CN105085844A - Diblock copolymer for oil-water separation with temperature control wetting property and preparing method thereof - Google Patents
Diblock copolymer for oil-water separation with temperature control wetting property and preparing method thereof Download PDFInfo
- Publication number
- CN105085844A CN105085844A CN201510487458.9A CN201510487458A CN105085844A CN 105085844 A CN105085844 A CN 105085844A CN 201510487458 A CN201510487458 A CN 201510487458A CN 105085844 A CN105085844 A CN 105085844A
- Authority
- CN
- China
- Prior art keywords
- block copolymer
- acrylic acid
- rare gas
- butyl ester
- gas element
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a diblock copolymer with a temperature response characteristic and relates to the field of high-molecular polymers. The diblock copolymer is a polymethyl hexafluorobutyl acrylate and poly-n-isopropyl acrylamide segmented copolymer. The number-average molecular weight of the diblock copolymer is 35700-57200 g/mol, and molecular weight distribution is 1.20-1.31. Due to the fact that n-isopropyl acrylamide molecules are contained in the prepared diblock copolymer, a temperature response hydrophilic-hydrophobic property is shown; meanwhile, due to the fact that methyl hexafluorobutyl acrylate existing on the main chain has a hydrophobic property, the copolymer can be used for preparing materials with temperature response wettability and for oil-water separation.
Description
Technical field
The present invention relates to high molecular polymer field, be specifically related to a kind of to there is di-block copolymer of temperature control wetting property and preparation method thereof.
Background technology
Environment-responsive polymkeric substance can form unique controlled hydrophobe behavior, and the performance of this uniqueness makes it at intelligent surface, drug conveying, organizational project, prepares sensor field and is with a wide range of applications.For the water-soluble polymers of environment sensitive, in aqueous, common outside atmosphere comprises temperature, pH, illumination and ionic strength etc. when changing, and polymkeric substance itself can experience from being dissolved into insoluble change procedure.Therefore, the attribute of functional materials under water surrounding prepared by the block polymer containing environment sensitive water soluble block has outside atmosphere responsiveness and susceptibility, is also referred to as intelligent material.The film that environment sensitive block polymer is formed is under extraneous conditioned stimulus, and film can be become hydrophilic or hydrophilic and become hydrophobic by hydrophobic, thus makes surface have different wetting propertys, i.e. so-called stimulating responsive intelligent surface.Specific to stimulating responsive intelligent surface, make it all receive in oily water separation field and pay close attention to widely.Functional modification is carried out to fluoropolymer, obtains temperature-responsive polymkeric substance, the amphipathic nature polyalcohol of unique performance can be formed, thus better realize controlling the wettability of material.Poly N-isopropyl acrylamide, as the temperature responsive polymer of a quasi-representative, can change the change of outside temperature, realizes its hydrophilic and hydrophobic and changes.In addition, because temperature height easily regulates, and the Synthesis and applications of temperature-responsive polymkeric substance is widely used in.The performance of this uniqueness makes it in Surface Engineering, and preparation oily water separation device is with a wide range of applications.
Summary of the invention:
The object of the invention is to for above-mentioned Problems existing, propose a kind of product structure clear and definite and there is the segmented copolymer of temperature response characteristics; And a kind of mild condition is provided, and easy and simple to handle, be easy to the preparation method of described block polymer structures.
Technical problem to be solved by this invention realizes by the following technical solutions:
Have a di-block copolymer for temperature response characteristics, it is characterized in that, described bi-block copolymer is the segmented copolymer of polymethyl acrylic acid hexafluoro butyl ester and poly N-isopropyl acrylamide, and the chemical structural formula of described bi-block copolymer is as follows:
Wherein, n is the integer between 75-120, and m is the integer between 150-240; The number-average molecular weight Mn of described di-block copolymer is 35700-57200g/mol, and molecular weight distribution is 1.20-1.31.
Preferably, in the chemical structural formula of di-block copolymer disclosed in the present invention, n is 75, m is 150.
The invention also discloses a kind of method of synthesizing di-block copolymer as described above, comprise the following steps:
The preparation of the polymethyl acrylic acid hexafluoro butyl ester macromole evocating agent of chlorine end-blocking:
Hexafluorobutyl mathacrylate, dimethyl formamide, pimelinketone and Catalysts Cu Cl
2powder joins in reaction vessel, vacuumizes and lead to rare gas element to reactor; Stir under the protection of rare gas element, add three (N, N-dimethyl aminoethyl) amine, and under the protection of rare gas element, add initiator dibromo-isobutyl acetoacetic ester, be placed in ultraviolet reactor and react; Reaction terminates rear reaction soln and dilutes through chloroform, removing catalysts and solvents, precipitation, the dry polymethyl acrylic acid hexafluoro butyl ester macromole evocating agent namely obtaining chlorine end-blocking;
2) preparation of the di-block copolymer of polymethyl acrylic acid hexafluoro butyl ester-b-poly N-isopropyl acrylamide:
By step 1) in the polymethyl acrylic acid hexafluoro butyl ester macromole evocating agent of chlorine end-blocking, dimethyl formamide, pimelinketone and Catalysts Cu Cl
2powder joins in reaction vessel, vacuumizes and lead to rare gas element to reactor; Airtight stirring under the protection of rare gas element, adds NIPA and three (N, N-dimethyl aminoethyl) amine, is placed in ultraviolet reactor and reacts; Reaction terminates rear reaction soln and dilutes through chloroform, removing catalysts and solvents, precipitation, dry namely obtain polymethyl acrylic acid hexafluoro butyl ester-b-poly N-isopropyl acrylamide di-block copolymer;
Preferably, above-mentioned steps 1) in, described rare gas element adopts High Purity Nitrogen; The temperature of reaction of described reaction is reactor environment temperature, between 35-15 DEG C; Reaction times is 8 ~ 24 hours; Precipitation agent in described precipitation process is methyl alcohol and the hydrochloric acid mixed solution of 3:1; Drying temperature in described drying treatment is 40 DEG C.
