CN103059314A - 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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- CN103059314A CN103059314A CN2012105932376A CN201210593237A CN103059314A CN 103059314 A CN103059314 A CN 103059314A CN 2012105932376 A CN2012105932376 A CN 2012105932376A CN 201210593237 A CN201210593237 A CN 201210593237A CN 103059314 A CN103059314 A CN 103059314A
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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 have fluorine-containing block graft polymkeric substance of Thermosensitive and preparation method thereof and an application.
Background technology
Along with the research of intelligent macromolecule material deepens continuously and the improving constantly of the market requirement, the research also intelligent material of exploitation with dual even multiple response has become the important development direction in this field.For the fluorinated intelligent macromolecule material, owing to possess all kinds of advantages and the specificity of fluorinated polymkeric substance, and its intelligent characteristic to external world stimulation of environment is made response, thereby so that such research with functional high molecule material of multiple characteristic receives great concern.
The fluorinated intelligent macromolecule material combines self fluorine-containing characteristic (such as special surface property, excellent anti-chemical and thermotolerance, good biocompatibility etc.) with intelligent characteristic, so that 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, such as traditional free radical or the controllable method utilization is treated different things alike or the method for fractional steps prepares functional fluorine material.Although this base polymer also can be realized advantage and the specificity of functional fluoropolymer material within the specific limits, but unicity and uncontrollability in view of synthetic method, so can not regulate and control its functional performance and responding range from the microtexture direction, thereby its range of application is had certain restriction.And that the polymkeric substance that utilizes controllable method will have in an orderly manner the line style of functional performance and non-linearity carries out is compound, and the functional materials (such as block graft type polymkeric substance) that preparation has a special construction becomes present study hotspot.This base polymer not only can the practical function Composite, thereby and since the specificity of self its range of application is extended and expansion.In addition, by adjusted and controlled preparation target product, and study its impact and consequent a series of macromolecular material with specific function on performance by the variation of structure and will have more far-reaching Research Significance and potential value.Given this, the this patent wish adopts the synthetic a series of macromolecular materials with complex function characteristic of controllable method for preparing, be intended to prepare a series of polymkeric substance with diverse microcosmic structure by the size of regulating its function block structure and molecular weight, be that side chain lengths and wetting ability power all can be regulated 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 the pertinent literature, the report of the fluorine-containing block polymer of Thermo-sensitive that particularly has 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 high and pure product of transformation efficiency, but the synthetic multipolymer of this method is binary block type structure, structure is single, severe reaction conditions, operation difficulty, 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 carry out the synthesis of super branched polymkeric substance owing to adopt the method for core first, synthesis condition is comparatively harsh, and because system adopts the method treat different things alike to carry out the growth of arm and nuclear, cause the sterically hindered increase of system and the growth of arm is restricted.
Although at present also relevant for synthetic report with Thermosensitive fluorine material, but the report for the block graft polymkeric substance of being combined with non-linearity by line style is less, and especially the research report of the master chain length by regulating this polymkeric substance and the grafting density Thermo-sensitive of regulating and control polymkeric substance and hydrophilic and hydrophobic this respect still less.
Summary of the invention
The shortcoming that primary and foremost purpose of the present invention is to overcome prior art provides a kind of fluorine-containing block graft polymkeric substance of Thermosensitive that has with not enough.
Another object of the present invention is to provide described preparation method with the fluorine-containing block graft polymkeric substance of Thermosensitive.
A further object of the present invention is to provide described application with the fluorine-containing block graft polymkeric substance of Thermosensitive.
Purpose of the present invention is achieved through the following technical solutions: a kind of have a fluorine-containing block graft polymkeric substance of Thermosensitive, 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
3X is 4～65, is preferably 4 or 65;
R
5Be fats alkane, be preferably normal-butyl or dodecyl;
Described preparation method with the fluorine-containing block graft polymkeric substance of Thermosensitive comprises the steps:
(1) preparation of fluorinated copolymer: with fluorine-containing methacrylate class monomer, CuX
