CN108164664A - Thermo-sensitive block copolymer and preparation method thereof - Google Patents

Thermo-sensitive block copolymer and preparation method thereof Download PDF

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Publication number
CN108164664A
CN108164664A CN201711386644.9A CN201711386644A CN108164664A CN 108164664 A CN108164664 A CN 108164664A CN 201711386644 A CN201711386644 A CN 201711386644A CN 108164664 A CN108164664 A CN 108164664A
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thermo
block copolymer
sensitive block
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sensitive
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张炉青
曹影
张书香
朱忠凯
徐安厚
杨涛
刘乾
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University of Jinan
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University of Jinan
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/145—Ultrafiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/80—Block polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/02—Monomers containing chlorine
    • C08F214/04—Monomers containing two carbon atoms
    • C08F214/08—Vinylidene chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/22—Thermal or heat-resistance properties

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  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

The invention discloses a kind of Thermo-sensitive block copolymers and preparation method thereof, belong to Chemical Engineering and Technology field.The structural formula of the Thermo-sensitive block copolymer is as follows：Wherein, n=20 150；M=20 150.Preparation process of the present invention and it is easy to operate, suitable for industrialized production and practical application and environmental protection, safety.

Description

Thermo-sensitive block copolymer and preparation method thereof
Technical field
The present invention relates to Chemical Engineering and Technology fields, particularly relate to a kind of Thermo-sensitive block copolymer and its preparation side Method.
Background technology
Since fluorine atom van der Waals radius is smallBig (485kJ/mol) with carbon-fluorine bond bond energy, fluoropolymer has It is resistant to chemical etching, heat-resisting cold-resistant and have excellent weather resistance, the features such as hydrophobic oleophobic, surface can be low.Kynoar (PVDF) has Fluoropolymer-containing features above, while there is melt-processable characteristic and dissolubility again, various forms of products can be processed, It is widely used in the industries such as building, aerospace, electronics, chemical industry, environmental protection, new energy.
Since pvdf membrane has stronger hydrophobicity in itself, easily film is caused to block in use, the antipollution of film Hydraulic performance decline, and cleaning is very difficult, in order to further improve the service life of pvdf membrane, extends use scope, how to increase Its hydrophilicity is added to become the hot spot direction of research.At present, blending, light are mainly included to the PVDF methods for carrying out hydrophilic modifying Chemical method (such as ultraviolet irradiation) or plasma surface grafting, surface elder generation order body are grafted hydrophilic molecules, directly grafting parent again Covalence graft polymer or bioactive macromolecule knead dough coating hydrophilic are high again for aqueous hydrone, graft reaction active small molecular Molecule.In existing method, using physical mixed, often there are compatibility differences for PVDF and modified component, it is difficult to it is uniformly mixed, And increase over time, hydrophilic molecule can gradually dissolve and migrate and be detached from PVDF, and hydrophily is caused to decline；If using table Face is grafted processing method, and technical process is typically complex, and usually to carry out surface activation process to PVDF, is re-introduced into corresponding Functional group, by the pvdf membrane of surface activation process there are active site it is inhomogenous the defects of, it is processed in follow-up grafting Cheng Zhong, it is not easy to form homopolymer, and polymerisation is uncontrollable.
In addition to above two method, it is also a kind of important modification method that PVDF forms block structure with hydrophilic polymer.By It is connect in hydrophilic segment with chemical bond with PVDF, for opposite blending and surface grafting, during the use of pvdf membrane not It is easy to run off, the long-acting pollution resistance and stability of pvdf membrane can be kept.
Patent (CN104610518A) discloses a kind of preparation method of Kynoar-polyacrylic acid block copolymer, This method is the method using iodine transfer activity free radical miniemulsion, and semi-continuous charging first prepares seed emulsion and subsequently adds in propylene Nitrile monomer continues to polymerize, and then product is post-processed and prepares Kynoar-polyacrylic acid block under alkaline condition Copolymer.The patent is using semi-continuous feed way, it is necessary to be iteratively repeated charging after the pressure of reaction kettle declines, grasp Make that mode is cumbersome, and it is that acrylic acid is straight that its Kynoar of target product in preparation-polyacrylic acid block copolymer, which is not, Connect be hydrolyzed under alkaline condition after polymerizeing with the product of active seed polyvinylidene fluoride polymer but polyacrylonitrile by A series of to post-process the Kynoar-polyacrylic acid block copolymer produced, operating process is cumbersome, complex process.
