CN103709345B - A kind of preparation method of thermo-sensitive fluorescent polymer - Google Patents
A kind of preparation method of thermo-sensitive fluorescent polymer Download PDFInfo
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- CN103709345B CN103709345B CN201310717601.XA CN201310717601A CN103709345B CN 103709345 B CN103709345 B CN 103709345B CN 201310717601 A CN201310717601 A CN 201310717601A CN 103709345 B CN103709345 B CN 103709345B
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Abstract
The invention discloses a kind of preparation method of thermo-sensitive fluorescent polymer, the method comprises the steps: (1) synthesizes NMA monomer; (2) P (St-co-NMA) is synthesized
mmacromolecular chain transfer agent; (3) P (St-co-NMA) is synthesized
m-b-PPEGMA
n, i.e. described thermo-sensitive fluorescent polymer.Nano microsphere prepared by method of the present invention has Thermo-sensitive and fluorescence concurrently, changes the fluorescent nanometer microsphere that ambient conditions can obtain a series of different-grain diameter size.
Description
Technical field
The present invention is specifically related to a kind of preparation method of thermo-sensitive fluorescent polymer.
Background technology
Environment-responsive functional polymer becomes the focus of people's research in recent years, when external environment (as light, temperature, pH, ionic strength, Electric and magnetic fields etc.) changes, can be there is reversible or irreversible change accordingly in some physics of polymkeric substance or chemical property (pattern, size, catalytic, identity etc.), have potential using value in fields such as medicine controlled releasing, separation, microelectronics, optics, catalysis.
Current emulsion polymerization is a kind of main stream approach preparing functional polymer Nano microsphere, can be prepared the functional nano micro-ball of different-grain diameter size, monodispersity by adjustment initiator amount, monomer consumption, temperature, pH, stirring intensity, emulsifier and consumption etc., but it is much in 200nm, the problem such as small particle size emulsification system is difficult to allotment, emulsifying agent residue is difficult to removing, small particle size (< 100nm) copolymer nanometer microsphere technology is immature to there is microspherulite diameter.ZL200910234001.1 provides a kind of method preparing monodisperse polymer nano-microspheres, the method prepares monodispersity homopolymer and copolymer nanometer microsphere in conjunction with emulsifier-free emulsion polymerization and conventional emulsion polymerizations technology, prepared homopolymer spheroid particle diameter little (< 100nm) and uniform particle sizes, but the emulsification system of copolymer nanometer microsphere (especially oleophylic and hydrophilic two kinds of monomer copolymerizations) is difficult to allotment, and easy breakdown of emulsion becomes cotton-shaped; CN103342768A discloses a kind of emulsifier-free emulsion polymerization that utilizes and prepares the method with nucleocapsid structure PMMA microsphere, the method is simple and without the need to except emulsifying agent, but microspherulite diameter is about 200nm, small particle size (< 100nm) Nano microsphere can not be prepared.
Amphipathic nature block polymer can be self-assembled into the functional nano micro-ball of small particle size in water, the segmented copolymer monodispersity adopting reversible addion-fragmentation chain transfer polymerization process (RAFT method) to synthesize is good, Nano microsphere uniform particle diameter, as (ShinjiSugihara such as Sugihara, etal.JournaloftheAmericanChemicalSociety, 2011, 133 (39): 15707-15713) the poly-2-(methacryloxy that adopted RAFT method to synthesize) ethylphosphocholine-b-gathers 2-HPMA amphipathic nature block polymer (PMPC-b-PHPMA), this multipolymer can be self-assembled into the small particle size Nano microsphere (10 ~ 60nm) of uniform particle diameter in water, RAFT method suitable monomers scope is wide simultaneously, select different monomers can prepare the segmented copolymer of varying environment responsiveness, as (J.Wei such as Wei, etal.Reactive & FunctionalPolymers, 2013,73 (8): 1009-1014) adopt RAFT method to synthesize polyethylene oxide-b-and gather 6-[4-(4-pyridylazo) phenoxy group] hexyl methacrylate (PEO-b-PAP) light/pH double responsiveness amphipathic nature block polymer.In addition, the Nano microsphere that amphipathic nature block polymer self-assembly in water obtains, by changing ambient conditions in each block length, cosolvent kind, copolymer solution concentration, temperature, pH etc., prepares the polymer nano-microspheres that a series of particle diameter is adjustable.
