CN103059314B - Fluorine-containing block graft polymer with thermosensitivity and preparation method and application thereof - Google Patents
Fluorine-containing block graft polymer with thermosensitivity and preparation method and application thereof Download PDFInfo
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- CN103059314B CN103059314B CN201210593237.6A CN201210593237A CN103059314B CN 103059314 B CN103059314 B CN 103059314B CN 201210593237 A CN201210593237 A CN 201210593237A CN 103059314 B CN103059314 B CN 103059314B
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Abstract
The invention discloses a fluorine-containing block graft polymer with thermosensitivity and a preparation method and application thereof. According to the invention, fluorine-containing acrylate monomers are polymerized into a macroinitiator by adopting atom transfer radical polymerization; the macroinitiator and glycidyl methacrylate are copolymerized; and after an azide group is introduced into a side chain epoxide cleavage of the obtained product, a polymer with thermosensibility is grafted by adopting the click chemical reaction so as to obtain the block graft polymer. The fluorine-containing block graft polymer has mild reaction conditions, is easy to operate and has high reaction speed and high conversion rate. The preparation method of the fluorine-containing block graft polymer with thermosensitivity, which is disclosed by the invention, is simple and convenient to operate, and has low toxicity and high product purity; and the prepared fluorine-containing block graft polymer with thermosensitivity not only has the advantages of fluorine-containing materials, but also has excellent performance of thermosensitivity and realizes function combination.
Description
Technical field
The invention belongs to field of polymer material preparing technology, particularly a kind of fluorine-containing block graft polymkeric substance with Thermo-sensitive and preparation method thereof and application.
Background technology
Along with the research of intelligent macromolecule material deepens continuously and the improving constantly of the market requirement, studying and develop the intelligent material with dual even multiple response has become the important development direction in this field.For fluorinated intelligent macromolecule material, owing to possessing all kinds of advantages and the specificity of fluorinated polymkeric substance, and response is made in the stimulation of environment to external world by its intelligent characteristic, thereby makes such research with the functional high molecule material of multiple characteristic receive great concern.
Fluorinated intelligent macromolecule material combines self fluorine-containing characteristic (as special surface property, excellent anti-chemical and thermotolerance, good biocompatibility etc.) with intelligent characteristic, such macromolecular material is with a wide range of applications and potentiality at aspects such as aviation special material, biosensor, functional membrane material, gene delivery carrier, control drug release.At present, about the Present study of such material, mainly concentrate on preparation and the performance study aspect of simple linear polymer, as traditional free radical or controllable method utilization is treated different things alike or the method for fractional steps is prepared functional fluorine material.Although this base polymer also can be realized advantage and the specificity of functional fluoropolymer material within the specific limits, but in view of unicity and the uncontrollability of synthetic method, therefore can not regulate and control its functional performance and responding range from microtexture direction, thereby its range of application is had to certain restriction.And utilize controllable method to be undertaken compoundly by thering is the line style of functional performance and the polymkeric substance of non-linearity in an orderly manner, and the functional materials (as block graft type polymkeric substance) that preparation has a special construction becomes current study hotspot.This base polymer not only can practical function Composite, thereby and because the specificity of self is extended its range of application and expands.In addition, by the adjusted and controlled target product of preparing, and study its impact and consequent a series of macromolecular material with specific function on performance by the variation of structure and will there is more far-reaching Research Significance and potential value.Given this, this patent wish adopts the synthetic a series of macromolecular materials with complex function characteristic of controllable method for preparing, the size being intended to by regulating its function block structure and molecular weight is prepared a series of polymkeric substance with diverse microcosmic structure, be that side chain lengths and wetting ability power all can regulate and control, and then inquire into performance difference and the range of application of the functional polymer with different structure.At present, few about the report with fluorine-containing block graft polymkeric substance in pertinent literature, the report of the fluorine-containing block polymer of Thermo-sensitive particularly with different side chain lengths, different grafting densities is few.
Patent 200610038477.4 discloses fluorinated block copolymer of a kind of pH response and preparation method thereof, the method has overcome the harsh reaction conditions of traditional anionoid polymerization, obtain the product that transformation efficiency is high and pure, but the synthetic multipolymer of this method is binary block type structure, structure is single, severe reaction conditions, operation are more difficult, and its assembling pattern is simple and limit its range of application; Patent 200610038134.8 discloses a kind of amphipathic fluoride block copolymer and preparation method thereof, although this product has temperature and pH value dual responsiveness, but still rests on the binary line style block polymer stage, structure is comparatively simple, and synthetic method is comparatively harsh, and range of application is less; Patent 200610041276.X discloses a kind of fluorine-containing superbranching-grafting block polymer and preparation thereof, but because the method that adopts core first is carried out synthesis of super branched polymkeric substance, synthesis condition is comparatively harsh, and carry out the growth of arm and core because system adopts the method for the treatment of different things alike, cause the sterically hindered increase of system and the growth of arm is restricted.
Although also there is the report about the synthetic fluorine material with Thermo-sensitive at present, but the report for the block graft polymkeric substance of being combined with non-linearity by line style is less, especially by regulating the master chain length of this polymkeric substance and grafting density regulates and controls the Thermo-sensitive of polymkeric substance and the research of hydrophilic and hydrophobic this respect is reported still less.
Summary of the invention
Primary and foremost purpose of the present invention is that the shortcoming that overcomes prior art, with not enough, provides a kind of fluorine-containing block graft polymkeric substance with Thermo-sensitive.
Another object of the present invention is to the preparation method of the fluorine-containing block graft polymkeric substance with Thermo-sensitive that provides described.
A further object of the present invention is the application of the fluorine-containing block graft polymkeric substance with Thermo-sensitive that provides described.
Object of the present invention is achieved through the following technical solutions: a kind of fluorine-containing block graft polymkeric substance with Thermo-sensitive, has following structural formula:
Wherein: n is 20～80, is preferably 20～61; M is 20～50, is preferably 22～48; T is 13～80, is preferably 13～78;