Preferably, step 1) in, Hexafluorobutyl mathacrylate, dibromo-isobutyl acetoacetic ester, CuCl
2the mol ratio of powder and three (N, N-dimethyl aminoethyl) amine is 100-150:1:0.02-0.05:0.12-0.30.
More preferably, step 1) in, the mol ratio of Hexafluorobutyl mathacrylate, dibromo-isobutyl acetoacetic ester, CuCl2 powder and three (N, N-dimethyl aminoethyl) amine is 100:1:0.02:0.12.
Preferably, step 1) in the number-average molecular weight Mn of polymethyl acrylic acid seven fluorine butyl ester macromole evocating agent of chlorine end-blocking be 18800-30000, molecular weight distribution is 1.11-1.20.
Preferably, step 2) described in rare gas element adopt High Purity Nitrogen; The temperature of reaction of described reaction is reactor environment temperature, between 35-15 DEG C; Reaction times is 24 ~ 36 hours; Precipitation agent in described precipitation is anhydrous diethyl ether; Drying temperature in described drying treatment is 40 DEG C.
Preferably, step 2) in, NIPA, macromole evocating agent, CuCl
2the mol ratio of powder and three (N, N-dimethyl aminoethyl) amine is 200-300:1:0.04-0.1:0.24-0.6.
More preferably, step 2) in, NIPA, macromole evocating agent, CuCl
2the mol ratio of powder and three (N, N-dimethyl aminoethyl) amine is 200:1:0.04:0.24.
Preferably, step 1) and step 2) in, in described photoreactor, the predominant wavelength of light source is 360nm, and light intensity is 15Mw/cm
2.
Process means used in the step of synthetic method disclosed in the present invention are conventional process means in this area if no special instructions; The consumption of organic solvent used is conventional amount used in prior art.
Post-processing step described in the present invention is conventional post-processing technology in this area if no special instructions.
Bi-block copolymer disclosed in the present invention has temperature response characteristics and the wettability operant behavior in prepared by intelligent surface thereof.
Fluorinated acrylate is that a class has hydrophobic molecule, NIPA molecule is a class temperature-responsive molecule, under the regulation and control of outside temperature, the transformation of hydrophilic and hydrophobic can be realized, the segmented copolymer of the present invention's synthesis, both are combined, achieves the behavior that temperature controls wettability modification.
The invention also discloses the di-block copolymer described above application in oily water separation field.
The method of block polymer synthesis mainly contains active anionic polymerization, living cationic polymerization and " activity "/controllable free-radical polymerisation.Compared with other " activity " radical polymerizations, the light regulation activity polymerization used in the present invention has obvious advantage: (1) polymerization can be carried out under room temperature or lower temperature; (2) rate of polymerization is fast, and the controllability of polymerization is good, narrow molecular weight distribution; (3) CuCl is used
2catalyzer, and consumption is few, is not easy the impact being subject to oxygen; (4) polymkeric substance of high molecular is easily obtained.First by the segmented copolymer of light-operated atom transfer radical copolymerization (ATRP) technology synthesize methyl acrylic acid hexafluoro butyl ester (HFBMA) with NIPA (NIPAAm) in the present invention; The synthetic route chart of the di-block copolymer of described polymethyl acrylic acid hexafluoro butyl ester-b-poly N-isopropyl acrylamide (PHFBMA-b-PNIPAAm) as shown in Figure 1.
Be spun on silicon chip by the block polymer of synthesis, can have the smart coat of temperature control wettability, the test result of its water contact angle as shown in Figure 2.
The polymkeric substance of synthesis is spun on stainless (steel) wire, the smart coat of temperature control wettability can be had, can be used as oily water separation film as shown in Figure 3.
Pour in tripping device by the mixing solutions of water and normal hexane, can realize normal hexane and be separated with the controlled of water, result as shown in Figure 4.
Compared with existing environment-responsive block polymer and technology of preparing thereof, the beneficial effect that the present invention has is:
Adopt light regulation activity radical polymerization technique, the method can be carried out in a mild condition, under described mild conditions comprises and there is stopper or aerobic existent condition, makes can effectively synthesize polymethacrylate polymkeric substance in this way;
The method is compared with other Controlled Living Radical Polymerization method, and the method rate of polymerization is fast, and the molecular weight distribution of synthesis is narrow, and polymer ends still can keep very high activity, and it is few that reaction terminates rear catalyst Cu salt residual volume;
Final product in the present invention has temperature response wettability, has unique advantage in oily water separation application aspect.
To sum up, a kind of temperature response segmented copolymer of design and synthesis of the present invention, synthesized polymer materials is because of containing NIPA molecule, show temperature-responsive, oily water separation under making this polymkeric substance can be used for temperature adjusting, which overcome the various shortcomings about block polymer and preparation method thereof in prior art, creative value.