2, CuX, initiator with carry out deoxidation treatment after solvent orange 2 A mixes, add part A, 55～80 ℃ of reactions obtained reactant after 2～30 hours, and reactant is carried out the purifying drying, obtained fluorine-containing homopolymer; With fluorine-containing homopolymer, side chain glycidyl methacrylate (GMA), the CuX ' with epoxy
2, CuX ' and solvent B carry out deoxidation treatment after mixing, and adds part B, 15～40 ℃ of reactions obtained reaction solution after 2～36 hours, and reaction solution is carried out purifying, obtained segmented copolymer; With segmented copolymer, sodiumazide, ammonium chloride and N, the N-dimethylformamide mixes, and 20～55 ℃ 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 are preferably 4～7 times of segmented copolymer mole number;
(2) have the preparation of the homopolymer of temperature-responsive: the chain-transfer agent that will have monomer, the Diisopropyl azodicarboxylate (AIBN) of temperature-responsive and contain alkynyl in molar ratio 13～80:0.1～0.3:1～3 obtains having the homopolymer of temperature-responsive in 50～75 ℃ of polyreactions 4～20 hours;
(3) preparation of the fluorine-containing block graft polymkeric substance of Thermosensitive: the fluorinated copolymer of step (1) preparation is mixed 1～2:0.13～0.6 in molar ratio with the homopolymer with temperature-responsive of step (2) preparation, in 20～35 ℃ of reactions afterwards dialysis in 2～5 days, centrifugal, get the vacuum-drying of precipitation room temperature, obtain having the fluorine-containing block graft polymkeric substance of Thermosensitive;
In the 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 the toluene;
Described part A is preferably pentamethyl-two vinylidenes, three ammonia (PMDETA) or bipyridine (Bpy);
The dry following methods that adopts of described purifying carries out: reactant is stirred oxidation 1h through liquid nitrogen freezing and after with the methylene dichloride dilution, (removal catalyzer) gets filtrate after neutral alumina column is processed, filtrate concentrating processed by reprecipitation, 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 the toluene;
Described part B is preferably pentamethyl-two vinylidenes, three ammonia (PMDETA) or bipyridine (Bpy);
Described purifying adopts following methods to carry out: reaction solution is stirred oxidation 1h through liquid nitrogen freezing and after with the methylene dichloride dilution, (removal catalyzer) gets filtrate after neutral alumina column is processed, and filtrate is concentrated by the reprecipitation processing, gets precipitation, room temperature vacuum-drying obtains segmented copolymer;
In the step (2):
The structural formula of described monomer with temperature-responsive is as follows:
Wherein: R
3Be preferably-H or-CH
3R
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
3X 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 with monomer of temperature-responsive;
Described polar solvent is preferably N, N-dimethylformamide, Isosorbide-5-Nitrae-dioxane, dehydrated alcohol or methyl alcohol;
In the step (3):
Described reaction is carried out in N-dimethylformamide (DMF) system preferably at N;
Described N, N-dimethylformamide system is by CuBr, pentamethyl-two vinylidenes, three ammonia (PMDETA) and N, the N-dimethylformamide mixes and forms, the mol ratio of CuBr and pentamethyl-two vinylidenes three ammonia is preferably 0.3～0.5:0.3～0.5, N, the quality optimization of N-dimethylformamide are 3～6 times of total mass of CuBr, pentamethyl-two vinylidenes three ammonia, fluorinated copolymer and the homopolymer with temperature-responsive;
Described dialysis preferably adopts following methods to carry out: first with methyl alcohol room temperature dialysis again water dialysis 2 days after 2～3 days;
Described Thermo-sensitive refers to produce volumetric shrinkage because temperature change causes the variation of intramolecule structure generation physics or chemical bonding structure, causes occuring incompatible and characteristic that occur being separated with solvent;
Described have the fluorine-containing block graft polymkeric substance of Thermosensitive and 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 macromole evocating agent, and carry out copolymerization with glyceral methacrylate, behind its side group epoxy open loop introducing azido group, the polymkeric substance of employing click chemistry reactive grafting temperature-responsive obtains the multipolymer of block graft type, reaction conditions is gentle, easy to operate, and speed of response is fast, transformation efficiency is high.
(2) easy, the low toxicity of preparation method with the fluorine-containing block graft polymkeric substance of Thermosensitive of the present invention, product purity is high; The fluorine-containing block graft polymkeric substance of Thermosensitive that has for preparing not only possesses the advantage of fluorinated material, and possesses the Thermosensitive excellent properties, has realized the function Composite.
Description of 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, and wherein: a is the infrared spectrum of PHFBMA, and b is the infrared spectrum of PHFBMA-b-PGMA, and 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) the hydrogen nuclear magnetic resonance spectrogram.
Embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but embodiments of the present invention are not limited to this.
Embodiment 1:PHFBMA-b-(PGMA-g-PNIPAM) and the preparation
(1) preparation of PHFBMA: with 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, after blasting argon gas-freeze-thaw three circulation 3 times, add again the 0.52g bipyridine and continue to pass through three circulation primary, place 65 ℃ oil bath pan to react 6h, stir oxidation 1h through liquid nitrogen freezing and after with the methylene dichloride dilution, remove catalyzer by neutral alumina, the concentrated 30min postprecipitation of room temperature also filters and solvent flashing in the 150mL normal hexane, get residue with 7mL tetrahydrofuran (THF) dissolving and 200mL normal hexane precipitation and circulate after 2 times, get precipitation, room temperature vacuum-drying obtains fluorine-containing homopolymer PTFEMA9.35g;
