CN104558453B - Method for preparing cationic fluorine-containing amphiphilic block copolymer micelles - Google Patents
Method for preparing cationic fluorine-containing amphiphilic block copolymer micelles Download PDFInfo
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- CN104558453B CN104558453B CN201510040763.3A CN201510040763A CN104558453B CN 104558453 B CN104558453 B CN 104558453B CN 201510040763 A CN201510040763 A CN 201510040763A CN 104558453 B CN104558453 B CN 104558453B
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Abstract
The invention discloses a method for preparing cationic fluorine-containing amphiphilic block copolymer micelles. The method comprises the following steps: preparing poly N,N-dimethylaminoethyl methacrylate macromolecular RAFT reagent by adopting an RAFT polymerization technology; mixing the poly N,N-dimethylaminoethyl methacrylate macromolecular RAFT reagent, deionized water and hexafluorobutyl acrylate to the temperature of 65-75 DEG C, dripping an initiator aqueous solution, preserving an oxygen-free environment after the dripping operation is finished, and reacting for 3-4.5 hours, thereby obtaining the product. The RAFT polymerization of a fluorine-containing acrylate monomer is regulated by adopting the hydrophilic macromolecular RAFT reagent, the fluorine-containing amphiphilic block copolymer micelles are prepared in situ in water and can be directly applied to soap-free emulsion polymerization, the fluorine-containing amphiphilic block copolymer needs not to be dissolved in advance, and the problems that the fluorine-containing amphiphilic block copolymer is low in dissolubility in water and stable micelles cannot be formed because the fluorine-containing chain segment is too long are solved.
Description
Technical field
The invention belongs to technical field of fluorine chemical industry, and in particular to a kind of cation fluoride Amphiphilic Block Copolymer Micelles
Preparation method.
Background technology
Cation fluoride polyacrylate not only has the good film property of polyacrylate polymers, pliability concurrently and glues
Knot property, and contain fluorine-containing side-chain radical in polymer, so surface free energy is relatively low.Due to fluoropolymer heat stability
Good, chemical inertness is strong, water repellent, the advantages of refuse oil and soil resistance, water-proof finish, oil-repellent finiss and soil resistant finish in textile etc.
Aspect is used widely.In addition cation fluoride emulsion is in electropositive, because electrostatic interaction can be negatively charged with various
With ionic bond combination, it has good balance quality to negative charge to fabric, while can also mix with other cationic auxiliaries, has
Sterilization, smooth effect.
In cationic fluorochemical polyacrylate dispersion prepared by traditional emulsion polymerization, small-molecular emulsifier is with physical absorption
Mode be attached to emulsion particle surface, it easily by external environment affected occur desorbing, cause emulsion particle collision cohesion, from
And make stability of emulsion be deteriorated；In film forming procedure, small-molecular emulsifier moves to film surface, limits fluorine component in latex
The enrichment on film surface, reduces the adhesion strength of film, water repellent, refuses oil and soil resistance etc., and the waste liquid containing small-molecular emulsifier can be right
Environment.
Small-molecular emulsifier is replaced using cation fluoride amphipathic nature block polymer, it is possible to resolve small-molecular emulsifier is deposited
Lower to emulsion and the adverse effect of film properties.But the fluorine-containing amphipathic nature block polymer for preparing at present is typically necessary and carries
It is pure, need to be dissolved in water when using, but fluorine-containing groupses are oversize to reduce can its dissolubility in water, it is impossible to form stable glue
Beam, fluorine-containing groupses are too short and can affect its performance, receive application of the fluorine-containing amphipathic nature block polymer in soap-free emulsion
To restriction.
The content of the invention
It is an object of the invention to provide a kind of preparation method of cation fluoride Amphiphilic Block Copolymer Micelles, solves
Cause the fluorine-containing amphipathic nature block polymer can not to form the problem of stable micelle because fluorine-containing groupses are oversize.
The technical solution adopted in the present invention is：A kind of preparation side of cation fluoride Amphiphilic Block Copolymer Micelles
Method, specifically includes following steps：
Step 1：Polymethylacrylic acid N, N dimethylaminoethyl Macro RAFT agents are prepared using RAFT polymerization techniques；
Step 2：The polymethylacrylic acid N that step 1 is obtained, N dimethylaminoethyls Macro RAFT agent and deionization
Water, hexafluorobutyl acrylate are the mixing of 1.5 ︰, 1500～11250 ︰ 75～450 according to mass ratio, obtain mixed liquor；
Step 3：The mixed liquor deoxygenation post-heating that step 2 is obtained is warming up to 65 DEG C～75 DEG C, then Deca initiator water
Solution, keeps oxygen-free environment to react 3～4.5h after completion of dropping, obtain cation fluoride Amphiphilic Block Copolymer Micelles.