Accompanying drawing explanation
Fig. 1 is the synthesis route figure of the di-block copolymer of the polymethyl acrylic acid hexafluoro butyl ester-b-poly N-isopropyl acrylamide described in the present invention.
The Static water contact angles test result on the smart coat surface of the temperature control wettability that Fig. 2 is prepared for polymkeric substance described in embodiment 1 in the present invention.
Fig. 3 is the scanning electron microscope diagram of the stainless (steel) wire scribbling block polymer film.
Fig. 4 is the separating resulting figure of normal hexane and water mixture under differing temps; Wherein A figure represents, when lowest critical solution temperature (LCST) lower than NIPA, this device crosses water only normal hexane; B schemes to represent, when lowest critical solution temperature (LCST) higher than NIPA, this device crosses normal hexane only water.
Embodiment
The technique means realized to make the present invention, creation characteristic, reaching object and effect is easy to understand, below in conjunction with specific embodiment, setting forth the present invention further.
The preparation of the polymethyl acrylic acid hexafluoro butyl ester macromole evocating agent of chlorine end-blocking:
1) Hexafluorobutyl mathacrylate, dimethyl formamide, pimelinketone and Catalysts Cu Cl
2powder joins in reaction vessel, vacuumizes and lead to rare gas element to reactor; Stir under the protection of rare gas element, add three (N, N-dimethyl aminoethyl) amine, and under the protection of rare gas element, add initiator dibromo-isobutyl acetoacetic ester, be placed in ultraviolet reactor and react; Reaction terminates rear reaction soln and dilutes through chloroform, removing catalysts and solvents, precipitation, the dry polymethyl acrylic acid hexafluoro butyl ester macromole evocating agent namely obtaining chlorine end-blocking; Hexafluorobutyl mathacrylate, dibromo-isobutyl acetoacetic ester, CuCl
2the mol ratio of powder and three (N, N-dimethyl aminoethyl) amine is 100-150:1:0.02-0.05:0.12-0.30.
2) preparation of the di-block copolymer of polymethyl acrylic acid hexafluoro butyl ester-b-poly N-isopropyl acrylamide:
By step 1) in the polymethyl acrylic acid hexafluoro butyl ester macromole evocating agent of chlorine end-blocking, dimethyl formamide, pimelinketone and Catalysts Cu Cl
2powder joins in reaction vessel, vacuumizes and lead to rare gas element to reactor; Airtight stirring under the protection of rare gas element, adds NIPA and three (N, N-dimethyl aminoethyl) amine, is placed in ultraviolet reactor and reacts; Reaction terminates rear reaction soln and dilutes through chloroform, removing catalysts and solvents, precipitation, dry namely obtain polymethyl acrylic acid hexafluoro butyl ester-b-poly N-isopropyl acrylamide di-block copolymer; NIPA, macromole evocating agent, CuCl
2the mol ratio of powder and three (N, N-dimethyl aminoethyl) amine is 200-300:1:0.04-0.1:0.24-0.6.
Step 1) in, described rare gas element adopts High Purity Nitrogen; The temperature of reaction of described reaction is reactor environment temperature, between 35-45 DEG C; Reaction times is 8 ~ 24 hours; Precipitation agent in described precipitation process is methyl alcohol and the hydrochloric acid mixed solution of 3:1; Drying temperature in described drying treatment is 40 DEG C.
Step 2) described in rare gas element adopt High Purity Nitrogen; The temperature of reaction of described reaction is reactor environment temperature, between 35-45 DEG C; Reaction times is 24 ~ 36 hours; Precipitation agent in described precipitation is anhydrous diethyl ether; Drying temperature in described drying treatment is 40 DEG C.
Step 1) and step 2) in, in described photoreactor, the predominant wavelength of light source is 360nm, and light intensity is 15Mw/cm
2.
The invention also discloses the di-block copolymer described above application in oily water separation field.
Embodiment 1
The preparation of the polymethyl acrylic acid hexafluoro butyl ester macromole evocating agent of chlorine end-blocking:
1) 100 parts of Hexafluorobutyl mathacrylates and 0.02 part of Catalysts Cu Cl2 powder are joined in reaction vessel, reactor is vacuumized and leads to rare gas element; Stir under the protection of rare gas element, add 0.12 part of three (N, N-dimethyl aminoethyl) amine, and under the protection of rare gas element, add 1 part of initiator dibromo-isobutyl acetoacetic ester, be placed in ultraviolet reactor and react; React 8 hours, terminate rear reaction soln and dilute through chloroform, removing catalysts and solvents, by methyl alcohol and the hydrochloric acid mixed solution precipitation of 3:1, namely obtain the polymethyl acrylic acid hexafluoro butyl ester macromole evocating agent of chlorine end-blocking 40 DEG C of vacuum-dryings;
2) preparation of the di-block copolymer of polymethyl acrylic acid hexafluoro butyl ester-b-poly N-isopropyl acrylamide:
By 1 part of step 1) in the polymethyl acrylic acid hexafluoro butyl ester macromole evocating agent of chlorine end-blocking and 0.04 part of Catalysts Cu Cl2 powder join in reaction vessel, reactor is vacuumized and leads to rare gas element; Airtight stirring under the protection of rare gas element, adds 200 parts of NIPAs and 0.24 part of three (N, N-dimethyl aminoethyl) amine, is placed in ultraviolet reactor and reacts; React 24 hours, reaction terminates rear reaction soln and dilutes through chloroform, removing catalysts and solvents, by anhydrous diethyl ether precipitation, 40 DEG C of vacuum-dryings namely obtain polymethyl acrylic acid hexafluoro butyl ester-b-poly N-isopropyl acrylamide di-block copolymer;
In the present embodiment, the number-average molecular weight Mn of bi-block copolymer is 35700g/mol, and molecular weight distribution is 1.20.