R
1be preferably-CH
3or-CH
2cH
3;
R
2be preferably-CH
2cF
2cF
2cF
2cF
2cF
2cF
3,-CH
2cF
2cF
2cF
2cF
2cF
2cHF
2,-CH
2cF
2cF
2cF
2cHF
2,-CH
2cF
3or-CH
2cF
2cHFCF
3;
R
3be preferably-H or-CH
3;
R
4be preferably-NHC(CH
3)
3,-N(C(CH
3)
3)
2,-N(CH
2cH
3)
2,-OCH
2cH
2n(CH
3)
2,-N(CH
3)
2or-OCH
2cH
2(OCH
2cH
2)
xoCH
3; X is 4～65, is preferably 4 or 65;
R
5for fats alkane, be preferably normal-butyl or dodecyl;
The preparation method of the described fluorine-containing block graft polymkeric substance with Thermo-sensitive, comprises the steps:
(1) preparation of fluorinated copolymer: by fluorine-containing methacrylate class monomer, CuX
2, CuX, initiator carry out deoxidation treatment after mixing with solvent orange 2 A, adds part A, 55～80 DEG C of reactions obtained reactant after 2～30 hours, reactant were carried out to purifying dry, obtained fluorine-containing homopolymer; Glycidyl methacrylate (GMA), CuX ' by fluorine-containing homopolymer, side chain with epoxy
2, CuX ' and solvent B carry out deoxidation treatment after mixing, and adds part B, 15～40 DEG C of reactions obtained reaction solution after 2～36 hours, and reaction solution is carried out to purifying, obtained segmented copolymer; By segmented copolymer, sodiumazide, ammonium chloride and N, N-dimethylformamide mixes, and 20～55 DEG C of ring-opening reactions 1～3 day, obtain fluorinated copolymer; Fluorine-containing methacrylate class monomer, part A, CuX
2, CuX, initiator mol ratio be 20～78:1.5～4:0.1～0.4:1～1.5:1～1.2; Glycidyl methacrylate (GMA), part B, fluorine-containing homopolymer, CuX '
2, CuX ' mol ratio be 20～50:1.5～3:1～1.2:0.1～0.3:1～1.2; The mol ratio of segmented copolymer, sodiumazide, ammonium chloride is 1～2:2～6:2～6; The volume ratio of solvent orange 2 A and fluorine-containing methacrylate class monomer is preferably 1～3:1, the quality of solvent B is fluorine-containing homopolymer and fluorine-containing methacrylate class monomer total mass 1～3 times, N, the volume of N-dimethylformamide is preferably 4～7 times of segmented copolymer mole number;
(2) there is the preparation of the homopolymer of temperature-responsive: the chain-transfer agent that has monomer, the Diisopropyl azodicarboxylate (AIBN) of temperature-responsive and contain alkynyl in 50～75 DEG C of polyreactions 4～20 hours, is obtained having the homopolymer of temperature-responsive in 13～80:0.1～0.3:1～3 in molar ratio;
(3) preparation of the fluorine-containing block graft polymkeric substance of Thermo-sensitive: fluorinated copolymer prepared by step (1) mixes 1～2:0.13～0.6 in molar ratio with the homopolymer with temperature-responsive prepared by step (2), in 20～35 DEG C of reactions dialysis afterwards in 2～5 days, centrifugal, get the vacuum-drying of precipitation room temperature, obtain having the fluorine-containing block graft polymkeric substance of Thermo-sensitive;
In step (1):
The structural formula of described fluorine-containing methacrylate class monomer is as follows:
Wherein: R
2be preferably-CH
2cF
3,-CH
2cF
2cHFCF
3,-CH
2cF
2cF
2cF
2cHF
2,-CH
2cF
2cF
2cF
2cF
2cF
2cHF
2or-CH
2cF
2cF
2cF
2cF
2cF
2cF
3;
Described CuX
2be preferably CuCl
2or CuBr
2;
Described CuX is preferably CuCl or CuBr;
Described initiator is preferably 2-isobutyl ethyl bromide or 2-isobutyl bromide methyl esters;
Described solvent orange 2 A is preferably one or both mixtures in pimelinketone, 2-butanone, methyl-phenoxide, phenyl ether and toluene;
Described part A is preferably pentamethyl-two vinylidene three ammonia (PMDETA) or bipyridine (Bpy);
The dry following methods that adopts of described purifying carries out: after reactant is diluted through liquid nitrogen freezing and with methylene dichloride, stir oxidation 1h, after neutral alumina column is processed, (removal catalyzer) gets filtrate, after filtrate is concentrated through reprecipitation processing, get precipitation, room temperature vacuum-drying, obtains fluorine-containing homopolymer;
Described CuX '
2be preferably CuCl
2or CuBr
2;
Described CuX ' is preferably CuCl or CuBr;
Described solvent B is preferably one or both mixtures in pimelinketone, 2-butanone, methyl-phenoxide, phenyl ether and toluene;
Described part B is preferably pentamethyl-two vinylidene three ammonia (PMDETA) or bipyridine (Bpy);
Described purifying adopts following methods to carry out: after reaction solution is diluted through liquid nitrogen freezing and with methylene dichloride, stir oxidation 1h, after neutral alumina column is processed, (removal catalyzer) gets filtrate, after filtrate is concentrated, through reprecipitation processing, gets precipitation, room temperature vacuum-drying, obtains segmented copolymer;
In step (2):
The structural formula of the described monomer with temperature-responsive is as follows:
Wherein: R
3be preferably-H or-CH
3; R
4be preferably-NHC(CH
3)
3,-N(C(CH
3)
3)
2,-N(CH
2cH
3)
2,-OCH
2cH
2n(CH
3)
2,-N(CH
3)
2or-OCH
2cH
2(OCH
2cH
2)
xoCH
3; X is 4～65, is preferably 4 or 65;
The described chain-transfer agent that contains alkynyl is preferably S-normal-butyl-S '-(Alpha-Methyl-α 〞-isopropyl acid alkynes propyl ester) three thioesters or S-dodecyl-S '-(Alpha-Methyl-α 〞-isopropyl acid alkynes propyl ester) three thioesters;
Described polyreaction is preferably carried out in polar solvent, and polar solvent is preferably 2.5～4.5:1 with the mass ratio of the monomer with temperature-responsive;
Described polar solvent is preferably N, N-dimethylformamide, Isosorbide-5-Nitrae-dioxane, dehydrated alcohol or methyl alcohol;
In step (3):
Described reaction, preferably at N, is carried out in N-dimethylformamide (DMF) system;
Described N, N-dimethylformamide system is by CuBr, pentamethyl-two vinylidene three ammonia (PMDETA) and N, N-dimethylformamide mixes composition, the mol ratio of CuBr and pentamethyl-two vinylidene three ammonia is preferably 0.3～0.5:0.3～0.5, N, the quality optimization of N-dimethylformamide is CuBr, pentamethyl-two vinylidene three ammonia, fluorinated copolymer and the total mass with the homopolymer of temperature-responsive 3～6 times;
Described dialysis preferably adopts following methods to carry out: after first dialysing 2～3 days by methyl alcohol room temperature, water is dialysed 2 days again;
Described Thermo-sensitive refers to because temperature change causes the variation of intramolecule structure generation physics or chemical bonding structure and produces volumetric shrinkage, causes occurring incompatible with solvent and occurring the characteristic being separated;
The described fluorine-containing block graft polymkeric substance with Thermo-sensitive can be applicable to prepare function special material or biological medicine material.
The present invention has following advantage and effect with respect to prior art:
(1) the present invention adopts atom transfer radical polymerization that fluorine-containing acrylic ester monomer polymerization is become to macromole evocating agent, and carry out copolymerization with glyceral methacrylate, its side group epoxy open loop is introduced after azido group, adopt the polymkeric substance of click chemistry reactive grafting temperature-responsive to obtain the multipolymer of block graft type, reaction conditions is gentleer, easy to operate, and speed of response is fast, transformation efficiency is high.
(2) easy, the low toxicity of the preparation method of the fluorine-containing block graft polymkeric substance with Thermo-sensitive of the present invention, product purity is high; The fluorine-containing block graft polymkeric substance with Thermo-sensitive preparing not only possesses fluorinated material, and possesses the excellent properties of Thermo-sensitive, has realized function Composite.
Brief description of the drawings
Fig. 1 is the PHFBMA-b-(PGMA-g-PNIPAM of embodiment 1) structural formula.
Fig. 2 is the infrared spectrum of each compound of embodiment 1, wherein: the infrared spectrum that a is PHFBMA, the infrared spectrum that b is PHFBMA-b-PGMA, c is PHFBMA-b-PGMA(OH/N
3) infrared spectrum, d is PHFBMA-b-(PGMA-g-PNIPAM) infrared spectrum.
