CN101492520A - Diblock copolymer containing full-fluorine cyclobutyl aryl aether block and uses thereof - Google Patents
Diblock copolymer containing full-fluorine cyclobutyl aryl aether block and uses thereof Download PDFInfo
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- CN101492520A CN101492520A CNA2009100469884A CN200910046988A CN101492520A CN 101492520 A CN101492520 A CN 101492520A CN A2009100469884 A CNA2009100469884 A CN A2009100469884A CN 200910046988 A CN200910046988 A CN 200910046988A CN 101492520 A CN101492520 A CN 101492520A
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Abstract
The invention provides a bi-block polymer containing perfluorocyclobutyl aryl ether-based polymer, a preparation method thereof and application thereof. The preparation method comprises two reaction steps: firstly, a macroinitiator formed through atom transfer radical polymerization is prepared; and then the macroinitiator is used for initiating an acrylic ester monomer and a metacrylic acid ester monomer, which contain perfluorocyclobutyl aryl ether structures, to carry out the atom transfer radical polymerization, thus obtaining the diblock polymer containing the perfluorocyclobutyl aryl ether-based polymer. The obtained diblock polymer can be used for preparing an aggregate with microscopic shape and can be potentially applied to such fields as a pollution-resistant reagent, a surfactant, an emulsifier, a drug carrier, photoconductive materials, photonic crystals, etc.
Description
Technical field
The present invention relates to contain bi-block copolymer, the Preparation method and use of perfluorocyclobutanearyl aryl-ether polymer blocks.
Background technology
The perfluorocyclobutanearyl aryl-ether polymkeric substance is by the researchist of DOW Chemical (Dow Chemical Co.) the new fluoropolymer of a class in exploitation in 1993.The polymkeric substance of perfluorocyclobutanearyl aryl-ether has not only improved the processing characteristics of fluoropolymer, and traditional premium properties with fluoropolymer, as low-k, agent of low hygroscopicity, high thermal stability, high anti-oxidation ability, high dn/dT value, low-birefringence and outstanding optical transparence, the potential application prospect is arranged in the fields such as proton exchange membrane of photoconductive fiber, polymer LED, nonlinear optical material, liquid crystal, aeroplane dope and fuel cell.In recent years, the perfluorocyclobutanearyl aryl-ether polymkeric substance of preparation ad hoc structure has attracted the interest of some research groups with the research that obtains specified property.Smith group with the perfluorocyclobutanearyl aryl-ether polymer thin membrane prepare of 100 micron thickness the optical diffraction gratings (580 nanometer) of submicron of photoconductive fiber structure; Jiang group prepares array photoconduction optical grating construction with perfluorocyclobutanearyl aryl-ether polymkeric substance and covering material and is used for making the wideband WDM device.
Segmented copolymer is connected to form by the different polymer blocks of chemical structure, and because polymer blocks has different physical propertiess, block polymer can carry out the aggregate that self-assembly forms nano-scale on molecular scale, thereby has special performances.Preparation has the segmented copolymer that different blocks are formed, and obtains cheapness and the novel material with specified property, is the target that many scientists pursue.The polymkeric substance of perfluorocyclobutanearyl aryl-ether research in recent years mainly concentrates on uses different trifluoro vinyl aryl ethers monomer polymerizations to synthesize different homopolymer and random copolymers by the perfluorocyclobutanearyl connection, and the segmented copolymer that contains the perfluorocyclobutanearyl aryl-ether block for preparing ad hoc structure simultaneously also begins to cause researchist's concern.Inventor group has prepared the polymkeric substance based on ABA three blocks of perfluorocyclobutanearyl aryl-ether polymkeric substance.Smith group has prepared perfluorocyclobutanearyl aryl-ether polymkeric substance and polyethylene oxide bi-block copolymer.
The more than synthetic method that contains the segmented copolymer of perfluorocyclobutanearyl polymer blocks is used the monomeric thermal cyclization polymerization of trifluoro vinyl aryl ethers, because higher relatively polymerization temperature (＞150 ℃) and unique polymerization mechanism, connect the design and synthetic being restricted of the functional group of trifluoro vinyl in the monomer, the preparation of segmented copolymer is difficulty.Recent two decades comes, and active free radical polymerization does not lose the superiority of radical polymerization again because of its ability that can either keep ionic living polymerization control reaction, has obtained fast development.The active free radical polymerization method of comparative maturity has: nitroxyl free radical regulation and control polymerization (NOMRP), atom transfer radical polymerization (ATRP) and reversible addition-fracture chain transfer polymerization (RAFT).The monomer scope that atom transfer radical polymerization is suitable for is wide, reaction conditions is gentle, uses the most extensive.And since atom transfer radical polymerization can controlling polymers molecular weight and molecular weight distribution, obtain the polymkeric substance of specified molecular weight and narrow molecular weight distribution, thereby can the chemical structure of polymkeric substance be control effectively, be widely used in the synthetic of segmented copolymer and graft copolymer.