Of the invention the characteristics of, also resides in,
Step 1 is specially：
Step 1.1：Under room temperature, by the isobutyl Jing ︰ methacrylic acid N of azo two, N dimethylamino Yi Zhi ︰ Isosorbide-5-Nitrae-Er oxygen Liu Huan ︰
RAFT reagents are added in reactor according to the ︰ 21 of 4 ︰ of mass ratio, 350 ︰ 630～1470, are stirred, and are obtained containing methacrylic acid
The mixture of N, N dimethylaminoethyl；
Step 1.2：To the N containing methacrylic acid that step 1.1 is obtained, argon 20 is led in the mixture of N dimethylaminoethyls
～30min, then heats and for temperature to rise to 60 DEG C～80 DEG C, and under argon protection 6～10h is reacted, and obtains polymethylacrylic acid
N, N dimethylaminoethyl Macro RAFT agent.
RAFT reagents are 2- { [(dodecyl sulfenyl) thioformyl] sulfanyl } succinic acid, 2- (ethoxies in step 1.1
Base carbonyl) isopropyl ester, any one in dithiobenzoic acid isopropyl phenyl ester.
The relative molecular mass of the polymethylacrylic acid N in step 1, N dimethylaminoethyl Macro RAFT agent is 1.7
×103～5.9 × 103, molecular weight distribution be 1.03～1.54.
Initiator solution in step 3 is azo diisobutyl amidine hydrochloric acid saline solution.
The concentration of the initiator solution in step 3 is 0.2～1mol/L, initiator and polymethylacrylic acid N, N diformazans
The mol ratio of amino ethyl ester Macro RAFT agent is 1:1.
The time for adding of initiator solution is 10～30min in step 3.
The mean diameter of the cation fluoride Amphiphilic Block Copolymer Micelles that step 3 is obtained is 15～200nm, Zeta
Current potential is+33.0mv～+36.3mv.
The invention has the beneficial effects as follows：A kind of preparation side of cation fluoride Amphiphilic Block Copolymer Micelles of the present invention
Method, using large hydrophilic molecular RAFT reagents the RAFT polymerizations of fluorinated acrylate monomer are adjusted, and are prepared in water situ and are contained
Fluorine Amphiphilic Block Copolymer Micelles, in can be directly used for emulsifier-free emulsion polymerization, without the need for first dissolving fluorine-containing amphiphilic block
Thing, solves because fluorine-containing groupses are oversize so that fluorine-containing amphipathic nature block polymer dissolubility in water is little, it is impossible to form stable glue
The problem of beam.
Description of the drawings
Fig. 1 is the cation fluoride Amphiphilic Block Copolymer Micelles that the embodiment of the present invention 1 is obtained1H-NMR spectrum；
Fig. 2 is the grain size distribution of the cation fluoride Amphiphilic Block Copolymer Micelles that the embodiment of the present invention 3 is obtained；
Fig. 3 is the TEM photos of the cation fluoride Amphiphilic Block Copolymer Micelles that the embodiment of the present invention 3 is obtained.
Specific embodiment
With reference to the accompanying drawings and detailed description the present invention is described in detail.