Fig. 3 is the PHFBMA-b-(PGMA-g-PNIPAM of embodiment 1) hydrogen nuclear magnetic resonance spectrogram.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1:PHFBMA-b-(PGMA-g-PNIPAM) and preparation
(1) preparation of PHFBMA: by fluorine-containing monomer's Hexafluorobutyl mathacrylate (HFBMA) 14.32g, 0.19g initiator 2-isobutyl bromide methyl esters, 0.17g cuprous bromide, 0.05g cupric bromide and 15mL methyl-phenoxide seal bottleneck after joining the single port reaction flask of 50mL, circulate after 3 times through blasting argon gas-freeze-thaw three, add again 0.52g bipyridine and continue by three circulation primary, the oil bath pan that is placed in 65 DEG C reacts 6h, through liquid nitrogen freezing and with stirring oxidation 1h after methylene dichloride dilution, remove catalyzer by neutral alumina, the concentrated 30min postprecipitation of room temperature also filters and solvent flashing in 150mL normal hexane, getting the dissolving of residue 7mL tetrahydrofuran (THF) and 200mL normal hexane precipitates and circulates after 2 times, get precipitation, room temperature vacuum-drying, obtain fluorine-containing homopolymer PTFEMA9.35g,
The preparation of PHFBMA-b-PGMA multipolymer: by PHFBMA2.4g, 1.64g glycidyl methacrylate (GMA), 0.018g cuprous chloride, the 2-butanone of 0.004g cupric bromide and 6mL and the phenyl ether of 4mL seal bottleneck after joining the single port reaction flask of 30mL, circulate after 3 times through blasting argon gas-freeze-thaw three, add again 0.063g part Bpy and continue by three circulation primary, the oil bath pan that is placed in 32 DEG C reacts 8h, through liquid nitrogen freezing and with stirring oxidation 1h after methylene dichloride dilution, remove catalyzer by neutral alumina, the concentrated 30min postprecipitation of room temperature also filters and solvent flashing in 120mL normal hexane, getting the dissolving of residue 4mL tetrahydrofuran (THF) and 150mL normal hexane precipitates and circulates after 2 times, get precipitation, room temperature vacuum-drying, obtain segmented copolymer, after 1.35g segmented copolymer, 1.60g sodiumazide, ammonium chloride 1.31g are mixed with the DMF of 10mL, react 2d in the oil bath pan of 35 DEG C after, system is added drop-wise in 500ml distilled water, filter, get filter residue and wash with water 3 times, room temperature vacuum-drying, obtains PHFBMA-b-PGMA copolymer 1 .08g,
The structural formula of PHFBMA-b-PGMA multipolymer is as follows:
Wherein: m is that 48, n is 41;
The Spectrum Analysis of PHFBMA-b-PGMA multipolymer is as follows:
1h-NMR(CDCl
3): 2.62,2.82(s, epoxide hydroformylation, 2H), 3.21(s, epoxide hydroformylation, 1H), 3.82,4.2(s ,-CH
2-CH-O-, 2H), 4.8-5.0(m ,-CF
2-CHF-, 1H); Gel exclusion chromatography to the characterization result of polymkeric substance is: the number-average molecular weight of polymkeric substance is 1.32 × 10
4gram/mol, dispersed index is 1.21;
(2) preparation of PNIPAM: will there is the monomer NIPA 5.45g of Thermo-sensitive, 0.22g chain-transfer agent S-normal-butyl-S '-(Alpha-Methyl-α 〞-isopropyl acid alkynes propyl ester) three thioesters, 0.013g initiator A IBN and 12mL DMF add in the single port flask of the 25mL that is full of argon gas and good seal, circulate after 2 times through air-blowing-freeze-thaw three, being placed in 70 DEG C of oil bath pans reacts 5h to be placed on ice-water bath cooling, 45 DEG C of underpressure distillation are removed most of DMF postprecipitation in 200mL cold diethyl ether, get precipitation, 25 DEG C are dissolved in 3mL tetrahydrofuran (THF) postprecipitation after dry in 200mL cold diethyl ether, filter, get precipitation, room temperature vacuum-drying, obtain jonquilleous PNIPAM4.32g,
The structural formula of PNIPAM is as follows:
Wherein t is 50;
The Spectrum Analysis of PNIPAM is as follows:
1h-NMR(CDCl
3): 3.96(s ,-CH(CH
3)
2-, 1H), 6.0-7.0(s ,-NH-, 1H); Gel exclusion chromatography to the characterization result of polymkeric substance is: the number-average molecular weight of polymkeric substance is 0.71 × 10
4gram/mol, dispersed index is 1.13;
(3) PTFEMA-b-(PGMA-g-PNIPAM) preparation: PNIPAM prepared by the PTFEMA-b-PGMA multipolymer of 0.3g step (1) and 1.03g step (2), 0.25g Catalysts Cu Br and 0.053g part PMDETA are dissolved in the N of 5mL, in N-dimethylformamide, after reacting 3d in the water-bath of 26 DEG C, the system that blasts sufficient argon gas after room temperature dialysis 3d, in 300mL distilled water, dialyses 2 days in 300mL methyl alcohol, centrifugal, get the vacuum-drying of precipitation room temperature, obtain having the fluorine-containing block graft polymer P TFEMA-b-(PGMA-g-PNIPAM of Thermo-sensitive) 3.87g,
PTFEMA-b-(PGMA-g-PNIPAM) structural formula is as follows:
Wherein, n is that 48, m is that 41, t is 50;
PTFEMA-b-(PGMA-g-PNIPAM) Spectrum Analysis is as follows:
1h-NMR(DMSO-d6): 3.83(s ,-CH(CH
3)
2-, 1H;-CH-OH, 1H), 4.44(s, C(=O) O-CH
2-, 2H), 5.3(s ,-CH
2-, 2H), 5.5(s ,-OH, 1H), 5.9-6.0(d ,-CF
2-CHF-, 1H), 6.0-7.0(s ,-NH-, 1H); Gel exclusion chromatography to the characterization result of polymkeric substance is: the number-average molecular weight of polymkeric substance is 83.44 × 10
4gram/mol, dispersed index is 1.11.
Embodiment 2:PHFBMA-b-(PGMA-g-PDNIPAM) and preparation
(1) preparation of PHFBMA: with embodiment 1 step (1);
The preparation of PHFBMA-b-PGMA multipolymer: with embodiment 1 step (1);
(2) preparation of PDNIPAM: will there is the monomer N of Thermo-sensitive, N-di-isopropyl acrylamide 7.46g, 0.28g chain-transfer agent S-dodecyl-S '-(Alpha-Methyl-α 〞-isopropyl acid alkynes propyl ester) three thioesters, the purified dioxane of 0.014g initiator A IBN and 14mL all joins in the single port flask of the 25mL that is filled with argon gas and good seal, after three circulations of air-blowing-freeze-thaw, being placed in the oil bath pan of 75 DEG C reacts after 7h in ice-water bath stopped reaction, 45 DEG C of underpressure distillation are removed most of dioxane postprecipitation in 200mL cold diethyl ether, get precipitation, 25 DEG C are dissolved in postprecipitation in 4mL tetrahydrofuran (THF) after dry and (repeat this operation 3 times) in 200mL cold diethyl ethers, filter, get the vacuum-drying of precipitation room temperature, obtain PDNIPAM5.43g,
The structural formula of PDNIPAM is as follows:
Wherein t is 57;
The Spectrum Analysis of PDNIPAM is as follows:
1h-NMR(CDCl
3): 1.25(d ,-CH
3, 12H), 1.92(s ,-CH
2-, 2H), 2.15(s ,-CH-, 1H), 3.95(s ,-CH(CH
3)
2-, 1H); Gel exclusion chromatography to the characterization result of polymkeric substance is: the number-average molecular weight of polymkeric substance is 1.03 × 10
4gram/mol, dispersed index is 1.11;
(3) PHFBMA-b-(PGMA-g-PDNIPAM) preparation: PDNIPAM prepared by the PTFEMA-b-PGMA multipolymer of 0.3g step (1) and 1.92g step (2), 0.036g Catalysts Cu Br and 0.057g part PMDETA are dissolved in the N of 6mL, in N-dimethylformamide, blast sufficient argon gas, 2d dialyses after room temperature dialysis 3d react 3d in 26 DEG C of water-baths after in 300mL methyl alcohol in 300mL distilled water, centrifugal, get precipitation, room temperature vacuum-drying, obtain having the fluorine-containing block graft polymer P HFBMA-b-(PGMA-g-PDNIPAM of Thermo-sensitive) 1.87g,
PHFBMA-b-(PGMA-g-PDNIPAM) structure is as follows:
Wherein, n is that 48, m is that 41, t is 57;
PHFBMA-b-(PGMA-g-PDNIPAM) Spectrum Analysis is as follows:
1h-NMR(DMSO-d6): 3.85(s ,-CH(CH
3)
2-, 1H;-CH-OH, 1H), 4.44(s, C(=O) O-CH
2-, 2H), 5.3(s ,-CH
2-, 2H), 5.5(s ,-OH, 1H), 5.9-6.0(d ,-CF
2-CHF-, 1H); Gel exclusion chromatography to the characterization result of polymkeric substance is: the number-average molecular weight of polymkeric substance is 104.36 × 10
4gram/mol, dispersed index is 1.13.
Embodiment 3:PHFBMA-b-(PGMA-g-PDMAEMA) and preparation
(1) preparation of PHFBMA: with embodiment 1 step (1);
The preparation of PHFBMA-b-PGMA multipolymer: with embodiment 1 step (1);
(2) preparation of PDMAEMA: will there is the monomer dimethylaminoethyl acrylate methyl base ammonia ethyl ester 8.76g of Thermo-sensitive, 0.25g chain-transfer agent S-dodecyl-S '-(Alpha-Methyl-α 〞-isopropyl acid alkynes propyl ester) three thioesters, 0.018g initiator A IBN and 25mL dioxane join in the single port flask of the 50mL that is full of argon gas and sealing, after three circulations of air-blowing-freeze-thaw, being placed in the oil bath pan of 65 DEG C reacts 6h and is placed on ice-water bath stopped reaction, 46 DEG C of underpressure distillation are removed most of dioxane postprecipitation in 200mL cold diethyl ether, get precipitation, 25 DEG C are dissolved in postprecipitation in 4mL tetrahydrofuran (THF) after dry and (repeat this operation 3 times) in 200mL cold diethyl ethers, filter, get the vacuum-drying of precipitation room temperature, obtain PDMAEMA7.29g,
The structure of PDMAEMA is as follows:
Wherein t is 78;
The Spectrum Analysis of PDMAEMA is as follows:
1h-NMR(CDCl
3): 2.26(s ,-CH
3, 6H), 2.55(s ,-CH
2-, 2H), 4.02(s ,-C(=O) O-CH
2-, 2H); Gel exclusion chromatography to the characterization result of polymkeric substance is: the number-average molecular weight of polymkeric substance is 1.54 × 10
4gram/mol, dispersed index is 1.18;
(3) PHFBMA-b-(PGMA-g-PDMAEMA) preparation: PDMAEMA, 0.025g Catalysts Cu Br prepared by the PTFEMA-b-PGMA multipolymer of 0.32g step (1) and 2.60g step (2) and 0.047g part PMDETA are dissolved in the N of 7mL, in N-dimethylformamide, blast sufficient argon gas, after 28 DEG C of water-bath 3d, after 300mL methyl alcohol room temperature dialysis 2d, in 300mL distilled water, dialyse after 2d, centrifugal, get precipitation, room temperature vacuum-drying, obtains having the fluorine-containing block graft polymer P HFBMA-b-(PGMA-g-PDMAEMA of Thermo-sensitive) 2.42g;
PHFBMA-b-(PGMA-g-PDMAEMA) structure is as follows:
Wherein, n is that 48, m is that 41, t is 78;
PHFBMA-b-(PGMA-g-PDMAEMA) Spectrum Analysis is as follows:
1h-NMR(DMSO-d6): 2.28(s ,-CH
3, 6H), 2.58(s ,-CH
2-, 2H), 3.85(s ,-CH-OH, 1H), 4.12(s ,-C(=O) and O-CH
2-, 2H), 4.44(s, C(=O) O-CH2-, 2H), 5.3(s ,-CH
2-, 2H), 5.5(s ,-OH, 1H), 5.9-6.0(d ,-CF
2-CHF-, 1H); Gel exclusion chromatography to the characterization result of polymkeric substance is: the number-average molecular weight of polymkeric substance is 245.25 × 10
4gram/mol, dispersed index is 1.15.
