CN102796217A - Method for preparing single-chain high molecule by using micro-fluidic chip micro-drop technique - Google Patents
Method for preparing single-chain high molecule by using micro-fluidic chip micro-drop technique Download PDFInfo
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Abstract
The invention discloses a method for preparing a single-chain high molecule by using a micro-fluidic chip micro-drop technique. The method comprises the following steps of: I, selecting an initiator, a monomer, a catalyst and a ligand; II, preparing an initiator solution and a monomer/catalyst/ligand solution; III, preparing a continuous phase; IV, injecting the continuous phase, the initiator solution and the monomer/catalyst/ligand solution into a micro-fluidic chip respectively, controlling the flow speed, mixing the initiator solution with the monomer/catalyst/ligand solution, dispersing into micro-drops in the continuous phase, and introducing the micro-drops into a polyfluortetraethylene tube for performing a polymerization reaction; and V, leading a micro-drop reaction liquid out, separating and removing the continuous phase, and volatilizing, washing, centrifuging and performing freeze drying in sequence to obtain a single-chain high molecule serving as a final polymerization product. The preparation method is simple, and the single-chain high molecule can be formed directly by performing a polymerization reaction in micro-fluidic micro-drops; and the molecular weight of the product is high, so that the product has wide applications on the aspects of monomolecular research, preparation of ultrahigh-molecular-weight polymers and the like.
Description
Technical field
The invention belongs to the macromolecule synthesising technology field, be specifically related to a kind of method of utilizing the micro-fluidic chip microdrop technique to prepare single chain polymer.
Background technology
Owing to there is not intermolecular entanglement, the motion of single chain polymer is relatively easy, thereby on physical properties, shows the not available property of polymer commonly used: be prone to crystallization, relative heatproof and super drawing property.Yet, owing to receive preparation technology's restriction, about the research of single chain polymer with use very few.
Also there is not at present suitable method to come a large amount of preparation single chain polymers.Be dispersed into the single chain polymer sample by multichain polymer, adopt methods such as utmost point rare earth-macromolecule solution (5mg/L) spraying, liquid level expansion, lyophilize usually because only in extremely dilute solution (good solvent) macromolecular chain could exist with the strand swollen coil.Yet if used strength of solution is too low, resulting sample size is difficult to further observe and research very little; If used solution is higher than boundary concentration, a polymer ball of string takes place to penetrate entanglement each other, then can have a certain amount of few chain and multichain sample in the resulting sample.Direct synthesizing single-stranded polymer adopts the method for micro-emulsion polymerization usually, but this method condition has significant limitation, selects suitable microemulsion system like needs, makes that the size of emulsion droplets is little of tens nanometers.In theory when a macromolecular chain initiated polymerization is only arranged in the emulsion droplets; Just can obtain the strand microballoon; And in actual polyreaction, the not only growth of the too small restriction molecule chain of the restriction of drop size, in each droplet to form high molecular quantity also uncontrollable.Also occurred utilizing interior contraction of macromolecular chain or crosslinked method to prepare the report of single chain polymer in recent years; Like (J.Am.Chem.Soc.2002 such as E.Harth; 124; 8653-8660.) utilize the group (cyclobutene) on the macromolecular chain to react to each other, make macromolecular chain generation intramolecular crosslinking; E.J.Foster, wait (J.Am.Chem.Soc.2009,131,6964-6966.) utilize non covalent bond effect (tetrahydrochysene key) to make macromolecular chain generation intramolecularly collapse, and carry out through ultraviolet or irradiation crosslinked, thereby obtain the single chain polymer microballoon.But aforesaid method is only applicable to have on a small quantity the polymer of specific functional groups, and can not avoid intermolecular effectively and react to each other.
Summary of the invention
Technical problem to be solved by this invention is the deficiency to above-mentioned prior art, and a kind of method of utilizing the micro-fluidic chip microdrop technique to prepare single chain polymer is provided.This method is through the concentration of adjustment initiator solution, and the quantity of initiator molecule in the droplet that micro-fluidic chip produced is controlled at one or several, further direct formation single chain polymer behind the initiated polymerization in droplet.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is: a kind of method of utilizing the micro-fluidic chip microdrop technique to prepare single chain polymer is characterized in that this method may further comprise the steps:
The single chain polymer of step 1, preparation is as required selected initiator, monomer, catalyzer and part, and the mole proportioning of definite monomer, catalyzer and part;
Step 2, initiator described in the step 1 is mixed with the initiator solution that concentration is 0.01fmol/L～10fmol/L, monomer described in the step 1, catalyzer and part are mixed with monomer/catalyst/ligand solution that monomer concentration is 0.1mol/L～10mol/L;
Step 3, tensio-active agent is added in the oil phase, obtain external phase; The add-on of said tensio-active agent is 0.05%～5% of an oil phase quality;
Step 4, under the protection of nitrogen or rare gas element; Initiator solution described in external phase described in the step 3, the step 2 and monomer/catalyst/ligand solution are injected micro-fluidic chip respectively; Flow velocity through syringe pump control external phase is 0.1 μ L/min～100 μ L/min; And the ratio of the flow velocity of control external phase, initiator solution and monomer/catalyst/ligand solution is 4～20: 1: 1; Make initiator solution and monomer/catalyst/ligand solution mix the back and in external phase, be dispersed into the droplet that volume is 10nL～100nL, said droplet is imported in the polyfluortetraethylene pipe that internal diameter is 250 μ m～500 μ m carry out polyreaction then;
After step 5, question response finish, derive the miostagmin reaction liquid in the polyfluortetraethylene pipe described in the step 4, separate and remove external phase, after volatilization, washing, centrifugal and lyophilize, obtain final polymerisate single chain polymer successively.
Above-mentioned a kind of method of utilizing the micro-fluidic chip microdrop technique to prepare single chain polymer, initiator described in the step 1 are haloalkane, benzyl halogenide, alpha-brominated ester, α-Lu Daitong, alpha-halogen nitrile, alkylsulfonyl halogenide or Diisopropyl azodicarboxylate.
Above-mentioned a kind of method of utilizing the micro-fluidic chip microdrop technique to prepare single chain polymer, monomer described in the step 1 are acrylic amide, propenoate, vinylbenzene, vinylamide, pyridine or vinyl ester monomer.
Above-mentioned a kind of method of utilizing the micro-fluidic chip microdrop technique to prepare single chain polymer; Catalyzer described in the step 1 is cuprous chloride, cuprous bromide or cuprous iodide, perhaps is the mixture of a kind of and xitix, glucose, stannous octoate or hydrazine in copper, cupric chloride and the cupric bromide.
