CN110585937A - Method for preparing homogeneous pore membrane by macromolecule co-assembly induced low-chi-value polymer - Google Patents
Method for preparing homogeneous pore membrane by macromolecule co-assembly induced low-chi-value polymer Download PDFInfo
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- CN110585937A CN110585937A CN201910745066.6A CN201910745066A CN110585937A CN 110585937 A CN110585937 A CN 110585937A CN 201910745066 A CN201910745066 A CN 201910745066A CN 110585937 A CN110585937 A CN 110585937A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0013—Casting processes
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- 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
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- 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
Abstract
The invention discloses a method for preparing a uniform pore membrane by inducing a low chi value polymer through macromolecular co-assembly. According to the method, a block polymer containing hydrogen bond receptors such as amido bonds or ester bonds is selected as a film forming material, the incompatibility among the block polymers is enhanced by utilizing the hydrogen bond action provided by exogenous macromolecules, and the self-assembly of the block polymers is promoted to form the homogeneous pore film. The method comprises the following steps: mixing the block polymer, the hydrogen bond donor polymer and the solvent to form a homogeneous solution, spreading the casting solution on a substrate by using a scraper, standing in air for a certain time, and immersing in a coagulating bath for phase conversion to form a film. The invention solves the problem that the low-chi-value block polymerization is difficult to generate microphase separation in the solution, provides a new idea for the preparation and the performance improvement of the homogeneous pore membrane, and also provides more choices for realizing the diversified design of the functions and the performances of the homogeneous pore membrane in different layers; the membrane prepared by the method has a looser internal structure, higher strength and higher flux.
Description
Technical Field
The invention belongs to the field of novel separation materials, and particularly relates to a block polymer with a weak phase separation tendency and a method for preparing a homogeneous pore membrane by using the block polymer.
Background
Homogeneous pore membranes, by virtue of their uniform pore size and relatively high porosity, can significantly improve separation accuracy and separation efficiency, and have recently been widely studied in the field of membrane technology. The block polymers currently used for preparing the mesoporous film are mostly polymers (such as polystyrene-block-polytetra ethylene pyridine, polystyrene-block-polyacrylic acid and related derivatives) with high phase separation capacity (Flory interaction parameter x is more than 0.2). However, the number of the polymers is small, so that the selection of materials of the homogeneous pore membrane is greatly limited; meanwhile, many polymers with weaker phase separation tendency have good performances such as stimulus responsiveness, high temperature resistance, flexibility and toughness, can endow the mesoporous membrane with more and better functions, and provide convenience for practical application.
However, the formation of block polymer based mesoporous films relies primarily on the self-assembly of block polymers into ordered structures under specific thermodynamic conditions. The low-chi-value block polymerization is difficult to generate microphase separation in a solution, which brings great inconvenience to the preparation of the mesoporous membrane by adopting the polymer, and is one of the reasons that the low-chi-value block polymerization is adopted to prepare the mesoporous membrane so far. At present, the conditions for preparing the mesoporous membrane by adopting the polymer are harsh, the polymer is generally required to have higher molecular weight, the membrane casting solution has higher concentration, and the types and the proportions of the solvents are relatively fixed, which are not beneficial to the regulation and control of the structure of the mesoporous membrane. Meanwhile, the problem of phase separation cannot be fundamentally solved, so that the obtained membrane is relatively compact and has low flux.
Disclosure of Invention
The invention aims to provide a method for preparing a uniform pore membrane by co-assembling a low-chi-value induced polymer, aiming at the defects of the prior art, and effectively solving the problems of weak phase separation tendency and difficult self-assembly of a block polymer in the membrane forming process.
The invention adopts the following technical scheme:
1. a method for preparing a homogeneous pore membrane by macromolecule co-assembly induced low chi value polymer comprises the following steps:
(1) mixing the block polymer, a solvent and an additive to form a homogeneous membrane casting solution; the mass fraction of the block polymer in the casting solution is 3-33 wt%, the block polymer is a block polymer containing a hydrogen bond receptor such as an ester bond or an amido bond, and the additive is a hydrogen bond donor polymer; the mass ratio of the additive to the block polymer is 0.01-0.5: 1.
