CN103665387A - Method for preparing accurate polymer network - Google Patents
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Abstract
The invention discloses a method for preparing an accurate polymer network. The number of azide functional groups at the tail end of a polymer is controlled accurately by using a method combining reversible addition-fragmentation chain transfer (RAFT) and click chemistry, so that the number of crosslinking points is controlled and a regular polymer cross-linked network structure is prepared. In the method disclosed by the invention, gel in the polymer network is generated by performing a click reaction on two or more accurately-controlled functional end group azide or alkyne functional groups (E) at the tail end of a polymer chain and two or more end alkynyl or azide functional groups (E) via multiple steps of RAFT. The method has the advantages of accurate controllability of the number of crosslinking points and density of a polymer cross-linked network structure and suitability for various polymer network structures containing different functional groups.
Description
Technical field
The invention belongs to filed of functional, relate to a kind of method of preparing accurate polymer network structure based on molecular designing control polymer ends functional group number.
Background technology
Macromolecule network structure, particularly hydrogel, there is the material of similar quality and performance the most in Shi Yu biological tissue.Hydrogel is that in polymer network gap, some small-molecule substances can move as in microbial film, carry out the transmission of information and material by the crosslinked macromolecule network forming of hydrophilic macromolecule.There is the macromolecule network of high strength, accurate molecular structure and function owing to thering is similar biomembranous function, so thering is the bionical organ of film function, as the aspects such as artificial blood vessel, kidney and skin have important application prospect.Therefore, high-intensity function water gel will have very important effect at following biomedical sector.The gel network of being prepared by traditional free radical polymerisation process, due to crosslinking structure irregularity, stress defect is more, so physical strength is not high.Except mechanical strength is lower, for the gel network in bionic films field, at aspects such as biocompatibility, the adhesion of anti-albumen and stalling characteristics, also has higher requirement.And gelatinous material prepared by traditional method can not meet the requirement of these specific functions, therefore limited the potential application of gelatinous material aspect Biomimetic membranes.
Click chemistry, particularly copper catalysis end be with the cycloaddition reaction (CuAAC) of nitrine/ethynylene group, has advantages of reaction conditions gentleness, transformation efficiency is high, cost is low.Experiment showed, that click chemistry technology can prepare the polymer network structure that molecular structure is regular, physical and mechanical properties is high.At present, by click chemistry method with polyoxyethylene glycol (PEG), poly(lactic acid), polyoxyethylene is that raw material has been prepared various polymer gel networks.Active free radical polymerization (LRP), as atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain transfer free radical polymerization (RAFT), can synthetic molecular weight the accurate macromole of controlled, narrow molecular weight distribution.In addition, LRP reaction conditions is gentle, suitable monomers is extensive, can prepare the high molecular polymer of different topology structure.If by living radical polymerization technique and the effective combination of click chemistry, can prepare the macromolecule network structure that molecular structure is regular, function is definite, this has important meaning for exploring the application of macromolecule network structure in having the bionical device of film function.Should be noted that especially, macromolecular reactive terminal functional group prepared by active free radical polymerization, as monothioester and halogen group, can be converted into easily nitrine and ethynylene group for click chemistry, this provides possibility for click chemistry combines to prepare regular polymer network structure with living radical polymerization technique.Yet by the initiation point of living-radical polymers being carried out to the end group of single functionality, change at present, namely an activity causes nitrine of dot generation or ethynylene group, this can not meet the requirement of preparation gel network polyfunctionality, has greatly limited in conjunction with active free radical polymerization and click chemistry in the application of preparing in functional polymer gel network.
Therefore need to study a kind of method that can accurately control the number of polymer ends nitrine/alkynes, thereby the cross-linking set number of control polymer network structure is prepared the polymer gel structure of compound with regular structure.
Summary of the invention
Technical problem: the invention provides a kind of accurate control cross-linked network structure cross-linking set number and density of realizing, can accurately control the method for the accurate polymer network of preparation of polymer ends functional group number.