Inventor group has prepared new esters of acrylic acid that contains the perfluorocyclobutanearyl aryl-ether structure and the methyl acrylic ester monomer 2 of a class, has the activity of good radical polymerization and active free radical polymerization.Utilize the molecular designing ability of atom transfer radical polymerization, in conjunction with other vinyl monomer or polymkeric substance, use monomer 2 to carry out the segmented copolymer that atom transfer radical polymerization is equipped with the particular chemical structure, obtain to have the perfluorocyclobutanearyl aryl-ether polymkeric substance of new performance and application.Based on this, the at first synthetic atom transfer radical polymerization macromole evocating agent 1 of the present invention, and the atom transfer radical polymerization of use macromole evocating agent 1 trigger monomer 2 obtain the novel di-block copolymer that contains the perfluorocyclobutanearyl aryl-ether polymer blocks.
Wherein: X is :-Cl or-Br; R
1Functional group is halogen, C
1～C
4Alkyl, C
1～C
4Alkoxyl group, phenyl, C
1～C
4Alkyl phenyl, C
1～C
4Alkoxyl phenyl, trifluoro-ethylene oxygen base phenyl ,-SO
2Ph ,-cumyl or-C (CF
3)
2Ph; R
2Functional group is-H or-CH
3M is 1～10 integer.
Summary of the invention
The object of the invention provides a kind of bi-block copolymer that contains the perfluorocyclobutanearyl aryl-ether polymer blocks;
Purpose of the present invention also provides a kind of above-mentioned preparation method who contains the bi-block copolymer of perfluorocyclobutanearyl aryl-ether polymer blocks;
Another object of the present invention provides a kind of above-mentioned purposes that contains the bi-block copolymer of perfluorocyclobutanearyl aryl-ether polymer blocks, preparation has the aggregate of microscopic appearance, in fields such as anti-soil reagent, tensio-active agent, emulsifying agent, pharmaceutical carrier, light-guide material, photonic crystals potential application is arranged.
Content of the present invention is the macromole evocating agent 1 that at first prepares atom transfer radical polymerization, use macromole evocating agent 1 to cause the esters of acrylic acid and the methyl acrylic ester monomer 2 that contain the perfluorocyclobutanearyl aryl-ether structure then and carry out atom transfer radical polymerization, obtain containing the bi-block copolymer of perfluorocyclobutanearyl aryl-ether polymer blocks.
The bi-block copolymer that contains the perfluorocyclobutanearyl aryl-ether polymer blocks provided by the present invention has following structure:
Wherein
For: polymer blocks such as polyethylene oxide, polystyrene, polyacrylic ester, polymethacrylate, polyacrylamide or PMAm;
R
1For: halogen, C
1～C
4Alkyl, C
1～C
4Alkoxyl group, phenyl, C
1～C
4Alkyl phenyl, C
1～C
4Alkoxyl phenyl, trifluoro-ethylene oxygen base phenyl ,-SO
2Ph ,-cumyl or-C (CF
3)
2Ph;
R
2For :-H or-CH
3
X is :-Cl or-Br;
N is 20～1000 integer;
M is 1～10 integer.
Preparation process of the present invention is as follows:
(1) use atom transfer radical polymerization to be equipped with macromole evocating agent 1:
Under atmosphere of inert gases, in body or organic solution, in the exsiccant reaction tubes, add monovalence copper halide, containing n-donor ligand, vinyl monomer.The reaction system liquid nitrogen freezing, substitute nitrogen three times after, add the alpha-halogen ester.Use liquid nitrogen freezing, substitute nitrogen three times after, put into oil bath at once and stir.Reacted 0.5～48 hour, reaction tubes is put into the freezing termination reaction of liquid nitrogen, wait to reply and add the tetrahydrofuran (THF) dissolving after the room temperature, solution is crossed the neutral alumina post, remove mantoquita.After the polymers soln of gained concentrated, in the poor solvent of polymkeric substance, precipitate, filter and vacuum-drying after obtain the polymer solids powder.