Above-mentioned a kind of method of utilizing the micro-fluidic chip microdrop technique to prepare single chain polymer; Part described in the step 1 is pentamethyl-diethylenetriamine, three [2-(dimethylamino) ethyl] amine, three (2-pyridylmethyl) amine or 4; 4 '-dinonyl-2,2 '-dipyridyl.
Above-mentioned a kind of method of utilizing the micro-fluidic chip microdrop technique to prepare single chain polymer, the mole proportioning of monomer described in the step 1, catalyzer and part is 50～500: 1～2: 2.
Above-mentioned a kind of method of utilizing the micro-fluidic chip microdrop technique to prepare single chain polymer; The solvent of initiator solution described in the step 2 is water, methyl alcohol, ethanol, Virahol, THF, N; In N N, acetone, dioxan, toluene and the YLENE one or more; The solvent of said monomer/catalyst/ligand solution is water, methyl alcohol, ethanol, Virahol, THF, N, one or more in N N, acetone, dioxan, toluene and the YLENE.
Above-mentioned a kind of method of utilizing the micro-fluidic chip microdrop technique to prepare single chain polymer, tensio-active agent described in the step 3 is fluorine surfactant, Silicon surfactant or hc-surfactant.
Above-mentioned a kind of method of utilizing the micro-fluidic chip microdrop technique to prepare single chain polymer, oil phase described in the step 3 is fluorocarbon oil, silicone oil, fluorinated silicone oil or n-tetradecane.
Above-mentioned a kind of method of utilizing the micro-fluidic chip microdrop technique to prepare single chain polymer, rare gas element described in the step 4 is an argon gas.
The present invention adopts the micro-fluidic chip microdrop technique, because the channel size of microreactor is generally in the scope of 10 μ m～300 μ m, the specific surface area of internal liquid also just is increased to 10000m accordingly
2/ m
3～50000m
2/ m
3, make the heat transfer of reaction system, mass transfer ability significantly strengthen, speed of response is apparently higher than the situation in the popular response device, and therefore reaction result also has highly selective, high yield and highly purified characteristic.
The present invention compared with prior art has the following advantages:
1, preparation method of the present invention is simple, in micro-fluidic droplet, carry out polyreaction and can be formed directly in single chain polymer, and the molecular weight of product is higher, therefore has purposes widely at aspects such as unit molecule research and extra high molecular polymer preparations.
2, the present invention carries out polyreaction in micro-fluidic reactor, can produce a large amount of droplets in the short period of time, and can amplify at double through parallel device, effectively improves output.
3, the present invention can be controlled at one or several with the initiator molecule quantity in the droplet through the concentration of adjustment initiator solution.
4, adopt method of the present invention to carry out polyreaction, speed of reaction is exceedingly fast, and can obtain the polymerisate of ultra-high molecular weight.
Below in conjunction with accompanying drawing and embodiment, technical scheme of the present invention is done further detailed description.
Description of drawings
Fig. 1 is the optical photograph that imports the droplet in the polyfluortetraethylene pipe in the embodiment of the invention 3.
Fig. 2 is the molecular weight size and the distribution curve of the PNIPAM single chain polymer of the embodiment of the invention 5 preparations.
Fig. 3 is the shape appearance figure of PNIPAM single chain polymer under transmission electron microscope of the embodiment of the invention 5 preparations.
Embodiment
Embodiment 1
Step 1, selection 2-hydroxyethyl-2-bromo acid ester (BrC (CH
3)
2COOCH
2CH
2OH) as initiator, acrylic amide is as monomer, and cupric chloride and xitix are as catalyzer, and pentamethyl-diethylenetriamine is as part, and the mol ratio between acrylic amide, cupric chloride, xitix and the pentamethyl-diethylenetriamine is 100: 1: 1: 2;
Step 2, with volume ratio 1: 1 water and N; The mixed solution of N N is as solvent; Compound concentration is the initiator solution of 0.1fmol/L; With volume ratio is 1: 1 water and N, and the mixed solution of N N is as solvent, and the preparation monomer concentration is monomer/catalyst/ligand solution of 0.6mol/L;
Step 3, fluorocarbon surfactant DuPont Zonyl FSO-100 is added in the fluorocarbon oil, obtain external phase; The add-on of said fluorocarbon surfactant is 0.05% of a fluorocarbon oil quality;
Step 4, under the rare gas element argon shield; Initiator solution described in external phase described in the step 3, the step 2 and monomer/catalyst/ligand solution are injected micro-fluidic chip respectively; Flow velocity through syringe pump control external phase, initiator solution and monomer/catalyst/ligand solution is respectively 10 μ L/min, 1 μ L/min and 1 μ L/min; Make initiator solution and monomer/catalyst/ligand solution mix the back and in external phase, be dispersed into the droplet that volume is 35nL, said droplet is imported in the polyfluortetraethylene pipe that internal diameter is 400 μ m carry out polyreaction then;
Derive the miostagmin reaction liquid in the polyfluortetraethylene pipe described in the step 4 behind step 5, the reaction 8h, separate and remove external phase, after volatilization, washing, centrifugal and lyophilize, obtain final polymerisate SEPIGEL 305 single chain polymer successively.
Embodiment 2
Present embodiment is identical with embodiment 1; Wherein difference is: said initiator is haloalkane (like trichloromethane, tetracol phenixin, a bromo-trichloromethane etc.); Perhaps be benzyl halogenide (like phenylbenzene methylene dichloride, trichlorotoluene zotrichloride, phenyl-chloride ethane etc.); It perhaps is α-Lu Daitong (like trichloroacetone, dichloroacetophenone etc.); Perhaps being alpha-halogen nitrile (like 2-chloroethyl nitrile, 2-bromine isopropyl cyanide etc.), perhaps is alkylsulfonyl halogenide (like benzene sulfonyl chloride etc.), perhaps is Diisopropyl azodicarboxylate; The solvent of said initiator solution is methyl alcohol, ethanol, Virahol, THF, N; In N N, acetone, dioxan, toluene and the YLENE one or more perhaps are the mixed solution of a kind of and water in methyl alcohol, ethanol, Virahol, THF, acetone and the dioxan; The solvent of said monomer/catalyst/ligand solution is methyl alcohol, ethanol, Virahol, THF, N; In N N, acetone, dioxan, toluene and the YLENE one or more perhaps are the mixed solution of a kind of and water in methyl alcohol, ethanol, Virahol, THF, acetone and the dioxan.