(2) Spreading the casting film liquid on a flat substrate by a scraper, and staying in the air for 5-120s to obtain a primary film;
(3) immersing the primary membrane into a coagulating bath for phase conversion to obtain a homogeneous pore membrane, and finally storing the homogeneous pore membrane in deionized water.
Further, the structural formula (1) or the structural formula (2):
wherein the structure of R is selected from the structural formula (3) to the structural formula (6); the structure of R' is selected from structural formula (7) to structural formula (9); r' is an alkane; n and m are natural numbers.
Further, in the step (1), the mass ratio of the hydrophobic block to the hydrophilic block in the block polymer is 2-20: 1.
Further, in the step (1), the solvent is composed of one, two or three of dioxane, pyridine, tetrahydrofuran, propylene glycol propyl ether, dimethylformamide, dimethylacetamide, acetonitrile, methanol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and polyethylene glycol with molecular weight less than 500 according to any ratio.
Further, in the step (1), the additive is selected from polyacrylic acid with the molecular weight of 500-25500 g/mol, polymethacrylic acid, carboxyl-containing hyperbranched polymer, sulfonated polystyrene and the like;
further, in the step (2), the substrate is a flat membrane or a hollow fiber membrane of glass, non-woven fabric, silicon wafer, glass modified by a silane coupling agent, polyimide, polysulfone, polyethersulfone, polyvinylidene fluoride, polyacrylonitrile, polyethylene, polypropylene.
Further, the coagulating bath is composed of one or two of deionized water, glycerol and ethanol according to any ratio.
The invention has the beneficial effects that: according to the invention, macromolecules are introduced as additives in the process of preparing the mesoporous membrane by the SNIPS method, so that the phase separation is enhanced, the problem that the microphase separation of low-chi-value block polymerization in a solution is difficult to occur is solved, a new thought is provided for the preparation and performance improvement of the mesoporous membrane, the requirements of the preparation of the mesoporous membrane by the SNIPS method on polymers are reduced, the selection range of raw materials is widened, and more choices are provided for realizing the diversified design of functions and performances of the mesoporous membrane at different layers; the membrane prepared by the method has a looser internal structure, higher strength and higher flux.
Drawings
FIG. 1: nuclear magnetic spectrum of a block polymer, wherein a is the block polymer prepared in example 1, b is the block polymer prepared in example 2, and c is the block polymer prepared in example 3;
FIG. 2: detecting the supermolecule effect by infrared;
FIG. 3: a homogeneous pore membrane forming structure, wherein a is the homogeneous pore membrane prepared in example 1, b is the homogeneous pore membrane prepared in example 2, and c is the homogeneous pore membrane prepared in example 3;
FIG. 4: an X-ray small angle scattering pattern.
Detailed Description
The invention takes the block polymer containing polyacrylamide, polyester and the like with hydrogen bond acceptors as a main film forming material, overcomes the problem of difficult self-assembly by adopting a simple co-assembly method on the basis of the original SNIPS method, and brings convenience for preparing the homogeneous pore film by using the block polymer with low chi value. The specific scheme is that a polymer additive which has strong repulsion with a hydrophobic block and can interact with a hydrophilic block is selected, and the additive is dynamically connected to the hydrophilic end of the block polymer through intermolecular force to promote the cooperative assembly of the block polymer; and the repulsion force between the additive and the hydrophobic block is utilized to promote the hydrophilic block and the hydrophobic block to be separated, so that the incompatibility between the two blocks of the polymer is improved, and the homogeneous pore membrane is formed by self-assembly. The introduction of the additive greatly reduces the requirements of the formation of the homogeneous pore membrane on the molecular weight of the polymer and the membrane forming conditions. In addition, the introduction of the additive enhances phase separation, and the prepared membrane has a looser internal structure and higher flux.