The preparation of PHFBMA-b-PGMA multipolymer: with PHFBMA2.4g, 1.64g glycidyl methacrylate (GMA), 0.018g cuprous chloride, 0.004g the 2-butanone of cupric bromide and 6mL and the phenyl ether of 4mL seal bottleneck after joining the single port reaction flask of 30mL, after blasting argon gas-freeze-thaw three circulation 3 times, add again 0.063g part Bpy and continue to pass through three circulation primary, place 32 ℃ oil bath pan to react 8h, stir oxidation 1h through liquid nitrogen freezing and after with the methylene dichloride dilution, remove catalyzer by neutral alumina, the concentrated 30min postprecipitation of room temperature also filters and solvent flashing in the 120mL normal hexane, get residue with 4mL tetrahydrofuran (THF) dissolving and 150mL normal hexane precipitation and circulate after 2 times, get precipitation, room temperature vacuum-drying obtains segmented copolymer; After the DMF of 1.35g segmented copolymer, 1.60g sodiumazide, ammonium chloride 1.31g and 10mL mixed, in 35 ℃ oil bath pan, behind the reaction 2d system is added drop-wise in the 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), and 3.21(s, epoxide hydroformylation, 1H), and 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
4G/mol, dispersed index is 1.21;
(2) preparation of PNIPAM: will have Thermosensitive monomer NIPA 5.45g, 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, after air-blowing-freeze-thaw three circulations 2 times, placing 70 ℃ of oil bath pan reaction 5h to be placed on ice-water bath cools off, 45 ℃ of underpressure distillation are removed most of DMF postprecipitation in the 200mL cold diethyl ether, get precipitation, be dissolved in the 3mL tetrahydrofuran (THF) postprecipitation after 25 ℃ of dryings in the 200mL cold diethyl ether, filter, get precipitation, room temperature vacuum-drying obtains 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
4G/mol, dispersed index is 1.13;
(3) preparation PTFEMA-b-(PGMA-g-PNIPAM): with the PTFEMA-b-PGMA multipolymer of 0.3g step (1) and the PNIPAM of 1.03g step (2) preparation, 0.25g Catalysts Cu Br and 0.053g part PMDETA are dissolved in the N of 5mL, in the N-dimethylformamide, the system that blasts sufficient argon gas was reacted behind the 3d in 300mL methyl alcohol behind the room temperature dialysis 3d in 300mL distilled water dialysis 2 days in 26 ℃ water-bath, centrifugal, get the vacuum-drying of precipitation room temperature, obtain having the fluorine-containing block graft polymer P of Thermosensitive TFEMA-b-(PGMA-g-PNIPAM) 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
4G/mol, dispersed index is 1.11.
Embodiment 2:PHFBMA-b-(PGMA-g-PDNIPAM) and the 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 have Thermosensitive monomer N, N-di-isopropyl acrylamide 7.46g, 0.28g chain-transfer agent S-dodecyl-S '-(Alpha-Methyl-α 〞-isopropyl acid alkynes propyl ester) three thioesters, 0.014g the purified dioxane of 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, place behind 75 ℃ the oil bath pan reaction 7h in the ice-water bath stopped reaction, 45 ℃ of underpressure distillation are removed most of dioxane postprecipitation in the 200mL cold diethyl ether, get precipitation, be dissolved in after 25 ℃ of dryings that postprecipitation (repeats this operation 3 times) in the 4mL tetrahydrofuran (THF) in the 200mL cold diethyl ether, 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
4G/mol, dispersed index is 1.11;
(3) preparation PHFBMA-b-(PGMA-g-PDNIPAM): with the PTFEMA-b-PGMA multipolymer of 0.3g step (1) and the PDNIPAM of 1.92g step (2) preparation, 0.036g Catalysts Cu Br and 0.057g part PMDETA are dissolved in the N of 6mL, in the N-dimethylformamide, blast sufficient argon gas, 2d dialyses in 300mL distilled water behind the room temperature dialysis 3d in 300mL methyl alcohol behind the reaction 3d in 26 ℃ of water-baths, centrifugal, get precipitation, room temperature vacuum-drying obtains having the fluorine-containing block graft polymer P of Thermosensitive HFBMA-b-(PGMA-g-PDNIPAM) 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
4G/mol, dispersed index is 1.13.
Embodiment 3:PHFBMA-b-(PGMA-g-PDMAEMA) and the 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 have Thermosensitive monomer dimethylaminoethyl acrylate methyl base ammonia ethyl ester 8.76g, 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, place 65 ℃ oil bath pan reaction 6h to be placed on the ice-water bath stopped reaction, 46 ℃ of underpressure distillation are removed most of dioxane postprecipitation in the 200mL cold diethyl ether, get precipitation, be dissolved in after 25 ℃ of dryings that postprecipitation (repeats this operation 3 times) in the 4mL tetrahydrofuran (THF) in the 200mL cold diethyl ether, 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
4G/mol, dispersed index is 1.18;
(3) preparation PHFBMA-b-(PGMA-g-PDMAEMA): with PTFEMA-b-PGMA multipolymer and PDMAEMA, the 0.025g Catalysts Cu Br of 2.60g step (2) preparation and the N that 0.047g part PMDETA is dissolved in 7mL of 0.32g step (1), in the N-dimethylformamide, blast sufficient argon gas, behind the 2d that after 300mL methyl alcohol room temperature is dialysed 2d, in 300mL distilled water, dialyses behind 28 ℃ of water-bath 3d, centrifugal, get precipitation, room temperature vacuum-drying obtains having the fluorine-containing block graft polymer P of Thermosensitive HFBMA-b-(PGMA-g-PDMAEMA) 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) 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
4G/mol, dispersed index is 1.15.