Embodiment 3
Step 1, selection octadecyl 2-bromo acid ester (BrC (CH
3)
2COOCH
2(CH
2)
16CH
3) as initiator, N, N-diethylammonium-2-acrylic amide is as monomer; Cupric chloride and glucose are as catalyzer; Pentamethyl-diethylenetriamine is as part, N, and the mol ratio between N-diethylammonium-2-acrylic amide, cupric chloride, glucose, the pentamethyl-diethylenetriamine is 200: 1: 1: 2;
Step 2, be that 1: 2 the mixed solution of water and methyl alcohol is as solvent with volume ratio; Compound concentration is the initiator solution of 0.02fmol/L; The mixed solution of water and methyl alcohol that with volume ratio is 1: 2 is as solvent, and the preparation monomer concentration is monomer/catalyst/ligand solution of 1.2mol/L;
Step 3, with hc-surfactant polyoxyethylene nonylphenol (DOW TEGITOL
TMNP-4) add in the n-tetradecane, obtain external phase; Said hc-surfactant polyoxyethylene nonylphenol (DOW TEGITOL
TMNP-4) add-on is 0.2% of a n-tetradecane quality;
Step 4, under the rare gas element argon shield; Initiator solution described in external phase described in the step 3, the step 2 and monomer/catalyst/ligand solution are injected micro-fluidic chip respectively; Flow velocity through syringe pump control external phase, initiator solution and monomer/catalyst/ligand solution is respectively 16 μ L/min, 2 μ L/min and 2 μ L/min; Make initiator solution and monomer/catalyst/ligand solution mix the back and in external phase, be dispersed into the droplet that volume is 70nL, said droplet is imported in the polyfluortetraethylene pipe that internal diameter is 500 μ m carry out polyreaction then;
Derive the miostagmin reaction liquid in the polyfluortetraethylene pipe described in the step 4 behind step 5, the reaction 8h, separate and remove external phase, after volatilization, washing, centrifugal and lyophilize, obtain final polymerisate successively and gather N, N-diethylammonium-2-acrylic amide single chain polymer.
Fig. 1 is the optical photograph of the droplet in the present embodiment importing polyfluortetraethylene pipe, and as can be seen from the figure, the droplet uniform form is dispersed in the external phase.
Embodiment 4
Present embodiment is identical with embodiment 3; Wherein difference is: said initiator is haloalkane (like trichloromethane, tetracol phenixin, a bromo-trichloromethane etc.); Perhaps be benzyl halogenide (like phenylbenzene methylene dichloride, trichlorotoluene zotrichloride, phenyl-chloride ethane etc.); It perhaps is α-Lu Daitong (like trichloroacetone, dichloroacetophenone etc.); Perhaps being alpha-halogen nitrile (like 2-chloroethyl nitrile, 2-bromine isopropyl cyanide etc.), perhaps is alkylsulfonyl halogenide (like benzene sulfonyl chloride etc.), perhaps is Diisopropyl azodicarboxylate; The solvent of said initiator solution is methyl alcohol, ethanol, Virahol, THF, N; In N N, acetone, dioxan, toluene and the YLENE one or more; Perhaps be ethanol, Virahol, THF, N, the mixed solution of a kind of and water in N N, acetone and the dioxan; The solvent of said monomer/catalyst/ligand solution is methyl alcohol, ethanol, Virahol, THF, N; In N N, acetone, dioxan, toluene and the YLENE one or more; Perhaps be ethanol, Virahol, THF, N, the mixed solution of a kind of and water in N N, acetone and the dioxan.
Embodiment 5
Step 1, selection 2-bromo acid ten diester (BrC (CH
3)
2COOCH
2(CH
2)
10CH
3) as initiator; NSC 11448 is as monomer; Cupric bromide and xitix are as catalyzer, and pentamethyl-diethylenetriamine is as part, and the mol ratio between NSC 11448, cupric bromide, xitix, the pentamethyl-diethylenetriamine is 100: 1: 1: 2;
Step 2, be that 1: 4 water and alcoholic acid mixed solution is as solvent with volume ratio; Compound concentration is the initiator solution of 0.15fmol/L; With volume ratio be 1: 4 water and alcoholic acid mixed solution as solvent, the preparation monomer concentration is monomer/catalyst/ligand solution of 0.6mol/L;
Step 3, with hc-surfactant polyoxyethylene nonylphenol (DOW TEGITOL
TMNP-4) add in the n-tetradecane, obtain external phase; Said hc-surfactant polyoxyethylene nonylphenol (DOW TEGITOL
TMNP-4) add-on is 0.1% of a n-tetradecane quality;
Step 4, under nitrogen protection; Initiator solution described in external phase described in the step 3, the step 2 and monomer/catalyst/ligand solution are injected micro-fluidic chip respectively; Flow velocity through syringe pump control external phase, initiator solution and monomer/catalyst/ligand solution is respectively 8 μ L/min, 1 μ L/min and 1 μ L/min; Make initiator solution and monomer/catalyst/ligand solution mix the back and in external phase, be dispersed into the droplet that volume is 20nL, said droplet is imported in the polyfluortetraethylene pipe that internal diameter is 320 μ m carry out polyreaction then;
Derive the miostagmin reaction liquid in the polyfluortetraethylene pipe described in the step 4 behind step 5, the reaction 12h, separate and remove external phase, after volatilization, washing, centrifugal and lyophilize, obtain final polymerisate PNIPAM single chain polymer successively.
Fig. 2 is the molecular weight size and the distribution results (atomic power-unit molecule force spectroscopy) of the PNIPAM single chain polymer of present embodiment preparation, and as can be seen from the figure, the number-average molecular weight of the PNIPAM single chain polymer of preparation is 2.9 * 10
5G/mol, weight-average molecular weight is 4.1 * 10
5G/mol, the molecular weight of maximum strand are 1.1 * 10
6G/mol.Fig. 3 is the shape appearance figure of PNIPAM single chain polymer under transmission electron microscope of present embodiment preparation; Reacted miostagmin reaction liquid is directly dripped to the copper mesh surface of surface with the ultra-thin carbon supporting film of 3nm, and with the stifling dyeing of the perosmic anhydride solution of 0.5wt% 10 minutes, lower left corner scale was 100nm; As can be seen from the figure; Macromolecular single-chain size homogeneous, and be uniformly dispersed, do not observe the situation of mutual winding.
Embodiment 6
Present embodiment is identical with embodiment 5; Wherein difference is: said initiator is haloalkane (like trichloromethane, tetracol phenixin, a bromo-trichloromethane etc.); Perhaps be benzyl halogenide (like phenylbenzene methylene dichloride, trichlorotoluene zotrichloride, phenyl-chloride ethane etc.); It perhaps is α-Lu Daitong (like trichloroacetone, dichloroacetophenone etc.); Perhaps being alpha-halogen nitrile (like 2-chloroethyl nitrile, 2-bromine isopropyl cyanide etc.), perhaps is alkylsulfonyl halogenide (like benzene sulfonyl chloride etc.), perhaps is Diisopropyl azodicarboxylate; The solvent of said initiator solution is methyl alcohol, ethanol, Virahol, THF, N; In N N, acetone, dioxan, toluene and the YLENE one or more; Perhaps be methyl alcohol, Virahol, THF, N, the mixed solution of a kind of and water in N N, acetone and the dioxan; The solvent of said monomer/catalyst/ligand solution is methyl alcohol, ethanol, Virahol, THF, N; In N N, acetone, dioxan, toluene and the YLENE one or more; Perhaps be methyl alcohol, Virahol, THF, N, the mixed solution of a kind of and water in N N, acetone and the dioxan.