Embodiment 4:PTFEMA-b-(PGMA-g-PNIPAM) and preparation
(1) preparation of fluorine-containing homopolymer PTFEMA: by fluorine-containing monomer's trifluoroethyl methacrylate (TFEMA) 11.32g, initiator 2-isobutyl ethyl bromide 0.18g, cuprous bromide 0.162g, cupric bromide 0.046g and 15mL pimelinketone seal bottleneck after adding the single port reaction flask of 50mL, circulate after 2 times through blasting argon gas-freeze-thaw three, add again 0.48g bipyridine and continue by three circulation primary, be placed in 60 DEG C of oil bath pans and react 6h, through liquid nitrogen freezing and with stirring oxidation 1h after methylene dichloride dilution, remove catalyzer by neutral alumina, the concentrated 30min postprecipitation of room temperature is in 150mL normal hexane, get precipitation, with after the dissolving of 5mL tetrahydrofuran (THF) and 200mL normal hexane precipitation (repetitive operation 3 times), get precipitation, room temperature vacuum-drying, obtain fluorine-containing homopolymer PTFEMA8.52g,
The preparation of PTFEMA-b-PGMA multipolymer: by 0.2g PTFEMA, 1.66g glycidyl methacrylate (GMA), 0.018g cuprous chloride, 0.004g cupric bromide and 6mL2-butanone and 4mL phenyl ether seal bottleneck after joining 30mL single port reaction flask, circulate after 3 times through blasting argon gas-freeze-thaw three, add again 0.06g part PMDETA and continue by three circulation primary, being placed in 32 DEG C of oil bath pans reacts after 8h, through liquid nitrogen freezing and with stirring oxidation 1h after methylene dichloride dilution, remove catalyzer by neutral alumina, the concentrated 30min postprecipitation of room temperature is in 150mL normal hexane, get precipitation, with after the dissolving of 5mL tetrahydrofuran (THF) and 200mL normal hexane precipitation (repetitive operation 3 times), get precipitation, room temperature vacuum-drying, obtain segmented copolymer, after 1.1g segmented copolymer, 1.60g sodiumazide, ammonium chloride 1.31g are mixed with the DMF of 10mL, react 2d in 45 DEG C of oil bath pans after, pour in 500ml distilled water, filter, get filter residue and wash with water 3 times, room temperature vacuum-drying, obtains PTFEMA-b-PGMA multipolymer 0.94g,
The structure of PTFEMA-b-PGMA is as follows, and wherein n is that 61, m is 48;
The Spectrum Analysis of PTFEMA-b-PGMA is as follows:
1h-NMR(CDCl
3): 2.62,2.82(s, epoxide hydroformylation, 2H), 3.21(s, epoxide hydroformylation, 1H), 3.82,4.20-4.35(m ,-CH
2-CH-O-, 2H;-CH
2-, 2H); Gel exclusion chromatography to the characterization result of polymkeric substance is: the number-average molecular weight of polymkeric substance is 1.82 × 10
4gram/mol, dispersed index is 1.23;
(2) preparation of PNIPAM: with embodiment 1 step (2);
(3) PTFEMA-b-(PGMA-g-PNIPAM) preparation: PNIPAM, 0.012g Catalysts Cu Br prepared by the PTFEMA-b-PGMA multipolymer of 0.2g step (1) and 0.52g step (2) and 0.026g part PMDETA are dissolved in the N of 5mL, in N-dimethylformamide, be filled with sufficient argon gas, 2d dialyses react 3d in 26 DEG C of water-baths after after 300mL methyl alcohol room temperature dialysis 3d in 300mL distilled water, centrifugal, get the vacuum-drying of precipitation room temperature, obtain having the fluorine-containing block graft polymer P TFEMA-b-(PGMA-g-PNIPAM of Thermo-sensitive) 0.47g;
PTFEMA-b-(PGMA-g-PNIPAM) structure is as follows,
Wherein, n is that 61, m is that 48, t is 50;
PTFEMA-b-(PGMA-g-PNIPAM) Spectrum Analysis is as follows:
1h-NMR(DMSO-d6): 3.83(s ,-CH(CH
3)
2-, 1H;-CH-OH, 1H), 5.3(s ,-CH
2-, 2H), 5.5(s ,-OH, 1H), 5.9-6.0(d ,-CF
2-CHF-, 1H), 6.0-7.0(s ,-NH-, 1H); Gel exclusion chromatography to the characterization result of polymkeric substance is: the number-average molecular weight of polymkeric substance is 75.62 × 10
4gram/mol, dispersed index is 1.11.
Embodiment 5:PTFEMA-b-(PGMA-g-PDMAEMA) and preparation
(1) preparation of PTFEMA: with embodiment 4 steps (1);
The preparation of PTFEMA-b-PGMA multipolymer: with embodiment 4 steps (1);
(2) preparation of PDMAEMA: with embodiment 3 steps (2);
(3) PTFEMA-b-(PGMA-g-PDMAEMA) preparation: PDMAEMA, 0.023g Catalysts Cu Br prepared by the PTFEMA-b-PGMA multipolymer of 0.25g step (1) and 2.45g step (2) and 0.042g part PMDETA are dissolved in the N of 8mL, in N-dimethylformamide, be filled with sufficient argon gas, 2d dialyses after 26 DEG C of water-bath 3d after 300mL methyl alcohol room temperature dialysis 3d in 300mL distilled water, centrifugal, get the vacuum-drying of precipitation room temperature, obtain having the fluorine-containing block graft polymer P TFEMA-b-(PGMA-g-PDMAEMA of Thermo-sensitive) 2.12g;
PTFEMA-b-(PGMA-g-PDMAEMA) structure is as follows:
Wherein, n is that 61, m is that 48, t is 78;
PTFEMA-b-(PGMA-g-PDMAEMA) Spectrum Analysis is as follows:
1h-NMR(DMSO-d6): 2.26(s ,-CH
3, 6H), 2.55(s ,-CH
2-, 2H), 3.83(s ,-CH-OH, 1H), 4.15(s ,-C(=O) and O-CH
2-, 2H), 5.3(s ,-CH
2-, 2H), 5.5(s ,-OH, 1H), 5.9-6.0(d ,-CF
2-CHF-, 1H); Gel exclusion chromatography to the characterization result of polymkeric substance is: the number-average molecular weight of polymkeric substance is 167.45 × 10
4gram/mol, dispersed index is 1.09.