(2) or use the esterification of the polyethylene oxide contain a terminal hydroxy group to prepare macromole evocating agent 1:
In the presence of triethylamine and in the organic solvent, in the exsiccant three-necked bottle, add polyethylene oxide, methylene dichloride and triethylamine, add alpha-halogen propionic ester or alpha-halogen isobutyrate (recommending to drip), stirred 24～48 hours.Behind the suction filtration, after filtrate concentrated, in poor solvent, precipitate at polymkeric substance, filter and vacuum-drying after obtain the polymer solids powder.
(3) with macromole evocating agent 1 trigger monomer 2 synthetic di-block copolymers:
Under atmosphere of inert gases and in the organic solvent, in the exsiccant reaction tubes, add monovalence copper halide, containing n-donor ligand, the monomer 2 that contains the perfluorocyclobutanearyl aryl-ether structure and macromole evocating agent 1.The reaction system liquid nitrogen freezing, substitute nitrogen three times after, put into oil bath at once and stir.React after 12～48 hours, reaction tubes is put into the freezing termination reaction of liquid nitrogen, wait to reply and add the tetrahydrofuran (THF) dissolving after the room temperature, solution is crossed the neutral alumina post, remove mantoquita.After the polymers soln of gained concentrated, in the poor solvent of polymkeric substance, precipitate, filter and vacuum-drying after obtain the polymer solids powder.
Used monovalence copper halide is cuprous chloride or cuprous bromide in step of the present invention (1) and the step (3).
Used containing n-donor ligand is multiple tooth aminated compounds of aliphatics or bipyridyliums compound in step of the present invention (1) and the step (3), recommends five methyl diethylentriamine (PMDETA), three (2-(dimethyl amido) ethylidene) amine (Me
6TREN), three (2-pyridylmethyl) amine (TPMA), four (three (2-pyridylmethyl)) ethylene diamine (TEPN), 2,2 '-dipyridyl (bpy), 4,4 '-diheptyl-2,2 '-dipyridyl (dHbpy), 4,4 '-di-t-butyl-2,2 '-dipyridyl (dTbpy), 4,4 '-two (5-nonyl)-2,2 '-dipyridyl (dNbpy).
The used alpha-halogen ester that is used for atom transfer radical polymerization initiator is alpha-chloro propionic ester, alpha-chloro isobutyrate, alpha-brominated propionic ester or alpha-brominated isobutyrate in the step of the present invention (1), recommends alpha-chloro methyl propionate, alpha-chloro phenylpropionate, alpha-chloro methyl isobutyrate, alpha-chloro isopropylformic acid phenyl ester, alpha-brominated methyl propionate, ethyl-alpha-bromopropionate, alpha-brominated phenylpropionate, alpha-brominated methyl isobutyrate, alpha-brominated ethyl isobutyrate or alpha-brominated isopropylformic acid phenyl ester.
Used vinyl monomer is a styrenic in the step of the present invention (1), esters of acrylic acid, methyl acrylic ester, vinyl cyanide, acrylic amide or methacryloyl amine monomer, recommend vinylbenzene, the 4-vinyl toluene, the 4-t-butyl styrene, the 4-bromstyrol, the 4-chloro-styrene, 4-fluorobenzene ethene, the 4-trifluoromethyl styrene, the 4-acetoxy-styrene, 4-vinylpridine, methyl acrylate, n-butyl acrylate, tert-butyl acrylate, Hydroxyethyl acrylate, vinyl acrylate, the acrylic acid epoxy propyl ester, methyl methacrylate, n-BMA, the methacrylic tert-butyl acrylate, hydroxyethyl methylacrylate, methacrylic acid (trimethylammonium silica ethyl) ester, methacrylic acid (N, N-dimethyl amido ethyl) ester, vinyl cyanide, N, the N-DMAA, N, N-diethyl acrylamide, N, N-di-isopropyl acrylamide, N, N-dimethyl-2-Methacrylamide, N, N-diethyl-2-Methacrylamide or N, N-di-isopropyl-2-Methacrylamide.
End group of polyethylene oxide used in the step of the present invention (2) is a hydroxyl, and another end group is a methoxyl group.
Used alpha-brominated acyl chlorides is alpha-brominated propionyl chloride or alpha-brominated isobutyryl chloride in the step of the present invention (2); Alpha-brominated acylbromide is alpha-brominated propionyl bromide or alpha-brominated isobutyl acylbromide.
Used organic solvent is recommended as benzene, toluene, methyl-phenoxide, phenyl ether, ethyl acetate, acetone, N in the step of the present invention (1), dinethylformamide, NSC 11801, ethanol or water.