Embodiment 7
Step 1, selection 2-bromo acid ten diester (BrC (CH
3)
2COOCH
2(CH
2)
10CH
3) as initiator, methylacrylic acid-2-hydroxy methacrylate is as monomer, cupric chloride and xitix are as catalyzer; 4; 4 '-dinonyl-2,2 '-dipyridyl be as part, methylacrylic acid-2-hydroxy methacrylate, cupric chloride, xitix and 4; 4 '-dinonyl-2, the mol ratio between 2 '-dipyridyl are 125: 1: 1: 2;
Step 2, be that 3: 2 the mixed solution of water and methyl alcohol is as solvent with volume ratio; Compound concentration is the initiator solution of 0.3fmol/L; The mixed solution of water and methyl alcohol that with volume ratio is 3: 2 is as solvent, and the preparation monomer concentration is monomer/catalyst/ligand solution of 0.42mol/L;
Step 3, fluorine surfactant DuPont Capstone 1157 is added in the fluorinated silicone oil, obtain external phase; The add-on of said fluorine surfactant DuPont Capstone 1157 is 1% of a fluorinated silicone oil quality;
Step 4, under the rare gas element argon shield; Initiator solution described in external phase described in the step 3, the step 2 and monomer/catalyst/ligand solution are injected micro-fluidic chip respectively; Flow velocity through syringe pump control external phase, initiator solution and monomer/catalyst/ligand solution is respectively 10 μ L/min, 1 μ L/min and 1 μ L/min; Make initiator solution and monomer/catalyst/ligand solution mix the back and in external phase, be dispersed into the droplet that volume is 10nL, said droplet is imported in the polyfluortetraethylene pipe that internal diameter is 250 μ m carry out polyreaction then;
Derive the miostagmin reaction liquid in the polyfluortetraethylene pipe described in the step 4 behind step 5, the reaction 8h, separate and remove external phase, after volatilization, washing, centrifugal and lyophilize, obtain final polymerisate polymethacrylate-2-hydroxy-ethyl ester single chain polymer successively.
Embodiment 8
Present embodiment is identical with embodiment 7; Wherein difference is: said initiator is haloalkane (like trichloromethane, tetracol phenixin, a bromo-trichloromethane etc.); Perhaps be benzyl halogenide (like phenylbenzene methylene dichloride, trichlorotoluene zotrichloride, phenyl-chloride ethane etc.); It perhaps is α-Lu Daitong (like trichloroacetone, dichloroacetophenone etc.); Perhaps being alpha-halogen nitrile (like 2-chloroethyl nitrile, 2-bromine isopropyl cyanide etc.), perhaps is alkylsulfonyl halogenide (like benzene sulfonyl chloride etc.), perhaps is Diisopropyl azodicarboxylate; The solvent of said initiator solution is methyl alcohol, ethanol, Virahol, THF, N; In N N, acetone, dioxan, toluene and the YLENE one or more; Perhaps be ethanol, Virahol, THF, N, the mixed solution of a kind of and water in N N, acetone and the dioxan; The solvent of said monomer/catalyst/ligand solution is methyl alcohol, ethanol, Virahol, THF, N; In N N, acetone, dioxan, toluene and the YLENE one or more; Perhaps be ethanol, Virahol, THF, N, the mixed solution of a kind of and water in N N, acetone and the dioxan.
Embodiment 9
Step 1, select bromo-trichloromethane, oligomeric ethylene glycol methacrylic ester (H as initiator
2CC (CH
3) CO (OCH
2CH
2)
nOH) as monomer, cupric bromide and xitix be as catalyzer, and 4; 4 '-dinonyl-2,2 '-dipyridyl be as part, oligomeric ethylene glycol methacrylic ester, cupric bromide, xitix and 4; 4 '-dinonyl-2, the mol ratio between 2 '-dipyridyl are 125: 1: 1: 2;
Step 2, with N, the N N is as solvent, compound concentration is the initiator solution of 0.3fmol/L, with N, the N N is as solvent, the preparation monomer concentration is monomer/catalyst/ligand solution of 0.4mol/L;
Step 3, Silicon surfactant FY-4902 is added in the silicone oil (or fluorinated silicone oil), obtain external phase; The add-on of said Silicon surfactant FY-4902 is 1% of silicone oil (or fluorinated silicone oil) quality;
Step 4, under the rare gas element argon shield; Initiator solution described in external phase described in the step 3, the step 2 and monomer/catalyst/ligand solution are injected micro-fluidic chip respectively; Flow velocity through syringe pump control external phase, initiator solution and monomer/catalyst/ligand solution is respectively 10 μ L/min, 1.5 μ L/min and 1.5 μ L/min; Make initiator solution and monomer/catalyst/ligand solution mix the back and in external phase, be dispersed into the droplet that volume is 10nL, said droplet is imported in the polyfluortetraethylene pipe that internal diameter is 250 μ m carry out polyreaction then;
Derive the miostagmin reaction liquid in the polyfluortetraethylene pipe described in the step 4 behind step 5, the reaction 8h, separate and remove external phase, after volatilization, washing, centrifugal and lyophilize, obtain final polymerisate polyethylene glycol methacrylate-styrene polymer single chain polymer successively.
Embodiment 10
Present embodiment is identical with embodiment 9; Wherein difference is: said initiator is alpha-brominated ester (like octadecyl 2-bromo acid ester, 2-bromo acid ten diester, 2-hydroxyethyl-2-bromo acid ester etc.); Perhaps be benzyl halogenide (like phenylbenzene methylene dichloride, trichlorotoluene zotrichloride, phenyl-chloride ethane etc.); It perhaps is α-Lu Daitong (like trichloroacetone, dichloroacetophenone etc.); Perhaps being alpha-halogen nitrile (like 2-chloroethyl nitrile, 2-bromine isopropyl cyanide etc.), perhaps is alkylsulfonyl halogenide (like benzene sulfonyl chloride etc.), perhaps is Diisopropyl azodicarboxylate; The solvent of said initiator solution is water, methyl alcohol, ethanol, Virahol, THF, N; In N N, acetone, dioxan, toluene and the YLENE at least two kinds perhaps are methyl alcohol, ethanol, Virahol, THF, acetone, dioxan, toluene or YLENE; The solvent of said monomer/catalyst/ligand solution is water, methyl alcohol, ethanol, Virahol, THF, N; In N N, acetone, dioxan, toluene and the YLENE at least two kinds perhaps are methyl alcohol, ethanol, Virahol, THF, acetone, dioxan, toluene or YLENE.