Embodiment 6:POFPMA-b-(PGMA-g-PNIPAM) and preparation
(1) preparation of fluorine-containing homopolymer POFPMA: by fluorine-containing monomer's methacrylic acid octafluoro pentyl ester (OFPMA) 14.32g, 0.22g initiator 2-isobutyl ethyl bromide, 0.17g cuprous bromide, 0.042g cupric bromide and 15mL pimelinketone seal bottleneck after joining the single port reaction flask of 50mL, circulate after 3 times through blasting argon gas-freeze-thaw three, add again 0.52g bipyridine and continue by three circulation primary, the oil bath pan that is placed in 70 DEG C reacts 4h, through liquid nitrogen freezing and with stirring oxidation 1h after methylene dichloride dilution, remove catalyzer by neutral alumina, the concentrated 30min postprecipitation of room temperature is in 200mL normal hexane, get after precipitation 5mL tetrahydrofuran (THF) dissolving and 200mL normal hexane precipitation (repetitive operation 3 times), get precipitation, room temperature vacuum-drying, obtain POFPMA10.52g,
The preparation of POFPMA-b-PGMA multipolymer: by P POFPMA-Br(2.8g), 1.83g glycidyl methacrylate (GMA), 0.032g cuprous bromide, the methyl-phenoxide of 0.004g cupric bromide and 10mL seals bottleneck after joining the single port reaction flask of 30mL, circulate after 3 times through blasting argon gas-freeze-thaw three, add again 0.08g part Bpy and continue by three circulation primary, the oil bath pan that is placed in 27 DEG C reacts 10h, through liquid nitrogen freezing and with stirring oxidation 1h after methylene dichloride dilution, remove catalyzer by neutral alumina, the concentrated 30min postprecipitation of room temperature is in 150mL normal hexane, get after precipitation 5mL tetrahydrofuran (THF) dissolving and 200mL normal hexane precipitation (repetitive operation 3 times), get precipitation, room temperature vacuum-drying, obtain segmented copolymer, after 1.52g segmented copolymer, 0.82g sodiumazide, ammonium chloride 0.68g are mixed with the DMF of 8mL, react 2d in 35 DEG C of oil bath pans after, pour in 500ml distilled water, filter, get filter residue and wash with water 3 times, room temperature vacuum-drying, obtains POFPMA-b-PGMA copolymer 1 .12g,
The structure of POFPMA-b-PGMA is as follows:
Wherein n is that 35, m is 40;
The Spectrum Analysis of POFPMA-b-PGMA is as follows:
1h-NMR(CDCl
3): 2.62,2.82(s, epoxide hydroformylation, 2H), 3.21(s, epoxide hydroformylation, 1H), 3.82,4.20-4.42(m ,-CH
2-CH-O-, 2H;-C(=O)-O-CH
2-, 2H), 5.72(s ,-CHF
2, 1H); Gel exclusion chromatography to the characterization result of polymkeric substance is: the number-average molecular weight of polymkeric substance is 1.68 × 10
4gram/mol, dispersed index is 1.25;
(2) preparation of PNIPAM: will there is the monomer NIPA 4.53g of Thermo-sensitive, 0.1556g chain-transfer agent S-dodecyl-S '-(Alpha-Methyl-α 〞-isopropyl acid alkynes propyl ester) three thioesters, 0.007g initiator A IBN and 10mL DMF add in the single port flask of the 25mL that is full of argon gas and good seal, circulate after 2 times through air-blowing-freeze-thaw three, being placed in 70 DEG C of oil bath pans reacts 4h to be placed on ice-water bath cooling, 45 DEG C of underpressure distillation are removed most of DMF postprecipitation in 200mL cold diethyl ether, get precipitation, 25 DEG C are dissolved in 3ml tetrahydrofuran (THF) postprecipitation after dry in 200mL cold diethyl ether, filter, get precipitation, room temperature vacuum-drying, obtain jonquilleous PNIPAM3.69g,
The structure of PNIPAM is as follows:
Wherein t is 36;
The Spectrum Analysis of PNIPAM is as follows:
1h-NMR(CDCl
3): 1.1(d ,-CH
3, 6H), 3.96(s ,-CH(CH
3)
2-, 1H), 6.0-7.0(s ,-NH-, 1H); Gel exclusion chromatography to the characterization result of polymkeric substance is: the number-average molecular weight of polymkeric substance is 0.46 × 10
4gram/mol, dispersed index is 1.11;
(3) POFPMA-b-(PGMA-g-PNIPAM) preparation: PNIPAM, 0.019g Catalysts Cu Br prepared by the POFPMA-b-PGMA multipolymer of 0.2g step (1) and 0.59g step (2) and 0.034g part PMDETA are dissolved in the N of 5mL, in N-dimethylformamide, be filled with sufficient argon gas, 2d dialyses after 25 DEG C of water-bath 3d after 300mL methyl alcohol room temperature dialysis 2d in 300mL distilled water, centrifugal, get precipitation, room temperature vacuum-drying, obtains having the fluorine-containing block graft polymer P OFPMA-b-(PGMA-g-PNIPAM of Thermo-sensitive) 0.69g;
POFPMA-b-(PGMA-g-PNIPAM) structure is as follows:
Wherein, n is that 35, m is that 40, t is 36;
POFPMA-b-(PGMA-g-PNIPAM) Spectrum Analysis is as follows:
1h-NMR(DMSO-d6): 3.82,4.20-4.42(m ,-CH
2-CH-O-, 2H;-C(=O)-O-CH
2-, 2H ,-CH-OH, 1H), 5.82(s ,-CHF
2, 1H), 5.3(s ,-CH
2-, 2H), 5.5(s ,-OH, 1H), 6.0-7.0(s ,-NH-, 1H); Gel exclusion chromatography to the characterization result of polymkeric substance is: the number-average molecular weight of polymkeric substance is 75.34 × 10
4gram/mol, dispersed index is 1.08.
Embodiment 7:POFPMA-b-(PGMA-g-PmPEGMA) and preparation
(1) preparation of fluorine-containing homopolymer POFPMA: with embodiment 6 steps (1);
The preparation of POFPMA-b-PGMA: with embodiment 6 steps (1);
(2) preparation of PmPEGMA: will there is the monomer polyethylene glycol monomethyl ethermethacrylic acid esters 9.82g of Thermo-sensitive, 0.28g chain-transfer agent S-normal-butyl-S '-(Alpha-Methyl-α 〞-isopropyl acid alkynes propyl ester) three thioesters, 0.018g initiator A IBN and 14mL DMF join in the single port flask of the 25mL that is full of argon gas and good seal, after three circulations of air-blowing-freeze-thaw, being placed in the oil bath pan of 70 DEG C reacts after 4.5h in ice-water bath stopped reaction, 45 DEG C of underpressure distillation are removed most of DMF postprecipitation in 200mL normal hexane, get 25 DEG C of precipitations and be dissolved in 3mL tetrahydrofuran (THF) postprecipitation after dry in 200mL normal hexane (repetitive operation 3 times), get precipitation, room temperature vacuum-drying, obtain PmPEGMA7.12g,
The structure of PmPEGMA is as follows: wherein, t is that 26, x is 4;
The Spectrum Analysis of PmPEGMA is as follows:
1h-NMR(CDCl
3): 3.35(s ,-CH
3-, 3H), 3.51,3.62(s ,-O-CH
2-CH
2-O-, 2H), 4.05(s ,-C(=O)-O-CH
2-, 2H); Gel exclusion chromatography to the characterization result of polymkeric substance is: the number-average molecular weight of polymkeric substance is 0.82 × 10
4gram/mol, dispersed index is 1.23;
(3) POFPMA-b-(PGMA-g-PmPEGMA) preparation: PmPEGMA, 0.036g Catalysts Cu Br prepared by the POFPMA-b-PGMA multipolymer of 0.35g step (1) and 1.84g step (2) and 0.066g part PMDETA are dissolved in the N of 7mL, in N-dimethylformamide, blast argon gas, 2d dialyses after room temperature dialysis 3d after 25 DEG C of water-bath 2.5d in 300mL methyl alcohol in 300mL distilled water, centrifugal, get the vacuum-drying of precipitation room temperature, obtain having the fluorine-containing block graft polymer P OFPMA-b-(PGMA-g-PmPEGMA of Thermo-sensitive) 1.89g;
POFPMA-b-(PGMA-g-PmPEGMA) structure is as follows:
Wherein, n is that 35, m is that 40, t is that 26, x is 4;
POFPMA-b-(PGMA-g-PmPEGMA) Spectrum Analysis is as follows:
1h-NMR(DMSO-d6): 3.35(s ,-CH
3-, 3H), 3.51,3.62(s ,-O-CH
2-CH
2-O-, 2H), 3.82,4.20-4.42(m ,-CH
2-CH-O-, 2H;-C(=O)-O-CH
2-, 2H ,-CH-OH, 1H), 5.3(s ,-CH
2-, 2H), 5.5(s ,-OH, 1H), 5.82(s ,-CHF
2, 1H); Gel exclusion chromatography to the characterization result of polymkeric substance is: the number-average molecular weight of polymkeric substance is, 112.42 × 10
4gram/mol, dispersed index is 1.12.