Example 1
A method for preparing a homogeneous pore membrane by macromolecule co-assembly induced low chi value polymer comprises the following steps:
1. the synthesis method of the homogeneous pore membrane material comprises the following steps: a three-necked flask was charged with styrene (81.3g, 0.8mol), azobisisobutyronitrile (8.6mg, 0.059mmol), dodecyl sulfate (117.1mg, 0.3mmol), and nitrogen purged at room temperature for 1 hour. Transferring the mixture into an oil bath kettle to react for 5 hours at the temperature of 90 ℃. After the reaction, n-hexane was used for precipitation to obtain 15.05g of a product. The product was weighed out (4 g, 0.08mmol), N-isopropylacrylamide (5g, 0.044mol) and azobisisobutyronitrile (4.4mg, 0.027mmol) were added as solvent, and nitrogen was bubbled at room temperature for 1 h. Reacting in an oil bath at 80 ℃ for 20h, and precipitating by using an n-hexane ethanol solution. Drying to obtain 4.1g of the required polymer. The structure of the product is analyzed by a nuclear magnetic resonance spectrometer, and a nuclear magnetic spectrum is shown in figure 1a, so that the successful synthesis of the target polymer is proved, the hydrophilic block accounts for 23 wt%, and the structural formula is shown as follows.
2. Dissolving the synthesized block polymer and the additive in a solvent to form a homogeneous solution, wherein the solvent is selected from 1, 4 dioxane/THF ═ 6: 4(w/w), wherein the additive is PAA (molecular weight is 8000g/mol), and the mass fractions of the polymer and the additive are respectively 20 wt% and 0.2 wt%;
3. spreading the casting solution on the polyacrylonitrile-supported membrane by a scraper of 150 μm, and staying in the air for 30 s;
4. immersing the film into a coagulating bath for phase conversion to form a film, and eluting the additive; the formation of the homopore structure was verified by scanning electron microscopy (fig. 3 a). The additive was found to be effective in promoting microphase separation of the block polymer (figure 4) by comparing the small angle data before and after addition of the additive, while the infrared data demonstrate the hydrogen bonding between the additive and the block polymer (figure 2), explaining the reason for its effect.
Example 2
A method for preparing a homogeneous pore membrane by macromolecule co-assembly induced low chi value polymer comprises the following steps:
1. the synthesis method of the homogeneous pore membrane material comprises the following steps: a three-necked flask was charged with styrene (81.3g, 0.8mol), azobisisobutyronitrile (8.6mg, 0.059mmol), dodecyl sulfate (117.1mg, 0.3mmol), and nitrogen purged at room temperature for 1 hour. Transferring the mixture into an oil bath kettle to react for 5 hours at the temperature of 90 ℃. After the reaction, n-hexane was used for precipitation to obtain 15.05g of a product. The product was weighed out (4 g, 0.08mmol), N-isopropylacrylamide (5g, 0.044mol) and azobisisobutyronitrile (4.4mg, 0.027mmol) were added as solvent, and nitrogen was bubbled at room temperature for 1 h. Reacting in an oil bath at 80 ℃ for 10h, and precipitating by using an n-hexane ethanol solution. Drying to obtain 4.02g of the required polymer. The structure of the product is analyzed by a nuclear magnetic resonance spectrometer, and a nuclear magnetic spectrum is shown in figure 1b, so that the successful synthesis of the target polymer is proved, the hydrophilic block accounts for 5 wt%, and the structural formula is shown as follows.
2. Dissolving the synthesized block polymer and the additive in a solvent to form a homogeneous solution, wherein the solvent is selected from 1, 4 dioxane/acetonitrile 7: 3(w/w), wherein the additive is PAA (molecular weight is 500g/mol), and the mass fractions of the polymer and the additive are respectively 33 wt% and 2 wt%;
3. spreading the casting solution on the polyacrylonitrile-supported membrane by a scraper of 150 μm, and staying in the air for 5 s;
4. immersing the film into a coagulating bath for phase conversion to form a film, and eluting the additive; the formation of the homopore structure was verified by scanning electron microscopy (fig. 3 b).