The di-block copolymer prepared in the present embodiment NIPA unit under temperature regulates can cause the hydrophilic and hydrophobic of this segment molecule chain to change.Therefore can regulate and control outside temperature condition to realize this block polymer and change in the wettability of solid surface, and then realize the application in oily water separation.Concrete surface wettability change to be shown in accompanying drawing shown in Fig. 2.
Particularly:
The preparation of polymeric film:
The di-block copolymer of the polymethyl acrylic acid hexafluoro butyl ester-b-poly N-isopropyl acrylamide of 50mg is dissolved in the tetrahydrofuran solvent of 1ml, to be dissolved completely after, solution is spun on clean silicon chip, can find from polymethyl acrylic acid hexafluoro butyl ester film (PHFBMA) Fig. 2 and polymethyl acrylic acid hexafluoro butyl ester-b-poly N-isopropyl acrylamide film (PHFBMA-b-PNIPAAm) contrast, the former water contact angle is not for be acted upon by temperature changes, maintain about 109 °, and after coating block polymer film, when temperature is elevated to 50 degree from 20 degree, water contact angle changes to 104.1 ° from 49.6, achieve the transformation of hydrophobe characteristic.
Or:
The di-block copolymer of the polymethyl acrylic acid hexafluoro butyl ester-b-poly N-isopropyl acrylamide of 50mg is dissolved in the tetrahydrofuran solvent of 1ml, to be dissolved completely after, solution is spun on clean stainless (steel) wire, scribbles the pattern of the stainless (steel) wire of bi-block copolymer as can see from Figure 3.This stainless (steel) wire is placed on tripping device, being separated of normal hexane under differing temps and water mixture can be realized.Can see from the A figure Fig. 4, when scribbling lowest critical solution temperature (LCST) of polymkeric substance stainless (steel) wire temperature lower than NIPA, present case is 20 degree, and this device crosses water only normal hexane; Can see from B figure, when lowest critical solution temperature (LCST) higher than NIPA, present case is 50 degree, and this device crosses normal hexane only water.
Embodiment 2
The preparation of the polymethyl acrylic acid hexafluoro butyl ester macromole evocating agent of chlorine end-blocking:
1) 100 parts of Hexafluorobutyl mathacrylates and 0.03 part of Catalysts Cu Cl2 powder are joined in reaction vessel, reactor is vacuumized and leads to rare gas element; Stir under the protection of rare gas element, add 0.18 part of three (N, N-dimethyl aminoethyl) amine, and under the protection of rare gas element, add 1 part of initiator dibromo-isobutyl acetoacetic ester, be placed in ultraviolet reactor and react; React 8 hours, terminate rear reaction soln and dilute through chloroform, removing catalysts and solvents, by methyl alcohol and the hydrochloric acid mixed solution precipitation of 3:1, namely obtain the polymethyl acrylic acid hexafluoro butyl ester macromole evocating agent of chlorine end-blocking 40 DEG C of vacuum-dryings;
2) preparation of the di-block copolymer of polymethyl acrylic acid hexafluoro butyl ester-b-poly N-isopropyl acrylamide:
By 1 part of step 1) in the polymethyl acrylic acid hexafluoro butyl ester macromole evocating agent of chlorine end-blocking and 0.06 part of Catalysts Cu Cl2 powder join in reaction vessel, reactor is vacuumized and leads to rare gas element; Airtight stirring under the protection of rare gas element, adds 200 parts of NIPAs and 0.36 part of three (N, N-dimethyl aminoethyl) amine, is placed in ultraviolet reactor and reacts; React 24 hours, reaction terminates rear reaction soln and dilutes through chloroform, removing catalysts and solvents, by anhydrous diethyl ether precipitation, 40 DEG C of vacuum-dryings namely obtain polymethyl acrylic acid hexafluoro butyl ester-b-poly N-isopropyl acrylamide di-block copolymer;
In the present embodiment, the number-average molecular weight Mn of bi-block copolymer is 38100g/mol, and molecular weight distribution is 1.28.