Technical scheme: the method for the accurate polymer network of preparation of the present invention, comprises following reactions steps:
A) adopt the double bond monomer (A) that contains function functional group, take azo-bis-isobutyl cyanide as initiator, difunctionality three thioesters
for chain-transfer agent, three's mol ratio is 50:0.05:1～1000:0.2:1, and reaction makes end with the linear polymer (B) of three thioesters functional groups;
B) with N-maleimide
for function monomer, Diisopropyl azodicarboxylate is initiator, and linear polymer prepared by step a) (B) is macromolecular chain transfer agent, and three's mol ratio is 2:0.01:1～100:1:1, makes polymer ends containing the linear polymer (C) of the R ' of functional group;
C) take beta-pinene as monomer, Diisopropyl azodicarboxylate is initiator, the synthetic polymkeric substance (C) of step b) is macromolecular chain transfer agent, and three's mol ratio 2:0.01:1～100:1:1 makes polymer ends containing the linear polymer (D) of beta-pinene functional group and R ' functional group;
D) take line polymer (D) prepared by step c) is macromolecular chain transfer agent, according to step b) and c) method flow, again carry out reversible addition-fragmentation chain transfer free radical polymerization reaction, so repeated multiple times, during each reversible addition-fragmentation chain transfer free radical polymerization reaction, the line polymer (D) generating in reversible addition-fragmentation chain transfer free radical polymerization reaction last time of all take is macromolecular chain transfer agent, thereby finally makes the polymkeric substance (E) that end group contains a plurality of R ' functional group;
E) click chemistry: the polymkeric substance (E) that the end group that step d) is prepared contains a plurality of R ' functional group, with polymkeric substance (F), chemical reaction occurs to click, obtain regular cross-linked network structure, polymkeric substance F) high polymer for containing two or more nitrine, alkynyl or sulfydryl, its molecular weight is 500～20000.
In the inventive method, monomer (A) is NIPA, pentafluorostyrene, Sodium styrene sulfonate, Styrene and its derivatives, tert-butyl acrylate, methyl methacrylate, methacrylic acid dihydroxy ethyl ester, 2-(dimethylamine) any in ethyl-methyl acrylate, vinyl cyanide.
In the inventive method, difunctionality three thioesters in step a)
r functional group is wherein ethylene glycol isopropyl acid esters, ethylene glycol isopropyl acid ester derivative or to benzene diisopropyl acyl, Z substituting group is phenyl ring or alkyl, and ethylene glycol isopropyl acid ester derivative is polyoxyethylene glycol isobutyrate, propylene glycol isobutyrate or butyleneglycol isobutyrate.
In the inventive method, the N-maleimide in step b)
on substituent R ' be halohydrocarbon or alkynyl.
In the inventive method, the molecular weight of the linear polymer preparing in step a) (B) is 1000～60000, and molecular weight distribution coefficient is 1.09～1.10.
In the inventive method, the number that polymkeric substance (E) end contains R ' functional group is by controlling the number of times of reversible addition-fragmentation chain transfer free radical polymerization reaction, i.e. repeating step c) reach to the number of times of step d).
In the inventive method, monomer (A) is prepared polymer chain (B) by reversible addition-fragmentation chain transfer free radical polymerization, and employing azo-bis-isobutyl cyanide is initiator, 40～70 ℃ of temperature of reaction, react to the scheduled time, molecular weight is at 2000-6000, and distribution coefficient is between 1.09-1.10.
Above-mentioned chain-transfer agent is that trithiocarbonate functional group is contained at two ends
chain-transfer agent, R functional group can be that ethylene glycol isopropyl acid esters and derivative thereof are as polyoxyethylene glycol isobutyrate, propylene glycol isobutyrate, butyleneglycol isobutyrate etc., with to benzene diisopropyl acyl etc., Z substituting group is phenyl ring or alkyl, and wherein preferably R group is ethylene glycol isopropyl acid esters, and Z group is dodecyl.
Adopt N-maleimide
for monomer, azo-bis-isobutyl cyanide, polymer chain (B) is that macromolecular chain transfer agent is in organic solvent, 40～70 ℃ of temperature of reaction, in 12～24 hours reaction times, make two ends respectively containing the linear polymer of a 3-bromopropyl maleimide, and molecular weight distribution coefficient is between 1.09-1.10.
Employing beta-pinene is monomer, azo-bis-isobutyl cyanide, by above-mentioned two ends, containing the linear polymer of a 3-bromopropyl maleimide, be respectively that macromolecular chain transfer agent is in organic solvent, 40～70 ℃ of temperature of reaction, 12～24 hours reaction times, make two ends and respectively contain the linear polymer of firpene, molecular weight distribution coefficient is between 1.09-1.10.
Repeatedly repeat above two steps, make the linear polymer (E) that end at least respectively contains two or more N-maleimide amine functional groups.
N-maleimide
substituent R ' be halohydrocarbon, alkynyl etc.
The optional toluene of solvent, methyl-phenoxide, 1,2-ethylene dichloride, N, N '-dimethyl formamide, tetrahydrofuran (THF).