Embodiment 4:PTFEMA-b-(PGMA-g-PNIPAM) and the preparation
(1) preparation of fluorine-containing homopolymer PTFEMA: with fluorine-containing monomer's trifluoroethyl methacrylate (TFEMA) 11.32g, initiator 2-isobutyl ethyl bromide 0.18g, cuprous bromide 0.162g, seal bottleneck behind the single port reaction flask of cupric bromide 0.046g and 15mL pimelinketone adding 50mL, after blasting argon gas-freeze-thaw three circulation 2 times, add again the 0.48g bipyridine and continue to pass through three circulation primary, place 60 ℃ of oil bath pans to react 6h, stir oxidation 1h through liquid nitrogen freezing and after with the methylene dichloride dilution, remove catalyzer by neutral alumina, the concentrated 30min postprecipitation of room temperature is in the 150mL normal hexane, get precipitation, after the dissolving of 5mL tetrahydrofuran (THF) and 200mL normal hexane precipitation (repetitive operation 3 times), get precipitation, room temperature vacuum-drying obtains fluorine-containing homopolymer PTFEMA8.52g;
The preparation of PTFEMA-b-PGMA multipolymer: with 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, after blasting argon gas-freeze-thaw three circulation 3 times, add again 0.06g part PMDETA and continue to pass through three circulation primary, after placing 32 ℃ of oil bath pan reaction 8h, stir oxidation 1h through liquid nitrogen freezing and after with the methylene dichloride dilution, remove catalyzer by neutral alumina, the concentrated 30min postprecipitation of room temperature is in the 150mL normal hexane, get precipitation, after the dissolving of 5mL tetrahydrofuran (THF) and 200mL normal hexane precipitation (repetitive operation 3 times), get precipitation, room temperature vacuum-drying obtains segmented copolymer; After the DMF of 1.1g segmented copolymer, 1.60g sodiumazide, ammonium chloride 1.31g and 10mL mixed, reaction is poured in the 500ml distilled water behind the 2d in 45 ℃ of oil bath pans, filters, and gets filter residue and washes 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), and 3.21(s, epoxide hydroformylation, 1H), and 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
4G/mol, dispersed index is 1.23;
(2) preparation of PNIPAM: with embodiment 1 step (2);
(3) preparation PTFEMA-b-(PGMA-g-PNIPAM): with PTFEMA-b-PGMA multipolymer and PNIPAM, the 0.012g Catalysts Cu Br of 0.52g step (2) preparation and the N that 0.026g part PMDETA is dissolved in 5mL of 0.2g step (1), in the N-dimethylformamide, be filled with sufficient argon gas, 2d dialyses in 300mL distilled water behind 300mL methyl alcohol room temperature dialysis 3d behind the reaction 3d in 26 ℃ of water-baths, centrifugal, get the vacuum-drying of precipitation room temperature, obtain having the fluorine-containing block graft polymer P of Thermosensitive TFEMA-b-(PGMA-g-PNIPAM) 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
4G/mol, dispersed index is 1.11.
Embodiment 5:PTFEMA-b-(PGMA-g-PDMAEMA) and the 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) preparation PTFEMA-b-(PGMA-g-PDMAEMA): with PTFEMA-b-PGMA multipolymer and PDMAEMA, the 0.023g Catalysts Cu Br of 2.45g step (2) preparation and the N that 0.042g part PMDETA is dissolved in 8mL of 0.25g step (1), in the N-dimethylformamide, be filled with sufficient argon gas, in the 2d that behind 300mL methyl alcohol room temperature dialysis 3d, in 300mL distilled water, dialyses behind 26 ℃ of water-bath 3d, centrifugal, get the vacuum-drying of precipitation room temperature, obtain having the fluorine-containing block graft polymer P of Thermosensitive TFEMA-b-(PGMA-g-PDMAEMA) 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) 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
4G/mol, dispersed index is 1.09.
Embodiment 6:POFPMA-b-(PGMA-g-PNIPAM) and the preparation
(1) preparation of fluorine-containing homopolymer POFPMA: with 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, after blasting argon gas-freeze-thaw three circulation 3 times, add again the 0.52g bipyridine and continue to pass through three circulation primary, place 70 ℃ oil bath pan to react 4h, stir oxidation 1h through liquid nitrogen freezing and after with the methylene dichloride dilution, remove catalyzer by neutral alumina, the concentrated 30min postprecipitation of room temperature is in the 200mL normal hexane, get and precipitate with after the dissolving of 5mL tetrahydrofuran (THF) and the 200mL normal hexane precipitation (repetitive operation 3 times), get precipitation, room temperature vacuum-drying obtains POFPMA10.52g;
The preparation of POFPMA-b-PGMA multipolymer: with P POFPMA-Br(2.8g), 1.83g glycidyl methacrylate (GMA), 0.032g cuprous bromide, 0.004g the methyl-phenoxide of cupric bromide and 10mL seals bottleneck after joining the single port reaction flask of 30mL, after blasting argon gas-freeze-thaw three circulation 3 times, add again 0.08g part Bpy and continue to pass through three circulation primary, place 27 ℃ oil bath pan to react 10h, stir oxidation 1h through liquid nitrogen freezing and after with the methylene dichloride dilution, remove catalyzer by neutral alumina, the concentrated 30min postprecipitation of room temperature is in the 150mL normal hexane, get and precipitate with after the dissolving of 5mL tetrahydrofuran (THF) and the 200mL normal hexane precipitation (repetitive operation 3 times), get precipitation, room temperature vacuum-drying obtains segmented copolymer; After the DMF of 1.52g segmented copolymer, 0.82g sodiumazide, ammonium chloride 0.68g and 8mL mixed, reaction is poured in the 500ml distilled water behind the 2d in 35 ℃ of oil bath pans, filters, and gets filter residue and washes 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), and 3.21(s, epoxide hydroformylation, 1H), and 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
4G/mol, dispersed index is 1.25;
