CN100412101C - Amphipathic fluoride block copolymer and production thereof - Google Patents
Amphipathic fluoride block copolymer and production thereof Download PDFInfo
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- CN100412101C CN100412101C CNB2006100381348A CN200610038134A CN100412101C CN 100412101 C CN100412101 C CN 100412101C CN B2006100381348 A CNB2006100381348 A CN B2006100381348A CN 200610038134 A CN200610038134 A CN 200610038134A CN 100412101 C CN100412101 C CN 100412101C
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Abstract
The present invention discloses a fluoric amphipathy block copolymer with temperature and pH dual response performance, and a preparation method thereof. The present invention is characterized in that a method using oxygen anions to initiate polymerization is used; polymers with terminal hydroxyl reacts with strong alkali for obtaining oligomer oxygen anions which successively react with ester methacrylate (alkyl substituted amino group) and fluoric ester methacrylate as initiating agents for obtaining amphipathy fluoric block copolymers. The present invention overcomes the defect that traditional anionic polymerization reaction needs to be carried out harsh conditions at very low temperature, in high vacuum, etc.; the present invention has the advantages of high reaction speed, high conversion rate, pure product and easy purification.
Description
Technical field
The present invention relates to a kind of multipolymer with one or more unsaturated aliphatic based compounds, each unsaturated aliphatic base has only a carbon-to-carbon two strong, and has only one to be to be terminal with the carboxylicesters; Be specifically related to a kind of segmented copolymer that constitutes by methacrylic acid (amino that alkyl replaces) ester and methacrylic acid fluorinated ester.
Background technology
The stimulating responsive amphipathic nature polyalcohol is one of focus of present polymeric material field research, because its special nature, can response external stimulate (chemical stimulations such as physical stimulation such as light, heat, electricity, magnetic, mechanics energy and pH value, salt concn, chemical substance), its molecular structure and physicals are changed, and relate to the exchange and the conversion of material, energy, information between itself and environment.Simultaneously, because its amphipathic character, this base polymer can take place intermolecular in selective solvent or the intramolecularly self-assembly again, shows different accumulation shapes and SOLUTION PROPERTIES.
Fluorine is the element of electronegativity maximum, because it has many special physicochemical character, therefore, fluorine-containing amphipathic nature polyalcohol is compared with non-fluorine-containing amphipathic nature polyalcohol, has lower surface energy, higher surfactivity and stronger self-assembly trend, this also makes fluorine-containing amphipathic nature polyalcohol have unique chemical and physical properties.Fluoropolymer has excellent properties such as resist chemical, heat-resisting, stable, hydrophobic, self-lubricating and electrical isolation.Because fluorochemicals is hydrophobic but also oleophobic not only, has in solution from laminarity, have to make the end be the tendency that pectination is arranged outwardly, thereby in coating, just can obtain the not viscosity stabilized coating of low surface energy by the content of control fluorochemicals.At biomedical aspect, fluorine-containing amphipathic nature polyalcohol has the effect of delivering oxygen and is suitable as blood substitute, can also self-assembly in selective solvent, the supramolecular aggregations such as stabilizing membrane, bimolecular tunic, ellipse, cast that form the structure exquisiteness are as control drug release, gene delivery carrier.In addition, compare with the hydrocarbon chain tensio-active agent of structural similitude, carbon fluorine chain tensio-active agent also has higher surfactivity and stronger hydrophobicity.In recent years, many superior characteristic of fluoropolymer have attracted the scientific research personnel to take to the research of the synthetic and performance of fluoropolymer.
In the prior art, the report about the preparation method of fluorinated block copolymer mainly concentrates on active anionic polymerization and atom transfer radical polymerization method.Utilize the method for active anionic polymerization to synthesize the amphipathic multipolymer of methacrylic tert-butyl acrylate and methacrylic acid-2-(N-methyl perfluoro butyl sulfoamido) ethyl ester [poly (t-BMA-b-FMA)] (Busse K. as people such as Busse K.; Kressler J.; Macromolecules, 2002,35:178).Yet active anionic polymerization severe reaction conditions, temperature of reaction are very low, are difficult to realize industrialization control and production.