Summary of the invention
The object of the invention is to overcome prior art defect, a kind of preparation method of thermo-sensitive fluorescent polymer is provided.
Building-up reactions formula of the present invention is as follows:
Concrete technical scheme of the present invention is as follows:
A preparation method for thermo-sensitive fluorescent polymer, comprises the steps:
(1) N-Alpha-Naphthyl Methacrylamide (NMA) monomer is synthesized;
(2) poly-(vinylbenzene-co-N-Alpha-Naphthyl Methacrylamide) (P (St-co-NMA) m) Macromolecular chain transfer agent of synthesis;
(3) poly-(vinylbenzene-co-N-Alpha-Naphthyl the Methacrylamide)-b-of synthesis gathers polyethylene glycol methacrylate-styrene polymer (P (St-co-NMA) m-b-PPEGMAn), i.e. described thermo-sensitive fluorescent polymer.
In a preferred embodiment of the invention, described step (1) is: N-alpha-naphthylamine, acid binding agent and solvent are fully mixed to get mixing solutions, and is cooled to 0 ~ 5 DEG C; Keep 0 ~ 5 DEG C, under magnetic agitation, slowly join in above-mentioned mixing solutions with dropping funnel react dissolving methacrylic chloride in a solvent; Solids removed by filtration after completion of the reaction, collects filtrate; This filtrate adds enough anhydrous magnesium sulfate dryings successively and filters after distilled water, dilute acid soln, rare brine, then revolves steaming except desolventizing, obtains crude product; Crude product is recrystallization in methyl alcohol, and vacuum-drying obtains the NMA monomer of final white.
Preferred further, in described step (1): acid binding agent is triethylamine or pyridine, solvent is benzene or toluene, and acid is hydrochloric acid or sulfuric acid, and salt is supercarbonate, and temperature of reaction is 30 ~ 40 DEG C, and the reaction times is 2 ~ 4h.
In a preferred embodiment of the invention, described step (2) is: be dissolved in solvent by NMA monomer, vinylbenzene (St) monomer, chain-transfer agent and initiator, after freeze thawing is degassed, carry out polyreaction in argon shield and under stirring; Reaction mixture after 1 times of dissolution with solvents in the precipitation agent of 20 ~ 30 times of volumes precipitation purification, precipitate to obtain pink solid, vacuum-drying obtains P (St-co-NMA)
m.
Preferred further, in described step (2): chain-transfer agent is dithiobenzoic acid cumyl ester (CDB), initiator is Diisopropyl azodicarboxylate (AIBN), solvent is toluene or tetrahydrofuran (THF) (THF), precipitation agent is methyl alcohol, polymeric reaction temperature is 80 DEG C, and the reaction times is 36 ~ 48h, and with quenching termination reaction.
In a preferred embodiment of the invention, described step (3) is: by P (St-co-NMA)
mmacromolecular chain transfer agent, polyethylene glycol methacrylate-styrene polymer (PEGMA) monomer and initiator are dissolved in solvent, after freeze thawing is degassed, carry out polyreaction in argon shield and under stirring; Reaction mixture after 1 times of dissolution with solvents in the precipitation agent of 20 ~ 30 times of volumes precipitation purification, precipitate to obtain light pink solid, vacuum-drying obtains P (St-co-NMA)
m-b-PPEGMA
n.
Preferred further, in described step (3): initiator is AIBN, solvent is toluene or THF, and precipitation agent is methyl alcohol, and the molecular-weight average of PEGMA monomer is 475 or 950, and polymeric reaction temperature is 65 DEG C, and the reaction times is 36 ~ 48h, and with quenching termination reaction.
In a preferred embodiment of the invention, step (4) is also comprised: preparation P (St-co-NMA)
m-b-PPEGMA
nnano microsphere.
In a preferred embodiment of the invention, described step (4) is: by P (St-co-NMA)
m-b-PPEGMA
nbe dissolved in volatile cosolvent, obtain polymkeric substance cosolvent solution, this solution is slowly added drop-wise in the distilled water of rapid stirring and also continues to stir to vapor away volatile cosolvent; Above-mentioned P (St-co-NMA)
m-b-PPEGMA
nthere is self-assembly in aqueous and form Nano microsphere, obtain the aqueous solution containing Nano microsphere; Change the temperature of the aqueous solution, the particle diameter of Nano microsphere also changes thereupon.