Embodiment 3
The preparation of the polymethyl acrylic acid hexafluoro butyl ester macromole evocating agent of chlorine end-blocking:
1) by 100 parts of Hexafluorobutyl mathacrylates and 0.02 part of Catalysts Cu Cl
2powder joins in reaction vessel, vacuumizes and lead to rare gas element to reactor; Stir under the protection of rare gas element, add 0.12 part of three (N, N-dimethyl aminoethyl) amine, and under the protection of rare gas element, add 1 part of initiator dibromo-isobutyl acetoacetic ester, be placed in ultraviolet reactor and react; React 10 hours, terminate rear reaction soln and dilute through chloroform, removing catalysts and solvents, by methyl alcohol and the hydrochloric acid mixed solution precipitation of 3:1, namely obtain the polymethyl acrylic acid hexafluoro butyl ester macromole evocating agent of chlorine end-blocking 40 DEG C of vacuum-dryings;
2) preparation of the di-block copolymer of polymethyl acrylic acid hexafluoro butyl ester-b-poly N-isopropyl acrylamide:
By 1 part of step 1) in the polymethyl acrylic acid hexafluoro butyl ester macromole evocating agent of chlorine end-blocking and 0.04 part of Catalysts Cu Cl
2powder joins in reaction vessel, vacuumizes and lead to rare gas element to reactor; Airtight stirring under the protection of rare gas element, adds 200 parts of NIPAs and 0.24 part of three (N, N-dimethyl aminoethyl) amine, is placed in ultraviolet reactor and reacts; React 30 hours, reaction terminates rear reaction soln and dilutes through chloroform, removing catalysts and solvents, by anhydrous diethyl ether precipitation, 40 DEG C of vacuum-dryings namely obtain polymethyl acrylic acid hexafluoro butyl ester-b-poly N-isopropyl acrylamide di-block copolymer;
In the present embodiment, the number-average molecular weight Mn of bi-block copolymer is 40500g/mol, and molecular weight distribution is 1.24.
Embodiment 4
The preparation of the polymethyl acrylic acid hexafluoro butyl ester macromole evocating agent of chlorine end-blocking:
1) by 150 parts of Hexafluorobutyl mathacrylates and 0.03 part of Catalysts Cu Cl
2powder joins in reaction vessel, vacuumizes and lead to rare gas element to reactor; Stir under the protection of rare gas element, add 0.18 part of three (N, N-dimethyl aminoethyl) amine, and under the protection of rare gas element, add 1 part of initiator dibromo-isobutyl acetoacetic ester, be placed in ultraviolet reactor and react; React 10 hours, terminate rear reaction soln and dilute through chloroform, removing catalysts and solvents, by methyl alcohol and the hydrochloric acid mixed solution precipitation of 3:1, namely obtain the polymethyl acrylic acid hexafluoro butyl ester macromole evocating agent of chlorine end-blocking 40 DEG C of vacuum-dryings;
2) preparation of the di-block copolymer of polymethyl acrylic acid hexafluoro butyl ester-b-poly N-isopropyl acrylamide:
By 1 part of step 1) in the polymethyl acrylic acid hexafluoro butyl ester macromole evocating agent of chlorine end-blocking and 0.06 part of Catalysts Cu Cl
2powder joins in reaction vessel, vacuumizes and lead to rare gas element to reactor; Airtight stirring under the protection of rare gas element, adds 300 parts of NIPAs and 0.36 part of three (N, N-dimethyl aminoethyl) amine, is placed in ultraviolet reactor and reacts; React 30 hours, reaction terminates rear reaction soln and dilutes through chloroform, removing catalysts and solvents, by anhydrous diethyl ether precipitation, 40 DEG C of vacuum-dryings namely obtain polymethyl acrylic acid hexafluoro butyl ester-b-poly N-isopropyl acrylamide di-block copolymer;
In the present embodiment, the number-average molecular weight Mn of bi-block copolymer is 50700g/mol, and molecular weight distribution is 1.25.
Embodiment 5
The preparation of the polymethyl acrylic acid hexafluoro butyl ester macromole evocating agent of chlorine end-blocking:
1) by 150 parts of Hexafluorobutyl mathacrylates and 0.04 part of Catalysts Cu Cl
2powder joins in reaction vessel, vacuumizes and lead to rare gas element to reactor; Stir under the protection of rare gas element, add 0.24 part of three (N, N-dimethyl aminoethyl) amine, and under the protection of rare gas element, add 1 part of initiator dibromo-isobutyl acetoacetic ester, be placed in ultraviolet reactor and react; React 8 hours, terminate rear reaction soln and dilute through chloroform, removing catalysts and solvents, by methyl alcohol and the hydrochloric acid mixed solution precipitation of 3:1, namely obtain the polymethyl acrylic acid hexafluoro butyl ester macromole evocating agent of chlorine end-blocking 40 DEG C of vacuum-dryings;
2) preparation of the di-block copolymer of polymethyl acrylic acid hexafluoro butyl ester-b-poly N-isopropyl acrylamide:
By 1 part of step 1) in the polymethyl acrylic acid hexafluoro butyl ester macromole evocating agent of chlorine end-blocking and 0.08 part of Catalysts Cu Cl
2powder joins in reaction vessel, vacuumizes and lead to rare gas element to reactor; Airtight stirring under the protection of rare gas element, adds 300 parts of NIPAs and 0.48 part of three (N, N-dimethyl aminoethyl) amine, is placed in ultraviolet reactor and reacts; React 36 hours, reaction terminates rear reaction soln and dilutes through chloroform, removing catalysts and solvents, by anhydrous diethyl ether precipitation, 40 DEG C of vacuum-dryings namely obtain polymethyl acrylic acid hexafluoro butyl ester-b-poly N-isopropyl acrylamide di-block copolymer;
In the present embodiment, the number-average molecular weight Mn of bi-block copolymer is 48500g/mol, and molecular weight distribution is 1.27.