(2) preparation of PNIPAM: will have Thermosensitive monomer NIPA 4.53g, 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, after air-blowing-freeze-thaw three circulations 2 times, placing 70 ℃ of oil bath pan reaction 4h to be placed on ice-water bath cools off, 45 ℃ of underpressure distillation are removed most of DMF postprecipitation in the 200mL cold diethyl ether, get precipitation, be dissolved in the 3ml tetrahydrofuran (THF) postprecipitation after 25 ℃ of dryings in the 200mL cold diethyl ether, filter, get precipitation, room temperature vacuum-drying obtains 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
4G/mol, dispersed index is 1.11;
(3) preparation POFPMA-b-(PGMA-g-PNIPAM): with POFPMA-b-PGMA multipolymer and PNIPAM, the 0.019g Catalysts Cu Br of 0.59g step (2) preparation and the N that 0.034g part PMDETA is dissolved in 5mL of 0.2g step (1), in the N-dimethylformamide, be filled with sufficient argon gas, in the 2d that behind 300mL methyl alcohol room temperature dialysis 2d, in 300mL distilled water, dialyses behind 25 ℃ of water-bath 3d, centrifugal, get precipitation, room temperature vacuum-drying obtains having the fluorine-containing block graft polymer P of Thermosensitive OFPMA-b-(PGMA-g-PNIPAM) 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
4G/mol, dispersed index is 1.08.
Embodiment 7:POFPMA-b-(PGMA-g-PmPEGMA) and the 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 have Thermosensitive monomer polyethylene glycol monomethyl ethermethacrylic acid esters 9.82g, 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, place behind 70 ℃ the oil bath pan reaction 4.5h in the ice-water bath stopped reaction, 45 ℃ of underpressure distillation are removed most of DMF postprecipitation in the 200mL normal hexane, get and be dissolved in the 3mL tetrahydrofuran (THF) postprecipitation after 25 ℃ of dryings of precipitation in 200mL normal hexane (repetitive operation 3 times), get precipitation, room temperature vacuum-drying obtains 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
4G/mol, dispersed index is 1.23;
(3) preparation POFPMA-b-(PGMA-g-PmPEGMA): with POFPMA-b-PGMA multipolymer and PmPEGMA, the 0.036g Catalysts Cu Br of 1.84g step (2) preparation and the N that 0.066g part PMDETA is dissolved in 7mL of 0.35g step (1), in the N-dimethylformamide, blast argon gas, in the 2d that in 300mL methyl alcohol, in 300mL distilled water, dialyses behind the room temperature dialysis 3d behind 25 ℃ of water-bath 2.5d, centrifugal, get the vacuum-drying of precipitation room temperature, obtain having the fluorine-containing block graft polymer P of Thermosensitive OFPMA-b-(PGMA-g-PmPEGMA) 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
4G/mol, dispersed index is 1.12.
Embodiment 8:PDFHMA-b-(PGMA-g-PNIPAM) and the preparation
(1) preparation of fluorine-containing homopolymer PDFHMA: with 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, after blasting argon gas-freeze-thaw three circulation 3 times, add again the 0.183g bipyridine and continue to pass through three circulation primary, place behind 73 ℃ the oil bath pan reaction 4.5h in the ice-water bath stopped reaction, stir oxidation 1h through liquid nitrogen freezing and after with the methylene dichloride dilution, remove catalyzer by neutral alumina, the concentrated 30min postprecipitation of room temperature is in the 200mL normal hexane, get and precipitate with after the dissolving of 5mL tetrahydrofuran (THF) and the 200mL normal hexane precipitation (repetitive operation 3 times), get precipitation, room temperature vacuum-drying obtains PDFHMA5.96g;
The preparation of PDFHMA-b-PGMA multipolymer: with PDFHMA-Br(3.2g), 1.83g glycidyl methacrylate (GMA), 0.067g cuprous bromide, 0.016g the methyl-phenoxide of cupric bromide and 10mL seals bottleneck after joining the single port reaction flask of 30mL, after blasting argon gas-freeze-thaw three circulation 3 times, add again 0.178g part Bpy and continue to pass through three circulation primary, place behind 70 ℃ the oil bath pan reaction 5h in the ice-water bath stopped reaction, 45 ℃ of underpressure distillation are removed most of DMF postprecipitation in the 200mL normal hexane, be dissolved in again in the 3ml tetrahydrofuran (THF) postprecipitation after 25 ℃ of dryings in 200mL normal hexane (repetitive operation 3 times), get precipitation, room temperature vacuum-drying obtains segmented copolymer 3.72g; After the DMF of 1.66g segmented copolymer, 0.41g sodiumazide, ammonium chloride 1.02g and 8mL mixed, reaction is poured in a large amount of distilled water behind the 3d in 25 ℃ oil bath pan, filters, and gets filter residue and washes 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), and 3.21(s, epoxide hydroformylation, 1H), 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
4G/mol, dispersed index is 1.25;
(2) preparation of PNIPAM: will have Thermosensitive monomer N, 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, place behind 65 ℃ the oil bath pan reaction 5h in the ice-water bath stopped reaction, 45 ℃ of underpressure distillation are removed most of DMF postprecipitation in the 200mL normal hexane, get and be dissolved in again in the 3mL tetrahydrofuran (THF) postprecipitation after 25 ℃ of dryings of precipitation in 200mL normal hexane (repetitive operation 3 times), get precipitation, room temperature vacuum-drying obtains 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
4G/mol, dispersed index is 1.12;
(3) preparation PDFHMA-b-(PGMA-g-PNIPAM): with PDFHMA-b-PGMA multipolymer and PNIPAM, the 0.65g Catalysts Cu Br of 1.26g step (2) and the N that 0.78g part PMDETA is dissolved in 6.5mL of 0.42g step (1), in the N-dimethylformamide, blast argon gas, 2d dialyses in 300mL distilled water behind the room temperature dialysis 3d in 300mL methyl alcohol behind the reaction 2.5d in 25 ℃ water-bath, centrifugal, get the vacuum-drying of precipitation room temperature, obtain having the fluorine-containing block graft polymer P of Thermosensitive DFHMA-b-(PGMA-g-PNIPAM) 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
4G/mol, dispersed index is 1.23.