Example 3
A method for preparing a homogeneous pore membrane by macromolecule co-assembly induced low chi value polymer comprises the following steps:
1. the synthesis method of the homogeneous pore membrane material comprises the steps of adding styrene (81.3g, 0.8mol), azobisisobutyronitrile (8.6mg, 0.059mmol), dodecyl sulfate (117.1mg, 0.3mmol) into a three-neck flask, and bubbling nitrogen for 1h at room temperature. Transferring the mixture into an oil bath kettle to react for 10 hours at the temperature of 90 ℃. After the reaction, n-hexane was used for precipitation to obtain 22.1g of a product. The product was weighed out (4 g, 0.05mmol), N-isopropylacrylamide (5g, 0.044mol) and azobisisobutyronitrile (4.4mg, 0.027mmol) were added as solvent, and nitrogen was bubbled at room temperature for 1 h. Oil bath reaction is carried out for 60 hours at the temperature of 85 ℃, and then normal hexane ethanol solution is used for precipitation. Drying to obtain 5.6g of the required polymer. The structure of the product is analyzed by a nuclear magnetic resonance spectrometer, and a nuclear magnetic spectrum is shown in figure 1, so that the successful synthesis of the target polymer is proved, the hydrophilic block accounts for 33 wt%, and the structural formula is shown as follows.
2. Dissolving the synthesized block polymer and the additive in a solvent to form a homogeneous solution, wherein the solvent is selected from 1, 4 dioxane/methanol (95): 5(w/w), wherein the additive is PAA (molecular weight is 25500g/mol), and the mass fractions of the polymer and the additive are respectively 3 wt% and 1.5 wt%;
3. spreading the casting solution on the polyacrylonitrile-supported membrane by a scraper of 150 μm, and staying in the air for 120 s;
4. immersing the film into a coagulating bath for phase conversion to form a film, and eluting the additive; the formation of the homopore structure was verified by scanning electron microscopy (fig. 3 c).
Example 4
A method for preparing a homogeneous pore membrane by macromolecule co-assembly induced low chi value polymer comprises the following steps:
1. the synthesis method of the homogeneous pore membrane material comprises the following steps: in a three-necked flask, 4-chloromethylstyrene (76g,0.5mol), azobisisobutyronitrile (5.8mg, 0.04mmol), dodecyl sulfate (97.6mg, 0.25mmol) and nitrogen were introduced at room temperature for 1 hour. Transferring the mixture into an oil bath kettle to react for 6 hours at the temperature of 80 ℃. After the reaction, n-hexane was used for precipitation to obtain 8.2g of a product. The product was weighed 4g (0.12mmol), N-dimethylaminopropylacrylamide (4.4g, 0.044mol) and azobisisobutyronitrile (3.6mg, 0.022mmol), DMF was added as solvent, and nitrogen was bubbled at room temperature for 1 h. Oil bath reaction at 85 ℃ for 26h, and precipitation by n-hexane ethanol solution. Drying to obtain 4.3g of the required polymer, wherein the hydrophilic block accounts for 15 wt%, and the structural formula of the polymer is shown in the specification.
2. Dissolving the synthesized block polymer and the additive in a solvent to form a homogeneous solution, wherein the solvent is selected from DOX/THF (5: 5(w/w), wherein the additive is PAA (molecular weight is 5000g/mol), and the mass fractions of the polymer and the additive are respectively 24 wt% and 2.5 wt%;
3. spreading the casting solution on the polyacrylonitrile-supported membrane by a scraper of 150 μm, and staying in the air for 30 s;
4. immersing the film into a coagulating bath for phase conversion to form a film, and eluting the additive; the formation of the homopore structure was verified by scanning electron microscopy.