Another kind of synthetic method is to adopt atom transfer radical polymerization (ATRP) method, has synthesized methacrylic tert-butyl acrylate and perfluoroalkyl methacrylate segmented copolymer (Li.H. as the method for human ATRP such as domestic Han Zhe literary composition; Wu P.P.; Han Z.W.; Polymer, 2002,43:4079).At present, few in the document for the report of fluorine-containing stimulating responsive block polymer.People such as Brittain method initiation by ATRP on the tripoli surface has prepared thermally sensitized brush type polymkeric substance: Si/SiO
2//PS-b-PPFS, Si/SiO
2//PS-b-PHFA, Si/SiO
2//PMA-b-PPFS, Si/SiO
2//PMA-b-PPFA, Si/SiO
2//structures such as PMA-b-PTFA (Granville A.M.; Boyes S.G.; Macromolecules, 2004,37:2790; Granville A.M.; Brittain W.J.Macromol.Rapid Commun., 2004,25:1298; Granville A.M.; Boyes S.G.; Macromolecules, 2005,38:3263.).The ATRP polymerization has its unique advantage, but its maximum shortcoming is to contain catalyzer in the final product, is difficult to remove, and product is impure.
Also occurred utilizing reversible addition-fracture chain transfer polymerization (RAFT) method to prepare report (the Rixens B. of fluorine-containing block polymer recently; Severac R.:Boutevin B.; Lacroix-Desmazes P.; Polymer, 2005,46:3579).The same with ATRP, though the RAFT method has characteristics such as reaction conditions gentleness, the RAFT reagent that is added in polymerization is difficult to remove in final polymkeric substance, and polymer properties is produced certain influence.
Therefore, provide a kind of fluorine-containing amphipathic nature block polymer that has the double-response of temperature sensitive property and pH sensitivity simultaneously, and a kind of preparation method that can obtain clean product, the application that makes fluorinated block copolymer is entered a new stage.
Summary of the invention
The object of the invention provides a kind of fluorine-containing amphipathic nature block polymer of the double-response with temperature sensitive property and pH sensitivity newly, and a kind of preparation method that can obtain clean product is provided simultaneously.
For achieving the above object, the technical solution used in the present invention is: a kind of amphipathic fluoride block copolymer, express by following formula:
In the formula, x is 16-45, and y is 10-50, and z is 3-10,
R1 is selected from
R
2Be selected from-CH
2CF
3,-CH
2CF
2CHFCF
3,-CH
2CF
2CF
2CF
2CHF
2,-CH
2CF
2CF
2CF
2CF
2CF
2CHF
2, or-CH
2CF
2CF
2CF
2CF
2CF
2CF
2CF
2CF
2CF
3
A kind of preparation method of amphipathic fluoride block copolymer adopts oxygen anion initiated polymerization method, comprises the following steps,
(1) preparation initiator: with the tetrahydrofuran (THF) is solvent, make potassium hydride KH with etc. behind the methyl-sulphoxide stirring reaction of amount, be added drop-wise in the poly glycol monomethyl ether, and adopt tritane as indicator, when solution begins to present pink, stop to drip, form the oligopolymer oxygen anion, as initiator;
(2) initiator and first monomer were constituted polymerization system in 1: 10 to 1: 50 with mol ratio, stir, reacted 0.5～1.5 hour, described first monomer is selected from methacrylic acid (amino that alkyl replaces) ester;
(3) add second monomer that is equivalent to 3 to 10 times of initiators with molar ratio computing, stir, reacted 0.5～1.5 hour, described second monomer is selected from the methacrylic acid fluorinated ester;
(4) use the methyl alcohol termination reaction, purify, promptly obtain required amphipathic fluoride block copolymer.
Wherein, the polymerization degree of poly glycol monomethyl ether is 16-45.