Patent (CN104558452A) discloses a kind of system of Kynoar-polyvinylpyrrolidone block copolymer Preparation Method, this method are the methods using iodine transfer activity free radical miniemulsion, and semi-continuous charging first prepares seed emulsion, to kind The Kynoar Macromolecular chain transfer agent that sub- lotion is demulsified, is filtered, washed, is dried to obtain, Kynoar is dissolved In organic solvent, it adds in vinylpyrrolidone monomer to continue to polymerize, post processing is then carried out to product and prepares poly- inclined fluorine Ethylene-propylene base pyrrolidones block copolymer.Patent preparation process is increasingly complex, and seed emulsion obtained is needed to carry out The post processings such as be demulsified, be filtered, washed, drying, cumbersome；And perfluorooctanoic acid has been used in the course of the polymerization process (in American-European state Family is forbidden to use in plain text), which enters after atmospheric environment it is difficult to degrade from environment, and can be migrated at a distance Or transhipment, it reaches ground with dried wet deposition or enters water body or soil, and then form environmental pollution；And possibly through food Object, air and water enter human body, may lead to fertility-rate decline and other disease of immune system.
Patent (CN103182257) discloses a kind of temperature sensitive automatically cleaning polyvinylidene fluoride film and preparation method thereof, with poly- inclined Titanium dioxide/n-isopropyl acrylamide nanometer is made for primary raw material in vinyl fluoride, titanium dioxide and n-isopropyl acrylamide Particle/polyvinylidene fluoride blending film.The preparation method of the patent is by first preparing modifying titanium dioxide/N- isopropyl acrylamides Amine nano particle on reactive polymeric to polyvinylidene fluoride film, forms blend film.The film is inhomogenous there are still active site, polymerization React uncontrollable defect.
Invention content
The technical problem to be solved in the present invention is to provide a kind of preparation process and it is easy to operate, suitable for industrialized production, And Thermo-sensitive block copolymer of Environmental Safety and preparation method thereof.
In order to solve the above technical problems, present invention offer technical solution is as follows：
On the one hand, a kind of Thermo-sensitive block copolymer is provided, structural formula is as follows：
Wherein, n=20-150；M=20-150.
Further, the Thermo-sensitive block copolymer average molecular weight is 9000-20000；The degree of polymerization is 20-103.
On the other hand, the present invention also provides the preparation method of above-mentioned Thermo-sensitive block copolymer, including：
Step 1：Initiator and chain-transferring agent are added in autoclave, vacuumizes, under nitrogen atmosphere, adds in inclined fluorine Ethylene adds in a certain amount of carbon dioxide, reacts at a certain temperature；Obtain Macromolecular chain transfer agent；
Step 2：Obtained Macromolecular chain transfer agent and temperature sensitive monomer are dissolved into solvent, add in initiator, is taken out true Sky reacts in nitrogen atmosphere；
Step 3：It dialysed with distilled water, dry and obtain Thermo-sensitive block copolymer.
Preferably, in the step 1 or 2, initiator is t-butyl peroxy pivalate (TBPPI), peroxidating neodecanoic acid The tert-butyl ester (TBPND), peroxide -2-ethyl hexanoic acid tert-butyl (TBPEH), the peroxidating -3,5,5 Trimethylhexanoic acid tert-butyl ester (TBPIN)；
Preferably, in the step 1, chain-transferring agent is perfluor iodobutane, one kind in perfluor iodohexane, perfluor iodo-octane It is or a variety of.
Preferably, in the step 1, the mass ratio of initiator and vinylidene is 0.1-0.5:20-100；Chain-transferring agent Mass ratio with vinylidene is 1-5:20-100；The mass ratio of carbon dioxide and vinylidene is 5-25:2-10.
Preferably, in the step 2, temperature sensitive monomer is n-isopropyl acrylamide；Solvent is N, N- dimethyl formyls Amine (DMF), DMAC N,N' dimethyl acetamide (DMAC), N-Methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) (DMSO).
Preferably, in the step 2, the mass ratio of Macromolecular chain transfer agent and temperature sensitive monomer is 1-5:2-12.5；Greatly The mass ratio of molecular chain transfer agent and solvent is 1-5:50-150；The mass ratio of Macromolecular chain transfer agent and initiator is 2-10: 0.1-0.5。
Preferably, in the step 1 or 2, the pressure of reaction kettle is 20-40MPa, is replaced after vacuumizing with nitrogen, is reacted Oxygen content in kettle is less than 10ppm, and reaction temperature is 50-80 DEG C, reaction time 8-24h.
Preferably, in the step 3, the condition of dialysis, which is that use is corresponding with target block copolymer amount, dialyses Bag is dialysed 3 times with water, and the molecular cut off of bag filter is the bag filter of 9000-20000, to remove the solvent in reaction system； The condition of drying is 60 DEG C of baking oven 12h.
The invention has the advantages that：
In said program, Thermo-sensitive block copolymer, preparation process and easy to operate, no waste water are prepared using one kettle way Exhaust gas discharges, solvent recovery Environmental Safety, production process green, environmental protection, safety, it is easy to accomplish industrialized production and reality should With.