Example 5
A method for preparing a homogeneous pore membrane by macromolecule co-assembly induced low chi value polymer comprises the following steps:
1. the synthesis method of the homogeneous pore membrane material comprises the following steps: 4-trimethylsilylstyrene (105.8g, 0.6mol), azobisisobutyronitrile (5.1mg, 0.035mmol), dodecyl sulfate (78.1mg, 0.2mmol) were charged in a three-necked flask and purged with nitrogen at room temperature for 1 h. Transferring the mixture into an oil bath kettle to react for 6 hours at the temperature of 95 ℃. After the reaction, n-hexane was used for precipitation to obtain 13.1g of a product. 3g (0.04mmol) of the product was weighed, N-isopropylacrylamide (2g, 0.017mol) and azobisisobutyronitrile (1.6mg, 0.01mmol) were added, DMF was used as a solvent, and nitrogen was bubbled at room temperature for 1 h. Reacting in an oil bath at 80 ℃ for 30h, and precipitating by using an n-hexane ethanol solution. Drying to obtain 3.05g of the required polymer, wherein the hydrophilic block accounts for 13 wt%, and the structural formula of the polymer is shown in the specification.
2. Dissolving the synthesized block polymer and the additive in a solvent to form a homogeneous solution, wherein the solvent is DMF/THF (1: 9(w/w), wherein the additive is carboxyl-containing hyperbranched polymer (molecular weight is 2000g/mol), and the mass fractions of the polymer and the additive are respectively 25 wt% and 3 wt%;
3. spreading the casting solution on the polyacrylonitrile-supported membrane by a scraper of 150 μm, and staying in the air for 15 s;
4. immersing the film into a coagulating bath for phase conversion to form a film, and eluting the additive; the formation of the homopore structure was verified by scanning electron microscopy.
Example 6
A method for preparing a homogeneous pore membrane by macromolecule co-assembly induced low chi value polymer comprises the following steps:
1. the synthesis method of the homogeneous pore membrane material comprises the following steps: styrene (62.4g, 0.6mol), lactide (14.4g, 0.1mol), azobisisobutyronitrile (3.3mg, 0.02mmol), 4-dimethylaminopyridine (2.5mg, 0.02mmol), hydroxyethylbenzylthioester (48.8mg, 0.2mmol), nitrogen sparged at room temperature for 1h were added to a three-necked flask. Transferring the mixture into an oil bath kettle to react for 36 hours at the temperature of 80 ℃. After the reaction, n-hexane is used for precipitation to obtain 15.6g of a product, the hydrophilic block accounts for 15 wt%, and the structural formula is shown as follows.
2. Dissolving the synthesized block polymer and the additive in a solvent to form a homogeneous solution, wherein the solvent is selected from DOX/acetonitrile (9): 1(w/w), the additive is selected from polymethacrylic acid (with the molecular weight of 10000g/mol), and the mass fractions of the polymer and the additive are respectively 18 wt% and 1.5 wt%;
3. spreading the casting solution on the polyacrylonitrile-supported membrane by a scraper of 150 μm, and staying in the air for 30 s;
4. immersing the film into a coagulating bath for phase conversion to form a film, and eluting the additive; the formation of the homopore structure was verified by scanning electron microscopy.
Example 7
A method for preparing a homogeneous pore membrane by macromolecule co-assembly induced low chi value polymer comprises the following steps:
1. a synthetic method of a homogeneous pore membrane material (R is 1, and the carbon atom number of R' is 6): in a three-necked flask, styrene (83.2g, 0.8mol), caprolactone (11.4g, 0.1mol), azobisisobutyronitrile (2.5mg, 0.015mmol), 4-dimethylaminopyridine (1.9mg, 0.015mmol), hydroxyethylbenzylthioester (36.6mg, 0.15mmol), and nitrogen purged at room temperature for 1 hour were added. Transferring the mixture into an oil bath kettle to react for 40 hours at the temperature of 80 ℃. After the reaction, n-hexane is used for precipitation to obtain 13.8g of a product, the hydrophilic block accounts for 19 wt%, and the structural formula is shown as follows.