Embodiment 11
Step 1, selection 2-bromo acid ten diester (BrC (CH
3)
2COOCH
2(CH
2)
10CH
3) as initiator; NSC 11448 is as monomer; Cupric chloride and xitix are as catalyzer, and pentamethyl-diethylenetriamine is as part, and the mol ratio between NSC 11448, cupric chloride, xitix and the pentamethyl-diethylenetriamine is 50: 1: 1: 2;
Step 2, be that 1: 1 the mixed solution of water and methyl alcohol is as solvent with volume ratio; Compound concentration is the initiator solution of 0.2fmol/L; The mixed solution of water and methyl alcohol that with volume ratio is 1: 1 is as solvent, and the preparation monomer concentration is monomer/catalyst/ligand solution of 0.6mol/L;
Step 3, fluorine surfactant DuPont Zonyl FSO-100 is added in the fluorocarbon oil, obtain external phase; The add-on of said fluorine surfactant DuPont Zonyl FSO-100 is 0.2% of a fluorocarbon oil quality;
Step 4, under the rare gas element argon shield; Initiator solution described in external phase described in the step 3, the step 2 and monomer/catalyst/ligand solution are injected micro-fluidic chip respectively; Flow velocity through syringe pump control external phase, initiator solution and monomer/catalyst/ligand solution is respectively 20 μ L/min, 2.5 μ L/min and 2.5 μ L/min; Make initiator solution and monomer/catalyst/ligand solution mix the back and in external phase, be dispersed into the droplet that volume is 15nL, said droplet is imported in the polyfluortetraethylene pipe that internal diameter is 300 μ m carry out polyreaction then;
Derive the miostagmin reaction liquid in the polyfluortetraethylene pipe described in the step 4 behind step 5, the reaction 24h, separate and remove external phase, after volatilization, washing, centrifugal and lyophilize, obtain final polymerisate PNIPAM single chain polymer successively.
Embodiment 12
Present embodiment is identical with embodiment 11; Wherein difference is: said initiator is haloalkane (like trichloromethane, tetracol phenixin, a bromo-trichloromethane etc.); Perhaps be benzyl halogenide (like phenylbenzene methylene dichloride, trichlorotoluene zotrichloride, phenyl-chloride ethane etc.); It perhaps is α-Lu Daitong (like trichloroacetone, dichloroacetophenone etc.); Perhaps being alpha-halogen nitrile (like 2-chloroethyl nitrile, 2-bromine isopropyl cyanide etc.), perhaps is alkylsulfonyl halogenide (like benzene sulfonyl chloride etc.), perhaps is Diisopropyl azodicarboxylate; The solvent of said initiator solution is methyl alcohol, ethanol, Virahol, THF, N; In N N, acetone, dioxan, toluene and the YLENE one or more; Perhaps be ethanol, Virahol, THF, N, the mixed solution of a kind of and water in N N, acetone and the dioxan; The solvent of said monomer/catalyst/ligand solution is methyl alcohol, ethanol, Virahol, THF, N; In N N, acetone, dioxan, toluene and the YLENE one or more; Perhaps be ethanol, Virahol, THF, N, the mixed solution of a kind of and water in N N, acetone and the dioxan.
Embodiment 13
Step 1, selection phenylbenzene methylene dichloride are as initiator; NSC 11448 is as monomer; Cuprous chloride is as catalyzer; Three [2-(dimethylamino) ethyl] amine is as part, and the mol ratio between NSC 11448, cuprous chloride and three [2-(dimethylamino) ethyl] amine is 100: 1: 2;
Step 2, with Virahol as solvent, compound concentration is the initiator solution of 0.2fmol/L, with Virahol as solvent, the preparation monomer concentration be monomer/catalyst/ligand solution of 3.5mol/L;
Step 3, fluorine surfactant DuPont Zonyl FSO-100 is added in the fluorocarbon oil, obtain external phase; The add-on of said fluorine surfactant DuPont Zonyl FSO-100 is 0.2% of a fluorocarbon oil quality;
Step 4, under the rare gas element argon shield; Initiator solution described in external phase described in the step 3, the step 2 and monomer/catalyst/ligand solution are injected micro-fluidic chip respectively; Flow velocity through syringe pump control external phase, initiator solution and monomer/catalyst/ligand solution is respectively 20 μ L/min, 2.5 μ L/min and 2.5 μ L/min; Make initiator solution and monomer/catalyst/ligand solution mix the back and in external phase, be dispersed into the droplet that volume is 15nL, said droplet is imported in the polyfluortetraethylene pipe that internal diameter is 300 μ m carry out polyreaction then;
Derive the miostagmin reaction liquid in the polyfluortetraethylene pipe described in the step 4 behind step 5, the reaction 24h, separate and remove external phase, after volatilization, washing, centrifugal and lyophilize, obtain final polymerisate PNIPAM single chain polymer successively.
Embodiment 14
Present embodiment is identical with embodiment 13; Wherein difference is: said initiator is alpha-brominated ester (like octadecyl 2-bromo acid ester, 2-bromo acid ten diester, 2-hydroxyethyl-2-bromo acid ester etc.); Perhaps be haloalkane (like trichloromethane, tetracol phenixin, bromo-trichloromethane etc.); It perhaps is α-Lu Daitong (like trichloroacetone, dichloroacetophenone etc.); Perhaps being alpha-halogen nitrile (like 2-chloroethyl nitrile, 2-bromine isopropyl cyanide etc.), perhaps is alkylsulfonyl halogenide (like benzene sulfonyl chloride etc.), perhaps is Diisopropyl azodicarboxylate; The solvent of said initiator solution is water, methyl alcohol, ethanol, Virahol, THF, N; In N N, acetone, dioxan, toluene and the YLENE at least two kinds; Perhaps be methyl alcohol, ethanol, N, N N, THF, acetone, dioxan, toluene or YLENE; The solvent of said monomer/catalyst/ligand solution is water, methyl alcohol, ethanol, Virahol, THF, N; In N N, acetone, dioxan, toluene and the YLENE at least two kinds; Perhaps be methyl alcohol, ethanol, N, N N, THF, acetone, dioxan, toluene or YLENE.