Technique scheme can be expressed as follows:
In the technique scheme, the structural formula of the described first monomer methacrylic acid (alkyl replace amino) ester is,
In the formula, R
1Be selected from
Be methacrylic acid-2-(dimethylamino) ethyl ester (DMAEMA), methacrylic acid-2-(diethylin) ethyl ester (DEAEMA), methacrylic acid-2-(diisopropylaminoethyl) ethyl ester (DPAEMA) or methacrylic acid (tertiary butyl amino) ethyl ester (BAEMA).
The fluorine ester contained structural formula of the described second monomer methacrylic acid is,
In the formula, R
2Be selected from
-CH
2CF
3,-CH
2CF
2CHFCF
3,-CH
2CF
2CF
2CF
2CHF
2,-CH
2CF
2CF
2CF
2CF
2CF
2CHF
2, or-CH
2CF
2CF
2CF
2CF
2CF
2CF
2CF
2CF
2CF
3
Be methacrylic acid-(2,2, the 2-trifluoro) ethyl ester (TFEMA), methacrylic acid-(2,2,3,4,4, the 4-hexafluoro) butyl ester (HFBMA), methacrylic acid-(2,2,3,3,4,4,5,5-octafluoro) pentyl ester (OFPMA), methacrylic acid-(2,2,3,3,4,4,5,5,6,6,7,7-ten difluoros) heptyl ester (DDFHMA), methacrylic acid-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-19 fluorine) ester in the last of the ten Heavenly stems (NDFDMA)
In the technique scheme, when generating initiator, must keep alcohol and sylvite reaction with same mole.If alcohol is excessive, can in product, there be the pollution of alcohol, if sylvite is excessive, because DMSO
-K
+Be alkaline, can the trigger monomer reaction form double activity center, cause the pollution of homopolymer.
Thereby in the described step (1), in the time of in being added drop-wise to poly glycol monomethyl ether, adopt tritane as indicator, when solution begins to present pink, stop to drip.
In the technique scheme, described purification processes is, steams to remove at 60～70 ℃ of backspins and desolvates, continue to carry out deposition and purification with cold normal hexane, triplicate, at last 40～50 ℃ of vacuum-dryings to constant weight.
When actual fabrication, for guaranteeing degree of purity of production, can make with extra care raw material earlier, its method is to use activatory alkalescence Al before methacrylic acid-2-(dimethylamino) ethyl ester uses
2O
3Post is handled, and uses then more than the dry 12h of CaH, at high-purity N
2Carry out underpressure distillation under the protection; Potassium hydride KH (KH) is sealed up for safekeeping in mineral oil standby to treat; Solvents tetrahydrofurane (THF) was used potassium hydroxide dry three days, added benzophenone as indicator, carried out anaerobic with the sodium silk and refluxed, and until being intense violet color, steamed before the use; Phenylcarbinol CaH
2More than the dry 12h, underpressure distillation before using.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
1. the present invention utilizes potassium hydride KH and DMSO reaction to form DMSO
-K
+After form oligopolymer oxygen anion active site with the reaction of the terminal hydroxyl of different molecular weight polyethylene glycol monomethyl ether (MePEG) again, then according to each required segmental length (pH response, temperature sensitive property, fluorine-containing), the methacrylic acid (amino that alkyl replaces) esters monomer and the fluorine-containing esters monomer of methacrylic acid that add different amounts successively, can obtain the fluorine-containing amphipathic nature block polymer of different structure, different block length, have temperature and pH double-response performance.
2. owing in final product, there is the polyoxyethylene glycol fragment, it has wetting ability preferably, methacrylic acid in the product (amino that alkyl replaces) ester fragment has temperature and pH responsiveness, thereby can improve the hydrophilicity and the temperature/pH response performance of the triblock copolymer of acquisition.
3. the present invention has overcome the shortcoming that traditional anionic polymerisation need carry out under severe condition such as extremely low temperature, high vacuum, and speed of response is fast, the transformation efficiency height, and product is pure, and easy purifying.