Description of the drawings
Fig. 1 is the nuclear-magnetism fluorine spectrogram of Macromolecular chain transfer agent that the embodiment of the present invention 1 is prepared；
Fig. 2 is the nucleus magnetic hydrogen spectrum of Thermo-sensitive block copolymer (PVDF-b-PNIPAM) that the embodiment of the present invention 1 is prepared Figure；
Fig. 3 is the infrared spectrum of Thermo-sensitive block copolymer (PVDF-b-PNIPAM) that the embodiment of the present invention 1 is prepared Figure；
Fig. 4 is the differential scanning of Thermo-sensitive block copolymer (PVDF-b-PNIPAM) that the embodiment of the present invention 1 is prepared Calorimetric determination collection of illustrative plates.
Specific embodiment
To make the technical problem to be solved in the present invention, technical solution and advantage clearer, below in conjunction with attached drawing and tool Body embodiment is described in detail.
The present invention is complicated for polyvinylidene fluoride alkene block copolymer preparation process in the prior art, cumbersome, and exists The problem of safety, provides a kind of Thermo-sensitive block copolymer and preparation method thereof.
Embodiment 1
The preparation method of Thermo-sensitive block copolymer, including:
Step 1：TBPPI the and 0.2g perfluor iodohexanes of 0.02g, vacuumized nitrogen are added in 100ml reaction kettles After three times, oxygen content 7ppm adds in the VDF of 5.0g, adds 10g carbon dioxide later；The pressure 50MPa of reaction kettle, 80 DEG C fully reaction 22h, cooling deflate, drying obtain 3.0g Macromolecular chain transfer agents；
Step 2：By 3.0g Macromolecular chain transfer agents, 6.0g NIPAM are substantially dissolved in 50g n,N-Dimethylformamide, 0.15g initiator TBPPI are added in, vacuumize the lower 80 DEG C of reactions 18h of nitrogen atmosphere；
Step 3：After reaction with distillation water sedimentation, filtering, drying, flaxen 5.0g PVDF-b-PNIPAM are obtained Block polymer.
The average molecular weight and the degree of polymerization of polymer are measured using Waters, US's gel permeation chromatograph (GPC). Test condition：Waters 1525HPLC are pumped, 2414 type RI refraction detectors, and setting column temperature is 32 DEG C, PS standard samples, DMF As mobile phase, flow velocity 1mL/min.Configuration polymer solution concentration is 2mg/ml, 200 μ l of hand sampling.The embodiment system Molecular weight for the Thermo-sensitive block copolymer gone out is 16094, the degree of polymerization 80, molecular weight distributing index 1.71, wherein n= 103, m=105.
As shown in 1 Macromolecular chain transfer agent nuclear-magnetism fluorine spectrogram of attached drawing, a is-CF3, b is-CF2Group, c are-CH2CF2, Chemical shift δ=- 92~-94.5ppm places are the-CH on PVDF segments2CF2Characteristic absorption peak, chemical shift δ=- 81ppm It is chain-transferring agent-CF3On F characteristic peak, chemical shift δ=- 122~-124ppm place is the-CF on PVDF segments2Spy Levy absorption peak；It can be obtained by nuclear-magnetism fluorine spectrum analysis, be successfully prepared Macromolecular chain transfer agent PVDF-I.
The nucleus magnetic hydrogen spectrum figure of attached drawing 2PVDF-b-PNIPAM is the DMSO and residual of deuterium band respectively in 2.48 and 3.30ppm H2O chemical shifts；The 3.9 and 1.0ppm in the nucleus magnetic hydrogen spectrum of PVDF-b-PNIPAM, belongs to the tertiary carbon on PNIPAM segments (C) chemical shift of the H and on methyl (D)；2.2ppm and 2.8ppm corresponds to the-CH on PVDF segments2CF2The change of H on (A) Displacement study；Occur weak signal at 7.2ppm, correspond to the H (B) on the amine in PNIPAM chains；Demonstrate PVDF-b-PNIPAM Successfully prepare.
Shown in 3 infrared spectrogram of attached drawing, 1125cm-1Locate the characteristic peak for C-F keys on Macromolecular chain transfer agent PVDF-I, 1645cm-1Locate as amide C=O stretching vibration characteristic peaks, 1490cm on PNIPAM-1Locate the characteristic peak for N-H, PVDF-b- PNIPAM is successfully prepared.
The differential scanning calorimetry of attached drawing 4PVDF-b-PNIPAM is measured shown in collection of illustrative plates, PVDF-b-PNIPAM block copolymerizations Nearby there is a faint exothermic peak at T=106 DEG C in the DSC curve of object, this is the crystallization process of PVDF；At T=147 DEG C There is an endothermic peak in left and right, is the melting temperature of PVDF segments, occurs a very high endothermic peak at T=157 DEG C, belongs to The melting temperature of PNIPAM segments.
Embodiment 2
The preparation method of Thermo-sensitive block copolymer, including:
Step 1：TBPND the and 0.2g perfluor iodohexanes of initiator 0.03g are added in 100ml reaction kettles, vacuumize nitrogen After gas displacement three times, the VDF of 5.0g is added in, adds 10g carbon dioxide later.The pressure 50MPa of reaction kettle, 80 DEG C fully anti- 22h is answered, cooling is deflated, and drying obtains 2.8g Macromolecular chain transfer agents；
Step 2：By 2.8g Macromolecular chain transfer agents, 4.0g NIPAM are substantially dissolved in 50g n,N-Dimethylformamide, 0.21g initiator TBPND are added in, vacuumize the lower 80 DEG C of reactions 18h of nitrogen atmosphere；
Step 3：After reaction with distillation water sedimentation, filtering, drying, flaxen 4.5g PVDF-b-PNIPAM are obtained Block polymer.
The molecular weight of Thermo-sensitive block copolymer that the embodiment is prepared is 13995, the degree of polymerization 61, molecular weight distribution Index is 1.61, wherein n=103, m=80.