If the linear polymer that end is contained to N-bromopropyl maleimide, the lower reaction of 60 ℃ of conditions of toluene solution of excessive Diisopropyl azodicarboxylate 12～24 hours, removes end thioesters.The polymkeric substance of gained and sodiumazide mol ratio 1:10, at N, react in N '-dimethyl formamide solution, and 30～60 ℃ of temperature of reaction are reacted 24～48 hours, make end and contain two or more azido polymers.
Azido-, alkynyl and a sulfydryl are at least respectively contained in polymkeric substance (F) two ends, as respectively contained the polyoxyethylene glycol of an alkynyl in two ends.Macrogol ester containing alkynyl is to be made by polyoxyethylene glycol and the esterification of 3-propargyl bromide.
By above-mentioned monomer (E) with (F) under catalyst system effect, click, form regular polymer network.Wherein E and F mol ratio are preferentially selected azido-: alkynyl mol ratio is 1:1.
Catalyzer is transition-metal catalyst, can adopt Fe-series catalyst, rhodium series catalysts as RhCl(PPh3) etc., lithium molybdenum (V) complex systems, rhenium system's (V) catalyzer or Cu-series catalyst, as cuprous bromide or cuprous chloride.Preferred cuprous bromide.
Part is nitrogenous polydentate ligand system, as 2, and 2 '-dipyridyl and derivative thereof or N, N, N ', N ' ', N ' '-five methyl diethylentriamine, Tetramethyl Ethylene Diamine 1, Isosorbide-5-Nitrae, 7,10,10 – hexamethyl Triethylenetetramine (TETA)s (HMTETA) and three (N, N-dimethyl aminoethyl) amine, N-n-hexyl-2 pyridinyl carboxamide.Preferred N, N, N ', N ' ', N ' '-five methyl diethylentriamine.
Solvent can be selected from toluene, ethyl acetate, methyl-phenoxide, 1,2-ethylene dichloride, N, N '-dimethyl formamide, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane.Preferred N, N '-dimethyl formamide, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane.
Excessive metalcatalyzing agent in the crosslinked polymer network structure obtaining by aforesaid method can be gone out with EDTA solution.Obtain colorless transparent gel.
Regularity polymer network structure prepared by the inventive method, its regularity structure is through reversible addition-fragmentation chain transfer free radical polymerization (RAFT), to form on the basis based on molecular designing.
Beneficial effect: the present invention compared with prior art, has the following advantages:
1. the macromolecule network that the present invention has accurate molecular structure and a controllable function for preparing in conjunction with click chemistry (CuAAC) and active free radical polymerization (RAFT) provides a kind of feasible method;
The present invention first ingenious utilize maleimide and firpene can not autohemagglutination and RAFT polymerization can repeat the characteristic that multistep causes, accurately functional group is controllably introduced to macromole desired location.This method that accurately regulates and controls macromole functional group number and molecular structure in the accurate synthetic technology of macromole that is based upon is that traditional technology is difficult to realize.
3. method of the present invention can accurately be controlled functional group at macromole specified location simply and easily, thereby can prepare function and the accurate polymer gel network of controlling of molecular topology structure, and this mode that is simple functional group changes was in the past inaccessiable.
4. the polymer gel network that prepared by the present invention, fully combines the feature of the reaction of RAFT active free radical polymerization and click chemistry.Gel network prepared by this method has that molecular structure is regular, molecular topology structure is various and the accurate controlled feature of function, and this is that existing method has no idea to realize.
5. the method for preparing compound with regular structure high-performance gel network that the present invention develops, for the application of gelatinous material in bionic membrane material field provides possibility.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail.Scope of the present invention is not limited with embodiment, but is limited by the scope of claim.
The method of preparing regular polymer network of the present invention, comprises following reactions steps:
Embodiment 1: the preparation of polystyrene/polyoxyethylene glycol amphipathic gel
A) accurately take dodecyl trithio isopropylformic acid 3g, 1-ethyl-(3-dimethylamino-propyl) carbodiimide hydrochloride 3.1642g, is dissolved in 80ml methylene dichloride, stirs 10 minutes in nitrogen atmosphere.Add again ethylene glycol 0.255g reaction 24 hours.After reaction finishes, reaction solution is used respectively 1mol/L sodium bicarbonate and distilled water wash three times, organic phase anhydrous magnesium sulfate drying, after being filtered, anhydrous magnesium sulfate removes methylene dichloride with Rotary Evaporators, crude product is separated with chromatography column, eluent is normal hexane: methylene dichloride=1:1, obtains two dodecyl trithiocarbonate 1.3g.