The temperature of reaction of step of the present invention (1) is 30～150 ℃.
Used organic solvent comprises methylene dichloride, acetone and butanone in the step of the present invention (2).
The temperature of reaction of step of the present invention (2) is 0～30 ℃.
Used organic solvent is benzene, toluene, methyl-phenoxide, phenyl ether, ethyl acetate, acetone or N in the step of the present invention (3), dinethylformamide.
The temperature of reaction of step of the present invention (3) is 50～100 ℃.
The used polymkeric substance poor solvent of the present invention comprises methyl alcohol, normal hexane, ether and water.
The used monovalence copper halide and the mol ratio of containing n-donor ligand are 1 in the step of the present invention (1): (1～3); The monovalence copper halide is 1: 1 with the mol ratio of alpha-halogen ester is arranged; The mol ratio of monovalence copper halide and vinyl monomer is 1: (20～1000).
The used polyethylene oxide and the mol ratio of alpha-brominated acyl chlorides or alpha-brominated acylbromide are 1 in the step of the present invention (2): (1～5); The mol ratio of polymkeric substance and triethylamine is 1: (1～5).
The used monovalence copper halide and the mol ratio of containing n-donor ligand are 1 in the step of the present invention (3): (1～3); The mol ratio of monovalence copper halide and macromole evocating agent 1 is 1: 1; The mole material of monovalence copper halide and monomer 2 is than being 1: (20～1000).
Contain two kinds of polymer blocks of different nature in the di-block copolymer of perfluorocyclobutanearyl aryl-ether block of the present invention, can form polymeric film, cellular polymer film, perhaps in body, be separated or solution in self-assembly form aggregate with microscopic appearance.When the contained polymer segment of macromole evocating agent was hydrophilic segment, preparing the micellar method with the described di-block copolymer that contains the perfluorocyclobutanearyl aryl-ether block had direct dripping method and dialysis method, as described below respectively:
Direct dripping method: bi-block copolymer is dissolved in the cosolvent of two kinds of blocks, polymers soln is added (recommending to drip) and in distilled water or salts solution, stirred 6～48 hours.
Dialysis method: bi-block copolymer is dissolved in the cosolvent of two kinds of blocks, is made into certain density mother liquor.Slowly dripping distilled water to solution in mother liquor just becomes turbid.This solution is moved in dialysis tubing, and dialysis 3～14 days is desolvated to remove (5～10 hours change one time water) in distilled water, finally obtains the micellar solution of polymkeric substance.
The method for preparing the cellular polymer film with the described di-block copolymer that contains the perfluorocyclobutanearyl aryl-ether block is: the bi-block copolymer chloroformic solution is applied on sheet mica or the silicon chip, blow in polymers soln ten to 20 minutes with aqueous vapor (nitrogen bubble generation), allow solvent volatilize at 20 ℃ then as far as possible slowly.
The chemical structure of polymkeric substance of the present invention is confirmed by nuclear magnetic resonance spectrum, infrared spectra and gel permeation chromatography, the pattern of self-assembly aggregate is by scanning electronic microscope, transmission electron microscope and atomic force microscope observation, and partial results is seen the specific embodiment part.Show, the bi-block copolymer of perfluorocyclobutanearyl aryl-ether polymer blocks of the present invention is simple synthetic method not only, and can form aggregate with microscopic appearance, can be used for antifouling reagent, tensio-active agent, emulsifying agent, pharmaceutical carrier, light-guide material or photonic crystal field.
Description of drawings
Fig. 1 is the self-assembly transmission electron microscope photo of polymkeric substance 8;
Wherein A is a spherical micelle, and B is the elliposoidal micella, and C is the tubulose micella, and D is spherical big composite micelle.
Fig. 2 be bi-block copolymer film of the present invention the atomic force microscope photo and with the atomic force microscope contrast photo of the water contact angle of the water contact angle of good bi-block copolymer film of the present invention and polyethylene oxide.
Wherein, A is the atomic force microscope photo of bi-block copolymer film; B is the water contact angle of polyethylene oxide; C is the water contact angle of bi-block copolymer film.
Fig. 3 is the electron scanning micrograph of cellular bi-block copolymer film and the synoptic diagram that cellular film is used for photonic crystal;
Wherein A, B and C are respectively the electron scanning micrographs of cellular bi-block copolymer film; D is the synoptic diagram that cellular film is used for photonic crystal.
Embodiment:
Can further understand the present invention by following examples, but not limit the scope of the invention.