Embodiment 3
The preparation method of Thermo-sensitive block copolymer, including:
Step 1：It is added in 100ml reaction kettles:TBPPI the and 0.16g perfluor iodobutanes of 0.02g, vacuumize nitrogen and put After changing three times, the VDF of 5.0g is added in, adds 10g carbon dioxide later.The pressure 50MPa of reaction kettle, 80 DEG C of fully reactions 22h, cooling are deflated, and drying obtains 3.0g PVDF Macromolecular chain transfer agents；
Step 2：By 3.0g Macromolecular chain transfer agents, the NIPAM of 3.0g is substantially dissolved in 60g n,N-Dimethylformamide, 0.15g initiator TBPPI are added in, vacuumize the lower 80 DEG C of reactions 18h of nitrogen atmosphere；
Step 3：After reaction with distillation water sedimentation, filtering, drying, flaxen 4.1g PVDF-b-PNIPAM are obtained Block polymer.
The molecular weight of Thermo-sensitive block copolymer that the embodiment is prepared is 11065, the degree of polymerization 35, molecular weight distribution Index is 1.25, wherein n=103, m=55.
Embodiment 4
The preparation method of Thermo-sensitive block copolymer, including:
Step 1：TBPPI the and 0.2g chain-transferring agent perfluor iodohexanes of initiator 0.02g are added in 100ml reaction kettles, Vacuumized nitrogen three times after, add in the VDF of 5.0g, add 10g carbon dioxide later.The pressure 50MPa of reaction kettle, 80 DEG C fully reaction 22h, cooling deflate, drying obtain 3.8g PVDF Macromolecular chain transfer agents；
Step 2：By 3.0g Macromolecular chain transfer agents, the NIPAM of 2.0g is substantially dissolved in 55g dimethyl sulfoxide (DMSO)s, adds in 0.15g initiator TBPPI vacuumize the lower 80 DEG C of reactions 18h of nitrogen atmosphere；
Step 3：After reaction with distillation water sedimentation, filtering, drying, flaxen 1.5g PVDF-b-PNIPAM are obtained Block polymer.
The molecular weight of Thermo-sensitive block copolymer that the embodiment is prepared is 9594, the degree of polymerization 22, molecular weight distribution Index is 1.13, wherein n=103, m=30.
By above-described embodiment 1-4 it is found that the PVDF-b-PNIPAM block polymers of the invention prepared are as the degree of polymerization increases Add, molecular weight distributing index increases to 1.71 by 1.13, illustrates that the iodine transfer polymerization method that the present invention uses can pass through tune The content of polymerized monomer is saved, achievees the purpose that regulate and control the molecular weight and the degree of polymerization of polymer, the iodine transfer polymerization method of use It is a kind of controllable polymerization of activity.The present invention is easy to operate, and the conversion ratio of NIPAM monomers is all higher than 80%.
The present invention has done test of many times discovery, with the increase of design molecular weight, the theoretical molecular weight of GPC test polymers There are relatively large deviations for the actual molecular weight of the polymer measured with nuclear-magnetism, may be caused the reason is that the chain length due to PNIPAM increases Add, deviation occurs in the index of refraction of block polymer, so the average molecular weight of Thermo-sensitive block copolymer provided by the invention For 9000-20000；The degree of polymerization is 20-103.
The advantageous effect of Thermo-sensitive block copolymer prepared in order to further illustrate the present invention, prepared by embodiment 1-4 The Thermo-sensitive block copolymer gone out is with PVDF with mass ratio 1:4 mixing using DMF as solvent, prepare the casting that weight concentration is 4% Film liquid is immersed in 25 DEG C of pure water coagulating baths and is solidified, and after film automatically disengages glass plate, measures the water of 25 DEG C, 50 DEG C lower films respectively Flux, related data are as shown in table 1 below.
Table 1
As shown in Table 1, the Thermo-sensitive block copolymer of synthesis is added in simple PVDF ultrafiltration membrane can not only improve The water flux of ultrafiltration membrane, and temperature is increased, due to the Thermo-sensitive of block copolymer prepared by the present invention, there is segment volume to receive The characteristic of contracting has expanded the bore of film, has increased irrigation flow rate, further improves the water flux of ultrafiltration membrane；And with The growth of PNIPAM segments, the quantity of hydrophilic radical increase, and the wettability of enhancing hydrophobic membrane materials PVDF reduces infiltration Resistance improves the water flux of film.
The advantageous effect of inventor in order to further illustrate the present invention, using uniform water flux assay method, with reference to special The preparation method of sharp (CN103182257A) embodiment 4 determines the water flux of 4% temperature sensitive polyvinylidene fluoride film blend film, It is 188L/m in the water flux of 25 DEG C of blend films2·h；It is 252L/m in the water flux of 50 DEG C of lower films2H, hence it is evident that less than this hair The water flux of bright preparation.
The above is the preferred embodiment of the present invention, it is noted that for those skilled in the art For, without departing from the principles of the present invention, several improvements and modifications can also be made, these improvements and modifications It should be regarded as protection scope of the present invention.