Embodiment 6
The preparation of the polymethyl acrylic acid hexafluoro butyl ester macromole evocating agent of chlorine end-blocking:
1) by 150 parts of Hexafluorobutyl mathacrylates and 0.05 part of Catalysts Cu Cl
2powder joins in reaction vessel, vacuumizes and lead to rare gas element to reactor; Stir under the protection of rare gas element, add 0.30 part of three (N, N-dimethyl aminoethyl) amine, and under the protection of rare gas element, add 1 part of initiator dibromo-isobutyl acetoacetic ester, be placed in ultraviolet reactor and react; React 12 hours, terminate rear reaction soln and dilute through chloroform, removing catalysts and solvents, by methyl alcohol and the hydrochloric acid mixed solution precipitation of 3:1, namely obtain the polymethyl acrylic acid hexafluoro butyl ester macromole evocating agent of chlorine end-blocking 40 DEG C of vacuum-dryings;
2) preparation of the di-block copolymer of polymethyl acrylic acid hexafluoro butyl ester-b-poly N-isopropyl acrylamide:
By 1 part of step 1) in the polymethyl acrylic acid hexafluoro butyl ester macromole evocating agent of chlorine end-blocking and 0.10 part of Catalysts Cu Cl
2powder joins in reaction vessel, vacuumizes and lead to rare gas element to reactor; Airtight stirring under the protection of rare gas element, adds 300 parts of NIPAs and 0.60 part of three (N, N-dimethyl aminoethyl) amine, is placed in ultraviolet reactor and reacts; React 24 hours, reaction terminates rear reaction soln and dilutes through chloroform, removing catalysts and solvents, by anhydrous diethyl ether precipitation, 40 DEG C of vacuum-dryings namely obtain polymethyl acrylic acid hexafluoro butyl ester-b-poly N-isopropyl acrylamide di-block copolymer;
In the present embodiment, the number-average molecular weight Mn of bi-block copolymer is 48100g/mol, and molecular weight distribution is 1.30.
Embodiment 7
The preparation of the polymethyl acrylic acid hexafluoro butyl ester macromole evocating agent of chlorine end-blocking:
By 120 parts of Hexafluorobutyl mathacrylates and 0.03 part of Catalysts Cu Cl
2powder joins in reaction vessel, vacuumizes and lead to rare gas element to reactor; Stir under the protection of rare gas element, add 0.18 part of three (N, N-dimethyl aminoethyl) amine, and under the protection of rare gas element, add 1 part of initiator dibromo-isobutyl acetoacetic ester, be placed in ultraviolet reactor and react; React 10 hours, terminate rear reaction soln and dilute through chloroform, removing catalysts and solvents, by methyl alcohol and the hydrochloric acid mixed solution precipitation of 3:1, namely obtain the polymethyl acrylic acid hexafluoro butyl ester macromole evocating agent of chlorine end-blocking 40 DEG C of vacuum-dryings;
2) preparation of the di-block copolymer of polymethyl acrylic acid hexafluoro butyl ester-b-poly N-isopropyl acrylamide:
By 1 part of step 1) in the polymethyl acrylic acid hexafluoro butyl ester macromole evocating agent of chlorine end-blocking and 0.06 part of Catalysts Cu Cl
2powder joins in reaction vessel, vacuumizes and lead to rare gas element to reactor; Airtight stirring under the protection of rare gas element, adds 250 parts of NIPAs and 0.36 part of three (N, N-dimethyl aminoethyl) amine, is placed in ultraviolet reactor and reacts; React 30 hours, reaction terminates rear reaction soln and dilutes through chloroform, removing catalysts and solvents, by anhydrous diethyl ether precipitation, 40 DEG C of vacuum-dryings namely obtain polymethyl acrylic acid hexafluoro butyl ester-b-poly N-isopropyl acrylamide di-block copolymer;
In the present embodiment, the number-average molecular weight Mn of bi-block copolymer is 47600g/mol, and molecular weight distribution is 1.24.
Embodiment 8
The preparation of the polymethyl acrylic acid hexafluoro butyl ester macromole evocating agent of chlorine end-blocking:
By 150 parts of Hexafluorobutyl mathacrylates and 0.02 part of Catalysts Cu Cl
2powder joins in reaction vessel, vacuumizes and lead to rare gas element to reactor; Stir under the protection of rare gas element, add 0.12 part of three (N, N-dimethyl aminoethyl) amine, and under the protection of rare gas element, add 1 part of initiator dibromo-isobutyl acetoacetic ester, be placed in ultraviolet reactor and react; React 12 hours, terminate rear reaction soln and dilute through chloroform, removing catalysts and solvents, by methyl alcohol and the hydrochloric acid mixed solution precipitation of 3:1, namely obtain the polymethyl acrylic acid hexafluoro butyl ester macromole evocating agent of chlorine end-blocking 40 DEG C of vacuum-dryings;
2) preparation of the di-block copolymer of polymethyl acrylic acid hexafluoro butyl ester-b-poly N-isopropyl acrylamide:
By 1 part of step 1) in the polymethyl acrylic acid hexafluoro butyl ester macromole evocating agent of chlorine end-blocking and 0.04 part of Catalysts Cu Cl
2powder joins in reaction vessel, vacuumizes and lead to rare gas element to reactor; Airtight stirring under the protection of rare gas element, adds 300 parts of NIPAs and 0.24 part of three (N, N-dimethyl aminoethyl) amine, is placed in ultraviolet reactor and reacts; React 36 hours, reaction terminates rear reaction soln and dilutes through chloroform, removing catalysts and solvents, by anhydrous diethyl ether precipitation, 40 DEG C of vacuum-dryings namely obtain polymethyl acrylic acid hexafluoro butyl ester-b-poly N-isopropyl acrylamide di-block copolymer;
In the present embodiment, the number-average molecular weight Mn of bi-block copolymer is 57200g/mol, and molecular weight distribution is 1.31.