Embodiment 15
Step 1, selection trichloroacetone are as initiator; 4-vinylpridine is as monomer; Cuprous bromide is as catalyzer, and three [2-(dimethylamino) ethyl] amine is as part, and the mol ratio between 4-vinylpridine, cuprous bromide and three [2-(dimethylamino) ethyl] amine is 500: 1: 2;
Step 2, with Virahol as solvent, compound concentration is the initiator solution of 0.2fmol/L, with Virahol as solvent, the preparation monomer concentration be monomer/catalyst/ligand solution of 1.1mol/L;
Step 3, fluorine surfactant DuPont Zonyl FSO-100 is added in the fluorocarbon oil, obtain external phase; The add-on of said fluorine surfactant DuPont Zonyl FSO-100 is 0.2% of a fluorocarbon oil quality;
Step 4, under the rare gas element argon shield; Initiator solution described in external phase described in the step 3, the step 2 and monomer/catalyst/ligand solution are injected micro-fluidic chip respectively; Flow velocity through syringe pump control external phase, initiator solution and monomer/catalyst/ligand solution is respectively 20 μ L/min, 2.5 μ L/min and 2.5 μ L/min; Make initiator solution and monomer/catalyst/ligand solution mix the back and in external phase, be dispersed into the droplet that volume is 15nL, said droplet is imported in the polyfluortetraethylene pipe that internal diameter is 300 μ m carry out polyreaction then;
Derive the miostagmin reaction liquid in the polyfluortetraethylene pipe described in the step 4 behind step 5, the reaction 12h, separate and remove external phase, after volatilization, washing, centrifugal and lyophilize, obtain final polymerisate poly 4 vinyl pyridine single chain polymer successively.
Embodiment 16
Present embodiment is identical with embodiment 15; Wherein difference is: said initiator is alpha-brominated ester (like octadecyl 2-bromo acid ester, 2-bromo acid ten diester, 2-hydroxyethyl-2-bromo acid ester etc.); Perhaps be haloalkane (like trichloromethane, tetracol phenixin, bromo-trichloromethane etc.); Perhaps be benzyl halogenide (like phenylbenzene methylene dichloride, trichlorotoluene zotrichloride, phenyl-chloride ethane etc.); Perhaps being alpha-halogen nitrile (like 2-chloroethyl nitrile, 2-bromine isopropyl cyanide etc.), perhaps is alkylsulfonyl halogenide (like benzene sulfonyl chloride etc.), perhaps is Diisopropyl azodicarboxylate; The solvent of said initiator solution is water, methyl alcohol, ethanol, Virahol, THF, N; In N N, acetone, dioxan, toluene and the YLENE at least two kinds; Perhaps be methyl alcohol, ethanol, N, N N, THF, acetone, dioxan, toluene or YLENE; The solvent of said monomer/catalyst/ligand solution is water, methyl alcohol, ethanol, Virahol, THF, N; In N N, acetone, dioxan, toluene and the YLENE at least two kinds; Perhaps be methyl alcohol, ethanol, N, N N, THF, acetone, dioxan, toluene or YLENE.
Embodiment 17
Step 1, selection 2-bromine isopropyl cyanide are as initiator; Phenyl acrylate is as monomer; Cuprous iodide is as catalyzer, and three (2-pyridylmethyl) amine is as part, and the mol ratio between phenyl acrylate, cuprous iodide and three (2-pyridylmethyl) amine is 100: 1: 2;
Step 2, with toluene as solvent, compound concentration is the initiator solution of 0.2fmol/L, with toluene as solvent, the preparation monomer concentration be monomer/catalyst/ligand solution of 1.1mol/L;
Step 3, fluorine surfactant DuPont Zonyl FSO-100 is added in the fluorocarbon oil, obtain external phase; The add-on of said fluorine surfactant DuPont Zonyl FSO-100 is 5% of a fluorocarbon oil quality;
Step 4, under the rare gas element argon shield; Initiator solution described in external phase described in the step 3, the step 2 and monomer/catalyst/ligand solution are injected micro-fluidic chip respectively; Flow velocity through syringe pump control external phase, initiator solution and monomer/catalyst/ligand solution is respectively 20 μ L/min, 2.5 μ L/min and 2.5 μ L/min; Make initiator solution and monomer/catalyst/ligand solution mix the back and in external phase, be dispersed into the droplet that volume is 15nL, said droplet is imported in the polyfluortetraethylene pipe that internal diameter is 300 μ m carry out polyreaction then;
Derive the miostagmin reaction liquid in the polyfluortetraethylene pipe described in the step 4 behind step 5, the reaction 10h, separate and remove external phase, after volatilization, washing, centrifugal and lyophilize, obtain final polymerisate polyphenylene propenoate single chain polymer successively.
Embodiment 18
Present embodiment is identical with embodiment 17; Wherein difference is: said initiator is alpha-brominated ester (like octadecyl 2-bromo acid ester, 2-bromo acid ten diester, 2-hydroxyethyl-2-bromo acid ester etc.); Perhaps be haloalkane (like trichloromethane, tetracol phenixin, bromo-trichloromethane etc.); Perhaps be benzyl halogenide (like phenylbenzene methylene dichloride, trichlorotoluene zotrichloride, phenyl-chloride ethane etc.); Perhaps being α-Lu Daitong (like trichloroacetone, dichloroacetophenone etc.), perhaps is alkylsulfonyl halogenide (like benzene sulfonyl chloride etc.), perhaps is Diisopropyl azodicarboxylate; The solvent of said initiator solution is water, methyl alcohol, ethanol, Virahol, THF, N; In N N, acetone, dioxan, toluene and the YLENE at least two kinds; Perhaps be methyl alcohol, ethanol, N, N N, THF, acetone, dioxan, Virahol or YLENE; The solvent of said monomer/catalyst/ligand solution is water, methyl alcohol, ethanol, Virahol, THF, N; In N N, acetone, dioxan, toluene and the YLENE at least two kinds; Perhaps be methyl alcohol, ethanol, N, N N, THF, acetone, dioxan, Virahol or YLENE.