Synthesizing of the embodiment 1. polyacrylic acid tert-butyl esters 3
With reaction tubes with gas fire dry dry substitute nitrogen after, (39.2mg 0.28mmol), substitutes nitrogen three times to add cuprous bromide.With tert-butyl acrylate (4.0mL, 27.6mmol), (0.06mL 0.28mmol) and after methyl-phenoxide (1mL) adds reaction tubes, with the reaction system liquid nitrogen freezing, vacuumized 5 minutes PMDETA, and inflated with nitrogen thaws.Behind the triplicate, (0.06mL, 0.55mmol), freezing once more-as to vacuumize-inflated with nitrogen thaws three times, puts into 70 ℃ oil bath and stirs 2h to add the 2 bromopropionic acid methyl esters.Reaction tubes is put into liquid nitrogen freezing cancellation reaction, add the THF dissolving, cross the neutral alumina post and remove mantoquita.After rotary evaporation removes and desolvates, add 5mL THF dissolving, precipitate in cold normal hexane, suction filtration obtains white polymer.Precipitate once more, suction filtration final vacuum drying obtains the 1.13g polymkeric substance.
GPC：M
n＝6,100g/mol，M
w/M
n＝1.10.
1H NMR (300MHz, CDCl
3): δ 4.09,2.08-2.38,1.73-1.94,1.26-1.70,1.43,1.13. ultimate analysis (Elemental Analysis) (Br%): 1.59%.
FT-IR(KBr)：v(cm
-1)2951，1731，1484，1243，1150，989，844。
The embodiment 2. polyacrylic acid tert-butyl ester-b-polymethyl acrylic acid
Synthesizing of (4-((2-(4-methylphenoxy)) hexafluoro cyclobutoxy group)) phenyl ester bi-block copolymer 5
With reaction tubes with gas fire dry dry substitute nitrogen after, with polymkeric substance 3 (525mg, 0.04mmol, M
n=12,500g/mol, M
w/ M
n=1.10), monomer 4 (0.7mL, 2.1mmol) and CuBr (6mg 0.04mmol) adds reaction tubes, substitutes nitrogen three times.After adding methyl-phenoxide 1mL, use liquid nitrogen freezing, vacuumized 5 minutes, inflated with nitrogen thaws.Behind the triplicate, (0.017mL, 0.084mmol), freezing once more-as to bleed-inflated with nitrogen thaws three times, puts into 70 ℃ oil bath and stirs 24h to add PMDETA.Reaction tubes is put into liquid nitrogen freezing cancellation reaction, add the THF dissolving, cross the neutral alumina post and remove mantoquita.After rotary evaporation removes and desolvates, add the 1mLTHF dissolving, precipitate in cold methyl alcohol, suction filtration obtains white polymer.Precipitate once more, suction filtration final vacuum drying obtains the 532mg polymkeric substance.
GPC：M
n＝23,000g/mol，M
w/M
n＝1.18.
1H?NMR(300MHz，CDCl
3)：δ6.97-7.51，2.25，1.81，1.43，1.36.
19F?NMR(282MHz，CDCl
3)：δ-128.3～-131.8(m，cyclobutyl-F
6).
FT-IR(KBr)：v(cm
-1)2951，2926，1731，1505，1444，1260，1183，1150，1120，980，963，844，802。
Synthesizing of embodiment 3. polyethylene oxide macromole evocating agents 6
The polyethylene oxide (5g, 2.5mmol, the M that end group are contained a methoxyl group
n=2,000g/mol) add in the exsiccant three-necked bottle, with new methylene dichloride (150mL) dissolving of steaming, add triethylamine (1.5mL, 12.5mmol) after, put into ice-water bath.(1.3mL 12.5mmol), dropwises the back and stirs 2h slowly to drip the 2-bromo propionyl chloro.Suction filtration is removed the salt of generation, and rotary evaporation removes the back of desolvating with 20mL THF dissolving, precipitates three times in cold ether, obtains white powder shaped polymer 4.23g after the vacuum-drying.