4. the present invention's amphipathic nature polyalcohol that will have a temperature and pH response is connected with covalent linkage with fluorine-containing section polymkeric substance, can improve the character of original amphipathic nature polyalcohol.
Embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment one: MePEG-b-PDMAEMA-b-POFPMA and preparation thereof
(1) preparation of KH: stirring rotator is put into the exsiccant reaction flask in advance, with turned welt soft rubber ball jam-pack.Link to each other with vacuum pump with syringe needle, emulsion tube then, charge into high-purity argon gas while vacuumizing, so repeatable operation is three times.After moving into a certain amount of KH in the reaction flask, inject 5ml exsiccant THF with the dry injection device, agitator treating, static back contains the THF of mineral oil with the syringe sucking-off, three times so repeatedly, dries up the THF solution of remnants at last with high-purity argon gas.Utilize the decrement method accurately in the weighing reaction flask amount of KH (0.2～0.3g about 5.0～7.5mmol).
(2) preparation of initiator: the THF of 15-30ml is expelled in the reaction flask, reaction flask placed 20 ℃ constant temperature oil bath, magnetic agitation is injected the methyl-sulphoxide (DMSO) with amount such as KH simultaneously, KH and methyl-sulphoxide is fully reacted form carbanion (DMSO
-K
+).Prepare a polymerization bottle that has stirring rotator, dewater after the deoxygenation, take by weighing through (750 represent the molecular weight of PEG) and 5～10mg tritane about the about 3.75g of exsiccant PEG-750 (making indicator uses), the THF that injects 20ml makes it dissolving, extracts DMSO with syringe then
-K
+Solution slowly is added drop-wise in the described polymerization bottle, after solution becomes pink in polymerization bottle, stops to drip, and (OH) fully reaction forms oxygen anion to the hydroxyl on the PEG end group at this moment.
(3) polyreaction: then add first monomer methacrylic acid-2-(dimethylamino) ethyl ester (DMAEMA) with the exsiccant syringe in the constant temperature oil bath with 40 ℃ of reaction flask immigrations, the mol ratio of controlling first monomer and initiator is 15: 1, be injected into the first monomer DMAEMA monomer that is equivalent to 15 times of meterings of initiator and carry out polyreaction 1～1.5h, the mol ratio of controlling second monomer and initiator is 6: 1, then add the second monomer methacrylic acid-(2 that is equivalent to 6 times of meterings of initiator with the exsiccant syringe, 2,3,3,4,4,5, the 5-octafluoro) pentyl ester (OFPMA), reaction 1～1.5h uses exsiccant methyl alcohol termination reaction at last.Reacted polymkeric substance under 60～70 ℃ of conditions, revolves to steam to remove and desolvates, and continues to carry out deposition and purification with cold normal hexane, and triplicate is dried to constant weight for 40～50 ℃ at vacuum drying oven at last.Obtain required product, record productive rate greater than 90%.Product through gel permeation chromatography (GPC) and proton nmr spectra and fluorine spectrum (
1HNMR,
19F NMR) detects the structure of its molecular weight, molecular weight distribution and multipolymer, prove to have obtained target product.
Embodiment two: MePEG-b-PDMAEMA-b-POFPMA and preparation thereof
(1) preparation of KH: identical with embodiment one.
(2) preparation of initiator: identical with embodiment one.
(3) polyreaction: add first monomer methacrylic acid-2-(dimethylamino) ethyl ester (DMAEMA) with the exsiccant syringe in the constant temperature oil bath with 40 ℃ of reaction flask immigrations, the mol ratio of controlling first monomer and initiator is 30: 1, be injected into the first monomer DMAEMA monomer that is equivalent to 30 times of meterings of initiator and carry out polyreaction 1～1.5h, the mol ratio of controlling second monomer and initiator is 6: 1, add the second monomer methacrylic acid-(2 that is equivalent to 6 times of meterings of initiator with the exsiccant syringe, 2,3,3,4,4,5, the 5-octafluoro) pentyl ester (OFPMA), reaction 1～1.5h uses exsiccant methyl alcohol termination reaction at last.Reacted polymkeric substance under 60～70 ℃ of conditions, revolves to steam to remove and desolvates, and continues to carry out deposition and purification with cold normal hexane, and triplicate is dried to constant weight for 40～50 ℃ at vacuum drying oven at last.Obtain required product, record productive rate greater than 90%.Product through gel permeation chromatography (GPC) and proton nmr spectra and fluorine spectrum (
1H NMR,
19F NMR) detects the structure of its molecular weight, molecular weight distribution and multipolymer, prove to have obtained target product.