Preferred further, in described step (4): volatile cosolvent is THF or Isosorbide-5-Nitrae-dioxane, the concentration of polymkeric substance cosolvent solution is 1 ~ 10mg/mL, and the temperature of the aqueous solution is 25 ~ 60 DEG C.
The invention has the beneficial effects as follows:
1, adopt methacrylic chloride and the reaction of N-alpha-naphthylamine to produce NMA fluorescent monomer, the reaction conditions of this amidate action is gentle and reaction yield is high;
2, adopt vinylbenzene to be easy to from the method for NMA random copolymerization the hydrophobic block preparing different block length, vinylbenzene is easily polymerized and hydrophobicity is good;
3, the block polymer monodispersity that RAFT legal system is standby is good, is self-assembled into the Nano microsphere of uniform particle diameter in Yi Shui;
4, the Nano microsphere of preparation has Thermo-sensitive and fluorescence concurrently, changes the fluorescent nanometer microsphere that ambient conditions can obtain a series of different-grain diameter size;
5, synthetic technology route of the present invention and method provide a good thinking for preparing other environmental sensitivity Nano microspheres.
Accompanying drawing explanation
Fig. 1 is NMA monomer of the present invention
1hNMR spectrogram;
Fig. 2 is the P (St-co-NMA) of the embodiment of the present invention 1
m-b-PPEGMA
n's
1hNMR schemes;
Fig. 3 is the P (St-co-NMA) of the embodiment of the present invention 1
m-b-PPEGMA
nthe fluorescence emission spectrogram of Nano microsphere;
Fig. 4 is Nano microsphere particle diameter-temperature (d-T) graph of a relation of the embodiment of the present invention 1;
Fig. 5 is one of Nano microsphere SEM shape appearance figure of the embodiment of the present invention 1;
Fig. 6 is the Nano microsphere SEM shape appearance figure two of the embodiment of the present invention 1.
Embodiment
By reference to the accompanying drawings below by way of embodiment technical scheme of the present invention is further detailed and is described.
Embodiment 1:
(1) synthesis of NMA monomer: add 1.4319g(0.01moL in the 250mL two mouthfuls of flasks being furnished with dropping funnel, prolong, magnetic stir bar) N-alpha-naphthylamine, 100mL benzene and 1.67mL(0.012moL) triethylamine, condition of ice bath lower magnetic force stirs to 0 DEG C.Continuing ice bath to stir, the 1.16mL(0.01moL will be dissolved in 15mL benzene with dropping funnel) methacrylic chloride slowly joins in above-mentioned mixing solutions.Heating mixed solution to 40 DEG C, reacts and is cooled to room temperature after 2 hours, crosses the triethylamine hydrochloride solid filtering generation, collects filtrate in separating funnel, uses distilled water, dilute hydrochloric acid, rare NaHCO successively
3solution respectively washes 3 times, adds 5g anhydrous magnesium sulfate and stirs dry, filter to obtain resultant benzole soln, and revolve steaming removing solvent benzol and obtain crude product, in methyl alcohol, recrystallization obtains 1.904g white NMA crystal (productive rate 82%) 3 times.NMA's
1hNMR spectrogram refers to Fig. 1.
(2) P (St-co-NMA)
mthe synthesis of Macromolecular chain transfer agent: by St(1.15mL; 10mmoL); NMA(0.2113g, 1mmoL), CDB(0.0272g; 0.1mmoL); AIBN(0.0041g, 0.025mmoL) and THF(2mL) add in 25mLShlenk pipe, to bleed applying argon gas protection after 3 ~ 5 times through continuous freeze thawing; polyase 13 6h under 80 DEG C of conditions, liquid nitrogen quenching terminates reaction.Reaction mixture, after 2mLTHF is uniformly dissolved, precipitates in 50mL methyl alcohol, and washing purification 3 times, crosses and filter methyl alcohol, solid vacuum-drying 24h, final 0.9515gP (St-co-NMA) Macromolecular chain transfer agent (productive rate 76%).Warp
1hNMR integrating peak areas is calculated as P (St
83-co-NMA
4).