FT-IR(KBr)：v(cm
-1)2929，1751，1610，1503，1318，1197，1104，962，818。
Embodiment 4. polyethylene oxides-b-polymethyl acrylic acid
Synthesizing of (4-((2-(4-methoxyl group phenoxy group)) hexafluoro cyclobutoxy group)) phenyl ester bi-block copolymer 8
With reaction tubes with gas fire dry dry substitute nitrogen after, with polymkeric substance 6 (500mg, 0.25mmol), monomer 7 (200mg, 0.4mmol) and CuBr (3mg 0.002mmol) adds reaction tubes, substitutes nitrogen three times.After adding methyl-phenoxide 1mL, use liquid nitrogen freezing, bled 5 minutes, inflated with nitrogen thaws.Behind the triplicate, (0.04mL, 0.002mmol), freezing once more-as to bleed-inflated with nitrogen thaws three times, puts into 70 ℃ oil bath and stirs 2h to add PMDETA.Reaction tubes is put into liquid nitrogen freezing cancellation reaction, add the THF dissolving, cross the neutral alumina post and remove mantoquita.After rotary evaporation removes and desolvates, add 1mL THF dissolving, precipitate in cold normal hexane, suction filtration obtains white polymer.Precipitate once more, suction filtration final vacuum drying obtains the 35mg polymkeric substance.
GPC：M
n＝5,400g/mol，M
w/M
n＝1.14.
1H?NMR(300MHz，CDCl
3)：δ7.10，6.80，3.78，3.65，2.35，1.38.
19F?NMR(282MHz，CDCl
3)：δ-128.3～-131.8(m，cyclobutyl-F
6).
FT-IR(KBr)：v(cm
-1)2959，2926，1739，1505，1444，1260，1183，1120，963，802。
The self-assembly preparation of embodiment 5. polymkeric substance 8
Polymkeric substance 8 is dissolved in the tetrahydrofuran (THF) as mother liquor, and concentration is 10mg/mL.Fully after the dissolving, the mother liquor of getting certain volume slowly is added dropwise in the distilled water, makes its concentration greater than 1 * 10
-4Mg/mL.Behind the solution stirring 7h, THF is fully volatilized.Or bi-block copolymer is dissolved in the tetrahydrofuran (THF), be made into the mother liquor of 0.2mg/mL.In mother liquor, slowly drip distilled water to solution just become turbid (naked-eye observation).This solution is moved in dialysis tubing, and dialysis 7 days is desolvated to remove (5～10 hours change one time water) in distilled water, finally obtains polymkeric substance 1 * 10
-4The micellar solution of mg/mL.Syringe with 1mL extracts a spot of drips of solution on copper mesh (being coated with the carbon support membrane), behind the room temperature nature volatile dry, with transmission electron microscope observation self-assembly pattern.As shown in Figure 1, the micellar structure of polymkeric substance self-assembly in solution formation different shape, the form of formed micella or vesica can be regulated by telomerized polymer segmental ratio and preparation condition.Wherein, A. spherical micelle, B. elliposoidal micella, C. tubulose micella, the spherical big composite micelle of D..A uses block polymer PEO
44-b-PPFCBMA
24, with direct dripping method preparation; B uses block polymer PEO
44-b-PPFCBMA
8, with direct dripping method preparation; C uses block polymer PEO
101-b-PPFCBMA
26, with direct dripping method preparation; D uses block polymer PEO
101-b-PPFCBMA
26, with dialysis method preparation (PEO represents poly-ethylene oxide block, and PPFCBMA represents to contain the polymer blocks of perfluorocyclobutanearyl aryl-ether, and footnote is represented the contained repeating unit number of polymer blocks).The self-assembly of polymkeric substance can be used in fields such as decontamination reagent, tensio-active agent, emulsifying agent and pharmaceutical carriers.
The preparation of embodiment 6. bi-block copolymer films
Polymers soln with 10% is spun on sheet glass or the silicon chip, and air drying was put into vacuum drying oven dry 24 hours after 72 hours, obtained polymeric film.The polymeric film of gained is compared with the polymeric film of one-component, has enhanced melt processable, bigger surface hydrophobicity, enhanced kindliness and ductility and environmental stability preferably; And by the length of control fluoropolymer segment, the performances such as surface energy, wettability, heat and mechanical property that can regulate resulting polymers.As shown in Figure 2, wherein, the atomic force microscope photo of A. bi-block copolymer film.B. the water contact angle of polyethylene oxide.C. the water contact angle of bi-block copolymer film.The block polymer that contains the perfluorocyclobutanearyl aryl-ether polymer segment has more coarse surface, and the water angle of wetting has bigger increase than the polymkeric substance of one-component.