The RAFT polymerization of polystyrene: take vinylbenzene 0.833ml as monomer, azo-bis-isobutyl cyanide (0.00119g) is initiator, two dodecyl trithiocarbonate (0.09558g) are chain-transfer agent, mol ratio is 50:0.05:1, temperature of reaction is 60 ℃, 9 hours reaction times, add the long-pending tetrahydrofuran (THF) dissolved product of monoploid, the tetrahydrofuran (THF) that is dissolved with product is added drop-wise in the methyl alcohol of 20 times of volumes, make product precipitation, filter, then vacuum-drying to constant weight obtains end with the polystyrene of three thioesters functional groups;
B) accurately take maleic anhydride 6.72g and 3-propantheline bromide hydrobromide 15g is dissolved in 200ml methylene dichloride, at 0 ℃, slowly drip 10.5ml triethylamine, be slowly warming up to room temperature, stir 2.5 hours.With Rotary Evaporators, remove methylene dichloride, solid is dissolved in methylene dichloride and drips 1.25ml Hydrogen bromide, stir half an hour.With the hydrobromic acid solution washing of 1mol/L, the organic layer that extraction obtains spends the night with anhydrous magnesium sulfate drying.Anhydrous magnesium sulfate is filtered, adopt Rotary Evaporators to remove methylene dichloride and obtain white solid 10g.Accurately take above-mentioned white solid 6.21g, anhydrous sodium acetate 1.1g, is dissolved in 65ml diacetyl oxide, and under 110 ℃ of conditions, condensing reflux is 24 hours.Reaction solution is poured in the sodium hydroxide solution of 400ml1mol/L and be adjusted to pH=7.0, with dichloromethane extraction, obtain anhydrous magnesium sulfate drying 8 hours for organic layer.Anhydrous magnesium sulfate is filtered, with Rotary Evaporators, remove methylene dichloride, crude product is separated with chromatography column, and eluent is methylene dichloride, obtains the finished product 1.2g.
Polystyrene/N-3-bromopropyl maleimide amine copolymer: the N-3-bromopropyl maleimide 0.0248g of take is monomer, Diisopropyl azodicarboxylate (0.00009g) is initiator, above-mentioned steps 1) synthetic end is macromolecular chain transfer agent with the polystyrene 0.35g of three thioesters functional groups, mol ratio is 2:0.01:1, be dissolved in toluene solvant 1ml, temperature of reaction is 60 ℃, 24 hours reaction times, add appropriate tetrahydrofuran (THF) dissolved product, the tetrahydrofuran (THF) that is dissolved with product is added drop-wise in the methyl alcohol of 20 times of volumes, make product precipitation, filter, then vacuum-drying to constant weight obtains end with polystyrene/N-3-bromopropyl maleimide copolymer of three thioesters functional groups.
C) polystyrene end/N-3-bromopropyl maleimide/beta-pinene copolymerization: take beta-pinene 0.019ml as monomer, Diisopropyl azodicarboxylate (0.00005g) is initiator, above-mentioned synthetic polystyrene/N-3-bromopropyl maleimide copolymer (0.2g) is macromolecular chain transfer agent, mol ratio is 2:0.01:1, be dissolved in 1, in 2-ethylene dichloride 2ml solvent, temperature of reaction is 60 ℃, 24 hours reaction times, add appropriate tetrahydrofuran (THF) dissolved product, the tetrahydrofuran (THF) that is dissolved with product is added drop-wise in the methyl alcohol of 20 times of volumes, make product precipitation, filter, then vacuum-drying to constant weight obtains end with polystyrene/N-3-bromopropyl maleimide/beta-pinene multipolymer of three thioesters functional groups.
D) take the polymer macromolecule of preparing is macromolecular chain transfer agent, and alternately execution step (b) and (c), by the control of polymerization procedure number of times, prepares the polymkeric substance that end group has the bromo functional groups end group of exact number.
E) preparation of end alkynyl radical PEG: accurately take PEG(M under room temperature condition
n=2000) and sodium hydride 0.432g be dissolved in 50ml anhydrous tetrahydro furan solvent, in nitrogen atmosphere, stir 3 hours, accurately take propine bromine (2ml) and be dissolved in 20ml anhydrous tetrahydro furan.Under 0 ℃ of condition, utilize constant voltage ground liquid funnel by approximately (20 minutes) in being slowly added dropwise to polyoxyethylene glycol tetrahydrofuran solution under propine bromine tetrahydrofuran solution.Slowly be warming up to room temperature, under magnetic agitation, react 12 hours.Obtain product and remove sodium hydride with neutral alumina and diatomite, with rotary evaporation, remove tetrahydrofuran (THF), resultant product precipitates in ether, obtains white powder 4.5g.