Claims (10)

1. a kind of Thermo-sensitive block copolymer, which is characterized in that structural formula is as follows
Wherein, n=20-150；M=20-150.
2. Thermo-sensitive block copolymer according to claim 1, which is characterized in that the Thermo-sensitive block copolymer is put down Average molecular weight is 9000-20000；The degree of polymerization is 20-103.
3. the preparation method of Thermo-sensitive block copolymer described in claim 1, which is characterized in that including：
Step 1：Initiator and chain-transferring agent are added in autoclave, vacuumizes, under nitrogen atmosphere, adds in inclined fluorine second Alkene adds in a certain amount of carbon dioxide, reacts at a certain temperature；Obtain Macromolecular chain transfer agent；
Step 2：Obtained Macromolecular chain transfer agent and temperature sensitive monomer are dissolved into solvent, initiator is added in, vacuumizes It is reacted in nitrogen atmosphere；
Step 3：It dialysed with distilled water, dry and obtain Thermo-sensitive block copolymer.
4. the preparation method of Thermo-sensitive block copolymer according to claim 3, which is characterized in that the step 1 or 2 In, initiator is t-butyl peroxy pivalate, new peroxide tert-butyl caprate, peroxide -2-ethyl hexanoic acid tert-butyl, peroxide Change -3,5,5 Trimethylhexanoic acid the tert-butyl ester.
5. the preparation method of Thermo-sensitive block copolymer according to claim 3, which is characterized in that in the step 1, chain Transfer agent is perfluor iodobutane, one or more in perfluor iodohexane, perfluor iodo-octane.
6. the preparation method of Thermo-sensitive block copolymer according to claim 3, which is characterized in that in the step 1, draw The mass ratio for sending out agent and vinylidene is 0.1-0.5:20-100；The mass ratio of chain-transferring agent and vinylidene is 1-5:20- 100；The mass ratio of carbon dioxide and vinylidene is 5-25:2-10.
7. the preparation method of Thermo-sensitive block copolymer according to claim 3, which is characterized in that in the step 2, temperature Quick property monomer is n-isopropyl acrylamide；Solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N- methylpyrroles Alkanone, dimethyl sulfoxide (DMSO).
8. the preparation method of Thermo-sensitive block copolymer according to claim 3, which is characterized in that in the step 2, greatly The mass ratio of molecular chain transfer agent and temperature sensitive monomer is 1-5:2-12.5；The mass ratio of Macromolecular chain transfer agent and solvent is 1- 5:50-150；The mass ratio of Macromolecular chain transfer agent and initiator is 2-10:0.1-0.5.
9. the preparation method of Thermo-sensitive block copolymer according to claim 3, which is characterized in that the step 1 or 2 In, the pressure of reaction kettle is 20-40MPa, is replaced after vacuumizing with nitrogen, and the oxygen content in reaction kettle is less than 10ppm, reaction temperature It is 50-80 DEG C to spend, reaction time 8-24h.
10. the preparation method of Thermo-sensitive block copolymer according to claim 3, which is characterized in that in the step 3, The bag filter that it is 9000-20000 using molecular weight that the condition of dialysis, which is, is dialysed 3 times；The condition of drying is 60 DEG C of baking oven 12h.
CN201711386644.9A 2017-12-20 2017-12-20 Thermo-sensitive block copolymer and preparation method thereof Pending CN108164664A (en)