Embodiment three: MePEG-b-PDMAEMA-b-POFPMA and preparation thereof
(1) preparation of KH: identical with embodiment one.
(2) preparation of initiator: identical with embodiment one.
(3) polyreaction: add first monomer methacrylic acid-2-(dimethylamino) ethyl ester (DMAEMA) with the exsiccant syringe in the constant temperature oil bath with 40 ℃ of reaction flask immigrations, the mol ratio of controlling first monomer and initiator is 50: 1, be injected into the first monomer DMAEMA monomer that is equivalent to 50 times of meterings of initiator and carry out polyreaction 1～1.5h, the mol ratio of controlling second monomer and initiator is 6: 1, then add the second monomer methacrylic acid-(2 that is equivalent to 6 times of meterings of initiator with the exsiccant syringe, 2,3,3,4,4,5, the 5-octafluoro) pentyl ester (OFPMA), reaction 1～1.5h uses exsiccant methyl alcohol termination reaction at last.Reacted polymkeric substance under 60～70 ℃ of conditions, revolves to steam to remove and desolvates, and continues to carry out deposition and purification with cold normal hexane, and triplicate is dried to constant weight for 40～50 ℃ at vacuum drying oven at last.Obtain required product, record productive rate greater than 90%.Product through gel permeation chromatography (GPC) and proton nmr spectra and fluorine spectrum (
1H NMR,
19F NMR) detects the structure of its molecular weight, molecular weight distribution and multipolymer, prove to have obtained target product.
Embodiment four: MePEG-b-PDMAEMA-b-PTFEMA and preparation thereof
(1) preparation of KH: identical with embodiment one.
(2) preparation of initiator: identical with embodiment one.
(3) polyreaction: add first monomer methacrylic acid-2-(dimethylamino) ethyl ester (DMAEMA) with the exsiccant syringe in the constant temperature oil bath with 40 ℃ of reaction flask immigrations, the mol ratio of controlling first monomer and initiator is 15: 1, be injected into the first monomer DMAEMA monomer that is equivalent to 15 times of meterings of initiator and carry out polyreaction 1～1.5h, the mol ratio of controlling second monomer and initiator is 6: 1, then add the second monomer methacrylic acid-(2 that is equivalent to 6 times of meterings of initiator with the exsiccant syringe, 2, the 2-trifluoro) ethyl ester (TFEMA), reaction 1～1.5h uses exsiccant methyl alcohol termination reaction at last.Reacted polymkeric substance under 60～70 ℃ of conditions, revolves to steam to remove and desolvates, and continues to carry out deposition and purification with cold normal hexane, and triplicate is dried to constant weight for 40～50 ℃ at vacuum drying oven at last.Obtain required product, record productive rate greater than 90%.Product through gel permeation chromatography (GPC) and proton nmr spectra and fluorine spectrum (
1H NMR,
19F NMR) detects the structure of its molecular weight, molecular weight distribution and multipolymer, prove to have obtained target product.
Embodiment five: MePEG-b-PDEAEMA-b-PHFBMA and preparation thereof
(1) preparation of KH: identical with embodiment one.
(2) preparation of initiator: identical with embodiment one.