2. Dissolving the synthesized block polymer and the additive in a solvent to form a homogeneous solution, wherein the solvent is DMF/THF (1: 9(w/w), the additive is sulfonated polystyrene (molecular weight is 4000g/mol), and the mass fractions of the polymer and the additive are respectively 20 wt% and 2 wt%;
3. spreading the casting solution on the polyacrylonitrile-supported membrane by a scraper of 150 μm, and staying in the air for 120 s;
4. immersing the film into a coagulating bath for phase conversion to form a film, and eluting the additive; the formation of the homopore structure was verified by scanning electron microscopy.
Claims (7)
1. A method for preparing a homogeneous pore membrane by macromolecule co-assembly induced low chi value polymer is characterized by comprising the following steps:
(1) mixing the block polymer, a solvent and an additive to form a homogeneous membrane casting solution; the mass fraction of the block polymer in the casting solution is 3-33 wt%, the block polymer is a block polymer containing an ester bond or amido bond hydrogen bond receptor, and the additive is a hydrogen bond donor polymer; the mass ratio of the additive to the block polymer is 0.01-0.5: 1.
(2) Spreading the casting film liquid on a flat substrate by a scraper, and staying in the air for 5-120s to obtain a primary film;
(3) immersing the primary membrane into a coagulating bath for phase conversion to obtain a homogeneous pore membrane, and finally storing the homogeneous pore membrane in deionized water.
2. The method of claim 1, wherein in step (1), the structure of the block polymer is represented by structural formula (1) or structural formula (2):
wherein the structure of R is selected from the structural formula (3) to the structural formula (6); the structure of R' is selected from structural formula (7) to structural formula (9); r' is an alkane; n and m are natural numbers.
3. The method according to claim 1, wherein in the step (1), the mass of the hydrophilic block in the block polymer accounts for 5-33% of the total mass of the polymer.
4. The method as claimed in claim 1, wherein in the step (1), the solvent is one, two or three of dioxane, pyridine, tetrahydrofuran, propylene glycol propyl ether, dimethylformamide, acetonitrile, methanol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and polyethylene glycol with molecular weight less than 500.
5. The method according to claim 1, wherein in the step (1), the additive is selected from polyacrylic acid with a molecular weight of 500-25500 g/mol, polymethacrylic acid, carboxyl-containing hyperbranched polymer, sulfonated polystyrene and the like;
6. the method according to claim 1, wherein in the step (2), the substrate is a flat membrane or a hollow fiber membrane of glass, non-woven fabric, silicon wafer, glass modified by silane coupling agent, polyimide, polysulfone, polyethersulfone, polyvinylidene fluoride, polyacrylonitrile, polyethylene, polypropylene.
7. The method of claim 1, wherein the coagulation bath consists of one or two of deionized water, glycerol, ethanol in any ratio.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150151256A1 (en) * | 2012-08-09 | 2015-06-04 | Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung GmbH | Membrane with an isoporous, active separation layer, and method for producing a membrane |
| CN109400829A (en) * | 2018-09-13 | 2019-03-01 | 浙江工业大学 | A method of being used to prepare the block copolymer and its preparation aperture Asia 10nm homopore membrane of homopore membrane |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150151256A1 (en) * | 2012-08-09 | 2015-06-04 | Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung GmbH | Membrane with an isoporous, active separation layer, and method for producing a membrane |
| CN109400829A (en) * | 2018-09-13 | 2019-03-01 | 浙江工业大学 | A method of being used to prepare the block copolymer and its preparation aperture Asia 10nm homopore membrane of homopore membrane |
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| ***: "《现代药物设计学》", 31 May 2006, 中国医药科技出版社 * |
| 朱国栋: ""Preparation of isoporous membranes from low χ block copolymers via co-assembly with H-bond interacting homopolymers"", 《JOURNAL OF MEMBRANE SCIENCE》 * |
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Application publication date: 20191220 |