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CN110483706A (en) * 2019-07-11 2019-11-22 江苏大学 A kind of preparation method and application based on the amphiphilic difunctional fluorescence probe of Thermo-sensitive block polymer of oligonucleotides
CN112029057A (en) * 2020-07-14 2020-12-04 乳源东阳光氟树脂有限公司 Hydrophilic modified polyvinylidene fluoride block copolymer, water treatment membrane, preparation method and application thereof
CN112023723A (en) * 2019-07-01 2020-12-04 江苏久吾高科技股份有限公司 Hollow fiber membrane and manufacturing method thereof
CN115212736A (en) * 2022-07-15 2022-10-21 中国科学院烟台海岸带研究所 Separation membrane for seawater industrial aquaculture water treatment

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103182257A (en) * 2013-04-07 2013-07-03 福州大学 Temperature-sensitive self-cleaning polyvinylidene fluoride film and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103182257A (en) * 2013-04-07 2013-07-03 福州大学 Temperature-sensitive self-cleaning polyvinylidene fluoride film and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
NAHAL GOLZARI等: "Inducing Phase Crystallinity in Block Copolymers of Vinylidene Fluoride with Methyl Methacrylate or Styrene", 《POLYMERS》 *
刘崎等: "PVDF-g-NIPAAm温敏膜的辐射合成及性能研究", 《辐射研究与辐射工艺学报》 *
黄志辉: "卤代乙烯单体活性自由基聚合及其嵌段共聚物的合成和膜改性应用", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112023723A (en) * 2019-07-01 2020-12-04 江苏久吾高科技股份有限公司 Hollow fiber membrane and manufacturing method thereof
CN110483706A (en) * 2019-07-11 2019-11-22 江苏大学 A kind of preparation method and application based on the amphiphilic difunctional fluorescence probe of Thermo-sensitive block polymer of oligonucleotides
CN110483706B (en) * 2019-07-11 2021-10-12 江苏大学 Preparation method and application of bifunctional fluorescent probe based on oligonucleotide amphiphilic temperature-sensitive block polymer
CN112029057A (en) * 2020-07-14 2020-12-04 乳源东阳光氟树脂有限公司 Hydrophilic modified polyvinylidene fluoride block copolymer, water treatment membrane, preparation method and application thereof
CN115212736A (en) * 2022-07-15 2022-10-21 中国科学院烟台海岸带研究所 Separation membrane for seawater industrial aquaculture water treatment

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