Embodiment 9:PDFHMA-b-(PGMA-g-PDMAEMA) and the preparation
(1) preparation of fluorine-containing homopolymer PDFHMA: with step (1) among the embodiment 8;
The preparation of PDFHMA-b-PGMA multipolymer: with step (1) among the embodiment 8;
(2) preparation of PDMAEMA: will have Thermosensitive monomer dimethylaminoethyl acrylate methyl base ammonia ethyl ester 8.78g, 0.481g chain-transfer agent S-normal-butyl-S '-(Alpha-Methyl-α 〞-isopropyl acid alkynes propyl ester) three thioesters, 0.029g the purified dioxane of 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, place behind 65 ℃ the oil bath pan reaction 4h in the ice-water bath stopped reaction, 44 ℃ of underpressure distillation are removed most of DMF postprecipitation in the 200mL normal hexane, be dissolved in again the 3mL postprecipitation in 200mL normal hexane (repetitive operation 3 times) after getting 25 ℃ of dryings of precipitation, get precipitation, room temperature vacuum-drying obtains 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
4G/mol, dispersed index is 1.23;
(3) preparation PDFHMA-b-(PGMA-g-PDMAEMA): with PDFHMA-b-PGMA multipolymer and PDMAEMA, the 0.014g Catalysts Cu Br of 0.425g step (2) and the N that 0.017g part PMDETA is dissolved in 4mL of 0.4g step (1), in the N-dimethylformamide, blast argon gas, 2d dialyses in 300mL distilled water behind the room temperature dialysis 3d in 300mL methyl alcohol behind the reaction 3d in 27 ℃ water-bath, centrifugal, get the vacuum-drying of precipitation room temperature, obtain having the fluorine-containing block graft polymer P of Thermosensitive DFHMA-b-(PGMA-g-PDMAEMA) 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
4G/mol, dispersed index is 1.23.
Embodiment 10:PPFOMA-b-(PGMA-g-PDNIPAM) and the preparation
(1) preparation of fluorine-containing homopolymer PPFOMA: with 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, after blasting argon gas-freeze-thaw three circulation 3 times, add again the 0.58g bipyridine and continue to pass through three circulation primary, placing temperature is that 75 ℃ oil bath pan reacts 12h, stir oxidation 1h through liquid nitrogen freezing and after with the methylene dichloride dilution, remove catalyzer by neutral alumina, the concentrated 30min postprecipitation of room temperature is in the 200mL normal hexane, get and precipitate with after the dissolving of 5mL tetrahydrofuran (THF) and the 200mL normal hexane precipitation (repetitive operation 3 times), get precipitation, room temperature vacuum-drying obtains PPFOMA8.63g;
The preparation of PPFOMA-b-PGMA multipolymer: with PPFOMA-Br(2.70g), 1.54g glycidyl methacrylate (GMA), 0.032g cuprous bromide, 0.015g the methyl-phenoxide of cupric bromide and 9mL seals bottleneck after joining the single port reaction flask of 30mL, after blasting argon gas-freeze-thaw three circulation 3 times, add again 0.078g part PMDETA and continue to pass through three circulation primary, placing temperature is that 28 ℃ oil bath pan reacts 16h, stir oxidation 1h through liquid nitrogen freezing and after with the methylene dichloride dilution, remove catalyzer by neutral alumina, the concentrated 30min postprecipitation of room temperature is in the 200mL normal hexane, get and precipitate with after the dissolving of 5mL tetrahydrofuran (THF) and the 200mL normal hexane precipitation (repetitive operation 3 times), get precipitation, room temperature vacuum-drying obtains segmented copolymer 3.24g; After the DMF of 1.23g segmented copolymer, 0.98g sodiumazide, ammonium chloride 0.81g and 8mL mixed, reaction is poured in the 400mL distilled water behind the 2.5d in 32 ℃ oil bath pan, filters, and gets precipitation and washes 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), and 3.21(s, epoxide hydroformylation, 1H), and 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
4G/mol, dispersed index is 1.26;
(2) preparation of PDNIPAM: will have Thermosensitive monomer NIPA 6.32g, 0.31g chain-transfer agent S-dodecyl-S '-(Alpha-Methyl-α 〞-isopropyl acid alkynes propyl ester) three thioesters, 0.019g the purified DMF of 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, place behind 67 ℃ the oil bath pan reaction 6.5h in the ice-water bath stopped reaction, 44 ℃ of underpressure distillation are removed most of DMF postprecipitation in the 200mL normal hexane, get and be dissolved in again in the 3mL tetrahydrofuran (THF) postprecipitation after 25 ℃ of dryings of precipitation in 200mL normal hexane (repetitive operation 3 times), get precipitation, room temperature vacuum-drying obtains 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