Embodiment 19
Step 1, selection benzene sulfonyl chloride are as initiator; Propionate is as monomer; Cupric chloride and stannous octoate are as catalyzer; Three (2-pyridylmethyl) amine is as part, and the mol ratio between propionate, cupric chloride, stannous octoate and three (2-pyridylmethyl) amine is 500: 1: 1: 2;
Step 2, be that 1: 2 the mixed solution of acetone and Virahol is as solvent with volume ratio; Compound concentration is the initiator solution of 0.01fmol/L; The mixed solution of acetone and Virahol that with volume ratio is 1: 2 is as solvent, and the preparation monomer concentration is monomer/catalyst/ligand solution of 0.1mol/L;
Step 3, fluorine surfactant DuPont Zonyl FSO-100 is added in the n-tetradecane, obtain external phase; The add-on of said fluorine surfactant DuPont Zonyl FSO-100 is 2% of a n-tetradecane quality;
Step 4, under nitrogen protection; Initiator solution described in external phase described in the step 3, the step 2 and monomer/catalyst/ligand solution are injected micro-fluidic chip respectively; Flow velocity through syringe pump control external phase, initiator solution and monomer/catalyst/ligand solution is respectively 100 μ L/min, 5 μ L/min and 5 μ L/min; Make initiator solution and monomer/catalyst/ligand solution mix the back and in external phase, be dispersed into the droplet that volume is 10nL, said droplet is imported in the polyfluortetraethylene pipe that internal diameter is 300 μ m carry out polyreaction then;
Derive the miostagmin reaction liquid in the polyfluortetraethylene pipe described in the step 4 behind step 5, the reaction 10h, separate and remove external phase, after volatilization, washing, centrifugal and lyophilize, obtain final polymerisate polyvinyl proprionate single chain polymer successively.
Present embodiment is identical with embodiment 19; Wherein difference is: said initiator is alpha-brominated ester (like octadecyl 2-bromo acid ester, 2-bromo acid ten diester, 2-hydroxyethyl-2-bromo acid ester etc.); Perhaps be haloalkane (like trichloromethane, tetracol phenixin, bromo-trichloromethane etc.); Perhaps be benzyl halogenide (like phenylbenzene methylene dichloride, trichlorotoluene zotrichloride, phenyl-chloride ethane etc.); Perhaps being α-Lu Daitong (like trichloroacetone, dichloroacetophenone etc.), perhaps is alpha-halogen nitrile (like 2-chloroethyl nitrile, 2-bromine isopropyl cyanide etc.), perhaps is Diisopropyl azodicarboxylate; The solvent of said initiator solution is water, methyl alcohol, ethanol, Virahol, THF, N; A kind of in N N, acetone, dioxan, toluene and the YLENE or more than three kinds; Perhaps be water, methyl alcohol, ethanol, THF, N; The mixed solution of a kind of and acetone in N N, dioxan, toluene and the YLENE; Perhaps be water, methyl alcohol, ethanol, THF, N, the mixed solution of a kind of and Virahol in N N, dioxan, toluene and the YLENE; The solvent of said monomer/catalyst/ligand solution is water, methyl alcohol, ethanol, Virahol, THF, N; A kind of in N N, acetone, dioxan, toluene and the YLENE or more than three kinds; Perhaps be water, methyl alcohol, ethanol, THF, N; The mixed solution of a kind of and acetone in N N, dioxan, toluene and the YLENE; Perhaps be water, methyl alcohol, ethanol, THF, N, the mixed solution of a kind of and Virahol in N N, dioxan, toluene and the YLENE.
Embodiment 21
Step 1, selection Diisopropyl azodicarboxylate are as initiator, and vinylbenzene is as monomer, and cuprous chloride is as catalyzer, and three (2-pyridylmethyl) amine is as part, and the mol ratio between vinylbenzene, cuprous chloride and three (2-pyridylmethyl) amine is 100: 1: 2;
Step 2, with toluene as solvent, compound concentration is the initiator solution of 10fmol/L, is solvent with toluene, the preparation monomer concentration be monomer/catalyst/ligand solution of 10mol/L;
Step 3, fluorine surfactant DuPont Zonyl FSO-100 is added in the n-tetradecane, obtain external phase; The add-on of said fluorine surfactant DuPont Zonyl FSO-100 is 5% of a n-tetradecane quality;
Step 4, under argon shield; Initiator solution described in external phase described in the step 3, the step 2 and monomer/catalyst/ligand solution are injected micro-fluidic chip respectively; Flow velocity through syringe pump control external phase, initiator solution and monomer/catalyst/ligand solution is respectively 1 μ L/min, 0.1 μ L/min and 0.1 μ L/min; Make initiator solution and monomer/catalyst/ligand solution mix the back and in external phase, be dispersed into the droplet that volume is 100nL, said droplet is imported in the polyfluortetraethylene pipe that internal diameter is 500 μ m carry out polyreaction then;
Derive the miostagmin reaction liquid in the polyfluortetraethylene pipe described in the step 4 behind step 5, the reaction 24h, separate and remove external phase, after volatilization, washing, centrifugal and lyophilize, obtain final polymerisate PS single chain polymer successively.
Embodiment 22
Present embodiment is identical with embodiment 21; Wherein difference is: said initiator is alpha-brominated ester (like octadecyl 2-bromo acid ester, 2-bromo acid ten diester, 2-hydroxyethyl-2-bromo acid ester etc.); Perhaps be haloalkane (like trichloromethane, tetracol phenixin, bromo-trichloromethane etc.); Perhaps be benzyl halogenide (like phenylbenzene methylene dichloride, trichlorotoluene zotrichloride, phenyl-chloride ethane etc.); Perhaps being α-Lu Daitong (like trichloroacetone, dichloroacetophenone etc.), perhaps is alpha-halogen nitrile (like 2-chloroethyl nitrile, 2-bromine isopropyl cyanide etc.), perhaps is alkylsulfonyl halogenide (like benzene sulfonyl chloride etc.); The solvent of said initiator solution is water, methyl alcohol, ethanol, Virahol, THF, N; In N N, acetone, dioxan, toluene and the YLENE at least two kinds; Perhaps be methyl alcohol, ethanol, N, N N, THF, acetone, dioxan, Virahol or YLENE; The solvent of said monomer/catalyst/ligand solution is water, methyl alcohol, ethanol, Virahol, THF, N; In N N, acetone, dioxan, toluene and the YLENE at least two kinds; Perhaps be methyl alcohol, ethanol, N, N N, THF, acetone, dioxan, Virahol or YLENE.
Embodiment 23
Step 1, selection Diisopropyl azodicarboxylate are as initiator; The N-vinyl formamide is as monomer; Cuprous chloride is as catalyzer, and pentamethyl-diethylenetriamine is as part, and the mol ratio between N-vinyl formamide, cuprous chloride and the pentamethyl-diethylenetriamine is 100: 1: 2;
Step 2, with toluene as solvent, compound concentration is the initiator solution of 0.03fmol/L, with toluene as solvent, the preparation monomer concentration be monomer/catalyst/ligand solution of 10mol/L;
Step 3, the hc-surfactant cetyl trimethylammonium bromide is added in the n-tetradecane, obtain external phase; The add-on of said hc-surfactant cetyl trimethylammonium bromide is 5% of a n-tetradecane quality;
Step 4, under argon shield; Initiator solution described in external phase described in the step 3, the step 2 and monomer/catalyst/ligand solution are injected micro-fluidic chip respectively; Flow velocity through syringe pump control external phase, initiator solution and monomer/catalyst/ligand solution is respectively 0.1 μ L/min, 0.025 μ L/min and 0.025 μ L/min; Make initiator solution and monomer/catalyst/ligand solution mix the back and in external phase, be dispersed into the droplet that volume is 100nL, said droplet is imported in the polyfluortetraethylene pipe that internal diameter is 500 μ m carry out polyreaction then;
Derive the miostagmin reaction liquid in the polyfluortetraethylene pipe described in the step 4 behind step 5, the reaction 24h, separate and remove external phase, after volatilization, washing, centrifugal and lyophilize, obtain final polymerisate poly N-vinyl methane amide single chain polymer successively.