Embodiment 8:PDFHMA-b-(PGMA-g-PNIPAM) and preparation
(1) preparation of fluorine-containing homopolymer PDFHMA: by fluorine-containing monomer's dodecafluoroheptyl methacrylate (DFHMA) 8.78g, 0.24g initiator 2-isobutyl bromide methyl esters, 0.112g cuprous bromide, 0.017g cupric bromide and 15mL pimelinketone seal bottleneck after joining the single port reaction flask of 50mL, circulate after 3 times through blasting argon gas-freeze-thaw three, add again 0.183g bipyridine and continue by three circulation primary, being placed in the oil bath pan of 73 DEG C reacts after 4.5h in ice-water bath stopped reaction, through liquid nitrogen freezing and with stirring oxidation 1h after methylene dichloride dilution, remove catalyzer by neutral alumina, the concentrated 30min postprecipitation of room temperature is in 200mL normal hexane, get after precipitation 5mL tetrahydrofuran (THF) dissolving and 200mL normal hexane precipitation (repetitive operation 3 times), get precipitation, room temperature vacuum-drying, obtain PDFHMA5.96g,
The preparation of PDFHMA-b-PGMA multipolymer: by PDFHMA-Br(3.2g), 1.83g glycidyl methacrylate (GMA), 0.067g cuprous bromide, the methyl-phenoxide of 0.016g cupric bromide and 10mL seals bottleneck after joining the single port reaction flask of 30mL, circulate after 3 times through blasting argon gas-freeze-thaw three, add again 0.178g part Bpy and continue by three circulation primary, being placed in the oil bath pan of 70 DEG C reacts after 5h in ice-water bath stopped reaction, 45 DEG C of underpressure distillation are removed most of DMF postprecipitation in 200mL normal hexane, 25 DEG C are dissolved in 3ml tetrahydrofuran (THF) postprecipitation after dry again in 200mL normal hexane (repetitive operation 3 times), get precipitation, room temperature vacuum-drying, obtain segmented copolymer 3.72g, after 1.66g segmented copolymer, 0.41g sodiumazide, ammonium chloride 1.02g are mixed with the DMF of 8mL, react 3d in the oil bath pan of 25 DEG C after, pour in a large amount of distilled water, filter, get filter residue and wash 3 times, room temperature vacuum-drying, obtains PDFHMA-b-PGMA copolymer 1 .18g,
The structure of PDFHMA-b-PGMA is as follows:
Wherein, n is that 20, m is 22;
The Spectrum Analysis of PDFHMA-b-PGMA is as follows:
1h-NMR(CDCl
3): 2.62,2.82(s, epoxide hydroformylation, 2H), 3.21(s, epoxide hydroformylation, 1H) and, 3.82(s ,-CH
2-CH-O-, 2H), 4.20-4.42(m ,-CH
2-CH-O-, 2H;-C(=O)-O-CH
2-, 2H), 5.74(s ,-CHF
2, 1H); Gel exclusion chromatography to the characterization result of polymkeric substance is: the number-average molecular weight of polymkeric substance is 1.16 × 10
4gram/mol, dispersed index is 1.25;
(2) preparation of PNIPAM: will there is the monomer N of Thermo-sensitive, N-diethyl acrylamide (NIPAM) 12.71g, 0.874g chain-transfer agent S-dodecyl-S '-(Alpha-Methyl-α 〞-isopropyl acid alkynes propyl ester) three thioesters, 0.111g initiator A IBN and 15mL DMF add in the single port flask of the 25mL that is full of argon gas and good seal, after three circulations of air-blowing-freeze-thaw, being placed in the oil bath pan of 65 DEG C reacts after 5h in ice-water bath stopped reaction, 45 DEG C of underpressure distillation are removed most of DMF postprecipitation in 200mL normal hexane, get 25 DEG C of precipitations and be dissolved in again in 3mL tetrahydrofuran (THF) postprecipitation after dry in 200mL normal hexane (repetitive operation 3 times), get precipitation, room temperature vacuum-drying, obtain glassy yellow PNIPAM8.76g,
The structure of PNIPAM is as follows:
Wherein, t is 42;
The Spectrum Analysis of PNIPAM is as follows:
1h-NMR(CDCl
3): 1.1(d ,-CH
3, 6H), 3.96(s ,-CH(CH
3)
2-, 1H), 6.0-7.0(s ,-NH-, 1H); Gel exclusion chromatography to the characterization result of polymkeric substance is: the number-average molecular weight of polymkeric substance is 0.48 × 10
4gram/mol, dispersed index is 1.12;
(3) PDFHMA-b-(PGMA-g-PNIPAM) preparation: the N that PNIPAM, the 0.65g Catalysts Cu Br of the PDFHMA-b-PGMA multipolymer of 0.42g step (1) and 1.26g step (2) and 0.78g part PMDETA is dissolved in to 6.5mL, in N-dimethylformamide, blast argon gas, 2d dialyses after room temperature dialysis 3d react 2.5d in the water-bath of 25 DEG C after in 300mL methyl alcohol in 300mL distilled water, centrifugal, get the vacuum-drying of precipitation room temperature, obtain having the fluorine-containing block graft polymer P DFHMA-b-(PGMA-g-PNIPAM of Thermo-sensitive) 1.89g;
PDFHMA-b-(PGMA-g-PNIPAM) structure is as follows:
Wherein, n is that 20, m is that 22, t is 42;
PDFHMA-b-(PGMA-g-PNIPAM) Spectrum Analysis is as follows:
1h-NMR(DMSO-d6): 3.8-3.9(s ,-CH(CH
3)
2-, 1H; ), 6.0-7.0(s ,-NH-, 1H), 4.0-4.2(s ,-C(=O)-O-CH
2-, 2H), 4.8(s ,-CHF
2, 1H), 5.3(s ,-CH
2-, 2H), 5.5(s ,-OH, 1H); Gel exclusion chromatography to the characterization result of polymkeric substance is: the number-average molecular weight of polymkeric substance is 63.43 × 10
4gram/mol, dispersed index is 1.23.
Embodiment 9:PDFHMA-b-(PGMA-g-PDMAEMA) and preparation
(1) preparation of fluorine-containing homopolymer PDFHMA: with step (1) in embodiment 8;
The preparation of PDFHMA-b-PGMA multipolymer: with step (1) in embodiment 8;
(2) preparation of PDMAEMA: will there is the monomer dimethylaminoethyl acrylate methyl base ammonia ethyl ester 8.78g of Thermo-sensitive, 0.481g chain-transfer agent S-normal-butyl-S '-(Alpha-Methyl-α 〞-isopropyl acid alkynes propyl ester) three thioesters, the purified dioxane of 0.029g initiator A IBN and 22mL all adds in the single port flask of the 50mL that is filled with argon gas and good seal, after three circulations of air-blowing-freeze-thaw, being placed in the oil bath pan of 65 DEG C reacts after 4h in ice-water bath stopped reaction, 44 DEG C of underpressure distillation are removed most of DMF postprecipitation in 200mL normal hexane, get after 25 DEG C of precipitations are dried and be dissolved in again 3mL postprecipitation in 200mL normal hexane (repetitive operation 3 times), get precipitation, room temperature vacuum-drying, obtain white PDMAEMA6.26g,
The structure of PDMAEMA is as follows:
Wherein, t is 25;
The Spectrum Analysis of PDMAEMA is as follows:
1h-NMR(CDCl
3): 2.26(s ,-CH
3, 6H), 2.55(s ,-CH
2-, 2H), 4.02(s ,-C(=O) O-CH
2-, 2H); Gel exclusion chromatography to the characterization result of polymkeric substance is: the number-average molecular weight of polymkeric substance is 0.43 × 10
4gram/mol, dispersed index is 1.23;
(3) PDFHMA-b-(PGMA-g-PDMAEMA) preparation: the N that PDMAEMA, the 0.014g Catalysts Cu Br of the PDFHMA-b-PGMA multipolymer of 0.4g step (1) and 0.425g step (2) and 0.017g part PMDETA is dissolved in to 4mL, in N-dimethylformamide, blast argon gas, 2d dialyses after room temperature dialysis 3d react 3d in the water-bath of 27 DEG C after in 300mL methyl alcohol in 300mL distilled water, centrifugal, get the vacuum-drying of precipitation room temperature, obtain having the fluorine-containing block graft polymer P DFHMA-b-(PGMA-g-PDMAEMA of Thermo-sensitive) 0.6g;
PDFHMA-b-(PGMA-g-PDMAEMA) structure is as follows:
Wherein, n is that 20, m is that 22, t is 25;
PDFHMA-b-(PGMA-g-PDMAEMA) Spectrum Analysis is as follows:
1h-NMR(DMSO-d6): 2.26(s ,-CH
3, 6H), 2.55(s ,-CH
2-, 2H), 4.0-4.2(s ,-C(=O)-O-CH
2-, 2H), 4.8(s ,-CHF
2, 1H), 5.3(s ,-CH
2-, 2H), 5.5(s ,-OH, 1H); Gel exclusion chromatography to the characterization result of polymkeric substance is: the number-average molecular weight of polymkeric substance is 43.56 × 10
4gram/mol, dispersed index is 1.23.