Click chemistry is prepared Vinyl ether structure: brominated hydrophobic polymer prepared by step d) is at N, and N '-dimethyl formamide makes the hydrophobic polymer containing nitrine with the sodiumazide replacement of ten times; The hydrophobic polymer that above-mentioned end is contained to four Ge Heliuge nitrine functional groups respectively with end alkynyl radical macrogol ester (M
n=2000) 0.16g/0.24g is dissolved in 1ml methylene dichloride and makes polymer dissolution, respectively be added on wherein 0.002g/0.003gCuBr catalysis and 10 μ l/15 μ lN, N, N ', N ' ', N ' '-five methyl diethylentriamine (PMDETA), sonic oscillation 2 minutes, under 50 ℃ of conditions, react 12 hours, make gel.
Embodiment 2: the preparation of polystyrene/polyoxyethylene glycol amphipathic gel
Basic procedure and operation are with embodiment 1, and difference is:
In step a), styrene monomer is 16.6ml, and initiator azo-bis-isobutyl cyanide is 0.476g;
In step b), N-3-bromopropyl maleimide is got 1.42g, and initiator azo-bis-isobutyl cyanide is 0.09g;
In step c), beta-pinene is got 4.75ml, and initiator Diisopropyl azodicarboxylate is got 0.05g.
All the other and embodiment 1 are in full accord.
Embodiment 3: the preparation of polystyrene/polyoxyethylene glycol amphipathic gel
Basic procedure and operation are with embodiment 1, and difference is:
In step a), styrene monomer is 5ml, and initiator azo-bis-isobutyl cyanide is 0.003g;
In step b), N-3-bromopropyl maleimide 0.124g, initiator azo-bis-isobutyl cyanide is 0.0009g;
In step c), beta-pinene 0.095ml, initiator Diisopropyl azodicarboxylate (0.0005g).
All the other and embodiment 1 are in full accord.
Embodiment 4: the preparation of polyacrylic acid pH response gel
A) accurately take dodecyl trithio isopropylformic acid 3g, 1-ethyl-(3-dimethylamino-propyl) carbodiimide hydrochloride 3.1642g, is dissolved in 80ml methylene dichloride, stirs 10 minutes in nitrogen atmosphere.Add again ethylene glycol 0.255g reaction 24 hours.After reaction finishes, reaction solution is used respectively 1mol/L sodium bicarbonate and distilled water wash three times, organic phase anhydrous magnesium sulfate drying, after being filtered, anhydrous magnesium sulfate removes methylene dichloride with Rotary Evaporators, crude product is separated with chromatography column, eluent is normal hexane: methylene dichloride=1:1, obtains final product 1.3g.
The RAFT polymerization of the polyacrylic acid tert-butyl ester: take tert-butyl acrylate as monomer 5ml, azo-bis-isobutyl cyanide (0.001885g) is initiator, two dodecyl trithiocarbonate (0.0857g) are chain-transfer agent, mol ratio is 300:0.2:1, temperature of reaction is 60 ℃, 9 hours reaction times, add the long-pending tetrahydrofuran (THF) dissolved product of monoploid, the tetrahydrofuran (THF) that is dissolved with product is added drop-wise in methanol/water (volume ratio 1::1) solution, make product precipitation, filter, then vacuum-drying to constant weight obtains end with the polyacrylic acid tert-butyl ester of three thioesters functional groups;
B) maleic anhydride 10.3g is dissolved in 50mL acetone, is placed in the round-bottomed flask of 250mL, 3-propargylamine 5.8g is dissolved in 25mL acetone, then with dropping funnel, is dropwise added drop-wise to round-bottomed flask, ice bath.After reaction 1h, acetone is removed in underpressure distillation, recrystallization in methyl alcohol then, and suction filtration, dry, obtain intermediate N butyl maleinamic acid.
In the round-bottomed flask of 100mL, add N-proyl maleinamic acid 17.1g and 7g anhydrous sodium acetate, 50mL diacetyl oxide.In 80oC oil bath, react 1h, pour in 150mL frozen water and stir, slowly add the pH of anhydrous Na OH regulator solution to neutral.Then use 30mL dichloromethane extraction three times, anhydrous anhydrous magnesium sulfate drying mistake for organic phase.Anhydrous magnesium sulfate is filtered, with Rotary Evaporators, remove methylene dichloride, crude product is separated with chromatography column, and eluent is methylene dichloride, obtains the finished product 1.2g.