The preparation of embodiment 7. cellular bi-block copolymer films
0.1% bi-block copolymer chloroformic solution is applied on the sheet mica, blows in polymers soln ten to 20 minutes, allow solvent volatilize at 20 ℃ then as far as possible slowly, obtain cellular bi-block copolymer film with aqueous vapor (nitrogen bubble generation).The cellular polymer membrane pore size of gained is homogeneous comparatively, and can be by the ratio of adjusting polymer segment and the size that the membrane prepare condition is come adjustment aperture, as shown in Figure 3, the electron scanning micrograph of A, B, the cellular bi-block copolymer film of C. wherein.A uses block polymer PEO
111-b-PPFCBMA
5, aqueous vapor was blown ten minutes; B uses block polymer PEO
5-b-PPFCBMA
54, aqueous vapor was blown ten minutes; C uses block polymer PEO
5-b-PPFCBMA
54, aqueous vapor is blown 15 minutes (PEO represents poly-ethylene oxide block, and PPFCBMA represents to contain the polymer blocks of perfluorocyclobutanearyl aryl-ether, and footnote is represented the contained repeating unit number of polymer blocks).D. cellular film is used for the synoptic diagram of photonic crystal.Cellular film has potential to use in fields such as nanoparticle self-assembly, mould material, optical material, photoelectron material, tissue engineering material, molecular engram film, bionic surface and super hydrophobic surfaces.
Claims (10)
1. di-block copolymer that contains the perfluorocyclobutanearyl aryl-ether block is characterized in that having following structure:
Wherein
For: polyethylene oxide, polystyrene, polyacrylic ester, polymethacrylate, polyacrylamide or PMAm polymer blocks;
R
1For: halogen, C
1～C
4Alkyl, C
1～C
4Alkoxyl group, phenyl, C
1～C
4Alkyl phenyl, C
1～C
4Alkoxyl phenyl, trifluoro-ethylene oxygen base phenyl ,-SO
2Ph ,-cumyl or-C (CF
3)
2Ph;
R
2For :-H or-CH
3
X is :-Cl or-Br;
N is 20～1000 integer;
M is 1～10 integer;
The structure of trifluoro-ethylene oxygen base phenyl is
-SO
2The structure of Ph is
The structure of-cumyl is
-C (CF
3)
2The structure of Ph is
2. a preparation method who contains the di-block copolymer of perfluorocyclobutanearyl aryl-ether block as claimed in claim 1 is characterized in that by following (1) and (3), and perhaps two kinds of methods of (2) and (3) step make:
(1) under atmosphere of inert gases, in body or organic solution, with the monovalence copper halide is that catalyzer, nitrogenous compound are that part, alpha-halogen ester are initiator, cause vinyl monomer and carry out atom transfer radical polymerization, react the macromole evocating agent 1 that obtained containing atom transfer free radical polymerization initiating group in 0.5～48 hour; The mol ratio of monovalence copper halide and containing n-donor ligand is 1: (1～3); The monovalence copper halide is 1: 1 with the mol ratio of alpha-halogen ester is arranged; The mol ratio of monovalence copper halide and vinyl monomer is 1: (20～1000); Polymerization temperature is 30～150 ℃;
(2) or in the presence of triethylamine and in the organic solvent, use the polyethylene oxide that contains a terminal hydroxy group to prepare the macromole evocating agent 1 that contains atom transfer free radical polymerization initiating group in 24～48 hours with alpha-brominated acyl chlorides or alpha-brominated acylbromide generation esterification; The mol ratio of polyethylene oxide and alpha-brominated acyl chlorides or alpha-brominated acylbromide is 1: (1～5); The mol ratio of polymkeric substance and triethylamine is 1: (1～5); Temperature of reaction is 0～30 ℃; (3) under atmosphere of inert gases and in the organic solvent, with the monovalence copper halide is that catalyzer, nitrogenous compound are part, cause the esters of acrylic acid or the methyl acrylic ester monomer 2 that contain the perfluorocyclobutanearyl aryl-ether structure with macromole evocating agent 1 and carry out atom transfer radical polymerization, reaction obtained containing the di-block copolymer of perfluorocyclobutanearyl aryl-ether block in 12～48 hours; The mole material of monovalence copper halide and containing n-donor ligand is than being 1: (1～3); The mol ratio of monovalence copper halide and macromole evocating agent 1 is 1: 1; The mol ratio of monovalence copper halide and monomer 2 is 1: (20～1000); Polymerization temperature is 50～100 ℃;
Described compound 1 and 2 structure are as follows:
3. the preparation method who contains the di-block copolymer of perfluorocyclobutanearyl aryl-ether block as claimed in claim 2 is characterized in that described monovalence copper halide is cuprous chloride or cuprous bromide.