A kind of preparation method of cation fluoride Amphiphilic Block Copolymer Micelles of the present invention, specifically includes following step
Suddenly：
Step 1：Polymethylacrylic acid N is prepared using RAFT polymerization techniques, N dimethylaminoethyl Macro RAFT agents,
Specially：
Step 1.1：Under room temperature, by the isobutyl Jing ︰ methacrylic acid N of azo two, N dimethylamino Yi Zhi ︰ Isosorbide-5-Nitrae-Er oxygen Liu Huan ︰
RAFT reagents are added in reactor according to the ︰ 21 of 4 ︰ of mass ratio, 350 ︰ 630～1470, are stirred, and are obtained containing methacrylic acid
The mixture of N, N dimethylaminoethyl；Wherein, RAFT reagents are 2- { [(dodecyl sulfenyl) thioformyl] sulfanyl } amber
Any one in amber acid, 2- (ethoxy carbonyl) isopropyl ester, dithiobenzoic acid isopropyl phenyl ester；
Step 1.2：To the N containing methacrylic acid that step 1.1 is obtained, argon 20 is led in the mixture of N dimethylaminoethyls
～30min, then heats and for temperature to rise to 60 DEG C～80 DEG C, and under argon protection 6～10h is reacted, and obtains relative molecular mass
For 1.7 × 103～5.9 × 103, the polymethylacrylic acid N that molecular weight distribution is 1.03～1.54, N dimethylaminoethyl macromole
RAFT reagents (PDMAEMA-RAFT)；
Step 2：The polymethylacrylic acid N that step 1 is obtained, N dimethylaminoethyl Macro RAFT agent (PDMAEMA-
RAFT) mix for the ︰ 75～450 of 1.5 ︰ 1500～11250 according to mass ratio with deionized water, hexafluorobutyl acrylate, mixed
Close liquid；
Step 3：Lead to argon 20～30min deoxygenation post-heating in the mixed liquor obtained to step 2 and be warming up to 65 DEG C～75 DEG C,
Then Deca concentration be 0.2～1mol/L azo diisobutyl amidine hydrochlorate (AIBA) aqueous solutions, AIBA and PDMAEMA-RAFT
Mol ratio be 1:1, AIBA time for adding is 10～30min, keeps oxygen-free environment to react 3～4.5h after completion of dropping, is led to
Cross dynamic light scattering (DLS) and transmission electron microscope (TEM) is characterized, obtain mean diameter is for 15～200nm, Zeta potential
The cation fluoride Amphiphilic Block Copolymer Micelles of+33.0mv～+36.3mv.Its result shows that it is fluorine-containing that reaction is obtained
Block copolymer can form micelle under different fluorochemical monomer proportionings, i.e., different fluorine-containing groupses length in water, and contain
Fluorine monomer consumption is related to the fluorinated copolymer micelle particle diameter for obtaining, and with the increase of fluorochemical monomer consumption, fluorine-containing groupses increase,
Fluorinated block copolymer micelle particle diameter gradually increases, and solves that fluorine-containing groupses length is water insoluble cannot to form stable micelle in water
Problem.Meanwhile, Zeta potential test result shows the micelle to be formed with positive charge, poly- in cation fluoride soap-free emulsion
Closing in application can play Stabilization.
The invention has the beneficial effects as follows：The present invention prepares stable fluorinated block copolymer micelle in water situ, and
And the fluorinated block copolymer micelle for obtaining, with more than+30 electric charges, its electrostatic effect can make emulsion particle more stable, solve
Because fluorine-containing groupses it is oversize so that fluorine-containing amphipathic nature block polymer dissolubility in water is little, it is impossible to form asking for stable micelle
Topic.
Embodiment 1
Step 1：Under room temperature, by azodiisobutyronitrile：Methacrylic acid N, N dimethylaminoethyl：Isosorbide-5-Nitrae-dioxane：2-
{ [(dodecyl sulfenyl) thioformyl] sulfanyl } succinic acid is according to mass ratio 4：350：1050：21 are added to equipped with backflow
In condensing tube, airway, the four-hole boiling flask of thermometer, wherein Isosorbide-5-Nitrae-dioxane obtains N containing methacrylic acid, N as solvent
The mixture of dimethylaminoethyl；
Step 2：To the gained N containing methacrylic acid of above-mentioned steps 1, argon is led in the mixture of N dimethylaminoethyls
30min, then heats and for temperature to rise to 60 DEG C, and under argon protection 10h is reacted, and obtains molecular weight for 4.5 × 103, molecular weight
It is distributed as 1.23 polymethylacrylic acid N, N dimethylaminoethyls (PDMAEMA-RAFT)；
Step 3：By PDMAEMA-RAFT：Deionized water：Hexafluorobutyl acrylate is according to mass ratio 1.5：11250：75
Ratio is added in four-hole boiling flask and mixed, and obtains mixture；
Step 4：To the logical argon 30min of the gained mixture of above-mentioned steps 3, then heat and temperature is risen to into 65 DEG C, then drip
Plus concentration is the mol ratio of azo diisobutyl amidine hydrochlorate (AIBA) aqueous solution of 0.6mol/L, AIBA and PDMAEMA-RAFT
For 1:1, time for adding is 20min, 4h is reacted under argon protection, by dynamic light scattering (DLS) and transmission electron microscope
(TEM) characterize, obtain the cation fluoride amphipathic nature block polymer glue that mean diameter 15nm, Zeta potential are+33.0mv
Beam.