(3) P (St-co-NMA)
m-b-PPEGMA
nthe synthesis of amphipathic nature block polymer: by P (St
83-co-NMA
4) Macromolecular chain transfer agent (0.4874g; 0.05mmoL); PEGMA-425(0.7125g; 1.5mmoL); AIBN(0.0004g, 0.0025mmoL) and THF(2mL) add in 25mLShlenk pipe, to bleed applying argon gas protection after 3 ~ 5 times through continuous freeze thawing; be polymerized 12h under 65 DEG C of conditions, liquid nitrogen quenching terminates reaction.Reaction mixture, after 2mLTHF is uniformly dissolved, precipitates in 50mL methyl alcohol, and washing purification 3 times, crosses and filter methyl alcohol, solid vacuum-drying 24h, final 0.6512gP (St-co-NMA)-PPEGMA amphipathic nature block polymer.P (St-co-NMA)-PPEGMA's
1hNMR spectrogram refers to Fig. 2.Warp
1hNMR integrating peak areas is calculated as P (St
83-co-NMA
4)-PPEGMA
18.
(4) P (St-co-NMA)
m-b-PPEGMA
nthe preparation of Nano microsphere: preparation 1mL10mg/mLP (St
83-co-NMA
4)-PPEGMA
18/ THF solution, slowly drips the above-mentioned THF solution of 50 μ L in the 2mL deionized water of high-speed stirring, and uncovered constant speed stirs 24h, obtains P (St after volatilization THF
83-co-NMA
4)-PPEGMA
18the Nano microsphere aqueous solution.Use FLS920 fluorescence spectrophotometer tests the fluorescence of Nano microsphere, excitation wavelength 310nm, excites and launch slit to be 2nm, and fluorescent emission spectrogram refers to Fig. 3.Use the particle diameter adopting dynamic light scattering method (DLS) to test Nano microsphere at 25 DEG C to be 166nm, progressively heat up in 25 ~ 60 DEG C of temperature ranges, particle diameter constantly diminishes, and particle diameter-temperature (d-T) graph of a relation refers to Fig. 4.The SEM shape appearance figure of this Nano microsphere is shown in Fig. 5 and Fig. 6.
Embodiment 2
Step (1) to (3) is with embodiment 1.
Step (4) P (St-co-NMA)
m-b-PPEGMA
nthe preparation of Nano microsphere: preparation 1mL2mg/mLP (St
83-co-NMA
4)-PPEGMA
18/ THF solution, slowly drips the above-mentioned THF solution of 50 μ L in the 2mL deionized water of high-speed stirring, and uncovered constant speed stirs 24h, obtains P (St after volatilization THF
83-co-NMA
4)-PPEGMA
18the Nano microsphere aqueous solution.At DLS tests 25 DEG C, Nano microsphere particle diameter is 86nm, and progressively heat up in 25 ~ 60 DEG C of temperature ranges, particle diameter constantly reduces.
Embodiment 3
Step (1) to (3) is with embodiment 1.
Step (4) P (St-co-NMA)
m-b-PPEGMA
nthe preparation of Nano microsphere: preparation 1mL5mg/mLP (St
83-co-NMA
4)-PPEGMA
18/ Isosorbide-5-Nitrae-dioxane solution, slowly drips the above-mentioned dioxane solution of 50 μ L in the 2mL deionized water of high-speed stirring, and uncovered constant speed stirs 24h, obtains P (St after volatilization Isosorbide-5-Nitrae-dioxane
83-co-NMA
4)-PPEGMA
18the Nano microsphere aqueous solution.At DLS tests 25 DEG C, Nano microsphere particle diameter is 118nm, and progressively heat up in 25 ~ 60 DEG C of temperature ranges, particle diameter constantly reduces.
The above, be only preferred embodiment of the present invention, therefore can not limit scope of the invention process according to this, the equivalence change namely done according to the scope of the claims of the present invention and description with modify, all should still belong in scope that the present invention contains.