4. the preparation method who contains the di-block copolymer of perfluorocyclobutanearyl aryl-ether block as claimed in claim 2, it is characterized in that described containing n-donor ligand is multiple tooth aminated compounds of aliphatics or bipyridyliums compound, recommend five methyl diethylentriamine, three (2-(dimethyl amido) ethylidene) amine, three (2-pyridylmethyl) amine, four (three (2-pyridylmethyl)) ethylene diamine, 2,2 '-dipyridyl, 4,4 '-diheptyl-2,2 '-dipyridyl, 4,4 '-di-t-butyl-2,2 '-dipyridyl or 4,4 '-two (5-nonyls)-2,2 '-dipyridyl.
5. the preparation method who contains the di-block copolymer of perfluorocyclobutanearyl aryl-ether block as claimed in claim 2, the alpha-halogen ester that it is characterized in that being used for atom transfer radical polymerization initiator is alpha-chloro methyl propionate, alpha-chloro phenylpropionate, alpha-chloro methyl isobutyrate, alpha-chloro isopropylformic acid phenyl ester, alpha-brominated methyl propionate, ethyl-alpha-bromopropionate, alpha-brominated phenylpropionate, alpha-brominated methyl isobutyrate, alpha-brominated ethyl isobutyrate, alpha-brominated isopropylformic acid phenyl ester.
6. the preparation method who contains the di-block copolymer of perfluorocyclobutanearyl aryl-ether block as claimed in claim 2, it is characterized in that described vinyl monomer is a vinylbenzene, the 4-vinyl toluene, the 4-t-butyl styrene, the 4-bromstyrol, the 4-chloro-styrene, 4-fluorobenzene ethene, the 4-trifluoromethyl styrene, the 4-acetoxy-styrene, 4-vinylpridine, methyl acrylate, n-butyl acrylate, tert-butyl acrylate, Hydroxyethyl acrylate, vinyl acrylate, the acrylic acid epoxy propyl ester, methyl methacrylate, n-BMA, the methacrylic tert-butyl acrylate, hydroxyethyl methylacrylate, methacrylic acid (trimethylammonium silica ethyl) ester, methacrylic acid (N, N-dimethyl amido ethyl) ester, vinyl cyanide, N, the N-DMAA, N, N-diethyl acrylamide, N, N-di-isopropyl acrylamide, N, N-dimethyl-2-Methacrylamide, N, N-diethyl-2-Methacrylamide, N, N-di-isopropyl-2-Methacrylamide.
7. the preparation method who contains the di-block copolymer of perfluorocyclobutanearyl aryl-ether block as claimed in claim 2 is characterized in that an end group of described polyethylene oxide is a hydroxyl, and another end group is a methoxyl group.
8. the preparation method who contains the di-block copolymer of perfluorocyclobutanearyl aryl-ether block as claimed in claim 2 is characterized in that described alpha-brominated acyl chlorides is alpha-brominated propionyl chloride or alpha-brominated isobutyryl chloride; Alpha-brominated acylbromide is alpha-brominated propionyl bromide or alpha-brominated isobutyl acylbromide.
9. the preparation method who contains the di-block copolymer of perfluorocyclobutanearyl aryl-ether block as claimed in claim 2 is characterized in that the R that the esters of acrylic acid of described perfluorocyclobutanearyl aryl-ether structure or methyl acrylic ester monomer 2 are contained
1Functional group is halogen, C
1～C
4Alkyl, C
1～C
4Alkoxyl group, phenyl, C
1～C
4Alkyl phenyl, C
1～C
4Alkoxyl phenyl, trifluoro-ethylene oxygen base phenyl ,-SO
2Ph ,-cumyl or-C (CF
3)
2Ph; R
2Functional group is-H or-CH
3M is 1～10 integer; Wherein trifluoro-ethylene oxygen base phenyl ,-SO
2Ph ,-cumyl and-C (CF
3)
2The structure of Ph according to claim 1.
10. a purposes that contains the di-block copolymer of perfluorocyclobutanearyl aryl-ether block as claimed in claim 1 is characterized in that it can form the aggregate with microscopic appearance and be used for antifouling reagent, tensio-active agent, emulsifying agent, pharmaceutical carrier, light-guide material or photonic crystal field.
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| CNA2009100469884A CN101492520A (en) | 2009-03-04 | 2009-03-04 | Diblock copolymer containing full-fluorine cyclobutyl aryl aether block and uses thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100469884A CN101492520A (en) | 2009-03-04 | 2009-03-04 | Diblock copolymer containing full-fluorine cyclobutyl aryl aether block and uses thereof |
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