Embodiment 24
Present embodiment is identical with embodiment 23; Wherein difference is: said initiator is alpha-brominated ester (like octadecyl 2-bromo acid ester, 2-bromo acid ten diester, 2-hydroxyethyl-2-bromo acid ester etc.); Perhaps be haloalkane (like trichloromethane, tetracol phenixin, bromo-trichloromethane etc.); Perhaps be benzyl halogenide (like phenylbenzene methylene dichloride, trichlorotoluene zotrichloride, phenyl-chloride ethane etc.); Perhaps being α-Lu Daitong (like trichloroacetone, dichloroacetophenone etc.), perhaps is alpha-halogen nitrile (like 2-chloroethyl nitrile, 2-bromine isopropyl cyanide etc.), perhaps is alkylsulfonyl halogenide (like benzene sulfonyl chloride etc.); The solvent of said initiator solution is water, methyl alcohol, ethanol, Virahol, THF, N; In N N, acetone, dioxan, toluene and the YLENE at least two kinds; Perhaps be methyl alcohol, ethanol, N, N N, THF, acetone, dioxan, Virahol or YLENE; The solvent of said monomer/catalyst/ligand solution is water, methyl alcohol, ethanol, Virahol, THF, N; In N N, acetone, dioxan, toluene and the YLENE at least two kinds; Perhaps be methyl alcohol, ethanol, N, N N, THF, acetone, dioxan, Virahol or YLENE.
The above; It only is preferred embodiment of the present invention; Be not that the present invention is done any restriction, every according to inventing technical spirit to any simple modification, change and equivalent structure variation that above embodiment did, all still belong in the protection domain of technical scheme of the present invention.
Claims (10)
1. a method of utilizing the micro-fluidic chip microdrop technique to prepare single chain polymer is characterized in that, this method may further comprise the steps:
The single chain polymer of step 1, preparation is as required selected initiator, monomer, catalyzer and part, and the mole proportioning of definite monomer, catalyzer and part;
Step 2, initiator described in the step 1 is mixed with the initiator solution that concentration is 0.01fmol/L～10fmol/L, monomer described in the step 1, catalyzer and part are mixed with monomer/catalyst/ligand solution that monomer concentration is 0.1mol/L～10mol/L;
Step 3, tensio-active agent is added in the oil phase, obtain external phase; The add-on of said tensio-active agent is 0.05%～5% of an oil phase quality;
Step 4, under the protection of nitrogen or rare gas element; Initiator solution described in external phase described in the step 3, the step 2 and monomer/catalyst/ligand solution are injected micro-fluidic chip respectively; Flow velocity through syringe pump control external phase is 0.1 μ L/min～100 μ L/min; And the ratio of the flow velocity of control external phase, initiator solution and monomer/catalyst/ligand solution is 4～20: 1: 1; Make initiator solution and monomer/catalyst/ligand solution mix the back and in external phase, be dispersed into the droplet that volume is 10nL～100nL, said droplet is imported in the polyfluortetraethylene pipe that internal diameter is 250 μ m～500 μ m carry out polyreaction then;
After step 5, question response finish, derive the miostagmin reaction liquid in the polyfluortetraethylene pipe described in the step 4, separate and remove external phase, after volatilization, washing, centrifugal and lyophilize, obtain final polymerisate single chain polymer successively.
2. a kind of method of utilizing the micro-fluidic chip microdrop technique to prepare single chain polymer according to claim 1; It is characterized in that initiator described in the step 1 is haloalkane, benzyl halogenide, alpha-brominated ester, α-Lu Daitong, alpha-halogen nitrile, alkylsulfonyl halogenide or Diisopropyl azodicarboxylate.
3. a kind of method of utilizing the micro-fluidic chip microdrop technique to prepare single chain polymer according to claim 1 is characterized in that, monomer described in the step 1 is acrylic amide, propenoate, vinylbenzene, vinylamide, pyridine or vinyl ester monomer.
4. a kind of method of utilizing the micro-fluidic chip microdrop technique to prepare single chain polymer according to claim 1; It is characterized in that; Catalyzer described in the step 1 is cuprous chloride, cuprous bromide or cuprous iodide, perhaps is the mixture of a kind of and xitix, glucose, stannous octoate or hydrazine in copper, cupric chloride and the cupric bromide.
5. a kind of method of utilizing the micro-fluidic chip microdrop technique to prepare single chain polymer according to claim 1; It is characterized in that; Part described in the step 1 is pentamethyl-diethylenetriamine, three [2-(dimethylamino) ethyl] amine, three (2-pyridylmethyl) amine or 4; 4 '-dinonyl-2,2 '-dipyridyl.
6. a kind of method of utilizing the micro-fluidic chip microdrop technique to prepare single chain polymer according to claim 1 is characterized in that the mole proportioning of monomer described in the step 1, catalyzer and part is 50～500: 1～2: 2.
7. a kind of method of utilizing the micro-fluidic chip microdrop technique to prepare single chain polymer according to claim 1; It is characterized in that; The solvent of initiator solution described in the step 2 is water, methyl alcohol, ethanol, Virahol, THF, N; In N N, acetone, dioxan, toluene and the YLENE one or more; The solvent of said monomer/catalyst/ligand solution is water, methyl alcohol, ethanol, Virahol, THF, N, one or more in N N, acetone, dioxan, toluene and the YLENE.
8. a kind of method of utilizing the micro-fluidic chip microdrop technique to prepare single chain polymer according to claim 1 is characterized in that tensio-active agent described in the step 3 is fluorine surfactant, Silicon surfactant or hc-surfactant.
9. a kind of method of utilizing the micro-fluidic chip microdrop technique to prepare single chain polymer according to claim 1 is characterized in that oil phase described in the step 3 is fluorocarbon oil, silicone oil, fluorinated silicone oil or n-tetradecane.
10. a kind of method of utilizing the micro-fluidic chip microdrop technique to prepare single chain polymer according to claim 1 is characterized in that rare gas element described in the step 4 is an argon gas.
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