(3) polyreaction: add first monomer methacrylic acid-2-(diethylin) ethyl ester (DEAEMA) with the exsiccant syringe in the constant temperature oil bath with 40 ℃ of reaction flask immigrations, the mol ratio of controlling first monomer and initiator is 20: 1, be injected into the first monomer DEAEMA monomer that is equivalent to 20 times of meterings of initiator and carry out polyreaction 1～1.5h, the mol ratio of controlling second monomer and initiator is 8: 1, then add the second monomer methacrylic acid-(2 that is equivalent to 8 times of meterings of initiator with the exsiccant syringe, 2,3,4,4, the 4-hexafluoro) butyl ester (HFBMA), reaction 1～1.5h uses exsiccant methyl alcohol termination reaction at last.Reacted polymkeric substance under 60～70 ℃ of conditions, revolves to steam to remove and desolvates, and continues to carry out deposition and purification with cold normal hexane, and triplicate is dried to constant weight for 40～50 ℃ at vacuum drying oven at last.Obtain required product, record productive rate greater than 90%.Product through gel permeation chromatography (GPC) and proton nmr spectra and fluorine spectrum (
1H NMR,
19FNMR) detect the structure of its molecular weight, molecular weight distribution and multipolymer, prove to have obtained target product.
Embodiment six: MePEG-b-PBAEMA-b-PNDFDMA and preparation thereof
(1) preparation of KH: identical with embodiment one.
(2) preparation of initiator: identical with embodiment one.
(3) polyreaction: add the first monomer methacrylic acid (tertiary butyl amino) ethyl ester (BAEMA) with the exsiccant syringe in the constant temperature oil bath with 40 ℃ of reaction flask immigrations, the mol ratio of controlling first monomer and initiator is 15: 1, is injected into the first monomers B AEMA monomer that is equivalent to 15 times of meterings of initiator and carries out polyreaction 1～1.5h, the mol ratio of controlling second monomer and initiator is 3: 1, then add the second monomer methacrylic acid-(2,2,3 that is equivalent to 3 times of meterings of initiator with the exsiccant syringe, 3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-19 fluorine) ester in the last of the ten Heavenly stems (NDFDMA), reaction 1～1.5h uses exsiccant methyl alcohol termination reaction at last.Reacted polymkeric substance under 60～70 ℃ of conditions, revolves to steam to remove and desolvates, and continues to carry out deposition and purification with cold normal hexane, and triplicate is dried to constant weight for 40～50 ℃ at vacuum drying oven at last.Obtain required product, record productive rate greater than 90%.Product through gel permeation chromatography (GPC) and proton nmr spectra and fluorine spectrum (
1H NMR,
19F NMR) detects the structure of its molecular weight, molecular weight distribution and multipolymer, prove to have obtained target product.
Embodiment seven: MePEG-b-PDMAEMA-b-POFPMA and preparation thereof
(1) preparation of KH: identical with embodiment one.
(2) THF of the preparation of initiator: 15-30ml is expelled in the reaction flask, reaction flask placed 20 ℃ constant temperature oil bath, magnetic agitation, the methyl-sulphoxide (DMSO) of amounts such as injection and KH makes KH and methyl-sulphoxide fully react and forms carbanion (DMSO simultaneously
-K
+).Prepare simultaneously to pack in advance in the bottle polymerization bottle of stirring rotator, dewater after the deoxygenation, take by weighing a certain amount of process exsiccant PEG-2000 (about about 3.75g, 2000 represent the molecular weight of PEG) and a spot of (5～10mg) tritanes (making indicator uses), the THF that injects 20ml makes it dissolving, extracts DMSO with syringe then
-K
+Solution slowly is added drop-wise in the polymerization bottle that PEG and a spot of tritane are housed, and after solution becomes pink in polymerization bottle, stops to drip, and (OH) fully reaction forms oxygen anion to the hydroxyl on the PEG end group at this moment.