More than show and describe ultimate principle of the present invention and principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection domain is defined by appending claims and equivalent thereof.
Claims (8)
1. have a di-block copolymer for temperature response characteristics, it is characterized in that, described bi-block copolymer is the segmented copolymer of polymethyl acrylic acid hexafluoro butyl ester and poly N-isopropyl acrylamide, and the chemical structural formula of described bi-block copolymer is as follows:
Wherein, n is the integer between 75-120, and m is the integer between 150-240; The number-average molecular weight Mn of described di-block copolymer is 35700-57200, and molecular weight distribution is 1.20-1.31.
2. synthesize a method for di-block copolymer as claimed in claim 1, comprise the following steps:
1) preparation of the polymethyl acrylic acid hexafluoro butyl ester macromole evocating agent of chlorine end-blocking: Hexafluorobutyl mathacrylate, dimethyl formamide, pimelinketone and Catalysts Cu Cl
2powder joins in reaction vessel, vacuumizes and lead to rare gas element to reactor; Stir under the protection of rare gas element, add three (N, N-dimethyl aminoethyl) amine, and under the protection of rare gas element, add initiator dibromo-isobutyl acetoacetic ester, be placed in ultraviolet reactor and react; Reaction terminates rear reaction soln and dilutes through chloroform, removing catalysts and solvents, precipitation, the dry polymethyl acrylic acid hexafluoro butyl ester macromole evocating agent namely obtaining chlorine end-blocking;
2) preparation of the di-block copolymer of polymethyl acrylic acid hexafluoro butyl ester-b-poly N-isopropyl acrylamide:
By step 1) in the polymethyl acrylic acid hexafluoro butyl ester macromole evocating agent of chlorine end-blocking, dimethyl formamide, pimelinketone and Catalysts Cu Cl
2powder joins in reaction vessel, vacuumizes and lead to rare gas element to reactor; Airtight stirring under the protection of rare gas element, adds NIPA and three (N, N-dimethyl aminoethyl) amine, is placed in ultraviolet reactor and reacts; Reaction terminates rear reaction soln and dilutes through chloroform, removing catalysts and solvents, precipitation, dry namely obtain polymethyl acrylic acid hexafluoro butyl ester-b-poly N-isopropyl acrylamide di-block copolymer.
3. the method for synthesis di-block copolymer as claimed in claim 2, is characterized in that, step 1) in, described rare gas element adopts High Purity Nitrogen; The temperature of reaction of described reaction is reactor environment temperature, between 35-45 DEG C; Reaction times is 8 ~ 12 hours; Precipitation agent in described precipitation process is methyl alcohol and the hydrochloric acid mixed solution of 3:1; Drying temperature in described drying treatment is 40 DEG C.
4. the method for synthesis di-block copolymer as claimed in claim 2, is characterized in that, step 1) in, Hexafluorobutyl mathacrylate, dibromo-isobutyl acetoacetic ester, CuCl
2the mol ratio of powder and three (N, N-dimethyl aminoethyl) amine is 100-150:1:0.02-0.05:0.12-0.30.
5. the method for synthesis di-block copolymer as claimed in claim 2, is characterized in that, step 2) described in rare gas element adopt High Purity Nitrogen; The temperature of reaction of described reaction is reactor environment temperature, at 35-45 DEG C; Reaction times is 24 ~ 36 hours; Precipitation agent in described precipitation is anhydrous diethyl ether; Drying temperature in described drying treatment is 40 DEG C.
6. the method for synthesis di-block copolymer as claimed in claim 2, is characterized in that, step 2) in, NIPA, macromole evocating agent, CuCl
2the mol ratio of powder and three (N, N-dimethyl aminoethyl) amine is 200-300:1:0.04-0.1:0.24-0.6.
7. the method for synthesis di-block copolymer as claimed in claim 2, is characterized in that, step 1) and step 2) in, in described photoreactor, the predominant wavelength of light source is 360nm, and light intensity is 15Mw/cm
2.