Embodiment 10:PPFOMA-b-(PGMA-g-PDNIPAM) and preparation
(1) preparation of fluorine-containing homopolymer PPFOMA: by fluorine-containing monomer's methacrylic acid ten trifluoro monooctyl ester (PFOMA) 13.21g, 0.218g initiator 2-isobutyl ethyl bromide, 0.11g cuprous bromide, 0.035g cupric chloride and 15mL pimelinketone seal bottleneck after joining the single port reaction flask of 50mL, circulate after 3 times through blasting argon gas-freeze-thaw three, add again 0.58g bipyridine and continue by three circulation primary, the oil bath pan that is placed in temperature and is 75 DEG C reacts 12h, through liquid nitrogen freezing and with stirring oxidation 1h after methylene dichloride dilution, remove catalyzer by neutral alumina, the concentrated 30min postprecipitation of room temperature is in 200mL normal hexane, get after precipitation 5mL tetrahydrofuran (THF) dissolving and 200mL normal hexane precipitation (repetitive operation 3 times), get precipitation, room temperature vacuum-drying, obtain PPFOMA8.63g,
The preparation of PPFOMA-b-PGMA multipolymer: by PPFOMA-Br(2.70g), 1.54g glycidyl methacrylate (GMA), 0.032g cuprous bromide, the methyl-phenoxide of 0.015g cupric bromide and 9mL seals bottleneck after joining the single port reaction flask of 30mL, circulate after 3 times through blasting argon gas-freeze-thaw three, add again 0.078g part PMDETA and continue by three circulation primary, the oil bath pan that is placed in temperature and is 28 DEG C reacts 16h, through liquid nitrogen freezing and with stirring oxidation 1h after methylene dichloride dilution, remove catalyzer by neutral alumina, the concentrated 30min postprecipitation of room temperature is in 200mL normal hexane, get after precipitation 5mL tetrahydrofuran (THF) dissolving and 200mL normal hexane precipitation (repetitive operation 3 times), get precipitation, room temperature vacuum-drying, obtain segmented copolymer 3.24g, after 1.23g segmented copolymer, 0.98g sodiumazide, ammonium chloride 0.81g are mixed with the DMF of 8mL, react 2.5d in the oil bath pan of 32 DEG C after, pour in 400mL distilled water, filter, get and precipitate and wash 3 times, room temperature vacuum-drying, obtains PPFOMA-b-PGMA copolymer 1 .89g,
The structure of PPFOMA-b-PGMA is as follows:
Wherein, n is that 25, m is 35;
The Spectrum Analysis of PPFOMA-b-PGMA is as follows:
1h-NMR(CDCl
3): 2.62,2.82(s, epoxide hydroformylation, 2H), 3.21(s, epoxide hydroformylation, 1H), 3.82,4.20-4.5(m ,-CH
2-CH-O-, 2H;-C(=O)-O-CH
2-, 2H); Gel exclusion chromatography to the characterization result of polymkeric substance is: the number-average molecular weight of polymkeric substance is 1.72 × 10
4gram/mol, dispersed index is 1.26;
(2) preparation of PDNIPAM: will there is the monomer NIPA 6.32g of Thermo-sensitive, 0.31g chain-transfer agent S-dodecyl-S '-(Alpha-Methyl-α 〞-isopropyl acid alkynes propyl ester) three thioesters, the purified DMF of 0.019g initiator A IBN and 12mL all adds in the single port flask of the 25mL that is filled with argon gas and good seal, after three circulations of air-blowing-freeze-thaw, being placed in the oil bath pan of 67 DEG C reacts after 6.5h in ice-water bath stopped reaction, 44 DEG C of underpressure distillation are removed most of DMF postprecipitation in 200mL normal hexane, get 25 DEG C of precipitations and be dissolved in again in 3mL tetrahydrofuran (THF) postprecipitation after dry in 200mL normal hexane (repetitive operation 3 times), get precipitation, room temperature vacuum-drying, obtain PDNIPAM4.64g,
The structure of PDNIPAM is as follows:
Wherein, t is 41;
The Spectrum Analysis of PDNIPAM is as follows:
1h-NMR(CDCl
3): 1.25(d ,-CH
3, 12H), 1.92(s ,-CH
2-, 2H), 2.15(s ,-CH-, 1H), 3.95(s ,-CH(CH
3)
2-, 1H); Gel exclusion chromatography to the characterization result of polymkeric substance is: the number-average molecular weight of polymkeric substance is 0.68 × 10
4gram/mol, dispersed index is 1.15;
(3) PPFOMA-b-(PGMA-g-PDNIPAM) preparation: the N that PDNIPAM, the 0.021g Catalysts Cu Br of the PPFOMA-b-PGMA multipolymer of 0.25g step (1) and 0.97g step (2) and 0.024g part PMDETA is dissolved in to 6.5mL, in N-dimethylformamide, blast argon gas, 2d dialyses after room temperature dialysis 3d react 3d in the water-bath of 28 DEG C after in 300mL methyl alcohol in 300mL distilled water, centrifugal, get the vacuum-drying of precipitation room temperature, obtain having the fluorine-containing block graft polymer P PFOMA-b-(PGMA-g-PDNIPAM of Thermo-sensitive) 0.89g;
PPFOMA-b-(PGMA-g-PDNIPAM) structure is as follows:
Wherein, n is that 25, m is that 35, t is 41;
PPFOMA-b-(PGMA-g-PDNIPAM) Spectrum Analysis is as follows:
1h-NMR(DMSO-d6): 1.25(d ,-CH
3, 12H), 1.92(s ,-CH
2-, 2H), 2.15(s ,-CH-, 1H), 3.85(s ,-CH(CH
3)
2-, 1H), 4.1-4.4(m ,-C(=O)-O-CH
2-, 2H), 5.3(s ,-CH
2-, 2H), 5.5(s ,-OH, 1H); Gel exclusion chromatography to the characterization result of polymkeric substance is: the number-average molecular weight of polymkeric substance is 106.34 × 10
4gram/mol, dispersed index is 1.14.