4G/mol, dispersed index is 1.15;
(3) preparation PPFOMA-b-(PGMA-g-PDNIPAM): with PPFOMA-b-PGMA multipolymer and PDNIPAM, the 0.021g Catalysts Cu Br of 0.97g step (2) and the N that 0.024g part PMDETA is dissolved in 6.5mL of 0.25g step (1), in the N-dimethylformamide, blast argon gas, 2d dialyses in 300mL distilled water behind the room temperature dialysis 3d in 300mL methyl alcohol behind the reaction 3d in 28 ℃ water-bath, centrifugal, get the vacuum-drying of precipitation room temperature, obtain having the fluorine-containing block graft polymer P of Thermosensitive PFOMA-b-(PGMA-g-PDNIPAM) 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
4G/mol, dispersed index is 1.14.
Embodiment 11:PPFOMA-b-(PGMA-g-PmPEGMA) and the preparation
(1) preparation of fluorine-containing homopolymer PPFOMA: with step (1) among the embodiment 10;
The preparation of PPFOMA-b-PGMA multipolymer: with step (1) among the embodiment 10;
(2) preparation of PmPEGMA: will have Thermosensitive monomer polyethylene glycol monomethyl ethermethacrylic acid esters 6.21g, 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, place behind 50 ℃ the oil bath pan reaction 6h in the ice-water bath stopped reaction, 44 ℃ of underpressure distillation are removed most of DMF postprecipitation in the 200mL normal hexane, get and be dissolved in again in the 3mL tetrahydrofuran (THF) postprecipitation after 25 ℃ of dryings of precipitation in 200mL normal hexane (repetitive operation 3 times), get precipitation, room temperature vacuum-drying obtains 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
4G/mol, dispersed index is 1.27;
(3) preparation PPFOMA-b-(PGMA-g-PmPEGMA): with PPFOMA-b-PGMA multipolymer and PmPEGMA, the 0.013g Catalysts Cu Br of 3.67g step (2) and the N that 0.042g part PMDETA is dissolved in 10mL of 0.25g step (1), in the N-dimethylformamide, blast argon gas, 2d dialyses in 300mL distilled water behind the room temperature dialysis 3d in 300mL methyl alcohol behind the reaction 4d in 25 ℃ water-bath, centrifugal, get the vacuum-drying of precipitation room temperature, obtain having the fluorine-containing block graft polymer P of Thermosensitive PFOMA-b-(PGMA-g-PmPEGMA) 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
4G/mol, dispersed index is 1.15.
Above-described embodiment is the better 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 the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. one kind has the fluorine-containing block graft polymkeric substance of Thermosensitive, it 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
3X is 4～65;
R
5Be fats alkane.
2. the preparation method with the fluorine-containing block graft polymkeric substance of Thermosensitive claimed in claim 1 is characterized in that comprising the steps:
(1) preparation of fluorinated copolymer: with fluorine-containing methacrylate class monomer, CuX
2, CuX, initiator with carry out deoxidation treatment after solvent orange 2 A mixes, add part A, 55～80 ℃ of reactions obtained reactant after 2～30 hours, and reactant is carried out the purifying drying, obtained fluorine-containing homopolymer; With fluorine-containing homopolymer, side chain glycidyl methacrylate, the CuX ' with epoxy
2, CuX ' and solvent B carry out deoxidation treatment after mixing, and adds part B, 15～40 ℃ of reactions obtained reaction solution after 2～36 hours, and reaction solution is carried out purifying, obtained segmented copolymer; With segmented copolymer, sodiumazide, ammonium chloride and N, the N-dimethylformamide mixes, and 20～55 ℃ 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 N, the volume of N-dimethylformamide are 4～7 times of segmented copolymer mole number;
(2) have the preparation of the homopolymer of temperature-responsive: the chain-transfer agent that will have monomer, the Diisopropyl azodicarboxylate of temperature-responsive and contain alkynyl in molar ratio 13～80:0.1～0.3:1～3 obtains having the homopolymer of temperature-responsive in 50～75 ℃ of polyreactions 4～20 hours;
(3) preparation of the fluorine-containing block graft polymkeric substance of Thermosensitive: the fluorinated copolymer of step (1) preparation is mixed 1～2:0.13～0.6 in molar ratio with the homopolymer with temperature-responsive of step (2) preparation, in 20～35 ℃ of reactions afterwards dialysis in 2～5 days, centrifugal, get the vacuum-drying of precipitation room temperature, obtain having the fluorine-containing block graft polymkeric substance of Thermosensitive.