8. the application of di-block copolymer in oily water separation as claimed in claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510487458.9A CN105085844A (en) | 2015-08-05 | 2015-08-05 | Diblock copolymer for oil-water separation with temperature control wetting property and preparing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510487458.9A CN105085844A (en) | 2015-08-05 | 2015-08-05 | Diblock copolymer for oil-water separation with temperature control wetting property and preparing method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105085844A true CN105085844A (en) | 2015-11-25 |
Family
ID=54567236
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510487458.9A Pending CN105085844A (en) | 2015-08-05 | 2015-08-05 | Diblock copolymer for oil-water separation with temperature control wetting property and preparing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105085844A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107474297A (en) * | 2017-09-07 | 2017-12-15 | 哈尔滨工业大学 | It is a kind of using shape-memory polymer and temperature-responsive molecule come the method for synergic adjustment wellability |
| CN114504880A (en) * | 2020-11-16 | 2022-05-17 | 清华大学 | Hydrophobic modified metal net and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1817925A (en) * | 2006-01-27 | 2006-08-16 | 苏州大学 | Amphipathic fluoride block copolymer and production thereof |
| CN101696312A (en) * | 2009-10-27 | 2010-04-21 | 华南理工大学 | Hydrophobic and oleophyllic bi-component acrylic resin and preparation method and application thereof |
| CN103881013A (en) * | 2014-03-18 | 2014-06-25 | 南京工业大学 | Method for quickly preparing fluorine-containing hydrogel by adopting frontal plasma polymerization |
| CN104151571A (en) * | 2014-07-31 | 2014-11-19 | 江南大学 | Method for preparing responsive liquid marble by using fluorine-containing self-assembled micelle |
-
2015
- 2015-08-05 CN CN201510487458.9A patent/CN105085844A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1817925A (en) * | 2006-01-27 | 2006-08-16 | 苏州大学 | Amphipathic fluoride block copolymer and production thereof |
| CN101696312A (en) * | 2009-10-27 | 2010-04-21 | 华南理工大学 | Hydrophobic and oleophyllic bi-component acrylic resin and preparation method and application thereof |
| CN103881013A (en) * | 2014-03-18 | 2014-06-25 | 南京工业大学 | Method for quickly preparing fluorine-containing hydrogel by adopting frontal plasma polymerization |
| CN104151571A (en) * | 2014-07-31 | 2014-11-19 | 江南大学 | Method for preparing responsive liquid marble by using fluorine-containing self-assembled micelle |
Non-Patent Citations (5)
| Title |
|---|
| ATHINA ANASTASAKI,等: "Copper(II)/Tertiary Amine Synergy in Photoinduced Living Radical", 《JOURNAL OF AMERICAN CHEMICAL SOCIETY》 * |
| ATHINA ANASTASAKI，等: "Photoinduced Synthesis of α,ω-Telechelic Sequence-Controlled", 《MACROMOLECULES》 * |
| GEORGE ODIAN著: "《聚合反应原理（中文版•原书第4版》", 30 July 2013 * |
| YUANYUAN AN,等: "Fluorine-containing thermo-sensitive microgels as carrier systems for biomacromolecules", 《COLLOIDS AND SURFACES B: BIOINTERFACES》 * |
| 刘国强，等: "温敏性含氟两亲接枝共聚物的制备及胶束化行为", 《高等学校化学学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107474297A (en) * | 2017-09-07 | 2017-12-15 | 哈尔滨工业大学 | It is a kind of using shape-memory polymer and temperature-responsive molecule come the method for synergic adjustment wellability |
| CN114504880A (en) * | 2020-11-16 | 2022-05-17 | 清华大学 | Hydrophobic modified metal net and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chambon et al. | Facile synthesis of methacrylic ABC triblock copolymer vesicles by RAFT aqueous dispersion polymerization | |
| RU2632886C2 (en) | Preparation of amphiphilic block copolymers by controlled radial micellar polymerization | |
| Zhang et al. | Polyion complex micelles possessing thermoresponsive coronas and their covalent core stabilization via “click” chemistry | |
| Liu et al. | pH-responsive supramolecular self-assembly of well-defined zwitterionic ABC miktoarm star terpolymers | |
| CN101649034B (en) | pH/temperature response double hydrophilic block copolymer and its preparation method | |
| Chen et al. | Synthesis of linear amphiphilic tetrablock quaterpolymers with dual stimulus response through the combination of ATRP and RAFT by a click chemistry site transformation approach | |
| CN104045778B (en) | Preparation method of star-like hybrid material with UCST and polyhedral oligomeric silsesquioxane (POSS) as core | |
| CN102395606A (en) | Branched copolymers, compositions and uses | |
| KR20140012941A (en) | Continuous flow polymerisation process | |
| CN105646891B (en) | A kind of amphipathic ternary molecular brush polymer and its vermiform unimolecular micelle constructed | |
| CN105085846B (en) | A kind of block copolymer and preparation method thereof | |
| Arjunan Vasantha et al. | Salt-responsive polysulfabetaines from acrylate and acrylamide precursors: robust stabilization of metal nanoparticles in hyposalinity and hypersalinity | |
| CN103232574A (en) | Preparation method of stable chitosan nano-micelle with CO2 responsiveness and temperature responsiveness | |
| CN104262555A (en) | Block polymer with multi-response property for temperature and carbon dioxide and preparation method thereof | |
| CN103694379B (en) | A kind of have di-block copolymer of light and pH response characteristic and preparation method thereof | |
| Suchao-In et al. | pH-and thermo-multi-responsive fluorescent micelles from block copolymers via reversible addition fragmentation chain transfer (RAFT) polymerization | |
| Hou et al. | Synthesis of poly (2-hydroxyethyl methacrylate) end-capped with asymmetric functional groups via atom transfer radical polymerization | |
| CN105085844A (en) | Diblock copolymer for oil-water separation with temperature control wetting property and preparing method thereof | |
| Byard et al. | Cationic Sterically Stabilized Diblock Copolymer Nanoparticles Exhibit Exceptional Tolerance toward Added Salt | |
| CN104262554B (en) | Self-crosslinkable responsive to temperature type hybrid block copolymer and preparation method thereof | |
| Xin et al. | Synthesis of zwitterionic block copolymers via RAFT polymerization | |
| CN106366225B (en) | Six arm temperature sensing polymers and preparation method thereof | |
| US8420771B2 (en) | PH-sensitive polyethylene oxide co-polymer and synthetic method thereof | |
| Billing et al. | Sulfo-and carboxybetaine-containing polyampholytes based on poly (2-vinyl pyridine) s: Synthesis and solution behavior | |
| JP2024028482A (en) | Synthetic method for preparation of rheological modifying polymers and use thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20151125 |