The fluorine-containing Amphiphilic Block Copolymer Micelles that the present embodiment is obtained1H-NMR spectrum is as shown in figure 1, can be with by Fig. 1
Find out, the proton peak-C in PDMAEMA-b-PHFBA near aminoH 2- N- and-N- (CH 3)2Go out at 3.13ppm and 2.89ppm
Peak ,-C in fluorine-containing groupsesHF- and-CH 2CF2- the appearance at 5.91ppm, 4.52ppm respectively, show successfully to have prepared sun from
The fluorine-containing Amphiphilic Block Copolymer Micelles of son.
Embodiment 2
Step 1：Under room temperature, by azodiisobutyronitrile：Methacrylic acid N, N dimethylaminoethyl：Isosorbide-5-Nitrae-dioxane：2-
(ethoxy carbonyl) isopropyl ester is according to mass ratio 4：350：1470：21 are added to equipped with reflux condensing tube, airway, thermometer
In four-hole boiling flask, wherein Isosorbide-5-Nitrae-dioxane obtains N containing methacrylic acid, the mixture of N dimethylaminoethyls as solvent；
Step 2：To the gained N containing methacrylic acid of above-mentioned steps 1, argon is led in the mixture of N dimethylaminoethyls
20min, then heats and for temperature to rise to 70 DEG C, and under argon protection 8h is reacted, and obtains molecular weight for 5.9 × 103, molecular weight point
Cloth is 1.54 polymethylacrylic acid N, N dimethylaminoethyls (PDMAEMA-RAFT)；
Step 3：By PDMAEMA-RAFT：Deionized water：Hexafluorobutyl acrylate is according to mass ratio 1.5：1500：450
Ratio mixes, and obtains mixture；
Step 4：Lead to argon 20min in the gained mixture of above-mentioned steps 3, then heat and temperature is risen to into 70 DEG C, then
Deca concentration for 0.2mol/L azo diisobutyl amidine hydrochlorate (AIBA) aqueous solution, AIBA and PDMAEMA-RAFT mole
Than for 1:1, time for adding is 30min, and under argon protection 4.5h is reacted, aobvious by dynamic light scattering (DLS) and transmitted electron
Micro mirror (TEM) is characterized, and obtains the cation fluoride block copolymer glue that mean diameter 200nm, Zeta potential are+36.3mv
Beam.
Embodiment 3
Step 1：Under room temperature, by azodiisobutyronitrile：Methacrylic acid N, N dimethylaminoethyl：Isosorbide-5-Nitrae-dioxane：Two
Thiobenzoate isopropyl phenyl ester is according to mass ratio 4：350：630：21 are added to equipped with reflux condensing tube, airway, thermometer
In four-hole boiling flask, wherein Isosorbide-5-Nitrae-dioxane obtains N containing methacrylic acid, the mixture of N dimethylaminoethyls as solvent；
Step 2：To the gained N containing methacrylic acid of above-mentioned steps 1, argon is led in the mixture of N dimethylaminoethyls
25min, then heats and for temperature to rise to 80 DEG C, and under argon protection 6h is reacted, and obtains molecular weight for 1.7 × 103, molecular weight point
Cloth is 1.03 polymethylacrylic acid N, N dimethylaminoethyls (PDMAEMA-RAFT)；
Step 3：By PDMAEMA-RAFT：Deionized water：Hexafluorobutyl acrylate is according to mass ratio 1.5：1500：450
Ratio mixes, and obtains mixture；
Step 4：Lead to argon 25min in the gained mixture of above-mentioned steps 3, then heat and temperature is risen to into 75 DEG C, then
Deca concentration is the mol ratio of azo diisobutyl amidine hydrochlorate (AIBA) aqueous solution of 1mol/L, AIBA and PDMAEMA-RAFT
For 1:1, time for adding is 10min, 3h is reacted under argon protection, by transmission electron microscope (TEM) and dynamic light scattering
(DLS) characterize, obtain the cation fluoride block copolymer micelle that mean diameter 45nm, Zeta potential are+34.4mv.
Fig. 2 is the cation fluoride block copolymer micelle that the embodiment 3 measured using dynamic light scattering (DLS) is obtained
Grain size distribution, as seen from Figure 2, the particle diameter of cation fluoride block copolymer micelle in 60nm or so, in single point
Bulk state.