(3) polyreaction: then add first monomer methacrylic acid-2-(dimethylamino) ethyl ester (DMAEMA) with the exsiccant syringe in the constant temperature oil bath with 40 ℃ of reaction flask immigrations, the mol ratio of controlling first monomer and initiator is 15: 1, be injected into the first monomer DMAEMA monomer that is equivalent to 15 times of meterings of initiator and carry out polyreaction 1～1.5h, the mol ratio of controlling second monomer and initiator is 6: 1, then add the second monomer methacrylic acid-(2 that is equivalent to 6 times of meterings of initiator with the exsiccant syringe, 2,3,3,4,4,5, the 5-octafluoro) pentyl ester (OFPMA), reaction 1～1.5h uses exsiccant methyl alcohol termination reaction at last.Reacted polymkeric substance under 60～70 ℃ of conditions, revolves to steam to remove and desolvates, and continues to carry out deposition and purification with cold normal hexane, and triplicate is dried to constant weight for 40～50 ℃ at vacuum drying oven at last.Obtain required product, record productive rate greater than 90%.Product through gel permeation chromatography (GPC) and proton nmr spectra and fluorine spectrum (
1HNMR,
19F NMR) detects the structure of its molecular weight, molecular weight distribution and multipolymer, prove to have obtained target product.
Embodiment eight: MePEG-b-PDPAEMA-b-PDDFHMA and preparation thereof
(1) preparation of KH: identical with embodiment one.
(2) preparation of initiator: identical with embodiment seven.
(3) polyreaction: add first monomer methacrylic acid-2-(diisopropylaminoethyl) ethyl ester (DPAEMA) with the exsiccant syringe in the constant temperature oil bath with 40 ℃ of reaction flask immigrations, the mol ratio of controlling first monomer and initiator is 30: 1, be injected into the first monomer DPAEMA monomer that is equivalent to 30 times of meterings of initiator and carry out polyreaction 1～1.5h, the mol ratio of controlling second monomer and initiator is 6: 1, then adds the second monomer methacrylic acid-(2,2 that is equivalent to 6 times of meterings of initiator with the exsiccant syringe, 3,3,4,4,5,5,6,6,7,7-ten difluoros) heptyl ester (DDFHMA), reaction 1～1.5h uses exsiccant methyl alcohol termination reaction at last.Reacted polymkeric substance under 60～70 ℃ of conditions, revolves to steam to remove and desolvates, and continues to carry out deposition and purification with cold normal hexane, and triplicate is dried to constant weight for 40～50 ℃ at vacuum drying oven at last.Obtain required product, record productive rate greater than 90%.Product through gel permeation chromatography (GPC) and proton nmr spectra and fluorine spectrum (
1H NMR,
19F NMR) detects the structure of its molecular weight, molecular weight distribution and multipolymer, prove to have obtained target product.
Embodiment nine: MePEG-b-PDEAEMA-b-PTFEMA and preparation thereof
(1) preparation of KH: identical with embodiment one.
(2) preparation of initiator: identical with embodiment seven.
(3) polyreaction: add first monomer methacrylic acid-2-(diethylin) ethyl ester (DEAEMA) with the exsiccant syringe in the constant temperature oil bath with 40 ℃ of reaction flask immigrations, the mol ratio of controlling first monomer and initiator is 20: 1, be injected into the first monomer DEAEMA monomer that is equivalent to 20 times of meterings of initiator and carry out polyreaction 1～1.5h, the mol ratio of controlling second monomer and initiator is 6: 1, then add the second monomer methacrylic acid-(2 that is equivalent to 6 times of meterings of initiator with the exsiccant syringe, 2, the 2-trifluoro) ethyl ester (TFEMA), reaction 1～1.5h uses exsiccant methyl alcohol termination reaction at last.Reacted polymkeric substance under 60～70 ℃ of conditions, revolves to steam to remove and desolvates, and continues to carry out deposition and purification with cold normal hexane, and triplicate is dried to constant weight for 40～50 ℃ at vacuum drying oven at last.Obtain required product, record productive rate greater than 90%.Product through gel permeation chromatography (GPC) and proton nmr spectra and fluorine spectrum (
1H NMR,
19F NMR) detects the structure of its molecular weight, molecular weight distribution and multipolymer, prove to have obtained target product.