The polyacrylic acid tert-butyl ester/N-propargyl maleimide amine copolymer: the N-propargyl maleimide 0.071g of take is monomer, Diisopropyl azodicarboxylate (0.0009g) is initiator, the synthetic polyacrylic acid tert-butyl ester 0.35g of above-mentioned steps (1) is macromolecular chain transfer agent, mol ratio is 10:0.1:1, be dissolved in toluene solvant 1ml, temperature of reaction is 60 ℃, 24 hours reaction times, add appropriate tetrahydrofuran (THF) dissolved product, the tetrahydrofuran (THF) that is dissolved with product is added drop-wise in methanol/water (volume ratio 1::1) solution, make product precipitation, filter, then vacuum-drying to constant weight obtains end with polystyrene/N-propargyl maleimide copolymer of three thioesters functional groups,
C) the polyacrylic acid tert-butyl ester/N-3-propargyl maleimide/beta-pinene copolymerization: take beta-pinene 0.095ml as monomer, Diisopropyl azodicarboxylate (0.0005g) is initiator, above-mentioned synthetic polystyrene/N-3-propargyl maleimide copolymer (0.2g) is macromolecular chain transfer agent, mol ratio is 10:0.1:1, be dissolved in 1, in 2-ethylene dichloride 2ml solvent, temperature of reaction is 60 ℃, 24 hours reaction times, add appropriate tetrahydrofuran (THF) dissolved product, the tetrahydrofuran (THF) that is dissolved with product is added drop-wise to methanol/water (volume ratio 1:1), make product precipitation, filter, then vacuum-drying to constant weight obtains end with polystyrene/N-3-bromopropyl maleimide/beta-pinene multipolymer of three thioesters functional groups,
D) repeating step b) and c), preparing end contains and respectively contains four and six polymkeric substance that alkynyl can be rolled into a ball.
E) in 100ml flask, accurately take the PEGM of double head belt epoxy-functional
n=20005g, sodiumazide 3.25g, ammonium chloride 0.27g is dissolved in 40mlN, and the mixed solvent of N '-dimethyl formamide/water (volume ratio 1:1) stirs 24 hours under 50 ℃ of conditions.Reaction finishes rear with dichloromethane extraction, uses anhydrous magnesium sulfate drying 12 hours, filters anhydrous magnesium sulfate, and filtrate is removed methylene dichloride with Rotary Evaporators, vacuum-drying.
Click chemistry is prepared pH responsive polymer network structure: prepared by step d) respectively containing four, each 0.1g of tert-butyl acrylate polymkeric substance of six alkynyls respectively with end azido-macrogol ester (M
n=2000) 0.16g/0.24g is dissolved in 1ml methylene dichloride and makes polymer dissolution, brother is added on 0.002g/0.003gCuBr catalysis and 10 μ l/15 μ lN wherein, N, N ', N ' ', N ' '-five methyl diethylentriamine (PMDETA), sonic oscillation 2 minutes, under 50 ℃ of conditions, react 12 hours, make gel.The gel making is put into 100ml flask in the abundant swelling of 50ml anhydrous methylene chloride, drips 4ml trifluoroacetic acid hydrolysis and stirs six hours, with methylene dichloride, cleans.Make poly propenoic acid ethylene glycol pH responsive gel.
Embodiment 5: the preparation of poly N-isopropyl acrylamide/polyoxyethylene glycol thermo-responsive hydro gel
Basic procedure and operation are with embodiment 4, and difference is:
In step a), take NIPA as monomer, get 0.390g, in methyl alcohol, dissolve, sedimentation and filtration in ether, finally makes end Dai San thioesters functional group poly N-isopropyl acrylamide;
In step b), polymkeric substance dissolves in methyl alcohol, and sedimentation and filtration in ether finally makes end with poly N-isopropyl acrylamide/N-propargyl maleimide copolymer of three thioesters functional groups;
In step c), polymkeric substance dissolves in methyl alcohol, and sedimentation and filtration in ether finally makes end with poly N-isopropyl acrylamide/N-propargyl maleimide/beta-pinene multipolymer of three thioesters functional groups;
In step e), gel does not need to use trifluoroacetic acid hydrolysis.
All the other and embodiment 4 are in full accord.
Embodiment 6: the preparation of poly-pentafluorostyrene/polyoxyethylene glycol amphipathic gel
Basic procedure and operation are with embodiment 1, and difference is:
In step a), take pentafluorostyrene as monomer, get 0.421g, in tetrahydrofuran (THF), dissolve, sedimentation and filtration in methyl alcohol, finally end processed is with the poly-pentafluorostyrene of three thioesters functional groups;
In step b), polymkeric substance dissolves in tetrahydrofuran (THF), and sedimentation and filtration in methyl alcohol finally makes end with poly-pentafluorostyrene/N-3-bromopropyl maleimide copolymer of three thioesters functional groups;
In step c), polymkeric substance dissolves in tetrahydrofuran (THF), and sedimentation and filtration in methyl alcohol finally makes end with poly-pentafluorostyrene/N-3-bromopropyl maleimide/beta-pinene multipolymer of three thioesters functional groups;
All the other and embodiment 1 are in full accord.