3. the preparation method with the fluorine-containing block graft polymkeric substance of Thermosensitive according to claim 2, it is characterized in that: the structural formula of the fluorine-containing methacrylate class monomer described in the 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 with the fluorine-containing block graft polymkeric substance of Thermosensitive according to claim 2 is characterized in that: the CuX described in the step (1)
2Be CuCl
2Or CuBr
2Described CuX is CuCl or CuBr.
5. the preparation method with the fluorine-containing block graft polymkeric substance of Thermosensitive according to claim 2 is characterized in that: in the 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 the toluene;
Described part A is pentamethyl-two vinylidenes, three ammonia or bipyridine;
Described CuX '
2Be 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 the toluene;
Described part B is pentamethyl-two vinylidenes, three ammonia or bipyridine.
6. the preparation method with the fluorine-containing block graft polymkeric substance of Thermosensitive according to claim 2, it is characterized in that: the structural formula of the monomer with temperature-responsive described in the step (2) is as follows:
Wherein: R
3For-H or-CH
3R
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
3X is 4～65.
7. the preparation method with the fluorine-containing block graft polymkeric substance of Thermosensitive according to claim 2,
It is characterized in that: the chain-transfer agent that contains alkynyl described in the 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 with monomer of temperature-responsive.
8. the preparation method with the fluorine-containing block graft polymkeric substance of Thermosensitive according to claim 7,
It is characterized in that: described polar solvent is N, N-dimethylformamide, Isosorbide-5-Nitrae-dioxane, dehydrated alcohol or methyl alcohol.
9. the preparation method with the fluorine-containing block graft polymkeric substance of Thermosensitive according to claim 2, it is characterized in that: the reaction described in the step (3) is carried out in the N-dimethylformamide system at N; Described N, N-dimethylformamide system is by CuBr, pentamethyl-two vinylidenes, three ammonia and N, the N-dimethylformamide mixes and forms, the mol ratio of CuBr and pentamethyl-two vinylidenes three ammonia is 0.3～0.5:0.3～0.5, N, the quality of N-dimethylformamide is 3～6 times of total mass of CuBr, pentamethyl-two vinylidenes three ammonia, fluorinated copolymer and the homopolymer with temperature-responsive.
10. claimed in claim 1 have the fluorine-containing block graft polymer application of Thermosensitive in preparation function special material or biological medicine material.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105801457A (en) * | 2016-03-30 | 2016-07-27 | 佛山市功能高分子材料与精细化学品专业中心 | Terminal alkynyl containing RAFT chain transfer agent and preparation method and application thereof |
| CN107602785A (en) * | 2017-08-15 | 2018-01-19 | 四川大学 | The block polymer ordered porous membrane material and its preparation and film build method of a kind of structure containing melamine |
| CN110156999A (en) * | 2019-05-28 | 2019-08-23 | 济南大学 | A kind of preparation method of click chemistry synthesizing amphipathic fluorine-containing block copolymer |
| WO2019227319A1 (en) * | 2018-05-29 | 2019-12-05 | 南通纺织丝绸产业技术研究院 | Fluorine-containing polycaprolactone film and preparation method therefor |
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| CN1817925A (en) * | 2006-01-27 | 2006-08-16 | 苏州大学 | Amphipathic fluoride block copolymer and production thereof |
| JP4337448B2 (en) * | 2003-07-11 | 2009-09-30 | ダイキン工業株式会社 | Fluorine-containing internal additive and synthetic resin film |
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| JP4337448B2 (en) * | 2003-07-11 | 2009-09-30 | ダイキン工業株式会社 | Fluorine-containing internal additive and synthetic resin film |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105801457A (en) * | 2016-03-30 | 2016-07-27 | 佛山市功能高分子材料与精细化学品专业中心 | Terminal alkynyl containing RAFT chain transfer agent and preparation method and application thereof |
| CN107602785A (en) * | 2017-08-15 | 2018-01-19 | 四川大学 | The block polymer ordered porous membrane material and its preparation and film build method of a kind of structure containing melamine |
| 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 |
| WO2019227319A1 (en) * | 2018-05-29 | 2019-12-05 | 南通纺织丝绸产业技术研究院 | Fluorine-containing polycaprolactone film and preparation method therefor |
| US11807728B2 (en) | 2018-05-29 | 2023-11-07 | Soochow University | Fluorine-containing polycaprolactone film and preparation method therefor |
| CN110156999A (en) * | 2019-05-28 | 2019-08-23 | 济南大学 | A kind of preparation method of click chemistry synthesizing amphipathic fluorine-containing block copolymer |
| CN110156999B (en) * | 2019-05-28 | 2020-04-21 | 济南大学 | Preparation method for synthesizing amphiphilic fluorine-containing block copolymer by click chemistry |
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