Claims (3)
1. amphipathic fluoride block copolymer, express by following formula:
In the formula, x is 16-45, and y is 10-50, and z is 3-10,
R1 is selected from
Or
R
2Be selected from-CH
2CF
3,-CH
2CF
2CHFCF
3,-CH
2CF
2CF
2CF
2CHF
2,-CH
2CF
2CF
2CF
2CF
2CF
2CHF
2, or-CH
2CF
2CF
2CF
2CF
2CF
2CF
2CF
2CF
2CF
3
2. the preparation method of an amphipathic fluoride block copolymer is characterized in that: adopts oxygen anion initiated polymerization method, comprises the following steps,
(1) preparation initiator: with the tetrahydrofuran (THF) is solvent, after making potassium hydride KH and waiting the methyl-sulphoxide stirring reaction of amount of substance, be added drop-wise in the poly glycol monomethyl ether, and adopt tritane as indicator, when solution begins to present pink, stop to drip, form the oligopolymer oxygen anion, as initiator, the polymerization degree of poly glycol monomethyl ether is 16-45;
(2) initiator and first monomer were constituted polymerization system in 1: 10 to 1: 50 with mol ratio, stir, react 0.5～1.5 hour, described first monomer is selected from methacrylic acid (amino of alkyl replacement) ester, and its structural formula is,
In the formula, R
1Be selected from
(3) add second monomer that is equivalent to 3 to 10 times of initiators with molar ratio computing, stir, reacted 0.5～1.5 hour, described second monomer is selected from the methacrylic acid fluorinated ester, and its structural formula is,
In the formula, R
2Be selected from
-CH
2CF
3,-CH
2CF
2CHFCF
3,-CH
2CF
2CF
2CF
2CHF
2,-CH
2CF
2CF
2CF
2CF
2CF
2CHF
2, or-CH
2CF
2CF
2CF
2CF
2CF
2CF
2CF
2CF
2CF
3
(4) use the methyl alcohol termination reaction, purify, promptly obtain required amphipathic fluoride block copolymer.
3. the preparation method of amphipathic fluoride block copolymer according to claim 2, it is characterized in that: described purification processes is, to continue to carry out deposition and purification with cold normal hexane except that desolvating 60～70 ℃ of backspins steamings, triplicate, at last 40～50 ℃ of vacuum-dryings to constant weight.
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| CNB2006100381348A CN100412101C (en) | 2006-01-27 | 2006-01-27 | Amphipathic fluoride block copolymer and production thereof |
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| CN101481438B (en) * | 2009-02-06 | 2011-03-16 | 苏州大学 | Random copolymerization fluorine-containing macromole emulsifying agent and preparation thereof |
| CN103113595B (en) * | 2012-12-31 | 2014-11-19 | 中科院广州化学有限公司 | Fluorescent block-grafted copolymer with temperature sensitivity and preparation method and application thereof |
| CN103059314B (en) * | 2012-12-31 | 2014-11-19 | 中科院广州化学有限公司 | Fluorine-containing block graft polymer with thermosensitivity and preparation method and application thereof |
| CN105085844A (en) * | 2015-08-05 | 2015-11-25 | 安徽岍汧漆业有限公司 | Diblock copolymer for oil-water separation with temperature control wetting property and preparing method thereof |
| CN110079181A (en) * | 2019-04-12 | 2019-08-02 | 西安理工大学 | A kind of preparation method of environmental response type super-amphiphobic coating |
| CN113801344B (en) * | 2021-09-15 | 2022-08-12 | 复旦大学 | Oxygen-loaded fluorine-containing temperature-sensitive hydrogel and preparation method and application thereof |
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| CN1324877A (en) * | 2001-07-10 | 2001-12-05 | 华东理工大学 | Fluoroacrylic ester block polymer and its prpen. |
| US6451287B1 (en) * | 2000-05-26 | 2002-09-17 | Smithkline Beecham Corporation | Fluorinated copolymer surfactants and use thereof in aerosol compositions |
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