Embodiment 7: the preparation of sodium polystyrene sulfonate/polyoxyethylene glycol ionic gel
Basic procedure and operation are with embodiment 4, and difference is:
In step a), Sodium styrene sulfonate is 0.709g, in methyl alcohol, dissolves, and sedimentation and filtration in ether, finally makes end Dai San thioesters functional group sodium polystyrene sulfonate;
In step b), polymkeric substance dissolves in methyl alcohol, and sedimentation and filtration in ether finally makes the end Dai San thioesters sodium polystyrene sulfonate/N-of functional group propargyl maleimide copolymer;
In step c), polymkeric substance dissolves in methyl alcohol, and sedimentation and filtration in ether finally makes the end Dai San thioesters polystyrolsulfon acid/N-of functional group propargyl maleimide sodium/beta-pinene multipolymer;
In step e), gel does not need to use trifluoroacetic acid hydrolysis.
All the other and embodiment 4 are in full accord.
Embodiment 8: the preparation of polymethylmethacrylate/polyoxyethylene glycol thermo-responsive hydro gel
Basic procedure and operation are with embodiment 4, and difference is:
In step a), methyl methacrylate 0.344g dissolves in tetrahydrofuran (THF), and methanol extraction filters, and finally makes end Dai San thioesters functional group polymethylmethacrylate;
In step b), polymkeric substance dissolves in tetrahydrofuran (THF), and sedimentation and filtration in methyl alcohol finally makes the end Dai San thioesters polymethylmethacrylate/N-of functional group propargyl maleimide copolymer;
In step c), polymkeric substance dissolves in tetrahydrofuran (THF), and sedimentation and filtration in methyl alcohol finally makes the end Dai San thioesters polymethylmethacrylate/N-of functional group propargyl maleimide/beta-pinene multipolymer
In step e), gel does not need to use trifluoroacetic acid hydrolysis.
All the other and embodiment 4 are in full accord.
Embodiment 9: the preparation of polymethyl acrylic acid dihydroxy ethyl ester/polyoxyethylene glycol thermo-responsive hydro gel
Basic procedure and operation are with embodiment 1, and difference is:
In step a), the methacrylic acid dihydroxy ethyl ester of take is monomer, gets 0.448g, in tetrahydrofuran (THF), dissolve, and sedimentation and filtration in methyl alcohol, finally end processed is with the polymethyl acrylic acid dihydroxy ethyl ester of three thioesters functional groups;
In step b), polymkeric substance dissolves in tetrahydrofuran (THF), and sedimentation and filtration in methyl alcohol finally makes end with polymethyl acrylic acid dihydroxy ethyl ester/N-3-bromopropyl maleimide copolymer of three thioesters functional groups;
In step c), polymkeric substance dissolves in tetrahydrofuran (THF), and sedimentation and filtration in methyl alcohol finally makes end with polymethyl acrylic acid dihydroxy ethyl ester/N-3-bromopropyl maleimide/beta-pinene multipolymer of three thioesters functional groups;
All the other and embodiment 1 are in full accord.
Embodiment 10: the poly-2-(dimethylamine) preparation of ethyl-methyl acrylate/polyoxyethylene glycol thermo-responsive hydro gel
Basic procedure and operation are with embodiment 4, and difference is:
In step a), take 2-(dimethylamine) ethyl-methyl acrylate is monomer, gets 0.689g, in tetrahydrofuran (THF), dissolve, sedimentation and filtration in methyl alcohol, finally end processed is with the poly-2-(dimethylamine of three thioesters functional groups) ethyl-methyl acrylate;
In step b), polymkeric substance dissolves in tetrahydrofuran (THF), and sedimentation and filtration in methyl alcohol finally makes end with the poly-2-(dimethylamine of three thioesters functional groups) ethyl-methyl acrylate/N-propargyl maleimide copolymer;
In step c), polymkeric substance dissolves in tetrahydrofuran (THF), and sedimentation and filtration in methyl alcohol finally makes end with the poly-2-(dimethylamine of three thioesters functional groups) ethyl-methyl acrylate/N-propargyl maleimide/beta-pinene multipolymer;
In step e), gel does not need to use trifluoroacetic acid hydrolysis.
