-60%, preferably 10%-30%.
8. preparation method according to claim 1, it is characterized in that: in step (2), poly glycol monomethyl ether-bFluorinated ester
Self-Assembling of Block Copolymer process carries out at room temperature;The good solvent is tetrahydrofuran.
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Cited By (3)
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CN111205486A (en) * | 2020-01-19 | 2020-05-29 | 浙江理工大学 | Two-dimensional sheet micelle and preparation method thereof |
CN113292706A (en) * | 2021-05-31 | 2021-08-24 | 苏州大学 | Fluorine-containing alternating block copolymer reverse-phase nano micelle and preparation method thereof |
CN114031733A (en) * | 2021-11-05 | 2022-02-11 | 安徽农业大学 | Preparation method of novel dsRNA (double-stranded ribonucleic acid) polymer nano-carrier, nano-carrier prepared by preparation method and application of nano-carrier |
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CN107056999A (en) * | 2017-01-16 | 2017-08-18 | 济南大学 | A kind of fluorine-containing porous material preparation method based on the stable High Internal Phase Emulsion of amphipathic fluoride macromolecular block thing |
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CN114031733A (en) * | 2021-11-05 | 2022-02-11 | 安徽农业大学 | Preparation method of novel dsRNA (double-stranded ribonucleic acid) polymer nano-carrier, nano-carrier prepared by preparation method and application of nano-carrier |
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