Claims (8)
1. a preparation method for thermo-sensitive fluorescent polymer, is characterized in that: comprise the steps:
(1) NMA monomer is synthesized;
(2) P (St-co-NMA) is synthesized
mmacromolecular chain transfer agent: be dissolved in solvent by NMA monomer, styrene monomer, chain-transfer agent and initiator, carries out polyreaction in argon shield and under stirring after freeze thawing is degassed; Reaction mixture after 1 times of dissolution with solvents in the precipitation agent of 20 ~ 30 times of volumes precipitation purification, precipitate to obtain pink solid, vacuum-drying obtains P (St-co-NMA)
mmacromolecular chain transfer agent;
(3) P (St-co-NMA) is synthesized
m-b-PPEGMA
n, i.e. described thermo-sensitive fluorescent polymer: by P (St-co-NMA)
mmacromolecular chain transfer agent, polyethylene glycol methacrylate-styrene polymer monomer and initiator are dissolved in solvent, after freeze thawing is degassed, carry out polyreaction in argon shield and under stirring; Reaction mixture after 1 times of dissolution with solvents in the precipitation agent of 20 ~ 30 times of volumes precipitation purification, precipitate to obtain light pink solid, vacuum-drying obtains P (St-co-NMA)
m-b-PPEGMA
n;
Described NMA monomer is N-Alpha-Naphthyl methyl acrylamide monomer;
Described PPEGMA
nfor poly-polyethylene glycol methacrylate-styrene polymer.
2. the preparation method of a kind of thermo-sensitive fluorescent polymer as claimed in claim 1, is characterized in that: described step (1) is: N-alpha-naphthylamine, acid binding agent and solvent are fully mixed to get mixing solutions, and is cooled to 0 ~ 5 DEG C; Keep 0 ~ 5 DEG C, under magnetic agitation, slowly join in above-mentioned mixing solutions with dropping funnel react dissolving methacrylic chloride in a solvent; Solids removed by filtration after completion of the reaction, collects filtrate; This filtrate adds enough anhydrous magnesium sulfate dryings successively and filters after distilled water, dilute acid soln, rare brine, then revolves steaming except desolventizing, obtains crude product; Crude product is recrystallization in methyl alcohol, and vacuum-drying obtains the NMA monomer of final white.
3. the preparation method of a kind of thermo-sensitive fluorescent polymer as claimed in claim 2, it is characterized in that: in described step (1): acid binding agent is triethylamine or pyridine, solvent is benzene or toluene, acid is hydrochloric acid or sulfuric acid, salt is supercarbonate, temperature of reaction is 30 ~ 40 DEG C, and the reaction times is 2 ~ 4h.
4. the preparation method of a kind of thermo-sensitive fluorescent polymer as claimed in claim 1, it is characterized in that: in described step (2): chain-transfer agent is CDB, initiator is AIBN, solvent is toluene or tetrahydrofuran (THF), precipitation agent is methyl alcohol, polymeric reaction temperature is 80 DEG C, and the reaction times is 36 ~ 48h, and with quenching termination reaction.
5. the preparation method of a kind of thermo-sensitive fluorescent polymer as claimed in claim 1, it is characterized in that: in described step (3): initiator is AIBN, solvent is toluene or tetrahydrofuran (THF), precipitation agent is methyl alcohol, the molecular-weight average of PEGMA monomer is 475 or 950, polymeric reaction temperature is 65 DEG C, and the reaction times is 36 ~ 48h, and with quenching termination reaction.
6. the preparation method of a kind of thermo-sensitive fluorescent polymer as described in claim arbitrary in claim 1 to 5, is characterized in that: also comprise step (4): preparation P (St-co-NMA)
m-b-PPEGMA
nnano microsphere.
7. the preparation method of a kind of thermo-sensitive fluorescent polymer as claimed in claim 6, is characterized in that: described step (4) is: by P (St-co-NMA)
m-b-PPEGMA
nbe dissolved in volatile cosolvent, obtain polymkeric substance cosolvent solution, this solution is slowly added drop-wise in the distilled water of rapid stirring and also continues to stir to vapor away volatile cosolvent; Above-mentioned P (St-co-NMA)
m-b-PPEGMA
nthere is self-assembly in aqueous and form Nano microsphere, obtain the aqueous solution containing Nano microsphere; Change the temperature of the aqueous solution, the particle diameter of Nano microsphere also changes thereupon.
8. the preparation method of a kind of thermo-sensitive fluorescent polymer as claimed in claim 6, it is characterized in that: in described step (4): volatile cosolvent is THF or 1,4-dioxane, the concentration of polymkeric substance cosolvent solution is 1 ~ 10mg/mL, and the temperature of the aqueous solution is 25 ~ 60 DEG C.
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