All the other and embodiment 4 are in full accord.
Embodiment 11: the preparation of polyacrylonitrile/polyoxyethylene glycol thermo-responsive hydro gel
Basic procedure and operation are with embodiment 4, and difference is:
In step a), take vinyl cyanide as monomer, get 0.526g, in tetrahydrofuran (THF), dissolve, sedimentation and filtration in methyl alcohol, finally end processed is with the polyacrylonitrile of three thioesters functional groups;
In step b), polymkeric substance dissolves in tetrahydrofuran (THF), and sedimentation and filtration in methyl alcohol finally makes end with polyacrylonitrile/N-propargyl maleimide copolymer of three thioesters functional groups;
In step c), polymkeric substance dissolves in tetrahydrofuran (THF), and sedimentation and filtration in methyl alcohol finally makes end with polyacrylonitrile/N-propargyl maleimide/beta-pinene multipolymer of three thioesters functional groups;
In step e), gel does not need to use trifluoroacetic acid hydrolysis.
All the other and embodiment 4 are in full accord.
Claims (6)
1. a method of preparing accurate polymer network, is characterized in that, the method comprises following reactions steps:
A) adopt the double bond monomer (A) that contains function functional group, take azo-bis-isobutyl cyanide as initiator, difunctionality three thioesters
for chain-transfer agent, three's mol ratio is 50:0.05:1～1000:0.2:1, and reaction makes end with the linear polymer (B) of three thioesters functional groups;
B) with N-maleimide
for function monomer, Diisopropyl azodicarboxylate is initiator, and linear polymer prepared by described step a) (B) is macromolecular chain transfer agent, and three's mol ratio is 2:0.01:1～100:1:1, makes polymer ends containing the linear polymer (C) of the R ' of functional group;
C) take beta-pinene as monomer, Diisopropyl azodicarboxylate is initiator, the synthetic polymkeric substance (C) of described step b) is macromolecular chain transfer agent, and three's mol ratio 2:0.01:1～100:1:1 makes polymer ends containing the linear polymer (D) of beta-pinene functional group and R ' functional group;
D) take line polymer (D) prepared by described step c) is macromolecular chain transfer agent, according to step b) and c) method flow, again carry out reversible addition-fragmentation chain transfer free radical polymerization reaction, so repeated multiple times, during each reversible addition-fragmentation chain transfer free radical polymerization reaction, the line polymer (D) generating in reversible addition-fragmentation chain transfer free radical polymerization reaction last time of all take is macromolecular chain transfer agent, thereby finally makes the polymkeric substance (E) that end group contains a plurality of R ' functional group;
E) click chemistry: the polymkeric substance (E) that the end group that described step d) is prepared contains a plurality of R ' functional group, with polymkeric substance (F), chemical reaction occurs to click, obtain regular cross-linked network structure, described polymkeric substance F) high polymer for containing two or more nitrine, alkynyl or sulfydryl, its molecular weight is 500～20000.
2. the method for the accurate polymer network of preparation according to claim 1, it is characterized in that, the monomer in described step a) (A) is NIPA, pentafluorostyrene, Sodium styrene sulfonate, Styrene and its derivatives, tert-butyl acrylate, methyl methacrylate, methacrylic acid dihydroxy ethyl ester, 2-(dimethylamine) any in ethyl-methyl acrylate, vinyl cyanide.
3. the method for the accurate polymer network of preparation according to claim 1, is characterized in that, difunctionality three thioesters in described step a)
r functional group is wherein ethylene glycol isopropyl acid esters, ethylene glycol isopropyl acid ester derivative or to benzene diisopropyl acyl, Z substituting group is phenyl ring or alkyl, and described ethylene glycol isopropyl acid ester derivative is polyoxyethylene glycol isobutyrate, propylene glycol isobutyrate or butyleneglycol isobutyrate.
4. the method for the accurate polymer network of preparation according to claim 1, is characterized in that, the N-maleimide in described step b)
on substituent R ' be halohydrocarbon or alkynyl.
5. according to the method for the accurate polymer network of preparation described in claim 1,2,3 or 4, it is characterized in that, the molecular weight of the linear polymer preparing in described step a) (B) is 1000～60000, and molecular weight distribution coefficient is 1.09～1.10.
6. according to the method for the accurate polymer network of preparation described in claim 1,2,3 or 4, it is characterized in that, the number that described polymkeric substance (E) end contains R ' functional group is by the number of times of control reversible addition-fragmentation chain transfer free radical polymerization reaction, i.e. repeating step c) reach to the number of times of step d).
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