Fig. 3 is that the transmission electron microscope (TEM) of the cation fluoride block copolymer micelle that embodiment 3 is obtained shines
Piece, as seen from Figure 3, has successfully prepared cationic fluorochemical Amphiphilic Block Copolymer Micelles.In test result, TEM
The micelle mean diameter for measuring is 45nm, and less than the micelle diameters 60nm of DLS tests, this is due to the sample needs of TEM tests
It is dried, during drying, micelle shrinks and makes it be smaller in size than size in the solution.
Claims (5)
1. a kind of preparation method of cation fluoride Amphiphilic Block Copolymer Micelles, it is characterised in that specifically include following
Step：
Step 1：Polymethylacrylic acid N is prepared using RAFT polymerization techniques, N dimethylaminoethyl Macro RAFT agents, specifically
For：
Step 1.1：Under room temperature, by the isobutyl Jing ︰ methacrylic acid N of azo two, N dimethylamino Yi Zhi ︰ Isosorbide-5-Nitrae-Er oxygen Liu Huan ︰ RAFT
Reagent is added in reactor according to the ︰ 21 of 4 ︰ of mass ratio, 350 ︰ 630～1470, is stirred, and obtains N containing methacrylic acid, N bis-
The mixture of methylamino ethyl ester；
Step 1.2：To the N containing methacrylic acid that step 1.1 is obtained, in the mixture of N dimethylaminoethyls lead to argon 20～
30min, then heats and for temperature to rise to 60 DEG C～80 DEG C, and under argon protection 6～10h is reacted, and obtaining relative molecular mass is
1.7×103～5.9 × 103, the polymethylacrylic acid N that molecular weight distribution is 1.03～1.54, N dimethylaminoethyl macromole
RAFT reagents；
Step 2：The polymethylacrylic acid N that step 1 is obtained, N dimethylaminoethyls Macro RAFT agent and deionized water, third
Olefin(e) acid hexafluoro butyl ester is the mixing of 1.5 ︰, 1500～11250 ︰ 75～450 according to mass ratio, obtains mixed liquor；
Step 3：The mixed liquor deoxygenation post-heating that step 2 is obtained is warming up to 65 DEG C～75 DEG C, then Deca initiator solution,
After completion of dropping keep oxygen-free environment react 3～4.5h, obtain mean diameter for 15～200nm, Zeta potential be+33.0mv～
The cation fluoride Amphiphilic Block Copolymer Micelles of+36.3mv.
2. a kind of preparation method of cation fluoride Amphiphilic Block Copolymer Micelles as claimed in claim 1, its feature
It is that RAFT reagents are 2- { [(dodecyl sulfenyl) thioformyl] sulfanyl } succinic acid, 2- (second in the step 1.1
Epoxide carbonyl) isopropyl ester, any one in dithiobenzoic acid isopropyl phenyl ester.
3. a kind of preparation method of cation fluoride Amphiphilic Block Copolymer Micelles as claimed in claim 1, its feature
It is that the initiator solution in the step 3 is azo diisobutyl amidine hydrochloric acid saline solution.
4. the preparation method of a kind of cation fluoride Amphiphilic Block Copolymer Micelles as described in claim 1 or 3, it is special
Levy and be, the concentration of the initiator solution in the step 3 is 0.2～1mol/L, initiator and polymethylacrylic acid N, N bis-
The mol ratio of methylamino ethyl ester Macro RAFT agent is 1:1.
5. a kind of preparation method of cation fluoride Amphiphilic Block Copolymer Micelles as claimed in claim 4, its feature
It is that the time for adding of initiator solution is 10～30min in the step 3.
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| CN111234142A (en) * | 2019-11-18 | 2020-06-05 | 浙江工业大学 | High-molecular copolymer probe |
| CN113292706B (en) * | 2021-05-31 | 2022-05-03 | 苏州大学 | Fluorine-containing alternating block copolymer reverse-phase nano micelle and preparation method thereof |
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| CN103483513A (en) * | 2013-09-09 | 2014-01-01 | 陕西科技大学 | Preparation method of fluorine-containing high-molecular surfactant |
| CN104031204A (en) * | 2014-06-06 | 2014-09-10 | 陕西科技大学 | Preparation method of cationic fluorine-containing polyacrylate soap-free emulsion |
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| CN103483513A (en) * | 2013-09-09 | 2014-01-01 | 陕西科技大学 | Preparation method of fluorine-containing high-molecular surfactant |
| CN104031204A (en) * | 2014-06-06 | 2014-09-10 | 陕西科技大学 | Preparation method of cationic fluorine-containing polyacrylate soap-free emulsion |
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