Embodiment 11:PPFOMA-b-(PGMA-g-PmPEGMA) and preparation
(1) preparation of fluorine-containing homopolymer PPFOMA: with step (1) in embodiment 10;
The preparation of PPFOMA-b-PGMA multipolymer: with step (1) in embodiment 10;
(2) preparation of PmPEGMA: will there is the monomer polyethylene glycol monomethyl ethermethacrylic acid esters 6.21g of Thermo-sensitive, 0.026g chain-transfer agent S-normal-butyl-S '-(Alpha-Methyl-α 〞-isopropyl acid alkynes propyl ester) three thioesters, 0.014g initiator A IBN and 11mL DMF all add in the single port flask of the 25mL that is filled with argon gas and good seal, after three circulations of air-blowing-freeze-thaw, being placed in the oil bath pan of 50 DEG C reacts after 6h in ice-water bath stopped reaction, 44 DEG C of underpressure distillation are removed most of DMF postprecipitation in 200mL normal hexane, get 25 DEG C of precipitations and be dissolved in again in 3mL tetrahydrofuran (THF) postprecipitation after dry in 200mL normal hexane (repetitive operation 3 times), get precipitation, room temperature vacuum-drying, obtain PmPEGMA4.04g,
The structure of PmPEGMA is as follows:
Wherein, t is that 13, x is 65;
The Spectrum Analysis of PmPEGMA is as follows:
1h-NMR(DMSO-d6): 3.35(s ,-CH
3-, 3H), 3.51,3.62(s ,-O-CH
2-CH
2-O-, 2H), 4.05(s ,-C(=O)-O-CH
2-, 2H); Gel exclusion chromatography to the characterization result of polymkeric substance is: the number-average molecular weight of polymkeric substance is 4.01 × 10
4gram/mol, dispersed index is 1.27;
(3) PPFOMA-b-(PGMA-g-PmPEGMA) preparation: the N that PmPEGMA, the 0.013g Catalysts Cu Br of the PPFOMA-b-PGMA multipolymer of 0.25g step (1) and 3.67g step (2) and 0.042g part PMDETA is dissolved in to 10mL, in N-dimethylformamide, blast argon gas, 2d dialyses after room temperature dialysis 3d react 4d in the water-bath of 25 DEG C after in 300mL methyl alcohol in 300mL distilled water, centrifugal, get the vacuum-drying of precipitation room temperature, obtain having the fluorine-containing block graft polymer P PFOMA-b-(PGMA-g-PmPEGMA of Thermo-sensitive) 3.02g;
PPFOMA-b-(PGMA-g-PmPEGMA) structure is as follows:
Wherein, n is that 25, m is that 35, t is that 13, x is 65;
PPFOMA-b-(PGMA-g-PmPEGMA) Spectrum Analysis is as follows:
1h-NMR(DMSO-d6): 3.35(s ,-CH
3-, 3H), 3.51,3.62(s ,-O-CH
2-CH
2-O-, 2H), 4.1-4.5(m ,-C(=O)-O-CH
2-, 2H), 5.3(s ,-CH
2-, 2H), 5.5(s ,-OH, 1H); Gel exclusion chromatography to the characterization result of polymkeric substance is: the number-average molecular weight of polymkeric substance is 324.13 × 10
4gram/mol, dispersed index is 1.15.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. a fluorine-containing block graft polymkeric substance with Thermo-sensitive, is characterized in that having following structural formula:
Wherein: n is that 20～80, m is that 20～50, t is 13～80;
R
1for-CH
3or-CH
2cH
3;
R
2for-CH
2cF
2cF
2cF
2cF
2cF
2cF
3,-CH
2cF
2cF
2cF
2cF
2cF
2cHF
2,-CH
2cF
3,-CH
2cF
2cF
2cF
2cHF
2or-CH
2cF
2cHFCF
3;
R
3for-H or-CH
3;
R
4for-NHC (CH
3)
3,-N (C (CH
3)
3)
2,-N (CH
2cH
3)
2,-OCH
2cH
2n (CH
3)
2,-N (CH
3)
2or-OCH
2cH
2(OCH
2cH
2)
xoCH
3; X is 4～65;
R
5for fats alkane group.
2. the preparation method of the fluorine-containing block graft polymkeric substance with Thermo-sensitive claimed in claim 1, is characterized in that comprising the steps:
(1) preparation of fluorinated copolymer: by fluorine-containing methacrylate class monomer, CuX
2, CuX, initiator carry out deoxidation treatment after mixing with solvent orange 2 A, adds part A, 55～80 DEG C of reactions obtained reactant after 2～30 hours, reactant were carried out to purifying dry, obtained fluorine-containing homopolymer; Glycidyl methacrylate, CuX ' by fluorine-containing homopolymer, side chain with epoxy
2, CuX ' and solvent B carry out deoxidation treatment after mixing, and adds part B, 15～40 DEG C of reactions obtained reaction solution after 2～36 hours, and reaction solution is carried out to purifying, obtained segmented copolymer; Segmented copolymer, sodiumazide, ammonium chloride and DMF are mixed, and 20～55 DEG C of ring-opening reactions 1～3 day, obtain fluorinated copolymer; Fluorine-containing methacrylate class monomer, part A, CuX
2, CuX, initiator mol ratio be 20～78:1.5～4:0.1～0.4:1～1.5:1～1.2; Glycidyl methacrylate, part B, fluorine-containing homopolymer, CuX '
2, CuX ' mol ratio be 20～50:1.5～3:1～1.2:0.1～0.3:1～1.2; The mol ratio of segmented copolymer, sodiumazide, ammonium chloride is 1～2:2～6:2～6; The volume ratio of solvent orange 2 A and fluorine-containing methacrylate class monomer is 1～3:1, and the quality of solvent B is fluorine-containing homopolymer and fluorine-containing methacrylate class monomer total mass 1～3 times, and the volume of DMF is 4～7 times of segmented copolymer mole number;
(2) there is the preparation of the homopolymer of temperature-responsive: the chain-transfer agent that has monomer, the Diisopropyl azodicarboxylate of temperature-responsive and contain alkynyl in 50～75 DEG C of polyreactions 4～20 hours, is obtained having the homopolymer of temperature-responsive in 13～80:0.1～0.3:1～3 in molar ratio;
(3) preparation of the fluorine-containing block graft polymkeric substance of Thermo-sensitive: fluorinated copolymer prepared by step (1) mixes 1～2:0.13～0.6 in molar ratio with the homopolymer with temperature-responsive prepared by step (2), in 20～35 DEG C of reactions dialysis afterwards in 2～5 days, centrifugal, get the vacuum-drying of precipitation room temperature, obtain having the fluorine-containing block graft polymkeric substance of Thermo-sensitive.
3. the preparation method of the fluorine-containing block graft polymkeric substance with Thermo-sensitive according to claim 2, is characterized in that: the structural formula of the fluorine-containing methacrylate class monomer described in step (1) is as follows:
Wherein: R
2for-CH
2cF
3,-CH
2cF
2cHFCF
3,-CH
2cF
2cF
2cF
2cHF
2,-CH
2cF
2cF
2cF
2cF
2cF
2cHF
2or-CH
2cF
2cF
2cF
2cF
2cF
2cF
3.
4. the preparation method of the fluorine-containing block graft polymkeric substance with Thermo-sensitive according to claim 2, is characterized in that: the CuX described in step (1)
2for CuCl
2or CuBr
2; Described CuX is CuCl or CuBr.
5. the preparation method of the fluorine-containing block graft polymkeric substance with Thermo-sensitive according to claim 2, is characterized in that: in step (1):
Described initiator is 2-isobutyl ethyl bromide or 2-isobutyl bromide methyl esters;
Described solvent orange 2 A is one or both mixtures in pimelinketone, 2-butanone, methyl-phenoxide, phenyl ether and toluene;
Described part A is pentamethyl-two vinylidene three ammonia or bipyridines;
Described CuX '
2for CuCl
2or CuBr
2;
Described CuX ' is CuCl or CuBr;
Described solvent B is one or both mixtures in pimelinketone, 2-butanone, methyl-phenoxide, phenyl ether and toluene;
Described part B is pentamethyl-two vinylidene three ammonia or bipyridines.
6. the preparation method of the fluorine-containing block graft polymkeric substance with Thermo-sensitive according to claim 2, is characterized in that: the structural formula of the monomer with temperature-responsive described in step (2) is as follows:
Wherein: R
3for-H or-CH
3; R
4for-NHC (CH
3)
3,-N (C (CH
3)
3)
2,-N (CH
2cH
3)
2,-OCH
2cH
2n (CH
3)
2,-N (CH
3)
2or-OCH
2cH
2(OCH
2cH
2)
xoCH
3; X is 4～65.
7. the preparation method of the fluorine-containing block graft polymkeric substance with Thermo-sensitive according to claim 2, is characterized in that: the chain-transfer agent that contains alkynyl described in step (2) is S-normal-butyl-S '-(Alpha-Methyl-α 〞-isopropyl acid alkynes propyl ester) three thioesters or S-dodecyl-S '-(Alpha-Methyl-α 〞-isopropyl acid alkynes propyl ester) three thioesters;
Described polyreaction is carried out in polar solvent, and polar solvent is 2.5～4.5:1 with the mass ratio of the monomer with temperature-responsive.
8. the preparation method of the fluorine-containing block graft polymkeric substance with Thermo-sensitive according to claim 7, is characterized in that: described polar solvent is DMF, Isosorbide-5-Nitrae-dioxane, dehydrated alcohol or methyl alcohol.
9. the preparation method of the fluorine-containing block graft polymkeric substance with Thermo-sensitive according to claim 2, is characterized in that: the reaction described in step (3) is carried out in DMF system; Described N, dinethylformamide system is by CuBr, pentamethyl-two vinylidene three ammonia and N, dinethylformamide mixes composition, the mol ratio of CuBr and pentamethyl-two vinylidene three ammonia is 0.3～0.5:0.3～0.5, the quality of DMF is CuBr, pentamethyl-two vinylidene three ammonia, fluorinated copolymer and the total mass with the homopolymer of temperature-responsive 3～6 times.
10. the fluorine-containing block graft polymer application with Thermo-sensitive claimed in claim 1 is in preparation function special material or biological medicine material.
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| CN107602785B (en) * | 2017-08-15 | 2019-04-02 | 四川大学 | A kind of block polymer ordered porous membrane material of the structure containing melamine and its preparation and film build method |
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